CA2103653C - Shaped organosiloxane polycondensates, processes for their preparation and use - Google Patents
Shaped organosiloxane polycondensates, processes for their preparation and useInfo
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- CA2103653C CA2103653C CA002103653A CA2103653A CA2103653C CA 2103653 C CA2103653 C CA 2103653C CA 002103653 A CA002103653 A CA 002103653A CA 2103653 A CA2103653 A CA 2103653A CA 2103653 C CA2103653 C CA 2103653C
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- 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
- C08G77/48—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 at least two but not all the silicon atoms are connected by linkages other than oxygen 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
- C08G77/48—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
-
- 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
- C08G77/48—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/58—Metal-containing linkages
Abstract
The invention relates to shaped organosiloxane polycondensates in the form of macroscopic spherical particles with a diameter of 0.01 to 2.5 mm, a specific surface area of 0.01 to 1000 m2/g , a specific pore volume of 0.01 to 5.0 ml/g and a bulk density of 50 to 1000 g/l, consisting of units of the formula X - R1 (I) and/or the formula R2 - Y - R3 (II) and the formula (see fig. I) or (see fig. II) as well as optionally in addition of units of the formula (see fig. III) or (see fig. IV) or (see fig. V) wherein R1 to R3 are identical or different and represent a group of the general formula (see fig. VI) R4being bonded directly to the X or Y group and representing a linear or branched, fully saturated or unsaturated alkylene group, a cycloalkylene group, a phenylene group or a unit of the general formula or
Description
~11)3~&~
The invention relates to organo-functional polysiloxanes with one or more functional or non-functional siloxane units, which have the applicational and techn;cal advantages of a macroscopic spherical shape and, unlike organosiloxanamine copolycondensates already described (DE 39 25 359, DE 39 25 360, P 38 37 416, P 38 37 418), do not contain components of the NR3 (with R = R'-SiO3/2) type.
Processes for the preparation of the new products in particle sizes which are ideal for the application being considered and with the currently appropriate physical properties and applications for these novel materials are described.
An lmch~red polymeric organosiloxane powder or organosiloxane gels, which are obtainable by precipitation with a base such as e.g. a lonia, are known and these are mechanically crushed after hardening and are available as particulate materials.
Use of the corresponding polysiloxanes, e.g. in stirred reactors, is connected with a considerable amount of friction and associated technical problems. Accessibility of organic functions on and in the polysiloxane structure is very poor due to unfavorable, or a lack of, porosity.
Spherical organosiloxanes or silica gels are also known, with particle sizes, however, in the region of a few micrometers.
(T. Kawaguchi, K. Ono; J. Non-Cryst. Solids 1990, 121, 383-388, P. Espinard, J.E. Mark, A. Guyot; Polym. Bull. (Berlin) 1990, 24, 173-179, Jap. Kokai Tokkyo Koho / 02225328 A 2.
2103~3~3 I
In this case, the fundamental methods of preparation are based on precipitation of siloxanes. Mainly due to process restrictions, larger spherical particles could not be S produced using this method. As a standard feature, the particles size achieved is in the range from 1 to at most 10 micrometers.
Known (but not previously published) are methods for the preparation of metal-cont~ininq organosiloxanamine copolycondensates in the form of spherical particles with a diameter of 0.01 to 3.0 mm (DE-PS 41 lo 705). In the case of these products, the organosilanamine fulfills the task of a subsequent stabilizing siloxane component, and also of a catalyst for the hydrolysis and polycondensation reaction.
The invention provides shaped organosiloxane polycondensates, consisting of units of the formula.
X - R1 (I) and/or the formula R2 _ y - R3 (II) and of the formula -O-M-O- or - o - Al = (III) O _ o ~1~3~3 as well as optionally in addition of units of the formula ~ 0-S -0-M-0- or -O-M-0- or -O-Al (IV) I I - R' in which the ratios of (I) to (III) are in the range from 95 to S to 5 to 95 mol-~, preferably from 50 to 50 to 10 to 90 mol-~, or lS (II) to (III) or the sum of (I) plus (II) to (III) are 100 to 0 to S to 95 mol-%, preferably from 90 to 10 to 10 to 90 mol-%, and with ratios of the sum of (I), (II) and (III) to (IV) of 100 to 0 to 50 to 50 mol-%, wherein R1 to R3 are identical or different and represent a group of the formula -R4 - Si - 0- (V) O--R4 being bonded directly to the group X or Y and representing a linear or branched, fully saturated or unsaturated alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 5 to 8 carbon atoms, a phenylene group or a unit of the general formula - ( CH 2 ) n--~ or -( CH 2 ) n ~
( C112 ) m ~ ( CH 2 ) m~
in which n is a number from 1 to 6 and gives the number of methylene groups adjacent to X or Y and m is a number from ~ 0 to 6, wherein M is a Si, Ti or Zr atom and R' is a linear or branched alkyl group with 1 to 5 carbon atoms or a - phenyl group and X in formula (I) represents 5 -H, -Cl, -Br, ~ CN, -SCN, -N3, -OR' ', -SH, -COOH, P (C6Hs) 2 ~ NH2, --N (CH3) 2~ --N ( C2Hs ) 2, --NH--~CH2) 2--NHz, --NH--(CH2) 2--NH--(CH2) 2--NH2, --NH--C ( S )--NR2 ' ', --NH-C (O)--NR2 ' ', --NR ' '--C ( S )--NR2 ' ', --O--C ( O )--C ( CH3 ) =CH2, --CH=CH2, CH2--CH=CH2 ~ --CHz--CH2--CH=CH2 ~
~
and Y in formula (II) represents 15 =N-H, = N-CH3, ~ N--C2HS, -S- ~ --S2 ~ S3 S4 , =P--( C6Hs ); --NH--C ( S )--NH--, N--C ( S )--NR2 ' "
R' ' R' ' 2 0 N--C ( S)--N \ , -NH--C (O)--NH--, N-C (O) -NR2 ' ' wherein R' ' is H or a linear or branched alkyl group with 1 to 5 carbon atoms, in the form of spherical particles with 25 a diameter of 0.01 to 2 . 5 mm, preferably 0. 05 to 1. 5 mm, a specific surface area of 0.01 to 1000 m2/g, particularly 50 to 800 m2/g, a specific pore volume of 0.01 to 5 . 0 ml/g and a bulk density of 90 to 1000 g/l, particularly 100 to 800 g/l.
Solid, shaped and well-defined products are obtained within the claimed ranges. There are no problems with regard to the relevant morphological, physical properties, i. e. the porosity, or chemical stability.
~1~36~;~
_ 5 In a particular embodiment, the polycondensates are present as random polycondensates, block polycondensates or mixed polycondensates. Preferably, R1, R2 and R3 are defined as -(CH2)3-Si ~ o-O--The suitable chemical composition of the polycondensates according to the invention depends mainly on their intended use. Depending on the desired application, a suitable density of functional groups is selected by varying the proportion of components of the formulas (I) and (II) and of components with the formulas (III) and (IV), which serve to cross-link the polysiloxane matrix and also to produce suitable physical properties, without impairing the intended mode of action by means of the organo-functional groups which are incorporated.
The following compounds, which are in principle known, may be used successfully, for instance, as monomeric units for the shaped organosiloxane polycondensates :
Cl-CH2CH2cH2si(Oc2Hs)3 Ncs-cH2cH2cH2si(oc2Hs)3 NC-CH2CH2Ch2si(OcH3)3 CH2=CHsi(OcH3) 3 C6Hssi(oc2Hs)3 S[CH2CH2CH2Si(OcH3) 3 ] 2 HNt(CH2)10si(oc2Hs)3]2 Si(Oc2Hs)4 Ti(OC3H7)4 (Hsc2o)2si(cH3) 2 2103~53 . .
As can also be seen from the examples, the particle size distribution, specific surface area, bulk density and thus also the porosity can be set selectively within wide limits.
Preferred ranges are: diameter of particles: 0.05 to 1.5 mm; specific surface area: 50 to 800 m2/g; and bulk density 100 to 800 g/l.
In general, random polycondensates are produced but it is also possible, using selective precondensation, to obtain block polycondensates, or mixed ploycondesates.
For technical reasons, and also because of the ready availability of the corresponding starting silanes, a C3 spacer group is preferred between the silicon atom and the organic functional group.
The invention also provides processes for preparing the polycondensates according to the invention. A process for the preparation of shaped random organosiloxane ploycondensates according to the invention is characterized in that components of the general formulas (VI) to (VIII) X-R5 (VI), R~-Y-R~ (VII~, M(OR8)2~R'a2 or Al(OR~23R'ot (VIII) corresponding to the stoichoimetric composition of the polysiloxane being prepared wherein R5 to R7 are identical or different and each represents a group of the general formula (IX) -R~-si(oR9)3 (IX~
.
6a X, Y, R , M and R4 are each defined as in the formulas (I) to (V) and R8 and R9 represent-a linear or branched alkyl group with 1 to s carbon atoms, are dissolved in a solvent which is predominantly water-miscible but dissolves the silane components, and amount of water which is at least sufficient for complete hydrolysis and condensation as well as optionally hydrolysis and condensation catalyst from the group HCl, H3PO4, CH3COOH, NH3, NR3'''wherein R''' represents an alkyl group which contains 1 to 6 carbon atoms, as the pure substance or in aqueous solution, is added to the solution with stirring, then the reaction mixture is allowed to gel with further stirring at a specific temperature in the range from room temperature to 200~C, and at the start of gelling or up to one hour afterwards 10 to 2000%, preferably 50 to 500% by weight, with reference to the total amount of silane components used, of a predominantly water-immiscible solvent, but one which dissolves and dilutes the (being) gelled reaction mixture, is added, homogenized and immediately or within a time interval of up to 3 hours later, optionally increasing the originally fixed temperature 10 to 2000% by weight, preferably 50 to 500% by weight, with reference to the total amount of silane components used, of water is added, the siloxane-containing organic phase is dispersed in the liquid two-phase system and the solid which is formed after hardening of the droplets in the shape of spheres is separated from the liquid phase after a sufficient reaction time, at room temperature to 250~C, optionally purified by extraction, optionally dried at room temperature to 250~C, optionally under a protective gas or under vacuum, and then optionally annealed and/or classified. Methanol, ethanol, n- or i- propanol, n- or i- butanol or n-pentanol, alone or in a mixture, are the preferred solvents for hydrolysis.
211~3~g~ .
- Preferably a linear or branched alcohol with 4 to 12 carbon atoms, toluene, xylene isomers (separately or in a mixture) or tert.-butyl-methyl-ether is added to the (being) gelled reaction mixture.
Some or all of the amount of water-insoluble solvent being added at or after the start of gelling may be used from the begi nn i ng of the process in addition to the solvent used at that point.
One or more of the silanes of the formulas (VI) to (VIII) may not be introduced to the mix from the beginning, but may be introduced later, during or shortly after gelling, optionally lS in the predominantly water-insoluble solvent being added.
Also, of the silane components, combined or each separately, may be pre-condensed and then added to the reaction mixture.
A process for after-treating the shaped but not dried organopolysiloxane condensates obtained in accordance with the above processes is characterized in that the solid obtained is subjected to a thermal treatment for 1 hour to one week at 50 to 300~C, preferably 100 to 200~C, in the liquid phase in the presence of at least the component water or else in the mother liquor, wherein the excess pressure corresponds to the sum of the partial pressures of the components used.
Preferably the after-treatment is performed in the presence of an acid or basic catalyst, preferably in the presence of ammonia.
In principle, the corresponding halide or phenoxy compounds may also be used as starting materials for the process instead of alkoxysilyl compounds, but their use does not ~103653 6c offer any advantaqes and may, e.g. in the case of the chlorides, cause difficulties as a result of hydrochloric acid being released during hydrolysis.
Hydrolysis of the starting materials and optional cross-linking agent must be performed in a solvent which is predominantly water-miscible but which dissolves the starting materials. Preferably therefore, alcohols are used which correspond to the alkoxy grouping in the monomeric precursor of the starting material or to the metal atoms in the optionally used cross-linking agent. The following are particularly suitable: methanol, ethanol, n- and i-propanol, n- and i-butanol or n-pentanol. Mixtures of such alcohols may also be used as the solvent for hydrolysis.
2103~
Instead of alcohols, other polar solvents which are predominantly water-miscible may also be used, but it has been shown that this is not as sensible from a technical point of view due to the solvent mixture which is produced with the hydrolytically eliminated alcohol.
Preferably the hydrolysis is performed with an excess of water as compared with the stoichiometrically required amount. The amount of water required for hydrolysis depends on the rate of hydrolysis of each organosilane or cross-linking agent used, in such a way that hydrolysis takes place more rapidly with increasing amounts of water. An upper limit can be set, however, by the occurrence of demixing and the formation of a two-phase system.
Basically, hydrolysis in homogeneous solution is preferred.
On the basis of the two aspects mentioned, in practice somewhat less water, with respect to the weight, is used than organosilanes plus cross-linking agent.
The duration of hydrolysis depends on the tendency to hydrolyse of the starting material and/or cross-linking agent and on the temperature. The readiness to hydrolyse and thus the rate of hydrolysis depends in particular on the type of alkoxy groups adjacent to the silicon or titanium, zirconium or aluminium atoms, wherein methoxy groups are hydrolysed the most rapidly and there is a slowing down with increasing chain length of the hydrocarbon group. In addition, the duration of the total hydrolysis and polycondensation procedure also depends on the basicity of the organosilane. Hydrolysis and polycondensation may be accelerated by the addition of bases, preferably ammonia, or of inorganic or organic acids, or else by the usual condensation catalysts, such as dibutyltin diacetate.
2::10~653 Basically, all Br0nsted acids and bases may also be considered as catalysts. Preventing precipitation of siloxanes causes many technical difficulties when performing the reaction and selecting the type and concentration of catalyst. Surprisingly, it was possible to prepare spherical products although the acid or base catalysed hydrolysis of organosilanes is known and is used in many different ways to prepare unshaped polysiloxanes with undefined physical properties.
The requirement of keeping the starting material, which is cross-linked with water and dissolved in solvent, at a certain temperature while still being stirred results in the rate of polycondensation, which is signalled by gelling, being temperature dependent.
The temperature to be applied during hydrolysis or the gelling phase is established empirically for individual cases. It should be noted here that a fluid, gel-like material which contains no solids is retained for the subsequent process step, the so-called shaping phase.
The shaping phase, accompanied by the transfer of the coherent fluid, gel-like mass (in which the condensation reaction continues further) into separate spherical particles, starts with the addition to the (being) gelled reaction mixture of a predominantly water-insoluble solvent, but one which dissolves the reaction mixture adequately, in the designated amount.
Suitable solvents are e.g. linear or branched alcohols with 4 to 18 carbon atoms or phenols, linear or branched symmetric or asymmetric dialkyl ethers and di- or tri-ethers (such as ethyleneglycol-dimethyl ether), chlorinated or fluorinated hydrocarbons, aromatic compounds or mixtures of aromatic compounds substituted with one or more alkyl 21~3~;3 - g groups, such as e.g. toluene or xylene, symmetric and asymmetric ketones which are predominantly immiscible with water.
Preferably, however, a linear or branched alcohol with 4 to 12 carbon atoms, toluene or o-, m- or p-xylene, separately or as a mixture, is added to the (being) gelled reaction mixture.
This addition of a solvent causes a dilution effect after homogenisation with the reaction mixture and thus causes a definite slowing down in the condensation reaction being accompanied by an increase in viscosity.
Assessment of the amount of this solvent used in the shaping phase depends in particular on what particle size is being sought for each shaped organosiloxane compound. A
rule of thumb which may be applied is that less has to be used for coarse particles (spheres with a larger diameter) and more for fine particles ~spheres with a smaller diameter).
In addition, the intensity with which the viscous -homogeneous mixture consisting of reaction mixture and predominantly water-insoluble solvent is dispersed in the extra water added as dispersion agent in the shaping phase also has a large effect on the particle size. The formation of a finer particle range is regularly encouraged by vigorous stirring. One of the known dispersion-aiding agents, such as long-chain carboxylic acids or their salts or polyalkylene glycols may be used in the normal concentrations to stabilise the aqueous dispersion of the organic phase (now containing siloxane).
According to one variant of the process according to the invention, some or even the whole amount of the 2103~3 predominantly water-insoluble solvent being added at or after the start of gelling is used in the hydrolysis step alongside the solvent used there. If only some is added, the residue is added after the start of gelling.
s In the extreme case, addition of the whole amount, the dispersion agent water may be added at or after the start of gelling. This variant is preferred when the organosilane and optional cross-linking agent mixture used exhibits an extraordinarily high tendency towards hydrolysis and polycondensation.
The preferred temperature at which dispersion of the siloxane-containing organic phase in the aqueous phase is lS performed and spherical solids are formed from the dispersed phase, is generally the reflux temperature of the whole mixture. Basically, however, the same temperatures as thosé used in the gelling steps may be applied. The total duration of the dispersion step and after-reaction is generally 0.5 to 10 hours.
Both gelling and shaping may be performed at atmospheric pressure or at an excess pressure which corresponds to the sum of the partial pressures of the components of the reaction mixture at the particular temperature being applied.
When preparing the shaped, cross-linked or non-cross-linked organosiloxanes according to the invention, this also being independent of the type of alkoxy group, it may so happen that one or more components in the mixture to be gelled has a different hydrolysis and polycondensation behaviour. In this case one version of the process according to the invention provides for the cross-linking agent(s) and/or the organo-functional silane not to be subjected to the gelling process together, but to be gelled separately 2103~5~
first, to homogenise them with the predominantly water-insoluble solvent and only then to add the cross-linking agent(s) or organosilane to the homogeneous mixture.
However, the solvent and the silane component which is still missing may also be added simultaneously to the gelled mix.
Separation of the spherical shaped moist product from the liquid dispersion agent may be performed using the usual measures such as decanting, filtering or centrifuging.
The liquid phase may also be removed from the reactor, the solids remaining behind being treated once or several times with a low-boiling extraction agent, preferably in a low-boiling alcohol, in order to facilitate subsequent drying of the shaped material by at least partially exchanging the mostly ~elatively high-boiling solvent from the shaping phase for the low-boiling extraction agent.
Drying may be performed basically at room temperature to 250~C, optionally under a protective gas or under vacuum.
The dried, shaped solids may be annealed at temperatures of 150 to 300~C to harden and stabilise them.
The dried or annealed product may be classified into various particle size fractions in the usual devices. One or more of the working-up measures of extracting, drying, annealing and classifying may be omitted, depending on the circumstances. Classification may be performed with the liquid-moist, dried or annealed product.
In order to compensate for different hydrolysis and polycondensation behaviour by the monomeric components in a random, optionally cross-linked, copolycondensate, the monomeric components with the formulas (V) and (VIII) could be initially pre-condensed.
A particularly important embodiment of the process according to the invention provides for subjecting the still solvent- and water-moist or -wet spherical material to a thermal treatment for 1 hour to one week at temperatures of 50 - 300~C, preferably 100 - 200~C, wherein excess pressure may be applied if so required.
This treatment under "vaporising" or digesting conditions also predominantly serves to improve the mechanical strength and porosity of the shaped material and may also be performed in the dispersion which is obtained last in the preparation process, which contains a liquid and the solid product phase, or in water on its own.
The previously described embodiment of an after-treatment of the shaped, but not dried, organosiloxane copolycondensate which is obtained thus comprises subjecting the solid produced in the form of spheres, in the presence of at least the component water or of the liquid phase which was present last in the preparation process as a vapour or a liquid, to a thermal treatment for 1 hour to one week at temperatures of 50 - 300~C, preferably 100 - 200~C, optionally under excess pressure.
The presence of an acid, basic or metal-containing catalyst may be of advantage here. A particularly advantageous embodiment provides for the use of ammonia.
The novel, shaped organosiloxane copolycondensates are characterised in particular by using the quantitative hydrolysis yields, by elemental analyses and by the determination of the individual functional groups.
210~3 _ 13 Purely optically, there is no difference between the copolycondensates obtained by the different methods of preparation. Depending on preliminary treatment, the spherically shaped copolycondensates according to the invention have a particle diameter of 0.01 to 2.5, preferably 0.05 to 1.5 mm, a specific surface area of 0.01 to 1000, preferably 150 to 800 m2/g, a specific pore volume of 0.01 to 5.0 ml/g and a bulk density of 50 to 1000 g/l, preferably 100 to 800 g/l. The adjustable pore diameters lo -are in the range 0.01 to more than 1000 nm.
Specific control of synthesis permits the preparation of products in the most technically applicable spherical shape and with the desired physical and morphological properties.
The spherical polycondensates may be used, optionally after further additional chemical modification, as active substance carriers in general or else as carriers for the preparation of noble metal catalysts.
A further use of all the copolycondensates according to the invention is use for the adsorptive bonding of gaseous organic compounds and/or water vapour, preferably of organic solvents.
It is in particular the pore volume, pore diameter, and surface properties which are critical for this adsorptive action.
These factors may be affected on the one hand by the methods of preparation and after-treatment according to the invention and on the other hand also by the chemical composition, e.g. by the incorporation of hydrophobic cross-linking groups in the polysiloxane structure.
Recovery of the adsorbed organic compounds or water is ~103~S3 readily achieved by raising the temperature and/or by flushing out with warm air.
In the following, the invention is explained in more detail by using working examples.
Example 1 383.8 g of Si(oc2H5)4 are introduced into a 3 l double-walled glass vessel together with S00 ml of ethanol and 100 ml of 1-octanol and heated to 80~C with stirring. 125 ml of water (pH = 4.0) are added, the mix is cooled to 60~C
and 0.1 ml of tributylamine is added. The mix itself is maintained at a temperature of 60~C with slow stirring.
After 20 minutes the mix gels, i.e. the viscosity increases noticeably. The rate of stirring is immediately increased (600 rpm) and 116.2 g of NC-CH2CH2CH2-Si(oCH3)3, dissolved in 400 ml of octanol, are added. 1500 ml of water (50~C) are added to the homogeneous solution after 10 min. and the organic solution is dispersed in the water. The emulsion which is present is heated and ~oiled under reflux for 2 hours. After cooling the mix, the solid which is produced is filtered off under suction and extracted three times with ethanol. The product is dried at 150~C for 24 hours under N2. After classifying the solid, 177 g (9S.9~ of theory) of product are obtained in the form of a solid with spherical particles in the particle size range from 0.1 to 0.6 mm (of which 65% is in the range from 0.2 to 0.4 mm) and with the composition NC-(CH2)3-Sio3/2.3Sio2.
Elemental analysis : % C % H % N ~ Si Theory: 15.9 2.0 4.6 37.4 Found: 14 2.3 3.2 35.7 Bulk density: 683 g/l (anhydrous) - 21~3~3 Example 2 After extraction with ethanol, the product prepared in the same way as in example 1 is first subjected to a hydrothermal treatment at 150~C in 5% aqueous ammonia solution (24 h) and then dried as in example 1. A solid is obtained as in example 1, but with a bulk density of 405 g/l.
Example 3 138.8 g of StCH2CH2CH2Si(OCH3)3]2 and 161.2 g of Si(oC2H5)4 are initially introduced into a 3 1 double-walled glass vessel together with 300 ml of ethanol and 120 ml of 1-octanol and heated to 75~C with stirring. 49 g of NH3 solution (25 % by weight in water) and 55 ml of distilled water are added and the mix is cooled to 70~C. After 5 minutes the mix gels, the rate of stirring is immediately increased (600 rpm) and 240 ml of octanol are added. 900 ml of water (50~C) are immediately added to the homogeneous solution and the organic phase is dispersed in the water.
The emulsion which is present is heated and boiled under reflux for 2 hours. The mix is filtered under suction, 5%
strength NH3 solution is added to the isolated solid and stirred in a laboratory autoclave at 150~C for 24 h. After cooling the mix, the solid which is produced is filtered off under suction and extracted three times with ethanol, with stirring.
The product is dried under N2 for 4 h at 60~C, for 4 h at sooc, for 4 h at 120~C and finally for 12 h at 150~C. After classifying the solid, 101 g of product in the form of a solid with spherical particles in the particle size range from 0.3 to 0.8 mm and the composition S[(CH2)3-siO3/~i2sio2 are obtained.
~1~3~53 Elemental analysis: % C % H % S % Si Theory: 21.2 3.6 9.4 32.9 Found: 23 4.1 9.9 30.7 Bulk density: 164 g/l (anhydrous) Example 4 62.4 g of CH3CH2CH2Si(OCH3)3 and 237.6 g of Si(oc2Hs) 4 are initially introduced into a 3 1 double-walled glass vessel together with 300 ml of ethanol and heated to 80~C with stirring. 71 g of HCl solution (37% by weight in water~ and 90 ml of distilled water are added stepwise, the mix is boiled under reflux for 2 h and then cooled to 70~C. After 15 minutes the mix gels, the rate of stirring is immediately increased (600 rpm) and after 1 minute 300 ml of octanol are added. After another 1 minute 900 ml of water (50~C) are added to the homogeneous solution and the organic phase is dispersed in the water. The emulsion which is present is heated and boiled under reflux for 2 h.
The mix is filtered under suction, 5% strength NH3 solution is added to the isolated solid and stirred in a laboratory autoclave at 150~C for 24 h.
After cooling the mix, the solid which is produced is filtered off under suction and extracted three times with ethanol, with stirring.
The product is dried under N2 for 4 h at 60OC, for 4 h at 90~C, for 4 h at 120~C and finally for 12 h at 150~C. After classification of the solid, 92 g of product, in the form of a solid with spherical particles in the particle size - 210~6~3 range from 0.1 to 0.8 mm and the composition CH2CH2CH2-sio3,2.3sio2 are obtained.
Elemental analysis: % C % H % Si Theory: 13.1 2.6 40.8 Found: 13.0 2.8 39.7 Bulk density: 240 g/l (anhydrous) Exam~le 5 60-6 g of NCS-CH2CH2CH2si(OC2H5) 3 and 239.5 g of Si(oC2H5) 4 are initially introduced into a 3 l double-walled glass vessel together with 300 ml of ethanol and heated to 80~C with stirring. 71 g of HCl solution (37~ by weight in water) and 45 ml of distilled water are added stepwise, the mix is boiled under reflux for 40 minutes, then cooled to 70~C.
After 215 minutes the mix gels, the rate of stirring is immediately increased (600 rpm) and after 1 min. 300 ml of octanol are added. After 5 minutes, 900 ml of water (50~C) are added to the homogeneous solution and the organic phase is dispersed in the water. The emulsion which is present is heated and boiled for 2 h under reflux.
After working-up in the same way as in example 4, a shaped polysiloxane with the composition NCS-CH2CH2CH2-Sio3~2.5sio2 was obtained.
ExamPle 6 57.8 g of CH2=CH2Si(OCH3) 3 and 242.2 g of Si(oc2Hs) 4 are initially introduced into a 3 l double-walled glass vessel together with 300 ml of ethanol and 120 ml of 1-octanol and ~1~36~
.. .
heated to 80~C with stirring. 75 ml of water (pH = 4.0) are added, the mix is cooled to 70~C and 2.0 ml of triethylamine are added. The mix itself is kept at a temperature of 60~C with slow stirring. After 15 minutes, the mix gels, the rate of stirring is immediately increased (600 rpm) and 240 ml of octanol are added. 900 ml of water (50~C) are immediately added to the homogeneous solution and the organic phase is dispersed in the water. Further working-up is performed in the same way as in example 1. A
shaped polysiloxane with the following composition was obtained : CH2=CH2-Sio3~2.3Sio2.
ExamPle 7 81.9 g of C8H17Si(oCH3)3 and 218.2 g of Si(oc2Hs)4 were reacted in precisely the same way as described in example 6 and a shaped polysiloxane of the composition CôH"Sio3~2.3Sio2 was obtained.
Exam~le 8 In the same way as in example 6, 73.1 g of phenyltriethoxysilane and 226.9 g of polydiethyl silicate 40 (pre-condensed tetraethoxysilane, corresponding to 40%
sio2 content) were reacted and a product with the composition C6HsSio3/Z~5sio2 was obtained.
Sieve analysis: 0.2 - 0.3 mm : 31%
0.3 - 0.6 mm : 59%
0.6 - 0.8 mm : 10%
BET surface area: 642 mZ/g Mesopores (2-30 nm): 0.72 ml/g Macropores: 0.84 ml/g 21~3~
Example g In the same way as in example 6, 26.9 g of propyltrimethoxysilane and 273.1 g of tetraethoxysilane were reacted and a product with the composition C3H~i3/2.8SiO2 was obtained.
BET surface area: 784 mZ/g Mesopores (2-30 nm): 0.48 ml/g 10 Macropores: 1.24 ml/g Bulk density: 390 g/l Example 10 The polysiloxane obtained in example 9 was stirred with 5%
NH3 solution before drying for 24 h at 150~C.
BET surface area: 491 m2/g Mesopores (2-30 nm): 1.81 ml/g Macropores: 3.35 ml/g Bulk density: 192 g/l Example 11 In the same way as in example 6, 83.44 g of chloropropyltriethoxysilane and 216.6 g of tetraethoxysilane were reacted and a shaped polysiloxane with the composition Cl-CH2CH2CH2SiO3/2.3SiO2 was obtained.
Chlorine content: 10.4% by wt. (Theory: 11.4% by wt.) Spec. surface area: 649 m2/g Micropores (< 2 nm): 0.42 ml/g Mesopores (2-30 nm): 0.02 ml/g 35 Macropores: 0.75 ml/g Bulk density: 545 g/l Exam~le 12 In the same way as in example 6, but using 1 ml of triethylamine, 50.9 g of HNtCH2CHzCH2Si(OC2H5)3]2 and 249.1 g of tetraethoxysilane were reacted and a shaped polysiloxane with the composition HNtCHzCHzCH2SiO3/2]2~l0SiO2 was obtained.
Spec. surface area: 112 m2/g Mesopores (2-30 nm): 0.22 ml/g Macropores: 4.47 ml/g Bulk density: 167 g~l
The invention relates to organo-functional polysiloxanes with one or more functional or non-functional siloxane units, which have the applicational and techn;cal advantages of a macroscopic spherical shape and, unlike organosiloxanamine copolycondensates already described (DE 39 25 359, DE 39 25 360, P 38 37 416, P 38 37 418), do not contain components of the NR3 (with R = R'-SiO3/2) type.
Processes for the preparation of the new products in particle sizes which are ideal for the application being considered and with the currently appropriate physical properties and applications for these novel materials are described.
An lmch~red polymeric organosiloxane powder or organosiloxane gels, which are obtainable by precipitation with a base such as e.g. a lonia, are known and these are mechanically crushed after hardening and are available as particulate materials.
Use of the corresponding polysiloxanes, e.g. in stirred reactors, is connected with a considerable amount of friction and associated technical problems. Accessibility of organic functions on and in the polysiloxane structure is very poor due to unfavorable, or a lack of, porosity.
Spherical organosiloxanes or silica gels are also known, with particle sizes, however, in the region of a few micrometers.
(T. Kawaguchi, K. Ono; J. Non-Cryst. Solids 1990, 121, 383-388, P. Espinard, J.E. Mark, A. Guyot; Polym. Bull. (Berlin) 1990, 24, 173-179, Jap. Kokai Tokkyo Koho / 02225328 A 2.
2103~3~3 I
In this case, the fundamental methods of preparation are based on precipitation of siloxanes. Mainly due to process restrictions, larger spherical particles could not be S produced using this method. As a standard feature, the particles size achieved is in the range from 1 to at most 10 micrometers.
Known (but not previously published) are methods for the preparation of metal-cont~ininq organosiloxanamine copolycondensates in the form of spherical particles with a diameter of 0.01 to 3.0 mm (DE-PS 41 lo 705). In the case of these products, the organosilanamine fulfills the task of a subsequent stabilizing siloxane component, and also of a catalyst for the hydrolysis and polycondensation reaction.
The invention provides shaped organosiloxane polycondensates, consisting of units of the formula.
X - R1 (I) and/or the formula R2 _ y - R3 (II) and of the formula -O-M-O- or - o - Al = (III) O _ o ~1~3~3 as well as optionally in addition of units of the formula ~ 0-S -0-M-0- or -O-M-0- or -O-Al (IV) I I - R' in which the ratios of (I) to (III) are in the range from 95 to S to 5 to 95 mol-~, preferably from 50 to 50 to 10 to 90 mol-~, or lS (II) to (III) or the sum of (I) plus (II) to (III) are 100 to 0 to S to 95 mol-%, preferably from 90 to 10 to 10 to 90 mol-%, and with ratios of the sum of (I), (II) and (III) to (IV) of 100 to 0 to 50 to 50 mol-%, wherein R1 to R3 are identical or different and represent a group of the formula -R4 - Si - 0- (V) O--R4 being bonded directly to the group X or Y and representing a linear or branched, fully saturated or unsaturated alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 5 to 8 carbon atoms, a phenylene group or a unit of the general formula - ( CH 2 ) n--~ or -( CH 2 ) n ~
( C112 ) m ~ ( CH 2 ) m~
in which n is a number from 1 to 6 and gives the number of methylene groups adjacent to X or Y and m is a number from ~ 0 to 6, wherein M is a Si, Ti or Zr atom and R' is a linear or branched alkyl group with 1 to 5 carbon atoms or a - phenyl group and X in formula (I) represents 5 -H, -Cl, -Br, ~ CN, -SCN, -N3, -OR' ', -SH, -COOH, P (C6Hs) 2 ~ NH2, --N (CH3) 2~ --N ( C2Hs ) 2, --NH--~CH2) 2--NHz, --NH--(CH2) 2--NH--(CH2) 2--NH2, --NH--C ( S )--NR2 ' ', --NH-C (O)--NR2 ' ', --NR ' '--C ( S )--NR2 ' ', --O--C ( O )--C ( CH3 ) =CH2, --CH=CH2, CH2--CH=CH2 ~ --CHz--CH2--CH=CH2 ~
~
and Y in formula (II) represents 15 =N-H, = N-CH3, ~ N--C2HS, -S- ~ --S2 ~ S3 S4 , =P--( C6Hs ); --NH--C ( S )--NH--, N--C ( S )--NR2 ' "
R' ' R' ' 2 0 N--C ( S)--N \ , -NH--C (O)--NH--, N-C (O) -NR2 ' ' wherein R' ' is H or a linear or branched alkyl group with 1 to 5 carbon atoms, in the form of spherical particles with 25 a diameter of 0.01 to 2 . 5 mm, preferably 0. 05 to 1. 5 mm, a specific surface area of 0.01 to 1000 m2/g, particularly 50 to 800 m2/g, a specific pore volume of 0.01 to 5 . 0 ml/g and a bulk density of 90 to 1000 g/l, particularly 100 to 800 g/l.
Solid, shaped and well-defined products are obtained within the claimed ranges. There are no problems with regard to the relevant morphological, physical properties, i. e. the porosity, or chemical stability.
~1~36~;~
_ 5 In a particular embodiment, the polycondensates are present as random polycondensates, block polycondensates or mixed polycondensates. Preferably, R1, R2 and R3 are defined as -(CH2)3-Si ~ o-O--The suitable chemical composition of the polycondensates according to the invention depends mainly on their intended use. Depending on the desired application, a suitable density of functional groups is selected by varying the proportion of components of the formulas (I) and (II) and of components with the formulas (III) and (IV), which serve to cross-link the polysiloxane matrix and also to produce suitable physical properties, without impairing the intended mode of action by means of the organo-functional groups which are incorporated.
The following compounds, which are in principle known, may be used successfully, for instance, as monomeric units for the shaped organosiloxane polycondensates :
Cl-CH2CH2cH2si(Oc2Hs)3 Ncs-cH2cH2cH2si(oc2Hs)3 NC-CH2CH2Ch2si(OcH3)3 CH2=CHsi(OcH3) 3 C6Hssi(oc2Hs)3 S[CH2CH2CH2Si(OcH3) 3 ] 2 HNt(CH2)10si(oc2Hs)3]2 Si(Oc2Hs)4 Ti(OC3H7)4 (Hsc2o)2si(cH3) 2 2103~53 . .
As can also be seen from the examples, the particle size distribution, specific surface area, bulk density and thus also the porosity can be set selectively within wide limits.
Preferred ranges are: diameter of particles: 0.05 to 1.5 mm; specific surface area: 50 to 800 m2/g; and bulk density 100 to 800 g/l.
In general, random polycondensates are produced but it is also possible, using selective precondensation, to obtain block polycondensates, or mixed ploycondesates.
For technical reasons, and also because of the ready availability of the corresponding starting silanes, a C3 spacer group is preferred between the silicon atom and the organic functional group.
The invention also provides processes for preparing the polycondensates according to the invention. A process for the preparation of shaped random organosiloxane ploycondensates according to the invention is characterized in that components of the general formulas (VI) to (VIII) X-R5 (VI), R~-Y-R~ (VII~, M(OR8)2~R'a2 or Al(OR~23R'ot (VIII) corresponding to the stoichoimetric composition of the polysiloxane being prepared wherein R5 to R7 are identical or different and each represents a group of the general formula (IX) -R~-si(oR9)3 (IX~
.
6a X, Y, R , M and R4 are each defined as in the formulas (I) to (V) and R8 and R9 represent-a linear or branched alkyl group with 1 to s carbon atoms, are dissolved in a solvent which is predominantly water-miscible but dissolves the silane components, and amount of water which is at least sufficient for complete hydrolysis and condensation as well as optionally hydrolysis and condensation catalyst from the group HCl, H3PO4, CH3COOH, NH3, NR3'''wherein R''' represents an alkyl group which contains 1 to 6 carbon atoms, as the pure substance or in aqueous solution, is added to the solution with stirring, then the reaction mixture is allowed to gel with further stirring at a specific temperature in the range from room temperature to 200~C, and at the start of gelling or up to one hour afterwards 10 to 2000%, preferably 50 to 500% by weight, with reference to the total amount of silane components used, of a predominantly water-immiscible solvent, but one which dissolves and dilutes the (being) gelled reaction mixture, is added, homogenized and immediately or within a time interval of up to 3 hours later, optionally increasing the originally fixed temperature 10 to 2000% by weight, preferably 50 to 500% by weight, with reference to the total amount of silane components used, of water is added, the siloxane-containing organic phase is dispersed in the liquid two-phase system and the solid which is formed after hardening of the droplets in the shape of spheres is separated from the liquid phase after a sufficient reaction time, at room temperature to 250~C, optionally purified by extraction, optionally dried at room temperature to 250~C, optionally under a protective gas or under vacuum, and then optionally annealed and/or classified. Methanol, ethanol, n- or i- propanol, n- or i- butanol or n-pentanol, alone or in a mixture, are the preferred solvents for hydrolysis.
211~3~g~ .
- Preferably a linear or branched alcohol with 4 to 12 carbon atoms, toluene, xylene isomers (separately or in a mixture) or tert.-butyl-methyl-ether is added to the (being) gelled reaction mixture.
Some or all of the amount of water-insoluble solvent being added at or after the start of gelling may be used from the begi nn i ng of the process in addition to the solvent used at that point.
One or more of the silanes of the formulas (VI) to (VIII) may not be introduced to the mix from the beginning, but may be introduced later, during or shortly after gelling, optionally lS in the predominantly water-insoluble solvent being added.
Also, of the silane components, combined or each separately, may be pre-condensed and then added to the reaction mixture.
A process for after-treating the shaped but not dried organopolysiloxane condensates obtained in accordance with the above processes is characterized in that the solid obtained is subjected to a thermal treatment for 1 hour to one week at 50 to 300~C, preferably 100 to 200~C, in the liquid phase in the presence of at least the component water or else in the mother liquor, wherein the excess pressure corresponds to the sum of the partial pressures of the components used.
Preferably the after-treatment is performed in the presence of an acid or basic catalyst, preferably in the presence of ammonia.
In principle, the corresponding halide or phenoxy compounds may also be used as starting materials for the process instead of alkoxysilyl compounds, but their use does not ~103653 6c offer any advantaqes and may, e.g. in the case of the chlorides, cause difficulties as a result of hydrochloric acid being released during hydrolysis.
Hydrolysis of the starting materials and optional cross-linking agent must be performed in a solvent which is predominantly water-miscible but which dissolves the starting materials. Preferably therefore, alcohols are used which correspond to the alkoxy grouping in the monomeric precursor of the starting material or to the metal atoms in the optionally used cross-linking agent. The following are particularly suitable: methanol, ethanol, n- and i-propanol, n- and i-butanol or n-pentanol. Mixtures of such alcohols may also be used as the solvent for hydrolysis.
2103~
Instead of alcohols, other polar solvents which are predominantly water-miscible may also be used, but it has been shown that this is not as sensible from a technical point of view due to the solvent mixture which is produced with the hydrolytically eliminated alcohol.
Preferably the hydrolysis is performed with an excess of water as compared with the stoichiometrically required amount. The amount of water required for hydrolysis depends on the rate of hydrolysis of each organosilane or cross-linking agent used, in such a way that hydrolysis takes place more rapidly with increasing amounts of water. An upper limit can be set, however, by the occurrence of demixing and the formation of a two-phase system.
Basically, hydrolysis in homogeneous solution is preferred.
On the basis of the two aspects mentioned, in practice somewhat less water, with respect to the weight, is used than organosilanes plus cross-linking agent.
The duration of hydrolysis depends on the tendency to hydrolyse of the starting material and/or cross-linking agent and on the temperature. The readiness to hydrolyse and thus the rate of hydrolysis depends in particular on the type of alkoxy groups adjacent to the silicon or titanium, zirconium or aluminium atoms, wherein methoxy groups are hydrolysed the most rapidly and there is a slowing down with increasing chain length of the hydrocarbon group. In addition, the duration of the total hydrolysis and polycondensation procedure also depends on the basicity of the organosilane. Hydrolysis and polycondensation may be accelerated by the addition of bases, preferably ammonia, or of inorganic or organic acids, or else by the usual condensation catalysts, such as dibutyltin diacetate.
2::10~653 Basically, all Br0nsted acids and bases may also be considered as catalysts. Preventing precipitation of siloxanes causes many technical difficulties when performing the reaction and selecting the type and concentration of catalyst. Surprisingly, it was possible to prepare spherical products although the acid or base catalysed hydrolysis of organosilanes is known and is used in many different ways to prepare unshaped polysiloxanes with undefined physical properties.
The requirement of keeping the starting material, which is cross-linked with water and dissolved in solvent, at a certain temperature while still being stirred results in the rate of polycondensation, which is signalled by gelling, being temperature dependent.
The temperature to be applied during hydrolysis or the gelling phase is established empirically for individual cases. It should be noted here that a fluid, gel-like material which contains no solids is retained for the subsequent process step, the so-called shaping phase.
The shaping phase, accompanied by the transfer of the coherent fluid, gel-like mass (in which the condensation reaction continues further) into separate spherical particles, starts with the addition to the (being) gelled reaction mixture of a predominantly water-insoluble solvent, but one which dissolves the reaction mixture adequately, in the designated amount.
Suitable solvents are e.g. linear or branched alcohols with 4 to 18 carbon atoms or phenols, linear or branched symmetric or asymmetric dialkyl ethers and di- or tri-ethers (such as ethyleneglycol-dimethyl ether), chlorinated or fluorinated hydrocarbons, aromatic compounds or mixtures of aromatic compounds substituted with one or more alkyl 21~3~;3 - g groups, such as e.g. toluene or xylene, symmetric and asymmetric ketones which are predominantly immiscible with water.
Preferably, however, a linear or branched alcohol with 4 to 12 carbon atoms, toluene or o-, m- or p-xylene, separately or as a mixture, is added to the (being) gelled reaction mixture.
This addition of a solvent causes a dilution effect after homogenisation with the reaction mixture and thus causes a definite slowing down in the condensation reaction being accompanied by an increase in viscosity.
Assessment of the amount of this solvent used in the shaping phase depends in particular on what particle size is being sought for each shaped organosiloxane compound. A
rule of thumb which may be applied is that less has to be used for coarse particles (spheres with a larger diameter) and more for fine particles ~spheres with a smaller diameter).
In addition, the intensity with which the viscous -homogeneous mixture consisting of reaction mixture and predominantly water-insoluble solvent is dispersed in the extra water added as dispersion agent in the shaping phase also has a large effect on the particle size. The formation of a finer particle range is regularly encouraged by vigorous stirring. One of the known dispersion-aiding agents, such as long-chain carboxylic acids or their salts or polyalkylene glycols may be used in the normal concentrations to stabilise the aqueous dispersion of the organic phase (now containing siloxane).
According to one variant of the process according to the invention, some or even the whole amount of the 2103~3 predominantly water-insoluble solvent being added at or after the start of gelling is used in the hydrolysis step alongside the solvent used there. If only some is added, the residue is added after the start of gelling.
s In the extreme case, addition of the whole amount, the dispersion agent water may be added at or after the start of gelling. This variant is preferred when the organosilane and optional cross-linking agent mixture used exhibits an extraordinarily high tendency towards hydrolysis and polycondensation.
The preferred temperature at which dispersion of the siloxane-containing organic phase in the aqueous phase is lS performed and spherical solids are formed from the dispersed phase, is generally the reflux temperature of the whole mixture. Basically, however, the same temperatures as thosé used in the gelling steps may be applied. The total duration of the dispersion step and after-reaction is generally 0.5 to 10 hours.
Both gelling and shaping may be performed at atmospheric pressure or at an excess pressure which corresponds to the sum of the partial pressures of the components of the reaction mixture at the particular temperature being applied.
When preparing the shaped, cross-linked or non-cross-linked organosiloxanes according to the invention, this also being independent of the type of alkoxy group, it may so happen that one or more components in the mixture to be gelled has a different hydrolysis and polycondensation behaviour. In this case one version of the process according to the invention provides for the cross-linking agent(s) and/or the organo-functional silane not to be subjected to the gelling process together, but to be gelled separately 2103~5~
first, to homogenise them with the predominantly water-insoluble solvent and only then to add the cross-linking agent(s) or organosilane to the homogeneous mixture.
However, the solvent and the silane component which is still missing may also be added simultaneously to the gelled mix.
Separation of the spherical shaped moist product from the liquid dispersion agent may be performed using the usual measures such as decanting, filtering or centrifuging.
The liquid phase may also be removed from the reactor, the solids remaining behind being treated once or several times with a low-boiling extraction agent, preferably in a low-boiling alcohol, in order to facilitate subsequent drying of the shaped material by at least partially exchanging the mostly ~elatively high-boiling solvent from the shaping phase for the low-boiling extraction agent.
Drying may be performed basically at room temperature to 250~C, optionally under a protective gas or under vacuum.
The dried, shaped solids may be annealed at temperatures of 150 to 300~C to harden and stabilise them.
The dried or annealed product may be classified into various particle size fractions in the usual devices. One or more of the working-up measures of extracting, drying, annealing and classifying may be omitted, depending on the circumstances. Classification may be performed with the liquid-moist, dried or annealed product.
In order to compensate for different hydrolysis and polycondensation behaviour by the monomeric components in a random, optionally cross-linked, copolycondensate, the monomeric components with the formulas (V) and (VIII) could be initially pre-condensed.
A particularly important embodiment of the process according to the invention provides for subjecting the still solvent- and water-moist or -wet spherical material to a thermal treatment for 1 hour to one week at temperatures of 50 - 300~C, preferably 100 - 200~C, wherein excess pressure may be applied if so required.
This treatment under "vaporising" or digesting conditions also predominantly serves to improve the mechanical strength and porosity of the shaped material and may also be performed in the dispersion which is obtained last in the preparation process, which contains a liquid and the solid product phase, or in water on its own.
The previously described embodiment of an after-treatment of the shaped, but not dried, organosiloxane copolycondensate which is obtained thus comprises subjecting the solid produced in the form of spheres, in the presence of at least the component water or of the liquid phase which was present last in the preparation process as a vapour or a liquid, to a thermal treatment for 1 hour to one week at temperatures of 50 - 300~C, preferably 100 - 200~C, optionally under excess pressure.
The presence of an acid, basic or metal-containing catalyst may be of advantage here. A particularly advantageous embodiment provides for the use of ammonia.
The novel, shaped organosiloxane copolycondensates are characterised in particular by using the quantitative hydrolysis yields, by elemental analyses and by the determination of the individual functional groups.
210~3 _ 13 Purely optically, there is no difference between the copolycondensates obtained by the different methods of preparation. Depending on preliminary treatment, the spherically shaped copolycondensates according to the invention have a particle diameter of 0.01 to 2.5, preferably 0.05 to 1.5 mm, a specific surface area of 0.01 to 1000, preferably 150 to 800 m2/g, a specific pore volume of 0.01 to 5.0 ml/g and a bulk density of 50 to 1000 g/l, preferably 100 to 800 g/l. The adjustable pore diameters lo -are in the range 0.01 to more than 1000 nm.
Specific control of synthesis permits the preparation of products in the most technically applicable spherical shape and with the desired physical and morphological properties.
The spherical polycondensates may be used, optionally after further additional chemical modification, as active substance carriers in general or else as carriers for the preparation of noble metal catalysts.
A further use of all the copolycondensates according to the invention is use for the adsorptive bonding of gaseous organic compounds and/or water vapour, preferably of organic solvents.
It is in particular the pore volume, pore diameter, and surface properties which are critical for this adsorptive action.
These factors may be affected on the one hand by the methods of preparation and after-treatment according to the invention and on the other hand also by the chemical composition, e.g. by the incorporation of hydrophobic cross-linking groups in the polysiloxane structure.
Recovery of the adsorbed organic compounds or water is ~103~S3 readily achieved by raising the temperature and/or by flushing out with warm air.
In the following, the invention is explained in more detail by using working examples.
Example 1 383.8 g of Si(oc2H5)4 are introduced into a 3 l double-walled glass vessel together with S00 ml of ethanol and 100 ml of 1-octanol and heated to 80~C with stirring. 125 ml of water (pH = 4.0) are added, the mix is cooled to 60~C
and 0.1 ml of tributylamine is added. The mix itself is maintained at a temperature of 60~C with slow stirring.
After 20 minutes the mix gels, i.e. the viscosity increases noticeably. The rate of stirring is immediately increased (600 rpm) and 116.2 g of NC-CH2CH2CH2-Si(oCH3)3, dissolved in 400 ml of octanol, are added. 1500 ml of water (50~C) are added to the homogeneous solution after 10 min. and the organic solution is dispersed in the water. The emulsion which is present is heated and ~oiled under reflux for 2 hours. After cooling the mix, the solid which is produced is filtered off under suction and extracted three times with ethanol. The product is dried at 150~C for 24 hours under N2. After classifying the solid, 177 g (9S.9~ of theory) of product are obtained in the form of a solid with spherical particles in the particle size range from 0.1 to 0.6 mm (of which 65% is in the range from 0.2 to 0.4 mm) and with the composition NC-(CH2)3-Sio3/2.3Sio2.
Elemental analysis : % C % H % N ~ Si Theory: 15.9 2.0 4.6 37.4 Found: 14 2.3 3.2 35.7 Bulk density: 683 g/l (anhydrous) - 21~3~3 Example 2 After extraction with ethanol, the product prepared in the same way as in example 1 is first subjected to a hydrothermal treatment at 150~C in 5% aqueous ammonia solution (24 h) and then dried as in example 1. A solid is obtained as in example 1, but with a bulk density of 405 g/l.
Example 3 138.8 g of StCH2CH2CH2Si(OCH3)3]2 and 161.2 g of Si(oC2H5)4 are initially introduced into a 3 1 double-walled glass vessel together with 300 ml of ethanol and 120 ml of 1-octanol and heated to 75~C with stirring. 49 g of NH3 solution (25 % by weight in water) and 55 ml of distilled water are added and the mix is cooled to 70~C. After 5 minutes the mix gels, the rate of stirring is immediately increased (600 rpm) and 240 ml of octanol are added. 900 ml of water (50~C) are immediately added to the homogeneous solution and the organic phase is dispersed in the water.
The emulsion which is present is heated and boiled under reflux for 2 hours. The mix is filtered under suction, 5%
strength NH3 solution is added to the isolated solid and stirred in a laboratory autoclave at 150~C for 24 h. After cooling the mix, the solid which is produced is filtered off under suction and extracted three times with ethanol, with stirring.
The product is dried under N2 for 4 h at 60~C, for 4 h at sooc, for 4 h at 120~C and finally for 12 h at 150~C. After classifying the solid, 101 g of product in the form of a solid with spherical particles in the particle size range from 0.3 to 0.8 mm and the composition S[(CH2)3-siO3/~i2sio2 are obtained.
~1~3~53 Elemental analysis: % C % H % S % Si Theory: 21.2 3.6 9.4 32.9 Found: 23 4.1 9.9 30.7 Bulk density: 164 g/l (anhydrous) Example 4 62.4 g of CH3CH2CH2Si(OCH3)3 and 237.6 g of Si(oc2Hs) 4 are initially introduced into a 3 1 double-walled glass vessel together with 300 ml of ethanol and heated to 80~C with stirring. 71 g of HCl solution (37% by weight in water~ and 90 ml of distilled water are added stepwise, the mix is boiled under reflux for 2 h and then cooled to 70~C. After 15 minutes the mix gels, the rate of stirring is immediately increased (600 rpm) and after 1 minute 300 ml of octanol are added. After another 1 minute 900 ml of water (50~C) are added to the homogeneous solution and the organic phase is dispersed in the water. The emulsion which is present is heated and boiled under reflux for 2 h.
The mix is filtered under suction, 5% strength NH3 solution is added to the isolated solid and stirred in a laboratory autoclave at 150~C for 24 h.
After cooling the mix, the solid which is produced is filtered off under suction and extracted three times with ethanol, with stirring.
The product is dried under N2 for 4 h at 60OC, for 4 h at 90~C, for 4 h at 120~C and finally for 12 h at 150~C. After classification of the solid, 92 g of product, in the form of a solid with spherical particles in the particle size - 210~6~3 range from 0.1 to 0.8 mm and the composition CH2CH2CH2-sio3,2.3sio2 are obtained.
Elemental analysis: % C % H % Si Theory: 13.1 2.6 40.8 Found: 13.0 2.8 39.7 Bulk density: 240 g/l (anhydrous) Exam~le 5 60-6 g of NCS-CH2CH2CH2si(OC2H5) 3 and 239.5 g of Si(oC2H5) 4 are initially introduced into a 3 l double-walled glass vessel together with 300 ml of ethanol and heated to 80~C with stirring. 71 g of HCl solution (37~ by weight in water) and 45 ml of distilled water are added stepwise, the mix is boiled under reflux for 40 minutes, then cooled to 70~C.
After 215 minutes the mix gels, the rate of stirring is immediately increased (600 rpm) and after 1 min. 300 ml of octanol are added. After 5 minutes, 900 ml of water (50~C) are added to the homogeneous solution and the organic phase is dispersed in the water. The emulsion which is present is heated and boiled for 2 h under reflux.
After working-up in the same way as in example 4, a shaped polysiloxane with the composition NCS-CH2CH2CH2-Sio3~2.5sio2 was obtained.
ExamPle 6 57.8 g of CH2=CH2Si(OCH3) 3 and 242.2 g of Si(oc2Hs) 4 are initially introduced into a 3 l double-walled glass vessel together with 300 ml of ethanol and 120 ml of 1-octanol and ~1~36~
.. .
heated to 80~C with stirring. 75 ml of water (pH = 4.0) are added, the mix is cooled to 70~C and 2.0 ml of triethylamine are added. The mix itself is kept at a temperature of 60~C with slow stirring. After 15 minutes, the mix gels, the rate of stirring is immediately increased (600 rpm) and 240 ml of octanol are added. 900 ml of water (50~C) are immediately added to the homogeneous solution and the organic phase is dispersed in the water. Further working-up is performed in the same way as in example 1. A
shaped polysiloxane with the following composition was obtained : CH2=CH2-Sio3~2.3Sio2.
ExamPle 7 81.9 g of C8H17Si(oCH3)3 and 218.2 g of Si(oc2Hs)4 were reacted in precisely the same way as described in example 6 and a shaped polysiloxane of the composition CôH"Sio3~2.3Sio2 was obtained.
Exam~le 8 In the same way as in example 6, 73.1 g of phenyltriethoxysilane and 226.9 g of polydiethyl silicate 40 (pre-condensed tetraethoxysilane, corresponding to 40%
sio2 content) were reacted and a product with the composition C6HsSio3/Z~5sio2 was obtained.
Sieve analysis: 0.2 - 0.3 mm : 31%
0.3 - 0.6 mm : 59%
0.6 - 0.8 mm : 10%
BET surface area: 642 mZ/g Mesopores (2-30 nm): 0.72 ml/g Macropores: 0.84 ml/g 21~3~
Example g In the same way as in example 6, 26.9 g of propyltrimethoxysilane and 273.1 g of tetraethoxysilane were reacted and a product with the composition C3H~i3/2.8SiO2 was obtained.
BET surface area: 784 mZ/g Mesopores (2-30 nm): 0.48 ml/g 10 Macropores: 1.24 ml/g Bulk density: 390 g/l Example 10 The polysiloxane obtained in example 9 was stirred with 5%
NH3 solution before drying for 24 h at 150~C.
BET surface area: 491 m2/g Mesopores (2-30 nm): 1.81 ml/g Macropores: 3.35 ml/g Bulk density: 192 g/l Example 11 In the same way as in example 6, 83.44 g of chloropropyltriethoxysilane and 216.6 g of tetraethoxysilane were reacted and a shaped polysiloxane with the composition Cl-CH2CH2CH2SiO3/2.3SiO2 was obtained.
Chlorine content: 10.4% by wt. (Theory: 11.4% by wt.) Spec. surface area: 649 m2/g Micropores (< 2 nm): 0.42 ml/g Mesopores (2-30 nm): 0.02 ml/g 35 Macropores: 0.75 ml/g Bulk density: 545 g/l Exam~le 12 In the same way as in example 6, but using 1 ml of triethylamine, 50.9 g of HNtCH2CHzCH2Si(OC2H5)3]2 and 249.1 g of tetraethoxysilane were reacted and a shaped polysiloxane with the composition HNtCHzCHzCH2SiO3/2]2~l0SiO2 was obtained.
Spec. surface area: 112 m2/g Mesopores (2-30 nm): 0.22 ml/g Macropores: 4.47 ml/g Bulk density: 167 g~l
Claims (23)
1. Shaped organosiloxane polycondensates, characterized in that they consist of units of the formula X - R1 (I) and/or the formula R2 - Y - R3 (II) and the formula or as well as optionally units of the formula or or in which the ratios (I) to (III) are in the range from 95 to 5 to 5 to 95 mol-%
or (II) to (III) or the sum of (I) plus (II) to (III) are from 100 to 0 to 5 to 95 mol-%
and with the ratio of the sum of (I), (II) and (III) of 100 to 0 to 50 to 50 mol-%, wherein R1 to R3 are identical or different and represent a group of the general formula (V) R4 being bonded directly to the group X or Y and representing a linear or branched, fully saturated or unsaturated alkylene group with 1 to 10 carbon atoms, a cyclolkylene group with 5 to 8 carbon atoms, a phenylene group or a unit of the general formula or in which n is a number from 1 to 6 and gives the number of methylene groups adjacent to X or Y and m is a number from 0 to 6, wherein M is a Si, Ti or Zr atom and R' is a linear or branched alkyl group with 1 to 5 carbon atoms or phenyl group and X in formula (I) represents -H, -Cl, -Br, -I, -CN, -SCN, -N3, -OR'', -SH, -COOH, P(C6H5)2, -NH2, -N(CH3)2, -N(C2H5)2, -NH-(CH2)2-NH2, -NH-(CH2)2-NH-(CH2)2-NH2, -NH-C(S)-NR2'', -NH-C(O)-NR2'', -NR''-C(S)-NR2'', -O-C(O)-C(CH3) = CH2, -CH=CH2, -CH2-CH=CH2, -CH2-CH2-CH=CH2, or and Y in formula (II) represents , , -S-, -S2-, -S3-, -S4-, ; -NH-C(S)-NH-, , , -NH-C(O)-NH-, or wherein R'' is H or represents a linear or branched alkyl group with 1 to 5 carbon atoms, characterized by macroscopic spherical particles with a diameter of 0.01 to
or (II) to (III) or the sum of (I) plus (II) to (III) are from 100 to 0 to 5 to 95 mol-%
and with the ratio of the sum of (I), (II) and (III) of 100 to 0 to 50 to 50 mol-%, wherein R1 to R3 are identical or different and represent a group of the general formula (V) R4 being bonded directly to the group X or Y and representing a linear or branched, fully saturated or unsaturated alkylene group with 1 to 10 carbon atoms, a cyclolkylene group with 5 to 8 carbon atoms, a phenylene group or a unit of the general formula or in which n is a number from 1 to 6 and gives the number of methylene groups adjacent to X or Y and m is a number from 0 to 6, wherein M is a Si, Ti or Zr atom and R' is a linear or branched alkyl group with 1 to 5 carbon atoms or phenyl group and X in formula (I) represents -H, -Cl, -Br, -I, -CN, -SCN, -N3, -OR'', -SH, -COOH, P(C6H5)2, -NH2, -N(CH3)2, -N(C2H5)2, -NH-(CH2)2-NH2, -NH-(CH2)2-NH-(CH2)2-NH2, -NH-C(S)-NR2'', -NH-C(O)-NR2'', -NR''-C(S)-NR2'', -O-C(O)-C(CH3) = CH2, -CH=CH2, -CH2-CH=CH2, -CH2-CH2-CH=CH2, or and Y in formula (II) represents , , -S-, -S2-, -S3-, -S4-, ; -NH-C(S)-NH-, , , -NH-C(O)-NH-, or wherein R'' is H or represents a linear or branched alkyl group with 1 to 5 carbon atoms, characterized by macroscopic spherical particles with a diameter of 0.01 to
2.5 mm, a specific surface area of 0.01 to 1000 m2/g, a specific pore volume of 0.01 to 5.0 ml/g and a bulk density of 50 to 1000 g/l.
2. Shaped organosiloxane polycondensates according to Claim 1, characterized in that the ratios of (I) to (III) are in the range from 50 to 50 to 10 to 90 mol-%
or (II) to (III) or the sum of (I) plus (II) to (III) are 90 to 10 to 10 to 90 mol-% and the ratio of the sum of (I), (II), and (III) to (IV) is 100 to 0 to 50 to 50.
2. Shaped organosiloxane polycondensates according to Claim 1, characterized in that the ratios of (I) to (III) are in the range from 50 to 50 to 10 to 90 mol-%
or (II) to (III) or the sum of (I) plus (II) to (III) are 90 to 10 to 10 to 90 mol-% and the ratio of the sum of (I), (II), and (III) to (IV) is 100 to 0 to 50 to 50.
3. Shaped organosiloxane polycondensates according to Claim 1 or 2, characterized in that the particles have a diameter of 0.05 to 1.5 mm.
4. Shaped organosiloxane polycondensates according to Claim 1, 2 or 3, characterized in that they have a specific surface area of 50 to 800 m2/g.
5. Shaped organosiloxane polycondensates according to any one of Claims 1 to 4, characterized in that they have a bulk density of 100 to 800 g/l.
6. Shaped organosiloxane polycondensates according to any one of Claims 1 to 5, characterized in that they are present as so-called random polycondensates, block polycondensates or mixed polycondensates.
7. Shaped organosiloxane polycondensates according to any one of Claims 1 to 6, characterized in that the groups to R3 represent a group of the general formula
8. A process for the preparation of shaped random organosiloxane polycondensates according to Claim 1, characterized in that components of the general formulas (VI) to (VIII):
X-R5 (VI), R6-Y-R7 (VII), M(OR8)2-4R'0-2 or Al(OR8)2-3R'0-1 (VIII) corresponding to the stoichiometric composition of the polysiloxane being prepared specified in Claim 1, wherein R5 to R7 are identical or different and each represents a group of the general formula (IX) -R4-Si(OR9)3 (IX) X, Y, R', M and R4 are each defined as in the formulas (I) to (V) and R8 and R9 represent a linear or branched alkyl group with 1 to 5 carbon atoms, are dissolved in a solvent which is predominantly water-miscible but dissolves the silane components, an amount of water which is at least sufficient for complete hydrolysis and condensation is added to the solution with stirring, then the reaction mixture is allowed to gel with further stirring at a specific temperature in the range from room temperature to 200°C, and at the start of gelling or up to one hour afterwards 10 to 2000% by weight, with reference to the total amount of silane components used, of a predominantly water-immiscible solvent, but one which dissolves and dilutes the reaction mixture being gelled, is added, homogenized and immediately or within a time interval of up to 3 hours later, optionally increasing the originally fixed temperature, 10 to 2000% by weight with reference to the total amount of silane components used, of water is added, the siloxane-containing organic phase is dispersed in the liquid two-phase system and the solid which is formed after hardening of the droplets in the shape of spheres is separated from the liquid phase after a sufficient reaction time, at room temperature to 250°C, optionally purified by extraction, optionally dried at room temperature to 250°C, optionally under a protective gas or under vacuum, and then optionally annealed and/or classified.
X-R5 (VI), R6-Y-R7 (VII), M(OR8)2-4R'0-2 or Al(OR8)2-3R'0-1 (VIII) corresponding to the stoichiometric composition of the polysiloxane being prepared specified in Claim 1, wherein R5 to R7 are identical or different and each represents a group of the general formula (IX) -R4-Si(OR9)3 (IX) X, Y, R', M and R4 are each defined as in the formulas (I) to (V) and R8 and R9 represent a linear or branched alkyl group with 1 to 5 carbon atoms, are dissolved in a solvent which is predominantly water-miscible but dissolves the silane components, an amount of water which is at least sufficient for complete hydrolysis and condensation is added to the solution with stirring, then the reaction mixture is allowed to gel with further stirring at a specific temperature in the range from room temperature to 200°C, and at the start of gelling or up to one hour afterwards 10 to 2000% by weight, with reference to the total amount of silane components used, of a predominantly water-immiscible solvent, but one which dissolves and dilutes the reaction mixture being gelled, is added, homogenized and immediately or within a time interval of up to 3 hours later, optionally increasing the originally fixed temperature, 10 to 2000% by weight with reference to the total amount of silane components used, of water is added, the siloxane-containing organic phase is dispersed in the liquid two-phase system and the solid which is formed after hardening of the droplets in the shape of spheres is separated from the liquid phase after a sufficient reaction time, at room temperature to 250°C, optionally purified by extraction, optionally dried at room temperature to 250°C, optionally under a protective gas or under vacuum, and then optionally annealed and/or classified.
9. A process according to Claim 8, characterized in that methanol, ethanol, n- or i-propanol, n- or i- butanol or n-pentanol, alone or in a mixture, is used as solvent for hydrolysis.
10. A process according to Claim 8 or 9, characterized in that a linear or branched alcohol with 4 to 12 carbon atoms, toluene, xylene isomers (separately or in a mixture) or tert-butyl-methyl-ether is added to the reaction mixture being gelled.
11. A process according to Claim 8, 9 or 10, characterized in that some or all of the amount of water-insoluble solvent being added at or after the start of gelling is used from the beginning of the process in addition to the solvent used at that point.
12. A process according to any one of Claims 8 to 11, characterized in that one or more of the silanes of the formulas (VI) to (VIII) is not introduced to the mix from the beginning, but is only introduced later, during or shortly after gelling, optionally in the predominantly water-insoluble solvent being added.
13. A process according to any one of Claims 8 to 12, characterized in that some silane components, combined or each separately, are precondensed and then added to the reaction mixture.
14. A process according to any one of Claims 8 to 13, characterized in that the weight ranges are 50 to 500%.
15. A process for after-treating the shaped but not dried organopolysiloxane condensates obtained in accordance with any one of Claims 8 to 14, characterized in that the solid obtained is subjected to a thermal treatment for 1 hour to one week at 50 to 300°C, in the liquid phase in the presence of at least the component water or else in the mother liquor, wherein the excess pressure corresponds to the sum of the partial pressures of the components used.
16. A process according to Claim 15, characterized in that the thermal treatment is 100 to 200°C.
17. A process according to Claim 15 or 16, characterized in that the after-treatment is performed in the presence of an acid or basic catalyst.
18. A process according to Claim 15 or 16, characterized in that the after-treatment is performed in the presence of ammonia.
19. A process according to any one of claims 8 to 18, characterized in that a hydrolysis and condensation catalyst from the group HC1, H3PO4, CH3COOH, NH3, NR3''', wherein R''' represents an alkyl group which contains 1 to 6 carbon atoms, as the pure substance or in aqueous solution is added to the solution with stirring prior to the reaction mixture being allowed to gel.
20. Use of the shaped organopolysiloxane condensates in accordance with any one of Claims 1 to 7, for absorbing gaseous organic compounds.
21. The use as defined in Claim 20, wherein solvent vapors are adsorbed.
22. Use of the shaped organopolysiloxane condensates in accordance with any one of Claims 1 to 7 as carrier materials for the preparation of heterogeneous noble metal catalysts.
23. Use of the shaped organopolysiloxane condensates in accordance with any one of Claims 1 to 7, with appropriate functional groups, for absorbing metals from aqueous or organic solvents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4225978A DE4225978C1 (en) | 1992-08-06 | 1992-08-06 | Shaped organosiloxane polycondensates, process for their preparation and use |
| DEP4225978.9 | 1992-08-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2103653A1 CA2103653A1 (en) | 1994-02-07 |
| CA2103653C true CA2103653C (en) | 1998-08-04 |
Family
ID=6464953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002103653A Expired - Fee Related CA2103653C (en) | 1992-08-06 | 1993-08-05 | Shaped organosiloxane polycondensates, processes for their preparation and use |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0582879B1 (en) |
| JP (1) | JPH06207018A (en) |
| AT (1) | ATE159962T1 (en) |
| CA (1) | CA2103653C (en) |
| DE (2) | DE4225978C1 (en) |
| ES (1) | ES2111094T3 (en) |
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| US7687558B2 (en) | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
| US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
| US7968634B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
| US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4338421A1 (en) * | 1993-11-10 | 1995-05-11 | Wacker Chemie Gmbh | Graft copolymers of organopolysiloxanes as free-radical macroinitiators |
| ES2140252B1 (en) * | 1995-01-11 | 2001-02-01 | Repsol Quimica Sa | A PROCEDURE FOR THE OBTAINING OF SHORT AND LONG FIBERS AND THEIR CHEMICAL INTERLOCKING FABRICS BY CENTRIFUGATION, STRETCHING OR EXTRUSION OF SOLES OBTAINED THROUGH CONTROLLED HYDROLYSIS OF METALLIC ALCOXIDE DISSOLUTIONS. |
| EP0852582B1 (en) * | 1995-09-19 | 2000-01-05 | E.I. Du Pont De Nemours And Company | Modified fluorosulfonic acids |
| US6262326B1 (en) | 2000-06-06 | 2001-07-17 | E. I. Du Pont De Nemours And Company | Process for the preparation of spherically shaped microcomposites |
| US6107233A (en) * | 1997-03-24 | 2000-08-22 | E. I. Du Pont De Nemours And Company | Process for the preparation of spherically shaped microcomposites |
| JP2003001106A (en) * | 2001-06-22 | 2003-01-07 | Nippon Steel Corp | Selective gas adsorbent and gas detecting system |
| JP4571393B2 (en) * | 2002-11-27 | 2010-10-27 | 三井化学株式会社 | Organopolymer siloxane and its use |
| JP4736388B2 (en) * | 2004-09-29 | 2011-07-27 | セントラル硝子株式会社 | Organic-inorganic hybrid glassy material and method for producing the same |
| JP5009705B2 (en) * | 2007-07-05 | 2012-08-22 | 株式会社テクノ菱和 | Resin removal system for volatile organic substances |
| DE102009029555A1 (en) | 2009-09-17 | 2011-03-24 | Wacker Chemie Ag | Continuous production of macroscopic silica materials with high specific surface and/or ordered pore structure, comprises continuously hydrolyzing homogeneous precursor and isolating silica particles as a macroscopic mold |
| US11148121B2 (en) * | 2016-05-31 | 2021-10-19 | Dow Silicones Corporation | Method of depleting a volatile component in a mixture using a sorbent crosslinked elastomer and apparatus for practicing the method |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3131954C2 (en) * | 1981-08-13 | 1984-10-31 | Degussa Ag, 6000 Frankfurt | Metal complexes of polymeric, optionally crosslinked organosiloxane amines, process for their preparation and use |
| DE3226091C2 (en) * | 1982-07-13 | 1986-11-20 | Degussa Ag, 6000 Frankfurt | Polymeric di-, tri- or tetrasulfides, process for their preparation and use |
| DE3800563C1 (en) * | 1988-01-12 | 1989-03-16 | Degussa Ag, 6000 Frankfurt, De | |
| DE3837418A1 (en) * | 1988-11-04 | 1990-05-10 | Degussa | ORGANOSILOXANAMINE COPOLY CONDENSATES, METHOD FOR THE PRODUCTION AND USE THEREOF (I) |
| DE3837415A1 (en) * | 1988-11-04 | 1990-05-10 | Degussa | ORGANOPOLYSILOXANE-UREA AND ORGANOPOLYSILOXANE-THIOURAE DERIVATIVES, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3837416A1 (en) * | 1988-11-04 | 1990-05-10 | Degussa | ORGANOSILOXANAMINE COPOLY CONDENSATES, METHOD FOR THE PRODUCTION AND USE THEREOF (II) |
| JPH02225328A (en) * | 1989-02-23 | 1990-09-07 | Nippon Muki Kk | Production of spherical silica glass |
| DE3925359C1 (en) * | 1989-07-31 | 1991-02-07 | Degussa Ag, 6000 Frankfurt, De | |
| DE3925360C1 (en) * | 1989-07-31 | 1991-02-07 | Degussa Ag, 6000 Frankfurt, De | |
| US4997944A (en) * | 1990-01-18 | 1991-03-05 | Indiana University Foundation | Aminopyridyl silanes |
| DE4035032C1 (en) * | 1990-11-03 | 1992-04-30 | Degussa Ag, 6000 Frankfurt, De | |
| DE4110705C1 (en) * | 1991-04-03 | 1992-10-22 | Degussa Ag, 6000 Frankfurt, De |
-
1992
- 1992-08-06 DE DE4225978A patent/DE4225978C1/en not_active Expired - Fee Related
-
1993
- 1993-07-23 AT AT93111811T patent/ATE159962T1/en not_active IP Right Cessation
- 1993-07-23 EP EP93111811A patent/EP0582879B1/en not_active Expired - Lifetime
- 1993-07-23 DE DE59307627T patent/DE59307627D1/en not_active Expired - Fee Related
- 1993-07-23 ES ES93111811T patent/ES2111094T3/en not_active Expired - Lifetime
- 1993-08-05 JP JP5194695A patent/JPH06207018A/en active Pending
- 1993-08-05 CA CA002103653A patent/CA2103653C/en not_active Expired - Fee Related
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| US7687558B2 (en) | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
| US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
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| US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US8067491B2 (en) | 2006-12-28 | 2011-11-29 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
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| US8383850B2 (en) | 2006-12-28 | 2013-02-26 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US8501849B2 (en) | 2006-12-28 | 2013-08-06 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
| US8669389B2 (en) | 2006-12-28 | 2014-03-11 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making the uses in rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06207018A (en) | 1994-07-26 |
| ES2111094T3 (en) | 1998-03-01 |
| DE4225978C1 (en) | 1994-04-07 |
| ATE159962T1 (en) | 1997-11-15 |
| EP0582879B1 (en) | 1997-11-05 |
| DE59307627D1 (en) | 1997-12-11 |
| EP0582879A1 (en) | 1994-02-16 |
| CA2103653A1 (en) | 1994-02-07 |
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