DE1074860B - Process for the preparation of polymeric compounds containing thiol groups and based on vinyl monochloroacetate - Google Patents
Process for the preparation of polymeric compounds containing thiol groups and based on vinyl monochloroacetateInfo
- Publication number
- DE1074860B DE1074860B DENDAT1074860D DE1074860DA DE1074860B DE 1074860 B DE1074860 B DE 1074860B DE NDAT1074860 D DENDAT1074860 D DE NDAT1074860D DE 1074860D A DE1074860D A DE 1074860DA DE 1074860 B DE1074860 B DE 1074860B
- Authority
- DE
- Germany
- Prior art keywords
- polymeric compounds
- preparation
- thiol groups
- compounds containing
- vinyl monochloroacetate
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 10
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- -1 Alkaline earth metal hydrosulfides Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 6
- 229920001567 Vinyl ester Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M Potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002522 swelling Effects 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
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/20—Esters containing halogen
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
Description
DEUTSCHESGERMAN
Mit Hilfe des im nachstehenden beschriebenen Verfahrens lassen sich in einfacher Weise und mit sehr guten Ausbeuten Thiolgruppen enthaltende polymere Verbindungen, die vornehmlich als Ionen- oder Elektronenaustauscher verwendet werden können, herstellen. Man geht dabei so vor, daß Monochloressigsäurevinylester in an sich bekannter Weise polymerisiert und das erhaltene Polymerisat im gelösten oder gequollenen Zustand mit Alkali- oder Erdalkalihydrosulfiden umgesetzt wird. Den genannten Monomeren können andere polymerisierbare monomere Verbindungen, die ebenfalls austauschfähige Gruppen enthalten können, zugesetzt und die daraus entstehenden Mischpolymerisate auf die genannte Weise in Thiolgruppen enthaltende makromolekulare Verbindungen übergeführt werden. Das erfindungsgemäße Verfahren läßt sich in besonders einfacher Weise derart durchführen, daß die Polymerisation der genannten Monomeren oder Monomerengemische in einer Flüssigkeit erfolgt, die für das entstehende Polymerisat Lösungsoder Quellungsmittel ist. In jenen Fällen, in denen die erfindungsgemäß hergestellten Produkte in Lösungsmitteln unlöslich oder unquellbar bzw. beschränkt quellbar sein sollen, läßt sich diese Eigenschaft in an sich bekannter Weise derart erzielen, daß dem zu polymerisierenden Monomeren oder Monomerengemisch vernetzend wirkende Zusätze, d. h. polymerisierbare Verbindungen mit mindestens 2 Kohlenstoffdoppelbindungen im Molekül, zugesetzt werden.With the help of the method described below can be in a simple manner and with very good yields of thiol group-containing polymeric compounds, which are primarily used as ion or electron exchangers can be used to produce. The procedure is such that vinyl monochloroacetate polymerized in a manner known per se and the polymer obtained in the dissolved or swollen state is reacted with alkali or alkaline earth metal hydrosulfides. The monomers mentioned can include other polymerizable monomeric compounds that are also interchangeable Groups may contain, added and the resulting copolymers based on the mentioned Way be converted into thiol groups containing macromolecular compounds. The inventive The process can be carried out in a particularly simple manner in such a way that the polymerization of the aforementioned Monomers or monomer mixtures takes place in a liquid that is a solvent or swelling agent for the resulting polymer. In those cases where the Products prepared according to the invention are insoluble or non-swellable or swellable to a limited extent in solvents should be, this property can be achieved in a manner known per se in such a way that the to be polymerized Additives having a crosslinking effect on monomers or a mixture of monomers, d. H. polymerizable compounds with at least 2 carbon double bonds in the molecule.
Es erscheint naheliegend, Polymercaptoessigsäurevinylester durch Polymerisation des entsprechenden Monomeren herzustellen. Versuche, zu diesem Monomeren auf eine dem erfindungsgemäßen Vorgehen analoge Weise zu kommen, d. h. Monochloressigsäurevinylester mit z. B. Alkalihydrosulfid umzusetzen, führen nicht zu dem gewünschten Erfolg, vielmehr entstehen auf diese Weise andere Produkte von bisher nicht näher bekannter Zusammensetzung.It seems obvious, polymercaptoacetic acid vinyl ester by polymerizing the corresponding monomer. Try to use a to come in a manner analogous to the procedure according to the invention, d. H. Vinyl monochloroacetate with z. B. Reacting alkali hydrosulfide does not lead to the desired success, rather arise in this way other products of previously unknown composition.
Mit Hilfe des grundsätzlich gleichen Vorgehens lassen sich auch Polymerisate von höheren Mercaptofettsäurevinylestern, z. B. Polymercaptopropionsäurevinylester oder Polymercaptobuttersäurevinylester, herzustellen, jedoch steht die praktische Bedeutung der so herstellbaren Produkte hinter der des Polymercaptoessigsäurevinylesters zurück.With the help of basically the same procedure, polymers of higher mercapto fatty acid vinyl esters, z. B. Polymercaptopropionic acid vinyl ester or Polymercaptobutyric acid vinyl ester, to prepare, however, the practical importance of the products which can be prepared in this way is behind that of the polymercaptoacetic acid vinyl ester return.
Der Austausch von Halogen gegen Mercaptogruppen ist zwar aus der niedermolekularen Chemie bekannt, jedoch hat die Übertragung der gleichen Reaktion auf polymere Verbindungen, wie Polyvinylchlorid, Polyvinylidenchlorid, Poly-p-chlorstyrol oder anderen chlorhaltigen makromolekularen Verbindungen, bisher im allgemeinen nicht zu entsprechenden Ergebnissen geführt. Es muß daher als überraschend bezeichnet werden, daß im vorliegenden Fall der Ersatz des Halogens durch die Marcaptogruppe in glatter Reaktion erfolgt und dabei Verfahren zur HerstellungThe exchange of halogen for mercapto groups is known from low molecular weight chemistry, however, the transfer of the same reaction to polymeric compounds, such as polyvinyl chloride, polyvinylidene chloride, Poly-p-chlorostyrene or other chlorine-containing macromolecular compounds, so far not generally led to corresponding results. It must It should therefore be described as surprising that in the present case the replacement of the halogen by the marcapto group takes place in smooth reaction and doing process of manufacture
von Thiolgruppen enthaltendenof containing thiol groups
polymeren Verbindungen auf Grundlagepolymeric compounds based
von Monochloressigsäurevinylesterof vinyl monochloroacetate
Anmelder:
Röhm & Haas G.m.b.H., DarmstadtApplicant:
Röhm & Haas GmbH, Darmstadt
Dr. Ernst Trommsdorff, Darmstadt,
und Dr. Herbert Zima, Darmstadt-Eberstadt,Dr. Ernst Trommsdorff, Darmstadt,
and Dr. Herbert Zima, Darmstadt-Eberstadt,
sind als Erfinder genannt wordenhave been named as inventors
technisch wertvolle Produkte, die als Ionen- und Elektronenaustauscher geeignet sind, erhalten werden.technically valuable products that act as ion and electron exchangers are suitable to be obtained.
60 g Monochloressigsäurevinylester wurden mit 0,06 g Benzoylperoxyd versetzt und unter Stickstoffatmosphäre im Licht polymerisiert. Das erhaltene Produkt wurde in 1,51 Aceton gelöst und in einem Rührkolben bei 50° C unter starkem Rühren mit einer Lösung von 69 g Kaliumhydrosulfid in 1,75 1 absolutem Alkohol langsam versetzt. Das Reaktionsprodukt fiel als weißer, flockiger Niederschlag aus. 1 Stunde nach Beendigung der Zugabe des Kaliumhydrosulfids wurde die weiße Fällung abfiltriert, mit einem Aceton-Alkohol-Gemisch (1:1) gewaschen und mit 3%iger Salzsäure behandelt. Schließlich wurde das Harz mit Wasser bis zur neutralen Reaktion gewaschen und im Vakuum bei etwa 500C getrocknet. Es wies einen Schwefelgehalt von 18,6% auf. Die Ausbeute betrug 77% der Theorie.60 g of vinyl monochloroacetate were mixed with 0.06 g of benzoyl peroxide and polymerized in the light under a nitrogen atmosphere. The product obtained was dissolved in 1.5 liters of acetone and a solution of 69 g of potassium hydrosulfide in 1.75 1 of absolute alcohol was slowly added in a stirred flask at 50 ° C. with vigorous stirring. The reaction product precipitated out as a white, flaky precipitate. 1 hour after the addition of the potassium hydrosulfide had ended, the white precipitate was filtered off, washed with an acetone-alcohol mixture (1: 1) and treated with 3% strength hydrochloric acid. Finally, the resin was washed with water until it had a neutral reaction and dried at about 50 ° C. in vacuo. It had a sulfur content of 18.6%. The yield was 77% of theory.
60 g Monochloressigsäurevinylester wurden unter Zusatz von 0,5% Divinylbenzol und 0,1 % Benzoylperoxyd in UV-Licht polymerisiert. Das spröde Produkt wurde zerrieben und mit 860 ecm Aceton während 24 Stunden angequollen. Das erhaltene Gemisch wurde unter starkem Rühren bei 500C mit einer Lösung von 39 g Kaliumhydrosulfid in 860 ecm absolutem Alkohol versetzt. Das gequollene, farblose Polymerisat färbte sich weiß. Nach60 g of vinyl monochloroacetate were polymerized in UV light with the addition of 0.5% divinylbenzene and 0.1% benzoyl peroxide. The brittle product was triturated and swollen with 860 ecm acetone for 24 hours. The resulting mixture was added under vigorous stirring at 50 0 C with a solution of 39 g of potassium hydrosulfide in 860 cc of absolute alcohol. The swollen, colorless polymer turned white. To
12stündigem Stehen wurde das Harzpulver von der Lösung abgetrennt, mit einem Aceton-Alkohol-Gemisch und danach mit 3 %iger Salzsäure behandelt. Dann wurde bis zur neutralen Reaktion mit Wasser gewaschen und getrocknet. Das Harz enthielt 13,2% Schwefel.Standing for 12 hours, the resin powder was separated from the solution with an acetone-alcohol mixture and then treated with 3% hydrochloric acid. It was then washed with water until the reaction was neutral and dried. The resin contained 13.2% sulfur.
909 728/539909 728/539
Claims (3)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1074860B true DE1074860B (en) | 1960-02-04 |
Family
ID=598822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1074860D Pending DE1074860B (en) | Process for the preparation of polymeric compounds containing thiol groups and based on vinyl monochloroacetate |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1074860B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE281688C (en) * | 1913-07-03 | |||
| DE829223C (en) * | 1947-07-05 | 1952-01-24 | Rohm & Haas | Process for the preparation of insoluble anion exchange resins |
| DE841796C (en) * | 1947-07-05 | 1952-06-19 | Rohm & Haas | Process for the preparation of insoluble resins for anion exchange |
| DE848256C (en) * | 1949-05-28 | 1952-09-01 | Rohm & Haas | Process for the production of insoluble ion resin exchangers |
| DE848257C (en) * | 1949-05-28 | 1952-09-01 | Rohm & Haas | Process for the production of insoluble ion resin exchangers |
-
0
- DE DENDAT1074860D patent/DE1074860B/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE281688C (en) * | 1913-07-03 | |||
| DE281687C (en) * | 1913-07-03 | |||
| DE829223C (en) * | 1947-07-05 | 1952-01-24 | Rohm & Haas | Process for the preparation of insoluble anion exchange resins |
| DE841796C (en) * | 1947-07-05 | 1952-06-19 | Rohm & Haas | Process for the preparation of insoluble resins for anion exchange |
| DE848256C (en) * | 1949-05-28 | 1952-09-01 | Rohm & Haas | Process for the production of insoluble ion resin exchangers |
| DE848257C (en) * | 1949-05-28 | 1952-09-01 | Rohm & Haas | Process for the production of insoluble ion resin exchangers |
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