DE1163550B - Process for the production of copolymers from unsaturated resinous epoxy compounds - Google Patents
Process for the production of copolymers from unsaturated resinous epoxy compoundsInfo
- Publication number
- DE1163550B DE1163550B DENDAT1163550D DE1163550DA DE1163550B DE 1163550 B DE1163550 B DE 1163550B DE NDAT1163550 D DENDAT1163550 D DE NDAT1163550D DE 1163550D A DE1163550D A DE 1163550DA DE 1163550 B DE1163550 B DE 1163550B
- Authority
- DE
- Germany
- Prior art keywords
- epoxy compounds
- resinous epoxy
- copolymers
- unsaturated
- production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000003700 epoxy group Chemical group 0.000 title claims description 18
- 229920000647 polyepoxide Polymers 0.000 title claims description 17
- 229920001577 copolymer Polymers 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- -1 unsaturated ether alcohols Chemical class 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 150000001253 acrylic acids Chemical class 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- 230000000379 polymerizing Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- ZQEKJUQOXJAPRX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C.CCC(CO)(CO)CO ZQEKJUQOXJAPRX-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N Cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical class C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N Acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000180 Alkyd Polymers 0.000 description 1
- 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 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N Crotyl alcohol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N Methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N Trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MKUWVMRNQOOSAT-UHFFFAOYSA-N but-3-en-2-ol Chemical compound CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052904 quartz Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Resins (AREA)
Description
Verfahren zum Herstellen von Mischpolymerisaten aus ungesättigten harzartigen Epoxyverbindungen Mischpolymerisate aus harzartigen Epoxyverbindungen, verestert mit ungesättigten Fettsäuren und monomeren polymerisierbaren Verbindungen, z. B.Process for the production of copolymers from unsaturated resinous epoxy compounds copolymers of resinous epoxy compounds, esterified with unsaturated fatty acids and monomeric polymerizable compounds, z. B.
Styrol, sind schon länger als Lackrohstoffe bekannt. Styrene have long been known as a raw material for coatings.
An Stelle des Styrols lassen sich auch monomere Acrylsäure- oder Methacrylsäurealkylester mit harzartigen Epoxyverbindungen, die mit Ricinenfettsäure verestert sind, in Gegenwart von Peroxyden mischpolymerisieren, wie es z. B. in der USA.-Patentschrift 2 689 834 beschrieben ist. Es ist auch bereits bekannt, Mischpolymerisate aus polymerisierbaren, olefinisch ungesättigten esterartigen Derivaten von harzartigen Epoxyverbindungen, nämlich den Umsetzungsprodukten von Acryl- oder Methacrylchlorid mit Hydroxylgruppen enthaltenden harzartigen Epoxyverbindungen, durch Polymerisation in Gegenwart von Peroxyden und von 1 bis 60 Gewichtsprozent, bezogen auf die Reaktionsmischung, Acrylsäure- oder Methacrylsäuremethylester herzustellen. Instead of styrene, monomeric acrylic acid or Methacrylic acid alkyl ester with resinous epoxy compounds, those with ricineal fatty acid are esterified, copolymerize in the presence of peroxides, as z. Am U.S. Patent 2,689,834. It is also already known, copolymers from polymerizable, olefinically unsaturated ester-like derivatives of resin-like Epoxy compounds, namely the reaction products of acrylic or methacrylic chloride with hydroxyl group-containing resinous epoxy compounds by polymerization in the presence of peroxides and from 1 to 60 percent by weight, based on the reaction mixture, To produce acrylic acid or methacrylic acid methyl ester.
Es wurde nun ein weiteres Verfahren zur Herstellung von Mischpolymerisaten durch Polymerisation olefinisch ungesättigter Derivate von harzartigen Epoxyverbindungen zusammen mit Acrylsäure- oder Methacrylsäureestern in Anwesenheit von Peroxyden gefunden, bei dem man ungesättigte ätherartige Reaktionsprodukte von harzartigen Epoxyverbindungen, die durch Verätherung von Hydroxylgruppen enthaltenden harzartigen Epoxyverbindungen mit äquivalenten Mengen an ungesättigten Ätheralkoholen, die im Rest bzw. in den Resten des Monoalkohols polymensationsfähige Doppelbindungen tragen, hergestellt worden sind, mit einem Überschuß einer Verbindung aus der Gruppe der Acrylsäure oder deren Estern oder der alkylierten Acrylsäuren oder deren Estern mischpolymerisiert. There has now been a further process for the production of copolymers by polymerizing olefinically unsaturated derivatives of resinous epoxy compounds together with acrylic or methacrylic acid esters in the presence of peroxides found, in which one unsaturated ethereal reaction products of resinous Epoxy compounds obtained by etherification of hydroxyl group-containing resinous Epoxy compounds with equivalent amounts of unsaturated ether alcohols, which are im Carry the remainder or in the remainder of the monoalcohol polymerizable double bonds, have been prepared, with an excess of a compound from the group of Acrylic acid or its esters or the alkylated acrylic acids or their esters copolymerized.
Die Hydroxylgruppen enthaltenden harzartigen Epoxyverbindungen leiten sich vorzugsweise von Reaktionsprodukten zweiwertiger Phenole mit Epichlorhydrin ab und entstehen z. B. in bekannter Weise bei der Umsetzung von 4,4'-Dihydroxydiphenyldimethylmethan mit Epichlorhydrin in alkalischer Lösung. Es entstehen bei dieser Reaktion in Abhängigkeit von Reaktionsbedingungen durch Ausbildungen von Ätherbrücken harzartige Produkte unterschiedlichen Molekulargewichts, die an den beiden Enden je einen Glycidylrest tragen und je nach Molekülgröße eine oder mehrere sekundäre Hydroxylgruppen besitzen. The hydroxyl group-containing resinous epoxy compounds conduct preferably from reaction products of dihydric phenols with epichlorohydrin from and arise z. B. in a known manner in the implementation of 4,4'-dihydroxydiphenyldimethylmethane with epichlorohydrin in alkaline solution. In this reaction, there are dependencies of reaction conditions through the formation of ether bridges resin-like products different molecular weights, each with a glycidyl residue at the two ends wear and, depending on the size of the molecule, have one or more secondary hydroxyl groups.
Die Reaktionsprodukte dieser harzartigen Epoxyverbindungen mit Trimethylolpropandiallyläther, die gemäß der vorliegenden Erfindung eine der zur Mischpolymerisation fähigen Komponente darstellen, lassen sich in Gegenwart von Friedel-Crafts-Katalysatoren im Zuge einer Verätherungsreaktion leicht herstellen. Außer den bereits genannten Allylätherverbindungen lassen sich aus Allyl-, Methallyl-, Chlorallyl- und Crotylalkohol oder Methylvinylcarbinol einerseits und mehrwertigen Alkoholen, wie Glyzerin, Trimethyloläthan, Trimethylolpropan oder Pentaerythrit, eine Reihe andere ungesättigte Reste enthaltende Ätheralkohole herstellen. The reaction products of these resinous epoxy compounds with trimethylolpropane diallyl ether, according to the present invention, one of the components capable of interpolymerization represent, can be in the presence of Friedel-Crafts catalysts in the course of a Easily produce etherification reaction. Except for the allyl ether compounds already mentioned can be made from allyl, methallyl, chlorallyl and crotyl alcohol or methyl vinyl carbinol on the one hand and polyhydric alcohols such as glycerine, trimethylolethane, trimethylolpropane or pentaerythritol, a number of other unsaturated radicals containing ether alcohols produce.
Die Herstellung der ungesättigten ätherartigen Reaktionsprodukte von harzartigen Epoxyverbindungen ist jedoch nicht Gegenstand der Erfindung. The production of the unsaturated ethereal reaction products of resinous epoxy compounds is not the subject of the invention.
Die nach dem Verfahren der Erfindung hergestellten Mischpolymerisate sind beständig gegenüber Wasser und wäßrigem Alkali. Sie eignen sich vorzüglich zum Herstellen von Lackierungen für Kraftfahrzeuge und Haushaltsmaschinen, wie Waschmaschinen oder Kühlschränke. Die mit den Mischpolymerisaten hergestellten Lacke lassen sich unmittelbar, d. h. ohne Grundierung, auf Metalle auftragen. Sie ergeben eine besonders hohe Haftfestigkeit auf Kunstharzoberflächen und lassen sich deshalb ohne vorangehendes Aufrauhen ohne weiteres auf eingebrannte Alkyd-Melaminharzlackschichten aufspritzen und einbrennen, was im allgemeinen wegen der Gefahr des Abblätterns derart hergestellter Überzüge nicht möglich ist. Die Lackierungen zeichnen sich durch gute Wetterfestigkeit aus. The copolymers produced by the process of the invention are resistant to water and aqueous alkali. They are excellent for producing coatings for motor vehicles and household machines, such as washing machines or refrigerators. The paints produced with the copolymers can be immediately, d. H. Apply to metals without a primer. They make one special high adhesive strength on synthetic resin surfaces and can therefore be used without prior Simply spray the roughening onto stoved alkyd melamine resin lacquer layers and baking, which is generally so produced because of the risk of flaking Overlay is not possible. The paintwork is characterized by good weather resistance the end.
Herstellung der verätherten harzartigen Epoxyverbindungen Zu einer Lösung aus 425 Gewichtsteilen einer harzartigen Epoxyverbindung mit einem Molgewicht von etwa 1400 und einem Epoxywert von etwa 0,1 und 228 Gewichtsteilen Cyclohexanon läßt man bei 125° C ein Gemisch aus 130 Gewichtsteilen Trimethylolpropandiallyläther und 2 cm3 Borfluoridessigsäure zulaufen und steigert dann die Temperatur innerhalb zweier Stunden auf 140"C, wodurch der Epoxywert auf 0,001 sinkt. Darauf wird mit Xylol eine 500/0ige Lösung eingestellt.Preparation of the etherified resinous epoxy compounds Solution of 425 parts by weight of a resinous epoxy compound with a molecular weight of about 1400 and an epoxy value of about 0.1 and 228 parts by weight of cyclohexanone a mixture of 130 parts by weight of trimethylolpropane diallyl ether is left at 125.degree and 2 cm3 of borofluoride acetic acid run up and then increase the temperature to 140 "C within two hours, whereby the epoxy value drops to 0.001. Then a 500/0 solution is set with xylene.
Beispiel Mischpolymerisation 252 Gewichtsteile der 500/0eigen Lösung werden mit 75 Gewichtsteilen Cyclohexanon und 60 Gewichtsteilen Xylol im Reaktionsgefäß auf 130 C erwärmt. Example of copolymerization 252 parts by weight of the 500/0 solution with 75 parts by weight of cyclohexanone and 60 parts by weight of xylene in the reaction vessel heated to 130 C.
Ein Gemisch aus 135 Gewichtsteilen Butylacrylat und 1,5 Gewichtsteilen di-tert.-Butylperoxyd läßt man innerhalb zweier Stunden zur Reaktionslösung zulaufen und erwärmt noch weitere 2 Stunden bei 130 bis 140"C, erforderlichenfalls muß eine weitere Zugabe von Peroxydkatalysator zur Erreichung des theoretischen Körpergehaltes der Lösung erfolgen.A mixture of 135 parts by weight of butyl acrylate and 1.5 parts by weight Di-tert-butyl peroxide is allowed to run into the reaction solution within two hours and heats for a further 2 hours at 130 to 140 "C, if necessary one must further addition of peroxide catalyst to achieve the theoretical body content the solution.
Zum Vergleich wurden Mischpolymerisate, hergestellt nach dem Verfahren der USA.-Patentschrift 2 689 834, Beispiel 14, und gemäß Beispiel des Verfahrens nach der Erfindung, mit Titandioxyd zu einem Lack angerieben, mit Xylol-Diacetonalkohol-Poly glykoläther verdünnt und in dünner Schicht auf Glasscheiben und Eisenbleche aufgetragen. Diese Vergleichsproben wurden 15 Minuten bei etwa 100°C getrocknet und 50 Stunden unter einer Quarzlampe bestrahlt. Die Probeanstriche, die ein Mischpolymerisat, hergestellt gemäß USA.-Patentschrift 2 689 834, enthielten, waren deutlich vergilbt, während der ein Mischpolymerisat nach dem Beispiel der Erfindung enthaltende Probeanstrich keinerlei Vergilbung zeigte. For comparison, copolymers produced according to the method were used U.S. Patent 2,689,834, Example 14, and according to Example Procedure according to the invention, rubbed with titanium dioxide to form a varnish, with xylene-diacetone alcohol-poly Glycol ether diluted and applied in a thin layer to glass panes and iron sheets. These comparative samples were dried at about 100 ° C. for 15 minutes and 50 hours under a quartz lamp irradiated. The sample paints, which are a mixed polymer, are made U.S. Pat. No. 2,689,834, were significantly yellowed, while the sample paint containing a copolymer according to the example of the invention showed no yellowing.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1163550B true DE1163550B (en) | 1964-02-20 |
Family
ID=601287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1163550D Pending DE1163550B (en) | Process for the production of copolymers from unsaturated resinous epoxy compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1163550B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3670047A (en) * | 1968-10-08 | 1972-06-13 | Reichhold Albert Chemie Ag | Epoxy resins etherified with ethylenically unsaturated alcohols and copolymerized with carboxy containing monomers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2689834A (en) * | 1952-05-19 | 1954-09-21 | American Can Co | Copolymers of vinyl compounds, polyphenylether alcohols, and unsaturated fatty acids |
| US2890202A (en) * | 1953-07-20 | 1959-06-09 | Pittsburgh Plate Glass Co | Method of preparing acrylate esters of epoxy resins |
-
0
- DE DENDAT1163550D patent/DE1163550B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2689834A (en) * | 1952-05-19 | 1954-09-21 | American Can Co | Copolymers of vinyl compounds, polyphenylether alcohols, and unsaturated fatty acids |
| US2890202A (en) * | 1953-07-20 | 1959-06-09 | Pittsburgh Plate Glass Co | Method of preparing acrylate esters of epoxy resins |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3670047A (en) * | 1968-10-08 | 1972-06-13 | Reichhold Albert Chemie Ag | Epoxy resins etherified with ethylenically unsaturated alcohols and copolymerized with carboxy containing monomers |
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