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DE3015890A1 - METHOD FOR ADDITIONING VOLCANIZATION OF POLYMETHYLVINYLSILOXANE - Google Patents

METHOD FOR ADDITIONING VOLCANIZATION OF POLYMETHYLVINYLSILOXANE

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Publication number
DE3015890A1
DE3015890A1 DE19803015890 DE3015890A DE3015890A1 DE 3015890 A1 DE3015890 A1 DE 3015890A1 DE 19803015890 DE19803015890 DE 19803015890 DE 3015890 A DE3015890 A DE 3015890A DE 3015890 A1 DE3015890 A1 DE 3015890A1
Authority
DE
Germany
Prior art keywords
dipl
munich
alkyl hydrogen
polymethylvinylsiloxane
hopf
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.)
Withdrawn
Application number
DE19803015890
Other languages
German (de)
Inventor
Miloslav Dipl.-Ing. Aisman
Marta Dipl.-Ing. Heidingsfeldova
Miroslav Praha Schatz
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.)
Vysoka Skola Chemicko Technologicka V Praze
Original Assignee
Vysoka Skola Chemicko Technologicka V Praze
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 Vysoka Skola Chemicko Technologicka V Praze filed Critical Vysoka Skola Chemicko Technologicka V Praze
Priority to DE19803015890 priority Critical patent/DE3015890A1/en
Priority to FR8009865A priority patent/FR2481706A1/en
Publication of DE3015890A1 publication Critical patent/DE3015890A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08K5/0091Complexes with metal-heteroatom-bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/12Polysiloxanes containing silicon bound to hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/14Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/20Polysiloxanes containing silicon bound to unsaturated aliphatic groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Description

SCHIFF ν. FONER STREHL SCHOBEL-HOPF EBBINGHAUS FlNCKSHIP ν. FONER STREHL SCHOBEL-HOPF EBBINGHAUS FlNCK

, Beschreibung, Description

Bisher ist es bekannt, bei der Additionsvulkanisation von Silikonkautschuk als Katalysator Platin in Metallform, Hexachlorplatin(IV)-säure und weitere verschiedene, insbesondere Komplexverbindungen von Platin anzuwenden. Dazu gehören beispielsweise ein Komplex von Platin mit Olefinen, mit Cyclohexan, mit Styrol oder Pyridin (Pomeranceva M.G., Beljakova Z.V., Golubcov S.A. und Svarc N.S.: Polutschenye karbofunkcialnych organosilanov po reakcii prisojedinenija - NIITI Moskva, 1971; US-PS 3 723 497, 3 732 330, 3 516 946, 3 862 081). Platin und dessen Verbindungen, insbesondere Hexachlorplatin-(IV)-säure sind Katalysatoren, die zwar eine hohe Ausbeute der Produkte der Additions- bzw. Hydrosilylierungs-Reaktion bieten, welche jedoch auch Nachteile aufweisen, wie z.B. Empfindlichkeit gegen Katalysatorgifte, Erregung der Nebenreaktionen und Notwendigkeit, Inhibitoren beim Aufbewahren von Kautschukgemischen bei Raumtemperatur einzusetzen.So far it is known in the addition vulcanization of silicone rubber as catalyst platinum in metal form, hexachloroplatinic acid and to use other different, in particular complex compounds of platinum. These include, for example a complex of platinum with olefins, with cyclohexane, with styrene or pyridine (Pomeranceva M.G., Beljakova Z.V., Golubcov S.A. and Svarc N.S .: Polutschenye karbofunkcialnych organosilanov po reakcii prisojedinenija - NIITI Moskva, 1971; U.S. Patents 3,723,497, 3,732,330, 3,516,946, 3,862,081). Platinum and its compounds, especially hexachloroplatinic (IV) acid are catalysts which, although a high yield of the products of the addition or hydrosilylation reaction which, however, also have disadvantages, such as sensitivity to catalyst poisons, excitation of side reactions and the need to use inhibitors when storing rubber compounds at room temperature.

Das vorliegende erfindungsgemäße Verfahren soll die oben erwähnten Nachteile des Standes der Technik ausschalten. Der Erfindung liegt also die Aufgabe zugrunde, ein verbessertes Verfahren zur Additionsvulkanisation von Polymethylvinylsi— loxan zu schaffen.The present inventive method is intended to accomplish those mentioned above Eliminate the disadvantages of the prior art. The invention is therefore based on the object of an improved Process for the addition vulcanization of polymethylvinylsi— to create loxane.

Erfindungsgemäß wird diese Aufgabe so gelöst, daß Polymethylvinylsiloxane, enthaltend von O,2 bis IO Mol-% von CHo(CH„=CH)OSi-Gruppen, einer Einwirkung von Siliziumhydridverbindungen, wie z.B. Alkylhydrogensilanen, Alkylhydrogenpolysiloxanen oder cyclischen Alkylhydrogenpolysiloxanen mit mindestens zwei Wasserstoffatomen im Molekül in Anwesenheit von Rhodium-Triacetylacetonat als Katalysator unterworfen werden. Bevorzugte Verbindungen besitzen im Alkylrest 1 bis 6According to the invention this object is achieved in such a way that polymethylvinylsiloxanes, containing from O, 2 to IO mol% of CHo (CH "= CH) OSi groups, an action of silicon hydride compounds, such as alkyl hydrogen silanes, alkyl hydrogen polysiloxanes or cyclic alkyl hydrogen polysiloxanes with at least two hydrogen atoms in the molecule in the presence of rhodium triacetylacetonate as a catalyst. Preferred compounds have 1 to 6 in the alkyl radical

130044/0381130044/0381

C-Atome. Der Rest kann geradketticf oder verzweigt sein.C atoms. The remainder can be straight chain or branched.

Das erfindungsgemäße Verfahren garantiert eine zumindest zweimonatige Lagerfähigkeit der Kautschukgemische bei Raumtemperatur ohne Verwendung von Inhibitoren und sichert die Bildung eines guten KautschukskeLetts. Im Vergleich zu den Katalysatoren auf Platinbasis weist der erfindungsgemäße Katalysator den Vorteil auf, daß er nicht die Alterung der Vulkanisate negativ beeinflußt. Da er z.B. im Aceton, Benzol oder Toluol gut löslich ist, läßt er sich in Lösungsform in den vorerwähnten Lösungsmitteln ohne Schwierigkeiten in Silikonkautschukgemische einmischen. Die Konzentration von Rhodium(III)-Acetylacetonat im Silikonkautschukgemisch kann nach Umrechnung auf RhodiumThe method according to the invention guarantees at least a two-month period The rubber mixtures can be stored at room temperature without the use of inhibitors and ensure formation a good rubber chain. Compared to the catalysts the platinum-based catalyst of the invention has the The advantage is that it does not adversely affect the aging of the vulcanizates. Because it works well in acetone, benzene or toluene, for example is soluble, it can be in solution form in the aforementioned solvents without difficulty in silicone rubber mixtures interfere. The concentration of rhodium (III) acetylacetonate in the silicone rubber mixture can be calculated after conversion to rhodium

-3 -3-3 -3

1.10 bis 5.10 g pro 100 g Polymethylvinylsiloxan, enthaltend von O, 2 bis 10 Mol-?.', von Vinyleinheiten im Makromolekül, betragen.1.10 to 5.10 g per 100 g of polymethylvinylsiloxane, containing from 0.2 to 10 mol ?. ', of vinyl units in the macromolecule, be.

Das erfindungsgemäße Verfahren soll weiterhin anhand zweier, den Erfindungsumfang keineswegs begrenzenden Ausführungsbeispiele näher erläutert werden.The method according to the invention should also be based on two, the scope of the invention by no means limiting embodiments are explained in more detail.

Beispiel 1example 1

Einem Silikonkautschukgomisch, bestehend aus 100 Gewichtsteilen Polymethylvinylsiloxan (Molekulargewicht. 4,6.3.0 ; Gehalt 1,4 Mol-SS ChU(CfU=CtI)OSi) und 35 GewichtsLeilen von pyrocjenem Siliciumdioxid, wurden 8,5 q Polymethylhydrocjonsiloxan (Molekulargewicht lOO; Wasserstoffgehalt O,5 bis 0,75 Gew.-%) und 5 g der Lösung von Rhodium-Triacetylacetonat in Toluol (O,11%-ige Konz.) zugegeben, worauf das Gemisch homogenisiert wurde. Das homogenisierte Gemisch wurde 30 Minuten bei 150°C vulkanisiert. Das Vulkanisat wies die nachfolgenden physiko-mechanischen Eigenschaften auf:A silicone rubber compound, consisting of 100 parts by weight Polymethylvinylsiloxane (molecular weight. 4,6.3.0; content 1.4 mol SS ChU (CfU = CtI) OSi) and 35 parts by weight of pyrocjenem Silicon dioxide, were 8.5 q polymethylhydrocionosiloxane (molecular weight lOO; Hydrogen content 0.5 to 0.75% by weight) and 5 g of the solution of rhodium triacetylacetonate in toluene (O, 11% strength Conc.) Was added, whereupon the mixture was homogenized. The homogenized mixture was vulcanized at 150 ° C. for 30 minutes. The vulcanizate exhibited the following physico-mechanical Features on:

Zugfestigkeit 4,6 MPaTensile strength 4.6 MPa

Dehnung 120 %Elongation 120%

Härte 67 ShHardness 67 Sh

1300U/03611300U / 0361

BAD ORIGINALBATH ORIGINAL

Gewichtsabnahme nach Alterung (2OO°C - 500 Stunden), 1,2 %.Weight loss after aging (200 ° C - 500 hours), 1.2%.

Beispiel 2Example 2

Polymethylvinylsiloxane mit O, 2 Mol-JS-igem, 1, 4 . Mol-%-igem und 3,5 Mol-%-igem Gehalt von Vinyleinheiten und dem Füllmittelgehalt wie im Beispiel 1 wurden in Anwesenheit von Rhodium-Acetylacetonat von gleicher Konzentration wie im Beispiel 1 und beim Verhältnis von H:Vi = 0,65 vulkanisiert. Zum Vergleich wurde die Vulkanisation dieser Polysiloxane mittels Dicumylperoxid und 2,4-Dichlorbenzoylperoxid vorgenommen.Polymethylvinylsiloxanes with O, 2 mol-JS-igem, 1, 4. Mol% and 3.5 mol% content of vinyl units and the filler content as in Example 1 were in the presence of rhodium acetylacetonate vulcanized at the same concentration as in Example 1 and at the ratio of H: Vi = 0.65. For comparison was the vulcanization of these polysiloxanes using dicumyl peroxide and 2,4-dichlorobenzoyl peroxide.

130044/0361130044/0361

ORIG/NAL"ORIG / NAL "

Claims (1)

FINCKFINCK SCHIFF ν. FÜNER STREHL SCH ÜBEL-HOPF ' "eBBI N G H AUSSHIP ν. FÜNER STREHL SCHÜBEL-HOPF '"eBBI N G H AUS MARIAHILFPI.ATZ 2 4 3, MÜNCHEN 9O POSTADHESSE: POSTFACH 95 O1 6O, D-8O0O MÜNCHEN 95MARIAHILFPI.ATZ 2 4 3, MUNICH 9O POSTADHESSE: POSTFACH 95 O1 6O, D-8O0O MUNICH 95 ALSO PROFGSSIONAL F-tiiPKf-:st?N ΓΛ r UKrORK THK EUROHi.-'Af-l ΪΆΚϊΝΓ Oi-ALSO PROFGSSIONAL F-tiiPKf-: st? N ΓΛ r UKrORK THK EUROHi .- 'Af-l ΪΆΚϊΝΓ Oi- Vysoka skola chemicko-technologicka PrahaVysoka skola chemicko-technologicka Praha KAP4L IUDWIO RCHIFF (1ΟΊ4 -Kj/8)KAP4L IUDWIO RCHIFF (1ΟΊ4 -Kj / 8) DIFM.. CHEM. OH. ALEXANDER V. KÜNS-WDIFM .. CHEM. OH. ALEXANDER V. KÜNS-W DIPL. INU. PETER STHEHLDIPL. INU. PETER STHEHL DIPL. CHEM. DR. URSULA HCHÜ8EL· HOPFDIPL. CHEM. DR. URSULA HCHÜ8EL HOPF DIPL. INO. DIETER EBE)INOHAUSDIPL. IN O. DIETER EBE) INOHAUS DR. ING. DIETER FINCKDR. ING. DIETER FINCK TELEFON (O8S) 48 2O 54TELEPHONE (O8S) 48 2O 54 TELEX 6-23 eeS AURO DTELEX 6-23 eeS AURO D TELEGRAMME AUROMAHCPAT MÜNCHENTELEGRAMS AUROMAHCPAT MUNICH DEA-21072DEA-21072 24. April 1980April 24, 1980 VERFAHREN 2UR ADDITIONSVULKANISATION VON POLY-METiIYLVINYLSILOXAM METHOD 2 FOR ADDITIONAL VULCANIZATION OF POLY-METIYLVINYLSILOXAM PatentanspruchClaim Verfahren zur Additionsvulkanisation von Polymethylvinylsiloxan, dadurch gekennzeichnet, daß Polymethylvinylsiloxane, enthaltend von 0,2 bis 10 Mol-% von CH3(CH2=CH)OSi-Gruppen, der Einwirkung von Siliziumhydridverbindungen, wie z.B. Alkylhydrogensilanen, Alkylhydrogenpolysiloxanen, oder cyclischen Alkylhydrogenpolysiloxanen mit mindestens zwei Wasserstof!'atomen im Molekül in Anwesenheit von Rhodium-Triacetylacetonat als Katalysator unterworfen werden.Process for addition vulcanization of polymethylvinylsiloxane, characterized in that polymethylvinylsiloxanes containing from 0.2 to 10 mol% of CH 3 (CH 2 = CH) OSi groups, the action of silicon hydride compounds, such as alkyl hydrogen silanes, alkyl hydrogen polysiloxanes, or cyclic alkyl hydrogen polysiloxanes with at least two hydrogen atoms in the molecule in the presence of rhodium triacetylacetonate as a catalyst. 13 0044/038113 0044/0381
DE19803015890 1980-04-24 1980-04-24 METHOD FOR ADDITIONING VOLCANIZATION OF POLYMETHYLVINYLSILOXANE Withdrawn DE3015890A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19803015890 DE3015890A1 (en) 1980-04-24 1980-04-24 METHOD FOR ADDITIONING VOLCANIZATION OF POLYMETHYLVINYLSILOXANE
FR8009865A FR2481706A1 (en) 1980-04-24 1980-04-30 Addn. vulcanisation of poly:methyl-vinyl-siloxane! - with silicon hydride using rhodium tri:acetyl-acetonate as catalyst (CS 28.11.80)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803015890 DE3015890A1 (en) 1980-04-24 1980-04-24 METHOD FOR ADDITIONING VOLCANIZATION OF POLYMETHYLVINYLSILOXANE
FR8009865A FR2481706A1 (en) 1980-04-24 1980-04-30 Addn. vulcanisation of poly:methyl-vinyl-siloxane! - with silicon hydride using rhodium tri:acetyl-acetonate as catalyst (CS 28.11.80)

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Publication Number Publication Date
DE3015890A1 true DE3015890A1 (en) 1981-10-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10235267A1 (en) * 2002-08-01 2004-02-12 Wacker-Chemie Gmbh Use of rhodium-crosslinking silicone elastomers for the production of baking tins
DE10235268A1 (en) * 2002-08-01 2004-02-12 Wacker-Chemie Gmbh Crosslinking silicone elastomers, processes for their production and the use of the crosslinkable compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1369989A (en) * 1970-11-27 1974-10-09 Dow Corning Ltd Organopolysiloxane elastomers
GB1476314A (en) * 1973-06-23 1977-06-10 Dow Corning Ltd Coating process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10235267A1 (en) * 2002-08-01 2004-02-12 Wacker-Chemie Gmbh Use of rhodium-crosslinking silicone elastomers for the production of baking tins
DE10235268A1 (en) * 2002-08-01 2004-02-12 Wacker-Chemie Gmbh Crosslinking silicone elastomers, processes for their production and the use of the crosslinkable compositions
US7129309B2 (en) 2002-08-01 2006-10-31 Wacker-Chemie Gmbh Use of rhodium-crosslinking silicone elastomers for producing baking molds
US7291670B2 (en) 2002-08-01 2007-11-06 Wacker Chemie Ag Cross-linking silicone elastomers, method for the production thereof, and use of the cross-linkable masses

Also Published As

Publication number Publication date
FR2481706A1 (en) 1981-11-06

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Legal Events

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Representative=s name: VON FUENER, A., DIPL.-CHEM. DR.RER.NAT. EBBINGHAUS

8139 Disposal/non-payment of the annual fee