EP2688951A1 - Use of epoxidized arylalkylphenols as reactive resin diluents - Google Patents
Use of epoxidized arylalkylphenols as reactive resin diluentsInfo
- Publication number
- EP2688951A1 EP2688951A1 EP12708815.1A EP12708815A EP2688951A1 EP 2688951 A1 EP2688951 A1 EP 2688951A1 EP 12708815 A EP12708815 A EP 12708815A EP 2688951 A1 EP2688951 A1 EP 2688951A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compounds
- formula
- mixture
- compound
- use 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.)
- Withdrawn
Links
- 239000003085 diluting agent Substances 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 title description 17
- 239000011347 resin Substances 0.000 title description 17
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 150000002989 phenols Chemical class 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical group [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims abstract description 9
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000005504 styryl group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000004848 polyfunctional curative Substances 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 13
- -1 epoxide compounds Chemical class 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 229930003836 cresol Natural products 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical class CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 3
- 150000004780 naphthols Chemical class 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 claims description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 235000019492 Cashew oil Nutrition 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 229940059459 cashew oil Drugs 0.000 claims 1
- 239000010467 cashew oil Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 244000226021 Anacardium occidentale Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000020226 cashew nut Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010466 nut oil Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- UBRFDRBFBYCBFS-UHFFFAOYSA-N 1-ethenyl-2,4-diethylbenzene Chemical compound CCC1=CC=C(C=C)C(CC)=C1 UBRFDRBFBYCBFS-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 1
- UDYMXCYYKTVPRJ-UHFFFAOYSA-N 2-ethenyl-1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1C=C UDYMXCYYKTVPRJ-UHFFFAOYSA-N 0.000 description 1
- OWRKXOZFTROHSH-UHFFFAOYSA-N 2-ethenyl-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1C=C OWRKXOZFTROHSH-UHFFFAOYSA-N 0.000 description 1
- FWHPFGQQBJRJLZ-UHFFFAOYSA-N 2-ethenyl-1,4-diethylbenzene Chemical compound CCC1=CC=C(CC)C(C=C)=C1 FWHPFGQQBJRJLZ-UHFFFAOYSA-N 0.000 description 1
- DBWWINQJTZYDFK-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(C=C)=C1 DBWWINQJTZYDFK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- AAFBMECIUXRJMV-UHFFFAOYSA-N 4-ethenyl-1,2-diethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1CC AAFBMECIUXRJMV-UHFFFAOYSA-N 0.000 description 1
- PMZXJPLGCUVUDN-UHFFFAOYSA-N 4-ethenyl-1,2-dimethylbenzene Chemical compound CC1=CC=C(C=C)C=C1C PMZXJPLGCUVUDN-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000012619 stoichiometric conversion Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000723 toxicological property Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/223—Di-epoxy compounds together with monoepoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Definitions
- the invention relates to the use of glycidylated mono (alkylaryl) -henols as reactive diluents for epoxy resin compositions, polymerizable compositions containing them and their use in epoxy resins.
- Glycidylated (epoxidized) compounds are used in various compositions for a wide variety of applications. Depending on their compositions, they are used for example for composite materials, electrical laminates, adhesives, paints, electro casting resins or in the construction sector.
- a composition intended for the abovementioned uses usually contains one or more epoxy resin components (thus based on bisphenol A and F, cycloaliphatic resins, brominated resins, phenol novolak resins), hardeners (such as base amines, Adduct hardener, Mannich base hardener, polyaminoamide and polyaminoimidazole hardeners), accelerators (such as benzyldimethylamine and 2, 4, 6-tri (N, -dimethylaminomethyl) phenol) and fillers.
- epoxy resin components such as base amines, Adduct hardener, Mannich base hardener, polyaminoamide and polyaminoimidazole hardeners
- accelerators such as benzyldimethylamine and 2, 4, 6-tri (N, -dimethylaminomethyl) phenol
- Antr 1 - ⁇ reactive fillers lead to difficulties in vera: trapped in the preparation of the composition on site until application, for example, as a coating.
- benzyl alcohol or high-boiling solvents such as styrenated phenol (mono (alkylaryl) phenol) to reduce the mixing viscosity of the composition.
- Styrenated phenol can be used to improve the flow, to accelerate the curing reaction and to obtain better surface properties, for example in coating systems.
- a reactive diluent serves to adjust the viscosity of the mixture and is chemically bound in the cured composition during the curing process so that, as a rule, the emission of solvents can be reduced.
- epoxy compounds based on phenolic compounds as reactive diluents. Such include phenol, resol, bisphenol-A or p-tert. Butylphenol. These show a significantly higher reactivity than epoxy compounds based on aliphatic alcohols. They also impart high chemical resistance to the cured product but are undesirable because of their toxicological properties.
- CH 324 686 describes the reaction of phenol with styrene and the reaction of the resulting product with a glycidyl ether in an alkaline medium to form an infusible product.
- the object of the invention is to provide reactive diluents with high reactivity for epoxy resin compositions which do not have the disadvantages indicated above.
- R 1 and R 2 independently of one another, denote -H, C 1-3 -alkyl, C 1-3 -alkyl and glycidyl, but R 1 and R 2 are not simultaneously glycidyl,
- R 3 is an optionally substituted styryl of the formula
- R 4 is a hydrogen radical or methyl
- R 5 and R 6 is a hydrogen radical, C 1 -.3-Alk.yl, Ci- 2 -Oxalkyl as reactive diluents in epoxy resin compositions.
- Ci-3-alkyl include methyl, ethyl, propyl and isopropyl.
- C 1 -3 - oxalkyl include methoxy, ethoxy, propoxy and isopropoxy.
- the invention further provides the use of a mixture of epoxidized mono (alkylaryl) phenols, i. styrenated phenols having a glycidyl radical as a reactive diluent for epoxy resin compositions.
- This mixture contains several compounds of the following chemical formulas Ia, Ib and Ic:
- R 4 , R s and R 6 have the meanings given above.
- the invention further provides a composition comprising one of the aforementioned compounds or a mixture of these compounds containing at least one crosslinkable polymer.
- composition of one or more inventive epoxy compounds as Reakti diluent despite a high steric hindrance compared to conventional aromatic diluents such as phenol, cresol or p-tert.
- aromatic diluents such as phenol, cresol or p-tert.
- Butyl phenol a comparable reactivity.
- the reactivity of the reactive diluents according to the invention is higher than the aliphatic reactive diluents based on mono- or difunctional alcohols.
- the mixture according to the invention which is used as reactive diluent preferably contains essentially the following compounds:
- R2 0-CH 2 - CH 2 CH- and c) Ri: O- CH 2 - CH 2 CH-
- These compounds may be present in at least 60% by weight, preferably at least 80% by weight, more preferably at least 90% by weight or at least 95% by weight in the mixture to be used according to the invention.
- a mixture based on the sum of the masses of the compounds of the formula Ia, Ib and Ic, 30 to 60 wt .-% of Ia, 10 to 25 wt .-% of Ib and 20 to 40 wt .-% of Ic ,
- the mixture used according to the invention can be obtained by epoxidation of styrenated phenol.
- the preparation of styrenated phenol by reacting a phenolic component with an olefin is known and described for example in EP 0 656 384 A2. These are essentially alkylation reactions in which the vinyl group of the styrenes is added ortho or para to the hydroxyl group of the phenol. In this reaction, Friedel-Crafts Catalysts, for example acids and Lewis acids used.
- the addition of the vinyl compound to phenols can be carried out at a molar ratio of the phenolic hydroxyl group in the phenol to the aromatic compound of 1: 1 to 1: 2.
- Suitable aromatic vinyl compounds are, in particular, alpha-methylstyrene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, commercial vinyltoluene (mixture of isomers), 3,4-dimethylstyrene, 2-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene , o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 3,4-diethylstyrene, 2,4-diethylstyrene, 2,5-diethylstyrene, 2,6-diethylstyrene.
- the cationically induced conversion to styrenated phenol results in a statistical distribution of 2-, 4- and 2,4-substituted phenol.
- the monostyrrated compounds can first be separated from the distyrenated phenol by vacuum distillation. The mixture of monostyrenated compounds can then be separated by crystallization into the 2-styrenated and 4-styrenated phenol.
- the styrenated phenol or a mixture of styrenated phenols is reacted with an oxirane compound to obtain the epoxidized compounds of this invention.
- the phenolic OH group reacts with the oxirane compound.
- the oxirane compound used is preferably epichlorohydrin.
- the reaction is generally carried out in the presence of alkali metal hydroxide, for example sodium hydroxide, at elevated temperature according to the theoretical equation with elimination of common salt and water to give the glycidyl compound according to the invention in accordance with the reaction scheme shown below:
- the mixture used according to the invention can be used as a reactive compound, even if a hydrophobicizing effect is to be achieved. This can be done, for example, in coating compositions by using the mixture according to the invention as a resin constituent or as a reactive diluent with at least one further resin constituent.
- the mixture can be used as a modifier in the polyester synthesis, for example for reducing acid groups or alcohol groups, while at the same time increasing the hydrophobicity.
- the mixture according to the invention can be used as a paper treatment agent without showing the known disadvantages of migration as in non-reactive phenolic components.
- this blend can be used to make reinforced or unreinforced plastics (e.g., thermosets, thermoplastics) and elastomers.
- reinforced or unreinforced plastics e.g., thermosets, thermoplastics
- elastomers e.g., thermosets, thermoplastics
- compositions which, as further component, comprise at least one crosslinkable plastic (thermopolast, Elastomer), in particular duroplastic plastic (such as polyester resin, epoxy resin, phenolic resin or melamine resin) have.
- crosslinkable plastic thermopolast, Elastomer
- duroplastic plastic such as polyester resin, epoxy resin, phenolic resin or melamine resin
- the mixture according to the invention with at least one crosslinkable plastic in a ratio of 5:95 to 50:50 is present.
- the preparation of the composition takes place in üb Licher way.
- the mixture to be used according to the invention as a further component at least d) an epoxy resin selected from glycidyl ether based on bisphenol A, bisphenol F or novolaks, mono-, di- or polyfunctional alcohols, mono- or polyfunctional phenol len such as phenol, cresol, resorcinols, naphthols, p-tert-butylphenols, nonylphenols, cashew nut oil compounds, C 12 C14 alcohols, butanediols and / or hexanediols e) a hardener selected from aminic or acidic compounds and such Hardeners which can initiate a homopolymerization of epoxy compounds and f) optionally further additives, such as processing aids ⁇ and inorganic fillers, preferably 5 to 20 parts by weight, based on all components of the composition.
- an epoxy resin selected from glycidyl ether based on bisphenol A, bisphenol F or novolaks, mono
- glycidyl ethers based on bisphenol A, bisphenol F or novolaks, mono-, di- or polyfunctional alcohols, mono- or polyfunctional phenols, such as phenol, cresol resorcinols, naphthols, p-tert.
- Butylphenols, nonylphenols, cashew nut oil compounds, C 2 -C 4 -alcohols, butanediol and / or Hexanediol as further component has the advantage that the composition is crystallization resistant and storable.
- the viscosity of this composition according to the invention can be adjusted in an appropriate range for the application.
- Usual hardeners for Bpoxide can be used.
- Typical representatives of the amine hardeners are compounds with one, two or more free amine hydrogens. These may have cyclic, aliphatic or aromatic linkages or polyether groups.
- Typical representatives of this hardener class are amines such as isophoronediamine, xylylenediamine, trimethylene-hexamethylenediamine, polyetheramines.
- suitable hardeners according to the invention are so-called acidic hardeners based on organic acids such as phthalic anhydride, hexahydrophthalic anhydride, methylhydrophthalic anhydride and other compounds of this class.
- latent systems which are applied via radiation curing and associated ionic hardening or by thermal curing ("latent 1-component system"). Preferred in the sense of the invention are amine hardeners for the range of curing
- adduct hardeners based on bisphenol A diglycidyl ether and isophoronediamine, which are further modified by the use of benzyl alcohol, accelerators and other additives to improve the processing properties or end uses.
- the mixing ratio with the epoxide-reactive components results from the stoichiometric conversion.
- the exact mixing ratio depends on the application and may include both a substoichiometric and a superstoichiometric implementation.
- the epoxy resin composition of the present invention is prepared by mixing the individual components according to known methods. By mixing the components at a higher temperature, for example at 60 ° to 80 ° C, the mixing and filling process can be accelerated.
- higher or lower proportions can also be used.
- the mixture according to the invention can be used for the production of thermosetting products.
- coatings or even shaped bodies are conceivable.
- the mixture according to the invention is used for coatings, in particular for self-leveling coatings.
- coatings for industrial floors, paints, adhesives or electrical laminates would be conceivable.
- the use according to the invention thus takes place preferably for the treatment of paper, for the production of cured polymer products, for the production of coatings, for the production of reinforced and unreinforced plastics, elastomers and moldings.
- the stirrer is switched off and after a Absitzezeit of 30 minutes, the lower aqueous phase is drained.
- the remaining organic phase in the reaction vessel is diluted with a further 200 g of epichlorohydrin and washed with 300 g of water, with a phase inversion takes place.
- the organic phase is then distilled off under reduced pressure up to a temperature of 120 ° C and freed from traces of volatiles by steam distillation in vacuo.
- the distillate contains epichlorohydrin, isopropanol, water and higher boiling impurities at a concentration of less than 1% and can be used for subsequent production.
- the distillation residue is taken up in 248 g of toluene, heated to 75 ° C and treated with 50% sodium hydroxide solution (MV 1: 2.5 - hydrolyzable chlorine: sodium hydroxide solution) within 30 minutes. Beforehand, the same amount of water is added. The reaction time with stirring is then 1 hour. 330 g of toluene are added for dilution. The stirrer is switched off and after a settling time of 10 minutes, the aqueous phase is separated off. The organic solution is washed several times with water until neutral.
- the toluene and remaining traces of volatiles are distilled off in vacuo to 125 ° C.
- the epoxide compound obtained as the distillation residue is purified by a pressure filter of organic and inorganic solid impurities.
- the yield, based on the precursor, is 95%.
- the glycidated "styrenated phenol" (B) produced in Example 1 is used for the preparation of epoxy resin mixtures.
- the bisphenol A diglycidyl ether is introduced into the mixing unit and the styrenated product (A) or the product (B) according to the invention is added with stirring.
- the temperature during the stirring is kept between 65 ° C and 70 ° C.
- This composition is optionally added after storage of the hardener in the indicated concentration (Table 1).
- a floor coating primary or self-leveling floor coating
- the properties of compositions containing the product (A) (styrenated phenol) are compared with compositions containing the product (B) of the invention.
- the coating composition is applied with a doctor blade to a glass plate in a layer thickness of 200 ⁇ m. After one hour, the glass plate is weighed. The glass plate is then stored for 96 hours at room temperature and then for two hours at 100 ° C in a drying oven. Then the weight is determined and the difference the two weight measurements determined the relative weight loss.
- Ci2-ci4 glycidyl ether 10
- Adduct hardener based on bisphenol 54 53 A diglycidyl ether and isophoronediamine
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Abstract
Description
VERWENDUNG EPOXIDIERTER ARYLALKYLPHENOLE USE OF EPOXYED ARYL ALKYLPHENOLS
ALS REAKTIVHAR VERDÜNNER AS REACTIVE THINNER
GEBIET DER ERFINDUNG FIELD OF THE INVENTION
Die Erfindung betrifft die Verwendung glycidylierter Mo- no (alkylaryl) henole als Reaktivverdünner für Epoxidharz- Zusammensetzungen, diese enthaltende polymerisierbare Zusammensetzungen und deren Verwendung in Epoxidharzen. The invention relates to the use of glycidylated mono (alkylaryl) -henols as reactive diluents for epoxy resin compositions, polymerizable compositions containing them and their use in epoxy resins.
HINTERGRUND DER ERFINDUNG BACKGROUND OF THE INVENTION
Glycidylierte (epoxidierte) Verbindungen werden in unterschiedlichen Zusammensetzungen für unterschiedlichste Anwendungen eingesetzt. In Abhängigkeit ihrer Zusammensetzungen kommen sie beispielsweise für Verbundwerkstoffe, Elektrolaminate, Klebstoffe, Lacke, Elektrogießharze oder auch im Baubereich zum Einsatz. Glycidylated (epoxidized) compounds are used in various compositions for a wide variety of applications. Depending on their compositions, they are used for example for composite materials, electrical laminates, adhesives, paints, electro casting resins or in the construction sector.
Damit die gewünschten Verarbeitungseigenschaften erzielt werden können, müssen die einzelnen Bestandteile der Zusammensetzungen aufeinander abgestimmt sein. So enthält eine Zusammensetzung, die für die oben genannten Verwendungen bestimmt ist, in der Regel eine oder mehrere Epoxidharzkomponenten (so auf Basis von Bisphenol- A und -F, cycloaliphatische Harze, bromierte Harze, Phenol-Novolak Harze) , Härter (wie Basisamine, Addukthärter , Mannichbasenhärter, Polyaminoamid- und Polyaminoimidazolhärter ) , Beschleuniger (wie Benzyldimethylamin und 2 , 4 , 6-Tri (N, -dimethylaminomethyl) phenol) und Füllstoffe. In order for the desired processing properties to be achieved, the individual components of the compositions must be coordinated. Thus, a composition intended for the abovementioned uses usually contains one or more epoxy resin components (thus based on bisphenol A and F, cycloaliphatic resins, brominated resins, phenol novolak resins), hardeners (such as base amines, Adduct hardener, Mannich base hardener, polyaminoamide and polyaminoimidazole hardeners), accelerators (such as benzyldimethylamine and 2, 4, 6-tri (N, -dimethylaminomethyl) phenol) and fillers.
Zur Verbesserung von mechanischen Eigenschaften und aus Kosten¬ gründen ist es häufig erwünscht, den Anteil an anorganischen Füll- Stoffen zu erhöhen. Allerdings führt ein zu hoher Antr 1 -~ reaktiven Füllstoffen zu Schwierigkeiten bei der Vera: gefangen bei der Herstellung der Zusammensetzung vor Ort bis zur Anwendung beispielsweise als Beschichtung . To improve the mechanical properties and cost ¬ reasons it is often desirable to increase the proportion of inorganic filler materials. However, too high Antr 1 - ~ reactive fillers lead to difficulties in vera: trapped in the preparation of the composition on site until application, for example, as a coating.
Es ist bekannt, zur Verringerung der Mischviskosität der Zusammen- setzung Benzylakohol oder hochsiedende Lösungsmittel wie styroli- siertes Phenol (Mono (alkylaryl) phenol) zuzugeben. Styrolisiertes Phenol kann zur Verbesserung des Verlaufs, zur Beschleunigung der Härtungsreaktion und zum Erhalt besserer Oberflächeneigenschaften, beispielsweise in Beschichtungssystemen, eingesetzt werden. It is known to add benzyl alcohol or high-boiling solvents such as styrenated phenol (mono (alkylaryl) phenol) to reduce the mixing viscosity of the composition. Styrenated phenol can be used to improve the flow, to accelerate the curing reaction and to obtain better surface properties, for example in coating systems.
Nachteilig am Einsatz styrolisierter Phenole sind erhöhte VOC-A disadvantage of the use of styrenated phenols is increased VOC
Werte und/oder verringerte mechanische Eigenschaften des ausgehärteten Epoxidharzes. Values and / or reduced mechanical properties of the cured epoxy resin.
Ferner ist bekannt, mono- oder multifunktionelle Reaktivverdünner als viskositätsverringernden Bestandteil zuzugeben. Ein Reaktivverdünner dient der Viskositätseinstellung der Mischung und wird während des Härtungsprozesses chemisch in der gehärteten Zusammensetzung gebunden, so dass in der Regel die Emission von Lösungsmitteln verringert werden kann. It is also known to add mono- or multifunctional reactive diluents as viscosity-reducing component. A reactive diluent serves to adjust the viscosity of the mixture and is chemically bound in the cured composition during the curing process so that, as a rule, the emission of solvents can be reduced.
Für die Herstellung von Epoxidharz sind verschiedene Reaktivverdünner bekannt. Diese umfassen niedrigviskose mono-, di- oder polyfunktionelle Epoxide oder Epoxidharze auf der Basis von monofunktionellen Fettalkoholen, Di- oder Polyalkoholen . Nachteilig an der Verwendung von monofunktionellen Reaktivverdünnern auf Basis aliphatischer Verbindungen wie C12-C14-Fettalkoholen ist eine deutliche Verzögerung der Härtungsreaktion (geringere Reaktivität) im Vergleich zum nicht reaktivverdünnten System. Außerdem besitzen aliphatische Reaktivverdünner einen im Vergleich zu den Basishar- zen erhöhten Dampfdruck, der während der Verarbeitung zu Einschränkungen führen kann. For the production of epoxy resin, various reactive diluents are known. These include low-viscosity mono-, di- or polyfunctional epoxies or epoxy resins based on monofunctional fatty alcohols, di- or polyalcohols. A disadvantage of the use of monofunctional reactive diluents based on aliphatic compounds such as C 12 -C 14 fatty alcohols is a significant delay of the curing reaction (lower reactivity) compared to the non-reactive diluted system. In addition, aliphatic reactive diluents have a higher vapor pressure compared to the base resins, which can lead to limitations during processing.
Es ist auch bekannt, Epoxidverbindungen auf der Basis von phenolischen Verbindungen als Reaktivverdünner einzusetzen. Solche umfas- sen Phenol, resol, Bisphenol-A oder p-tert . -Butylphenol . Diese zeigen eine deutlich höhere Reaktivität als Epoxidverbindungen auf Basis aliphatischer Alkohole. Sie verleihen dem gehärteten Produkt auch eine hohe chemische Beständigkeit, sind aber aufgrund ihrer toxikologischen Eigenschaften nicht erwünscht. It is also known to use epoxy compounds based on phenolic compounds as reactive diluents. Such include phenol, resol, bisphenol-A or p-tert. Butylphenol. These show a significantly higher reactivity than epoxy compounds based on aliphatic alcohols. They also impart high chemical resistance to the cured product but are undesirable because of their toxicological properties.
Die CH 324 686 beschreibt die Umsetzung von Phenol mit Styrol und die Reaktion des erhaltenen Produkts mit einem Glycidylether in alkalischem Medium zu einem unschmelzbaren Produkt. CH 324 686 describes the reaction of phenol with styrene and the reaction of the resulting product with a glycidyl ether in an alkaline medium to form an infusible product.
ZUSAMMENFASSUNG DER ERFINDUNG SUMMARY OF THE INVENTION
Aufgabe der Erfindung ist es, Reaktivverdünner mit hoher Reaktivität für Epoxidharz-Zusammensetzungen bereitzustellen, die die zuvor aufgezeigten Nachteile nicht aufweisen. The object of the invention is to provide reactive diluents with high reactivity for epoxy resin compositions which do not have the disadvantages indicated above.
Gelöst wird diese Aufgabe durch die Verwendung von einer oder mehreren Verbindung (en) l I This object is achieved by the use of one or more compound (s) I
I, I,
worin R1 und R2 unabhängig voneinander -H, Ci-3-Alkyl, C1-3- Oxalkyl und Glycidyl bedeuten, aber R1 und R2 nicht gleichzeitig Glycidyl sind, in which R 1 and R 2, independently of one another, denote -H, C 1-3 -alkyl, C 1-3 -alkyl and glycidyl, but R 1 and R 2 are not simultaneously glycidyl,
R3 ein gegebenenfalls substituiertes Styryl der Formel R 3 is an optionally substituted styryl of the formula
R4 ein Wasserstoffrest oder Methyl ist, R 4 is a hydrogen radical or methyl,
R5 und R6 ein Wasserstoffrest, C1-.3-Alk.yl, Ci-2-Oxalkyl ist als Reaktivverdünner in Epoxidharz-Zusammensetzungen. R 5 and R 6 is a hydrogen radical, C 1 -.3-Alk.yl, Ci- 2 -Oxalkyl as reactive diluents in epoxy resin compositions.
Ci-3-Alkyl umfassen Methyl, Ethyl, Propyl und Isopropyl. C1-3 - Oxalkyl umfassen Methoxy, Ethoxy, Propoxy und Isopropoxy. Ci-3-alkyl include methyl, ethyl, propyl and isopropyl. C 1 -3 - oxalkyl include methoxy, ethoxy, propoxy and isopropoxy.
Gegenstand der Erfindung ist ferner die Verwendung eines Gemischs epoxidierter Mono (alkylaryl) phenole, d.h. styrolisierter Phenole mit einem Glycidylrest als Reaktivverdünner für Epoxidharz- Zusammensetzungen . The invention further provides the use of a mixture of epoxidized mono (alkylaryl) phenols, i. styrenated phenols having a glycidyl radical as a reactive diluent for epoxy resin compositions.
Dieses Gemisch enthält mehrere Verbindungen der nachfolgend gezeigten chemischen Formel Ia, Ib und Ic: This mixture contains several compounds of the following chemical formulas Ia, Ib and Ic:
wobei die Verbindungbeing the connection
und die Verbindung Ib R1, R3: H and the compound Ib R 1 , R 3 : H
und and
H H
0— C— C— CH2 die Verbindung Ic R1 : 0-C-C-CH 2 the compound Ic R 1 :
und R4, Rs und R6 die oben angegebenen Bedeutungen haben. and R 4 , R s and R 6 have the meanings given above.
Gegenstand der Erfindung ist ferner eine Zusammensetzung mit einer der vorgenannten Verbindungen oder einem Gemisch dieser Verbindungen, die mindestens ein vernetzbares Polymer enthält. The invention further provides a composition comprising one of the aforementioned compounds or a mixture of these compounds containing at least one crosslinkable polymer.
Überraschenderweise zeigt eine Zusammensetzung aus einer oder meh reren erfindungsgemäßen Epoxidverbindungen als Reakti verdünner trotz einer hohen sterischen Hinderung im Vergleich zu üblichen aromatischen Verdünnern wie Phenol, Kresol oder p-tert . -Butyl- phenol eine vergleichbare Reaktivität. Die Reaktivität der erfindungsgemäßen Reaktivverdünner ist höher als die aliphatischer Reaktivverdünner auf Basis mono- oder difunktioneller Alkohole. Surprisingly, a composition of one or more inventive epoxy compounds as Reakti diluent despite a high steric hindrance compared to conventional aromatic diluents such as phenol, cresol or p-tert. Butyl phenol a comparable reactivity. The reactivity of the reactive diluents according to the invention is higher than the aliphatic reactive diluents based on mono- or difunctional alcohols.
BESCHREIBUNG DER BEVORZUGTEN AUSFÜHRUNGS FORMEN DESCRIPTION OF THE PREFERRED EMBODIMENTS
Vorzugsweise enthält das erfindungsgemäße als Reaktivverdünner verwendende Gemisch im Wesentlichen folgende Verbindungen: The mixture according to the invention which is used as reactive diluent preferably contains essentially the following compounds:
wobei in which
b) R i, R3. H b) R i, R 3. H
R2: 0-CH2— CH— CH2 und c) Ri : O— CH2— CH— CH2 R2: 0-CH 2 - CH 2 CH- and c) Ri: O- CH 2 - CH 2 CH-
O O
R2: H R2: H
CH3 CH 3
Diese Verbindungen können zu mindestens 60 Gew.-%, vorzugsweise zu mindestens 80 Gew.-%, besonders bevorzugt zu mindestens 90 Gew.-% oder zu mindestens 95 Gew.-% in dem erfindungsgemäß zu verwendenden Gemisch enthalten sein. These compounds may be present in at least 60% by weight, preferably at least 80% by weight, more preferably at least 90% by weight or at least 95% by weight in the mixture to be used according to the invention.
Vorzugsweise enthält ein Gemisch, bezogen auf die Summe der Massen der Verbindungen der Formel Ia, Ib und Ic, 30 bis 60 Gew.-% von Ia, 10 bis 25 Gew.-% von Ib und 20 bis 40 Gew.-% von Ic. Preferably, a mixture, based on the sum of the masses of the compounds of the formula Ia, Ib and Ic, 30 to 60 wt .-% of Ia, 10 to 25 wt .-% of Ib and 20 to 40 wt .-% of Ic ,
Das erfindungsgemäß verwendete Gemisch kann durch Epoxidierung von styrolisiertem Phenol erhalten werden. Die Herstellung von styro- lisiertem Phenol durch Umsetzung einer phenolischen Komponente mit einem Olefin ist bekannt und beispielsweise beschrieben in der EP 0 656 384 A2. Dabei handelt es sich im Wesentlichen um Alkylie- rungsreaktionen, bei denen sich die Vinylgruppe der Styrole in Ortho- oder para-Stellung zur Hydroxylgruppe des Phenols addiert. Bei dieser Reaktion werden im Allgemeinen Friedel-Crafts- Katalysatoren, beispielsweise Säuren und Lewissäuren, verwendet. Die Addition der Vinylverbindung an Phenole kann bei einem molaren Verhältnis der phenolischen Hydroxylgruppe im Phenol zur aromatischen Verbindung von 1:1 bis 1:2 erfolgen. The mixture used according to the invention can be obtained by epoxidation of styrenated phenol. The preparation of styrenated phenol by reacting a phenolic component with an olefin is known and described for example in EP 0 656 384 A2. These are essentially alkylation reactions in which the vinyl group of the styrenes is added ortho or para to the hydroxyl group of the phenol. In this reaction, Friedel-Crafts Catalysts, for example acids and Lewis acids used. The addition of the vinyl compound to phenols can be carried out at a molar ratio of the phenolic hydroxyl group in the phenol to the aromatic compound of 1: 1 to 1: 2.
Geeignete aromatische Vinylverbindungen sind insbesondere alpha- Methylstyrol, Styrol, o-Methylstyrol , m-Methylstyrol , p- Methylstyrol , handelsübliches Vinyltoluol (Isomerengemisch) 3,4- Dimethylstyrol, 2 , -Dimethylstyrol , 2 , 5-Dimethylstyrol , 2,6- Dimethylstyrol , o-Ethylstyrol , m-Ethylstyrol , p-Ethylstyrol , 3,4- Diethylstyrol, 2 , 4-Diethylstyrol , 2 , 5-Diethylstyrol, 2,6- Diethylstyrol . Suitable aromatic vinyl compounds are, in particular, alpha-methylstyrene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, commercial vinyltoluene (mixture of isomers), 3,4-dimethylstyrene, 2-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene , o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 3,4-diethylstyrene, 2,4-diethylstyrene, 2,5-diethylstyrene, 2,6-diethylstyrene.
Gemische von styrolisierten Phenolen werden beispielsweise durch die RÜTGERS Novares GmbH unter der Marke „Novares®" angeboten. Mixtures of styrenated phenols are offered for example by the RÜTGERS Novares® GmbH under the brand "Novares® ®".
Die kationisch induzierte Umsetzung zu styrolisiertem Phenol resultiert in einer statistischen Verteilung von 2-, 4- und 2,4- substituiertem Phenol. Zur Gewinnung der einzelnen styrolisierten Verbindungen können zunächst durch Vakuumdestillation die monosty- rolisierten Verbindungen von dem distyrolisierten Phenol getrennt werden. Das Gemisch der monostyrolisierten Verbindungen kann anschließend durch Kristallisation in das 2-styrolisierte und das 4- styrolisierte Phenol getrennt werden. The cationically induced conversion to styrenated phenol results in a statistical distribution of 2-, 4- and 2,4-substituted phenol. To obtain the individual styrenated compounds, the monostyrrated compounds can first be separated from the distyrenated phenol by vacuum distillation. The mixture of monostyrenated compounds can then be separated by crystallization into the 2-styrenated and 4-styrenated phenol.
Das styrolisierte Phenol oder ein Gemisch styrolisierter Phenole wird mit einer Oxiranverbindung zum Erhalt der epoxidierten erfindungsgemäßen Verbindungen umgesetzt. Dabei reagiert die phenolischen OH-Gruppe mit der Oxiranverbindung. Als Oxiranverbindung wird vorzugsweise Epichlorhydrin eingesetzt. Die Reaktion erfolgt im Allgemeinen in Gegenwart von Alkalihydroxid, beispielsweise Natriumhydroxid, bei erhöhter Temperatur nach der theoretischen Gleichung unter Abspaltung von Kochsalz und Wasser zur erfindungsgemäßen Glycidylverbindung gemäß dem folgend gezeigten Reaktion- schema: The styrenated phenol or a mixture of styrenated phenols is reacted with an oxirane compound to obtain the epoxidized compounds of this invention. The phenolic OH group reacts with the oxirane compound. The oxirane compound used is preferably epichlorohydrin. The reaction is generally carried out in the presence of alkali metal hydroxide, for example sodium hydroxide, at elevated temperature according to the theoretical equation with elimination of common salt and water to give the glycidyl compound according to the invention in accordance with the reaction scheme shown below:
Diese Reaktion ist grundsätzlich bekannt, wobei R der gemeinsame Grundbaustein der Substanzen Ia, Ib und Ic ist und der Benzolring an den entsprechenden Positionen eine OH-Gruppe aufweist. This reaction is basically known, wherein R is the common basic building block of the substances Ia, Ib and Ic and the benzene ring has an OH group at the corresponding positions.
Überraschenderweise kann das erfindungsgemäß verwendete Gemisch als reaktive Verbindung verwendet werden, wenn auch eine hydropho- bierende Wirkung erzielt werden soll. Dies kann beispielsweise in Beschichtungszusammensetzungen durch Verwendung des erfindungsgemäßen Gemischs als Harzbestandteil oder als Reaktivverdünner mit mindestens einem weiteren Harzbestandteil erfolgen. Ebenso kann die Mischung als Modifizierungsmittel bei der Polyestersynthese, beispielsweise zur Verringerung von Säuregruppen oder Alkoholgrup- pen verwendet werden bei gleichzeitiger Erhöhung der Hydrophobizi- tät . Ferner kann das erfindungsgemäße Gemisch als Papierbehandlungsmittel verwendet werden, ohne die bekannten Nachteile einer Migration wie bei nicht reaktiven phenolischen Komponenten zu zeigen . Surprisingly, the mixture used according to the invention can be used as a reactive compound, even if a hydrophobicizing effect is to be achieved. This can be done, for example, in coating compositions by using the mixture according to the invention as a resin constituent or as a reactive diluent with at least one further resin constituent. Likewise, the mixture can be used as a modifier in the polyester synthesis, for example for reducing acid groups or alcohol groups, while at the same time increasing the hydrophobicity. Furthermore, the mixture according to the invention can be used as a paper treatment agent without showing the known disadvantages of migration as in non-reactive phenolic components.
Überraschend wurde ferner festgestellt, dass bei Einsatz des erfindungsgemäß zu verwendenden Gemischs die Beständigkeit von Com- posite-Werkstoffen, wie sie vermehrt bei der Gewinnung von Windenergie eingesetzt werden, gegenüber Wasser oder wässerigen Medien, erhöht wird. Surprisingly, it has also been found that the use of the mixture to be used according to the invention increases the resistance of composite materials, such as are increasingly used in the production of wind energy, to water or aqueous media.
Generell kann diese Mischung zur Herstellung von verstärkten oder unverstärkten Kunststoffen (z.B. duroplastische Werkstoffe, Thermoplasten) und Elastomeren verwendet werden. Generally, this blend can be used to make reinforced or unreinforced plastics (e.g., thermosets, thermoplastics) and elastomers.
Besonders bevorzugt sind Zusammensetzungen, die als weitere Komponente zumindest einen vernetzbaren Kunststoff (Thermpolast, Elastomer) , insbesondere duroplastische Kunststoff (wie Polyester harz, Epoxidharz, Phenolharz oder Melaminharz) , aufweisen. Particular preference is given to compositions which, as further component, comprise at least one crosslinkable plastic (thermopolast, Elastomer), in particular duroplastic plastic (such as polyester resin, epoxy resin, phenolic resin or melamine resin) have.
Vorteilhaft ist, wenn das erfindungsgemäße Gemisch mit zumindest einem vernetzbaren Kunststoff in einem Verhältnis von 5:95 bis 50:50 vorliegt. Die Herstellung der Zusammensetzung erfolgt in üb licher Weise. It is advantageous if the mixture according to the invention with at least one crosslinkable plastic in a ratio of 5:95 to 50:50 is present. The preparation of the composition takes place in üb Licher way.
Besonders bevorzugt ist, wenn das erfindungsgemäß zu verwendende Gemisch als weitere Komponente zumindest d) ein Epoxidharz, ausgewählt aus Glycidylether auf Basis von Bisphenol-A, Bisphenol-F oder Novolaken, mono-, di-, oder polyfunktionellen Alkoholen, mono- oder polyfunktionellen Pheno len wie Phenol, Kresol, Resorcinole, Naphtholen, p-tert.- Butylphenolen, Nonylphenolen, Cashew-Nut-Oil-Verbindungen, C12 C14 -Alkoholen, Butandiolen und/oder Hexandiolen e) einen Härter ausgewählt aus aminischen oder sauren Verbindungen sowie solche Härter, welche eine Homopolymerisation von Epoxidverbindungen initiieren können und f) gegebenenfalls weitere Zusatzstoffe, wie Verarbeitungshilfs¬ mittel und anorganische Füllstoffe, bevorzugt 5 bis 20 Gewichtsteile, bezogen auf alle Komponenten der Zusammensetzung enthält . It is particularly preferred if the mixture to be used according to the invention as a further component at least d) an epoxy resin selected from glycidyl ether based on bisphenol A, bisphenol F or novolaks, mono-, di- or polyfunctional alcohols, mono- or polyfunctional phenol len such as phenol, cresol, resorcinols, naphthols, p-tert-butylphenols, nonylphenols, cashew nut oil compounds, C 12 C14 alcohols, butanediols and / or hexanediols e) a hardener selected from aminic or acidic compounds and such Hardeners which can initiate a homopolymerization of epoxy compounds and f) optionally further additives, such as processing aids ¬ and inorganic fillers, preferably 5 to 20 parts by weight, based on all components of the composition.
Die Verwendung von Glycidylether auf Basis von Bisphenol-A, Bisphenol-F oder Novolaken, mono-, di-, oder polyfunktionellen AI koholen, mono- oder polyfunktionellen Phenolen wie Phenol, Kresol Resorcinole, Naphtholen, p-tert . -Butylphenolen, Nonylphenolen, Cashew-Nut-Oil-Verbindungen, Ci2-Ci4-Alkoholen, Butandiol und/oder Hexandiol als weitere Komponente hat den Vorteil, dass die Zusammensetzung kristallisationsbeständig und lagerfähig ist. Außerdem kann die Viskosität dieser erfindungsgemäßen Zusammensetzung an- wendungsbezogen im geeigneten Bereich eingestellt werden. The use of glycidyl ethers based on bisphenol A, bisphenol F or novolaks, mono-, di- or polyfunctional alcohols, mono- or polyfunctional phenols, such as phenol, cresol resorcinols, naphthols, p-tert. Butylphenols, nonylphenols, cashew nut oil compounds, C 2 -C 4 -alcohols, butanediol and / or Hexanediol as further component has the advantage that the composition is crystallization resistant and storable. In addition, the viscosity of this composition according to the invention can be adjusted in an appropriate range for the application.
Übliche Härter für Bpoxide können eingesetzt werden. Typische Vertreter der aminischen Härter sind Verbindungen mit einem, zwei oder mehreren freien aminischen Wasserstoffen. Diese können über cyclische, aliphatische oder aromatische Verknüpfungen oder über Polyethergruppen verfügen. Typische Vertreter für diese Härterklasse sind Amine wie Isophorondiamin, Xylylendiamin, Trimethylen- hexamethylendiamin, Polyetheramine . Ebenfalls geeignete Härter im Sinne der Erfindung sind sogenannte saure Härter auf Basis von organischen Säuren wie Phthalsäureanhydrid, Hexahydrophthalsäurean- hydrid, Methylhydrophthalsäureanhydrid sowie weitere Verbindungen dieser Klasse. Ebenfalls nicht ausgeschlossen sind latente Systeme, welche über eine Strahlenhärtung und einer damit verbundenen ionischen Härtung oder durch thermische Härtung („latentes 1- Komponentensystem") angewendet werden. Bevorzugt im Sinne der Er- findung sind aminische Härter für den Bereich der Härtung beiUsual hardeners for Bpoxide can be used. Typical representatives of the amine hardeners are compounds with one, two or more free amine hydrogens. These may have cyclic, aliphatic or aromatic linkages or polyether groups. Typical representatives of this hardener class are amines such as isophoronediamine, xylylenediamine, trimethylene-hexamethylenediamine, polyetheramines. Also suitable hardeners according to the invention are so-called acidic hardeners based on organic acids such as phthalic anhydride, hexahydrophthalic anhydride, methylhydrophthalic anhydride and other compounds of this class. Also not excluded are latent systems which are applied via radiation curing and associated ionic hardening or by thermal curing ("latent 1-component system"). Preferred in the sense of the invention are amine hardeners for the range of curing
Raumtemperatur, hier insbesondere sogenannte Addukthärter auf Basis von Bisphenol-A-Diglycidylether und Isophorondiamin, welche weiter modifiziert werden durch den Einsatz von Benzylalkohol, Beschleunigern sowie weiterer Additive zur Verbesserung der Verar- beitungseigenschaften oder Endanwendungen. Das Mischungsverhältnis mit den epoxid-reaktiven Komponenten ergibt sich aus der stöchio- metrischen Umsetzung. Das genaue Mischungsverhältnis richtet sich nach der Anwendung und kann sowohl eine unterstöchiometrische als auch eine überstöchiometrische Umsetzung beinhalten. Room temperature, here in particular so-called adduct hardeners based on bisphenol A diglycidyl ether and isophoronediamine, which are further modified by the use of benzyl alcohol, accelerators and other additives to improve the processing properties or end uses. The mixing ratio with the epoxide-reactive components results from the stoichiometric conversion. The exact mixing ratio depends on the application and may include both a substoichiometric and a superstoichiometric implementation.
Die erfindungsgemäße Epoxidharzzusammensetzung wird hergestellt durch Mischen der einzelnen Komponenten entsprechend bekannten Methoden. Durch das Vermischen der Komponenten bei höherer Temperatur, beispielsweise bei 60° bis 80°C, kann der Misch- und Abfüll- prozess beschleunigt werden. Vorzugsweise liegt die Epoxidharzkomponente d) zur Summe der Komponenten a) bis c) in einem Verhältnis 95:5 bis 50:50, besonders bevorzugt 95:5 bis 85:20, vor. In diesem Bereich werden im gehär- teten Zustand ausgezeichnete mechanische Eigenschaften erzielt. Je nach Anwendungszweck können auch höhere oder niedrigere Anteile verwendet werden. The epoxy resin composition of the present invention is prepared by mixing the individual components according to known methods. By mixing the components at a higher temperature, for example at 60 ° to 80 ° C, the mixing and filling process can be accelerated. Preferably, the epoxy resin component d) to the sum of components a) to c) in a ratio of 95: 5 to 50:50, more preferably 95: 5 to 85:20, before. In this area, excellent mechanical properties are achieved in the hardened state. Depending on the application, higher or lower proportions can also be used.
Die erfindungsgemäße Mischung kann zur Herstellung von wärmehärt- baren Produkten verwendet werden. So sind Beschichtungen oder aber auch Formkörper denkbar. Besonders bevorzugt ist, wenn die erfindungsgemäße Mischung verwendet wird für Beschichtungen, insbesondere für selbstverlaufende Beschichtungen. So wären Beschichtungen für Industriefußböden, Lacke, Klebstoffe oder Elektrolaminate denkbar. Die erfindungsgemäße Verwendung erfolgt somit vorzugsweise zur Behandlung von Papier, zur Herstellung von gehärteten Polymerprodukten, zur Erzeugung von Beschichtungen, zur Herstellung von verstärkten und unverstärkten Kunststoffen, Elastomeren und Formkörpern. The mixture according to the invention can be used for the production of thermosetting products. Thus, coatings or even shaped bodies are conceivable. It is particularly preferred if the mixture according to the invention is used for coatings, in particular for self-leveling coatings. For example, coatings for industrial floors, paints, adhesives or electrical laminates would be conceivable. The use according to the invention thus takes place preferably for the treatment of paper, for the production of cured polymer products, for the production of coatings, for the production of reinforced and unreinforced plastics, elastomers and moldings.
Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung . The following examples serve to further illustrate the invention.
BEISPIELE EXAMPLES
Beispiel 1 - Herstellung des erfindungsgemäß zu verwendenden Ge- mischs Example 1 Preparation of the Mixture to be Used According to the Invention
Es werden 925 g Epichlorhydrin (10 Mol) in einem 2 1 Laborreaktor mit Ablasshahn vorgelegt. Die Temperatur wird auf 65°C erhöht. Anschließend werden 466 g (2 Mol OH) Novares® LS 500 (RÜTGERS Novares GmbH) ( styrolisiertes Phenol) ebenso wie 29,3 g (0,1 Mol) Natriumhydroxidlösung (20 %ig) zugegeben. Nach Ende des Lösevorgangs wird auf 100 °C erhitzt. Die Reaktionsmischung wird 3 Stunden lang ge- rührt und anschließend auf 45 °C abgekühlt. Nun werden der Reaktionsmischung 50 g Isopropanol und 140 g Wasser zugesetzt. Innerhalb von 120 min werden 400 g an 20 %iger Natronlauge { stöchiometrische Menge) zudosiert. Die Temperatur wird zwei Stunden lang bei konstant 45 °C gehalten (2 h Nachreaktion) . There are presented to 925 g of epichlorohydrin (10 mol) in a 2 1 laboratory reactor with drain cock. The temperature is raised to 65 ° C. Subsequently, 466 g (2 mol OH) Novares LS 500 ® (RÜTGERS Novares GmbH) (styrenated phenol) as well as 29.3 g (0.1 mol) of sodium hydroxide solution (20% strength) are added. After the dissolution process is heated to 100 ° C. The reaction mixture is stirred for 3 hours and then cooled to 45.degree. Now 50 g of isopropanol and 140 g of water are added to the reaction mixture. Within 120 min, 400 g of 20% sodium hydroxide solution {stoichiometric amount) are added. The temperature is maintained at a constant 45 ° C for two hours (2 h after-reaction).
Es werden 36 g NaCl zugegeben und das Gemisch weitere 60 Minuten lang zur Nachreaktion belassen. Anschließend wird auf 60 °C erwärmt . 36 g of NaCl are added and the mixture is allowed to react for a further 60 minutes. It is then heated to 60.degree.
Der Rührer wird ausgeschaltet und nach einer Absitzzeit von 30 Minutren wird die untere wässrige Phase abgelassen. Die im Reaktionsgefäß verbleibende organische Phase wird mit weiteren 200 g Epichlorhydrin verdünnt und mit 300 g Wasser gewaschen, wobei eine Phasenumkehr erfolgt. The stirrer is switched off and after a Absitzezeit of 30 minutes, the lower aqueous phase is drained. The remaining organic phase in the reaction vessel is diluted with a further 200 g of epichlorohydrin and washed with 300 g of water, with a phase inversion takes place.
Die organische Phase wird dann unter Vakuum bis zu einer Temperatur von 120 °C ausdestilliert und durch Wasserdampfdestillation im Vakuum von Spuren von flüchtigen Stoffen befreit. The organic phase is then distilled off under reduced pressure up to a temperature of 120 ° C and freed from traces of volatiles by steam distillation in vacuo.
Das Destillat enthält Epichlorhydrin, Isopropanol, Wasser und höher siedende Verunreinigungen in einer Konzentration geringer als 1 % und kann für eine Folgeproduktion eingesetzt werden. Der Destillationsrückstand wird in 248 g Toluol aufgenommen, auf 75 °C erwärmt und mit 50 %iger Natronlauge (MV 1 : 2,5 - hydrolisierbares Chlor: Natronlauge) innerhalb von 30 Minuten versetzt. Zuvor wird die gleiche Menge an Wasser zugegeben. Die Reaktionszeit unter Rühren beträgt dann 1 Stunde. Es werden 330 g To- luol zur Verdünnung zugegeben. Der Rührer wird ausgeschaltet und nach einer Absetzzeit von 10 min wird die wässrige Phase abgetrennt. Die organische Lösung wird mehrfach mit Wasser neutral gewaschen . Das Toluol und verbleibende Spuren an flüchtigen Bestandteilen werden im Vakuum bis 125 °C abdestilliert. Die als Destillationsrückstand erhaltene Epoxidverbindung wird über einen Druckfilter von organischen und anorganischen festen Begleitstoffen gereinigt. Die Ausbeute, bezogen auf die Vorstufe, beträgt 95 %. The distillate contains epichlorohydrin, isopropanol, water and higher boiling impurities at a concentration of less than 1% and can be used for subsequent production. The distillation residue is taken up in 248 g of toluene, heated to 75 ° C and treated with 50% sodium hydroxide solution (MV 1: 2.5 - hydrolyzable chlorine: sodium hydroxide solution) within 30 minutes. Beforehand, the same amount of water is added. The reaction time with stirring is then 1 hour. 330 g of toluene are added for dilution. The stirrer is switched off and after a settling time of 10 minutes, the aqueous phase is separated off. The organic solution is washed several times with water until neutral. The toluene and remaining traces of volatiles are distilled off in vacuo to 125 ° C. The epoxide compound obtained as the distillation residue is purified by a pressure filter of organic and inorganic solid impurities. The yield, based on the precursor, is 95%.
Analysenergebnisse der Epoxidverbindung: Analysis results of the epoxy compound:
Epoxidäquivalent 384 g/Äq Epoxide equivalent 384 g / eq
Viskosität 25°C 545 mPas Viscosity 25 ° C 545 mPas
Gehalt an hydrolysierbarem Chlor 0,36 % Hydrolyzed chlorine content 0.36%
Farbe nach Gardner Color after Gardner
Beispiel 2 - Anwendung des Gemischs Example 2 - Application of the mixture
Das in Beispiel 1 erzeugte glycidierte "styrolisierte Phenol" (B) wird zur Herstellung von Epoxidharzmischungen eingesetzt. Dazu wird der Bisphenol-A-Diglycidether im Mischaggregat vorgelegt und das styrolisierte Produkt (A) bzw. das erfindungsgemäße Produkt (B) unter Rühren zudosiert. Die Temperatur während des Rührvorganges wird zwischen 65 °C und 70 °C gehalten. Dieser Zusammensetzung wird gegebenenfalls nach einer Lagerung der Härter in angegebener Konzentration (Tabelle 1) zugesetzt. An einer Bodenbeschichtung (Grundierung oder als selbstverlaufende Bodenbeschichtung) werden die Eigenschaften von Zusammensetzungen, die das Produkt (A) ( styrolisiertes Phenol) enthalten, mit Zusammensetzungen, die das erfindungsgemäße Produkt (B) enthalten, verglichen . Rezepturbestandteile I II The glycidated "styrenated phenol" (B) produced in Example 1 is used for the preparation of epoxy resin mixtures. For this purpose, the bisphenol A diglycidyl ether is introduced into the mixing unit and the styrenated product (A) or the product (B) according to the invention is added with stirring. The temperature during the stirring is kept between 65 ° C and 70 ° C. This composition is optionally added after storage of the hardener in the indicated concentration (Table 1). On a floor coating (primer or self-leveling floor coating), the properties of compositions containing the product (A) (styrenated phenol) are compared with compositions containing the product (B) of the invention. Formulation ingredients I II
(Erfindung) (Invention)
Harz : Resin:
Bisphenol-A-Diglycidether 80 80 EPIKOTE® Resin 828LVEL Bisphenol-A diglycidyl ether 80 80 EPIKOTE ® Resin 828LVEL
Styrolisiertes Phenol (A) : 20 - Styrenated Phenol (A): 20 -
Styrolisiertes Phenol, glycidiert 20 (B) : Styrenated phenol, glycidated 20 (B):
Epoxidäquivalent 232 202 Epoxide equivalent 232 202
Härter: Harder:
EPIKURE® Curing Agent 551 EPIKURE ® Curing Agent 551
(Addukthärter aus Bisphenol-A- Diglycidylether und Isophorondiamin, (Adduct hardener of bisphenol A diglycidyl ether and isophoronediamine,
modifiziert u.a. mit Benzylalkohol) modified u.a. with benzyl alcohol)
Aminäquivalent 93 93 Amine equivalent 93 93
Harz: Härter [Masseteile] 100:40 100 : 46 Resin: Hardener [parts by weight] 100: 40 100: 46
Eigenschaften : Properties :
Relativer Abdam fverlust 0 -31 % Relative waste f loss 0 -31%
[Aushärtung 96h bei 23°C, Bestimmung [Curing 96h at 23 ° C, determination
des Abdampfverlusts durch Gewichtsmessung lh nach Auftrag und nach Lagerung [2h, 100°C, Schichtdicke 200 of evaporation loss by weight measurement lh after application and after storage [2h, 100 ° C, layer thickness 200
μπι] ] μπι]]
Zur Bestimmung des Abdampfverlusts wird die Beschichtungszusammen- setzung mit einem Rakel auf eine Glasplatte in einer Schichtdicke von 200 um aufgetragen. Nach einer Stunde wird die Glasplatte gewogen. Die Glasplatte wird dann 96 Stunden bei Raumtemperatur und anschließend zwei Stunden bei 100 °C in einem Trockenschrank gelagert. Anschließend wird das Gewicht bestimmt und aus der Differenz der beiden Gewichtsmessungen die relative Gewichtsabnahme bestimmt . To determine the evaporation loss, the coating composition is applied with a doctor blade to a glass plate in a layer thickness of 200 μm. After one hour, the glass plate is weighed. The glass plate is then stored for 96 hours at room temperature and then for two hours at 100 ° C in a drying oven. Then the weight is determined and the difference the two weight measurements determined the relative weight loss.
Es konnte belegt werden, dass der Anteil der flüchtigen Verbindun- gen während der Härtung erfindungsgemäß drastisch verringert wird, da das erfindungsgemäße Gemisch II in die organische Matrix eingebaut wird, was durch die Bestimmung des Abdampfverlusts gezeigt wird. It has been demonstrated that the proportion of volatile compounds during curing is drastically reduced according to the invention, since the mixture II according to the invention is incorporated into the organic matrix, which is shown by the determination of the evaporation loss.
Weiterhin konnte eine Verbesserung des Eigenschaftsprofils in selbstverlaufenden Beschichtungen beobachtet werden (Tabelle 2) . Die Zusammensetzungen wurden wie bereits beschrieben, hergestellt Furthermore, an improvement in the property profile in self-leveling coatings was observed (Table 2). The compositions were prepared as previously described
Tabelle 2: Table 2:
Rezepturbestandteile Referenz : I II III Recipe components Reference: I II III
Erfindung invention
Harz : Resin:
Bisphenol-A- 100 90 90 90 Diglycidether Bisphenol A 100 90 90 90 diglycidyl ether
EPIKOTE® Resin 828LVEL EPIKOTE ® Resin 828LVEL
Ci2-ci4-Glycidylether : 10 Ci2-ci4 glycidyl ether: 10
Styrolisiertes Phenol, 10 Styrenated phenol, 10
glycidiert (B) : glycidated (B):
Hexandioldiglycidether 10 Hexanediol diglycidyl ether 10
Epoxidäquivalent 186 193 194 180 [g/Aquiv . ] Epoxide equivalent 186 193 194 180 [g / Aquiv. ]
Viskosität [25°C, Pas] 10.6 1.6 6.6 2.3 Viscosity [25 ° C, Pas] 10.6 1.6 6.6 2.3
Härter : Harder :
Addukthärter auf Basis Addukthärter based
von Bisphenol-A- Diglycidylether und of bisphenol A diglycidyl ether and
Isophorondiamin modifi- ziert mit Benzylalkohol Isophoronediamine modifi- decorated with benzyl alcohol
und Beschleuniger and accelerator
EPIKURE® Curing Agent EPICURE ® Curing Agent
F205 F205
Aminäquivalent 105 105 105 105 Amine equivalent 105 105 105 105
Harz."Härter [Massentei100:56 100:54 100:54 100:58 le] Resin. "Hardener [Mass: 100: 56 100: 54 100: 54 100: 58 le]
Eigenschaften : Properties :
Topfzeit [100 g, t bis 39 44 43 37 Tmax, min] , DIN 16945 Pot life [100 g, t to 39 44 43 37 Tmax, min], DIN 16945
Gelzeit [23°C, Min], DIN 103 166 133 156 16945 Gel time [23 ° C, min], DIN 103 166 133 156 16945
Frühwasserbeständigkeit -/-/o/o _/_/_/0 0/0/+/+ -/0/0/+ 10°C [4/8/24/48 Stunden] , ISO 2812-4 Early water resistance - / - / o / o _ / _ / _ / 0 0/0 / + / + - / 0/0 / + 10 ° C [4/8/24/48 hours], ISO 2812-4
Frühwasserbeständigkeit -/o/o/o -/0/0/+ 0/+/+++/+ 0/+/+/+ 23°C [4/8/24/48 Stunden] , ISO 2812-4 Early water resistance - / o / o / o - / 0/0 / + 0 / + / +++ / + 0 / + / + / + 23 ° C [4/8/24/48 hours], ISO 2812-4
Oberfläche 10°C [48 h] Matt Matt Leicht Matt visuell DIN 53230 Matt Surface 10 ° C [48 h] Matt Matt Light Matt Visually DIN 53230 Matt
Oberfläche 23°C [48 h] Gut Gut Glänzend Gut visuell DIN 53230 Surface 23 ° C [48 h] Good Good Glossy Good visually DIN 53230
Durch die Verwendung des erfindungsgemäßen Gemischs II (styroli- siertes Phenol, glycidiert (B) ) wird eine signifikante Beschleunigung der Härtungsreaktion im direkten Vergleich zu den aliphati- sehen Reaktivverdünnern (III) gefunden. Gleichzeitig wird dieBy using the mixture II according to the invention (styrenated phenol, glycidated (B)), a significant acceleration of the curing reaction is found in direct comparison to the aliphatic reactive diluents (III). At the same time the
Frühwasserbeständigkeit (Beständigkeit gegenüber unerwünschten Ne¬ benreaktionen durch Wasser während der Härtung, z.B. Carbamatbil- dung) - gemessen im Vergleich zur Referenz- deutlich verbessert. In der Tabelle 3 wird die Verbesserung der mechanischen Eigenschaften gezeigt. Tabelle 3: Early water resistance (resistance against undesired Ne ¬ benreaktionen by water during the curing, for example Carbamatbil- formation) - measured in comparison to the reference significantly improved. Table 3 shows the improvement in mechanical properties. Table 3:
Rezepturbestandteilte I II Recipe ingredients I II
(Erfindung) (Invention)
Harz resin
Bisphenol-A-Diglycidether 85 85 EPIKOTE® Resin 828LVEL Bisphenol A diglycidyl ether 85 85 EPIKOTE ® Resin 828LVEL
Neodecansäureglycidylether 15 - Neodecanoic acid glycidyl ether 15 -
Styrolisiertes Phenol, glycidiert (B) . - 15 Styrenated phenol, glycated (B). - 15
Harz : Resin:
Epoxidäquivalent 193 198 Epoxide equivalent 193 198
Viskosität [25°C, Pas] 1.5 5.6Viscosity [25 ° C, Pas] 1.5 5.6
Härter : Harder :
Addukthärter auf Basis von Bisphenol- 54 53 A-Diglycidylether und Isophorondiamin Adduct hardener based on bisphenol 54 53 A diglycidyl ether and isophoronediamine
modifiziert mit Benzylalkohol und Beschleuniger modified with benzyl alcohol and accelerator
EPIKURE® Curing Agent F205 EPIKURE ® Curing Agent F205
(Aminäquivalent 105 g/Äquiv.) (Amine equivalent 105 g / equiv.)
Tabelle 4 Table 4
Ausgangswerte : I II Initial values: I II
(Erfindung) (Invention)
Mechanische Eigenschaften Mechanical properties
[Härtung 7 Tage 23°C] [Hardening 7 days 23 ° C]
Shore D-Härte, DIN EN ISO 868 79 83 Shore D hardness, DIN EN ISO 868 79 83
Biegefestigkeit [MPa] , DIN EN ISO 178 69 93Bending strength [MPa], DIN EN ISO 178 69 93
E-Modul [MPa], DIN EN ISO 178 1900 2700Modulus of elasticity [MPa], DIN EN ISO 178 1900 2700
Zugfestigkeit [MPa] , DIN EN ISO 527 45 62Tensile strength [MPa], DIN EN ISO 527 45 62
Dehnung [MPa], DIN EN ISO 527 3,1 2,7Elongation [MPa], DIN EN ISO 527 3.1 2.7
Druckfestigkeit [MPa] , DIN EN ISO 604 67 87Compressive strength [MPa], DIN EN ISO 604 67 87
Tg [°C, DSC] , IEC 1006 42 46Tg [° C, DSC], IEC 1006 42 46
Tg [ °C, DMA] , IEC 1006 58 60 DSC: Dynamische Differenzkalometrie Tg [° C, DMA], IEC 1006 58 60 DSC: Dynamic Differential Scalometry
DMA: Dynamisch mechanische Analyse Obwohl es sich in beiden Fällen um monofunktionelle Reaktivverdünner handelt, werden unter Verwendung von (B) höhere mechanische Werte erzielt. DMA: Dynamic Mechanical Analysis Although both are monofunctional reactive diluents, higher mechanical values are achieved using (B).
Der Test der Chemikalienbeständigkeit zeigt zunächst, dass die ge- messenen Shore-D-Werte (Härte) unter Verwendung der monofunktionellen Reaktivverdünner vergleichbar sind. Bei Einsatz von (B) dauert es jedoch doppelt so lange bis es zu einer mechanischen Zerstörung kommt (4 anstatt 2 Wochen) (Tabelle 5) . The chemical resistance test first shows that the measured Shore D values (hardness) are comparable using the monofunctional reactive diluents. However, using (B) it takes twice as long to cause mechanical damage (4 instead of 2 weeks) (Table 5).
Tabelle 5: Table 5:
In Klammern: % vom Ausgangswert (7d 23°C) In brackets:% of initial value (7d 23 ° C)
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011015193A DE102011015193A1 (en) | 2011-03-25 | 2011-03-25 | Epoxidized arylalkylphenols |
| PCT/EP2012/053890 WO2012130570A1 (en) | 2011-03-25 | 2012-03-07 | Use of epoxidized arylalkylphenols as reactive resin diluents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2688951A1 true EP2688951A1 (en) | 2014-01-29 |
Family
ID=45833396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12708815.1A Withdrawn EP2688951A1 (en) | 2011-03-25 | 2012-03-07 | Use of epoxidized arylalkylphenols as reactive resin diluents |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20140179890A1 (en) |
| EP (1) | EP2688951A1 (en) |
| JP (1) | JP2014515045A (en) |
| KR (1) | KR20140041470A (en) |
| CN (1) | CN103459482A (en) |
| DE (1) | DE102011015193A1 (en) |
| WO (1) | WO2012130570A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2015003494A (en) * | 2012-10-31 | 2015-06-04 | Dow Global Technologies Llc | Curable compositions. |
| DE202013012733U1 (en) | 2012-12-11 | 2018-12-12 | Fischerwerke Gmbh & Co. Kg | Epoxy-based compound for fixing purposes |
| CA2942354A1 (en) * | 2015-10-15 | 2017-04-15 | Dow Global Technologies Llc | Tristyrylphenol monogycidyl ether |
| WO2023171572A1 (en) * | 2022-03-09 | 2023-09-14 | 株式会社Adeka | One-pack type epoxy resin composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL187191B (en) * | 1953-05-01 | Dvsg Patentverwaltungs Gmbh | INNER SHAPE WITH ANGLED HEEL ARCH FOR A HEEL FORMING MACHINE. | |
| US4102862A (en) * | 1976-03-31 | 1978-07-25 | Kenrich Petrochemicals, Inc. | Application of cumylphenol and derivatives thereof in plastic compositions |
| CA1153770A (en) * | 1978-07-20 | 1983-09-13 | Salvatore J. Monte | Cumylphenol derivatives |
| US4365103A (en) * | 1981-12-04 | 1982-12-21 | The Dow Chemical Company | Process for the preparation of bis(1-phenylethenyl) compounds |
| JPS6028422A (en) * | 1983-07-26 | 1985-02-13 | Mitsubishi Electric Corp | Production of low-viscosity epoxy resin for impregnation |
| TW289024B (en) | 1993-11-02 | 1996-10-21 | Hoechst Ag |
-
2011
- 2011-03-25 DE DE102011015193A patent/DE102011015193A1/en not_active Ceased
-
2012
- 2012-03-07 EP EP12708815.1A patent/EP2688951A1/en not_active Withdrawn
- 2012-03-07 CN CN2012800151392A patent/CN103459482A/en active Pending
- 2012-03-07 KR KR1020137028320A patent/KR20140041470A/en not_active Withdrawn
- 2012-03-07 US US14/007,212 patent/US20140179890A1/en not_active Abandoned
- 2012-03-07 JP JP2014500314A patent/JP2014515045A/en active Pending
- 2012-03-07 WO PCT/EP2012/053890 patent/WO2012130570A1/en active Application Filing
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2012130570A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012130570A1 (en) | 2012-10-04 |
| KR20140041470A (en) | 2014-04-04 |
| CN103459482A (en) | 2013-12-18 |
| US20140179890A1 (en) | 2014-06-26 |
| JP2014515045A (en) | 2014-06-26 |
| DE102011015193A1 (en) | 2012-09-27 |
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