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DE1128855B - Process for the production of phenol ethers or esters suitable as vulcanization or crosslinking agents for organic polymers - Google Patents

Process for the production of phenol ethers or esters suitable as vulcanization or crosslinking agents for organic polymers

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Publication number
DE1128855B
DE1128855B DEH35981A DEH0035981A DE1128855B DE 1128855 B DE1128855 B DE 1128855B DE H35981 A DEH35981 A DE H35981A DE H0035981 A DEH0035981 A DE H0035981A DE 1128855 B DE1128855 B DE 1128855B
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Germany
Prior art keywords
group
vulcanization
general formula
carboxylic acid
production
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Pending
Application number
DEH35981A
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German (de)
Inventor
Dr Helmut Ringsdorf
Dr Gerd Greber
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ELFRIEDE HUSEMANN DR
Original Assignee
ELFRIEDE HUSEMANN DR
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Filing date
Publication date
Application filed by ELFRIEDE HUSEMANN DR filed Critical ELFRIEDE HUSEMANN DR
Priority to DEH35981A priority Critical patent/DE1128855B/en
Publication of DE1128855B publication Critical patent/DE1128855B/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72Hydrazones
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00Compounds having —CHO groups
    • C07C47/52Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/575Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/21Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
    • C07C65/28Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups having unsaturation outside the aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025Crosslinking or vulcanising agents; including accelerators

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung von als Vulkanisations- oder Vernetzungsmittel für organische Polymere geeigneten Phenoläthern oder -estern Es wurde gefunden, daß eine Reihe von neuen ungesättigten Phenoläthern oder -estern mit reaktionsfähigen Gruppen der allgemeinen Formel CH2 = C(R)-R1-O-C6H4-X in welcher R ein Wasserstoffatom oder eine Alkylgruppe, R1 eine Methylen- oder eine Carbonylgruppe und X eine Aldehydgruppe, eine durch den Anilin-, Hydroxylamin- oder Phenylhydrazinrest substituierte Aldehydgruppe, eine Hydroxylgruppe, eine Carbonsäuregruppe, eine Carbonsäurealkyl- oder -arylestergruppe, eine Aminogruppe oder eine durch den Benzaldehydrest substituierte Aminogruppe bedeutet, durch Umsetzung eines o;-ungesättigten Alkylchlorids oder eines oc-ungesättigten Carbonsäurechlorids der allgemeinen Formel CH2 = C(R)-R1-Cl in welcher R und R1 die obige Bedeutung haben, mit einem Phenol in Gegenwart eines säurebindenden Mittels, gegebenenfalls einem Phenolat, der allgemeinen Formel HO-C6H4-X worin X die obige Bedeutung hat, hergestellt werden können. Die azomethingruppenhaltigen Phenoläther oder -ester lassen sich auch durch nachträgliche Umsetzung der aldehyd- oder aminogruppenhaltigen ungesättigten Phenoläther oder -ester mit den entsprechenden Verbindungen, wie z. B. Anilin oder Benzaldehyd, herstellen. Process for the preparation of as a vulcanizing or crosslinking agent Phenolic ethers or esters suitable for organic polymers It has been found that a number of new unsaturated phenolic ethers or esters with reactive Groups of the general formula CH2 = C (R) -R1-O-C6H4-X in which R is a hydrogen atom or an alkyl group, R1 a methylene or a carbonyl group and X an aldehyde group, an aldehyde group substituted by the aniline, hydroxylamine or phenylhydrazine radical, a hydroxyl group, a carboxylic acid group, a carboxylic acid alkyl or aryl ester group, denotes an amino group or an amino group substituted by the benzaldehyde radical, by reacting an o; -unsaturated alkyl chloride or an oc-unsaturated one Carboxylic acid chloride of the general formula CH2 = C (R) -R1-Cl in which R and R1 have the above meaning, with a phenol in the presence of an acid-binding agent, optionally a phenolate, of the general formula HO-C6H4-X in which X has the above Has meaning, can be produced. The phenol ethers containing azomethine groups or esters can also be obtained by subsequent reaction of the aldehyde or amino groups unsaturated phenol ethers or esters with the appropriate compounds, such as. B. aniline or benzaldehyde.

Die verfahrensmäßig hergestellten Phenoläther- oder -ester sind als Vernetzungsmittel verwendbar, denn sie ermöglichen auf Grund ihrer reaktionsfähigen Gruppen die Aufpfropfung der ungesättigten Phenoläther- oder -esterreste auf Polymere, welche geeignete funktionelle Gruppen tragen. Über diese ungesättigten Gruppen erfolgt dann beim Erhitzen eine Vernetzung der ursprünglichen Makromoleküle. Diese monomeren Phenoläther oder -ester können außerdem auch homo-und copolymerisiert werden, wobei die reaktionsfähigen Gruppen der so erhaltenen Polymerisate Pfropf- und Vernetzungsreaktionen ermöglichen. The phenolic ethers or esters produced by the process are as Crosslinking agents can be used because they allow due to their reactive Groups the grafting of unsaturated phenol ether or ester residues onto polymers, which carry suitable functional groups. Takes place through these unsaturated groups then, when heated, a crosslinking of the original macromolecules. These monomers Phenol ethers or esters can also be homo- and copolymerized, with the reactive groups of the polymers thus obtained, grafting and crosslinking reactions enable.

Beispiel 1 a) 24 g 4-Hydroxybenzaldehydkalium wurden in 200 ccm trockenem Äther aufgeschlämmt. Unter heftigem Rühren wurden bei Zimmertemperatur 14,1 g Methacrylsäurechlorid eingetropft. Die Reaktion verlief, obwohl sie heterogen ist, sehr rasch und unter schwacher Erwärmung. Nach der Säurechloridzugabe wurde noch 1/2 Stunde nachgerührt, von dem ausgeschiedenen Kaliumchlorid abfiltriert und die ätherische Lösung über Natriumsulfat getrocknet. Beim Abdestillieren des Äthers fiel das Rohprodukt als schwach gelbes Ö1 an. Als günstigstes Reinigungsverfahren erwies sich sie chromatographische Reinigung an Aluminiumoxyd. Die Ausbeute betrug 23 g, das sind etwa 900/o der Theorie. F. = 27 bis 28° C, Kpzoßol = 84 bis 85" C. Example 1 a) 24 g of 4-hydroxybenzaldehyde potassium were in 200 ccm of dry Ether slurried. With vigorous stirring, 14.1 g of methacrylic acid chloride were obtained at room temperature dripped in. The reaction, although heterogeneous, was very rapid and subtle weak heating. After the acid chloride had been added, the mixture was stirred for a further 1/2 hour, filtered off from the precipitated potassium chloride and the ethereal solution over Dried sodium sulfate. When distilling off the ether, the crude product fell as pale yellow Ö1. Chromatographic proved to be the most favorable purification method Cleaning with aluminum oxide. The yield was 23 g, which is about 900 / o of theory. F. = 27 to 28 ° C, Kpzoßol = 84 to 85 "C.

Analyse für CllHl003: Berechnet .. . C 69,45, H 5,31; gefunden .. ........ C 69,50, H 5,31, 69,70, 5,30. b) 85 ccm der ätherischen Lösung des 4-Methacryloxybenzaldehyd, wie sie oben erhalten wurde und die etwa 9,5 g Aldehyd enthielt, wurden mit 4,65 g Anilin versetzt und 1/2 Stunde am Rückfluß gekocht. Beim Einengen kristallisierte die Schiffsche Base aus. Sie wurde abgesaugt und aus Methanol umkristallisiert.Analysis for CllHl003: Calculated ... C 69.45, H 5.31; found .. ........ C 69.50, H 5.31, 69.70, 5.30. b) 85 cc of the ethereal solution of 4-methacryloxybenzaldehyde, as obtained above and which contained about 9.5 g of aldehyde, were 4.65 g of aniline are added and the mixture is refluxed for 1/2 hour. Crystallized on concentration the Schiff's base. It was filtered off with suction and recrystallized from methanol.

Es wurden farblose Kristallplättchen vom F. = 83 bis 84° C in einer Ausbeute von 12,5 g, das sind etwa 93 der Theorie, erhalten, die löslich in Benzol, Styrol, Methanol und Äther waren. Diese Verbindung polymerisiert und copolymerisiert radikalisch.There were colorless crystal flakes with a melting point of 83 to 84 ° C in one Yield of 12.5 g, that is about 93 of theory, obtained, which is soluble in benzene, Styrene, methanol and ether were. This compound polymerizes and copolymerizes radical.

Analyse für Cl7HlsNO2 Berechnet . . C 76,96, H 5,70, N 5,28; gefunden . C 76,77, H 5,79, N 5,51.Analysis calculated for Cl7HlsNO2. . C 76.96, H 5.70, N 5.28; found . C 76.77, H 5.79, N 5.51.

Beispiel 2 70,6 g 4-Hydroxybenzaldehydkalium wurden analog der Vorschrift im Beispiel 1 mit Acrylsäurechlorid umgesetzt. Das Rohprodukt ist ein schwach gelbes, nicht kristallisierendes Öl. Die Ausbeute betrug 18,5 g, das sind etwa 830/o der Theorie. Die Reinigung erfolgte ebenfalls durch chromatographische Adsorption der Verunreinigung an Aluminiumoxyd. Example 2 70.6 g of 4-hydroxybenzaldehyde potassium were obtained analogously to the instructions in example 1 with acrylic acid chloride implemented. The raw product is a pale yellow, non-crystallizing oil. The yield was 18.5 g that are about 830 / o of theory. The purification was also carried out by chromatography Adsorption of the impurity on aluminum oxide.

Hierbei fällt der Aldehyd in kristalliner Form an und kann bei 0°C ohne Stabilisator aufbewahrt werden.The aldehyde is obtained in crystalline form and can be used at 0 ° C stored without stabilizer.

F. = 29 bis 30°C, Kp. 126 bis 127°C.M.p. = 29 to 30 ° C, b.p. 126 to 127 ° C.

Analyse für CloH803 Berechnet , C 68,17,C68,17, H4,58; gefunden ................. C 68,55, H 5,02, 68,54, 5,05. Analysis for CloH803 Calculated, C 68.17, C68.17, H4.58; found ................. C 68.55, H 5.02, 68.54, 5.05.

Beispiel 3 21,7 g Benzyliden-Phydroxyanilin wurden mit 5,7 g KO H in 150 ccm Methanol umgesetzt, und danach wurden bei Siedetemperatur 14,5 g Allylbromid in das Gemisch eingetropft. Die sofort einsetzende KBr-Ausscheidung war nach etwa 3 Stunden beendet. Example 3 21.7 g of benzylidene-hydroxyaniline were mixed with 5.7 g of KO H reacted in 150 cc of methanol, and then 14.5 g of allyl bromide were added at the boiling point dripped into the mixture. The KBr excretion, which started immediately, was about Finished 3 hours.

Die filtrierte Lösung wurde eingeengt und die ausfallende Verbindung abgesaugt und aus Äthanol umkristallisiert. Es wurden farblose Kristalle vom F. = 72 bis 73°C in einer Ausbeute von 15,2 g, das sind etwa 64°/o der Theorie, erhalten, die löslich in Methanol und Benzol sind.The filtered solution was concentrated and the compound which precipitated was concentrated suctioned off and recrystallized from ethanol. Colorless crystals of F. = 72 to 73 ° C in a yield of 15.2 g, that is about 64% of theory, which are soluble in methanol and benzene.

Analyse für Cl6Hl5NO: Berechnet ............ C 80,98, H 6,37, N 5,90; gefunden ............ C 81,15, H 6,13, N 5,97, 81,17, 6,19.Analysis for Cl6Hl5NO: Calculated ............ C 80.98, H 6.37, N 5.90; Found ............ C 81.15, H 6.13, N 5.97, 81.17, 6.19.

Beispiel 4 12 g 4-Aminophenol wurden mit 5,7 g KO H in 100 ccm Methanol umgesetzt. In das Gemisch wurden bei Siedetemperatur 14,5 g Allylbromid eingetropft. Example 4 12 g of 4-aminophenol were mixed with 5.7 g of KO H in 100 cc of methanol implemented. 14.5 g of allyl bromide were added dropwise to the mixture at the boiling point.

Die KBr-Ausscheidung setzt sofort ein. Nach 3 Stunden wird die Lösung filtriert und das Methanol abdestilliert. Das Rohprodukt wird durch Destillation gereinigt. Die Ausbeute betrug etwa 51 0/o der Theorie, Kp. 103 bis 105° C. Das Produkt ist löslich in Methanol, Chloroform und Styrol.KBr excretion starts immediately. After 3 hours the solution will filtered and the methanol was distilled off. The crude product is made by distillation cleaned. The yield was about 51% of theory, Bp 103 to 105 ° C. The product is soluble in methanol, chloroform and styrene.

Analyse für CSHllON: Berechnet ...................... N 9,46, - ; gefunden ....................... N 9,62, 9,27.Analysis for CSHIION: Calculated ...................... N 9.46, -; found ....................... N 9.62, 9.27.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von als Vulkanisations- oder Vernetzungsmittel für organische Polymere geeigneten Phenoläthern oder -estern der allgemeinen Formel CH2 = C(R)-R1-O-CßH4-X in welcher R ein Wasserstoffatom oder eine Alkylgruppe, R1 eine Methylen- oder eine Carbonylgruppe und X eine Aldehydgruppe, eine durch den Anilin-, Hydroxylamin- oder Phenylhydrazinrest substituierte Aldehydgruppe, eine Carbonsäurealkyl- oder -arylestergruppe, eine Aminogruppe oder eine durch den Benzaldehydrest substituierte Aminogruppe bedeuten, durch Umsetzung eines oc-ungesättigten Alkylchlorids oder eines o;-ungesättigten Carbonsäurechlorids mit einem Phenol in Gegenwart von säurebindenden Mitteln, dadurch gekennzeichnet, daß man ein ungesättigtes Carbonsäurechlorid oder ein Allylhalogenid der allgemeinen Formel CH2= C(R)-R1-Cl in welcher R und R1 die obige Bedeutung haben, mit einem Phenol, gegebenenfalls einem Phenolat, der allgemeinen Formel HO-CßH4-X umsetzt, in welcher X die obige Bedeutung hat. PATENT CLAIM: Process for the production of vulcanization or phenolic ethers or esters suitable for organic polymers of the general formula CH2 = C (R) -R1-O-CßH4-X in which R is a hydrogen atom or an alkyl group, R1 a methylene or a carbonyl group and X an aldehyde group, an aldehyde group substituted by the aniline, hydroxylamine or phenylhydrazine radical, a carboxylic acid alkyl or aryl ester group, an amino group or one through the Benzaldehyde radical means substituted amino group, by reaction of an oc-unsaturated one Alkyl chloride or an o; -unsaturated carboxylic acid chloride with a phenol in Presence of acid-binding agents, characterized in that one is an unsaturated Carboxylic acid chloride or an allyl halide of the general formula CH2 = C (R) -R1-Cl in which R and R1 have the above meaning, with a phenol, optionally a phenolate which converts the general formula HO-CßH4-X, in which X the above Has meaning. In Betracht gezogene Druckschriften: Fieser und Fieser, Lehrbuch der Organischen Chemie, 1954, S. 719 und 733. Publications considered: Fieser and Fieser, textbook der Organic Chemie, 1954, pp. 719 and 733.
DEH35981A 1957-12-23 1957-12-23 Process for the production of phenol ethers or esters suitable as vulcanization or crosslinking agents for organic polymers Pending DE1128855B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEH35981A DE1128855B (en) 1957-12-23 1957-12-23 Process for the production of phenol ethers or esters suitable as vulcanization or crosslinking agents for organic polymers

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Application Number Priority Date Filing Date Title
DEH35981A DE1128855B (en) 1957-12-23 1957-12-23 Process for the production of phenol ethers or esters suitable as vulcanization or crosslinking agents for organic polymers

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DE1128855B true DE1128855B (en) 1962-05-03

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