DE1162568B - Process for the production of copolymers - Google Patents
Process for the production of copolymersInfo
- Publication number
- DE1162568B DE1162568B DER35254A DER0035254A DE1162568B DE 1162568 B DE1162568 B DE 1162568B DE R35254 A DER35254 A DE R35254A DE R0035254 A DER0035254 A DE R0035254A DE 1162568 B DE1162568 B DE 1162568B
- Authority
- DE
- Germany
- Prior art keywords
- copolymers
- unsaturated
- epoxy compounds
- methacrylic acid
- 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
- 229920001577 copolymer Polymers 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 fatty acid esters Chemical class 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 108010039491 Ricin Proteins 0.000 description 1
- LVZGQWKTUCVPBQ-UHFFFAOYSA-N acetic acid;trifluoroborane Chemical compound CC(O)=O.FB(F)F LVZGQWKTUCVPBQ-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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)
Description
Verfahren zum Herstellen von Mischpolymerisaten Mischpolymerisate aus harzartigen Epoxyverbindungen, verestert mit ungesättigten Fettsäuren, und monomeren polymerisierbaren Verbindungen, z. B.Process for the production of copolymers Copolymers made of resinous epoxy compounds, esterified with unsaturated fatty acids, and monomers polymerizable compounds, e.g. B.
Styrol, sind als Lackrohstoffe schon länger bekannt.Styrene has long been known as a paint raw material.
An Stelle des Styrols lassen sich auch monomere Acrylsäure- oder Methacrylsäurealkylester mit Ricinenfettsäureestern harzartiger Epoxyverbindungen mischpolymerisieren, wie es z. B. in der USA.-Patentschrift 2 689 834 beschrieben ist.Monomeric acrylic acid or methacrylic acid alkyl esters can also be used in place of styrene copolymerize with ricin fatty acid esters of resinous epoxy compounds, such as it z. As described in U.S. Patent 2,689,834.
Gegenstand eines älteren Vorschlags ist ein Verfahren, bei dem an Stelle der Ester von harzartigen Epoxyverbindungen mit ungesättigten Fettsäuren ätherartige ungesättigte Gruppen enthaltende Reaktionsprodukte aus harzartigen Epoxyverbindungen und Allylglycidyläther oder partiellen Allyläthern von mehrwertigen Alkoholen, z. B. Trimethylolpropandi- allyläther mit monomeren Acrylsäure- und/oder Methacrylsäurealkylestern, gegebenenfalls im Gemisch mit Acrylsäure oder Methacrylsäure und gegebenenfalls anderen Vinylverbindungen, mischpolymerisiert werden. An older proposal concerns a procedure in which an Place the esters of resinous epoxy compounds with unsaturated fatty acids ethereal unsaturated groups-containing reaction products of resinous epoxy compounds and allyl glycidyl ethers or partial allyl ethers of polyhydric alcohols, e.g. B. Trimethylolpropandi- allylether with monomeric acrylic and / or methacrylic acid alkyl esters, optionally in a mixture with acrylic acid or methacrylic acid and optionally other vinyl compounds.
Es wurde nun ein Verfahren zur Herstellung von Mischpolymerisaten mit verbesserten Eigenschaften gefunden, bei dem man Mischpolymerisate, die durch Polymerisation von ätherartigen Reaktionsprodukten aus harzartigen Epoxyverbindungen mit ungesättigte Äthergruppen tragenden partiellen Äthern mehrwertiger Alkohole bzw. mit ungesättigte Äthergruppen aufweisenden aliphatischen Epoxyverbindungen zusammen mit monomeren Acryl- und/oder Methacrylsäureestern, gegebenenfalls im Gemisch mit Acrylsäure oder Methacrylsäure und gegebenenfalls anderen Vinylverbindungen, hergestellt worden sind, mit p,y-ungesättigte Alkylreste tragenden Glycidyläthern umsetzt. There has now been a process for the production of copolymers found with improved properties, in which one copolymers, which by Polymerization of ethereal reaction products from resinous epoxy compounds with partial ethers of polyhydric alcohols bearing unsaturated ether groups or with aliphatic epoxy compounds containing unsaturated ether groups together with monomeric acrylic and / or methacrylic acid esters, optionally in a mixture with acrylic acid or methacrylic acid and optionally other vinyl compounds, have been prepared with glycidyl ethers carrying p, y-unsaturated alkyl radicals implements.
Die bei dem Verfahren der Erfindung als Ausgangspolymerisat eingesetzten Mischpolymerisate, deren Herstellung nicht Gegenstand der Erfindung ist, liefern bereits gegen Wasser und verdünntes wäßriges Alkali beständige und wetterfeste Lacke. The starting polymer used in the process of the invention Copolymers, the production of which is not the subject of the invention, provide Weatherproof paints that are already resistant to water and diluted aqueous alkali.
Durch das Verfahren der Erfindung wird die Härte der Mischpolymerisate bzw. der daraus herzustellenden Lackfilme jedoch in weiten Grenzen verbessert. The process of the invention increases the hardness of the copolymers or the paint films to be produced therefrom, however, are improved within wide limits.
Je nach der Menge des ß,y-ungesättigten Glycidyläthers läßt sich die Flexibilität und Härte der entstehenden Lackfilme weitgehend den Erfordernissen der Praxis anpassen.Depending on the amount of ß, γ-unsaturated glycidyl ether, the Flexibility and hardness of the resulting paint films largely meet the requirements adapt to practice.
Überraschenderweise hat es sich gezeigt, daß die durch nachträgliche Verätherung erhaltenen Mischpolymerisate sowohl bei Härtung an der Luft mittels Kobaltnaphthenat als auch beim Einbrennen Lackfilme ergeben, die eine sehr hohe Beständigkeit gegenüber aromatischen Treibstoffen haben. Surprisingly, it has been shown that the subsequent Copolymers obtained etherification both by curing in air Cobalt naphthenate as well as baking paint films result in a very high Have resistance to aromatic fuels.
Die angegebenen Teile sind Gewichtsteile, soweit nicht anders angegeben. The parts given are parts by weight, unless otherwise stated.
Herstellung des Ausgangsmischpolymerisats Die hierfür als Ausgangsmaterialien dienenden harzartigen Epoxyverbindungen leiten sich von Reaktionsprodukten zweiwertiger Phenole mit Epichlorhydrin ab und entstehen z. B. in bekannter Weise bei der Umsetzung von 4,4'-Dihydroxydiphenyl-dimethylmethan mit Epichlorhydrin in alkalischer Lösung. Production of the starting copolymers The starting materials for this Serving resinous epoxy compounds are derived from reaction products of divalent Phenols with epichlorohydrin and arise z. B. in a known manner in the implementation of 4,4'-dihydroxydiphenyl-dimethylmethane with epichlorohydrin in an alkaline solution.
Es entstehen bei dieser Reaktion in Abhängigkeit von Reaktionsbedingungen durch Ausbildung 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.It is formed in this reaction depending on the reaction conditions through the formation of ether bridges, resin-like products of different molecular weights, each of which has a glycidyl residue at both ends and one, depending on the size of the molecule or have multiple secondary hydroxyl groups.
450 Teile einer harzartigen Epoxyverbindung mit einem Molgewicht von etwa 900 und einem Epoxywert von etwa 0,2 und 286 Teile Cyclohexanon werden bis zur Lösung erwärmt. Bei 1000 C läßt man ein Gemisch aus 214 Teilen Trimethylolpropandiallyläther und 1 cma Borfluoridessigsäure in 30 Minuten zulaufen. Nach dem Einfließen hält man noch die Temperatur weitere 30 Minuten auf 100"C und stellt dann mit Xylol eine 50°/Oige Lösung her. Der anfängliche Epoxywert von 0,2 sinkt auf einen Wert von 0,008 ab. 220 Teile der 50 0/0eigen Lösung werden mit 93 Teilen Cyclohexanon und 92 Teilen Xylol in einem mit Rührer ausgestatteten Reaktionsgefäß auf 130"C erwärmt. Ein Gemisch aus 148 Teilen Methylmethacrylat, 38 Teilen Butylmethacrylat und 1,5 Teilen di-tert.Butylperoxyd läßt man innerhalb von 2 Stunden zulaufen, wobei die Temperatur auf 130"C gehalten wird. Die Viskosität einer 40 0/0eigen Lösung des Reaktionsproduktes beträgt 185 DIN-sec. 450 parts of a resinous epoxy compound having a molecular weight of about 900 and an epoxy value of about 0.2 and 286 parts of cyclohexanone warmed to solution. A mixture of 214 parts of trimethylolpropane diallyl ether is left at 1000.degree and 1 cma borofluoride acetic acid run in in 30 minutes. Holds after flowing in the temperature is raised to 100 "C for a further 30 minutes and then set with xylene 50% solution. The initial epoxy value of 0.2 drops to a value of 0.008 from. 220 parts of the 50% strength solution are mixed with 93 parts of cyclohexanone and 92 parts of xylene were heated to 130.degree. C. in a reaction vessel equipped with a stirrer. A mixture of 148 parts of methyl methacrylate, 38 parts of butyl methacrylate and 1.5 Parts of di-tert-butyl peroxide are left within 2 hours run towards the temperature being kept at 130 "C. The viscosity of a 40% strength solution of the reaction product is 185 DIN-sec.
Beispiel Zu der wie oben beschrieben hergestellten Lösung wird bei 1200C eine Lösung von 0,5 cm3 Bortrifluoridessigsäure in 10 cm3 Cyclohexanon gegeben. Dann läßt man in 30 Minuten 50 Teile Allylglycidyläther hinzufließen und die Verätherung bei gleichbleibender Temperatur ablaufen. Der Epoxywert beträgt 0,01, bezogen auf Allylglycidyläther, und die Lösung hat bei einem Feststoffgehalt von 40 °/0 eine Viskosität von 140 DIN-sec. Example The solution prepared as described above is added to 1200C a solution of 0.5 cm3 of boron trifluoride acetic acid in 10 cm3 of cyclohexanone was added. Then 50 parts of allyl glycidyl ether are allowed to flow in over 30 minutes and the etherification is carried out run at a constant temperature. The epoxy value is 0.01 based on Allyl glycidyl ether, and the solution has a solids content of 40 ° / 0 Viscosity of 140 DIN-sec.
Die vorteilhaften Eigenschaften des nach dem Verfahren der Erfindung hergestellten Produktes zeigen sich darin, daß nach Zusatz von Kobaltnaphthenat bei der Lufttrocknung Lackfilme mit guter Treibstoff- festigkeit erhalten werden, die durch Einbrennen noch verbessert wird. The advantageous properties of the according to the method of the invention produced product show that after the addition of cobalt naphthenate with air drying paint films with good fuel stability is maintained, which is further improved by baking.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER35254A DE1162568B (en) | 1962-01-18 | 1962-01-18 | Process for the production of copolymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER35254A DE1162568B (en) | 1962-01-18 | 1962-01-18 | Process for the production of copolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1162568B true DE1162568B (en) | 1964-02-06 |
Family
ID=7404564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DER35254A Pending DE1162568B (en) | 1962-01-18 | 1962-01-18 | Process for the production of copolymers |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1162568B (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 |
-
1962
- 1962-01-18 DE DER35254A patent/DE1162568B/en active Pending
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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