DE1013067B - Vulcanizing agents - Google Patents

Vulcanizing agents

Info

Publication number
DE1013067B
DE1013067B DED18740A DED0018740A DE1013067B DE 1013067 B DE1013067 B DE 1013067B DE D18740 A DED18740 A DE D18740A DE D0018740 A DED0018740 A DE D0018740A DE 1013067 B DE1013067 B DE 1013067B
Authority
DE
Germany
Prior art keywords
parts
diamines
ketones
vulcanizing agents
reaction products
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
DED18740A
Other languages
German (de)
Inventor
Rudolf Nagelschmidt
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
Degussa GmbH
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.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to DED18740A priority Critical patent/DE1013067B/en
Publication of DE1013067B publication Critical patent/DE1013067B/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • B21C37/15Making tubes of special shape; Making tube fittings
    • B21C37/22Making finned or ribbed tubes by fixing strip or like material to tubes
    • B21C37/26Making finned or ribbed tubes by fixing strip or like material to tubes helically-ribbed tubes
    • 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
    • C08K5/16Nitrogen-containing compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

Vulkanis ationsmittel Es ist bekannt, daß sich Naturkautschuk oder synthetische Kautschukarten vulkanisieren lassen. Zu diesem Zweck dient in der Praxis, vor allem bei Naturkautschuk, der Schwefel, dem häufig noch Aktivatoren oder/und Beschleuniger zugesetzt werden. Es ist aber auch möglich, die Vulkanisation ohne Schwefel unter Zusatz bestimmter Chemikalien, wie z. B. Metalloxyden oder organischer Verbindungen. durchzuführen. Dieses letztere Verfahren hat sich vorwiegend für die Vulkanisation von synthetischem Kautschuk bewährt. Insbesondere bei der Vulkanisation von Polychloroprenen ist die Verwendung von Diaminen, monofunktionellen Aldehyd-Amin-Verbindungen u. a. m., aber auch von Kombinationen dieser Verbindungen mit Metalloxyden, wie z. B. mit Bleioxyd, Zinkoxyd oder Magnesiumoxyd, bekannt.Vulkanis ationsmittel It is known that natural rubber or Let synthetic rubbers vulcanize. For this purpose, in practice, Especially with natural rubber, the sulfur, which often still activators and / or Accelerators can be added. But it is also possible to vulcanize without Sulfur with the addition of certain chemicals, such as. B. metal oxides or organic Links. perform. This latter procedure has predominantly been used for the Proven vulcanization of synthetic rubber. Especially when it comes to vulcanization of polychloroprenes is the use of diamines, monofunctional aldehyde-amine compounds i.a. m., But also of combinations of these compounds with metal oxides, such as z. B. with lead oxide, zinc oxide or magnesium oxide, known.

Diese Beschleuniger bzw. ihre Kombinationen können theoretisch sowohl zur Heiß- wie auch zur Kaltvulkanisation verwendet werden. In der praktischen Anwendung hat sich jedoch gezeigt, daß die Kaltvulkanisation meist zu langsam verläuft, und insbesondere für die Vulkanisation von lösungsmittelhaltigen Kautschuk- oder Kunstkautschukmischungen reichen die vorbekannten Vulkanisationsmittel in der Kälte meist nicht aus. These accelerators or their combinations can theoretically both can be used for both hot and cold vulcanization. In practical application However, it has been shown that the cold vulcanization usually proceeds too slowly, and especially for the vulcanization of solvent-based rubber or synthetic rubber mixtures The previously known vulcanizing agents are usually not sufficient in the cold.

Überraschenderweise hat es sich gezeigt, daß Umsetzungsprodukte von Diaminen, insbesondere aliphatischen Diaminen, mit Ketonen, wobei sich zyklische Ketone als besonders vorteilhaft erweisen, mit Kautschukmischungen, insbesondere aber mit Kunstkautschuken, hervorragende Vulkanisate ergeben. Mit Hilfe dieser Diamin-Keton-Umsetzungsprodukte ist es möglich, bei normalen oder mäßig erhöhten Temperaturen in kurzer Zeit allen praktischen Anforderungen genügende Vulkanisate zu erhalten. Dieser Vorteil wirkt sich besonders bei der Verwendung von Kautschuk- bzw. Kunstkautschuklösungen aus, bei denen sonst erfahrungsgemäß mit sehr langen Vulkanisationszeiten gerechnet werden mußte. Surprisingly, it has been shown that reaction products of Diamines, especially aliphatic diamines, with ketones, being cyclic Ketones prove to be particularly beneficial with rubber compounds, in particular but with synthetic rubbers, excellent vulcanizates result. With the help of these diamine-ketone reaction products it is possible at normal or moderately elevated temperatures in a short time all to obtain vulcanizates that meet practical requirements. This advantage works especially when using rubber or synthetic rubber solutions, where experience has shown that otherwise very long vulcanization times are expected had to.

Die hier nicht geschützte Herstellung dieser Kondensationsprodukte kann nach den an sich bekannten \methoden durch Umsetzung von Diaminen mit Ketonen bei Gegenwart von Kondensationsmitteln, beispielsweise von Bleioxyd oder Zinkoxyd, vorgenormen werden. Es wurde dabei gefunden, daß es nicht erforderlich ist, nach Beendigung der Umsetzung die metalloxydhaltigen Kondensationsmittel aus der Reaktionslösung zu entfernen, sondern daß es vorteilhaft ist, diese Kondensationsmittel in den Keton- Diamin- Umsetzungsprodukten zu belassen und als Ganzes als Vulkanisationsmittel zu verwenden. The production of these condensation products that is not protected here can according to the methods known per se by reacting diamines with ketones in the presence of condensation agents, for example lead oxide or zinc oxide, be pre-standardized. It was found that it is not necessary after Completion of the reaction, the metal oxide-containing condensation agents from the reaction solution to remove, but that it is advantageous to these condensation agents in the ketone To leave diamine reaction products and as a whole as vulcanizing agents to use.

Beispiel 1 38,0 Teile Naturkautschuk 35,0 ,, Kreide 10,0 ,, aktiver Gasruß 15,0 ,, weicher Gasruß 0,5 5,. Schwefel 1,5 eines aus 50 Teilen Zinkoxyd, 500 Teilen Aceton und 52,4 Teilen Tetramethylendiamin gewonnenen Umsetzungsproduktes 100.0 Teile Diese Mischung wird nach dem Mastizieren auf einem Kalander zu einer endlosen Bahn ausgezogen und ohne Druck bei einer Temperatur von etwa 1000 kontinuierlich ausvulkanisiert. Das auf diese Weise erhaltene Vulkanisat kann für die Herstellung von z. B. Fußbodenbelag oder Sohlenplatten verwendet werden. Example 1 38.0 parts of natural rubber 35.0 "chalk 10.0" more active Carbon black 15.0 ,, soft carbon black 0.5 5 ,. Sulfur 1.5 one of 50 parts zinc oxide, 500 parts of acetone and 52.4 parts of tetramethylenediamine obtained reaction product 100.0 parts After mastication on a calender, this mixture becomes a endless web drawn and without pressure at a temperature of about 1000 continuously fully vulcanized. The vulcanizate obtained in this way can be used for production from Z. B. floor covering or soleplates can be used.

Beispiel 2 Ein Gemisch aus 60,0 Teilen chlorsulfoniertem Polyäthvlen 6,0 härtbarem Phenolharz 28,0 ,, aktivem Gasruß 6,0 Umsetzungsprodukt von Methyläthylketon mit p-Phenylendiamin wird nach dem Mastizieren zu Platten kalandert, deren Ausvulkanisation bei normaler Temperatur innerhalb kurzer Zeit erfolgt. Diese Platten können beispielsweise als säurefestes Dichtungsmaterial verwendet werden. Sie eignen sich besonders gut dazu, um Metalle vor dem Angriff von Säuren zu schützen. Example 2 A mixture of 60.0 parts of chlorosulfonated polyethylene 6.0 curable phenolic resin 28.0 ,, active carbon black 6.0 reaction product of methyl ethyl ketone After mastication, p-phenylenediamine is used for calendering to form sheets, which are then fully vulcanized takes place within a short time at normal temperature. These plates can for example can be used as acid-proof sealing material. They do particularly well to protect metals from attack by acids.

Beispiel 3 18,0 Teile Polychloropren 6,0 ,, aktiver Füllstoff (hochdisperses, durch thermische Umsetzung von Siliciumtetrachlorid in der Gasphase hergestelltes Kieselsäuregel) 2,0 0., lockeres Calciumsilikat 0,2 ,, Magnesiumoxyd 0,2 ,, Zinkoxyd 4,0 ,, Xylol 32,0 ,, Methylenchlorid 10,0 ,, Äthylacetat 27,6 ,, Leichtbenzin 100,0 Teile werden innig miteinander vermischt. Dieses Gemisch wird in der Weise als Klebstoff verwendet, daß dasselbe mit 10 Teilen einer Lösung von 0,8 Teilen des Umsetzungsproduktes von Cyclohexanon- mit Hexamethylendiamin in 9,2 Teilen Cyclohexanon innig vermischt wird. Mit diesem Gemisch werden die zu verklebenden Stellen bestrichen. Nach dem Verdunsten der Lösungsmittel werden die zu verklebenden Teile durch geringen Druck miteinander verbunden, wobei der Klebefilm in der Kälte ausvulkanisiert und eine sehr fest haftende Verklebung hebeiführt. Example 3 18.0 parts of polychloroprene 6.0, active filler (highly dispersed, produced by thermal conversion of silicon tetrachloride in the gas phase Silica gel) 2.0 0., loose calcium silicate 0.2, magnesium oxide 0.2, zinc oxide 4.0 ,, xylene 32.0 ,, methylene chloride 10.0 ,, ethyl acetate 27.6 ,, petrol 100.0 Parts are intimately mixed with one another. This mixture is used in the way as an adhesive used the same with 10 parts of a solution of 0.8 parts of the reaction product of cyclohexanone intimately mixed with hexamethylenediamine in 9.2 parts of cyclohexanone will. With this mixture the to coated areas to be glued. After this The parts to be bonded will evaporate as a result of low pressure connected to one another, the adhesive film vulcanized in the cold and a very firmly adhering bond.

Claims (2)

P A T E N T A N S P R Ü C H E 1. Vulkanisationsmittel für natürlichen Kautschuk und synthetische Kautschukarten, enthaltend Umsetzungsprodukte von Diaminen mit Ketonen. P A T E N T A N S P R Ü C H E 1. Vulcanizing agent for natural Rubber and synthetic rubbers containing reaction products of diamines with ketones. 2. Vulkanisationsmittel nach Anspruchs, gekennzeichnet durch einen Gehalt von Umsetzungsprodukten von Diaminen mit Ketonen, die nicht oder nur teilweise von den bei ihrer Herstellung als Kondensationsmittel verwendeten Metallverbindungen befreit sind. 2. Vulcanizing agent according to claim, characterized by a Content of reaction products of diamines with ketones that are not or only partially of the metal compounds used as condensation agents in their manufacture are exempt. In Betracht gezogene Druckschriften: Deutsche Patentschriften Nr. 444 441, 560 353, 564913,567146. Considered publications: German Patent Specifications No. 444 441, 560 353, 564913,567146.
DED18740A 1954-09-24 1954-09-24 Vulcanizing agents Pending DE1013067B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DED18740A DE1013067B (en) 1954-09-24 1954-09-24 Vulcanizing agents

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DED18740A DE1013067B (en) 1954-09-24 1954-09-24 Vulcanizing agents

Publications (1)

Publication Number Publication Date
DE1013067B true DE1013067B (en) 1957-08-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
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DE (1) DE1013067B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300425A (en) * 1959-03-03 1967-01-24 Degussa Halogen-containing thermoplastic compositions for the production of cured products suitable for artificial leathers, sheets, coatings and impregnations

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE444441C (en) * 1925-08-07 1927-05-20 I G Farbenindustrie Akt Ges Process to accelerate the vulcanization of natural or synthetic rubbers
DE560353C (en) * 1930-08-30 1932-10-08 I G Farbenindustrie Akt Ges Process for the production of vulcanization accelerators
DE564913C (en) * 1930-06-25 1932-11-24 I G Farbenindustrie Akt Ges Vulcanization accelerator for natural rubber and synthetic rubber-like polymers
DE567146C (en) * 1930-04-04 1932-12-29 I G Farbenindustrie Akt Ges Vulcanization accelerator

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE444441C (en) * 1925-08-07 1927-05-20 I G Farbenindustrie Akt Ges Process to accelerate the vulcanization of natural or synthetic rubbers
DE567146C (en) * 1930-04-04 1932-12-29 I G Farbenindustrie Akt Ges Vulcanization accelerator
DE564913C (en) * 1930-06-25 1932-11-24 I G Farbenindustrie Akt Ges Vulcanization accelerator for natural rubber and synthetic rubber-like polymers
DE560353C (en) * 1930-08-30 1932-10-08 I G Farbenindustrie Akt Ges Process for the production of vulcanization accelerators

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300425A (en) * 1959-03-03 1967-01-24 Degussa Halogen-containing thermoplastic compositions for the production of cured products suitable for artificial leathers, sheets, coatings and impregnations

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