DE10223312A1 - Modified epoxy resin for use e.g. as casting resin, paint resin or binder, contains groups derived from polyglycidyl ether compounds and aromatic hydroxy-carboxylic acids - Google Patents
Modified epoxy resin for use e.g. as casting resin, paint resin or binder, contains groups derived from polyglycidyl ether compounds and aromatic hydroxy-carboxylic acidsInfo
- Publication number
- DE10223312A1 DE10223312A1 DE2002123312 DE10223312A DE10223312A1 DE 10223312 A1 DE10223312 A1 DE 10223312A1 DE 2002123312 DE2002123312 DE 2002123312 DE 10223312 A DE10223312 A DE 10223312A DE 10223312 A1 DE10223312 A1 DE 10223312A1
- Authority
- DE
- Germany
- Prior art keywords
- ether
- epoxy
- groups
- resin
- triglycidyl ether
- 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- Withdrawn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
- -1 aromatic hydroxy-carboxylic acids Chemical class 0.000 title claims abstract description 13
- 229920005989 resin Polymers 0.000 title claims description 14
- 239000011347 resin Substances 0.000 title claims description 14
- 239000003822 epoxy resin Substances 0.000 title claims description 10
- 229920000647 polyepoxide Polymers 0.000 title claims description 10
- 239000011230 binding agent Substances 0.000 title claims description 9
- 150000002170 ethers Chemical class 0.000 title abstract 2
- 238000005266 casting Methods 0.000 title description 2
- 239000003973 paint Substances 0.000 title description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 claims abstract description 4
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 4
- 239000004305 biphenyl Substances 0.000 claims abstract description 4
- 125000001624 naphthyl group Chemical group 0.000 claims abstract 2
- 239000004593 Epoxy Substances 0.000 claims description 19
- 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
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229930185605 Bisphenol Natural products 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 229920003986 novolac Polymers 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 238000000576 coating method Methods 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
- 229930003836 cresol Natural products 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002118 epoxides Chemical group 0.000 abstract 2
- UHUUGQDYCYKQTC-UHFFFAOYSA-N 4-[2,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1CC(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UHUUGQDYCYKQTC-UHFFFAOYSA-N 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 150000007965 phenolic acids Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 1
- XYXBMCIMPXOBLB-UHFFFAOYSA-N 3,4,5-tris(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC(O)=C(C)C(N(C)C)=C1N(C)C XYXBMCIMPXOBLB-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 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
- 150000002148 esters Chemical class 0.000 description 1
- HZZUMXSLPJFMCB-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;acetate Chemical compound CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 HZZUMXSLPJFMCB-UHFFFAOYSA-M 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- 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
- C08G59/625—Hydroxyacids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Es ist bekannt, das Molekulargewicht von Epoxidverbindungen auf Basis von Bisphenolen zu erhöhen, indem man entweder bei der Synthese das Einsatzverhältnis von Bisphenol zu Epichlorhydrin erhöht, oder indem man in einer zweiten Reaktion Bisphenol- Diglycidylether mit weiterem Bisphenol umsetzt (vergl. ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, Wiley-Verlag, 1986, Band 6, Seiten 327-328). Dabei entstehen in der Polymerkette ausschließlich Polyetherstrukturen mit endständigen Epoxidgruppen. Diese Harze werden allgemein als Advancementharze bezeichnet. It is known the molecular weight of epoxy compounds based on bisphenols to increase by either using the ratio of bisphenol in the synthesis Epichlorohydrin, or by using bisphenol Reacting diglycidyl ether with further bisphenol (see ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, Wiley-Verlag, 1986, volume 6, pages 327-328). Only polyether structures are created in the polymer chain terminal epoxy groups. These resins are commonly called advancement resins designated.
Obwohl diese Harze ein sehr gutes Eigenschaftsprofil zeigen, besteht in der Praxis das Bedürfnis nach Verbesserungen, insbesondere nach einer Verbesserung der Zähigkeit und gleichzeitig nach Erhöhung des Tg-Wertes der mit üblichen Härtungsmitteln gehärteten Epoxidharze. Although these resins show a very good property profile, there is a need in practice for improvements, in particular for an improvement in the toughness and at the same time for increasing the T g value of the epoxy resins cured with conventional curing agents.
Die Lösung dieser Aufgabe erfolgt durch modifizierte Epoxidharze gemäß der Ansprüche 1 und 2 und durch Verfahren zu ihrer Herstellung gemäß der Ansprüche 3 bis 5. Die modifizierten Epoxidharze eignen sich insbesondere als Elektrogießharze, als Lackharze oder als Bindemittel oder Bindemittelkomponente in Formmassen, Epoxidharz- Dispersionen oder Pulverlacken wie dies in den Ansprüchen 6 bis 10 beansprucht ist. This problem is solved by modified epoxy resins according to the claims 1 and 2 and by processes for their preparation according to claims 3 to 5. Die modified epoxy resins are particularly suitable as electro-casting resins, as coating resins or as a binder or binder component in molding compositions, epoxy resin Dispersions or powder coatings as claimed in claims 6 to 10.
Es wurde gefunden, daß modifizierte Epoxidharze, die in ihrer Polymerstruktur Ether- und Esterbindungen enthalten, mit den üblichen Epoxidharz-Härtungsmitteln deutlich zähere Formstoffe bei gleichzeitig höheren Tg-Werten ergeben als die gemäß dem geschilderten Stand der Technik hergestellten Epoxidharze. It has been found that modified epoxy resins which contain ether and ester linkages in their polymer structure, using the customary epoxy resin curing agents, give markedly tougher molding materials with at the same time higher T g values than the epoxy resins prepared according to the prior art described.
Die erfindungsgemäßen Epoxidharze entsprechen der allgemeinen Formel I:
in der n eine Zahl von 1 bis 5 ist und
R ein Biphenyl-, ein Bisphenyl- oder ein Naphthyl-Rest oder ein Rest eines Novolak-,
Bisphenolnovolak- oder Kresolnovolak-Polyglycidylethers, eines Alkyl-Diglycidylethers,
des Tetrakis(4-hydoxyphenyl)ethan-tetragylcidylethers, Triglycidyl-p-aminophenols,
Hexahydrophthalsäurediglycidylesters, 3,4-Epoxycyclohexancarboxylats oder N,N,N',N'-
tetraglycidyl-4,4'-diaminodiphenylmethans bei dem jeweils zwei oder mehr
Glycidylethergruppen fehlen,
R1 ein Phenylenrest
R' und R" gleich oder verschieden sind und Wasserstoff oder eine Hydroxylgruppe
bedeuten.
The epoxy resins according to the invention correspond to the general formula I:
in which n is a number from 1 to 5 and
R is a biphenyl, a bisphenyl or a naphthyl radical or a radical of a novolak, bisphenol novolak or cresol novolak polyglycidyl ether, an alkyl diglycidyl ether, the tetrakis (4-hydoxyphenyl) ethane-tetragylcidyl ether, triglyidyl-phenyl-phenyl-ethyl-phenyl-ethylenedyl-phenyl-ethylenedyl-phenyl-triglycidyl ether-triglyaldehyde-triglycidyl-phenyl-tryl-glycidyl ether , 3,4-epoxycyclohexane carboxylate or N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, each of which is missing two or more glycidyl ether groups,
R 1 is a phenylene radical
R 'and R "are the same or different and are hydrogen or a hydroxyl group.
Bevorzugt sind -O-R-O- ein Rest eines Bisphenols, insbesondere ein Bisphenol A-Rest und die Gruppe -O-C-R1(R',R")-COO- ein Salicylsäurerest. Preferred are -ORO- a residue of a bisphenol, in particular a bisphenol A residue and the group -OCR 1 (R ', R ") - COO- a salicylic acid residue.
Die modifizierten Epoxidharze werden hergestellt durch Umsetzung von Epoxidverbindungen mit mindestens zwei Epoxidgruppen mit aromatischen Hydroxycarbonsäuren (Phenolcarbonsäuren), wobei das molare Verhältnis der Epoxidgruppen zur Summe der Carbonsäure- und Hydroxylgruppen der Hydroxycarbonsäuren im Bereich von 2 : 1 bis 6 : 5 liegt. Die Umsetzung erfolgt entsprechend den Bedingungen wie sie auch zur Reaktion von Epoxidverbindungen mit Phenolen üblich sind und wie sie z. B. in DE-A 15 43 884 offenbart sind. The modified epoxy resins are produced by reacting Epoxy compounds with at least two epoxy groups with aromatic Hydroxycarboxylic acids (phenol carboxylic acids), the molar ratio of Epoxy groups to the sum of the carboxylic acid and hydroxyl groups Hydroxycarboxylic acids are in the range from 2: 1 to 6: 5. The implementation takes place according to the conditions also used for the reaction of epoxy compounds Phenols are common and how they z. B. are disclosed in DE-A 15 43 884.
Aus CHIMIE DES PEINTURES Nr. 386 (Dez. 1987), Seiten 426-430 ist auch die Umsetzung von Epoxidverbindungen wie z. B. Bisphenol A-Diglycidylether mit Hydroxycarbonsäuren bekannt. Dabei werden aber die Reaktanten in exakt stöchiometrischen Verhältnissen der Epoxidgruppen zu der Summe aus Hydroxyl- und Carbonsäuregruppen miteinander eingesetzt. Erhalten werden dabei Produkte mit im wesentlichen endständigen Carbonsäuregruppen weil auch die bei der primären Reaktion der Epoxidgruppen mit Hydroxylgruppen der Hydroxycarbonsäuren entstehenden sec. Hydroxylgruppen mit Epoxidgruppen reagieren. From CHIMIE DES PEINTURES No. 386 (Dec. 1987), pages 426-430 is also the Implementation of epoxy compounds such. B. bisphenol A diglycidyl ether Hydroxycarboxylic acids are known. But the reactants are in exact stoichiometric ratios of the epoxy groups to the sum of hydroxyl and Carboxylic acid groups used together. Products with im essential terminal carboxylic acid groups because also those in the primary reaction of the epoxy groups with hydroxyl groups of the hydroxycarboxylic acids resulting sec. Hydroxyl groups react with epoxy groups.
Es ist daher überraschend, daß bei Umsetzung der Epoxidverbindungen mit aromatischen Hydroxycarbonsäuren selbst bei geringfügiger Änderung der Mengenverhältnisse der eingesetzten Reaktionspartner eine im Prinzip andere Reaktion im Sinne einer Bildung von Advancementharzen mit endständigen Epoxidgruppen erfolgt. It is therefore surprising that when the epoxy compounds are reacted with aromatic ones Hydroxycarboxylic acids even with a slight change in the proportions of the used reaction partner a basically different reaction in the sense of a formation of Advancement resins with terminal epoxy groups.
Für die erfindungsgemäße Umsetzung sind alle Epoxidverbindungen mit mehr als einer Epoxidgruppe geeignet. Insbesondere geeignet sind Biphenyldiglycidylether, Bisphenol A- oder Bisphenol F-Diglycidylether, epoxidierte Novolake, Bisphenolnovolake oder Kresolnovolake, Glycidylether aliphatischer Di- oder Polyole einschließlich der Glycidylether des Glycerins, Trimethylolpropans oder Pentaerythrits, Tetrakis(4- hydoxyphenyl)ethan-tetragylcidylether, Triglycidyl-p-aminophenol, Hexahydrophthalsäurediglycidylester, 3,4-Epoxycyclohexancarboxylat oder N,N,N',N'- tetraglycidyl-4,4'-diaminodiphenylmethan. All epoxy compounds with more than one are for the implementation according to the invention Suitable epoxy group. Biphenyl diglycidyl ether, bisphenol A- are particularly suitable. or bisphenol F-diglycidyl ether, epoxidized novolaks, bisphenol novolaks or Cresol novolaks, glycidyl ethers of aliphatic di- or polyols including the Glycidyl ether of glycerol, trimethylolpropane or pentaerythritol, tetrakis (4- hydoxyphenyl) ethane tetragyl cidyl ether, triglycidyl p-aminophenol, Hexahydrophthalic acid diglycidyl ester, 3,4-epoxycyclohexane carboxylate or N, N, N ', N'- tetraglycidyl-4,4'-diaminodiphenylmethane.
Die eingesetzten Hydroxycarbonsäuren sind aromatische Hydroxycarbonsäuren, auch Phenolcarbonsäuren genannt, wie o- oder p-Hydroxybenzoesäure, Dihydroxybenzoesäure oder Gallussäure. The hydroxy carboxylic acids used are aromatic hydroxy carboxylic acids, too Called phenol carboxylic acids, such as o- or p-hydroxybenzoic acid, dihydroxybenzoic acid or gallic acid.
Zur Herstellung der modifizierten Epoxidharze werden Epoxidverbindungen und die Hydroxycarbonsäuren im molaren Verhältnis von 2 : 1 bis 6 : 5 in an sich bekannter Weise unter Einwirkung eines an sich bekannten Katalysators bei Temperaturen im Bereich von 120 bis 180°C miteinander umgesetzt. Die Umsetzung erfolgt entweder in einer Schmelze der Reaktanten oder in der Lösung in einem hochsiedenden inerten Lösemittel. Die dabei anfallenden Harzlösungen können direkt als Lackharzlösungen eingesetzt werden. Festharze werden bevorzugt in Form von Pellets aus der Schmelze ausgetragen. To produce the modified epoxy resins, epoxy compounds and the Hydroxycarboxylic acids in a molar ratio of 2: 1 to 6: 5 in a manner known per se under the action of a known catalyst at temperatures in the range of 120 to 180 ° C implemented with each other. The reaction takes place either in a melt of the reactants or in solution in a high boiling inert solvent. The one there Resin solutions can be used directly as paint resin solutions. Solid resins are preferably discharged from the melt in the form of pellets.
Die Abkürzung GT bedeutet Gewichtsteile The abbreviation GT means parts by weight
In einem mit Rührer, Thermometer und Zugabevorrichtung versehenen Reaktor werden 2640 g (2 mol) epoxidierter Novolak (Epoxyäquivalentgewicht: 211 g/Äquivalent; Schmelzviskosität bei 150°C: 1.450 mPA.s) in Butylglykolacetat (BGA) bei 120°C gelöst. Unter Rühren werden nacheinander 2 g Katalysator (Ethyltriphenylphosphoniumacetat) und 138 g (1 mol) Salicylsäure zugegeben. Das Reaktionsgemisch wird auf 155 bis 160°C erwärmt und solange bei dieser Temperatur gehalten, bis die Säurezahl < 1 mgKOH/g ist. Es entsteht ein modifiziertes Epoxidharz mit einem Molekulargewicht von etwa 2778 g/mol, dessen 65%ige Lösung in BGA bei 25°C eine Viskosität von 4.600 mPa.s beträgt. In a reactor equipped with a stirrer, thermometer and addition device 2640 g (2 mol) epoxidized novolak (epoxy equivalent weight: 211 g / equivalent; Melt viscosity at 150 ° C: 1,450 mPA.s) dissolved in butyl glycol acetate (BGA) at 120 ° C. 2 g of catalyst (ethyl triphenylphosphonium acetate) are added in succession with stirring. and 138 g (1 mol) of salicylic acid were added. The reaction mixture is at 155 to 160 ° C. heated and kept at this temperature until the acid number is <1 mgKOH / g. The result is a modified epoxy resin with a molecular weight of approximately 2778 g / mol, whose 65% solution in BGA at 25 ° C has a viscosity of 4,600 mPa.s
712 g (2 Mol) Bisphenol-A-diglycidylether (Epoxyäquivalent: 178 g) werden unter Rühren
auf 140-160°C erhitzt. Nach Zugabe von 0,5 g Triphenylphosphin als Katalysator werden
portionsweise 138 g (1 Mol) Salicylsäure zugegeben. Nach einer Reaktionszeit von 3 h bei
160°C ist die Reaktion beendet und es resultiert ein festes Epoxidharz mit folgenden
Werten:
Viskosität bei 120°C: 2300 mPa.s
Epoxyäquivalent: 450 g/Äquivalent
712 g (2 mol) of bisphenol A diglycidyl ether (epoxy equivalent: 178 g) are heated to 140-160 ° C. with stirring. After adding 0.5 g of triphenylphosphine as a catalyst, 138 g (1 mol) of salicylic acid are added in portions. After a reaction time of 3 h at 160 ° C, the reaction is complete and a solid epoxy resin results with the following values:
Viscosity at 120 ° C: 2300 mPa.s
Epoxy equivalent: 450 g / equivalent
712 g (2 Mol) Bisphenol-A-diglycidylether (Epoxyäquivalent: 178 g) werden unter Rühren
auf 140-160°C erhitzt. Nach Zugabe von 0,5 g Triphenylphosphin als Katalysator werden
portionsweise 228 g (1 Mol) Bisphenol A zugegeben. Nach einer Reaktionszeit von 3 h bei
160°C ist die Reaktion beendet und es resultiert ein festes Epoxidharz mit folgenden
Werten:
Viskosität bei 120°C: 2600 mPa.s
Epoxyäquivalent: 485 g/Äquivalent
712 g (2 mol) of bisphenol A diglycidyl ether (epoxy equivalent: 178 g) are heated to 140-160 ° C. with stirring. After adding 0.5 g of triphenylphosphine as catalyst, 228 g (1 mol) of bisphenol A are added in portions. After a reaction time of 3 h at 160 ° C, the reaction is complete and a solid epoxy resin results with the following values:
Viscosity at 120 ° C: 2600 mPa.s
Epoxy equivalent: 485 g / equivalent
Zur Bestimmung der Formstoffeigenschaften werden Prüfkörper aus jeweils 100 g der
Harze gemäß der Beispiele 2 und 3 in Verbindung mit Phthalsäureanhydrid (PSA) als
Härter und Tris-dimethylaminomethylphenol (DMP 30) als Beschleuniger hergestellt und
nach der Härtung geprüft.
Harzformulierungen
To determine the properties of the molding material, test specimens are produced from 100 g of the resins according to Examples 2 and 3 in connection with phthalic anhydride (PSA) as the hardener and tris-dimethylaminomethylphenol (DMP 30) as the accelerator and are tested after hardening. resin formulations
Nach der Härtung (jeweils 4 h bei 120°C und 12 h Nachhärtung bei 140°C) werden
folgende Ergebnisse erhalten:
After curing (4 hours each at 120 ° C and 12 hours post-curing at 140 ° C), the following results are obtained:
Claims (10)
in der n eine Zahl von 1 bis 5 ist und
R ein Biphenyl-, ein Bisphenyl- oder ein Naphthyl-Rest oder ein Rest eines Novolak-, Bisphenolnovolak- oder Kresolnovolak-Polyglycidylethers, eines Alkyl- Diglycidylethers, des Tetrakis(4-hydoxyphenyl)ethan-tetragylcidylethers, Triglycidyl-p-aminophenols, Hexahydrophthalsäurediglycidylesters, 3,4- Epoxycyclohexancarboxylats oder N,N,N',N'-tetraglycidyl-4,4'- diaminodiphenylmethans bei dem jeweils zwei oder mehr Glycidylethergruppen fehlen,
R1 ein Phenylenrest
R' und R" gleich oder verschieden sind und Wasserstoff oder eine Hydroxylgruppe bedeuten. 1. Modified epoxy resins of the general formula
in which n is a number from 1 to 5 and
R is a biphenyl, a bisphenyl or a naphthyl residue or a residue of a novolak, bisphenol novolak or cresol novolak polyglycidyl ether, an alkyl diglycidyl ether, the tetrakis (4-hydoxyphenyl) ethane-tetragylcidyl ether, triglyidyl-phenyl-phenyl-ethyl-phenyl-ethylenedyl-phenyl-tri-glycidyl ether-triglycidyl ether-triglycidyl ether-triglycidyl ether-triglycidyl ether-triglycidyl ether-triglycidyl ether-triglycidyl ether-triglycidyl ether , 3,4-epoxycyclohexane carboxylate or N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, each of which is missing two or more glycidyl ether groups,
R 1 is a phenylene radical
R 'and R "are the same or different and are hydrogen or a hydroxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2002123312 DE10223312A1 (en) | 2002-05-24 | 2002-05-24 | Modified epoxy resin for use e.g. as casting resin, paint resin or binder, contains groups derived from polyglycidyl ether compounds and aromatic hydroxy-carboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2002123312 DE10223312A1 (en) | 2002-05-24 | 2002-05-24 | Modified epoxy resin for use e.g. as casting resin, paint resin or binder, contains groups derived from polyglycidyl ether compounds and aromatic hydroxy-carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE10223312A1 true DE10223312A1 (en) | 2003-12-11 |
Family
ID=29432308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2002123312 Withdrawn DE10223312A1 (en) | 2002-05-24 | 2002-05-24 | Modified epoxy resin for use e.g. as casting resin, paint resin or binder, contains groups derived from polyglycidyl ether compounds and aromatic hydroxy-carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE10223312A1 (en) |
-
2002
- 2002-05-24 DE DE2002123312 patent/DE10223312A1/en not_active Withdrawn
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8127 | New person/name/address of the applicant |
Owner name: HEXION SPECIALTY CHEMICALS GMBH, 58642 ISERLOHN, D |
|
| 8141 | Disposal/no request for examination |