EP4255945A1 - Adhesive two-component composition based on itaconate monomer - Google Patents
Adhesive two-component composition based on itaconate monomerInfo
- Publication number
- EP4255945A1 EP4255945A1 EP21836592.2A EP21836592A EP4255945A1 EP 4255945 A1 EP4255945 A1 EP 4255945A1 EP 21836592 A EP21836592 A EP 21836592A EP 4255945 A1 EP4255945 A1 EP 4255945A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- meth
- itaconate
- acrylate
- composition according
- 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 87
- 239000000178 monomer Substances 0.000 title claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 26
- 239000000853 adhesive Substances 0.000 title claims abstract description 25
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 25
- 229920002635 polyurethane Polymers 0.000 claims abstract description 25
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 19
- 239000011258 core-shell material Substances 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 70
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 4
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims description 4
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 4
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 claims description 3
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 3
- OYOQFCOWKUHVMM-UHFFFAOYSA-N 4-o-cyclohexyl 1-o-ethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)C(=C)CC(=O)OC1CCCCC1 OYOQFCOWKUHVMM-UHFFFAOYSA-N 0.000 claims description 2
- OICRDFIVTSEVJJ-UHFFFAOYSA-N bis(1,1,1,3,3,3-hexafluoropropan-2-yl) 2-methylidenebutanedioate Chemical compound FC(F)(F)C(C(F)(F)F)OC(=O)CC(=C)C(=O)OC(C(F)(F)F)C(F)(F)F OICRDFIVTSEVJJ-UHFFFAOYSA-N 0.000 claims description 2
- JYMCPGMXHKUZGC-UHFFFAOYSA-N bis(2-methylpropyl) 2-methylidenebutanedioate Chemical compound CC(C)COC(=O)CC(=C)C(=O)OCC(C)C JYMCPGMXHKUZGC-UHFFFAOYSA-N 0.000 claims description 2
- WZAPMKYCDNQBOC-UHFFFAOYSA-N dibenzyl 2-methylidenebutanedioate Chemical compound C=1C=CC=CC=1COC(=O)C(=C)CC(=O)OCC1=CC=CC=C1 WZAPMKYCDNQBOC-UHFFFAOYSA-N 0.000 claims description 2
- GFHMGSFDHKDJSG-UHFFFAOYSA-N dicyclohexyl 2-methylidenebutanedioate Chemical compound C1CCCCC1OC(=O)C(=C)CC(=O)OC1CCCCC1 GFHMGSFDHKDJSG-UHFFFAOYSA-N 0.000 claims description 2
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 claims description 2
- NAPZWBMEGHXRJS-UHFFFAOYSA-N diphenyl 2-methylidenebutanedioate Chemical compound C=1C=CC=CC=1OC(=O)C(=C)CC(=O)OC1=CC=CC=C1 NAPZWBMEGHXRJS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 2
- -1 polyene polyols Chemical class 0.000 description 37
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 229920005862 polyol Polymers 0.000 description 23
- 150000003077 polyols Chemical class 0.000 description 18
- 239000005056 polyisocyanate Substances 0.000 description 10
- 229920001228 polyisocyanate Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 150000004072 triols Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012764 mineral filler Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 3
- JFZVSHAMRZPOPA-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)-4-methylanilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=C(C)C=C1 JFZVSHAMRZPOPA-UHFFFAOYSA-N 0.000 description 3
- HXCWOOAEAHVMBJ-UHFFFAOYSA-N 2-(n,4-dimethylanilino)ethanol Chemical compound OCCN(C)C1=CC=C(C)C=C1 HXCWOOAEAHVMBJ-UHFFFAOYSA-N 0.000 description 3
- VIIZJXNVVJKISZ-UHFFFAOYSA-N 2-(n-methylanilino)ethanol Chemical compound OCCN(C)C1=CC=CC=C1 VIIZJXNVVJKISZ-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-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
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- UDKSLGIUCGAZTK-UHFFFAOYSA-N phenyl pentadecane-1-sulfonate Chemical compound CCCCCCCCCCCCCCCS(=O)(=O)OC1=CC=CC=C1 UDKSLGIUCGAZTK-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004588 polyurethane sealant Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical class OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- 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
- C08F290/08—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 side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/147—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Definitions
- the present invention relates to a two-component adhesive composition based on itaconate monomer.
- the invention also relates to the use of said composition for repairing and/or structural or semi-structural bonding of materials in the field of transport, automotive (car, bus or truck), marine, assembly, electronics, batteries or construction
- Acrylic compositions are known reactive systems that crosslink by radical polymerization. They are used as adhesives, sealants and coatings. Radical polymerization is typically initiated by a redox system which, through an oxidation-reduction reaction, leads to the production of radicals.
- the majority of acrylic systems are two-component systems.
- the first component traditionally contains the reducing agent and the reactive monomers, and the second component contains the oxidizing agent. Once the two components are mixed, the reducing agent induces the cleavage of the 0-0 bond of the organic peroxide, for example, and initiates the polymerization.
- the hydroxyl index of an alcoholic compound represents the number of hydroxyl functions per gram of product, which is expressed in the form of the equivalent number of milligrams of potash (mg KOH/g) used in the assay of the hydroxyl functions, per gram of product;
- the measurement of viscosity at 23°C can be done using a Brookfield viscometer according to the ISO 2555 standard.
- the measurement carried out at 23°C (or at 100°C) can be done using a Brookfield RVT viscometer, a needle adapted to the viscosity range and at a speed of rotation of 20 revolutions per minute (rpm).
- the present invention relates to a two-component adhesive composition
- a two-component adhesive composition comprising:
- component A comprising:
- each of R 1 and R 2 represents, independently of one another, organic radicals;
- component B comprising:
- the polyurethane P may have a number-average molecular mass (Mn) greater than or equal to 700 g/mol, preferably greater than or equal to 900 g/mol.
- the polyurethane P may have a number-average molecular weight (Mn) less than or equal to 30,000 g/mol, preferably less than or equal to 10,000 g/mol, even more preferably less than or equal to 5,000 g/mol.
- Mn number-average molecular weight
- the polyurethane P has a number-average molecular mass (Mn) ranging from 700 g/mol to 30,000 g/mol, preferentially from 900 g/mol to 20,000 g/mol, and even more preferentially from 900 g/mol to 10,000 g/mol.
- Mn number-average molecular mass
- the Mn of the polyurethane is measured by GPC with comparison with a PS reference.
- Polyurethane P can be obtained by a process comprising:
- step E2 the reaction of the product formed at the end of step E1) with at least one (meth)acrylate monomer M2 comprising at least one hydroxyl function.
- the usable polyisocyanate(s) can be added sequentially or reacted as a mixture.
- the polyisocyanate(s) can be chosen from diisocyanates or triisocyanates.
- the polyisocyanate(s) can be monomeric(s), oligometic(s) or polymeric(s).
- the polyisocyanate(s) may be selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate , nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 2,4'- methylenebis(cyclohexylisocyanate) (2,4'-H6MDI), 4,4'- methylenebis(cyclohexylisocyanate) (4,4'-H6MDI), norbornane diisocyanate, norbornene diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyl
- the polyisocyanate(s) that can be used can be triisocyanate(s), for example chosen from isocyanurates, biurets, and adducts of diisocyanates and triols.
- the isocyanurate(s) can be used in the form of a technical mixture of (poly)isocyanurate(s) with a purity greater than or equal to 70% by weight isocyanurate(s).
- the diisocyanate isocyanurate(s) which can be used according to the invention may correspond to the following general formula (W): in which R 5 represents a linear or branched, cyclic, aliphatic, arylaliphatic or aromatic alkylene group, comprising from 4 to 9 carbon atoms, provided that the NCO groups are not linked by a covalent bond to a carbon atom making part of an aromatic hydrocarbon ring such as a phenyl group.
- diisocyanate trimers which can be used, mention may be made of the isocyanurate trimer of hexamethylene diisocyanate (HDI).
- HDI hexamethylene diisocyanate
- adducts of diisocyanates and triols which can be used according to the invention, mention may be made of the adduct of meta-xylylene diisocyanate and of trimethylolpropane, as represented below.
- This adduct is marketed for example by the company MITSUI CHEMICALS, Inc under the name “TAKENATE® D-110N”.
- the polyisocyanate(s) which can be used are typically commercially available.
- SCURANATE® TX marketed by the company VENCOREX, corresponding to a 2,4-TDI with a purity of around 95%
- SCURANATE® T100 marketed by the company VENCOREX, corresponding to a 2,4-TDI with a purity greater than 99% by weight.
- the polyol(s) may be chosen from polyester polyols, polyether polyols, polyene polyols, polycarbonate polyols, poly(ether-carbonate) polyols, and mixtures thereof.
- the polyol(s) that can be used can be chosen from aromatic polyols, aliphatic polyols, arylaliphatic polyols and mixtures of these compounds.
- the polyol(s) that can be used can be chosen from those having a number-average molecular mass (Mn) ranging from 200 g/mol to 20,000 g/mol, preferably from 400 g/mol to 18,000 g/mol.
- Mn number-average molecular mass
- the number average molecular mass of the polyols can be calculated from the hydroxyl number (IOH) expressed in mg KOH/g and the functionality of the polyol or determined by methods well known to those skilled in the art, for example by steric exclusion chromatography (or SEC in English) with PEG (polyethylene glycol) standard.
- polyester polyols mention may be made, for example, of polyester polyols of natural origin such as castor oil; polyester polyols resulting from polycondensation:
- aliphatic (linear, branched or cyclic) or aromatic polyols such as, for example, monoethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, butenediol, 1,6-hexanediol, cyclohexane dimethanol, tricyclodecane dimethanol, neopentyl glycol, cyclohexane dimethanol, a polyether polyol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, sucrose, glucose , sorbitol, pentaerythritol, mannitol, N-methyldiethanolamine, triethanolamine, dimer fatty alcohol, trimer fatty alcohol and mixtures thereof, with
- polycarboxylic acid or its ester or anhydride derivative such as 1,6-hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1,18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, a dimer fatty acid, a trimer fatty acid and mixtures of these acids, an unsaturated anhydride such as for example l maleic or phthalic anhydride, or a lactone.
- anhydride derivative such as 1,6-hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1,18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, a dimer fatty acid,
- polyester polyols can be prepared conventionally, and are mostly commercially available.
- the polyether polyol(s) which can be used according to the invention may be chosen from polyoxyalkylene polyols, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms, plus preferably from 2 to 3 carbon atoms.
- polyoxyalkylene diols or triols that can be used according to the invention, mention may be made of polyoxypropylene diols or triols (also designated by polypropylene glycol (PPG) diols or triols) having a number-average molecular mass (Mn) ranging from 300 at 12,000 g/mol; polyoxyethylene diols or triols (also designated by polyethylene glycol (PEG) diols or triols) having a number-average molecular weight (Mn) ranging from 300 to 12,000 g/mol; and their mixtures.
- PPG polypropylene glycol
- PEG polyethylene glycol
- Mn number-average molecular weight
- VORANOL® P1010 marketed by the company DOW with a number-average molecular mass (Mn) close to 1020 g/mol and whose hydroxyl index is approximately 110 mgKOH/g.
- polyether triol mention may be made of the polyoxypropylene triol marketed under the name “VORANOL® CP 450” by the company DOW, with a number-average molecular mass (Mn) close to 450 g/mol and whose hydroxyl index ranges from 370 to 396 mg KOH/g.
- polyene polyols mention may be made of butadiene homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups, optionally epoxidized, such as for example those marketed under the name “POLY BD® or KRASOL®” by the company CRAY VALLEY, as well as isoprene homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups, such as for example those marketed under the name “POLY IPTM or EPOLTM” by the company IDEMITSU KOSAN.
- butadiene homopolymers saturated or unsaturated, comprising terminal hydroxyl groups, optionally epoxidized, such as for example those marketed under the name “POLY BD® or KRASOL®” by the company CRAY VALLEY
- isoprene homopolymers saturated or unsaturated, comprising terminal hydroxyl groups, such as for example those marketed under the name “POLY IPTM or EPOLTM” by the company IDEMITSU KO
- CONVERGE® POLYOL 212-10 and “CONVERGE® POLYOL 212-20” marketed by the company NOVOMER respectively with a molecular weight in number (M n ) equal to 1000 and 2000 g/mol whose hydroxyl indices are respectively 112 and 56 mg KOH/g.
- the (meth)acrylate monomer M2 can be chosen from hydroxyalkyl (meth)acrylates.
- the (meth)acrylate M2 monomer is chosen from 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4-HBA), (for example available from SARTOMER, BASF).
- HEMA 2-hydroxyethyl methacrylate
- HPA 2-hydroxypropyl methacrylate
- HPA 2-hydroxypropyl acrylate
- 4-hydroxybutyl acrylate (4-HBA) for example available from SARTOMER, BASF.
- the polyaddition reaction E1) can be carried out at a temperature preferably below 95° C. and/or under preferably anhydrous conditions.
- the polyaddition reaction can be carried out in the presence or absence of at least one catalyst.
- the reaction catalyst(s) used during the polyaddition reaction can be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reaction of at least one polyisocyanate with at least one polyol.
- the polyaddition reaction E1) can be carried out in the presence or absence of at least one solvent.
- the solvent can be chosen from solvents that do not react with the reactive functions of the ingredients used in step E1). It may, for example, be methyl methacrylate, toluene, ethyl acetate, xylene, and mixtures thereof.
- Step E2) can be implemented at a temperature preferably below 80° C., preferably below or equal to 60° C., and/or under preferably anhydrous conditions.
- Step E2) can be implemented in the presence or absence of at least one catalyst. It may be the same catalyst as that used in step E1).
- Step E2) can be implemented in the presence or absence of at least one solvent.
- the solvent can be chosen from solvents that do not react with the reactive functions of the ingredients used in step E2). It may for example be methyl methacrylate, toluene, ethyl acetate, xylene, and mixtures thereof.
- step E2) is implemented by adding the monomer(s) M2 to the reaction medium of step E1), without isolating the product formed in step E1).
- the polyurethane P according to the invention may also be commercially available. Mention may be made, for example, of CN®981 (polyurethane-acrylate having an Mn of 2200 g/mol, and an acrylate functionality of 2), CN®9210 (polyurethane-acrylate having an Mn of 1500 g/mol, and an acrylate functionality of acrylate of 6), CN® 9165A (polyurethane-acrylate having an Mn of 900 g/mol and an acrylate functionality of 6), marketed by Sartomer.
- CN®981 polyurethane-acrylate having an Mn of 2200 g/mol, and an acrylate functionality of 2
- CN®9210 polyurethane-acrylate having an Mn of 1500 g/mol, and an acrylate functionality of acrylate of 6
- CN® 9165A polyurethane-acrylate having an Mn of 900 g/mol and an acrylate functionality of 6
- the polyurethane P comprises at least three (meth)acrylate functions, preferably six (meth)acrylate functions.
- the polyurethane P does not include epoxy functions.
- component A comprises at least two polyurethanes P comprising at least two terminal (meth)acrylate functions.
- component A comprises a polyurethane P1 comprising two terminal (meth)acrylate functions and a polyurethane P2 (different from P1) comprising more than two terminal (meth)acrylate functions (more preferably six terminal (meth)acrylate functions).
- the total content of polyurethane(s) P in component A can be less than or equal to 50% by weight, preferably less than or equal to 40% by weight.
- the total content of polyurethane(s) P in component A may be greater than or equal to 5% by weight, preferably greater than or equal to 10% by weight, and even more preferably greater than or equal to 20% by weight relative to the total weight of component A.
- the reducing agent can be chosen from tertiary amines, sodium metabisulfite, sodium bisulfite, transition metals, alpha-aminosulfones, and mixtures thereof.
- the reducing agent may be contained in the aforementioned polyurethane P.
- This embodiment is for example possible when in step E1) mentioned above, the polyols and the polyisocyanates are reacted with a tertiary amine having pendent hydroxyl functions such as for example the bisomer® PTE marketed by GEO SPECIALTY CHEMICALS or even N-(2-hydroxyethyl)-N-methyl aniline or alternatively N-(2-hydroxyethyl)-N-methyl-p-toluidine.
- alpha-sulfones mention may be made, for example, of bis(tolylsulfonmethyl)benzylamine.
- DIIPT diisopropanol-p-toluidine
- dimethyl-p-toluidine dipropoxy-p-toluidine
- dimethylaniline N,N-dimethylaminomethylphenol
- N,N-diisopropanol-p-chloroaniline N,N-diisopropanol-p-bromoaniline
- N,N-dimethyl-p-bromoaniline N,N-diethyl-p-chloroaniline
- N,N-diethyl-p-bromoaniline N,N-diethyl-p-bromoaniline
- - m and n are, independently of each other, an integer ranging from 1 to 150, preferably from 1 to 100, preferably from 1 to 72, advantageously from 1 to 36, even more advantageously from 1 to 18 ;
- - r is an integer ranging from 1 to 200, preferably from 1 to 104, preferably from 1 to 72, advantageously from 1 to 36;
- R 6 represents a radical chosen from the group consisting of an alkyl, linear or branched, saturated or unsaturated, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; a (hetero)aryl comprising from 6 to 12 carbon atoms; a cycloalkyl comprising from 3 to 12 carbon atoms;
- - v represents an integer ranging from 0 to 5;
- R 7 and R 3 represent, independently of one another, a halogen atom, a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom;
- R 4 represents a hydrogen atom, an arylalkyl group, or an alkyl group, linear or branched, comprising from 1 to 20 carbon atoms, preferably an alkyl group comprising from 1 to 12 carbon atoms, advantageously from 1 to 6 carbon atoms;
- amines of formula (B) mention may be made, for example, of “BISOMER® PTE” (CAS number: 878391-30-1) marketed by GEO SPECIALTY CHEMICALS, “Accelerator PT25E” (CAS number: 878391-30-1 ) marketed by LANXESS, N,N-Bis(2-hydroxypropyl)-p-aniline (CAS number: 3077-13-2) available from BIOSYNTH, N,N-Bis(2-hydroxypropyl)-p-toluidine ( CAS number: 38668-48-3) marketed by BASF, “ETHOX ANA-10” (CAS number: 36356-83-9) available from ETHOX CHEMICAL.
- N-(2-hydroxyethyl)-N-methyl aniline available from SIGMA-ALDRICH and N-(2-hydroxyethyl )-N-methyl-p-toluidine (MHPT, CAS number: 2842-44-6) available from PARCHEM.
- component A comprises at least one tertiary amine, and even more preferably an amine of formula (B) above.
- Component A may comprise a total content of reducing agent(s) ranging from 0.5% to 5%, preferably from 0.5% to 3%, by weight relative to the total weight of component A.
- Component A according to the invention comprises at least one itaconate monomer of formula (I) below: wherein each of R 1 and R 2 represents, independently of one another, organic radicals.
- each of R 1 and R 2 can represent, independently of one another, an alkyl, an alkenyl, a cycloalkyl, a heterocycloalkyl, an aryl, a heteroaryl, an arylalkyl, a heteroarylalkyl, an alkylheteroaryl, or an alkylheterocycloalkyl, said groups possibly being substituted.
- substituents can be chosen from alkyls, halogens, cycloalkyls, halo-alkyls, halo-cycloalkyls, heteroaryls, aryls, heterocycloalkyls, alkoxys, alkylthios, hydroxyls, nitros, azidos, cyano, acyloxy, carboxy or esters.
- alkyl is understood to mean a linear or branched radical preferably comprising from 1 to 20 carbon atoms.
- alkenyl means a linear or branched hydrocarbon radical comprising at least one double bond, said radical preferably comprising from 2 to 20 carbon atoms.
- arylalkyl means an alkyl group substituted by an aryl group, the arylalkyl group preferably comprising from 7 to 20 carbon atoms.
- arylalkyl group mention may be made, for example, of benzyl.
- heteroarylalkyl means an alkyl group substituted by a heteroaryl group, the heteroarylalkyl group preferably comprising from 7 to 20 carbon atoms.
- alkylheteroaryl means a heteroaryl group substituted by an alkyl group, said alkylheteroaryl group preferably comprising from 7 to 20 carbon atoms and at least one heteroatom.
- alkylheterocycloalkyl means a heterocycloalkyl group substituted by an alkyl group, said alkylheterocycloalkyl group preferably comprising from 4 to 20 carbon atoms and at least one heteroatom.
- aryl is understood to mean a monocyclic or bicyclic aromatic radical preferably comprising from 6 to 12 carbon atoms. Mention may be made, for example, of phenyl.
- heteroaryl is understood to mean a monocyclic or bicyclic aromatic radical comprising at least one heteroatom such as for example O, S or N, and preferably comprising from 4 to 12 carbon atoms. Mention may be made, for example, of the furanyl, thiophenyl, pyrrolyl, pyridinyl, indolyl or imidazolyl radicals.
- cycloalkyl means a monocyclic or polycyclic system, preferably mono or bicyclic, saturated, preferably comprising from 3 to 12 carbon atoms, the rings possibly being fused or bridged in pairs, such as the cyclopropyl, cyclopentyl, cyclohexyl or even norbornyl groups.
- heterocycloalkyl means a monocyclic or polycyclic system, preferably mono or bicyclic, saturated, preferably comprising from 3 to 12 carbon atoms and at least one heteroatom such as for example O or N, the cycles being able to be fused or bridged in pairs.
- each of R 1 and R 2 represents, independently of one another, a C1-C15 alkyl, C2-C15 alkenyl, halo-(C1- C15)alkyl, C3-C12 cycloalkyl, halo(C3-C12)cycloalkyl, a heterocycle, an aryl, a heteroaryl, or an alkoxy-(C1-C15)alkyl, each of which may optionally be substituted by one at least of the following radicals: C1-C15 alkyl, halo(C1-C15 alkyl), C3-12 cycloalkyl, halo(C3-C12 cycloalkyl), heterocycle, aryl, heteroaryl, CICI 5 alkoxy, C1-C15 alkylthio, halo, hydroxyl , nitro, azido, cyano, acyloxy, carboxy or ester.
- each of R 1 and R 2 represents, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl, benzyl, 2-phenylethyl, and isobornyl.
- the itaconate of formula (I) is chosen from dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, di-isobutyl itaconate, dicyclohexyl itaconate, bis(hexafluoroisopropyl) itaconate, diphenyl itaconate, dibenzyl itaconate, ethyl isobornyl itaconate, ethyl cyclohexyl itaconate, and mixtures thereof. Even more preferentially, the itaconate of formula (I) is dimethyl itaconate or dibutyl itaconate.
- the total content of itaconate monomer(s) of formula (I) in component A may be greater than 40% by weight, preferably greater than or equal to 45% by weight relative to the total weight of component A.
- the monomers of formula (I) can be obtained by processes such as for example described in WO2015181310, which are in particular fermentation processes.
- the monomers of formula (I) are advantageously biosourced.
- the impact modifier having a core-shell type structure is typically known by the English designation "core-shell impact modifier”.
- Impact modifiers are well known to those skilled in the art, and include in particular impact modifiers having a core-shell type structure.
- the impact modifier having a core-shell type structure may be in the form of spherical particles.
- the weight average particle size (diameter) can range from 40 nm to 900 nm, preferably from 80 to 500 nm. Particle size can be measured with a Zetasizer (Malvern).
- the impact modifier having a core-shell type structure can be obtained by any process known to those skilled in the art, for example by a multi-step process as described in FR 3 052 169 or in EP 2 465 884.
- the polymer is prepared by emulsion polymerization.
- the core of the impact modifier may comprise a polymer L1 chosen from isoprene homopolymers, butadiene homopolymers, isoprene-butadiene copolymers, isoprene copolymers with a vinyl monomer, butadiene copolymers with a monomer vinyl.
- the vinyl monomer can be chosen from styrene, alkylstyrene, acrylonitrile, alkyl (meth)acrylates, butadiene or isoprene.
- the shell may comprise an L2 polymer obtained from (meth)acrylic monomers such as for example those chosen from CICI 2 alkyl (meth)acrylates.
- the shell comprises an L2 polymer obtained from C1-C4 alkyl methacrylate monomers and/or C1-C8 alkyl acrylate monomers.
- the shell comprises a polymer L2 obtained from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof.
- the impact modifier having a core-shell type structure comprises: a core comprising a polymer L1 being a butadiene-styrene copolymer; a shell comprising a polymer L2 being a polymethyl methacrylate (PMMA).
- Impact modifiers having a core-shell type structure may be commercially available. Mention may be made, for example, of Clearstrength® (for example Clearstrength® XT 100) or the Durastrength® sold by Arkema. Mention may also be made of the Paraloids (Paraloid 2650A, Paraloid 2691 A) marketed by Dow Corning.
- Clearstrength® for example Clearstrength® XT 100
- Durastrength® sold by Arkema
- Mention may also be made of the Paraloids (Paraloid 2650A, Paraloid 2691 A) marketed by Dow Corning.
- the total content of polymer(s) having a core-shell type structure in component A can range from 2% to 20% by weight, preferably from 5% to 20% by weight, and even more. preferably from 10% to 18% by weight relative to the total weight of component A.
- Component B
- the oxidizing agent can be chosen from peroxides, organic salts of transition metals, compounds containing labile chlorine, and mixtures thereof.
- the peroxide can be chosen from organic peroxides, inorganic peroxides, and mixtures thereof.
- peroxydisulfuric acid and their salts such as ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
- oganic peroxides mention may be made of cumene hydroperoxide, para-menthane hydroperoxide, ferf-butyl peroxyisobutyrate, ferf-butyl peroxybenzoate, ferf-butyl peroxyneodecanoate, ferf-amyl peroxypivalate, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis-(t-butylperoxyisopropyl)benzene, diacetyl peroxide, t-butylcumyl peroxide, ferf-butyl peroxyacetate, cumyl, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne, 4-methyl-2,2 -di-t-butylperoxypentane,
- component B comprises benzoyl peroxide
- Component B may comprise a total content of reducing agent greater than or equal to 20% by weight, preferably greater than or equal to 30% by weight, advantageously greater than or equal to 35% by weight relative to the total weight of component B.
- composition according to the invention may typically comprise a redox system, a reducing agent being included in part A and an oxidizing agent being included in part B.
- a reducing agent being included in part A
- an oxidizing agent being included in part B.
- Mention may be made, for example, of the following combinations: persulphates (oxidant)/(sodium metabisulphite and/or sodium bisulphite) (reducers); organic peroxides (oxidant) / tertiary amines (reducer); organic hydroperoxides (oxidant) / transition metals (reducer);
- Component B may optionally comprise at least one (meth)acrylate monomer M1.
- the (meth)acrylate monomers M1 may comprise one (monofunctional) or several (meth)acrylate (polyfunctional) functions.
- the (meth)acrylate monomer(s) M1 can be chosen from the group consisting of:
- R 8 represents a hydrogen atom or an alkyl group comprising from 1 to 4 carbon atoms
- R 9 is selected from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls which may optionally be substituted and/or interrupted by at least one silane, one silicone, one oxygen, one halogen, one carbonyl, one hydroxyl, one ester, one urea, one urethane, one carbonate, one amine, one amide, one sulfur, a sulfonate, or a sulfone;
- the monomer (meth) acrylate M1 is chosen from methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl (meth) acrylate, heptyl, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecy
- the two-component composition according to the invention may comprise at least one additive chosen from the group consisting of fillers, antioxidants, light stabilizers/UV absorbers, metal deactivators, antistatics, antifogging agents, foaming agents , biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, anti-bleeding agents, nucleation, solvents, and mixtures thereof.
- additives chosen from the group consisting of fillers, antioxidants, light stabilizers/UV absorbers, metal deactivators, antistatics, antifogging agents, foaming agents , biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, anti-bleeding agents, nucleation, solvents, and mixtures thereof.
- additives may be present in component A and/or component B of the composition according to the invention.
- plasticizer usually used in the field of adhesives such as, for example, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane, glycerol esters, pentaerythritol esters, oils napthenic minerals, adipates, cyclohexyldicarboxylates, paraffinic oils, natural
- soybean oil such as, for example, marketed under the name VIKOFLEX® 7170 by ARKEMA.
- the plasticizer content may be greater than or equal to 1%, preferably greater than or equal to 3%, and even more preferably greater than or equal to 5% by weight relative to the total weight of said composition.
- the composition comprises at least one plasticizer, and even more preferentially at least in component B.
- (thixotropic) rheology agent(s) that can be used, mention may be made of any rheology agent usually used in the field of adhesive compositions.
- the thixotropic agents are chosen from:
- - PVC plastisols corresponding to a suspension of PVC in a plasticizer miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C.
- These plastisols can be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6,
- urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine.
- the preparation of such urea derivatives is described in particular in application FR 1 591 172;
- - micronized amide waxes such as CRAYVALLAC SLT marketed by ARKEMA.
- composition according to the invention may also comprise at least one organic and/or mineral filler.
- the mineral filler(s) that can be used is (are) advantageously chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.
- any mineral filler(s) usually used in the field of adhesive compositions can be used.
- These fillers are typically in the form of particles of various geometry. They can be for example spherical, fibrous, or have an irregular shape.
- the filler(s) can be chosen from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clays, and mixtures thereof, preferably the) filler(s) is (are) chosen from carbonate fillers, such as alkali or alkaline-earth metal carbonates, and more preferably calcium carbonate or chalk.
- These fillers can be untreated or treated, for example using an organic acid such as stearic acid, or a mixture of organic acids mainly consisting of stearic acid.
- hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or of aluminosilicate.
- a solvent in particular a volatile solvent
- its content is preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight, relative to the total weight of the composition.
- the content of solvent(s) in the composition is between 0% and 5% by weight.
- the composition can comprise an amount of 0.1% to 3%, preferably 1% to 3% by weight, of at least one UV stabilizer or antioxidant.
- These compounds are typically introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat or light.
- These compounds can include primary antioxidants that scavenge free radicals.
- the primary antioxidants can be used alone or in combination with other secondary antioxidants or UV stabilizers. Mention may be made, for example, of IRGANOX® 1010, IRGANOX® B561, IRGANOX® 245, IRGAFOS® 168, TINUVIN® 328 or TINUVINTM 770 marketed by BASF.
- the aforementioned adhesive composition does not include a photoinitiator.
- the component A/component B volume ratio in the composition of the invention ranges from 20/1 to 1/1, preferably from 10/1 to 1/1.
- the aforementioned adhesive composition may have a Brookfield viscosity at 23° C. ranging from 20,000 mPa.s to 150,000 mPa.s, preferably from 30,000 mPa.s to 100,000 mPa.s, even more preferably from 40,000 to 80 000 mPa.s
- the aforementioned composition comprises:
- component A comprising:
- component B comprising:
- the present invention also relates to a ready-to-use kit, comprising component A as defined above on the one hand and component B as defined above on the other hand, packaged in two separate compartments. It may for example be a two-component cartridge.
- composition according to the invention can be in a two-component form, for example within a ready-to-use kit, comprising component A on the one hand in a first compartment or barrel and component B d on the other hand in a second compartment or drum, in proportions suitable for direct mixing of the two components, for example using a metering pump.
- the kit further comprises one or more means allowing the mixing of components A and B.
- the mixing means are chosen from metering pumps, static mixers with a diameter adapted to the quantities used.
- the present invention also relates to the use of a composition as defined above, as an adhesive, sealant or coating, preferably as an adhesive.
- the invention also relates to the use of said composition for repairing and/or structural or semi-structural bonding of materials in the field of transport, automotive (car, bus or truck), assembly, marine, electronics, batteries or construction.
- the present invention also relates to a method for assembling two substrates by bonding, comprising:
- the crosslinking step can be carried out at a temperature between 0°C and 200°C, preferably between 10°C and 150°C, preferably between 23 and 80°C and in particular between 20°C and 25°C.
- Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or else organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and composites coated with paint.
- inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or else organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and composites coated with paint.
- compositions according to the invention once lead advantageously, after crosslinking, to an adhesive joint having semi-structural or structural properties.
- compositions according to the invention advantageously exhibit, after crosslinking, good adhesive properties, while having a low or even zero odor.
- compositions are also advantageously low in toxicity compared to the usual acrylic compositions, due in particular to the use of itaconate monomer of formula (I) whose toxicity is lower than that of the usual acrylics.
- between x and y or “ranging from x to y”, is meant an interval in which the limits x and y are included.
- the range “between 0% and 25%” includes the values 0% and 25% in particular.
- SR9054 (CAS Number: 1628778-81-3) marketed by SARTOMER: difunctional acrylic acid adhesion promoter; - AEROSIL® R202 (CAS Number: 67762-90-7): a hydrophobic fumed silica (PDMS post-treated) with a specific surface area (BET) equal to 100 ⁇ 20 m 2 /g marketed by EVONIK;
- - VIKOFLEX® 7170 marketed by ARKEMA is an epoxidized soybean oil used as a plasticizer
- ARKEMA is a micronized amide wax used as a rheological agent
- PEROXAN BP 50 50% benzoyl peroxide paste marketed by PERGAN.
- Example 1 Preparation of Compositions No. 1 and No. 2
- Component A and component B above were mixed, in a 10:1 volume ratio (A:B).
- the mixing is carried out at a temperature of approximately 23° C., according to the volume ratio given with a static mixer.
- the principle of the measurement consists in stretching in a tensile machine, the mobile jaw of which moves at a constant speed equal to 200 mm/minute, a standard test piece made up of the crosslinked composition and in recording, at the moment when the rupture occurs. of the specimen, the tensile stress applied (in MPa) as well as the elongation of the specimen (in %).
- the standard specimen is in the shape of a dumbbell, as illustrated in the international standard ISO 37 of 2011.
- the narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 n.
- the collages are made on aluminum sterigmas (anodized or 6060) from the RocholL company. 25*12.5mm. This area was filled with the composition to be tested, then a second sterigma of the same material was laminated. The assembly was held by clamps and placed in an air-conditioned room at 23°C or 100°C and 50% RH (relative humidity) for one week before traction on a dynamometer. The purpose of traction on a dynamometer is to assess the maximum force (in MPa) to be exerted on the assembly to separate it.
- a traction machine makes it possible to subject a simple lap joint placed between two rigid supports to a shearing stress until failure by exerting a traction on the supports parallel to the surface of the assembly and to the main axis. of the test piece.
- the result to be reported is the force or stress at break.
- the shear stress is applied via the movable jaw of the tensile machine with a displacement at the speed of 5 mm/min. This traction method is carried out as defined by the EN 1465 standard of 2009.
- Compositions No. 1 and No. 2 according to the invention advantageously lead to an adhesive joint having, after crosslinking, a high tensile strength (12 and 25 MPa respectively).
- compositions No. 1 and No. 2 advantageously lead to breaking strengths of 9 and 11 MPa respectively for bonding on anodized aluminum, demonstrating good adhesion.
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Abstract
The present invention relates to a two-component adhesive composition comprising: - a component A comprising: - at least one polyurethane P comprising at least two methacrylate end functions; - at least one reducing agent; and - at least one itaconate monomer of following formula (I): Formula (I) in which each of R1 and R2 represents, independently from one another, organic radicals; - at least one impact modifier having core-shell type structure; - a component B comprising: - at least one oxidising agent; and - optionally at least one methacrylate monomer M1.
Description
Composition adhésive bicomposante à base de monomère itaconate Two-component adhesive composition based on itaconate monomer
DOMAINE DE L’INVENTION FIELD OF THE INVENTION
La présente invention concerne une composition adhésive bicomposante à base de monomère itaconate. The present invention relates to a two-component adhesive composition based on itaconate monomer.
L’invention concerne également l’utilisation de ladite composition pour la réparation et/ou le collage structural ou semi-structural de matériaux dans le domaine du transport, automobile (voiture, bus ou camion), de la marine, de l’assemblage, de l’électronique, des batteries ou de la construction The invention also relates to the use of said composition for repairing and/or structural or semi-structural bonding of materials in the field of transport, automotive (car, bus or truck), marine, assembly, electronics, batteries or construction
ARRIERE-PLAN TECHNOLOGIQUE TECHNOLOGICAL BACKGROUND
Les compositions acryliques sont des systèmes réactifs connus réticulant par polymérisation radicalaire. Elles sont utilisées comme adhésifs, mastics et revêtements. La polymérisation radicalaire est typiquement amorcée par un système rédox qui par le biais d’une réaction d’oxydo-réduction conduit à la production de radicaux. Acrylic compositions are known reactive systems that crosslink by radical polymerization. They are used as adhesives, sealants and coatings. Radical polymerization is typically initiated by a redox system which, through an oxidation-reduction reaction, leads to the production of radicals.
La majorité des systèmes acryliques sont des systèmes bicomposants. Le premier composant contient traditionnellement l’agent réducteur et les monomères réactifs, et le second composant contient l’agent oxydant. Une fois les deux composants mélangés, l’agent réducteur induit la coupure de la liaison 0-0 du peroxyde organique par exemple, et initie la polymérisation. The majority of acrylic systems are two-component systems. The first component traditionally contains the reducing agent and the reactive monomers, and the second component contains the oxidizing agent. Once the two components are mixed, the reducing agent induces the cleavage of the 0-0 bond of the organic peroxide, for example, and initiates the polymerization.
Les acrylates et méthacrylates, notamment ceux avec des radicaux alkyles, sont des monomères présentant une pression de vapeur élevée. Ceci a pour conséquence qu’ils sont odorants lors de leur application. Acrylates and methacrylates, especially those with alkyl radicals, are monomers with high vapor pressure. This has the consequence that they are fragrant when applied.
Des alternatives à ces composants ont été développées. Toutefois, ces compositions alternatives ne permettent pas d’obtenir de bonnes propriétés adhésives et/ou mécaniques. Alternatives to these components have been developed. However, these alternative compositions do not make it possible to obtain good adhesive and/or mechanical properties.
Il existe donc un besoin pour de nouvelles compositions ayant à la fois une faible odeur et de bonnes propriétés mécaniques (telles que par exemple de bonnes propriétés d’adhésion). There is therefore a need for new compositions having both low odor and good mechanical properties (such as, for example, good adhesion properties).
DESCRIPTION DE L’INVENTION DESCRIPTION OF THE INVENTION
Dans la présente demande, en l'absence d'indication contraire :
- les quantités exprimées sous la forme de pourcentage correspondent à des pourcentages poids/poids ; In this application, unless otherwise indicated: - the quantities expressed as a percentage correspond to weight/weight percentages;
- l’indice hydroxyle d’un composé alcoolique représente le nombre de fonctions hydroxyles par gramme de produit, lequel est exprimé sous la forme du nombre équivalent de milligrammes de potasse (mg KOH/g) utilisés dans le dosage des fonctions hydroxyles, par gramme de produit ; - the hydroxyl index of an alcoholic compound represents the number of hydroxyl functions per gram of product, which is expressed in the form of the equivalent number of milligrams of potash (mg KOH/g) used in the assay of the hydroxyl functions, per gram of product;
- la mesure de viscosité à 23°C (ou à 100°C) peut se faire à l’aide d’un viscosimètre Brookfield selon la norme ISO 2555. Typiquement, la mesure réalisée à 23°C (ou à 100°C) peut se faire à l’aide d’un viscosimètre Brookfield RVT, d’une aiguille adaptée au domaine de viscosité et à une vitesse de rotation de 20 tours par minute (tr/mn). - the measurement of viscosity at 23°C (or at 100°C) can be done using a Brookfield viscometer according to the ISO 2555 standard. Typically, the measurement carried out at 23°C (or at 100°C) can be done using a Brookfield RVT viscometer, a needle adapted to the viscosity range and at a speed of rotation of 20 revolutions per minute (rpm).
COMPOSITION COMPOSITION
La présente invention concerne une composition adhésive bicomposante comprenant :The present invention relates to a two-component adhesive composition comprising:
- un composant A comprenant : - a component A comprising:
- au moins un polyuréthane P comprenant au moins deux fonctions (méth)acrylate terminales ; - at least one polyurethane P comprising at least two terminal (meth)acrylate functions;
- au moins un agent réducteur ; et - at least one reducing agent; and
- au moins un monomère itaconate de formule (I) suivante :
dans laquelle chacun de R1 et R2 représente, indépendamment l’un de l’autre, des radicaux organiques ; - at least one itaconate monomer of the following formula (I): in which each of R 1 and R 2 represents, independently of one another, organic radicals;
- au moins un modificateur d’impact ayant structure de type cœur-écorce (ou « coreshell impact modifier » en anglais) ; - at least one impact modifier with a core-shell type structure (or "coreshell impact modifier" in English);
- un composant B comprenant : - a component B comprising:
- au moins un agent oxydant ; et - at least one oxidizing agent; and
- éventuellement au moins un monomère (méth)acrylate M1.
Composant A
- optionally at least one (meth)acrylate monomer M1. Component A
Le polyuréthane P peut avoir une masse moléculaire moyenne en nombre (Mn) supérieure ou égale à 700 g/mol, de préférence supérieure ou égale à 900 g/mol. The polyurethane P may have a number-average molecular mass (Mn) greater than or equal to 700 g/mol, preferably greater than or equal to 900 g/mol.
Le polyuréthane P peut avoir une masse moléculaire moyenne en nombre (Mn) inférieure ou égale à 30 000 g/mol, préférentiellement inférieure ou égale à 10 000 g/mol, encore plus préférentiellement inférieur ou égale à 5 000 g/mol. The polyurethane P may have a number-average molecular weight (Mn) less than or equal to 30,000 g/mol, preferably less than or equal to 10,000 g/mol, even more preferably less than or equal to 5,000 g/mol.
Selon un mode de réalisation préféré, le polyuréthane P a une masse moléculaire moyenne en nombre (Mn) allant de 700 g/mol à 30 000 g/mol, préférentiellement de 900 g/mol à 20 000 g/mol, et encore plus préférentiellement de 900 g/mol à 10 000 g/mol. According to a preferred embodiment, the polyurethane P has a number-average molecular mass (Mn) ranging from 700 g/mol to 30,000 g/mol, preferentially from 900 g/mol to 20,000 g/mol, and even more preferentially from 900 g/mol to 10,000 g/mol.
La Mn du polyuréthane est mesurée par GPC avec comparaison avec une référence PS. The Mn of the polyurethane is measured by GPC with comparison with a PS reference.
Le polyuréthane P peut être obtenu par un procédé comprenant : Polyurethane P can be obtained by a process comprising:
- E1 ) une étape de préparation d’un polyuréthane comprenant au moins deux groupements terminaux NCO comprenant la réaction de polyaddition entre : - E1) a step for preparing a polyurethane comprising at least two NCO end groups comprising the polyaddition reaction between:
- i) au moins un polyisocyanate ; et - i) at least one polyisocyanate; and
- ii) au moins un polyol ; - ii) at least one polyol;
- E2) la réaction du produit formé à l’issue de l’étape E1 ) avec au moins un monomère (méth)acrylate M2 comprenant au moins une fonction hydroxyle. - E2) the reaction of the product formed at the end of step E1) with at least one (meth)acrylate monomer M2 comprising at least one hydroxyl function.
Polyisocyanate(s) Polyisocyanate(s)
Le(s) polyisocyanate(s) utilisable(s) peut(vent) être ajouté(s) séquentiellement ou mis à réagir sous la forme de mélange. The usable polyisocyanate(s) can be added sequentially or reacted as a mixture.
Le(s) polyisocyanate(s) peut(vent) être choisi(s) parmi les diisocyanates ou les triisocyanates. The polyisocyanate(s) can be chosen from diisocyanates or triisocyanates.
Le(s) polyisocyanate(s) peut(vent) être monomérique(s), oligométique(s) ou polymérique(s). The polyisocyanate(s) can be monomeric(s), oligometic(s) or polymeric(s).
Le(s) polyisocyanate(s) peut(vent) être choisi(s) dans le groupe constitué de l’isophorone diisocyanate (IPDI), de l’hexaméthylène diisocyanate (HDI), de l’heptane diisocyanate, de l’octane diisocyanate, du nonane diisocyanate, du décane diisocyanate, de l’undécane diisocyanate, du dodécane diisocyanate, du 2,4’- méthylènebis(cyclohexylisocyanate) (2,4’-H6MDI), du 4,4’-
méthylènebis(cyclohexylisocyanate) (4,4’-H6MDI), du norbornane diisocyanate, du norbornène diisocyanate, du 1 ,4-cyclohexane diisocyanate (CHDI), du méthylcyclohexane diisocyanate, de l’éthylcyclohexane diisocyanate, du propylcyclohexane diisocyanate, du méthyldiéthylcyclohexane diisocyanate, du cyclohexane diméthylène diisocyanate, du 1 ,5- diisocyanato-2-méthylpentane (MPDI), du 1 ,6-diisocyanato-2,4,4-triméthylhexane, du 1 ,6- diisocyanato-2,2,4-triméthylhexane (TMDI), du 4-isocyanatométhyl-1 ,8-octane diisocyanate (TIN), du (2,5)-bis(isocyanatométhyl)bicyclo[2.2.1]heptane (2,5-NBDI), du (2,6)- bis(isocyanatométhyl)bicyclo[2.2.1]heptane (2,6-NBDI), du bis(isocyanatomethyl)cyclohexane (H6-XDI) (en particulier le 1 ,3-bis(isocyanatomethyl)cyclohexane (1 ,3-H6-XDI)), du xylylène- diisocyanate (XDI) (en particulier le m-xylylène diisocyanate (m-XDI)), du toluène diisocyanate (en particulier le 2,4-toluène diisocyanate (2,4-TDI) et/ou le 2,6-toluène diisocyanate (2,6- TDI)), du diphénylméthane diisocyanate (en particulier le 4,4'-diphénylméthane diisocyanate (4,4’-MDI) et/ou le 2,4'-diphénylméthane diisocyanate (2,4’-MDI), du tétraméthylxylylène diisocyanate (TMXDI) (en particulier le tétraméthyl m-xylylène diisocyanate), d’un allophanate de HDI ayant par exemple la formule (Y) suivante :
dans laquelle p est un nombre entier allant de 1 à 2, q est un nombre entier allant de 0 à 9, et de préférence 2 à 5, Rc représente une chaine hydrocarbonée, saturée ou insaturée, cyclique ou acyclique, linéaire ou ramifiée, comprenant de 1 à 20 atomes de carbone, de préférence de 6 à 14 atomes de carbone, Rd représente un groupe divalent alkylène, linéaire ou ramifié, ayant de 2 à 4 atomes de carbones, et de préférence un groupe divalent propylène ; et de leurs mélanges. The polyisocyanate(s) may be selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate , nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 2,4'- methylenebis(cyclohexylisocyanate) (2,4'-H6MDI), 4,4'- methylenebis(cyclohexylisocyanate) (4,4'-H6MDI), norbornane diisocyanate, norbornene diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, 1,5-diisocyanato-2-methylpentane (MPDI), 1,6-diisocyanato-2,4,4-trimethylhexane, 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI ), 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), (2,5)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (2,5-NBDI), (2,6)- bis(isocyanatomethyl)bicyclo[2.2.1]heptane (2,6-NBDI), bis(isocyanatomethyl)cyclohexane (H6-XDI) (in particular 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6- XDI)), xylylene diisocyanate (XDI) (in particular m-xylylene diisocyanate (m-XDI)), toluene diisocyanate (in particular 2,4-toluene diisocyanate (2,4-TDI) and/or 2,6-toluene diisocyanate (2,6-TDI)), diphenylm ethane diisocyanate (especially 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and/or 2,4'-diphenylmethane diisocyanate (2,4'-MDI), tetramethylxylylene diisocyanate (TMXDI) (especially tetramethyl m-xylylene diisocyanate), an HDI allophanate having, for example, the following formula (Y): in which p is an integer ranging from 1 to 2, q is an integer ranging from 0 to 9, and preferably 2 to 5, R c represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms, preferably from 6 to 14 carbon atoms, Rd represents a divalent alkylene group, linear or branched, having from 2 to 4 carbon atoms, and preferably a divalent propylene group; and their mixtures.
Le(s) polyisocyanate(s) utilisable(s) peut(vent) être des triisocyanate(s), par exemple choisi(s) parmi les isocyanurates, les biurets, et les adduits de diisocyanates et de triols. The polyisocyanate(s) that can be used can be triisocyanate(s), for example chosen from isocyanurates, biurets, and adducts of diisocyanates and triols.
Le(s) isocyanurate(s) peut(vent) être utilisé(s) sous la forme d’un mélange technique de (poly)isocyanurate(s) de pureté supérieure ou égale à 70% en poids isocyanurate(s). The isocyanurate(s) can be used in the form of a technical mixture of (poly)isocyanurate(s) with a purity greater than or equal to 70% by weight isocyanurate(s).
Le(s) isocyanurate(s) de diisocyanate utilisable(s) selon l’invention peut(vent) répondre à la formule générale (W) suivante :
dans laquelle R5 représente un groupe alkylène, linéaire ou ramifié, cyclique, aliphatique, arylaliphatique ou aromatique, comprenant de 4 à 9 atomes de carbones, sous réserve que les groupes NCO ne soient pas reliés par une liaison covalente à un atome de carbone faisant parti d’un cycle hydrocarboné aromatique tel qu’un groupe phényle. The diisocyanate isocyanurate(s) which can be used according to the invention may correspond to the following general formula (W): in which R 5 represents a linear or branched, cyclic, aliphatic, arylaliphatic or aromatic alkylene group, comprising from 4 to 9 carbon atoms, provided that the NCO groups are not linked by a covalent bond to a carbon atom making part of an aromatic hydrocarbon ring such as a phenyl group.
A titre d’exemple de trimères de diisocyanates utilisables, on peut citer le trimère isocyanurate d’hexaméthylène diisocyanate (HDI). By way of example of diisocyanate trimers which can be used, mention may be made of the isocyanurate trimer of hexamethylene diisocyanate (HDI).
A titre d’exemple d’adduits de diisocyanates et de triols utilisables selon l’invention, on peut citer l’adduit de méta-xylylène diisocyanate et de triméthylolpropane, tel que représenté ci-dessous. Cet adduit est commercialisé par exemple par la société MITSUI CHEMICALS, Inc sous la dénomination « TAKENATE® D-110N ». By way of example of adducts of diisocyanates and triols which can be used according to the invention, mention may be made of the adduct of meta-xylylene diisocyanate and of trimethylolpropane, as represented below. This adduct is marketed for example by the company MITSUI CHEMICALS, Inc under the name “TAKENATE® D-110N”.
Le(s) polyisocyanate(s) utilisable(s) est(sont) typiquement disponible(s) dans le commerce. A titre d’exemple, on peut citer le SCURANATE® TX commercialisé par la société VENCOREX, correspondant à un 2,4-TDI de pureté de l’ordre de 95%, le SCURANATE® T100 commercialisé par la société VENCOREX, correspondant à un 2,4-TDI de pureté supérieure à 99% en poids. The polyisocyanate(s) which can be used are typically commercially available. By way of example, mention may be made of SCURANATE® TX marketed by the company VENCOREX, corresponding to a 2,4-TDI with a purity of around 95%, SCURANATE® T100 marketed by the company VENCOREX, corresponding to a 2,4-TDI with a purity greater than 99% by weight.
Polyol (s) Polyol(s)
Le(s) polyol(s) peut(vent) être choisi(s) parmi les polyester polyols, les polyéther polyols, les polyène polyols, les polycarbonate polyols, les poly(éther-carbonate) polyols, et leurs mélanges. The polyol(s) may be chosen from polyester polyols, polyether polyols, polyene polyols, polycarbonate polyols, poly(ether-carbonate) polyols, and mixtures thereof.
Le(s) polyol(s) utilisable(s) peu(ven)t être choisi(s) parmi les polyols aromatiques, les polyols aliphatiques, les polyols arylaliphatiques et les mélanges de ces composés. The polyol(s) that can be used can be chosen from aromatic polyols, aliphatic polyols, arylaliphatic polyols and mixtures of these compounds.
Le(s) polyol(s) utilisable(s) peu(ven)t être choisi(s) parmi celui(ceux) possédant une masse moléculaire moyenne en nombre (Mn) allant de 200 g/mol à 20 000 g/mol, de préférence de 400 g/mol à 18 000 g/mol. The polyol(s) that can be used can be chosen from those having a number-average molecular mass (Mn) ranging from 200 g/mol to 20,000 g/mol, preferably from 400 g/mol to 18,000 g/mol.
La masse moléculaire moyenne en nombre des polyols peut être calculée à partir de l’indice d’hydroxyle (IOH) exprimé en mg KOH/g et de la fonctionnalité du polyol ou déterminée
par des méthodes bien connues de l’homme du métier, par exemple par chromatographie d’exclusion stérique (ou SEC en anglais) avec étalon PEG (polyéthylène glycol). The number average molecular mass of the polyols can be calculated from the hydroxyl number (IOH) expressed in mg KOH/g and the functionality of the polyol or determined by methods well known to those skilled in the art, for example by steric exclusion chromatography (or SEC in English) with PEG (polyethylene glycol) standard.
Parmi les polyester polyols, on peut par exemple citer les polyesters polyols d’origine naturelle tel que l’huile de ricin ; les polyesters polyols résultant de la polycondensation : Among the polyester polyols, mention may be made, for example, of polyester polyols of natural origin such as castor oil; polyester polyols resulting from polycondensation:
- d’un ou plusieurs polyols aliphatiques (linéaires, ramifiés ou cycliques) ou aromatiques tels que par exemple le monoéthylène glycol, le diéthylène glycol, le 1 ,2- propanediol, le 1 ,3-propanediol, le 1 ,4-butanediol, le butènediol, le 1 ,6-hexanediol, le cyclohexane diméthanol, le tricyclodécane diméthanol, le néopentyl glycol, le cyclohexane diméthanol, un polyéther polyol, le glycérol, le triméthylolpropane, le 1 ,2,6-hexanetriol, le sucrose, le glucose, le sorbitol, le pentaérythritol, le mannitol, la N- méthyldiéthanolamine, la triéthanolamine, un alcool gras dimère, un alcool gras trimère et leurs mélanges, avec - one or more aliphatic (linear, branched or cyclic) or aromatic polyols such as, for example, monoethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, butenediol, 1,6-hexanediol, cyclohexane dimethanol, tricyclodecane dimethanol, neopentyl glycol, cyclohexane dimethanol, a polyether polyol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, sucrose, glucose , sorbitol, pentaerythritol, mannitol, N-methyldiethanolamine, triethanolamine, dimer fatty alcohol, trimer fatty alcohol and mixtures thereof, with
- un ou plusieurs acide polycarboxylique ou son dérivé ester ou anhydride tel que l’acide 1 ,6-hexanedioïque (acide adipique), l’acide dodécanedioïque, l’acide azélaïque, l’acide sébacique, l’acide adipique, l’acide 1 ,18-octadécanedioïque, l’acide phtalique, l’acide isophtalique, l’acide téréphtalique, l’acide succinique, un acide gras dimère, un acide gras trimère et les mélanges de ces acides, un anhydride insaturé tel que par exemple l’anhydride maléique ou phtalique, ou une lactone. - one or more polycarboxylic acid or its ester or anhydride derivative such as 1,6-hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1,18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, a dimer fatty acid, a trimer fatty acid and mixtures of these acids, an unsaturated anhydride such as for example l maleic or phthalic anhydride, or a lactone.
Les polyester polyols suscités peuvent être préparés de manière conventionnelle, et sont pour la plupart disponibles commercialement. The aforementioned polyester polyols can be prepared conventionally, and are mostly commercially available.
Le(s) polyéther polyol(s) utilisable(s) selon l’invention peut(vent) être choisi(s) parmi les polyoxyalkylène polyols, dont la partie alkylène, linéaire ou ramifiée, comprend de 1 à 4 atomes de carbone, plus préférentiellement de 2 à 3 atomes de carbone. The polyether polyol(s) which can be used according to the invention may be chosen from polyoxyalkylene polyols, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms, plus preferably from 2 to 3 carbon atoms.
A titre d’exemple de polyoxyalkylène diols ou triols utilisables selon l’invention, on peut citer les polyoxypropylène diols ou triols (aussi désignés par polypropylène glycol (PPG) diols ou triols) ayant une masse moléculaire moyenne en nombre (Mn) allant de 300 à 12 000 g/mol; les polyoxyéthylène diols ou triols (aussi désignés par polyéthylène glycol (PEG) diols ou triols) ayant une masse moléculaire moyenne en nombre (Mn) allant de 300 à 12 000 g/mol; et leurs mélanges. By way of example of polyoxyalkylene diols or triols that can be used according to the invention, mention may be made of polyoxypropylene diols or triols (also designated by polypropylene glycol (PPG) diols or triols) having a number-average molecular mass (Mn) ranging from 300 at 12,000 g/mol; polyoxyethylene diols or triols (also designated by polyethylene glycol (PEG) diols or triols) having a number-average molecular weight (Mn) ranging from 300 to 12,000 g/mol; and their mixtures.
A titre d’exemple de polyéther diol, on peut citer le « VORANOL® P1010 » commercialisé par la société DOW de masse moléculaire moyenne en nombre (Mn) voisine de 1 020 g/mol et dont l’indice hydroxyle est d’environ 110 mg KOH/g. A titre d’exemple de polyéther triol, on peut citer le polyoxypropylène triol commercialisé sous la dénomination
« VORANOL® CP 450 » par la société DOW, de masse moléculaire moyenne en nombre (Mn) voisine de 450 g/mol et dont l’indice hydroxyle va de 370 à 396 mg KOH/g. As an example of a polyether diol, mention may be made of "VORANOL® P1010" marketed by the company DOW with a number-average molecular mass (Mn) close to 1020 g/mol and whose hydroxyl index is approximately 110 mgKOH/g. As an example of a polyether triol, mention may be made of the polyoxypropylene triol marketed under the name “VORANOL® CP 450” by the company DOW, with a number-average molecular mass (Mn) close to 450 g/mol and whose hydroxyl index ranges from 370 to 396 mg KOH/g.
A titre d’exemples de polyène polyols, on peut citer les homopolymères de butadiène, saturé ou insaturé, comprenant des groupes hydroxyles terminaux, éventuellement époxydés, tels que par exemple ceux commercialisés sous la dénomination « POLY BD® ou KRASOL® » par la société CRAY VALLEY, ainsi que les homopolymères d’isoprène, saturés ou insaturés, comprenant des groupes hydroxyles terminaux, tels que par exemple ceux commercialisés sous la dénomination « POLY IP™ ou EPOL™ » par la société IDEMITSU KOSAN. As examples of polyene polyols, mention may be made of butadiene homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups, optionally epoxidized, such as for example those marketed under the name "POLY BD® or KRASOL®" by the company CRAY VALLEY, as well as isoprene homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups, such as for example those marketed under the name “POLY IP™ or EPOL™” by the company IDEMITSU KOSAN.
A titre d’exemple de polycarbonate diol, on peut citer le « CONVERGE® POLYOL 212- 10 » et « CONVERGE® POLYOL 212-20 » commercialisés par la société NOVOMER respectivement de masse moléculaire en nombre (Mn) égales à 1 000 et 2 000 g/mol dont les indices hydroxyles sont respectivement de 112 et 56 mg KOH/g. By way of example of polycarbonate diol, mention may be made of "CONVERGE® POLYOL 212-10" and "CONVERGE® POLYOL 212-20" marketed by the company NOVOMER respectively with a molecular weight in number (M n ) equal to 1000 and 2000 g/mol whose hydroxyl indices are respectively 112 and 56 mg KOH/g.
Monomère(s) M2 Monomer(s) M2
Le monomère (méth)acrylate M2 peut être choisi parmi les hydroxyalkyl(méth)acrylates. The (meth)acrylate monomer M2 can be chosen from hydroxyalkyl (meth)acrylates.
De préférence, le monomère (méth)acrylate M2 est choisi parmi le 2-hydroxyéthyl méthacrylate (HEMA), le 2-hydroxypropyl méthacrylate, le 4-hydroxybutyl méthacrylate, le 2- hydroxybutyl méthacrylate, le 2-hydroxyéthyl acrylate (HEA), le 2-hydroxypropyl acrylate (HPA), le 4-hydroxybutyl acrylate (4-HBA), (par exemple disponibles chez SARTOMER, BASF). Preferably, the (meth)acrylate M2 monomer is chosen from 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4-HBA), (for example available from SARTOMER, BASF).
Etape E1) Step E1)
La réaction de polyaddition E1 ) peut être mise en oeuvre à une température de préférence inférieure à 95°C et/ou dans des conditions de préférence anhydres. La réaction de polyaddition peut être mise en oeuvre en présence ou non d’au moins un catalyseur. Le(s) catalyseur(s) de réaction utilisable(s) au cours de la réaction de polyaddition peu(ven)t être tout catalyseur connu de l'homme du métier pour catalyser la formation de polyuréthane par réaction d’au moins un polyisocyanate avec au moins un polyol. La réaction de polyaddition E1 ) peut être mise en oeuvre en présence ou non d’au moins un solvant. Le solvant peut être choisi parmi les solvants ne réagissant pas avec les fonctions réactives des ingrédients utilisés dans l’étape E1 ). Il peut par exemple s’agir du méthacrylate de méthyle, du toluène, de l’acétate d’éthyle, du xylène, et de leurs mélanges. The polyaddition reaction E1) can be carried out at a temperature preferably below 95° C. and/or under preferably anhydrous conditions. The polyaddition reaction can be carried out in the presence or absence of at least one catalyst. The reaction catalyst(s) used during the polyaddition reaction can be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reaction of at least one polyisocyanate with at least one polyol. The polyaddition reaction E1) can be carried out in the presence or absence of at least one solvent. The solvent can be chosen from solvents that do not react with the reactive functions of the ingredients used in step E1). It may, for example, be methyl methacrylate, toluene, ethyl acetate, xylene, and mixtures thereof.
Etape E2)
L’étape E2) peut être mise en œuvre à une température de préférence inférieure à 80°C, préférentiellement inférieure ou égale à 60°C, et/ou dans des conditions de préférence anhydres. L’étape E2) peut être mise en œuvre en présence ou non d’au moins un catalyseur. Il peut s’agir du même catalyseur que celui utilisé dans l’étape E1 ). L’étape E2) peut être mise en œuvre en présence ou non d’au moins un solvant. Le solvant peut être choisi parmi les solvants ne réagissant pas avec les fonctions réactives des ingrédients utilisés dans l’étape E2). Il peut par exemple s’agir du méthacrylate de méthyle, du toluène, de l’acétate d’éthyle, du xylène, et de leurs mélanges. De préférence, l’étape E2) est mise en œuvre par ajout du(des) monomère(s) M2 dans le milieu réactionnel de l’étape E1 ), sans isolation du produit formé à l’étape E1 ). Step E2) Step E2) can be implemented at a temperature preferably below 80° C., preferably below or equal to 60° C., and/or under preferably anhydrous conditions. Step E2) can be implemented in the presence or absence of at least one catalyst. It may be the same catalyst as that used in step E1). Step E2) can be implemented in the presence or absence of at least one solvent. The solvent can be chosen from solvents that do not react with the reactive functions of the ingredients used in step E2). It may for example be methyl methacrylate, toluene, ethyl acetate, xylene, and mixtures thereof. Preferably, step E2) is implemented by adding the monomer(s) M2 to the reaction medium of step E1), without isolating the product formed in step E1).
Le polyuréthane P selon l’invention peut également être disponible commercialement. On peut par exemple citer le CN®981 (polyuréthane-acrylate ayant une Mn de 2200 g/mol, et une fonctionnalité acrylate de 2), le CN®9210 (polyuréthane-acrylate ayant une Mn de 1500 g/mol, et une fonctionnalité acrylate de 6), le CN® 9165A (polyuréthane-acrylate ayant une Mn de 900 g/mol et une fonctionnalité acrylate de 6), commercialisés par Sartomer. The polyurethane P according to the invention may also be commercially available. Mention may be made, for example, of CN®981 (polyurethane-acrylate having an Mn of 2200 g/mol, and an acrylate functionality of 2), CN®9210 (polyurethane-acrylate having an Mn of 1500 g/mol, and an acrylate functionality of acrylate of 6), CN® 9165A (polyurethane-acrylate having an Mn of 900 g/mol and an acrylate functionality of 6), marketed by Sartomer.
Selon un mode de réalisation, le polyuréthane P comprend au moins trois fonctions (méth)acrylate, de préférence six fonctions (méth)acrylate. According to one embodiment, the polyurethane P comprises at least three (meth)acrylate functions, preferably six (meth)acrylate functions.
Selon un mode de réalisation, le polyuréthane P ne comprend pas de fonctions époxy.According to one embodiment, the polyurethane P does not include epoxy functions.
Selon un mode de réalisation, le composant A comprend au moins deux polyuréthanes P comprenant au moins deux fonctions (méth)acrylate terminales. De préférence, le composant A comprend un polyuréthane P1 comprenant deux fonctions terminales (méth)acrylates et un polyuréthane P2 (différent de P1 ) comprenant plus de deux fonctions terminales (méth)acrylates (plus préférentiellement six fonctions terminales (méth)acrylates). According to one embodiment, component A comprises at least two polyurethanes P comprising at least two terminal (meth)acrylate functions. Preferably, component A comprises a polyurethane P1 comprising two terminal (meth)acrylate functions and a polyurethane P2 (different from P1) comprising more than two terminal (meth)acrylate functions (more preferably six terminal (meth)acrylate functions).
La teneur totale en polyuréthane(s) P dans le composant A peut être inférieure ou égale à 50% en poids, de préférence inférieure ou égale à 40% en poids. The total content of polyurethane(s) P in component A can be less than or equal to 50% by weight, preferably less than or equal to 40% by weight.
La teneur totale en polyuréthane(s) P dans le composant A peut être supérieure ou égale à 5% en poids, de préférence supérieure ou égale à 10% en poids, et encore plus préférentiellement supérieure ou égale à 20% en poids par rapport au poids total du composant A. The total content of polyurethane(s) P in component A may be greater than or equal to 5% by weight, preferably greater than or equal to 10% by weight, and even more preferably greater than or equal to 20% by weight relative to the total weight of component A.
Agent réducteur Reducing agent
L’agent réducteur peut être choisi parmi les amines tertiaires, le sodium métabisulfite, le sodium bisulfite, les métaux de transition, les alpha-aminosulfones, et leurs mélanges.
L’agent réducteur peut être contenu dans le polyuréthane P susmentionné. Ce mode de réalisation est par exemple possible lorsque dans l’étape E1 ) susmentionnée, les polyols et les polyisocyanates sont mis en réaction avec une amine tertiaire ayant des fonctions hydroxyles pendantes tel que par exemple la bisomer® PTE commercialisée par GEO SPECIALITY CHEMICALS ou encore la N-(2-hydroxyethyl)-N-méthyl aniline ou encore la N- (2-hydroxyéthyl)-N-méthyl-p-toluidine. The reducing agent can be chosen from tertiary amines, sodium metabisulfite, sodium bisulfite, transition metals, alpha-aminosulfones, and mixtures thereof. The reducing agent may be contained in the aforementioned polyurethane P. This embodiment is for example possible when in step E1) mentioned above, the polyols and the polyisocyanates are reacted with a tertiary amine having pendent hydroxyl functions such as for example the bisomer® PTE marketed by GEO SPECIALTY CHEMICALS or even N-(2-hydroxyethyl)-N-methyl aniline or alternatively N-(2-hydroxyethyl)-N-methyl-p-toluidine.
Parmi les alpha-sulfones, on peut par exemple citer la bis(tolylsulfonméthyl)benzylamine. Among the alpha-sulfones, mention may be made, for example, of bis(tolylsulfonmethyl)benzylamine.
Parmi les amines tertiaires, on peut par exemple citer la diisopropanol-p-toluidine (DIIPT) ; la diméthyl-p-toluidine ; la dipropoxy-p-toluidine ; la diméthylaniline ; la N,N- diméthylaminométhylphénol ; la N,N-diisopropanol-p-chloroaniline; la N,N-diisopropanol-p- bromoaniline; la N,N-diisopropanol-p-bromo-m-methylaniline; la N,N-diméthyl-p-chloroaniline; la N,N-diméthyl-p-bromoaniline; la N,N-diéthyl-p-chloroaniline; la N,N-diéthyl-p-bromoaniline ; les amines de formules (B) ou (C) suivantes :
dans laquelle : Among the tertiary amines, mention may be made, for example, of diisopropanol-p-toluidine (DIIPT); dimethyl-p-toluidine; dipropoxy-p-toluidine; dimethylaniline; N,N-dimethylaminomethylphenol; N,N-diisopropanol-p-chloroaniline; N,N-diisopropanol-p-bromoaniline; N,N-diisopropanol-p-bromo-m-methylaniline; N,N-dimethyl-p-chloroaniline; N,N-dimethyl-p-bromoaniline; N,N-diethyl-p-chloroaniline; N,N-diethyl-p-bromoaniline; the amines of formulas (B) or (C) below: in which :
- m et n sont, indépendamment l’un de l’autre, un nombre entier allant de 1 à 150, de préférence de 1 à 100, préférentiellement de 1 à 72, avantageusement de 1 à 36, encore plus avantageusement de 1 à 18; - m and n are, independently of each other, an integer ranging from 1 to 150, preferably from 1 to 100, preferably from 1 to 72, advantageously from 1 to 36, even more advantageously from 1 to 18 ;
- r est un nombre entier allant de 1 à 200, de préférence de 1 à 104, préférentiellement de 1 à 72, avantageusement de 1 à 36 ; - r is an integer ranging from 1 to 200, preferably from 1 to 104, preferably from 1 to 72, advantageously from 1 to 36;
- R6 représente un radical choisi dans le groupe constitué d’un alkyle, linéaire ou ramifié, saturé ou insaturé, comprenant de 1 à 20 atomes de carbone, de préférence de 1 à 10 atomes de carbone ; d’un (hétéro)aryle comprenant de 6 à 12 atomes de carbone ; d’un cycloalkyle comprenant de 3 à 12 atomes de carbone ; - R 6 represents a radical chosen from the group consisting of an alkyl, linear or branched, saturated or unsaturated, comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; a (hetero)aryl comprising from 6 to 12 carbon atoms; a cycloalkyl comprising from 3 to 12 carbon atoms;
- v représente un nombre entier allant de 0 à 5 ; - v represents an integer ranging from 0 to 5;
- R7 et R3 représentent, indépendamment l’un de l’autre, un atome d’halogène, un atome d’hydrogène ou un groupe alkyle, linéaire ou ramifié, comprenant de 1 à 12
atomes de carbone, ledit groupe alkyle étant éventuellement interrompu par au moins un atome d’oxygène ; - R 7 and R 3 represent, independently of one another, a halogen atom, a hydrogen atom or an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms, said alkyl group being optionally interrupted by at least one oxygen atom;
- R4 représente un atome d’hydrogène, un groupe arylalkyle, ou un groupe alkyle, linéaire ou ramifié, comprenant de 1 à 20 atomes de carbone, de préférence un groupe alkyle comprenant de 1 à 12 atomes de carbone, avantageusement de 1 à 6 atomes de carbone ; - R 4 represents a hydrogen atom, an arylalkyl group, or an alkyl group, linear or branched, comprising from 1 to 20 carbon atoms, preferably an alkyl group comprising from 1 to 12 carbon atoms, advantageously from 1 to 6 carbon atoms;
- à condition que m + n > 2, de préférence n + m > 2,5. - provided that m + n > 2, preferably n + m > 2.5.
Parmi les amines de formule (B), on peut par exemple citer la « BISOMER® PTE » (numéro CAS : 878391-30-1 ) commercialisée par GEO SPECIALITY CHEMICALS, le « Accelerator PT25E » (numéro CAS : 878391-30-1 ) commercialisé par LANXESS, la N,N- Bis(2-hydroxypropyl)-p-aniline (numéro CAS : 3077-13-2) disponible chez BIOSYNTH, la N,N- Bis(2-hydroxypropyl)-p-toluidine (numéro CAS : 38668-48-3) commercialisée par BASF, le « ETHOX ANA-10 » (numéro CAS : 36356-83-9) disponible chez ETHOX CHEMICAL. Among the amines of formula (B), mention may be made, for example, of “BISOMER® PTE” (CAS number: 878391-30-1) marketed by GEO SPECIALTY CHEMICALS, “Accelerator PT25E” (CAS number: 878391-30-1 ) marketed by LANXESS, N,N-Bis(2-hydroxypropyl)-p-aniline (CAS number: 3077-13-2) available from BIOSYNTH, N,N-Bis(2-hydroxypropyl)-p-toluidine ( CAS number: 38668-48-3) marketed by BASF, “ETHOX ANA-10” (CAS number: 36356-83-9) available from ETHOX CHEMICAL.
Parmi les amines de formule (C), on peut par exemple citer la N-(2-hydroxyéthyl)-N- méthyl aniline (numéro CAS : 93-90-3) disponible chez SIGMA-ALDRICH et la N-(2- hydroxyéthyl)-N-méthyl-p-toluidine (MHPT, numéro CAS : 2842-44-6) disponible chez PARCHEM. Among the amines of formula (C), mention may be made, for example, of N-(2-hydroxyethyl)-N-methyl aniline (CAS number: 93-90-3) available from SIGMA-ALDRICH and N-(2-hydroxyethyl )-N-methyl-p-toluidine (MHPT, CAS number: 2842-44-6) available from PARCHEM.
De préférence, le composant A comprend au moins une amine tertiaire, et encore plus préférentiellement une amine de formule (B) susmentionnée. Preferably, component A comprises at least one tertiary amine, and even more preferably an amine of formula (B) above.
Le composant A peut comprendre une teneur totale en agent(s) réducteur(s) allant de 0,5% à 5%, de préférence de 0,5% à 3%, en poids par rapport au poids total du composant A. Component A may comprise a total content of reducing agent(s) ranging from 0.5% to 5%, preferably from 0.5% to 3%, by weight relative to the total weight of component A.
Monomère itaconate Itaconate monomer
Le composant A selon l’invention comprend au moins un monomère itaconate de formule (I) suivante :
dans laquelle chacun de R1 et R2 représente, indépendamment l’un de l’autre, des radicaux organiques.
Dans la formule (I) ci-dessus, chacun de R1 et R2 peut représenter, indépendamment l’un de l’autre, un alkyle, un alcényle, un cycloalkyle, un hétérocycloalkyle, un aryle, un hétéroaryle, un arylalkyle, un hétéroarylalkyle, un alkylhétéroaryle, ou un alkylhétérocycloalkyle, lesdits groupes pouvant éventuellement être substitués. Component A according to the invention comprises at least one itaconate monomer of formula (I) below: wherein each of R 1 and R 2 represents, independently of one another, organic radicals. In formula (I) above, each of R 1 and R 2 can represent, independently of one another, an alkyl, an alkenyl, a cycloalkyl, a heterocycloalkyl, an aryl, a heteroaryl, an arylalkyl, a heteroarylalkyl, an alkylheteroaryl, or an alkylheterocycloalkyl, said groups possibly being substituted.
Les substituants susmentionnés peuvent être choisis parmi les alkyles, les halogènes, les cycloalkyles, les halo-alkyles, les halo-cycloalkyles, les hétéroaryles, les aryles, les hétérocycloalkyles, les alcoxys, les alkylthio, les hydroxyles, les nitro, les azido, les cyano, les acyloxy, les carboxy ou les esters. The aforementioned substituents can be chosen from alkyls, halogens, cycloalkyls, halo-alkyls, halo-cycloalkyls, heteroaryls, aryls, heterocycloalkyls, alkoxys, alkylthios, hydroxyls, nitros, azidos, cyano, acyloxy, carboxy or esters.
Dans le cadre de l’invention, on entend par « alkyle » un radical linéaire ou ramifié comprenant de préférence de 1 à 20 atomes de carbone. In the context of the invention, the term “alkyl” is understood to mean a linear or branched radical preferably comprising from 1 to 20 carbon atoms.
Dans le cadre de l’invention, on entend par « alcényle » un radical hydrocarboné linéaire ou ramifié comportant au moins une double liaison, ledit radical comprenant de préférence de 2 à 20 atomes de carbone. A titre d’exemple, on peut citer le propényle, le butényle. In the context of the invention, the term "alkenyl" means a linear or branched hydrocarbon radical comprising at least one double bond, said radical preferably comprising from 2 to 20 carbon atoms. By way of example, mention may be made of propenyl, butenyl.
Dans le cadre de l’invention, on entend par « arylalkyle », un groupe alkyle substitué par un groupe aryle, le groupe arylalkyle comprenant de préférence de 7 à 20 atomes de carbone. A titre de groupe arylalkyle, on peut par exemple citer le benzyle. In the context of the invention, the term "arylalkyl" means an alkyl group substituted by an aryl group, the arylalkyl group preferably comprising from 7 to 20 carbon atoms. As an arylalkyl group, mention may be made, for example, of benzyl.
Dans le cadre de l’invention, on entend par « hétéroarylalkyle », un groupe alkyle substitué par un groupe hétéroaryle, le groupe hétéroarylalkyle comprenant de préférence de 7 à 20 atomes de carbone. In the context of the invention, the term "heteroarylalkyl" means an alkyl group substituted by a heteroaryl group, the heteroarylalkyl group preferably comprising from 7 to 20 carbon atoms.
Dans le cadre de l’invention, on entend par « alkylhétéroaryle », un groupe hétéroaryle substitué par un groupe alkyle, ledit groupe alkylhétéroaryle comprenant de préférence de 7 à 20 atomes de carbone et au moins un hétéroatome. In the context of the invention, the term "alkylheteroaryl" means a heteroaryl group substituted by an alkyl group, said alkylheteroaryl group preferably comprising from 7 to 20 carbon atoms and at least one heteroatom.
Dans le cadre de l’invention, on entend par « alkylhétérocyclolalkyle », un groupe hétérocycloalkyle substitué par un groupe alkyle, ledit groupe alkylhétérocycloalkyle comprenant de préférence de 4 à 20 atomes de carbone et au moins un hétéroatome. In the context of the invention, the term "alkylheterocycloalkyl" means a heterocycloalkyl group substituted by an alkyl group, said alkylheterocycloalkyl group preferably comprising from 4 to 20 carbon atoms and at least one heteroatom.
Dans le cadre de l’invention, on entend par « aryle », un radical aromatique monocyclique ou bicyclique comprenant de préférence de 6 à 12 atomes de carbone. On peut par exemple citer le phényle. In the context of the invention, the term “aryl” is understood to mean a monocyclic or bicyclic aromatic radical preferably comprising from 6 to 12 carbon atoms. Mention may be made, for example, of phenyl.
Dans le cadre de l’invention, on entend par « hétéroaryle », un radical aromatique monocyclique ou bicyclique comprenant au moins un hétéroatome tel que par exemple O, S ou N, et de préférence comprenant de 4 à 12 atomes de carbone. On peut par exemple citer les radicaux furanyle, thiophényle, pyrrolyle, pyridinyle, indolyle ou imidazolyle. In the context of the invention, the term “heteroaryl” is understood to mean a monocyclic or bicyclic aromatic radical comprising at least one heteroatom such as for example O, S or N, and preferably comprising from 4 to 12 carbon atoms. Mention may be made, for example, of the furanyl, thiophenyl, pyrrolyl, pyridinyl, indolyl or imidazolyl radicals.
Dans le cadre de l’invention, on entend par « cycloalkyle », un système monocyclique ou polycyclique, de préférence mono ou bicyclique, saturé, comportant de préférence de 3 à
12 atomes de carbone, les cycles pouvant être deux à deux fusionnés ou pontés, tel que les groupes cyclopropyle, cyclopentyle, cyclohexyle ou encore norbornyle. In the context of the invention, the term "cycloalkyl" means a monocyclic or polycyclic system, preferably mono or bicyclic, saturated, preferably comprising from 3 to 12 carbon atoms, the rings possibly being fused or bridged in pairs, such as the cyclopropyl, cyclopentyl, cyclohexyl or even norbornyl groups.
Dans le cadre de l’invention, on entend par « hétérocycloalkyle », un système monocyclique ou polycyclique, de préférence mono ou bicyclique, saturé, comportant de préférence de 3 à 12 atomes de carbone et au moins un hétéroatome tel que par exemple O ou N, les cycles pouvant être deux à deux fusionnés ou pontés. In the context of the invention, the term "heterocycloalkyl" means a monocyclic or polycyclic system, preferably mono or bicyclic, saturated, preferably comprising from 3 to 12 carbon atoms and at least one heteroatom such as for example O or N, the cycles being able to be fused or bridged in pairs.
Selon un mode de réalisation préféré, dans la formule (I) susmentionnée, chacun de R1 et R2 représente, indépendamment l’un de l’autre, un groupe C1-C15 alkyle, C2-C15 alcényle, halo-(C1-C15)alkyle, C3-C12 cycloalkyle, halo(C3-C12)cycloalkyle, un hétérocycle, un aryle, un hétéroaryle, ou un alcoxy-(C1-C15)alkyle, chacun d’entre eux pouvant être éventuellement substitué par l’un au moins des radicaux suivants : C1-C15 alkyle, halo(C1- C15 alkyle), C3-12 cycloalkyle, halo(C3-C12 cycloalkyle), hétérocycle, aryle, hétéroaryle, CICI 5 alcoxy, C1-C15 alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy ou ester. According to a preferred embodiment, in the aforementioned formula (I), each of R 1 and R 2 represents, independently of one another, a C1-C15 alkyl, C2-C15 alkenyl, halo-(C1- C15)alkyl, C3-C12 cycloalkyl, halo(C3-C12)cycloalkyl, a heterocycle, an aryl, a heteroaryl, or an alkoxy-(C1-C15)alkyl, each of which may optionally be substituted by one at least of the following radicals: C1-C15 alkyl, halo(C1-C15 alkyl), C3-12 cycloalkyl, halo(C3-C12 cycloalkyl), heterocycle, aryl, heteroaryl, CICI 5 alkoxy, C1-C15 alkylthio, halo, hydroxyl , nitro, azido, cyano, acyloxy, carboxy or ester.
De préférence, dans la formule (I) ci-dessus, chacun de R1 et R2 représente, indépendamment l’un de l’autre, un méthyle, un éthyle, un n-propyle, un isopropyle, un n- butyle, un tert-butyle, un cyclopentyle, un cyclohexyle, un cyclohexylméthyle, un phényle, un benzyle, un 2-phényléthyl, et un isobornyle. Preferably, in formula (I) above, each of R 1 and R 2 represents, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl, benzyl, 2-phenylethyl, and isobornyl.
De préférence, l’itaconate de formule (I) est choisi parmi l’itaconate de diméthyle, l’itaconate de diéthyle, l’itaconate de di-n-butyle, l’itaconate de di-isobutyle, l’itaconate de dicyclohexyle, l’itaconate de bis(hexafluoroisopropyle), l’itaconate de diphényle, l’itaconate de dibenzyle, l’itaconate d’éthyle isobornyle, l’itaconate d’éthyl cyclohexyle, et leurs mélanges. Encore plus préférentiellement, l’itaconate de formule (I) est l’itaconate de diméthyle ou l’itaconate de dibutyle. Preferably, the itaconate of formula (I) is chosen from dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, di-isobutyl itaconate, dicyclohexyl itaconate, bis(hexafluoroisopropyl) itaconate, diphenyl itaconate, dibenzyl itaconate, ethyl isobornyl itaconate, ethyl cyclohexyl itaconate, and mixtures thereof. Even more preferentially, the itaconate of formula (I) is dimethyl itaconate or dibutyl itaconate.
Selon l’invention, la teneur totale en monomère(s) itaconate(s) de formule (I) dans le composant A peut être supérieure à 40% en poids, de préférence supérieure ou égale à 45% en poids par rapport au poids total du composant A. According to the invention, the total content of itaconate monomer(s) of formula (I) in component A may be greater than 40% by weight, preferably greater than or equal to 45% by weight relative to the total weight of component A.
Les monomères de formule (I) peuvent être obtenus par des procédés tels que par exemple décrits dans W02015181310, qui sont notamment des procédés de fermentation. The monomers of formula (I) can be obtained by processes such as for example described in WO2015181310, which are in particular fermentation processes.
Les monomères de formule (I) sont avantageusement biosourcés. The monomers of formula (I) are advantageously biosourced.
Modificateur d’impact ayant structure de type cœur-écorce Impact modifier with core-shell type structure
Le modificateur d’impact ayant une structure de type cœur-écorce est typiquement connu sous la désignation anglaise « core-shell impact modifier ». The impact modifier having a core-shell type structure is typically known by the English designation "core-shell impact modifier".
Les modificateurs d’impact sont bien connus de l’homme du métier, et comprennent notamment les modificateurs d’impact ayant une structure de type cœur-écorce.
Le modificateur d’impact ayant une structure de type cœur-écorce peut être sous forme de particules sphériques. La taille de particules moyenne en poids (diamètre) peut aller de 40 nm à 900 nm, de préférence de 80 à 500 nm. La taille des particules peut être mesurée avec un Zetasizer (Malvern). Impact modifiers are well known to those skilled in the art, and include in particular impact modifiers having a core-shell type structure. The impact modifier having a core-shell type structure may be in the form of spherical particles. The weight average particle size (diameter) can range from 40 nm to 900 nm, preferably from 80 to 500 nm. Particle size can be measured with a Zetasizer (Malvern).
Le modificateur d’impact ayant une structure de type cœur-écorce peut être obtenu par tout procédé connu de l’homme du métier, par exemple par un procédé à étapes multiples tel que décrit dans FR 3 052 169 ou dans EP 2 465 884. En particulier, le polymère est préparé par polymérisation en émulsion. The impact modifier having a core-shell type structure can be obtained by any process known to those skilled in the art, for example by a multi-step process as described in FR 3 052 169 or in EP 2 465 884. In particular, the polymer is prepared by emulsion polymerization.
Le cœur du modificateur d’impact peut comprendre un polymère L1 choisi parmi les homopolymères d’isoprène, les homopolymères de butadiène, les copolymères d’isoprène- butadiène, les copolymères d’isoprène avec un monomère vinylique, les copolymères de butadiène avec un monomère vinylique. Le monomère vinylique peut être choisi parmi le styrène, les alkylstyrène, l’acrylon itrile, les (méth)acrylates d’alkyle, le butadiène ou l’isoprène. The core of the impact modifier may comprise a polymer L1 chosen from isoprene homopolymers, butadiene homopolymers, isoprene-butadiene copolymers, isoprene copolymers with a vinyl monomer, butadiene copolymers with a monomer vinyl. The vinyl monomer can be chosen from styrene, alkylstyrene, acrylonitrile, alkyl (meth)acrylates, butadiene or isoprene.
L’écorce peut comprendre un polymère L2 obtenu à partir de monomères (méth)acryliques tels que par exemple ceux choisis parmi les (méth)acrylates d’alkyle en CICI 2. En particulier, l’écorce comprend un polymère L2 obtenu à partir de monomères de méthacrylate d’alkyle en C1-C4 et/ou des monomères d’acrylate d’alkyle en C1-C8. The shell may comprise an L2 polymer obtained from (meth)acrylic monomers such as for example those chosen from CICI 2 alkyl (meth)acrylates. In particular, the shell comprises an L2 polymer obtained from C1-C4 alkyl methacrylate monomers and/or C1-C8 alkyl acrylate monomers.
De manière préférée, l’écorce comprend un polymère L2 obtenu à partir d’acrylate de méthyle, d’acrylate de propyle, d’acrylate d’isopropyle, d’acrylate de butyle, de méthacrylate de méthyle, de méthacrylate d’éthyle, de méthacrylate de butyle, et de leurs mélanges. Preferably, the shell comprises a polymer L2 obtained from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof.
Selon un mode de réalisation, le modificateur d’impact ayant une structure de type cœur-écorce comprend : un cœur comprenant un polymère L1 étant un copolymère butadiène-styrène ; une écorce comprenant un polymère L2 étant un polyméthacrylate de méthyle (PMMA). According to one embodiment, the impact modifier having a core-shell type structure comprises: a core comprising a polymer L1 being a butadiene-styrene copolymer; a shell comprising a polymer L2 being a polymethyl methacrylate (PMMA).
Les modificateurs d’impact ayant une structure de type cœur-écorce peuvent être commercialement disponibles. On peut par exemple citer le Clearstrength® (par exemple Clearstrength® XT 100) ou les Durastrength® commercialisés par Arkema. On peut également citer les Paraloid (Paraloid 2650A, Paraloid 2691 A) commercialisés par Dow Corning. Impact modifiers having a core-shell type structure may be commercially available. Mention may be made, for example, of Clearstrength® (for example Clearstrength® XT 100) or the Durastrength® sold by Arkema. Mention may also be made of the Paraloids (Paraloid 2650A, Paraloid 2691 A) marketed by Dow Corning.
Selon l’invention, la teneur totale en polymère(s) ayant une structure de type cœur- écorce dans le composant A peut aller de 2 % à 20 % en poids, de préférence de 5% à 20% en poids, et encore plus préférentiellement de 10 % à 18 % en poids par rapport au poids total du composant A.
Composant B According to the invention, the total content of polymer(s) having a core-shell type structure in component A can range from 2% to 20% by weight, preferably from 5% to 20% by weight, and even more. preferably from 10% to 18% by weight relative to the total weight of component A. Component B
Agent oxydant Oxidizing agent
L’agent oxydant peut être choisi parmi les peroxydes, les sels organiques de métaux de transition, les composés contenant un chlore labile, et leurs mélanges. The oxidizing agent can be chosen from peroxides, organic salts of transition metals, compounds containing labile chlorine, and mixtures thereof.
Le peroxyde peut être choisi parmi les peroxydes organiques, les peroxydes inorganiques, et leurs mélanges. The peroxide can be chosen from organic peroxides, inorganic peroxides, and mixtures thereof.
Parmi les peroxydes inorganiques, on peut citer l'acide peroxydisulfurique et leurs sels, tels que le peroxodisulfate d'ammonium, le peroxodisulfate de sodium et le peroxodisulfate de potassium. Among the inorganic peroxides, mention may be made of peroxydisulfuric acid and their salts, such as ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
Parmi les peroxides oganiques, on peut citer l’ hydroperoxyde de cumène, l’ hydroperoxyde de para-menthane, le peroxyisobutyrate de ferf-butyle, le peroxybenzoate de ferf-butyle, le peroxynéodécanoate de ferf-butyle, le peroxypivalate de ferf-amyle, le peroxyde d'acétyle, le peroxyde de benzoyle, le peroxyde de dibenzoyle, le 1 ,3-bis-(t- butylperoxyisopropyl)benzène, le diacétyl peroxyde, le t-butylcumyl peroxyde, le peroxyacétate de ferf-butyle, le peroxyde de cumyle, le 2,5-diméthyl-2,5-di-t- butylperoxyhexane, le 2,5-diméthyl-2,5-di-t-butyl-peroxyhex-3-yne, le 4-méthyl-2,2-di-t- butylperoxypentane, et leurs mélanges. Among the oganic peroxides, mention may be made of cumene hydroperoxide, para-menthane hydroperoxide, ferf-butyl peroxyisobutyrate, ferf-butyl peroxybenzoate, ferf-butyl peroxyneodecanoate, ferf-amyl peroxypivalate, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis-(t-butylperoxyisopropyl)benzene, diacetyl peroxide, t-butylcumyl peroxide, ferf-butyl peroxyacetate, cumyl, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne, 4-methyl-2,2 -di-t-butylperoxypentane, and mixtures thereof.
De préférence, le composant B comprend le peroxyde de benzoyle Preferably component B comprises benzoyl peroxide
Le composant B peut comprendre une teneur totale en agent réducteur supérieure ou égale à 20% en poids, de préférence supérieure ou égale à 30% en poids, avantageusement supérieure ou égale à 35% en poids par rapport au poids total du composant B. Component B may comprise a total content of reducing agent greater than or equal to 20% by weight, preferably greater than or equal to 30% by weight, advantageously greater than or equal to 35% by weight relative to the total weight of component B.
La composition selon l’invention peut typiquement comprendre un système rédox, un agent réducteur étant compris dans la partie A et un agent oxydant étant compris dans la partie B. On peut par exemple citer les combinaisons suivantes : persulfates (oxydant) / (sodium metabisulfite et/ ou sodium bisulfite) (réducteurs) ; peroxydes organiques (oxydant) / amines tertiaires (réducteur) ; hydroperoxydes organiques (oxydant) / métaux de transitions (réducteur) ; The composition according to the invention may typically comprise a redox system, a reducing agent being included in part A and an oxidizing agent being included in part B. Mention may be made, for example, of the following combinations: persulphates (oxidant)/(sodium metabisulphite and/or sodium bisulphite) (reducers); organic peroxides (oxidant) / tertiary amines (reducer); organic hydroperoxides (oxidant) / transition metals (reducer);
H2O2 (oxydant)ZFer (réducteur). H2O2 (oxidant)ZFer (reducer).
Monomère (méth)acrylate M1 Monomer (meth)acrylate M1
Le composant B peut optionnellement comprendre au moins un monomère (méth)acrylate M1.
Les monomères (méth)acrylate M1 peuvent comprendre une (monofonctionnels) ou plusieurs fonctions (méth)acrylate (polyfonctionnels). Component B may optionally comprise at least one (meth)acrylate monomer M1. The (meth)acrylate monomers M1 may comprise one (monofunctional) or several (meth)acrylate (polyfunctional) functions.
Le(s) monomère(s) (méth)acrylate(s) M1 peut(vent) être choisi(s) dans le groupe constitué : The (meth)acrylate monomer(s) M1 can be chosen from the group consisting of:
- des composés ayant la formule (II) suivante : - compounds having the following formula (II):
CH2=C(R8)-COOR9 (II) dans laquelle : CH 2 =C(R 8 )-COOR 9 (II) in which:
- R8 représente un atome d’hydrogène ou un groupe alkyle comprenant de 1 à 4 atomes de carbone ; - R 8 represents a hydrogen atom or an alkyl group comprising from 1 to 4 carbon atoms;
- R9 est choisi dans le groupe constitué des alkyles, des cycloalkyles, des alcényles, des cycloalcényles, des alkylaryles, des arylalkyles ou des aryles, lesdits alkyles, des cycloalkyles, des alcényles, des cycloalcényles, des alkylaryles, des arylalkyles ou des aryles pouvant être éventuellement substitués et/ou interrompus par au moins un silane, un silicone, un oxygène, un halogène, un carbonyle, un hydroxyle, un ester, une urée, un uréthane, un carbonate, une amine, une amide, un soufre, un sulfonate, ou un sulfone ; - R 9 is selected from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls, said alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryls, arylalkyls or aryls which may optionally be substituted and/or interrupted by at least one silane, one silicone, one oxygen, one halogen, one carbonyl, one hydroxyl, one ester, one urea, one urethane, one carbonate, one amine, one amide, one sulfur, a sulfonate, or a sulfone;
- des polyéthylène glycol di(méth)acrylates ; - polyethylene glycol di(meth)acrylates;
- des tétrahydrofurane (méth)acrylates ; - tetrahydrofuran (meth) acrylates;
- de l’hydroxypropyl (méth)acrylate ; - hydroxypropyl (meth)acrylate;
- de l’hexanediol di(méth)acrylate ; - hexanediol di(meth)acrylate;
- du triméthylol propane tri(méth)acrylate ; - trimethylol propane tri(meth)acrylate;
- du diéthylèneglycol di(méth)acrylate ; - diethylene glycol di(meth)acrylate;
- du triéthylène glycol di(méth)acrylate ; - triethylene glycol di(meth)acrylate;
- du tétraéthylène glycol di(méth)acrylate ; - tetraethylene glycol di(meth)acrylate;
- du dipropylène glycol di(méth)acrylate ; - dipropylene glycol di(meth)acrylate;
- du di-(pentaméthylène glycol di(méth)acrylate ; - di-(pentamethylene glycol di(meth)acrylate;
- du diglycérol tétra(méth)acrylate ; - diglycerol tetra(meth)acrylate;
- du tétraméthylène di(méth)acrylate ; - tetramethylene di (meth) acrylate;
- de l’éthylène di(méth)acrylate ;
- des bisphénol A mono- et di(méth)acrylates ; - ethylene di(meth)acrylate; - Bisphenol A mono- and di(meth)acrylates;
- des bisphénol F mono- et di(méth)acrylates; et - bisphenol F mono- and di(meth)acrylates; and
- de leurs mélanges. - their mixtures.
Selon un mode de réalisation, le monomère (méth)acrylate M1 est choisi parmi le (méth)acrylate de méthyle, le (méth)acrylate d’éthyle, le (méth)acrylate de 2-éthylhexyle, le (méth)acrylate d’heptyle, le (méth)acrylate de 2-tert-butylheptyle, le (méth)acrylate d’octyle, le (méth)acrylate de 3-isopropylheptyle, le (méth)acrylate de nonyle, le (méth)acrylate de décyle, le (méth)acrylate d’undécyle, le (méth)acrylate de 5-méthylundécyle, le (méth)acrylate de dodécyle, le (méth)acrylate de 2-méthyldodécyle, le (méth)acrylate de tridécyle, le (méth)acrylate de 5-méthyltridécyl, le (méth)acrylate de tétradécyle, le (méth)acrylate de pentadécyle, le (méth)acrylate d’hexadécyle, le (méth)acrylate de 2-méthylhexadécyle, le (méth)acrylate d’heptadécyl, le (méth)acrylate de 5-isopropylheptadécyle, le (méth)acrylate de 4-tert-butyloctadécyle, le (méth)acrylate de 5-éthyloctadécyle, le (méth)acrylate de 3- isopropyloctadécyle, le (méth)acrylate d’octadécyle, le (méth)acrylate de nonadécyle, le (méth)acrylate d’eicosyle, le (méth)acrylate de 3-vinylcyclohexyle, le (métha)crylate de bornyle, le (méth)acrylate de 2,4,5-tri-t-butyl-3-vinylcyclohexyle, le (méth)acrylate de 2, 3,4,5- tétra-t-butylcyclohexyle; le (méth)acrylate de benzyle, le (méth)acrylate de phényle, le 2-(2- éthoxyéthoxy)éthyl (méth)acrylate, le (méth)acrylate de 2-phénoxyéthyle, et leurs mélanges. According to one embodiment, the monomer (meth) acrylate M1 is chosen from methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl (meth) acrylate, heptyl, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, ( 5-isopropylheptadecyl meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, (meth )eicosyl acrylate, 3-vinylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth)acrylate, (meth)acrylate 2,3,4,5-tetra-t-butylcyclohexyl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and mixtures thereof.
Composition Composition
La composition bicomposante selon l’invention peut comprendre au moins un additif choisi dans le groupe constitué des charges, des antioxydants, des stabilisants à la lumière/ absorbeurs d’UV, des désactivateurs de métaux, des antistatiques, des agents antivoile, des agents moussants, des biocides, des plastifiants, des lubrifiants, des émulsifiants, des colorants, des pigments, des agents rhéologiques, des modificateurs d’impact, des promoteurs d’adhésion, des azurants optiques, des ignifugeants, des agents anti-suintement, des agents de nucléation, des solvants, et de leurs mélanges. The two-component composition according to the invention may comprise at least one additive chosen from the group consisting of fillers, antioxidants, light stabilizers/UV absorbers, metal deactivators, antistatics, antifogging agents, foaming agents , biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, anti-bleeding agents, nucleation, solvents, and mixtures thereof.
Ces additifs peuvent être présents dans le composant A et/ou le composant B de la composition selon l’invention. These additives may be present in component A and/or component B of the composition according to the invention.
A titre d’exemple d’agent plastifiant utilisable, on peut citer n’importe quel agent plastifiant habituellement utilisé dans le domaine des adhésifs tels que par exemple les phtalates, les benzoates, les esters de trimethylolpropane, les esters de triméthyloléthane, les esters de triméthylolméthane, les esters de glycérol, les esters de pentaerythritol, les huiles
minérales napthéniques, les adipates, les cyclohexyldicarboxylates, les huiles paraffiniques, les huiles naturelles (éventuellement époxydées), les polypropylènes, les polybutylènes, les polyisoprènes hydrogénés, et leurs mélanges. By way of example of a plasticizer that can be used, mention may be made of any plasticizer usually used in the field of adhesives such as, for example, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane, glycerol esters, pentaerythritol esters, oils napthenic minerals, adipates, cyclohexyldicarboxylates, paraffinic oils, natural oils (optionally epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.
De préférence, on utilise : Preferably, we use:
- le diisodecyl phtalate, tel que par exemple commercialisé sous le nom PALATINOL™ DIDP par la Société BASF, - diisodecyl phthalate, such as for example marketed under the name PALATINOL™ DIDP by the company BASF,
- un ester d’acide alkylsulphonique et de phénol, tel que par exemple commercialisé sous le nom MESAMOLL® par la société LANXESS, - an ester of alkylsulphonic acid and phenol, such as for example marketed under the name MESAMOLL® by the company LANXESS,
- le diisononyl-1 ,2-cyclohexanedicarboxylate, tel que par exemple commercialisé sous le nom HEXAMOLL DINCH® par la société BASF, - diisononyl-1,2-cyclohexanedicarboxylate, such as for example marketed under the name HEXAMOLL DINCH® by the company BASF,
- le tétravalérate de pentaérythritol, tel que par exemple commercialisé sous le nom PEVALENTM par la Société PERSTORP, - pentaerythritol tetravalerate, such as for example marketed under the name PEVALEN TM by the company PERSTORP,
- l’huile de Soja époxydée tel que par exemple commercialisée sous le nom VIKOFLEX® 7170 par la Société ARKEMA. - epoxidized soybean oil such as, for example, marketed under the name VIKOFLEX® 7170 by ARKEMA.
Lorsqu’il est présent dans la composition, la teneur en plastifiant peut être supérieure ou égale à 1 %, de préférence supérieure ou égale à 3 %, et encore plus préférentiellement supérieure ou égale à 5 % en poids par rapport au poids total de ladite composition. When present in the composition, the plasticizer content may be greater than or equal to 1%, preferably greater than or equal to 3%, and even more preferably greater than or equal to 5% by weight relative to the total weight of said composition.
Selon un mode préféré, la composition comprend au moins un plastifiant, et encore plus préférentiellement au moins dans le composant B. According to a preferred embodiment, the composition comprises at least one plasticizer, and even more preferentially at least in component B.
A titre d’exemple d’agent(s) de rhéologie (thixotropiques) utilisable(s), on peut citer n’importe quel agent de rhéologie habituellement utilisé dans le domaine des compositions adhésives. By way of example of (thixotropic) rheology agent(s) that can be used, mention may be made of any rheology agent usually used in the field of adhesive compositions.
De préférence, les agents thixotropiques sont choisis parmi : Preferably, the thixotropic agents are chosen from:
- les plastisols de PVC, correspondant à une suspension de PVC dans un agent plastifiant miscible avec le PVC, obtenue in situ par chauffage à des températures allant de 60°C à 80°C. Ces plastisols peuvent être ceux décrits notamment dans l’ouvrage « Polyurethane Sealants », Robert M. Evans, ISBN 087762-998-6, - PVC plastisols, corresponding to a suspension of PVC in a plasticizer miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C. These plastisols can be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6,
- la silice pyrogénée, telle que par exemple vendu sous la dénomination HDK® N20 par la société WACKER ;
- des dérivés d’urée issus de la réaction d’un monomère diisocyanate aromatique tel que le 4,4’-MDI avec une amine aliphatique telle que la butylamine. La préparation de tels dérivés d’urée est décrite notamment dans la demande FR 1 591 172 ; - fumed silica, such as for example sold under the name HDK® N20 by the company WACKER; - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172;
- les cires d’amides micronisées, telles que le CRAYVALLAC SLT commercialisé par ARKEMA. - micronized amide waxes, such as CRAYVALLAC SLT marketed by ARKEMA.
La composition selon l’invention peut comprendre en outre au moins une charge organique et/ou minérale. The composition according to the invention may also comprise at least one organic and/or mineral filler.
La (ou les) charge(s) minérale(s) utilisable(s) est (sont) avantageusement choisie(s) de manière à améliorer les performances mécaniques de la composition selon l’invention à l’état réticulée. The mineral filler(s) that can be used is (are) advantageously chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.
A titre d’exemple de charge(s) minérale(s) utilisable(s), on peut utiliser n’importe quelle(s) charge(s) minérale(s) habituellement utilisée(s) dans le domaine des compositions adhésives. Ces charges se présentent typiquement sous la forme de particules de géométrie diverse. Elles peuvent être par exemples sphériques, fibreuses, ou présenter une forme irrégulière. By way of example of mineral filler(s) that can be used, any mineral filler(s) usually used in the field of adhesive compositions can be used. These fillers are typically in the form of particles of various geometry. They can be for example spherical, fibrous, or have an irregular shape.
La(les) charge(s) peut(vent) être choisie(s) dans le groupe constitué de l’argile, du quartz, des charges carbonatées, du kaolin, du gypse, des argiles, et de leurs mélanges, préférentiellement la(les) charge(s) est(sont) choisie(s) parmi les charges carbonatées, telles que les carbonates de métaux alcalin ou alcalino-terreux, et plus préférentiellement le carbonate de calcium ou la craie. The filler(s) can be chosen from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clays, and mixtures thereof, preferably the) filler(s) is (are) chosen from carbonate fillers, such as alkali or alkaline-earth metal carbonates, and more preferably calcium carbonate or chalk.
Ces charges peuvent être non traitée ou traitées, par exemple à l’aide d’un acide organique tel que l’acide stéarique, ou d’un mélange d’acides organiques constitué majoritairement d’acide stéarique. These fillers can be untreated or treated, for example using an organic acid such as stearic acid, or a mixture of organic acids mainly consisting of stearic acid.
On peut utiliser également des microsphères creuses minérales telles que des microsphères creuses de verre, et plus particulièrement celles en borosilicate de sodium et de calcium ou en aluminosilicate. It is also possible to use hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or of aluminosilicate.
Lorsqu’un solvant, en particulier un solvant volatil, est présent dans la composition, sa teneur est de préférence inférieure ou égale à 5% en poids, de préférence encore inférieure ou égale à 3% en poids, par rapport au poids total de la composition. When a solvent, in particular a volatile solvent, is present in the composition, its content is preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight, relative to the total weight of the composition.
De préférence, la teneur en solvant(s) dans la composition est comprise entre 0% et 5% en poids. Preferably, the content of solvent(s) in the composition is between 0% and 5% by weight.
La composition peut comprendre une quantité de 0,1% à 3%, de préférence de 1 % à 3% en poids, d’au moins un stabilisant UV ou antioxydant. Ces composés sont typiquement
introduits pour protéger la composition d’une dégradation résultant d’une réaction avec de l’oxygène qui est susceptible de se former par action de la chaleur ou de la lumière. Ces composés peuvent inclure des antioxydants primaires qui piègent les radicaux libres. Les antioxydants primaires peuvent être utilisés seuls ou en combinaison avec d’autres antioxydants secondaires ou des stabilisants UV. On peut par exemple citer l’IRGANOX ® 1010, l’IRGANOX ® B561 , l’IRGANOX ® 245, l’IRGAFOS ® 168, TINUVIN® 328 ou TINUVIN™ 770 commercialisés par BASF. The composition can comprise an amount of 0.1% to 3%, preferably 1% to 3% by weight, of at least one UV stabilizer or antioxidant. These compounds are typically introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat or light. These compounds can include primary antioxidants that scavenge free radicals. The primary antioxidants can be used alone or in combination with other secondary antioxidants or UV stabilizers. Mention may be made, for example, of IRGANOX® 1010, IRGANOX® B561, IRGANOX® 245, IRGAFOS® 168, TINUVIN® 328 or TINUVIN™ 770 marketed by BASF.
Selon un mode de réalisation, la composition adhésive susmentionnée ne comprend pas de photoinitiateur. According to one embodiment, the aforementioned adhesive composition does not include a photoinitiator.
Selon un mode de réalisation, le ratio volumique composant A/composant B dans la composition de l’invention va de 20/1 à 1/1 , préférentiellement de 10/1 à 1/1. According to one embodiment, the component A/component B volume ratio in the composition of the invention ranges from 20/1 to 1/1, preferably from 10/1 to 1/1.
La composition adhésive susmentionnée peut avoir une viscosité Brookfield à 23°C allant de 20 000 mPa.s à 150 000 mPa.s, de préférence de 30 000 mPa.s à 100 000 mPa.s, encore plus préférentiellement de 40 000 à 80 000 mPa.s The aforementioned adhesive composition may have a Brookfield viscosity at 23° C. ranging from 20,000 mPa.s to 150,000 mPa.s, preferably from 30,000 mPa.s to 100,000 mPa.s, even more preferably from 40,000 to 80 000 mPa.s
Selon un mode de réalisation préféré, la composition susmentionnée comprend :According to a preferred embodiment, the aforementioned composition comprises:
- un composant A comprenant : - a component A comprising:
- une teneur totale en polyuréthane(s) P tel(s) que décrit(s) ci-dessus supérieure ou égale à 5% en poids; - a total content of polyurethane(s) P as described above greater than or equal to 5% by weight;
- de 0,5 % à 5 % en poids d’agent(s) réducteur(s) ; - from 0.5% to 5% by weight of reducing agent(s);
- une teneur totale en monomère itaconate de formule (I) supérieure ou égale à 40% en poids, de préférence supérieure ou égale à 45% en poids ; - a total content of itaconate monomer of formula (I) greater than or equal to 40% by weight, preferably greater than or equal to 45% by weight;
- une teneur totale en modificateur d’impact ayant une structure de type cœur-écorce allant de 5 à 20% en poids ; par rapport au poids total du composant A ; - a total content of impact modifier having a core-shell type structure ranging from 5 to 20% by weight; relative to the total weight of component A;
- un composant B comprenant : - a component B comprising:
- une teneur totale en agent(s) oxydant(s) supérieure ou égale à 20% en poids; et- a total content of oxidizing agent(s) greater than or equal to 20% by weight; and
- une teneur totale en plastifiant(s) supérieure ou égale à 40% en poids ; par rapport au poids total du composant B. - a total content of plasticizer(s) greater than or equal to 40% by weight; relative to the total weight of component B.
Kit
La présente invention concerne également un kit prêt à l’emploi, comprenant le composant A tel que défini ci-dessus d’une part et le composant B tel que défini ci-dessus d’autre part, conditionnés dans deux compartiments séparés. Il peut par exemple s’agir d’une cartouche bicomposante. set The present invention also relates to a ready-to-use kit, comprising component A as defined above on the one hand and component B as defined above on the other hand, packaged in two separate compartments. It may for example be a two-component cartridge.
En effet, la composition selon l’invention peut se trouver sous une forme bicomposante, par exemple au sein d’un kit prêt à l’emploi, comprenant le composant A d’une part dans un premier compartiment ou fût et le composant B d’autre part dans un second compartiment ou fût, dans des proportions adaptées pour un mélange direct des deux composants, par exemple à l’aide d’une pompe doseuse. Indeed, the composition according to the invention can be in a two-component form, for example within a ready-to-use kit, comprising component A on the one hand in a first compartment or barrel and component B d on the other hand in a second compartment or drum, in proportions suitable for direct mixing of the two components, for example using a metering pump.
Selon un mode de réalisation de l’invention, le kit comprend en outre un ou plusieurs moyens permettant le mélange des composants A et B. De préférence, les moyens de mélange sont choisis parmi des pompes doseuses, des mélangeurs statiques de diamètre adapté aux quantités utilisées. According to one embodiment of the invention, the kit further comprises one or more means allowing the mixing of components A and B. Preferably, the mixing means are chosen from metering pumps, static mixers with a diameter adapted to the quantities used.
Utilisations des compositions Uses of compositions
La présente invention concerne également l’utilisation d’une composition telle que définie ci-dessus, comme adhésif, mastic ou revêtement, de préférence comme adhésif. The present invention also relates to the use of a composition as defined above, as an adhesive, sealant or coating, preferably as an adhesive.
L’invention concerne également l’utilisation de ladite composition pour la réparation et/ou le collage structural ou semi-structural de matériaux dans le domaine du transport, automobile (voiture, bus ou camion), de l’assemblage, de la marine, de l’électronique, des batteries ou de la construction. The invention also relates to the use of said composition for repairing and/or structural or semi-structural bonding of materials in the field of transport, automotive (car, bus or truck), assembly, marine, electronics, batteries or construction.
La présente invention concerne également un procédé d'assemblage de deux substrats par collage, comprenant : The present invention also relates to a method for assembling two substrates by bonding, comprising:
- l’enduction sur au moins un des deux substrats à assembler d’une composition obtenue par mélange des composants A et B tels que définis précédemment ; puis - the coating on at least one of the two substrates to be assembled of a composition obtained by mixing components A and B as defined previously; then
- la mise en contact effective des deux substrats ; - the effective contacting of the two substrates;
- la réticulation de la composition. - the crosslinking of the composition.
L’étape de réticulation peut être mise en oeuvre à une température comprise entre 0°C et 200°C, de préférence entre 10°C et 150°C, de préférence entre 23 et 80°C et en particulier entre 20°C et 25°C. The crosslinking step can be carried out at a temperature between 0°C and 200°C, preferably between 10°C and 150°C, preferably between 23 and 80°C and in particular between 20°C and 25°C.
La réticulation peut également être induite à l’aide des micro-ondes.
Les substrats appropriés sont, par exemple, des substrats inorganiques tels que le béton, les métaux ou les alliages (comme les alliages d’aluminium, l’acier, les métaux non- ferreux et les métaux galvanisés) ; ou bien des substrats organiques comme le bois, des plastiques comme le PVC, le polycarbonate, le PMMA, le polyéthylène, le polypropylène, les polyesters, les résines époxy ; les substrats en métal et les composites revêtus de peinture. Cross-linking can also be induced using microwaves. Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or else organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and composites coated with paint.
Les compositions selon l’invention une fois conduisent avantageusement, après réticulation, à un joint adhésif présentant des propriétés semi-structurales ou structurales. The compositions according to the invention once lead advantageously, after crosslinking, to an adhesive joint having semi-structural or structural properties.
Les compositions selon l’invention présentent avantageusement, après réticulation, de bonnes propriétés adhésives, tout en ayant une odeur faible voire nulle. The compositions according to the invention advantageously exhibit, after crosslinking, good adhesive properties, while having a low or even zero odor.
Les compositions sont également avantageusement faiblement toxiques par rapport aux compositions acryliques usuelles, du fait notamment de l’utilisation de monomère itaconate de formule (I) dont la toxicité est inférieure à celle des acryliques usuels. The compositions are also advantageously low in toxicity compared to the usual acrylic compositions, due in particular to the use of itaconate monomer of formula (I) whose toxicity is lower than that of the usual acrylics.
Tous les modes de réalisation décrits ci-dessus peuvent être combinés les uns avec les autres. En particulier, les différents constituants susmentionnés de la composition, et notamment les modes préférés, de la composition peuvent être combinés les uns avec les autres. All the embodiments described above can be combined with each other. In particular, the various aforementioned constituents of the composition, and in particular the preferred modes, of the composition can be combined with each other.
Dans le cadre de l’invention, par « comprise entre x et y », ou « allant de x à y », on entend un intervalle dans lequel les bornes x et y sont incluses. Par exemple, la gamme «comprise entre 0% et 25% » inclus notamment les valeurs 0% et 25%. In the context of the invention, by “between x and y”, or “ranging from x to y”, is meant an interval in which the limits x and y are included. For example, the range “between 0% and 25%” includes the values 0% and 25% in particular.
L'invention est à présent décrite dans les exemples de réalisation suivants qui sont donnés à titre purement illustratif, et ne sauraient être interprétés pour en limiter la portée. The invention is now described in the following exemplary embodiments which are given for purely illustrative purposes, and cannot be interpreted to limit the scope thereof.
EXEMPLES EXAMPLES
Les ingrédients suivants ont été utilisés : The following ingredients were used:
- diméthylitaconate commercialisé par ALDRICH ; - dimethylitaconate marketed by ALDRICH;
- dibutylitaconate commercialisé par ALDRICH ; - dibutylitaconate marketed by ALDRICH;
- BISOMERE PTE (CAS Number : 103671-44-9) commercialisée par GEO Specialty Chemicals ; - BISOMERE PTE (CAS Number: 103671-44-9) marketed by GEO Specialty Chemicals;
- SR9054 (CAS Number : 1628778-81-3) commercialisé par SARTOMER : promoteur d’adhésion acide acrylique difonctionnel ;
- AEROSIL® R202 (CAS Number : 67762-90-7) : une silice pyrogénée hydrophobe (posttraitée PDMS) de surface spécifique (BET) égale à 100±20 m2/g commercialisée par EVONIK ;- SR9054 (CAS Number: 1628778-81-3) marketed by SARTOMER: difunctional acrylic acid adhesion promoter; - AEROSIL® R202 (CAS Number: 67762-90-7): a hydrophobic fumed silica (PDMS post-treated) with a specific surface area (BET) equal to 100±20 m 2 /g marketed by EVONIK;
- MBS Clearstrength® XT100 commercialisé par ARKEMA : un modificateur d’impact cœur- écorce (ou « core-shell impact modifier « en anglais) sur base MMA-butadiène-styrène ;- MBS Clearstrength® XT100 marketed by ARKEMA: a core-shell impact modifier based on MMA-butadiene-styrene;
- VIKOFLEX® 7170 commercialisée par ARKEMA est une huile de Soja époxydée utilisée comme plastifiant ; - VIKOFLEX® 7170 marketed by ARKEMA is an epoxidized soybean oil used as a plasticizer;
- CRAYVALLAC® SLT commercialisée par ARKEMA est une cire micronisée d’amide utilisée comme agent rhéologique ; - CRAYVALLAC® SLT marketed by ARKEMA is a micronized amide wax used as a rheological agent;
- CN®981 : uréthane-acrylate de fonctionnalité 2 et Mn de 2200 g/mol, commercialisé par ARKEMA ; - CN®981: urethane-acrylate with functionality 2 and Mn of 2200 g/mol, marketed by ARKEMA;
- CN®9210 : uréthane-acrylate de fonctionnalité 6 et Mn de 1500 g/mol, commercialisé par ARKEMA ; - CN®9210: urethane-acrylate with functionality 6 and Mn of 1500 g/mol, marketed by ARKEMA;
- CN®9165 A : uréthane-acrylate de fonctionnalité 6 et Mn de 900 g/mol, commercialisé par ARKEMA ; - CN®9165 A: urethane-acrylate with functionality 6 and Mn of 900 g/mol, marketed by ARKEMA;
- MESAMOLL® : ester d’acide alkylsulphonique et de phénol commercialisé par LANXESS ;- MESAMOLL®: ester of alkylsulphonic acid and phenol marketed by LANXESS;
- acide méthacrylique commercialisé par ALDRICH ; - methacrylic acid marketed by ALDRICH;
- PEROXAN BP 50 : pâte de peroxyde de benzoyle à 50% commercialisé par PERGAN. - PEROXAN BP 50: 50% benzoyl peroxide paste marketed by PERGAN.
Exemple 1 : préparation des compositions n°1 et n°2 Example 1: Preparation of Compositions No. 1 and No. 2
Dans un réacteur maintenu sous agitation constante et sous azote, les différents ingrédients constituant le composant A sont mélangés dans les proportions indiquées dans le tableau suivant à une température de 23°C. In a reactor maintained under constant stirring and under nitrogen, the various ingredients constituting component A are mixed in the proportions indicated in the following table at a temperature of 23°C.
Dans un réacteur maintenu sous agitation constante et sous azote, les différents ingrédients constituant le composant B sont mélangés dans les proportions indiquées dans le tableau suivant à une température de 23°C.
In a reactor kept under constant stirring and under nitrogen, the various ingredients constituting component B are mixed in the proportions indicated in the following table at a temperature of 23°C.
Le composant A et le composant B ci-dessus (pour chaque composition) ont été mélangés, dans un ratio volumique 10 : 1 (A : B).
Le mélange est effectué à une température de 23°C environ, selon le ratio volumique donné avec un mélangeur statique. Component A and component B above (for each composition) were mixed, in a 10:1 volume ratio (A:B). The mixing is carried out at a temperature of approximately 23° C., according to the volume ratio given with a static mixer.
Exemple 2 : résultats Example 2: results
Mesure de la résistance à la rupture par essai de traction : Measurement of breaking strength by tensile test:
La mesure de la résistance (contrainte à la rupture) par essai de traction a été effectuée selon le protocole décrit ci-après. The measurement of the resistance (breaking stress) by tensile test was carried out according to the protocol described below.
Le principe de la mesure consiste à étirer dans une machine de traction, dont la mâchoire mobile se déplace à une vitesse constante égale à 200 mm/minute, une éprouvette standard constituée de la composition réticulée et à enregistrer, au moment où se produit la rupture de l'éprouvette, la contrainte de traction appliquée (en MPa) ainsi que l'allongement de l'éprouvette (en %). L'éprouvette standard est en forme d'haltère, comme illustré dans la norme internationale ISO 37 de 2011. La partie étroite de l'haltère utilisée a pour longueur 20 mm, pour largeur 4 mm et pour épaisseur 500 n. The principle of the measurement consists in stretching in a tensile machine, the mobile jaw of which moves at a constant speed equal to 200 mm/minute, a standard test piece made up of the crosslinked composition and in recording, at the moment when the rupture occurs. of the specimen, the tensile stress applied (in MPa) as well as the elongation of the specimen (in %). The standard specimen is in the shape of a dumbbell, as illustrated in the international standard ISO 37 of 2011. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 n.
Tests de collage Bonding tests
Les collages sont réalisés sur des stérigmes en aluminium (anodisé ou 6060) provenant de la société RocholL Sur un stérigme, une zone de 25*12.5mm a été délimitée à l’aide de cales en téflon de 250 pm d’épaisseur une zone de 25*12.5mm. Cette zone a été remplie avec la composition à tester, puis un second stérigme du même matériau a été contrecollé. L’ensemble a été maintenu par une pince et placé en salle climatisée à 23°C ou à 100°C et 50% HR (humidité relative) durant une semaine avant traction sur dynamomètre. La traction sur dynamomètre a pour but d’évaluer la force maximale (en MPa) à exercer sur l’assemblage pour désolidariser celui-ci. Le recours à une machine de traction permet de soumettre un joint à recouvrement simple placé entre deux supports rigides à une contrainte de cisaillement jusqu’à rupture en exerçant une traction sur les supports parallèlement à la surface de l’assemblage et à l’axe principal de l’éprouvette. Le résultat à consigner est la force ou la contrainte à la rupture. La contrainte de cisaillement est appliquée via la mâchoire mobile de la machine de traction avec un déplacement à la vitesse de 5 mm/min. Cette méthode de traction est réalisée telle que définie par la norme EN 1465 de 2009. The collages are made on aluminum sterigmas (anodized or 6060) from the RocholL company. 25*12.5mm. This area was filled with the composition to be tested, then a second sterigma of the same material was laminated. The assembly was held by clamps and placed in an air-conditioned room at 23°C or 100°C and 50% RH (relative humidity) for one week before traction on a dynamometer. The purpose of traction on a dynamometer is to assess the maximum force (in MPa) to be exerted on the assembly to separate it. The use of a traction machine makes it possible to subject a simple lap joint placed between two rigid supports to a shearing stress until failure by exerting a traction on the supports parallel to the surface of the assembly and to the main axis. of the test piece. The result to be reported is the force or stress at break. The shear stress is applied via the movable jaw of the tensile machine with a displacement at the speed of 5 mm/min. This traction method is carried out as defined by the EN 1465 standard of 2009.
Les propriétés obtenues des compositions préparées sont résumées dans le tableau suivant :
The properties obtained from the compositions prepared are summarized in the following table:
Les compositions n°1 et n°2 selon l’invention conduisent avantageusement à un joint adhésif présentant après réticulation, une contrainte à la rupture élevée (12 et 25 MPa respectivement). Compositions No. 1 and No. 2 according to the invention advantageously lead to an adhesive joint having, after crosslinking, a high tensile strength (12 and 25 MPa respectively).
En outre, les compositions n°1 et n°2 conduisent avantageusement à des forces à la ruptures de 9 et 11 MPa respectivement pour les collages sur aluminium anodisé, démontrant une bonne adhésion.
In addition, compositions No. 1 and No. 2 advantageously lead to breaking strengths of 9 and 11 MPa respectively for bonding on anodized aluminum, demonstrating good adhesion.
Claims
REVENDICATIONS Composition adhésive bicomposante comprenant : CLAIMS Two-component adhesive composition comprising:
- un composant A comprenant : - a component A comprising:
- au moins un polyuréthane P comprenant au moins deux fonctions (méth)acrylate terminales ; - at least one polyurethane P comprising at least two terminal (meth)acrylate functions;
- au moins un agent réducteur ; et - at least one reducing agent; and
- au moins un monomère itaconate de formule (I) suivante :
dans laquelle chacun de R1 et R2 représente, indépendamment l’un de l’autre, des radicaux organiques ; - at least one itaconate monomer of the following formula (I): in which each of R 1 and R 2 represents, independently of one another, organic radicals;
- au moins un modificateur d’impact ayant structure de type cœur-écorce ;- at least one impact modifier having a core-shell type structure;
- un composant B comprenant : - a component B comprising:
- au moins un agent oxydant ; et - at least one oxidizing agent; and
- éventuellement au moins un monomère (méth)acrylate M1. Composition adhésive selon la revendication 1 , caractérisée en ce que la viscosité Brookfield à 23°C va de 20 000 mPa.s à 150 000 mPa.s, de préférence de 30 000 mPa.s à 100 000 mPa.s, encore plus préférentiellement de 40 000 à 80 000 mPa.s Composition adhésive selon l’une quelconque des revendications 1 ou 2, caractérisée en ce que dans la formule (I), chacun de R1 et R2 représente, indépendamment l’un de l’autre, un alkyle, un alcényle, un cycloalkyle, un hétérocycloalkyle, un aryle, un hétéroaryle, un arylalkyle, un hétéroarylalkyle, un alkylhétéroaryle, ou un alkylhétérocycloalkyle, lesdits groupes pouvant éventuellement être substitués.
Composition adhésive selon l’une quelconque des revendications 1 à 3, caractérisée en ce que chacun de R1 et R2 représente, indépendamment l’un de l’autre, un groupe C1-C15 alkyle, C2-C15 alcényle, halo-(C1-C15)alkyle, C3-C12 cycloalkyle, halo(C3- C12)cycloalkyle, un hétérocycle, un aryle, un hétéroaryle, ou un alcoxy-(C1-C15)alkyle, chacun d’entre eux pouvant être éventuellement substitué par l’un au moins des radicaux suivants : C1-C15 alkyle, halo(C1-C15 alkyle), C3-12 cycloalkyle, halo(C3- C12 cycloalkyle), hétérocycle, aryle, hétéroaryle, C1-C15 alcoxy, C1-C15 alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy ou ester. Composition adhésive selon l’une quelconque des revendications 1 à 4, caractérisée en ce que l’itaconate de formule (I) est choisi parmi l’itaconate de diméthyle, l’itaconate de diéthyle, l’itaconate de di-n-butyle, l’itaconate de di-isobutyle, l’itaconate de dicyclohexyle, l’itaconate de bis(hexafluoroisopropyle), l’itaconate de diphényle, l’itaconate de dibenzyle, l’itaconate d’éthyle isobornyle, l’itaconate d’éthyl cyclohexyle, et leurs mélanges. Composition adhésive selon l’une quelconque des revendications 1 à 5, caractérisée en ce que la teneur totale en monomère(s) itaconate(s) de formule (I) dans le composant A est supérieure à 40% en poids, de préférence supérieure ou égale à 45% en poids par rapport au poids total du composant A. Composition adhésive selon l’une quelconque des revendications 1 à 6, caractérisée en ce que le polyuréthane P a une masse moléculaire moyenne en nombre (Mn) supérieure ou égale à 700 g/mol, de préférence supérieure ou égale à 900 g/mol. Composition adhésive selon l’une quelconque des revendications 1 à 7, caractérisée en ce que le polyuréthane P comprend au moins trois fonctions (méth)acrylate, de préférence six fonctions (méth)acrylate. Composition selon l’une quelconque des revendications 1 à 8, caractérisée en ce que la teneur totale en polyuréthane(s) P dans le composant A est inférieure ou égale à 50% en poids, de préférence inférieure ou égale à 40% en poids par rapport au poids total du composant A. Composition selon l’une quelconque des revendications 1 à 9, caractérisée en ce que le composant A comprend un polyuréthane P1 comprenant deux fonctions terminales
(méth)acrylates et un polyuréthane P2 (différent de P1 ) comprenant plus de deux fonctions terminales (méth)acrylates. - optionally at least one (meth)acrylate monomer M1. Adhesive composition according to Claim 1, characterized in that the Brookfield viscosity at 23°C ranges from 20,000 mPa.s to 150,000 mPa.s, preferably from 30,000 mPa.s to 100,000 mPa.s, even more preferably from 40,000 to 80,000 mPa.s Adhesive composition according to any one of Claims 1 or 2, characterized in that in formula (I), each of R 1 and R 2 represents, independently of one another , an alkyl, an alkenyl, a cycloalkyl, a heterocycloalkyl, an aryl, a heteroaryl, an arylalkyl, a heteroarylalkyl, an alkylheteroaryl, or an alkylheterocycloalkyl, said groups possibly being substituted. Adhesive composition according to any one of Claims 1 to 3, characterized in that each of R 1 and R 2 represents, independently of one another, a C1-C15 alkyl, C2-C15 alkenyl, halo-( C1-C15)alkyl, C3-C12 cycloalkyl, halo(C3-C12)cycloalkyl, a heterocycle, an aryl, a heteroaryl, or an alkoxy-(C1-C15)alkyl, each of which may optionally be substituted by at least one of the following radicals: C1-C15 alkyl, halo (C1-C15 alkyl), C3-12 cycloalkyl, halo (C3-C12 cycloalkyl), heterocycle, aryl, heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy or ester. Adhesive composition according to any one of Claims 1 to 4, characterized in that the itaconate of formula (I) is chosen from dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, di-isobutyl itaconate, dicyclohexyl itaconate, bis(hexafluoroisopropyl) itaconate, diphenyl itaconate, dibenzyl itaconate, ethyl isobornyl itaconate, ethyl cyclohexyl itaconate , and mixtures thereof. Adhesive composition according to any one of Claims 1 to 5, characterized in that the total content of itaconate monomer(s) of formula (I) in component A is greater than 40% by weight, preferably greater than or equal to 45% by weight relative to the total weight of component A. Adhesive composition according to any one of Claims 1 to 6, characterized in that the polyurethane P has a number-average molecular mass (Mn) greater than or equal to 700 g/mol, preferably greater than or equal to 900 g/mol. Adhesive composition according to any one of Claims 1 to 7, characterized in that the polyurethane P comprises at least three (meth)acrylate functions, preferably six (meth)acrylate functions. Composition according to any one of Claims 1 to 8, characterized in that the total content of polyurethane(s) P in component A is less than or equal to 50% by weight, preferably less than or equal to 40% by weight per relative to the total weight of component A. Composition according to any one of Claims 1 to 9, characterized in that component A comprises a polyurethane P1 comprising two terminal functions (meth)acrylates and a polyurethane P2 (different from P1) comprising more than two terminal (meth)acrylate functions.
11 . Composition selon l’une quelconque des revendications 1 à 10, caractérisée en ce que le cœur du modificateur d’impact ayant une structure de type cœur-écorce comprend un polymère L1 choisi parmi les homopolymères d’isoprène, les homopolymères de butadiène, les copolymères d’isoprène-butadiène, les copolymères d’isoprène avec un monomère vinylique, les copolymères de butadiène avec un monomère vinylique. 11 . Composition according to any one of Claims 1 to 10, characterized in that the core of the impact modifier having a core-shell type structure comprises a polymer L1 chosen from isoprene homopolymers, butadiene homopolymers, copolymers of isoprene-butadiene, copolymers of isoprene with a vinyl monomer, copolymers of butadiene with a vinyl monomer.
12. Composition selon l’une quelconque des revendications 1 à 11 , caractérisée en ce que l’écorce du modificateur d’impact ayant une structure cœur-écorce comprend un polymère L2 obtenu à partir de monomères (méth)acryliques tels que par exemple ceux choisis parmi les (méth)acrylates d’alkyle en C1-C12. 12. Composition according to any one of claims 1 to 11, characterized in that the shell of the impact modifier having a core-shell structure comprises an L2 polymer obtained from (meth)acrylic monomers such as for example those chosen from C1-C12 alkyl (meth)acrylates.
13. Composition selon l’une quelconque des revendications 1 à 12, caractérisée en ce le ratio volumique composant A/composant B dans la composition de l’invention va de 20/1 à 1/1 , préférentiellement de 10/1 à 1/1. 13. Composition according to any one of claims 1 to 12, characterized in that the component A/component B volume ratio in the composition of the invention ranges from 20/1 to 1/1, preferably from 10/1 to 1/ 1.
14. Kit prêt à l’emploi, comprenant le composant A tel que défini selon l’une quelconque des revendications 1 à 13 d’une part et le composant B tel que défini selon l’une quelconque des revendications 1 à 13 d’autre part, conditionnés dans deux compartiments séparés. 14. Ready-to-use kit, comprising component A as defined according to any one of claims 1 to 13 on the one hand and component B as defined according to any one of claims 1 to 13 on the other hand, packaged in two separate compartments.
15. Utilisation de la composition adhésive selon l’une quelconque des revendications 1 à 13, pour la réparation et/ou le collage structural ou semi-structural de matériaux dans le domaine du transport, automobile (voiture, bus ou camion), de la marine, de l’assemblage, de l’électronique, des batteries ou de la construction
15. Use of the adhesive composition according to any one of claims 1 to 13, for repairing and/or structural or semi-structural bonding of materials in the field of transport, automobile (car, bus or truck), marine, assembly, electronics, batteries or construction
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FR2012462A FR3116824B1 (en) | 2020-12-01 | 2020-12-01 | Two-component adhesive composition based on itaconate monomer |
PCT/FR2021/052127 WO2022117940A1 (en) | 2020-12-01 | 2021-11-29 | Adhesive two-component composition based on itaconate monomer |
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US3547848A (en) | 1967-11-03 | 1970-12-15 | Armour Ind Chem Co | Thixotropic coating compositions comprising a varnish and a di-substituted urea |
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WO2014103878A1 (en) * | 2012-12-27 | 2014-07-03 | 昭和電工株式会社 | Resin composition, covering method using same, and covered structure covered by said method |
JP6404940B2 (en) * | 2014-03-11 | 2018-10-17 | ローム アンド ハース カンパニーRohm And Haas Company | Water-based adhesive composition |
US20170191089A1 (en) | 2014-05-28 | 2017-07-06 | Dsm Ip Assets B.V. | Itaconic acid and itaconate methylester and dimethylester production |
FR3052169B1 (en) | 2016-06-07 | 2020-01-31 | Arkema France | POLYMER COMPOSITION, PROCESS FOR THE PREPARATION THEREOF, USE THEREOF AND COMPOSITION COMPRISING SAME |
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