[go: up one dir, main page]

DE1049581B - Process for the polymerization of organic compounds - Google Patents

Process for the polymerization of organic compounds

Info

Publication number
DE1049581B
DE1049581B DENDAT1049581D DE1049581DA DE1049581B DE 1049581 B DE1049581 B DE 1049581B DE NDAT1049581 D DENDAT1049581 D DE NDAT1049581D DE 1049581D A DE1049581D A DE 1049581DA DE 1049581 B DE1049581 B DE 1049581B
Authority
DE
Germany
Prior art keywords
polymerization
organic
salts
peroxide
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.)
Pending
Application number
DENDAT1049581D
Other languages
German (de)
Inventor
Oberursel Dipl.-Chem. Wilhelm Querfurth (Taunus), Dipl.-Chem. Dr. Erich Bäder, Hanau/M., und Dr. Otto Schweitzer, Königstein (Taunus)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Deutsche Gold und Silber Scheideanstalt
Priority date (The priority date 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 date listed.)
Publication date
Publication of DE1049581B publication Critical patent/DE1049581B/en
Pending legal-status Critical Current

Links

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

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)
  • Polymerization Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

DEUTSCHESGERMAN

Es ist bekannt,; organische Verbindungen mit: endständigen oder mittelständigen Doppelbindungen zwischen 2 Kohlenstoffatomen zu polymerisieren. Als solche Verbindungen kommen beispielsweise Styrol oder seine Derivate, Acrylsäure und Methacrylsäure oder: ihre Ester, Vinylverbindungen, Acrylnitril, Butadien, Chlorbutadien, Dimethylbutadien, für sich oder in Gemischen miteinander, .in.., Betracht.' Die Polymerisation dieser Verbindungen kann in Lösung oder Emulsion oder im Block durchgeführt werden. Für viele Zwecke kann mit Vorteil ein System polymerisiert werden, das aus einer Lösung oder Suspension eines hochmolekularen Stoffes in einem polymerisierbaren monomeren Stoff besteht. Derartige Mischungen können z. B. mit gutem Erfolg für "Dentalzwecke' verwendet werden. "It is known,; to polymerize organic compounds with : terminal or central double bonds between 2 carbon atoms. Such compounds include, for example, styrene or its derivatives, acrylic acid and methacrylic acid or: their esters, vinyl compounds, acrylonitrile, butadiene, chlorobutadiene, dimethylbutadiene, alone or in mixtures with one another, .in ... The polymerization of these compounds can be carried out in solution or emulsion or in the block. For many purposes, a system can be polymerized with advantage, which consists of a solution or suspension of a high molecular weight substance in a polymerizable monomeric substance. Such mixtures can, for. B. be used with good success for "dental purposes".

Als Katalysatoren für die Polymerisation dieser Stoffe sind Redoxsysteme Vorgeschlagen worden, die einerseits Sauerstoff, wie z. B. Luftsauerstoff, vorzugsweise aber Sauerstoff in peroxydischer Form, wie z.B. Benzoylperoxyd, enthalten. Als reduzierende Bestandteile derartiger Redoxysysteme sind Sulfinsäuren oder ihre Salze, a-Oxysulf one oder ihre Salze, SuIf oxylverbindungen, wie das durch Umsetzen von Natriumhydrosulfit mit Formaldehyd erhaltene Natriumformaldehydsulfoxylat oder die entsprechenden Zink-, Calcium- oder Wismutsalze, a-Aminosulfone, besonders von sekundären oder tertiären Aminen, und Mercaptane vorgeschlagen worden.Redox systems have been proposed as catalysts for the polymerization of these substances, on the one hand Oxygen, such as B. atmospheric oxygen, but preferably oxygen in peroxide form, such as benzoyl peroxide, contain. Sulfinic acids or theirs are the reducing components of such redox systems Salts, a-oxysulfones or their salts, sulfoxyl compounds, such as the sodium formaldehyde sulfoxylate obtained by reacting sodium hydrosulfite with formaldehyde or the corresponding zinc, calcium or bismuth salts, α-aminosulfones, especially of secondary or tertiary amines, and mercaptans have been proposed.

Es wurde nun gefunden, daß die Blockpolymerisation derartiger Systeme erheblich beschleunigt und verbessert werden kann, wenn als Polymerisationsbeschleuniger organische Oniumverbindungen verwendet werden. Als derartige, an sich bekannte Verbindungen seien die Phosphonium-, Arsonium- oder Stiboniumsalze genannt oder die entsprechenden Salze von Quecksilber, Zink, Wismut, Zinn oder Blei.It has now been found that the bulk polymerization of such systems is considerably accelerated and improved can be used when organic onium compounds are used as the polymerization accelerator. as Such compounds known per se may be mentioned as the phosphonium, arsonium or stibonium salts or the corresponding salts of mercury, zinc, bismuth, tin or lead.

Als besonders wirksam haben sich die organischen Ammonium-, Sulfonium- oder Oxoniumsalze der allgemeinen Formern ; The organic ammonium, sulfonium or oxonium salts of the general formulas have proven to be particularly effective ;

Verfahren zpr Polymerisation: organis.ch.ez VerbindungenProcess for polymerisation: organis.ch.ez connections

R,R,

R4 R 4

RiRi XX R2-OR 2 -O XX R2-SR 2 -S R3 R 3 V R3 VR 3

erwiesen/ in denen R1, R2, R3 und R4 gleiche oder verschiedene organische Radikale bedeuten, die mit einem Kohlenstoff direkt mit dem N-, S- oder O-Atom verbunden sind, χ bedeutet einen Säurerest. Derartige Salze sind leicht zugänglich.proven / in which R 1 , R 2 , R 3 and R 4 denote identical or different organic radicals which are connected to a carbon directly with the N, S or O atom, χ denotes an acid radical. Such salts are readily available.

Es hat sich ferner gezeigt, daß die Wirksamkeit dieser Polymerisationsbeschleuniger noch weiter, verbessert werden kann, wenn man ihnen geringe Mengen vonIt has also been shown that the effectiveness of these polymerization accelerators Even further, it can be improved if you give them small amounts of

: Anmelder: ■.:.' ;: Applicant: ■.:. ' ;

Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, ' I-■German gold and silver separator formerly Roessler, 'I- ■

Ffänkfurt/M., Weißfrauenstr. 9 'Ffänkfurt / M., Weißfrauenstr. 9 '

Dipl.-Chem. Wilhelm Querfurth, Oberursel (Taunu$J, ': Dipl.-Chem. Dr. 'Erich Bäder, Hanau/M., jDipl.-Chem. Wilhelm Querfurth, Oberursel (Taunu $ J, ': Dipl.-Chem. Dr. 'Erich Bäder, Hanau / M., J

und Dr. Otto Schweitzer, Königstein (Taunus), ; sind als Erfinder genannt worden iand Dr. Otto Schweitzer, Koenigstein (Taunus),; have been named as inventors i

Schwermetallverbindungen, wie z. B. Kupfer- o-der Eisenverbindungen und/öder geringe Mengen ein- o;der mehrwertiger aliphatischer Alkohole, wie z. B. Methanol, Äthanol oder ein Glykol, zusetzt. \Heavy metal compounds, such as. B. copper or the Iron compounds and / or small amounts of one or the other polyhydric aliphatic alcohols, such as. B. methanol, ethanol or a glycol is added. \

Für viele Zwecke hat es sich als vorteilhaft erwiesen, dem Gemisch organische oder anorganische Säuren, wie Acrylsäure, Methacrylsäure oder Phosphorsäure, jzuzusetzen, und zwar in solchen Mengen, daß etwa vorhandene freie Basen gebunden werden. ' ■-.' } For many purposes it has been found to be advantageous to add organic or inorganic acids, such as acrylic acid, methacrylic acid or phosphoric acid, to the mixture in such amounts that any free bases present are bound. '■ -.' }

Schließlich hat es sich in manchen Fällen, gezeigt, daß es vorteilhaft ist, das Polymerisationsgemisch nicht ganz wasserfrei zu halten, sondern für die Gegenwart geringer Wassermengen zu sorgen* · ; jFinally, it has been shown in some cases that it is advantageous not to keep the polymerization mixture completely anhydrous, but to ensure the presence of small amounts of water * · ; j

Über die Ergebnisse von Versuchen mit Mischungen gemäß der Erfindung gibt die nachstehende Tabelle I eine Übersicht. Hierbei wurde jeweils ein Gemisch von 1,3 g polymeren Methacrylsäuremethylester mit" 0,75 ml monomer em Methacrylsäuremethylester unter Zusatz der in der Tabelle erwähnten Stoffe bei einer Ausgangstemperatur von .22 bis 23° C polymerisiert und die Zeit bis zur Erreichung des Temperaturmaximums festgestellt. - — : - '·-.· - · Table I below gives an overview of the results of tests with mixtures according to the invention. In each case, a mixture of 1.3 g of polymeric methyl methacrylate with 0.75 ml of monomeric methyl methacrylate was polymerized with the addition of the substances mentioned in the table at an initial temperature of .22 to 23 ° C and the time to reach the maximum temperature was determined. - - : - '· -. · - ·

Über die Ergebnissev^einer weiteren Versuchsreihe unterrichtet die Tabelle II. ~ jAbout the results of a further series of experiments informs Table II. ~ j

809 747/467809 747/467

. Quartäre Verbindungen. Quaternary connections " TabeUe I"TabeUe I PeroxydPeroxide 2% Methanol2% methanol Weitere ZusätzeOther additions —- PolymeriPolymeri 2% Methanol2% methanol 5% Methacryl
säure5% methacrylic
acid sations-
zeitstation
Time 0,5 % Triäthyl-benzyl-änimonium-
chlorid0.5% triethyl-benzyl-denimonium-
chloride S-haltige StaftmittelS-containing agents —- 2% Methanol2% methanol lOyCu+ +
(als Acetyl-
acetonat)lOyCu + +
(as acetyl
acetonate) 0,5«/ο H3PO4 0.5 «/ ο H 3 PO 4 MinutenMinutes 0,5 °/ö Octadecyl-dimethyi-benzyl-
affiraoniumchlorid0.5 ° / ö octadecyl-dimethyl-benzyl-
affiraonium chloride —- 2% Methanol2% methanol 1Oy Cu+ +1Oy Cu ++ 3% Methacryl
säure3% methacrylic
acid 88th 0,5 % Octadecyl-diinethyl'benzyl-
amiiioniumclüorid0.5% octadecyl-diinethyl'benzyl-
amiiionium chloride 2°/0 Toluolsülfinsäure 2 ° / 0 Toluolsülfinsäure —- —- 1Oy Cu++1Oy Cu ++ 7% Methacryl
säure
0,6"/0H3PO4 7% methacrylic
acid
0.6 "/ 0 H 3 PO 4 ■11■ 11 2.2. 0,5 Q/j Dodecyl-dibenzyl-rnethyl-
arnmoniurnchlorid0.5 Q / j dodecyl-dibenzyl-methyl-
ammonium chloride 2 0J0 toluolsulfinSäures-Nä2 0 J 0 toluenesulfinic acid Na 1 °/„ Benzoyl-
peroxyd1 ° / "Benzoyl
peroxide 2% Methanol2% methanol 1Oy Cu++1Oy Cu ++ —- 3.3. 0,5 ö/ö Pheityläthyl-dibütyl-äthyl-
ammoniumchlorid0.5 ö / ö phenylethyl-dibutyl-ethyl-
ammonium chloride 2 0J0 toluolsulfinsäures»Nä2 0 J 0 toluenesulfinic acid »Nä l,5°/0Benzoyl-
peroxydl, 5 ° / 0 benzoyl
peroxide —- 5 y Fe++-*
(als Naph-
thenat)5 y Fe ++ - *
(as naph-
thenat) ii V2 ii V 2 4.4th 0,5 % Dödecyl-dibenzyl-methyl-
ammoniumchlorid0.5% dodecyl-dibenzyl-methyl-
ammonium chloride 2 °/0 toluolsulfinsaures-Na2 ° / 0 toluolsulfinsaures-Na —- 2% Methanol2% methanol 1Oy Cu++1Oy Cu ++ —- 93/4 9 3/4 5.5. 0,5 % Triäthyl-benzyl-amrnoniuitt-
chlorid0.5% triethylbenzyl ammonia
chloride 1 % benzolsulfinsaures-Ca1% benzenesulfinic acid-Ca 2% 1,3-Bu-
tandiol2% 1,3-Bu-
tandiol 1Oy Cu+ +1Oy Cu ++ —- 77th 6.6th 0,5 °/a Äthanol-diäthyl-benzyl-
ammoniümchlorid0.5 ° / a ethanol diethyl benzyl
ammonium chloride 2»/0 CH3-C6H4-SO2-CH2OH2 »/ 0 CH 3 -C 6 H 4 -SO 2 -CH 2 OH —- 2% Methanol2% methanol 1Oy Cu++1Oy Cu ++ —- 13Va13Va 7,7, 0,5 % Öctadecyl-dimethyl-benzyl-
ammoniumcMorid0.5% octadecyl-dimethyl-benzyl-
ammonium chloride 2% (CH3 · C6H4 · SO2 · CH2)aN C2H5 2% (CH 3 • C 6 H 4 • SO 2 • CH 2 ) a NC 2 H 5 —- 2% Methanol2% methanol 1Oy Cu++1Oy Cu ++ 99 8.8th. 0,5 % Octadecyl-dimethyR>enzyl-
ammoniurnchlorid0.5% octadecyl-dimethyR> enzyl-
ammonium chloride 2% (CH3 · C6H4 · SO2 · CH2J8 N C2H6 2% (CH 3 • C 6 H 4 • SO 2 • CH 2 J 8 NC 2 H 6 —- 1Oy Cu+ +1Oy Cu ++ 99 9.9. 0,5 °/o Dodecyl-dibenzyl-methyl-
amtnoniumchlori d0.5% dodecyl-dibenzyl-methyl-
amtnoniumchlori d 2% (CH3 ■ C6H4 -SO2- CH2)a N C2H6 2% (CH 3 · C 6 H 4 -SO 2 -CH 2 ) a NC 2 H 6 1 % Benzoyl·
pefoxyd1% benzoyl
pefoxyd 1Oy Cu++1Oy Cu ++ 1010 10.10. 2% (CH3 - C6H4 -SO2 · CH2)äN C2H4 · C6H5 2% (CH 3 - C 6 H 4 -SO 2 X CH 2) ä NC 2 H 4 · C 6 H 5 1010 11-11- 1% (CH3C6H4SO2-CH2)2 NH1% (CH 3 C 6 H 4 SO 2 -CH 2 ) 2 NH

Quartale VerbindungenQuarterly connections Tabelle I (Fortsetzung)Table I (continued) PeroxydPeroxide 2% Methanol2% methanol Weitere ZusätzeOther additions 5 % Acrylsäure5% acrylic acid Polymeri-Polymeric 2% Methanol2% methanol 1,5% Meth
acrylsäure1.5% meth
acrylic acid sations-
zeitstation
Time 0,5 % Dodecyl-dibenzyl-methyl-
ammoniumchlorid0.5% dodecyl-dibenzyl-methyl-
ammonium chloride S-haltige StartmittelS-containing starting agents —- 2 % Methanol2% methanol 1Oy Cu+ +1Oy Cu ++ l,5%p-Toluol-
sulfonsäure1.5% p-toluene
sulfonic acid MinutenMinutes 0,5 % Triäthyl-benzyl-ammonium-
methacrylat0.5% triethyl benzyl ammonium
methacrylate —- 2% Methanol2% methanol 1Oy Cu++1Oy Cu ++ —- 1111 12.12th 0,5 % Triäthyl-benzyl-ammonium- .
p-toluolsulfonat0.5% triethyl benzyl ammonium.
p-toluenesulfonate 1 % Dodecylmercaptan1% dodecyl mercaptan —- 2% Methanol2% methanol lOyCir*"·"lOyCir * "·" —- 99 13.13th 0,5 % Trimethyl-benzyl-ammonium-
phospbat0.5% trimethyl benzyl ammonium
phospbat 2% (CH3 ■ C6H4 · SO2 · CH2)2 N C2H5 2% (CH 3 • C 6 H 4 • SO 2 • CH 2 ) 2 NC 2 H 5 .—.— 1,7%1,2-Pro-
pandiol1.7% 1.2 per
pandiol 1Oy Cu++1Oy Cu ++ —- 1616 14.14th 0,5 °/0 Trimethyl-benzyl-ammonium-
nitrat0.5 ° / 0 trimethyl-benzyl-ammonium
nitrate 2% (CH3 · C6H4 · SO2 · CH2)2 N C2H8 2% (CH 3 • C 6 H 4 • SO 2 • CH 2 ) 2 NC 2 H 8 —- 1,70/,,1,2-Pro-
pandiol1.70 / ,, 1.2-Pro-
pandiol 1Oy Cu++1 Oy Cu + + ■■ ■' ■ __ ■ ■■■ ■ '■ __ ■ ■ 99 15.15th 0,5 °/0 Trimethyl-benzyl-ammonmm-
sulfat0.5 ° / 0 trimethyl-benzyl-ammonmm-
sulfate 2% (CH3 · C8H4 · SO2 · CH2)2 N C2H6 2% (CH 3 • C 8 H 4 • SO 2 • CH 2 ) 2 NC 2 H 6 —- 2% Wasser2% water 1Oy Cu++1Oy Cu ++ 1 % Acrylsäure1% acrylic acid 88th 16.16. 0,5% Phenyläthyl-dibutyl-methyl-
amuioniumsulfat0.5% phenylethyl-dibutyl-methyl-
ammonium sulfate 2% (CH3 · C6H4 · SO2 · CH2)2 N C2H6 2% (CH 3 • C 6 H 4 • SO 2 • CH 2 ) 2 NC 2 H 6 0,6%Dichlor-
peroxyd0.6% dichloro
peroxide 2% Wasser2% water 10 y Cu++10 y Cu ++ 2»y0H3PO4 2 »y 0 H 3 PO 4 91/·9 1 / · 17.17th 0,5 °/0 Phenyläthyl-dibutyl-methyl-
ammoniumbromid0.5 ° / 0 phenylethyl-dibutyl-methyl-
ammonium bromide 2% (CH3 · C6H4 · SO2 · CH2)2 N C2H6 2% (CH 3 • C 6 H 4 • SO 2 • CH 2 ) 2 NC 2 H 6 0,4% Benzoyl-
peroxyd0.4% benzoyl
peroxide lOyCu+ +lOyCu ++ 21.21. 0,5 % Phenyläthyl-dibutyl-methyl-0.5% phenylethyl-dibutyl-methyl- 0,8.% (CH3 ■ C6H4 · SO2 · CH2)2 NH0.8% (CH 3 • C 6 H 4 • SO 2 • CH 2 ) 2 NH 0,5%Dichlor-
benzoyl-
peroxyd0.5% dichloro
benzoyl
peroxide 2% Methanol2% methanol 1OyFeCl3 1OyFeCl 3 i 6i 6 22.22nd CIIIIIXI(JJIIlLIlIiOxXlUI IUCIIIIIXI (JJIIlLIlIiOxXlUI IU 2% Natriumformaldehydsulfoxylat2% sodium formaldehyde sulfoxylate 2% Methanol2% methanol 5 % Acrylsäure5% acrylic acid 88th 23.23 2 % Zinkformaldehydsulfoxylat2% zinc formaldehyde sulfoxylate —- 2% Methanol2% methanol 1Oy Cu+ +1Oy Cu ++ 5% Acrylsäure5% acrylic acid —- 10 y Cu++10 y Cu ++ nach
lSStd.
noch
; weichafter
lSStd.
still
; soft 24.24. 0,5 % Dodecyl-dibenzyl-methyl-
ammoniumchlorid0.5% dodecyl-dibenzyl-methyl-
ammonium chloride 2% (CH3 · C6H4 · SO2 · CH,), NCH3 2% (CH 3 • C 6 H 4 • SO 2 • CH,), NCH 3 1Oy Cu++1Oy Cu ++ - ti - ti 25.25th 1 % Dodecylmercaptan1% dodecyl mercaptan 26.26th —-

CJi OOCJi OO

Tabelle IITable II

Polyinerisatiönsfähiges GemischPolymerizable mixture Quartäre Verbindung (0,3 °/o)Quaternary connection (0.3%) S-haltiges Startmittel (2%)S-containing starting agent (2%) PerOxydePeroxyde Schwermetallzusatz'Heavy metal additive ' Polymeri-
sat'ions-
zeit
MinutenPolymeric
sat'ion
Time
Minutes 62°/0 ungesättigtes Polyesterharz
-^-_33:% Monostyrol
-}- ■ 5 % Acrylsäure62 ° / 0 unsaturated polyester resin
- ^ -_ 33 : % monostyrene
-} - ■ 5% acrylic acid Dodecyl-dibenzyl-methyl-
ammoniumchlorid. . ,Dodecyl-dibenzyl-methyl-
ammonium chloride. . , DodecylmercaptanDodecyl mercaptan 1 % Benzoyl-
peroxyd
2% Cumolhydro-
peroxyd1% benzoyl
peroxide
2% cumene hydro
peroxide 5 y Cu++/ml (als Acetyl-
acetonat)5 y Cu + + / ml (as acetyl
acetonate) 22 62 % ungesättigtes Polyesterharz62% unsaturated polyester resin Phenyläthyl-dibutyl-methyl-Phenylethyl-dibutyl-methyl- p-Toluolsulfinsäurep-toluenesulfinic acid . 1 % Benzoyl-. 1% benzoyl 1Oy Cu++/ml (als .Naphthenat)1Oy Cu ++ / ml (as naphthenate) 77th + 33 % Monostyrol
+ 5 % Acrylsäure+ 33% monostyrene
+ 5% acrylic acid ammoniumsulfatammonium sulfate peroxyd
2% Cumolhydro-
peroxydperoxide
2% cumene hydro
peroxide " 95% Äthylacrylat
+ 5 °/0 Acrylsäure"95% ethyl acrylate
+ 5 ° / 0 acrylic acid Phenyläthyl-dibutyl-methyl-
ammoniumsulfatPhenylethyl-dibutyl-methyl-
ammonium sulfate p-Toluolsulfinsäurep-toluenesulfinic acid 1 % Benzoyl-
peroxyd1% benzoyl
peroxide 1Oy Cu++/ml (als Naphthenat)1Oy Cu ++ / ml (as naphthenate) 11 95 % Äthylacrylat
+ 5 % Acrylsäure95% ethyl acrylate
+ 5% acrylic acid Trimethyl-benzyl-ammonium-
phosphatTrimethyl benzyl ammonium
phosphate CH3C6H4SO2CH2OHCH 3 C 6 H 4 SO 2 CH 2 OH 2%Benzoyl-
peroxyd
2%Cumolhydro-
peroxyd2% benzoyl
peroxide
2% cumene hydro
peroxide 1Oy Cu++/ml (als Naphthenat)1Oy Cu ++ / ml (as naphthenate) 22 95% Äthylacrylat
+ .■ 5% Acrylsäure ' -": 95% ethyl acrylate
+. ■ 5% acrylic acid '- ": Dodecyl-dibenzyl-methyl-
ammoniumchloridDodecyl-dibenzyl-methyl-
ammonium chloride (CH3C6H4SO2CH2)2NC2H5 (CH 3 C 6 H 4 SO 2 CH 2 ) 2 NC 2 H 5 —- 1Oy Cu++/ml (als Naphthenat) '■. 10y Cu ++ / ml (as naphthenate) '■. 2V2 2V 2 75 % Monostyrol
+ 20% Maleinsäureanhydrid. ■
+' 5% Acrylsäure75% monostyrene
+ 20% maleic anhydride. ■
+ '5% acrylic acid Dodecyl-dibenzyl-methyl-
ammoniumchloridDodecyl-dibenzyl-methyl-
ammonium chloride (CH3 C6H4SO2CH2)2NC2H4 C6H5 (CH 3 C 6 H 4 SO 2 CH 2 ) 2 NC 2 H 4 C 6 H 5 2%Lauroyl-
peroxyd...,.. .
2% Cumolhydro-
peroxyd2% lauroyl
peroxide ..., ...
2% cumene hydro
peroxide 10 y Cu++/ml (als Naphthenat)10 y Cu ++ / ml (as naphthenate) 2V2 2V 2 75 % Monostyrol
+ 20 % Maleinsäureanhydrid
+ 5 % Acrylsäure75% monostyrene
+ 20% maleic anhydride
+ 5% acrylic acid Dodecyl-dibenzyl-methyl-
ammoniumchloridDodecyl-dibenzyl-methyl-
ammonium chloride p-Tolüolsulfinsäurep-toluenesulfinic acid 2%Lauroyl-
peroxyd
2% Cumolhydro-
peroxyd ;2% lauroyl
peroxide
2% cumene hydro
peroxide; 1Oy Cu++/ml (als Naphthenat)1Oy Cu + + / ml (as naphthenate) IV2 IV 2 87% Diallyl-diglykol-carbonat
-|- 10 % Maleinsäureanhydrid
+ 3 % Acrylsäure87% diallyl diglycol carbonate
- | - 10% maleic anhydride
+ 3% acrylic acid Dodecyl-dibenzyl-methyl-
ammonium chlorid ■-Dodecyl-dibenzyl-methyl-
ammonium chloride ■ - (CH3CeH4SO2CH2)2NC2H6 (CH 3 C e H 4 SO 2 CH 2 ) 2 NC 2 H 6 2%Lauroyl-
.peroxyd.,
2% Cumolhydro-
peroxyd2% lauroyl
.peroxide.,
2% cumene hydro
peroxide 1Oy Cu++/ml (als Naphthenat)1Oy Cu + + / ml (as naphthenate) 33 84% DiaUyl-diglykol-carbonat
+ 10 % Maleinsäureanhydrid
■j- 6 % Acrylsäure84% dialyl diglycol carbonate
+ 10% maleic anhydride
■ j- 6% acrylic acid Dodecyl-dibenzyi-methjd-
ammonium chloridDodecyl-dibenzyi-methjd-
ammonium chloride " (CH3C6H4SÖ2CH2)2NC2H4C6H5 "(CH 3 C 6 H 4 SO 2 CH 2 ) 2 NC 2 H 4 C 6 H 5 2%Lauroyl-
peroxyd
2%Cumolhydro-
peroxyd2% lauroyl
peroxide
2% cumene hydro
peroxide 10y Cu++/ml (als Naphthenat)!10y Cu + + / ml (as naphthenate)! : 3: 3

Claims (5)

Patentansprüche:Patent claims: 1. Verfahren zur Blockpolymerisation organischer Verbindungen mit endständigen oder mittelständigen Doppelbindungen zwischen 2 Kohlenstofiatomen durch Katalyse mit Sauerstoff, vorzugsweise in peroxydischer Form, und mit organischen Schwefelverbindungen, wie Sulfinsäuren oder ihren Salzen, a-Oxysulfonen, Sulfoxylaten, a-Aminosulfonen oder Mercaptanen, dadurch gekennzeichnet, daß als Polymerisationsbeschleuniger organische Oniumsalze verwendet werden.1. Process for the bulk polymerization of organic compounds with terminal or intermediate positions Double bonds between 2 carbon atoms by catalysis with oxygen, preferably in peroxidic Form, and with organic sulfur compounds, such as sulfinic acids or their salts, a-oxysulfones, Sulphoxylates, α-aminosulphones or mercaptans, characterized in that as polymerization accelerators organic onium salts can be used. 2. Verfahren nach Anspruch 1, gekennzeichnet •durch die Verwendung von organischen Ammonium-, Sulfonium- oder Oxoniumsalzen als Polymerisationsbeschleuniger. 2. The method according to claim 1, characterized • by the use of organic ammonium, Sulfonium or oxonium salts as polymerization accelerators. 3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß als weitere Polymerisationsbeschleuniger Schwermetallverbindungen in geringen Mengen und/oder ein- oder mehrwertige aliphatische Alkohole verwendet werden.3. Process according to Claims 1 and 2, characterized in that as a further polymerization accelerator Heavy metal compounds are used in small amounts and / or mono- or polyhydric aliphatic alcohols. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß Säuren zugesetzt werden.4. Process according to claims 1 to 3, characterized in that acids are added. 5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Polymerisation in Gegenwart geringer Wassermengen durchgeführt wird.5. Process according to claims 1 to 4, characterized in that the polymerization in the presence small amounts of water is carried out. In Betracht gezogene Druckschriften:
Deutsche Patentschriften Nr. 863 414, 907 220.Considered publications:
German patent specifications No. 863 414, 907 220. ( 809 747/467 1.59(809 747/467 1.59
DENDAT1049581D 1954-07-30 Process for the polymerization of organic compounds Pending DE1049581B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE343642X 1954-07-30

Publications (1)

Publication Number Publication Date
DE1049581B true DE1049581B (en) 1959-01-29

Family

ID=6247088

Family Applications (1)

Application Number Title Priority Date Filing Date
DENDAT1049581D Pending DE1049581B (en) 1954-07-30 Process for the polymerization of organic compounds

Country Status (2)

Country Link
CH (1) CH343642A (en)
DE (1) DE1049581B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1146254B (en) * 1961-07-07 1963-03-28 Degussa Hardening fluid for curing monomeric, polymerizable, organic compounds
DE1301074B (en) * 1964-06-20 1969-08-14 Resart Ihm Ag Process for the preparation of polymerization products

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1146254B (en) * 1961-07-07 1963-03-28 Degussa Hardening fluid for curing monomeric, polymerizable, organic compounds
DE1301074B (en) * 1964-06-20 1969-08-14 Resart Ihm Ag Process for the preparation of polymerization products

Also Published As

Publication number Publication date
CH343642A (en) 1959-12-31

Similar Documents

Publication Publication Date Title
DE1720854C3 (en) Process for the production of macromolecular water-soluble polymers
EP0175317B1 (en) Process for the manufacture of polymers containing carboxylic groups
DE2406557A1 (en) DIESTERS OF ACRYLIC ACIDS CONTAINING HYDROXY GROUPS AND THEIR USE IN DENTAL MATERIAL
US2946770A (en) Polymerization of vinylidene compounds using organic peroxide, organic sulfur and quaternary ammonium compounds as catalysts
DE2508346A1 (en) PROCESS FOR THE PRODUCTION OF WATER-SOLUBLE, PRACTICAL LINEAR POLYMERISATE WITH HIGH MOLECULAR WEIGHT AND A POLYMERISATE PRODUCED BY THE PROCESS
DE1570758B2 (en) Process for the preparation of addition polymers having a terminal carboxyl group
DE4219700A1 (en) ADHESIVES FOR DENTIN
DE894321C (en) Process for polymerizing acrylic acid amides, particularly N-di-substituted acrylic acid amides
DE2142742C2 (en) Process for the production of ammonium polyacrylates
DE2546182C2 (en) Process for the production of a copolymer from styrene and acrylonitrile which is practically free of acrylonitrile
DE919432C (en) Process for the suspension polymerization of unsaturated organic compounds with a CH: C <group in the molecule
DE69311867T2 (en) Process for the preparation of crosslinked polymers containing carboxyl groups
DE1049581B (en) Process for the polymerization of organic compounds
DE2317712B2 (en) Thermoplastic molding compound
DE2163504A1 (en) Heat-cured rubber-modified acrylic copolymer
DE1221450B (en) Process for the production of copolymers of acrylic acid esters
DE2461164C2 (en) Process for telomerizing water-soluble acrylic compounds
DE2005043C3 (en) Process for the production of anaerobically polymerizable liquid mixtures with increased hardening speed
DE2919096A1 (en) METHOD FOR CLEANING ACRYLIC ACID ESTERHOMO OR MIXED POLYMERISATES BY LOWERING THE FREE ACRYLIC ACID ESTERMONOMER
EP0017897A1 (en) Thiocarbamoylhydroxylamine derivatives and their use as polymerization initiators
DE1170146B (en) Process for the production of high molecular weight polymers from unsaturated aldehydes by irradiation
DE941672C (en) Soil improvers
DE2257769A1 (en) COPOLYMERS AND METHOD OF MANUFACTURING THE SAME
DE2158196B2 (en) Process for preparing silver halide photographic emulsions
DE1595727C3 (en) Crosslinked acrylic acid copolymers which are insoluble in water, aliphatic and aromatic hydrocarbons