DE373369C - Process for the production of vinyl esters of organic acids and their polymers - Google Patents
Process for the production of vinyl esters of organic acids and their polymersInfo
- Publication number
- DE373369C DE373369C DET23324D DET0023324D DE373369C DE 373369 C DE373369 C DE 373369C DE T23324 D DET23324 D DE T23324D DE T0023324 D DET0023324 D DE T0023324D DE 373369 C DE373369 C DE 373369C
- Authority
- DE
- Germany
- Prior art keywords
- organic acids
- vinyl esters
- pressure
- polymers
- compounds
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims description 8
- 229920001567 vinyl ester resin Polymers 0.000 title claims description 7
- 150000007524 organic acids Chemical class 0.000 title claims description 6
- 235000005985 organic acids Nutrition 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 title claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- -1 acetylene hydrocarbon Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical class [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 2
- 238000012986 modification Methods 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002730 mercury Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GOKCJCODOLGYQD-UHFFFAOYSA-N 4,6-dichloro-2-imidazol-1-ylpyrimidine Chemical compound ClC1=CC(Cl)=NC(N2C=NC=C2)=N1 GOKCJCODOLGYQD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000589614 Pseudomonas stutzeri Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Verfahren zur Herstellung von Vinylestern organischer Säuren und ihren Polymeren. Zusatz zum Patent 362750. Nach dem Hauptpatent können Salzsäuregas und Kohlenwasserstoffe der Acetylenreihe unter Anwendung von Druck ohne Zusatz von Katalysatoren zu Halogenvinylen kondensiert werden. Es wurde,nun gefunden, daß auf die gleiche Weise auch organische Carbonsäuren mit Kohlenwasserstoffen der Acetylenreihe kondensiert werden können.Process for the preparation of vinyl esters of organic acids and their polymers. Addition to patent 362750. According to the main patent, hydrochloric acid gas and hydrocarbons of the acetylene series can be condensed to form halovinylene using pressure without the addition of catalysts. It has now been found that organic carboxylic acids can also be condensed with hydrocarbons of the acetylene series in the same way.
Die Anlagerung von Halogenwasserstoff, also von starken anorganischen Säuren, an Acetylen erfolgt nach der österreichischen Patentschrift 69o66 und der französischen Patentschrift 462711 in Gegenwart von Quecksilberverbindungen als Katalysatoren und kann durch Anwendung von Druck beschleunigt werden. Danach war aber nicht vorauszusehen, daß die schwächeren organischen Carbonsäuren und Acetylen bereits ohne Mitverwendung von Katalysatoren allein durch erhöhten Druck unter Bildung von Estern des Vinylalkohols aufeinander wirken würden.The addition of hydrogen halide, i.e. strong inorganic ones Acids, acetylene takes place according to the Austrian patent specification 69o66 and the French patent 462711 in the presence of mercury compounds as Catalysts and can be accelerated by applying pressure. After that was but do not anticipate that the weaker organic carboxylic acids and acetylene even without the use of catalysts, solely through increased pressure with formation of esters of ethanol would interact.
Aus der Patentschrift 271381 und der französischen Patentschrift 461223 ist es bekannt, daß sich Ester des Vinylalkohols und des Äthylidenglykols bilden, wenn man Acetylen mit organischen Säuren in Gegenwart von Quecksilbersalzen zur Reaktion bringt.From patent specification 271381 and French patent specification 461223 it is known that esters of vinyl alcohol and ethylidene glycol are formed, when acetylene is used with organic acids in the presence of mercury salts Reaction brings.
Quecksilbersalze verteuern- und erschweren das Verfahren naturgemäß und verhindern außerdem ein ununterbrochenes Arbeiten, da sie mit der Zeit zu Metall reduziert werden, in ihrer katalytischen Wirkung nachlassen und schließlich ersetzt werden müssen.Mercury salts naturally make the process more expensive and more difficult and also prevent uninterrupted work, as they become metal over time be reduced, diminish in their catalytic effect and finally replaced Need to become.
Arbeitet man dagegen unter erhöhtem Druck, so verläuft das Verfahren einfacher und glatter als nach den bisherigen Methoden in Gegenwart von Katalysatoren. Durch gewisse Zusätze kann der Verlauf des Verfahrens beschleunigt werden. Wie festgestellt wurde, eignen sich als solche z. B. die Metalle Magnesium, Zinn, Kupfer oder ihre Verbindungen,. ferner Jod, Jodwasserstoff und Borverbindungen und organische Verbindungen, wie Anhydride oder Superoxyde organischer Säuren. Ihre Wirkung ist eigenartig; denn sie tritt nur unter erhöhtem, nicht bei gewöhnlichem Druck ein. Vor den Quecksilbersalzen besitzen sie den Vorzug größerer Beständigkeit. Sie brauchen nicht wie jene auf umständlichen Wegen regeneriert werden.If, on the other hand, you work under increased pressure, the process proceeds easier and smoother than previous methods in the presence of catalysts. The course of the process can be accelerated by adding certain additives. As stated was, are suitable as such z. B. the metals magnesium, tin, copper or theirs Links,. also iodine, hydrogen iodide and boron compounds and organic compounds, such as anhydrides or superoxides of organic acids. Their effect is peculiar; because it only occurs under increased, not ordinary, pressure. Before the mercury salts they have the advantage of greater durability. You don't need to like that cumbersome ways to be regenerated.
Das neue Verfahren gestattet schließlich, in einem Arbeitsgang zu den technisch wichtigen Polymerisationsprodukten der Vinylester zu gelangen, wenn man den Druck oder die Temperatur entsprechend erhöht oder die Einwirkungsdauer verlängert oder - diese Maßnahmen kombiniert.The new process finally allows in one operation to reach the technically important polymerization products of vinyl esters, if the pressure or the temperature or the duration of exposure are increased accordingly extended or - these measures combined.
Die Herstellung derartiger Polymerisationsprodukte von organischen Vinylestern ist an sich bekannt (v g1. z. B. die Patentschriften 281687 und 28i688). Man ging aber bisher von den isolierten Estern aus, während man nach der Erfindung vom Acetylen und einer Carbonsäure aus in einem einzigen Arbeitsgang, ohne ein Zwischenprodukt zu isolieren, die gewünschten Polymeren erhält.The preparation of such polymerization products of organic Vinyl star is known per se (v g1. e.g. the patents 281687 and 28i688). So far, however, the isolated esters have been used as the starting point according to the invention from acetylene and a carboxylic acid in a single Operation without isolating an intermediate product, the desired polymers are obtained.
Beispiel i.Example i.
Zu 6o Gewichtsteilen wasserfreier Essigsäure und i Teil Essigsäureanhydrid werden in einem druckfesten Gefäß 26 bis 28 Gewichtsteile trockenes Acitty len in kleinen Anteilen eingedrückt. Hierauf erwärmt man allmählich auf etwa 4o bis 6o'.To 60 parts by weight of anhydrous acetic acid and 1 part of acetic anhydride 26 to 28 parts by weight of dry Acitty len in a pressure-tight vessel indented small portions. Then the temperature is gradually increased to about 4o to 6o '.
Läßt man dieses Gemisch einige Stunden. in der Wärme und unter Druck, den man durch Zuführen eines inerten Gases, z. B. Stickstoff, auf ungefähr 5 Atm. hält, stehen, so wird das Acetylen von der Essigsäure absorbiert. Es bilden sich 75 Gewichtsteile Essigsäurevinylester, daneben 3 bis 5 Teile Athylidendiacetat.Leave this mixture for a few hours. in the warmth and under pressure, which can be obtained by supplying an inert gas, e.g. B. nitrogen, to approximately 5 atm. stands, the acetylene is absorbed by the acetic acid. It is formed 75 parts by weight of vinyl acetate, in addition 3 to 5 parts of ethylidene diacetate.
Den ersteren erhält man durch fraktionierte Destillation rein.The former is obtained pure by fractional distillation.
Beispiel z.Example
Man arbeitet nach Beispiel i, erhitzt aber nach der Bindung des Acetylens stärker und erhöht gleichzeitig den Druck. Bei einer Temperatur von etwa 12o bis 2oo° und einem Druck von io und mehr Atmosphären wird der primär gebildete Vinylester völlig in seine polymere Form übergeführt, die als mehr oder weniger zähe Masse erhalten wird.The procedure is as in Example i, but heating is carried out after the acetylene has been bonded stronger and at the same time increases the pressure. At a temperature of about 12o to 200 ° and a pressure of 10 and more atmospheres is the primarily formed vinyl ester completely converted into its polymeric form as a more or less viscous mass is obtained.
Durch Veränderung des Druckes, der Temperatur und der Reaktionsdauer können Endprodukte von verschiedenen Polymerisations- und Konsistenzgraden halbflüssig bis fest und mehr oder weniger zäh erhalten werden.By changing the pressure, the temperature and the reaction time end products of various degrees of polymerization and consistency can be semi-liquid until firm and more or less tough are obtained.
Die Essigsäure kann durch ihre Oxy-, Amino- und Chlorderivate oder Arylessigsäuren ersetzt «-erden. Auch aus Propionsäure oder rein aromatischen Säuren und Acetylen erhält man analoge Vinylester.The acetic acid can by its oxy, amino and chlorine derivatives or Aryl acetic acid replaces «earths. Also from propionic acid or purely aromatic acids and acetylene, analogous vinyl esters are obtained.
An Stelle des Acetylens können seine Homologen verwendet werden.Its homologues can be used in place of acetylene.
Schließlich kann das Verfahren auch in einer ununterbrochen arbeitenden Vorrichtung, deren Einzelheiten in dem Hauptpatent beschrieben sind, ausgeführt werden.Finally, the process can also work in an uninterrupted manner Device, the details of which are described in the main patent executed will.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DET23324D DE373369C (en) | 1918-05-25 | 1918-05-25 | Process for the production of vinyl esters of organic acids and their polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DET23324D DE373369C (en) | 1918-05-25 | 1918-05-25 | Process for the production of vinyl esters of organic acids and their polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE373369C true DE373369C (en) | 1923-04-12 |
Family
ID=7550943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DET23324D Expired DE373369C (en) | 1918-05-25 | 1918-05-25 | Process for the production of vinyl esters of organic acids and their polymers |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE373369C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE751853C (en) * | 1938-08-02 | 1951-10-31 | Albert Ag Chem Werke | Process for polymerizing vinyl compounds |
| US3033151A (en) * | 1960-06-30 | 1962-05-08 | Sheehan Leo James | Ship and pier fender |
-
1918
- 1918-05-25 DE DET23324D patent/DE373369C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE751853C (en) * | 1938-08-02 | 1951-10-31 | Albert Ag Chem Werke | Process for polymerizing vinyl compounds |
| US3033151A (en) * | 1960-06-30 | 1962-05-08 | Sheehan Leo James | Ship and pier fender |
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