DE1191968B - Process for the production of linear polymeric silicic acid mixed esters - Google Patents
Process for the production of linear polymeric silicic acid mixed estersInfo
- Publication number
- DE1191968B DE1191968B DES57724A DES0057724A DE1191968B DE 1191968 B DE1191968 B DE 1191968B DE S57724 A DES57724 A DE S57724A DE S0057724 A DES0057724 A DE S0057724A DE 1191968 B DE1191968 B DE 1191968B
- Authority
- DE
- Germany
- Prior art keywords
- silicic acid
- aromatic
- production
- mixed esters
- linear polymeric
- 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
- 150000002148 esters Chemical class 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 11
- 241000790917 Dioxys <bee> Species 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- -1 aromatic substituents Orthosilicic acid esters Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004870 electrical engineering Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Verfahren zur Herstellung von linear-polymeren Kieselsäuremischestern Es ist bekannt. Orthokieselsäureester der Formel Si(OR) (R stets das gleiche Alkyl bzw. Aryl) mit Dioxyverbindungen umzusetzen. Je nach den Reaktionsbedingungen und dem molaren Verhältnis der Reaktionspartner entstehen hierbei, da sämtliche vier OR-Gruppen des Si(OR) hinsichtlich der Umesterung mit Dioxyverbindungen gleichwertig sind, mehr oder weniger stark vernetzte polymere Kieselsäureester. so daß in den Polymerisaten sehr leicht unerwünschte räumliche Vernetzung über Struktureinheiten des Typs eintritt (HO - R' - OH aliphatische bzw. aromatische Dioxyverbindung).Process for the production of linear polymeric silicic acid mixed esters It is known. Orthosilicic acid esters of the formula Si (OR) (R always the same alkyl or aryl) to react with dioxy compounds. Depending on the reaction conditions and the molar ratio of the reactants, since all four OR groups of Si (OR) are equivalent in terms of transesterification with dioxy compounds, more or less strongly crosslinked polymeric silicic acid esters are formed. so that in the polymers very easily undesired spatial crosslinking via structural units of the type occurs (HO - R '- OH aliphatic or aromatic dioxy compound).
Durch die Vernetzung erhält das Polymerisat insbesondere ungünstige lacktechnische Eigenschaften. The crosslinking gives the polymer particularly unfavorable properties paint properties.
Es wird unlöslich in organischen Lösungsmitteln und neigt zum Verspröden.It becomes insoluble in organic solvents and tends to become brittle.
Beansprucht ist ein Verfahren zur Herstellung von linear-polymeren Kieselsäuremischestern durch Umesterung von aromatische Substituenten tragenden Orthokieselsäureestern mit organischen Dioxyverbindungen, das dadurch gekennzeichnet ist, daß man als aromatische Substituenten tragenden Orthokieselsäureester den aliphatisch-aromatischen Mischester o,o'-Diphenyldioxy-diisopropoxysilan und als organische Dioxyverbindung 4,4'-Dioxydiphenylpropan verwendet. What is claimed is a process for the production of linear polymers Silica mixed esters by transesterification of aromatic substituents Orthosilicic acid esters with organic dioxy compounds, which is characterized is that the orthosilicic acid ester bearing aromatic substituents is the aliphatic-aromatic Mixed esters o, o'-diphenyldioxy-diisopropoxysilane and as an organic dioxy compound 4,4'-Dioxydiphenylpropane is used.
Die nach dem beanspruchten Verfahren verwendeten Mischester werden nach folgendem Reaktionsschema nach hier nicht beanspruchtem Verfahren gewonnen: Geeignete Alkohole sind z. B. Sithyl-, Butyl- oder Isopropylalkohol.The mixed esters used according to the claimed process are obtained according to the following reaction scheme using a process not claimed here: Suitable alcohols are e.g. B. sithyl, butyl or isopropyl alcohol.
Die erfindungsgemäß als Ausgangsmaterial benutzten Mischester sind im Gegensatz zu Mischestern des Typs (RO)2Si(OR')2 (R und R' = verschiedene Alkyl- bzw. Arylreste) einmal in quantitativer Ausbeute, zum anderen in ausgezeichneter Reinheit erhältlich. Außerdem aber zeigen sie keinerlei Tendenz zur Dismutation, z. B. nach folgendem Schema Ihre Umesterung mit Dioxyverbindungen verläuft nach dem folgenden Reaktionsschema In den erfindungsgemäß erhaltenen Polyestern sind die Si-Atome durch Brücken verbunden, die aus den Resten der Dioxyverbindungen OR'O bestehen.In contrast to mixed esters of the type (RO) 2Si (OR ') 2 (R and R' = different alkyl or aryl radicals), the mixed esters used according to the invention as starting material are obtainable on the one hand in quantitative yield and on the other hand in excellent purity. In addition, however, they show no tendency to dismutation, e.g. B. according to the following scheme Their transesterification with dioxy compounds proceeds according to the following reaction scheme In the polyesters obtained according to the invention, the Si atoms are connected by bridges which consist of the residues of the dioxy compounds OR'O.
Der Hauptvorteil liegt darin, daß bei der erwähnten Arbeitsweise die verwendeten Mischester hinsichtlich der Umesterung mit HO R' - OH nur bifunktionell sind, da bei diesem Prozeß nur das leichtflüchtige ROH aus dem Gleichgewicht entfernt wird.The main advantage is that the mixed esters used in the procedure mentioned are only bifunctional with regard to the transesterification with HO R '- OH, since in this process only the volatile ROH is removed from the equilibrium.
Hierdurch gelangt man zu linearen, thermisch recht stabilen Hochpolymeren, die - wie bereits erwähnt - den vernetzten Produkten lacktechnisch weit überlegen sind. This leads to linear, thermally quite stable high polymers, which - as already mentioned - are far superior to the networked products in terms of coating technology are.
Ein anderer Vorteil beruht auf der Verwendung halogenfreier Ausgangsmaterialien, was vor allem für die Anwendung der Produkte auf dem Gebiet der Elektrotechnik sehr wichtig ist. Another advantage is based on the use of halogen-free starting materials, which especially for the application of the products in the field of electrical engineering important is.
Darüber hinaus sind die so erhaltenen Hochpolymeren nicht nur thermisch, sondern auch chemisch außerordentlich resistent und hierin den bekannten Reaktionsprodukten von aliphatischen oder aromatischen Halogensilanen mit Polyoxyverbindungen überlegen. In addition, the high polymers obtained in this way are not only thermal, but also extremely chemically resistant and the known reaction products superior to aliphatic or aromatic halosilanes with polyoxy compounds.
Die nach dem erfindungsgemäßen Verfahren erhaltenen linear-polymeren Kieselsäuremischester haben insbesondere lacktechnisch wesentlich günstigere Eigenschaften als die bekannten Umsetzungsprodukte aus aromatischen Kieselsäureestern der allgemeinen Formel Si(OR)4 (R stets gleiche aromatische Reste) mit Dioxyverbindungen. The linear polymers obtained by the process according to the invention Mixed silicic acid esters have, in particular, properties that are significantly more favorable in terms of paint technology than the known reaction products of aromatic silicic acid esters of the general Formula Si (OR) 4 (R always the same aromatic radicals) with dioxy compounds.
Auch die rein aromatischen Kieselsäureester, die durch Verwendung von Ortho- oder Polykieselsäureester des Oxydiphenyls erhalten werden, weisen noch nicht die Vorteile der nach dem erfindungsgemäßen Verfahren erhaltenen Produkte auf. Even the purely aromatic silicic acid esters produced by using obtained from orthosilicic or polysilicic acid esters of oxydiphenyl, show still not the advantages of the products obtained by the process according to the invention on.
Während die bekannten Produkte in aromatischen Lösungsmitteln unlöslich sind und zum Verspröden neigen, weisen die erfindungsgemäß erhaltenen linearpolymeren Produkte in lacktechnischer Hinsicht besonders günstige Eigenschaften auf. While the known products are insoluble in aromatic solvents and tend to become brittle, the linear polymers obtained according to the invention have Products have particularly favorable properties in terms of paint technology.
Beispiel Ein Gemisch von 66,0 g (11ã Mol) o,o'-Diphenyldiisopropoxysilan und 45,8 g (1/5 Mol) 4,4'-Dioxydiphenylpropan wird unter Rühren langsam bis auf 1500C erhitzt und 2 Stunden auf dieser Temperatur gehalten. Während der Reaktion destilliert die berechnete Menge Isopropanol (2/ã Mol) ab, und ein braunes viskoses Di wird erhalten, das bei Raumtemperatur zu einem lichtbraunen, transparenten Harz erstarrt. Dieses ist in Benzol, Toluol und Xylol löslich. Sein Si-Gehalt beträgt etwa 15,50in. Die Molgewichte liegen bei etwa 4000. Example A mixture of 66.0 g (11α mol) of o, o'-diphenyldiisopropoxysilane and 45.8 g (1/5 mol) of 4,4'-dioxydiphenylpropane is slowly added to with stirring Heated to 1500C and held at this temperature for 2 hours. During the reaction distilled the calculated amount of isopropanol (2 / ã mol) from, and a brown viscous Di is obtained, which at room temperature to a light brown, transparent resin stiffens. This is soluble in benzene, toluene and xylene. Its Si content is about 15.50in. The molecular weights are around 4000.
Die so gewonnenen Stoffe sind gut hitzebeständig und zeichnen sich auch sonst durch große Stabilität aus. Sie finden als Kunststoffe in der Elektrotechnik, namentlich für Isolations- und Tränkzwecke oder als Lackgrundkörper Verwendung. The substances obtained in this way are good heat-resistant and stand out also otherwise characterized by great stability. You will find plastics in electrical engineering, specifically for insulation and impregnation purposes or as a paint base.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DES57724A DE1191968B (en) | 1958-04-05 | 1958-04-05 | Process for the production of linear polymeric silicic acid mixed esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DES57724A DE1191968B (en) | 1958-04-05 | 1958-04-05 | Process for the production of linear polymeric silicic acid mixed esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1191968B true DE1191968B (en) | 1965-04-29 |
Family
ID=7492042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DES57724A Pending DE1191968B (en) | 1958-04-05 | 1958-04-05 | Process for the production of linear polymeric silicic acid mixed esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1191968B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE285285C (en) * | ||||
| US2630446A (en) * | 1948-08-04 | 1953-03-03 | Du Pont | Polymeric silicates |
| DE945936C (en) * | 1952-09-24 | 1956-07-19 | Siemens Ag | Process for the production of an electrical insulating material |
| DE1009813B (en) | 1952-11-21 | 1957-06-06 | Siemens Ag | Process for the preparation of polymeric silicic acid esters of higher molecular weight |
| DE1010739B (en) | 1954-11-03 | 1957-06-19 | Kali Chemie Ag | Process for the production of polysilicic acid esters of higher alcohols or phenols |
| DE973716C (en) * | 1950-07-07 | 1960-05-19 | Siemens Ag | Process for the production of a curable silicon-containing synthetic resin |
-
1958
- 1958-04-05 DE DES57724A patent/DE1191968B/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE285285C (en) * | ||||
| US2630446A (en) * | 1948-08-04 | 1953-03-03 | Du Pont | Polymeric silicates |
| DE973716C (en) * | 1950-07-07 | 1960-05-19 | Siemens Ag | Process for the production of a curable silicon-containing synthetic resin |
| DE945936C (en) * | 1952-09-24 | 1956-07-19 | Siemens Ag | Process for the production of an electrical insulating material |
| DE1009813B (en) | 1952-11-21 | 1957-06-06 | Siemens Ag | Process for the preparation of polymeric silicic acid esters of higher molecular weight |
| DE1010739B (en) | 1954-11-03 | 1957-06-19 | Kali Chemie Ag | Process for the production of polysilicic acid esters of higher alcohols or phenols |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2743843A1 (en) | BORSILOXANE POLYMERS AND A PROCESS FOR THE PREPARATION | |
| DE102007063284A1 (en) | spiro compounds | |
| DE2708469C3 (en) | Process for the preparation of N, N'-alkylene-bis-tetrabromophthalimides | |
| DE934889C (en) | Process for the preparation of esters and / or polyesters of the tricyclodecane series | |
| DE1191968B (en) | Process for the production of linear polymeric silicic acid mixed esters | |
| DE2020224C3 (en) | Methyl or methylphenylpolysiloxane resins | |
| US3053777A (en) | New polymeric materials of diboronic acid and derivatives | |
| DE1570948C3 (en) | Process for the preparation of polyaromatic compounds | |
| DE916117C (en) | Plastic mass | |
| EP0375974A2 (en) | Chlorine-containing polysubstituted silazane polymers, method for their preparation, and their use for preparing silicon nitride-containing ceramic materials | |
| DE903994C (en) | Process for the preparation of organosiloxanes | |
| DE859952C (en) | Process for the production of synthetic resins | |
| DE919423C (en) | Process for the production of compounds with the properties of drying oils | |
| DE854264C (en) | Process for the production of organosiloxanes by hydrolyzing hydrolyzable silanes and condensing the hydrolyzed products | |
| DE1173660B (en) | Process for the preparation of organopolyalumoxsiloxanes | |
| DE1720513A1 (en) | Process for the production of transparent, boil-resistant polyamides | |
| DE962464C (en) | Coating compound, especially air-drying paint | |
| DE833123C (en) | Process for the production of organosiloxane resins by hydrolysis of a hydrolyzable silane and condensation of the hydrolyzed products | |
| US2885297A (en) | Production of drying oils | |
| DE1067814B (en) | Process for the preparation of boron trialkyls | |
| DE1209753B (en) | Process for the production of polymeric organic boron-nitrogen compounds | |
| DE969104C (en) | Plasticizer for plastic mixtures on the basis of cellulose triacetate | |
| AT295854B (en) | Process for the preparation of esterimide resins | |
| CH344562A (en) | Process for the production of synthetic resins containing aluminum | |
| DE1013640B (en) | Process for the production of polyaluminum alcoholates or -phenolates and silicic acid esters |