NZ270935A - Reacting polysiloxanes with an alkoxy silane in the presence of fluoride as activator - Google Patents
Reacting polysiloxanes with an alkoxy silane in the presence of fluoride as activatorInfo
- Publication number
- NZ270935A NZ270935A NZ270935A NZ27093595A NZ270935A NZ 270935 A NZ270935 A NZ 270935A NZ 270935 A NZ270935 A NZ 270935A NZ 27093595 A NZ27093595 A NZ 27093595A NZ 270935 A NZ270935 A NZ 270935A
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- NZ
- New Zealand
- Prior art keywords
- fluoride
- process according
- alkyl
- group
- reaction
- Prior art date
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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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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)
Abstract
The novel feature in the reaction of polysiloxanes with alkoxysilanes is that fluoride ions are present as activator, such ions pref. having as their source: (i) an alkali metal fluoride; or (ii) a non-metallic cpd. esp. a tetra-alkylammonium fluoride and/or NH4F as well as trialkylamine-HF and other polyhydrofluorides or tert. org. amines.
Description
New Zealand Paient Spedficaiion for Paient Number £70935
•V
Patents Form 5
Priority Date(s):.. Oo)u|flW;
13}'o|<r< incomplete Specification f:iled:
Class: (6)
Publication Data: .....2..6.iMAR..iS.38
P.O. Journal No: i.<rt.<P..'.2r:
I !
N.Z. No.
NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION
OfitoArJO^lLOXAM fc.S,
PREPARING REACTION PRODUCTS FROM POLYtBteRefrNeSffc^WBS*
We, BAYER AKTIENGESELLSCHAR\, a Company registered under the laws of the Federal Republic of Germany of, D-51368 Leverkusen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
- 1 - (Followed by 1A)
r, „ .. €
J jl
DC/m '03 DM?1
Preparing reaction products from polv(diorqano"i 1 nvanog)
The present invention relates to a process for preparing reaction products from poly(diorganosiloxanes) and alkoxy-5 silanes.
The objective when reacting poly(diorganosiloxanes) with alkoxysilanes is to produce poly(diorganosiloxanes) with diorganyloxy-organosilyl or triorganyloxysilyl terminal groups. The following ways for doing this are shown in the 10 literature:
1. Reaction of a, 6-dihydroxy-poly(diorganosiloxanes) with alkoxysilanes in the presence of suitable catalysts and
2 . the reaction of cc,u-dihydroxy-poly-(diorganosiloxanes)
• 15 with mixed functional silanes, such as e.g. alkoxy-
/(equivalent to US 3,364,160) amidosilanes (DE-PS 1,247,646), alkoxy-oximosilanes
(EP 98,369) and alkoxy-acetoxysilanes (US-PS
3,296,165), without an additional catalyst.
Known catalysts for the method first described, are mainly
amines (EP 21,859) mixed with metal carboxylates (US-PS
3,161,614) and amines mixed with carboxylic acids (EP
137,883) , ammonium carbamates, preferably
/ (equivalent to US 4,705,826) (CH3) 2NH2OCON (CH3 ) 2 (DE-PS 3,523,206) and hydroxylamine derivatives (EP 70,786).
All the catalysts or catalysts systems described hitherto for use during the production of alkoxy-terminated poly-siloxanes, however, require long reaction times and lie A- 30 160-FC
- 1A-
(Ti > ^^74
I I U t' v' 3
elevated temperatures. In addition, the catalysts have to be used in substantial amounts, their removal from the polymer generally being difficult or even impossible. These disadvantages can be eliminated by the use of alkali metal , , . , , , , „ /(equivalent to US 5,196,497)
hydroxides and alcohols (DE-OS 4, 022, 661, EP-A 457,693, E?P-
A 376,696) as catalysts. The high degree of activation produced by hydroxide ions or alcoholate ions, however,
leads to unwanted side reactions such as, e.g. polymer rearrangements, so the catalyst has to be inactivated by
neutralization as rapidly as possible after termination of the reaction.
In the second case, the silanes used, in contrast to pure organyloxy or organyloxyorganosilanes, are sufficiently reactive to react with a,u-dihydroxy-poly(diorganosil-15 oxanes) without the use of catalysts. Production of the silanes, however, is costly and removal of the cleavage products is difficult or impossible.
Principally for economic reasons, the last mentioned method, with the use of appropriate catalysts, is preferred 20 for the reaction of a,u-dihydroxy-poly(diorganosiloxanes)
with alkoxysilanes.
The object of the invention is the provision of a process for reacting poly(diorganosiloxanes) with alkoxysilanes,
which particularly permits the production of poly (diorgano-25 siloxanes) with diorganyloxy-organosilyl or triorganyloxy-silyl terminal groups after a shorter reaction time even at room temperature.
Surprisingly, it has now been found that the reaction of poly (diorganosiloxanes) and alkoxysilanes in the presence 30 of fluorides leads to the production of alkoxy-terminated poly (diorganosiloxanes) within a few minutes even at room temperature and in addition the fluoride ions introduced in this mixture are suitable for the controlled degradation of
•he A 30 100-re
270$^
high-molecular poly (diorganosiloxanes) with exfeideaSrecfc -v v tion times.
The present invention therefore provides a process for preparing reaction products from poly(diorganosiloxanes) 5 and alkoxysilanes, wherein the reaction is performed in the presence of fluoride ions as activator.
A polysiloxane for use in the sense of the invention is a polysiloxane or a mixture of several polysiloxanes of the formula (I)
r1
r2o-
-Si o-
(I) ,
in which
R, R1 may be a C^-C-La-alkyl or alkoxy group, phenyl or substituted phenyl or a C2-C18-alkenyl or alkoxy-alkyl group and R may be identical to or 15 different from R '
R2, R3 may be H-, a Cj-Cm-alkyl, C6-C14-aryl or SiR5 group, where R5 = a C2-C18-alkyl/alkoxy, C6-C14
aryl, C2-C18-alkenyl or alkoxyalkyl group, wherein R2 and R3 may be identical or different, 20 and x = 10 to 10,000.
In a preferred embodiment, the polysiloxane has a network structure.
Examples of these polysiloxanes with a network structure 25 are vulcanized elastomers such as, for example, high-
270$?J
temperature vulcanizing (HV), liquid silicone (LSR), room temperature vulcanizing (RTV) single component (1C) or two-component (2C) elastomers.
The network structure of the polysiloxanes can be built up, 5 inter alia, by means of
R
Si—0 Si=
| , and/or
0
Si EE
Si =
O
Q-unit =Si O Si — O Si= ,
0
1
SiEEE
and groups which are formed by hydrosilylation or peroxidic cross-linking reactions such as alkylene groups.
An alkoxysilane for use in the sense of the invention is at least one alkoxysilane or a mixture of several alkoxysilanes of the formula (II)
R7nSi(OR6)4_n (II),
in which
R6 represents an optionally substituted C^-Cg-alkyl,
C2-C8-alkoxyalkyl group, or a C5-C7-cy-loalipha-tic hydrocarbon group,
EESi-
T-unit
27093 ^
R7 represents an optionally substituted alkyl, C2-C10-alkenyl, phenyl or substituted phenyl group, and n is 0, 1 or 2.
Particularly preferred alkoxysilanes are tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrieth-oxysilane and dimethyldimethoxysilane. Also suitable are alkoxysilanes with substituents in the alkyl group such as, for example, XCH2CH2CH? (OR1) 3, where X = HS-, H2N-, R2N-, Cl-10 and other substituents.
Activators in the sense of the invention are metal and non-metal fluorides which are soluble in the system.
Metal fluorides in the sense of the invention are preferably alkali metal fluorides such as, e.g. sodium 15 fluoride, potassium fluoride, and the like. Non-metal fluorides are preferably used as sources of fluoride ions. Ammonium trifluoride and/or tetraalkylammonium fluorides are particularly preferred, in particular tetrabutyl-ammonium fluoride, and trialkylamine hydrofluorides such 20 as, for instance, triethylamine trishydrofluoride [ (C2H5)3N-3HF] and other polyhydrofluorides of tertiary organic amines. The activators may be added to the reaction mixtures either in the pure form or in the dissolved state in suitable solvents or in alkoxysilanes. Alcohols and 25 alkoxysilanes have proved to be particularly suitable solvents.
Using the present invention, it has been established that very low concentrations of fluoride ions are sufficient to function as an activator in the reaction. In the process 30 according to the invention for preparing reaction products from polysiloxanes and alkoxysilanes 0.001 to 5 wt.%, preferably 0.001 to 1 wt.%, in particular 0.001 to 0.5 wt.%
of fluoride ions, with respect to the total mixture, are preferably used.
The process according to the invention takes place at temperatures between 0 and 3 00°C.
In a preferred embodiment of the present invention, the process for reacting polysiloxanes and alkoxysilanes in the presence of fluoride ions is terminated after the production of triorganylsilyl or diorganyloxy-organylsilyl-terminated poly(diorganosiloxanes) by precipitating the 10 fluoride ions as barely soluble alkaline earth metal fluorides, wherein the polysiloxanes of the formula (I) used have at least one OH function available. Polysiloxanes with a content of 0.01 to 19 wt.% of SiOH, with respect to the polymer, in particular a,u-dihydroxy-poly(diorgano-15 siloxanes), are preferably used.
All the previously described alkoxysilanes with formulae analogous to the formula (II) and all the previously described alkali metal and non-metal fluorides may also be used. Termination of the reaction can be achieved by adding 20 alkaline earth metal ions. In this case, barely soluble alkaline earth metal fluorides are formed which can no longer act as activators in the system. Any alkaline earth metal salts which are soluble in this system are suitable as alkaline earth metal compounds. Calcium chloride is 25 particularly suitable. In order to achieve the greatest possible distribution in the reaction mixture and the shortest possible reaction times, the alkaline earth metal salts are added to the reaction mixture in dissolved form. Alcohols such as methanol and ethanol have proved to be 30 particularly appropriate solvents.
The amount of alkaline earth metal compound used depends on the concentration of fluoride ions in the reaction mixture. The alkaline earth metal ions must be used in at least a
stoichiometric ratio, with respect to the fluoride ions,- a 20 to 100 % strength excess, with respect to the amount which is stoichiometric with respect to fluoride has proved advantageous.
The reaction conditions during the reaction of poly-(diorganosiloxanes) and alkoxysilanes depends on the reactivity of the alkoxysilane used and the reaction products which are desired. The process according to the invention takes place at temperatures between 0 and 300°C, preferably 10 15 to 60°C, in particular 18 to 40°C and specifically at room temperature. The reaction time is then at least 3 minutes, preferably 5 to 30 minutes. The reaction time depends on the desired degree of termination. The particularly preferred duration of reaction at room temperature is 15 less than 10 minutes.
If the polymer is intended for preparing RTV-1C (room temperature vulcanizing single component) materials, then a one-pot process is used in the mixing unit.
In another embodiment of the present invention, the 20 reaction of polysiloxanes with alkoxysilanes in the presence of fluoride ions at temperatures between 0 and 3 00°C lasts for at least 5 minutes.
In this embodiment of the process according to the invention, polysiloxanes of the formula (I) are used. Pre-25 ferably, however, the previously mentioned polysiloxanes with a network structure are used. Likewise, all the previously described alkoxysilanes with formulae analogous to formula (II) and all the previously described metal and non-metal fluorides can be used.
In this embodiment of the process according to the invention, compounds of the general formula (III)
,La h 30 100 PC
W V-'
(III),
in which
R, R1 represent linear or branched C1-C18-alkyl or
Ci-C18-alkoxy, C6-C14-aryl, C2-C18-alkoxyalkyl/alk-enyl groups and R may be identical to or different from R1, and y =
3 to 20, preferably y = 3 to 6, in particular y = 3,
are preferably prepared as low-molecular siloxanes.
In a further embodiment, linear and/or branched short-chain siloxanes of the general formula (IV)
^ R1
R40-
■Si O-
-R4
(IV),
in which
R, R1 represent C1-C18-alkyl or C1-C18-alkoxy, Ce-C14-
aryl, C2-C10-alkoxyalkyl/'aIkenyl groups and R may be identical to or different from R1,
represents a C1-C18-alkyl group or -SiR53 where R5 = Cx-C18-alkoxy/alkyl, C6-C14-aryl or C2-C18-alkenyl/alkoxyalkyl and
■Le A JO Ibu-f'C
z is 1 to 200, preferably 3 to 100 and in particular 3 to 10,
are preferably prepared as low-molecular siloxanes.
Low-molecular, branched, short-chain siloxanes of the for-5 mula (IV) , however, may also be produced admixed with low-molecular rings of the formula (III) .
The reaction may be performed either at room temperature or at elevated temperature. The reaction time depends on the type of poly(diorganosiloxane) used and the temperature. It 10 may be between a few hours and several days. The volatile reaction products, such as cyclic diorganosiloxanes, may be separated from the reaction mixture by distillation under reduced pressure. Reaction of polysiloxanes and alkoxysilanes in the presence of fluoride ions may also be per-15 formed in solvents. Any organic solvent such as, for instance, toluene, xylene, alcohol or even low viscosity poly(diorganosiloxanes) or cyclic diorganosiloxanes may be considered as a solvent.
The process according to the invention is explained in more 20 detail by means of the following examples.
2/cr^!)
Working examples
To check the termination procedure, the products from the examples and the comparison examples were tested as follows:
1. viscosity determination using a Haake rotational viscometer,
2. cross-linking test and
3. determination of the SiOH content by FT- IR differential spectroscopy.
In the cross-linking test described under 2, 20 parts by wt. of the mixture being tested were cross-linked with 1 part by wt. of a test solution. This test solution was prepared by dissolving 40 % of dibutyltin oxide in tetra-ethyl silicate at 100°C. If, after adding the test 15 solution,a rapid increase in viscosity and gelling of the mixture is observed, then this is taken to indicate incomplete reaction of the SiOH groups. If this type of behavior is not observed and the material cures under the effects of atmospheric moisture, then it can be concluded 20 that a successful termination reaction has occurred.
uli ii so loo re
70®^
* v* <>.#> O*
Example 1
A mixture of 55 parts by wt. of an OH-terminated poly-(dimethylsiloxane) with a viscosity of 80 Pa.s and 29 parts by wt. of a trimethylsilyl-terminated poly(diorganosil-oxane) with a viscosity of 100 mPa.s was initially placed in a planetary mixer. 2.5 parts by wt. of methyltrimethoxy-silane which contained 1.0 wt.% of tetrabutylammonium fluoride were added to this mixture. After 10 minutes 0.55 parts by wt. of a solution of 1 wt.% of calcium chloride in ethanol were added.
The polymer mixture had a viscosity of 15.7 Pa.s immediately after preparation, and this did not alter in re; eat measurements which were performed after one day and 7 days. No SiOH groups could be detected by means of FT-IR spectroscopy. The cross-linking test did not show rapid gelling, but. after 24 hours in the presence of moisture, a 2 mm thick layer had thoroughly hardened to produce a test sample. From these results it was concluded that the desired termination reaction had taken place.
Example 2 (comparison example)
Example 1 was repeated without adding a catalyst and using methyltrimethoxysilane. The mixture had a viscosity of 16.5 Pa.s and an SiOH content of 0.16 wt.%. On adding the test solution in the cross-linking test, intense gelling occurred.
Example 3 (comparison example)
Example 1 was repeated without adding the calcium chloride solution. The viscosity of the polymer decreased greatly and after 24 hours was about 1 Pa.s. The SiOH content was a maximum of 0.01 wt.%. In the cross-linking test, there
was neither gelling nor cross-linking of the tnaterial after 24 hours.
TCvampI 4
Example 1 was repeated with the addition of 0.92 parts by 5 wt. of a solution of 1 wt.% of calcium chloride in ethanol. The viscosity of the polymer mixture was 15.0 Pa.s and did not alter over the course of 7 days. SiOH groups could no longer be detected and the cross-linking test did not produce any gelling. A fully cured test sample was produced 10 after 24 hours.
Ryamp] 5
Example 1 was performed with the addition of 1.25 parts by wt. of methyltrimethoxysilane and 1.25 parts by wt. of a methyltrimethoxysilane with 1 wt.% of tetrabutyl-ammonium 15 fluoride. After 15 minutes, 0.27 parts by wt. of a solution of 1 % of calcium chloride in ethanol were added. SiOH groups could no longer be detected. The viscosity remained unaltered at 18.2 Pa.s over an interval of 7 days. In the cross-linking test, no gelling was observed.
Example 6
Example 1 was performed using 2.5 parts by wt. of methyltrimethoxysilane and 0.25 parts by wt. of a solution of 10 % of tetrabutylammonium fluoride in methanol. Deactivation of the fluoride ions was performed by adding 0.6 parts 25 by wt. of a solution of 1 % of calcium chloride in ethanol after 10 minutes. The cross-linking test led to no gelling and the SiOH content was at most 0.01 %.
TC-vawple 7
This example demonstrates using the process according to the invention to produce a RTV-lC material in a one-pot process during the course of a compounding procedure.
55 parts by wt. of an OH-terminated poly(dimethylsiloxane) with a viscosity of 80 Pa.s and 29 parts by wt. of a tri-methylsilyl-terminated poly (dimethylsiloxane) with a viscosity of 100 mPa.s were initially introduced into a planetary mixer. Then, 2.5 parts by wt. of a solution of 1 % of tetrabutylammonium fluoride in methyltrimethoxysilane were stirred in and left for 10 minutes. The termination reaction was concluded by adding 0.55 parts by wt. of a solution of 1 % of calcium chloride in ethanol. Then 9.5 parts by wt. of a hydrophobized, pyrogenic silica (BET surface area 110 m2/g) were added and stirred slightly. Afterwards, 1 part by wt. of a titanium diisobutoxy-bis-ethyl-acetate chelate was added and stirred in. Incorporation of the titanium complex proceeded without any problem. Since, when using OH-terminated polymers, an undesirable increase in viscosity is generally observed after adding a titanium catalyst, it can be concluded that the termination reaction of the polymer had finished.
The mixture was placed in cartridges. To check the mechanical data, 2 mm thick compacted sheets were drawn out and a tensile/stretching test was performed in accordance with DIN 53 504 after curing for 14 days at 23°C and 50 % relative humidity.
Tensile stress at 100 % extension 0.32 [MPa]
Tear strength 1.80 [MPa]
Elongation at break 670 [%]
Hardness (after 21 days, DIN 53505) 21 Shore A
T n A .1 go ■ gg-
270?
The paste showed no noticeable differences from the behavior of freshly prepared material and was in perfect condition when the mechanical tests were repeated after storing for 3 months in cartridges at room temperature and 50°C.
Example 8
42 parts by wt. of an OH-terminated poly- (dimethylsiloxane) with a viscosity of 80 Pa.s and 18 parts by wt. of a tri-methylsilyl-terminated poly (dimethylsiloxane) with a viscosity of 100 mPa.s were initially placed in a planetary mixer. Then, 2 parts by wt. of a solution of 1 % of tetra-butylammonium fluoride in methyltrimethoxysilane were stirred in and 0.55 parts by wt. of a solution of 1 % of calcium chloride in ethanol were added after 10 minutes standing time. 30 parts by wt. of chalk milled with stearic acid and 5.5 parts by wt. of a hydrophobized pyrogenic silica (BET surface area 110 m2/g) were then added and stirred slightly. Afterwards, l part by wt. of a titanium diisobutoxy-bis-ethyl-acetate chelate was added and stirred in. Incorporation of the titanium complex proceeded without any problem. Checking the mechanical properties in accordance with Example 7 produced the following results:
Tensile stress at 100 % extension 0.49 [MPa]
Tear strength 1.71 [MPa]
Elongation at break 599 [%]
Hardness (after 21 days, DIN 53505) 25 Shore A
It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
270635
Claims (14)
1. In the reaction of a polysiloxane with an alkoxysilane to produce polysiloxanes with special terminal groups, the improvement which comprises effecting the reaction 5 in the presence of fluoride ions as activator.
2. A process according to claim 1, wherein the starting polysiloxane comprises at least one polysiloxane of the formula r20- -Si O- R 10 in which R and R1 each independently is Cj-C-^-alkyl or alkoxy, phenyl or substituted phenyl or a C2-C18-alkenyl or alkoxyalkyl group, 15 R2 and R3 each independently is H-, or a C^-Cig-alkyl, Cg-C14-aryl or SiR53 group, is a Cx - C-t 8-alkyl/alkoxy, C6-C14-aryl, C2-C18-alkenyl or alkoxyalkyl group, and x - 10 to 10,000.
A process according to Claim l, wherein the poly-2 0 siloxane has a network structure.
A process according to Claim 1, wherein the alkoxysilane comprises at least one alkoxysilane of the formula L * V V-" V-' ^ R7nSi (OR6) 4.n in which R6 is an optionally substituted C1-Cs-alkyl or C2-C8-alkoxyalkyl group, or a Cs-C7-cyclo-5 aliphatic hydrocarbon group, R7 is an optionally substituted C^-C^-alkyl, C2-C10-alkenyl, phenyl or substituted phenyl group, and n is 0, 1 or 2. 10
5. A process according to Claim 1, wherein the source of the fluoride ions is a non-metal fluoride.
6. A process according to Claim 1, wherein the source of the fluoride ions is at least one member selected from the group consisting of a tetraalkylammonium fluoride, 15 ammonium fluoride, a trialkylamine hydrofluoride and another polyhydrofluoride of a tertiary organic amine.
7. A process according to Claim 1, wherein the source of the fluoride ions is an alkali metal fluoride.
8. A process according to Claim 1, wherein the fluoride 20 ions are present in 0.001 to 5 wt.%, of the total mixture.
9. A process according to Claim 1, wherein the polysiloxane of the formula (I) has at least one OH function available, and including the further step of 25 precipitating the fluoride ions as barely soluble alkaline aarth metal fluorides, thereby to terminate the reaction after the production of triorganyloxy- ■Uj JI 3 0-*GO PC1-- - 16 - ! / 0 8 5 silyl or diorganyloxyorganylsilyl-terriiinated poly (diorganosiloxanes) .
10. A process according to Claim 1, wherein the reaction time is at least 5 minutes at a temperature between 0 and 300°C.
11. A process according to Claim 1, wherein the polysiloxanes produced are of the general formula 10 R an R1 represent linear or branched C1-C18-alkyl or q-Cig-alkoxy, C6-C14-aryl, C2-C18 - alkoxy -alkyl/alkenyl groups and R may be identical to or different: from R1, and y = 3 to 20.
12. A process according to Claim 1, wherein the 15 polysiloxane produced is a linear or branched short- chain siloxane of the formula ^ R9 R40- -Si O- -R in which 27 u y 3 5 R8 and R9 each independently is a Cj^C^-allcyl, C^C^-alkoxy,C6-C14-aryl or C2-C18-alkoxyalkyl or alkenyl group, R4 is a Cj^-Cj^g-alkyl group or -SiR53, is a Cj^-Cia-alkoxy or alkyl, C6-C14-aryl or C2-Cia-alkenyl or alkoxyalkyl, and is 1 Co 200.
13. A process according to Claim 2, wherein the starting polysiloxane has at least one OH function available, 10 the scarting alkoxysilane comprises at alkoxysilane of the formula R7n Si (OR6) 4_n in which Rs is an optionally substituted C^Cg-alkyl or 15 C2-C8-alkoxyalkyl group, or a C5-C7-cyclo- aliphatic hydrocarbon group, R7 is an opCionally subscituted C1-C10-alkyl, C2-C10-alkenyl, phenyl or substituted phenyl group, and 20 n is 0, 1 or 2, Che source of the fluoride ions is at least one member selected from the group consisting of an alkali metal fluoride, a tetraalkylammonium fluoride, ammonium fluoride, a trialkylamine hydrofluoride and another 25 polyhydrofluoride of a tertiary organic amine, the reaction is conducted for at least Lq "A 3'0 1 GO* ■r^T - 18 - 5 minutes at a temperature between 0 and 300°C, and including the further step of precipitating the fluoride ions as barely soluble alkaline earth metal fluorides.
14. A process according to claim 1 substantially as herein described or exemplified. BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4413706 | 1994-04-20 | ||
DE4436536A DE4436536A1 (en) | 1994-04-20 | 1994-10-13 | Process for the preparation of reaction products of poly (diorganosiloxanes) |
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Publication Number | Publication Date |
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NZ270935A true NZ270935A (en) | 1996-03-26 |
Family
ID=25935792
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NZ270935A NZ270935A (en) | 1994-04-20 | 1995-04-13 | Reacting polysiloxanes with an alkoxy silane in the presence of fluoride as activator |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0678541B1 (en) |
JP (1) | JPH07292114A (en) |
AT (1) | ATE189687T1 (en) |
AU (1) | AU684337B2 (en) |
CA (1) | CA2147054A1 (en) |
CZ (1) | CZ99795A3 (en) |
FI (1) | FI951836A (en) |
HU (1) | HU217777B (en) |
NO (1) | NO951472L (en) |
NZ (1) | NZ270935A (en) |
PL (1) | PL308198A1 (en) |
SK (1) | SK50495A3 (en) |
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DE102007034711A1 (en) | 2007-07-25 | 2009-01-29 | Wacker Chemie Ag | Process for the preparation of organosilicon-containing organosilicon compounds |
CN111116918A (en) * | 2019-12-26 | 2020-05-08 | 仙桃市蓝化有机硅有限公司 | Preparation method of organosilane oligomer |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59108033A (en) * | 1982-12-10 | 1984-06-22 | Dainippon Ink & Chem Inc | Preparation of ladder-type polyphenylsiloxane having high molecular weight |
JPS59129230A (en) * | 1983-01-14 | 1984-07-25 | Dainippon Ink & Chem Inc | Production of high-molecular weight ladder polyorganosiloxane copolymer |
US4611040A (en) * | 1985-06-05 | 1986-09-09 | Ppg Industries, Inc. | Fluoride ion as a curing catalyst for silicon-containing resins |
DE4116014A1 (en) * | 1991-05-16 | 1992-11-26 | Wacker Chemie Gmbh | METHOD FOR PRODUCING ORGANO (POLY) SILOXANES |
EP0576166A2 (en) * | 1992-06-08 | 1993-12-29 | General Electric Company | Heat curable silicone hardcoat compositions |
DE4405851A1 (en) * | 1994-02-23 | 1995-08-31 | Wacker Chemie Gmbh | Process for the preparation of organopolysiloxanes containing organyloxy groups |
-
1995
- 1995-04-07 AT AT95105238T patent/ATE189687T1/en active
- 1995-04-07 EP EP95105238A patent/EP0678541B1/en not_active Expired - Lifetime
- 1995-04-13 CA CA002147054A patent/CA2147054A1/en not_active Abandoned
- 1995-04-13 NZ NZ270935A patent/NZ270935A/en unknown
- 1995-04-13 AU AU16489/95A patent/AU684337B2/en not_active Ceased
- 1995-04-14 JP JP7112601A patent/JPH07292114A/en active Pending
- 1995-04-18 FI FI951836A patent/FI951836A/en unknown
- 1995-04-18 SK SK504-95A patent/SK50495A3/en unknown
- 1995-04-18 PL PL95308198A patent/PL308198A1/en unknown
- 1995-04-19 CZ CZ95997A patent/CZ99795A3/en unknown
- 1995-04-19 HU HU9501110A patent/HU217777B/en not_active IP Right Cessation
- 1995-04-19 NO NO951472A patent/NO951472L/en unknown
Also Published As
Publication number | Publication date |
---|---|
CA2147054A1 (en) | 1995-10-21 |
CZ99795A3 (en) | 1995-11-15 |
HU217777B (en) | 2000-04-28 |
NO951472L (en) | 1995-10-23 |
NO951472D0 (en) | 1995-04-19 |
SK50495A3 (en) | 1995-11-08 |
EP0678541A3 (en) | 1996-01-17 |
FI951836A (en) | 1995-10-21 |
PL308198A1 (en) | 1995-10-30 |
FI951836A0 (en) | 1995-04-18 |
JPH07292114A (en) | 1995-11-07 |
HUT73048A (en) | 1996-06-28 |
HU9501110D0 (en) | 1995-06-28 |
ATE189687T1 (en) | 2000-02-15 |
AU1648995A (en) | 1995-11-02 |
AU684337B2 (en) | 1997-12-11 |
EP0678541A2 (en) | 1995-10-25 |
EP0678541B1 (en) | 2000-02-09 |
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