DE2008426A1 - - Google Patents
Info
- Publication number
- DE2008426A1 DE2008426A1 DE19702008426 DE2008426A DE2008426A1 DE 2008426 A1 DE2008426 A1 DE 2008426A1 DE 19702008426 DE19702008426 DE 19702008426 DE 2008426 A DE2008426 A DE 2008426A DE 2008426 A1 DE2008426 A1 DE 2008426A1
- Authority
- DE
- Germany
- Prior art keywords
- carbon atoms
- groups
- general formula
- molecular weight
- alkyl groups
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
Landscapes
- 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
Anmelder? Ceskoslovenskö äkademie ved#/ Praha 1 Applicant? Ceskoslovenskö Academy ved # / Praha 1
11 Verfahren zur Zubereitung räumlich vernetzter Silikonpolymere " 11 Process for the preparation of spatially crosslinked silicone polymers "
Die Erfindung betrifft ein neues Verfahren zur Zubereitung vernetzter Polysiloxane.The invention relates to a new method for the preparation of crosslinked Polysiloxanes.
In der letzten Zeit wird bei der Herstellung räumlich vernetzter Silikonpolymere immer häufiger die hohe Reaktivität einiger funktioneller Gruppen ausgenützt, durch welche die Seitenkette des SiIaxanskeletts substituiert ist. Mit diesem Ziele wurden Silylamine, Silyalkohole, siliziumorganische Epoxyverbindungen und Säuren als auch Siloxane mit ungesättigten Gruppen in der Seitenkette verwendet. Diese Polymere finden eine ausgedehnte praktische Anwendung.Recently, in the production of spatially crosslinked silicone polymers, the high reactivity of some functional ones has become more and more common Exploited groups through which the side chain of the SiIaxanskelett is substituted. With this goal in mind, silylamines, Sily alcohols, organosilicon epoxy compounds and acids as well as siloxanes with unsaturated groups in the side chain used. These polymers find extensive practical use.
Gegenstand der Erfindung bildet ein Verfahren zur Herstellung räumlich vernetzter Silikonpolymere, das auf der Additionsreaktion der SH-Gruppe von Thioalkylsiloxanen mit der Doppelbindung C=C von Alkenylsiloxanen oder der NCO-Gruppe organischer Diisozyanate beruht. Es wurde gefunden, daß zur Bildung der vorerwähnten Polymere folgende Möglichkeiten ausgenützt werden können:The invention relates to a method for production spatially cross-linked silicone polymer that is based on the addition reaction the SH group of thioalkylsiloxanes with the double bond C = C of alkenylsiloxanes or the NCO group of organic diisocyanates is based. It has been found that the following possibilities can be used to form the aforementioned polymers:
009837/2109009837/2109
1. Reaktionen von Alkenylsiloxanen der allgemeinen Formel I mit niedermolekularen siliziumorganischen Dithiolen der allgemeinen Formel II als netzbildende Komponenten.1. Reactions of alkenylsiloxanes of the general formula I with low molecular weight organosilicon dithiols of the general formula II as network-forming components.
Si -*0 R1 Si - * 0 R 1
R" SiR "Si
(CH2)(CH 2 )
= CH,= CH,
m + n>30,m + n> 30,
n/m = 1/10 bis 1/60 χ = 0 bis 4,n / m = 1/10 to 1/60 χ = 0 to 4,
R, R1, R" sind Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, Zykloalkylgruppen mit 5 bis 8 Kohlenstoffatomen, Arylgruppen oder Siloxygruppen im Falle eines dreidimensionalen Polymers.R, R 1 , R "are alkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 5 to 8 carbon atoms, aryl groups or siloxy groups in the case of a three-dimensional polymer.
HS(CH9) -Si - 0 -HS (CH 9 ) -Si - 0 -
S: - 0S: - 0
R"R "
Si - (CH2)xSHSi - (CH 2 ) x SH
ρ = 0 bis 30, x=1 bis 4,ρ = 0 to 30, x = 1 to 4,
R, R1, R" sind Alkylgruppen mit T bis 6 Kohlenstoffatomen, Zykloalkylgruppen mit 5 bis 8 Kohlenstoffatomen oder Arylgruppen. R, R 1 , R "are alkyl groups with T to 6 carbon atoms, cycloalkyl groups with 5 to 8 carbon atoms or aryl groups.
2. Reaktionen von Alkenylsiloxanen der allgemeinen Formel I mit hochmolekularen Thioalkylpolysiloxanen der allgemeinen Formel III.2. Reactions of alkenylsiloxanes of the general formula I with high molecular weight thioalkylpolysiloxanes of the general formula III.
009837/2109009837/2109
R' Si R"R 'Si R "
- β- β
R"R "
Si - O RSHSi - O RSH
IIIIII
ρ + q > 30,ρ + q> 30,
σ/ρ = 1/10 bis 1/60,σ / ρ = 1/10 to 1/60,
3. Reaktionen von Polysiloxanen der allgemeinen Formel III mit niedernolekularen Alkenylsiloxanen der allgemtinen Formel IV als netzbildenden Komponenten.3. Reactions of polysiloxanes of the general formula III with low molecular weight alkenylsiloxanes of the general formula IV as network-forming components.
CH2 = CH - (CH.) -Si-O-CH2 = CH - (CH.) -Si-O-
= CH2 IV= CH 2 IV
r = 0 bis 30,r = 0 to 30, x=0 bis 4,x = 0 to 4,
4. Reaktionen hochmolekularer mit Thioalkyl- und Alkenylgruppen substituierter Siloxane der allgemeinen Formel4. Reactions of high molecular weight with thioalkyl and alkenyl groups substituted siloxanes of the general formula
R1 R 1
Si -RSHSi -RSH
I DIlI DIl
R1 R 1
i - Ci - C
R111 R 111
R HI R HI
Si-o RCH=CH,Si-o RCH = CH,
009837/2109009837/2109
-A--A-
wobeiwhereby
m + η + ρ y 30 undm + η + ρ y 30 and
m/p a 1 bis 1/60 ist, undm / p a is 1 to 1/60, and
R eine Alkylengruppe mit 1 bis 6 Kohlenstoffatomen, eine Zykloalkylengruppe mit 5 bis 8 Kohlenstoffatomen oder eine Arylengruppe undR is an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms or an arylene group and
R'7 R", R"1 Alkylengruppen mit 1 bis 6 Kohlenstoffatomen, Zykloalkylgruppen mit 5 bis 8 Kohlenstoffatomen oder Arylgruppen bedeutet.R ' 7 R ", R" 1 denotes alkylene groups with 1 to 6 carbon atoms, cycloalkyl groups with 5 to 8 carbon atoms or aryl groups.
5. Reaktionen hochmolekularer Thioalkylpolysiloxane der allgemeinen Formel III oder der allgemeinen Formel5. Reactions of high molecular weight thioalkylpolysiloxanes of the general Formula III or the general formula
HO(RSiO1 5)a(Rf R"SiO)b/Rl(I (RSH)Si/cOHHO (RSiO 1 5) a (R f R "SiO) b / R L (I (RSH) Si / c OH
wobeiwhereby
a + b + c y 5 unda + b + c y 5 and
c/a + b = 1/5 bis 1/60 ist, undc / a + b = 1/5 to 1/60, and
R, R1, R", R1" Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, Zykloalkylgruppen mit 5 bis 8 Kohlenstoffatomen oder Arylgruppen bedeutet, mit organischen Diisozyanate, wie z.B. mit Hexamethylendiisozyanat, Toluol-2,4-diisozyanat, Benzol-!,4-diisozyanat u.äo R, R 1 , R ", R 1 " denotes alkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 5 to 8 carbon atoms or aryl groups, with organic diisocyanates, such as with hexamethylene diisocyanate, toluene-2,4-diisocyanate, benzene - !, 4 -diisocyanate and the like
Es wurde festgestellt, daß die Reaktion der Alkylensiloxane mit siliziumorganischen Thiolen leicht bei Temperaturen von 30 - 110 C in Anwesenheit von Initiatoren für Radikalreaktionen (wie z.B. Azobisisobutyronitril, Azomethylvinyldinitril u.a.) oder bei Initiierung durch Ultraviolett-Licht verläuft. Die Reaktion kann ohne Lösungsmittel und mit einer optimalen Initiatorkonzentration von 0,5-7 Gew. % (bezogen auf das Monomer) durchgeführt werden.It has been found that the reaction of the alkylenesiloxanes with organosilicon thiols proceeds easily at temperatures of 30-110 ° C. in the presence of initiators for radical reactions (such as azobisisobutyronitrile, azomethylvinyldinitrile, etc.) or when initiated by ultraviolet light. The reaction can be carried out without solvent and with an optimal initiator concentration of 0.5-7 wt.% (Based on monomer).
009837/2109009837/2109
~5~ 2008A26~ 5 ~ 2008A26
Es wurde weiter gefunden, daß die Reaktion der siliziumorganischen Thiole mit organischen Diisozyanaten in dem Milieu aprotischer Lösungsmittel, bzwo ohne Lösungsmittel bei mäßig erhöhten Temperaturen (am besten zwischen 50 -120 C) durchgeführt werden kann. Weiter wurde festgestellt, daß eine Zugabe von organischen Substanzen basischer Natur, wie z.B. tertiärer Amine in der Menge von 1/2 bis 7 Gew. % (bezogen auf das Gewicht des Reaktionsgemisches) zu einer wesentlichen Verkürzung der zur Ausbildung des räumlich vernetzten Polymers benötigten Zeit führt.It was further found that the reaction of the organosilicon thiols with organic diisocyanates in the medium aprotic solvents, or o can be carried out (preferably between 50 -120 C) without a solvent at moderately elevated temperatures. Further, it was found that an addition of organic substances of a basic nature, such as tertiary amines in the amount of 1.2 to 7 wt.% Of the required (based on the weight of the reaction mixture) in a substantial reduction to form the three-dimensionally networked polymer Time leads.
Das erfindungsgemäßeVerfahren zur Zubereitung räumlich vernetzter Polymere besitzt gegenüber den bisher bekannten Verfahren eine ganze Reihe von Vorteilen, die darin bestehen, daßThe process according to the invention for the preparation of spatially crosslinked polymers has one compared to the previously known processes whole series of advantages that consist in that
a) die Bildung der Querbrücken zwischen den einzelnen Polysiloxanketten unter milderen Bedingungen und in wesentlich kürzeren Zeiten durchgeführt werden kann, und daß sicha) the formation of the cross bridges between the individual polysiloxane chains can be carried out under milder conditions and in much shorter times, and that
b) die entstandenen Polymere durch eine hervorragende thermische und chemische Beständigkeit auszeichnen und ihre mechanischen Eigenschaften in breitem Ausmaße durch die Wahl verschiedener gegenseitiger Verhälthisse der Reaktionspartner variiert werden können.b) the resulting polymers are characterized by excellent thermal and chemical resistance and their mechanical Properties can be varied to a large extent by the choice of different mutual proportions of the reactants can.
Das gegenständliche Verfahren kann praktisch z.B. zur gelenkten Vernetzung linearer Siloxanelastomere, d. h. zu deren Vulkanisation bei verhältnismäßig niedrigen Temperaturen, oder zur'Aushärtung von Silikonlacken oder von Silikonharzen bei niedrigen Temperaturen verwendet werden.The subject method can be practically used, for example, for directed crosslinking of linear siloxane elastomers, i.e. H. for their vulcanization at relatively low temperatures, or for the hardening of Silicone varnishes or silicone resins can be used at low temperatures.
009837/2109009837/2109
Die im weiteren angeführten Beispiele dienen der detailierten Beschreibung des den Gegenstand dieser Erfindung bildenden Verfahrens, ohne es aber irgendwie begrenzen oder einschränken zu wollen.The examples given below serve as a detailed description of the process forming the subject of this invention, but without in any way limiting or restricting it want.
Ein Gemisch aus 290 g eines linearen Vinylmethylpolysiloxans der Zusammensetzung ( (CH0=CH) ,.(CH0), ORSi0 ) , mit demA mixture of 290 g of a linear vinylmethylpolysiloxane of the composition ((CH 0 = CH) ,. (CH 0 ), OR Si0), with the
Z. Ο·οΰ «3 1 « VO ι χ Z. Ο · οΰ «3 1« VO ι χ
ψ Molekulargewicht 60.000 aus 18 g des symmetrischen bis -(Thiomethyl)tetramethyldisilixane und aus 3 g Azomethylvinyldinitril (MVN) wurde eine halbe Stunde bei der Temperatur von 50 C erwärmt. Während dieser Zeit entstand ein farbloses hochelastisches räumlich vernetztes Polyeer. Eine achtstündige Erhitzung des derart zubereiteten Polymers in Luft bei 200 C hatte keine Veränderungen seiner mechanischen Eigenschaften zur Folge. ψ Molecular weight 60,000 from 18 g of the symmetrical bis (thiomethyl) tetramethyldisilixane and from 3 g of azomethylvinyldinitrile (MVN) was heated for half an hour at the temperature of 50 C. During this time, a colorless, highly elastic, spatially networked polyene was created. Heating the polymer prepared in this way in air at 200 ° C. for eight hours did not result in any changes in its mechanical properties.
Ein Gemisch aus 10 g eines hochmolekularen linearen (Thiomethyl)-
W -methylpolysiloxans der Zusammensetzung ( (HSCHp) _ .(CH-) _ (C0Hc)1
flSiO) und 350 g eines linearen Vinylmethylpolysioxans der
Zusammensetzung ( (CHO=CH)_ 05(^^0)1 οκ^ίΟ) mit degi Molekulargewicht
60.000 wurde zusammen mit 100 g eines Si00-Aerogels unter
Zugabe von 5 g Azobisisobutyronitril auf die Temperatur von 90 105 C erhitzt. Nach 20 Minuten entst«
artiges räumlich vernetztes Polymer«A mixture of 10 g of a high molecular weight linear (thiomethyl) - W -methylpolysiloxane of the composition ((HSCHp) _. (CH-) _ (C 0 Hc) 1 flSiO) and 350 g of a linear vinylmethylpolysioxane of the composition ((CH O = CH ) _ 05 (^^ 0) 1 οκ ^ ίΟ) with degi molecular weight 60,000 was heated to the temperature of 90 105 C together with 100 g of a Si0 0 airgel with the addition of 5 g of azobisisobutyronitrile. After 20 minutes
like spatially cross-linked polymer "
105 C erhitzt. Nach 20 Minuten entstand ein farbloses, kautschuk-Heated to 105 C. After 20 minutes, a colorless, rubber-
009837/2109009837/2109
Ein Gemisch aus 7 g eines hochmolekularen linearen (Thiopropyl)-methylpolysiloxans der Zusammensetzung ( (HSCH-CHLChL)n nc-A mixture of 7 g of a high molecular weight linear (thiopropyl) methylpolysiloxane of the composition ((HSCH-CHLChL) nn c-
(CH.). 05^^) urMJ aus 1/2 g eines symmetrischen Divinyltetramethyldisiloxans wurde 3 Stunden mit UV-Licht bestrahlt. Während dieser Zeit bildete sich ein durchsichtiges elastisches räumlich vernetztes Polymer aus.(CH.). 05 ^^) urM J from 1/2 g of a symmetrical divinyltetramethyldisiloxane was irradiated with UV light for 3 hours. During this time, a transparent, elastic, spatially crosslinked polymer formed.
Ein Gemisch öl> 10 g eines hochmolekularen linearen (Thiomethyl)-allylmethylpol/siloxans der Zusammensetzung ( (HSCH9). m-A mixture of oil> 10 g of a high molecular weight linear (thiomethyl) allylmethylpol / siloxane of the composition ((HSCH 9 ). M -
(CH2=CHCH2)0 O5(CHg)1 94Si0)x und 1,5 g Azomethylvinyldinitril(CH 2 = CHCH 2 ) 0 O 5 (CHg) 1 94 SiO) x and 1.5 g of azomethylvinyldinitrile wurde eine halbe Stunde auf die Temperatur von 50 C erwärmt. Es entstand ein farbloses elastisches räumlich vernetztes Polymer.was heated to the temperature of 50 C for half an hour. It a colorless, elastic, spatially cross-linked polymer was created.
In eine Lösung von 40 g eines hochmolekularen linearen Vinylmethylpolysiloxans der Zusammensetzung ( (CH3). λ(^6Η_)_ _- (CH„=CH)0 In a solution of 40 g of a high molecular weight linear vinylmethylpolysiloxane with the composition ((CH 3 ). Λ (^ 6 Η _) _ _- (CH „= CH) 0 (HO)n «SiO. .) mit dem Molekulargewicht 9.800 von 3 g eines Thiome-(HO) n «SiO. .) with the molecular weight of 9,800 of 3 g of a thiome
thy !polysiloxans der Zusammensetzung ( (HSCH-Jn nc(CHQ). Of-Si0)thy! polysiloxane of the composition ((HSCH-J nn c (CH Q ). Of -Si0)
£. U. UO <5 I »"Ο χ £. U. UO <5 I »" Ο χ
mit dem Molekulargewicht 10.000 und 0.6 g Azobisisobutyronitril in 100 ml Toluol wurden Tran^formatorenbleche eingetaucht. Nach Abdampfung des Lösungsmittels (nach 2 Stunden) wurde die isolierendewith a molecular weight of 10,000 and 0.6 g of azobisisobutyronitrile transformer plates were immersed in 100 ml of toluene. To Evaporation of the solvent (after 2 hours) became the insulating
entstand ein nicht lösliches, nicht schmelzbares Polymer. a non- soluble, non-meltable polymer was created.
- 8 009837/2109 ©^ oBl^ — - 8 009837/2109 © ^ oBl ^ -
Ein Gemisch aus 15Og eines linearen Thiomethylpolysiloxans der Zusammensetzung ( (HSChL)n ,.(Ci-L). .,SiO) mit depi Molekular-A mixture of 150 g of a linear thiomethylpolysiloxane of the composition ((HSChL) n ,. (Ci-L).., SiO) with depi molecular
i. υ« ι v> ». y χ i. υ «ι v>». y χ
gewicht von unaefähr 30,000 und 15 g Hexamethylendiisozyanat wurde 16 Stunden lang unter Stickstoff auf 80 C erwärmt. Nach dieser Zeit bildete sich ein farbloses, elastisches räumlich vernetztes Polymer.weight of about 30,000 and 15 g of hexamethylene diisocyanate Heated to 80 ° C. for 16 hours under nitrogen. After this time, a colorless, elastic, spatially networked structure formed Polymer.
Ein Gemisch aus 40 g eines linearen Thiomethylethalpolysiloxans der Zusammensetzung ( (HSCH0)n „(C-hL). öSi0 ) mit dem Molekular-A mixture of 40 g of a linear thiomethylethalpolysiloxane of the composition ((HSCH 0 ) n "(C-hL). Ö Si0) with the molecular
gewicht von ungefähr 60.000, aus 7 g Benzol-1,4-diisozyanat und 1.5 g Pyridin wurde 8 Stunden lang unter Stickstoff auf 70 C erwärmt. Es entstand ein farbloses, kautschukartiges räumlich vernetztes Polymer. Eine zwölfstUndige Erhitzung des derart zubereiteten Polymers in Luft bei 120 C hatte keine Veränderungen seiner mechanischen Eigenschaften zur Folge.weight of about 60,000, made from 7 g of benzene-1,4-diisocyanate and 1.5 g of pyridine was heated to 70 ° C. for 8 hours under nitrogen warmed up. A colorless, rubber-like, spatially crosslinked polymer was produced. A twelve hour heating of the so prepared Polymer in air at 120 C did not result in any changes in its mechanical properties.
In eine Lösung von 60 g eines Thiopropylmethylphenylpolysiloxans der Zusammensetzung (In a solution of 60 g of a thiopropylmethylphenylpolysiloxane of the composition (
mit dem Molekulargewicht 8.60O7 von 3 g Toluol-2/4-diisozyanat und 1 g Zyklohexyldimethylamin in 100 ml eines Gemisches Benzol-N, N-Dimethylformamid (2:1) wurden Transformatorenbleche eingetaucht. Nach Abdampfung des Lösungsmittels (nach 2 Stunden) wurde die isolierende Lackschicht für 2 Stunden auf 120°C erhitzt. Die gebildete Polymerschicht erwies sich als unlöslich.With a molecular weight of 8.60O 7 of 3 g of toluene 2 / 4-diisocyanate and 1 g of cyclohexyldimethylamine in 100 ml of a mixture of benzene-N, N-dimethylformamide (2: 1), transformer sheets were immersed. After evaporation of the solvent (after 2 hours), the insulating lacquer layer was heated to 120 ° C. for 2 hours. The polymer layer formed was found to be insoluble.
009837/2109 ~9~009837/2109 ~ 9 ~
Claims (11)
Si -R "
Si -
4- Si - 0 I (CH0) CHCH0 Γ R "
4- Si - 0 I (CH 0 ) CHCH 0
Si - C
RSHR 1 Ί
Si - C
RSH
Si-O
R"1 Τ? "
Si-O
R " 1
m/p = 1 bis 1/60 ist undm + η + ρ ^> 30,
m / p = 1 to 1/60 and
geführt wird.7. The method according to claims 1 to 5, characterized in that the reaction in the presence of an initiator for radical reactions at a concentration of 0.5-7 wt. Based on d
to be led.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CS143469 | 1969-02-27 | ||
CS143569 | 1969-02-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE2008426A1 true DE2008426A1 (en) | 1970-09-10 |
Family
ID=25745427
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19702008426 Pending DE2008426A1 (en) | 1969-02-27 | 1970-02-24 |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE2008426A1 (en) |
FR (1) | FR2033086A5 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2649854A1 (en) * | 1975-11-10 | 1977-05-12 | Sws Silicones Corp | PROCESS FOR THE PREPARATION OF ORGANOPOLYSILOXANES HAVING THIO FUNCTIONAL GROUPS |
US4107390A (en) | 1977-12-02 | 1978-08-15 | Dow Corning Corporation | Radiation-curable organopolysiloxane coating composition comprising mercaptoalkyl and silacyclopentenyl radicals, method of coating and article therefrom |
FR2446850A1 (en) * | 1979-01-18 | 1980-08-14 | Dow Corning | PROCESS FOR THE PREPARATION OF A CROSSLINKED POLYDIORGANOSILOXANE |
US4268655A (en) | 1979-12-03 | 1981-05-19 | Dow Corning Corporation | Ferrocene catalyzed elastomer formation |
US4269963A (en) | 1979-12-03 | 1981-05-26 | Dow Corning Corporation | Mercaptoorganopolysiloxanes and curable compositions including same |
US4272415A (en) | 1979-12-03 | 1981-06-09 | Dow Corning Corporation | Compositions including mercaptoorganopolysiloxanes and metal salts of carboxylic acids |
US4272623A (en) | 1979-12-03 | 1981-06-09 | Dow Corning Corporation | Mercaptoorganopolysiloxane elastomers catalyzed by metallic compounds in the presence of peroxides |
US4279792A (en) | 1979-12-03 | 1981-07-21 | Dow Corning Corporation | Compositions including mercaptoorganopolysiloxanes and stannous salts of carboxylic acids |
US4284539A (en) | 1979-12-03 | 1981-08-18 | Dow Corning Corporation | Compositions including mercaptoorganopolysiloxanes, aliphatically unsaturated polydiorganosiloxanes and carboxylic acid salts of metals |
EP0237757A2 (en) * | 1986-02-06 | 1987-09-23 | Wacker-Chemie GmbH | Compositions convertible into elastomers by irradiation |
US5378790A (en) * | 1992-09-16 | 1995-01-03 | E. I. Du Pont De Nemours & Co. | Single component inorganic/organic network materials and precursors thereof |
CN105849175A (en) * | 2013-12-27 | 2016-08-10 | 株式会社普利司通 | Vulcanizates and tire components prepared from compositions including mercapto-functional siloxanes |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4002794A (en) * | 1975-07-18 | 1977-01-11 | Nashua Corporation | Adhesive material and articles incorporating same |
-
1970
- 1970-02-24 DE DE19702008426 patent/DE2008426A1/de active Pending
- 1970-02-26 FR FR7006887A patent/FR2033086A5/en not_active Expired
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2649854A1 (en) * | 1975-11-10 | 1977-05-12 | Sws Silicones Corp | PROCESS FOR THE PREPARATION OF ORGANOPOLYSILOXANES HAVING THIO FUNCTIONAL GROUPS |
US4107390A (en) | 1977-12-02 | 1978-08-15 | Dow Corning Corporation | Radiation-curable organopolysiloxane coating composition comprising mercaptoalkyl and silacyclopentenyl radicals, method of coating and article therefrom |
FR2446850A1 (en) * | 1979-01-18 | 1980-08-14 | Dow Corning | PROCESS FOR THE PREPARATION OF A CROSSLINKED POLYDIORGANOSILOXANE |
US4234697A (en) | 1979-01-18 | 1980-11-18 | Dow Corning Corporation | Method of preparing cross-linked polydiorganosiloxane using organic isocyanates and products prepared therefrom |
US4268655A (en) | 1979-12-03 | 1981-05-19 | Dow Corning Corporation | Ferrocene catalyzed elastomer formation |
US4269963A (en) | 1979-12-03 | 1981-05-26 | Dow Corning Corporation | Mercaptoorganopolysiloxanes and curable compositions including same |
US4272415A (en) | 1979-12-03 | 1981-06-09 | Dow Corning Corporation | Compositions including mercaptoorganopolysiloxanes and metal salts of carboxylic acids |
US4272623A (en) | 1979-12-03 | 1981-06-09 | Dow Corning Corporation | Mercaptoorganopolysiloxane elastomers catalyzed by metallic compounds in the presence of peroxides |
US4279792A (en) | 1979-12-03 | 1981-07-21 | Dow Corning Corporation | Compositions including mercaptoorganopolysiloxanes and stannous salts of carboxylic acids |
US4284539A (en) | 1979-12-03 | 1981-08-18 | Dow Corning Corporation | Compositions including mercaptoorganopolysiloxanes, aliphatically unsaturated polydiorganosiloxanes and carboxylic acid salts of metals |
EP0237757A2 (en) * | 1986-02-06 | 1987-09-23 | Wacker-Chemie GmbH | Compositions convertible into elastomers by irradiation |
EP0237757A3 (en) * | 1986-02-06 | 1990-01-24 | Wacker-Chemie GmbH | Compositions convertible into elastomers by irradiation |
US5378790A (en) * | 1992-09-16 | 1995-01-03 | E. I. Du Pont De Nemours & Co. | Single component inorganic/organic network materials and precursors thereof |
US5548051A (en) * | 1992-09-16 | 1996-08-20 | E. I Du Pont De Nemours And Company | Single component inorganic/organic network materials and precursors thereof |
CN105849175A (en) * | 2013-12-27 | 2016-08-10 | 株式会社普利司通 | Vulcanizates and tire components prepared from compositions including mercapto-functional siloxanes |
US10150845B2 (en) | 2013-12-27 | 2018-12-11 | Bridgestone Corporation | Vulcanizates and tire components prepared from compositions including mercapto-functional siloxanes |
US10662298B2 (en) | 2013-12-27 | 2020-05-26 | Bridgestone Corporation | Vulcanizates and tire components prepared from compositions including mercapto-functional siloxanes |
Also Published As
Publication number | Publication date |
---|---|
FR2033086A5 (en) | 1970-11-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2649854C2 (en) | Process for the preparation of organopolysiloxanes containing thiofunctional groups | |
DE4204305C2 (en) | Process for the preparation of platinum complexes and their use | |
DE2429772C3 (en) | Process for the surface coating of paper | |
DE2421038C3 (en) | Process for the production of thermoset adducts from silicon hydrogen compounds and trialkenyl isocyanurates, as well as for the production of thermoset products therefrom | |
DE2008426A1 (en) | ||
DE1495920A1 (en) | Clear organopolysiloxane material | |
DE1214234B (en) | Process for the preparation of new organosilicon compounds with radicals containing oxime groups | |
DE2557940B2 (en) | Organosilicon compounds containing maleimide groups, processes for their preparation and their use | |
DE3447636A1 (en) | WHEN DILUTED WITH WATER, TRANSPARENT MIXTURE COMPOSITIONS CONTAINING POLYSILOXANE | |
DE3932231C2 (en) | Organopolysiloxane compound | |
DE957662C (en) | Process for the preparation of stable alkyl and / or aryl polysiloxane oils | |
DE1768084C3 (en) | Platinum complexes, processes for their production and their uses | |
DE1291122B (en) | Manufacture of embedding compounds that harden with platinum catalysts | |
DE1546410A1 (en) | Process for treating paper with siloxanes | |
DE19957336A1 (en) | Crosslinkable organopolysiloxane compositions | |
DE1794219A1 (en) | Process for the preparation of organopolysiloxane elastomers | |
EP0123321A2 (en) | Process for reticulating organopolysiloxane compositions | |
DE1420470C3 (en) | Process for the preparation of carbalkoxypolysiloxanes | |
DE1420792B2 (en) | Process for the preparation of aminoalkylalkoxypolysiloxanes | |
DE2619186A1 (en) | PROCESS FOR MANUFACTURING DIORGANOPOLYSILOXANE OILS | |
DE1646152C3 (en) | Process for the preparation of a coating of a mercaptohydrocarbyl silicon compound | |
DE1795324A1 (en) | New organosilicon compositions that can be vulcanized to form elastomers | |
DE2205143C3 (en) | Process for making leather permanently water-repellent | |
DE938879C (en) | Process for the production of organosilicon copolymers | |
DE840001C (en) | Process for stabilizing liquid organopolysiloxanes |