DE1111396B - Process for the polymerization of vinyl acetate and vinyl chloride - Google Patents
Process for the polymerization of vinyl acetate and vinyl chlorideInfo
- Publication number
- DE1111396B DE1111396B DES67668A DES0067668A DE1111396B DE 1111396 B DE1111396 B DE 1111396B DE S67668 A DES67668 A DE S67668A DE S0067668 A DES0067668 A DE S0067668A DE 1111396 B DE1111396 B DE 1111396B
- Authority
- DE
- Germany
- Prior art keywords
- polymerization
- methanol
- vinyl acetate
- water
- vinyl
- 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims description 9
- 238000006116 polymerization reaction Methods 0.000 title claims description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 4
- 229920000642 polymer Polymers 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- -1 Heptane Tetrahydrofuran acetone Methanol Methanol - water Chemical compound 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
- C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
BUNDESREPUBLIK DEUTSCHLAND
DEUTSCHES Mt^Ik PATENTAMT FEDERAL REPUBLIC OF GERMANY
GERMAN Mt ^ Ik PATENT OFFICE
kl. 39 c 25/01 kl. 39 c 25/01
ESTERNAT.KL. C 08 fESTERNAT.KL. C 08 f
AUSLEGESCHRIFT 1111396EDITORIAL 1111396
S67668IVb/39cS67668IVb / 39c
"BEKANNTMACHUNG DER ANMELDUNG UNDAUSGABEDER AUSLEGESCHRIFT: 20. JULI 1961"NOTICE THE REGISTRATION ANDOUTPUTE EDITORIAL: JULY 20, 1961
Die vorliegende Erfindung betrifft eine Verbesserung der Verfahren zur Polymerisation von Vinylacetat und -chlorid in Gegenwart von Boralkylkatalysatoren. The present invention relates to an improvement in the methods of polymerizing vinyl acetate and chloride in the presence of boroalkyl catalysts.
Es ist bekannt, organische ungesättigte Verbindüngen in Gegenwart von Bortrialkylen als Katalysatoren zu polymerisieren und zu copolymerisieren. Als verwendbare Lösungsmittel wurden entweder nicht polare organische Lösungsmittel, wie aliphatische, alicyclische und aromatische Kohlen-Wasserstoffe, oder polare organische Lösungsmittel, wie Ketone oder Alkohole, oder Wasser vorgeschlagen. It is known to use organic unsaturated compounds to polymerize and copolymerize in the presence of boron trialkyls as catalysts. Either non-polar organic solvents such as aliphatic, alicyclic and aromatic hydrocarbons, or polar organic solvents, such as ketones or alcohols, or water are suggested.
In nicht polarem organischem Medium verläuft die Polymerisation langsam und unvollständig und führt zu Produkten mit niedriger Viskosität. Wenn man polare organische Lösungsmittel, wie beispielsweise Aceton oder Methanol, verwendet, so sind die Umwandlungsgrade höher, doch bleiben die Viskositäten gering; Methanol weist außerdem, insbesondere im Falle von Vinylacetat, den Nachteil auf, das Polymere zu lösen. Arbeitet man in wäßrigem Medium, so ist man gezwungen, Emulgiermittel zu verwenden, deren vollständige Entfernung von den erhaltenen Polymeren schwierig, wenn nicht unmöglich ist und die die Eigenschaften, insbesondere die elektrischen Eigenschaften der Polymeren nachteilig beeinflussen.In a non-polar organic medium, the polymerization proceeds slowly and incompletely and leads to products with low viscosity. If you have polar organic solvents, such as Acetone or methanol, the degrees of conversion are higher, but the viscosities remain small amount; Methanol also has the disadvantage, especially in the case of vinyl acetate, that the polymer to solve. If you work in an aqueous medium, you are forced to use emulsifiers, their complete removal of the polymers obtained is difficult, if not impossible, and the adversely affect the properties, in particular the electrical properties, of the polymers.
Es wurde nun gefunden, daß man ausgezeichnete Umwandlungsgrade und viel höhere Viskositäten erzielt, wenn man die Polymerisation von Vinylacetat und von Vinylchlorid mit Boralkylen in einem wäßrig-alkoholischen Medium durchführt, das aus einem Gemisch von Alkohol (z. B. Methyl- oder Äthylalkohol) und Wasser in einem solchen Mengenverhältnis besteht, daß das Monomere darin löslich ist, das Polymere jedoch ausfällt.It has now been found that there are excellent degrees of conversion and much higher viscosities achieved when the polymerization of vinyl acetate and vinyl chloride with boron alkylene in one Aqueous-alcoholic medium, which consists of a mixture of alcohol (e.g. methyl or Ethyl alcohol) and water in such a proportion that the monomer is soluble therein but the polymer precipitates.
Im Falle von Vinylacetat eignet sich ein Verhältnis von etwa 1 Volumen Methanol je 1 Volumen Wasser gut. Ein solches Gemisch löst etwa ein Drittel seines Volumens an Vinylacetat bei 20° C.In the case of vinyl acetate, a ratio of about 1 volume of methanol per 1 volume of water is suitable Well. Such a mixture dissolves about a third of its volume in vinyl acetate at 20 ° C.
Im Falle von Vinylchlorid kann man gleiche Mengenverhältnisse verwenden. Die Grenzen sind hier jedoch weit, und ein Gemisch von 20 Volumina Wasser und 60 Volumina Methanol ist ebenfalls noch geeignet.In the case of vinyl chloride, the same proportions can be used. The limits are here, however, far, and a mixture of 20 volumes of water and 60 volumes of methanol is also still available suitable.
Als Boralkyle kann man die niedrigen Bortrialkyle, wie beispielsweise Bortrimethyl, Bortriäthyl, Bortrin-propyl oder -triisopropyl, Bortributyle u. dgl., verwenden. The lower boron trialkyls, such as, for example, boron trimethyl, boron triethyl, boron-propyl, can be used as boron alkyls or triisopropyl, boron tributyls, and the like.
In der folgenden Tabelle sind die Versuchsergebnisse von Polymerisationen von Vinylacetat zusammengestellt, die bei 20° C mit 0,6% Bortri-Verfahren zur Polymerisation von Vinylacetat und VinylchloridIn the following table are the experimental results of polymerizations of vinyl acetate compiled that at 20 ° C with 0.6% Bortri process for the polymerization of vinyl acetate and vinyl chloride
Anmelder:Applicant:
Societe des Usines Chimiques Rhöne-Poulenc, ParisSociete des Usines Chimiques Rhone-Poulenc, Paris
Vertreter: Dr. F. Zumstein,Representative: Dr. F. Zumstein,
Dipl.-Chem. Dr. rer. nat. E. AssmannDipl.-Chem. Dr. rer. nat. E. Assmann
und Dipl.-Chem. Dr. R. Koenigsberger,and Dipl.-Chem. Dr. R. Koenigsberger,
Patentanwälte, München 2, Bräuhausstr. 4Patent Attorneys, Munich 2, Bräuhausstr. 4th
Beanspruchte Priorität-Frankreich vom 21. April 1959Claimed priority France from April 21, 1959
Andre Fournet, Gilbert Paul Christen und Rene Jean Marcel Chambard,Andre Fournet, Gilbert Paul Christen and Rene Jean Marcel Chambard,
Lyon (Frankreich), sind als Erfinder genannt wordenLyon (France) have been named as inventors
äthyl, bezogen auf das Monomere, und einer Dauer von 7 Stunden durchgeführt wurden.ethyl, based on the monomer, and a duration of 7 hours were carried out.
lungsgrad
°/oConversion
degree of efficiency
° / o
Viskosität *Specific
Viscosity *
Tetrahydrofuran
Aceton
Methanol
Methanol—Wasser,
50:50 Volumen
Methanol—Wasser,
55 :45 Volumen Heptane
Tetrahydrofuran
acetone
Methanol
Methanol - water,
50:50 volume
Methanol - water,
55: 45 volume
57,9
57,5
71,5
94,7
10039
57.9
57.5
71.5
94.7
100
0,036
0,100
0,130
0,329
0,3300.155
0.036
0.100
0.130
0.329
0.330
* Berechnet für eine Lösung mit 0,5 °/o in Benzol bei 25° C.* Calculated for a solution with 0.5% in benzene at 25 ° C.
Aus dieser Tabelle ist ersichtlich, daß die Polymerisation in dem Gemisch Methanol—Wasser quantitative Umwandlungen in Polymere mit einer Viskosität ermöglicht, die doppelt so hoch als die in anderen Lösungsmitteln erzielte ist.It can be seen from this table that the polymerization in the methanol-water mixture is quantitative Allows conversions to polymers with a viscosity twice that of other solvents.
109 648/445109 648/445
In der nachfolgenden Tabelle sind die Ergebnisse für die Polymerisation von Vinylchlorid bei — 20° C mit 2 g Katalysator und 500 g Lösungsmittel zusammengestellt. The table below shows the results for the polymerization of vinyl chloride at -20 ° C compiled with 2 g of catalyst and 500 g of solvent.
Lösungsmittelsolvent
des eingesetztenweight
of the used
des erhaltenenweight
of the received
lungsgradConversion
degree of efficiency
Heptan Heptane
Tetrahydrofuran Tetrahydrofuran
Diäthyläther Diethyl ether
Methanol Methanol
Methanol—Wasser, 80:20 Volumen ... Methanol—Wasser, 50:50 Volumen ... Methanol—Wasser, 50: 50 Volumen ...Methanol — water, 80:20 volume ... Methanol — water, 50:50 volume ... Methanol — water, 50:50 volume ...
* Berechnet für eine Lösung mit 0,5 °/o in Cyclohexanon bei 25° C.* Calculated for a solution with 0.5% in cyclohexanone at 25 ° C.
Aus dieser Tabelle ist ersichtlich, daß man bei Ersatz des Tetrahydrofurans und des Diäthyläthers durch Methanol zwar viel höhere Umwandlungsgrade erzielt, jedoch bei Verwendung von Gemischen Wasser—Methanol — bei Umwandlungsgraden, die ebenso hoch sind wie mit Methanol allein—Polymere mit sehr viel höherer spezifischer Viskosität erhält und diese um so größer ist, je mehr Wasser das Medium enthält.From this table it can be seen that when replacing tetrahydrofuran and diethyl ether Much higher degrees of conversion are achieved with methanol, but when mixtures are used Water — methanol - at degrees of conversion that are as high as with methanol alone — polymers with a much higher specific viscosity and this is the greater, the more water is in the medium contains.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR792696A FR1232428A (en) | 1959-04-21 | 1959-04-21 | Improvement in the polymerization processes of chloride and vinyl acetate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1111396B true DE1111396B (en) | 1961-07-20 |
Family
ID=8713915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DES67668A Pending DE1111396B (en) | 1959-04-21 | 1960-03-21 | Process for the polymerization of vinyl acetate and vinyl chloride |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE1111396B (en) |
| FR (1) | FR1232428A (en) |
| GB (1) | GB887398A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3138577A (en) * | 1961-10-12 | 1964-06-23 | Borden Co | Suspension polymerization of vinyl chloride and vinyl acetate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE570024A (en) * | ||||
| BE560624A (en) * | 1957-09-06 | |||
| BE569632A (en) * | 1958-07-22 | |||
| DE1056372B (en) * | 1956-07-14 | 1959-04-30 | Bayer Ag | Process for the polymerization of unsaturated compounds |
-
1959
- 1959-04-21 FR FR792696A patent/FR1232428A/en not_active Expired
-
1960
- 1960-03-21 DE DES67668A patent/DE1111396B/en active Pending
- 1960-03-30 GB GB1122660A patent/GB887398A/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE570024A (en) * | ||||
| DE1056372B (en) * | 1956-07-14 | 1959-04-30 | Bayer Ag | Process for the polymerization of unsaturated compounds |
| BE560624A (en) * | 1957-09-06 | |||
| BE562433A (en) * | 1957-09-06 | |||
| BE569632A (en) * | 1958-07-22 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3138577A (en) * | 1961-10-12 | 1964-06-23 | Borden Co | Suspension polymerization of vinyl chloride and vinyl acetate |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1232428A (en) | 1960-10-07 |
| GB887398A (en) | 1962-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1109901B (en) | Process for the production of polymers from olefin oxides | |
| DE1184960B (en) | Process for the production of halogen-containing polyethers containing terminal epoxyalkyl radicals | |
| DE1165268B (en) | Process for the preparation of higher molecular weight condensation products by reacting benzene or toluene with polyoxymethylenes | |
| DE1111396B (en) | Process for the polymerization of vinyl acetate and vinyl chloride | |
| DE1128148B (en) | Process for the preparation of polymeric alkylene oxides | |
| DE2437093C2 (en) | Process for preventing crosslinking of vinyl chloride-vinyltrialkoxysilane copolymers | |
| DE861156C (en) | Process for the production of polymers or copolymers of unsaturated compounds | |
| DE1264069B (en) | Process for the production of copolymers based on styrene and acrylonitrile that are stable against the effects of light and heat | |
| DE925130C (en) | Process for the preparation of Oxyaetheramiden of polyacrylic acid | |
| DE679587C (en) | Emulsion polymerization of butadiene or its derivatives | |
| DE746655C (en) | Process for the preparation of polymerization products | |
| DE719675C (en) | Process for the production of methacrylic polymers with a low degree of polymerization | |
| DE863415C (en) | Process for the production of synthetic rubber by emulsion polymerisation of isoprene with vinyl ethynyl alkyl carbinol | |
| DE1266502B (en) | Process for the production of high molecular weight polymers of vinyl alkyl ethers | |
| DE1180129B (en) | Process for stabilizing polyoxymethylenes | |
| DE1048028B (en) | Polymerization catalyst in solution for the production of polymers and copolymers from unsaturated organic compounds | |
| AT236646B (en) | Process for the production of high molecular weight formaldehyde polymers | |
| CH439718A (en) | Process for the preparation of aqueous dispersions | |
| DE703582C (en) | Process for the preparation of polymerization products from butadienes | |
| DE2411496A1 (en) | PROCESS FOR MANUFACTURING LIQUID POLYMERS WITH VERY HIGH VISCOSITY | |
| DE1128142B (en) | Process for the production of impact-resistant polystyrene | |
| DE750609C (en) | Process for polymerizing a vinyl acetate which is not very readily polymerizable | |
| DE1236779B (en) | Process for the production of high molecular weight polyoxymethylenes | |
| DE706177C (en) | Injection molding compounds | |
| DE767475C (en) | Lacquers |