JPH04502779A - Organically modified silicic acid heteropolycondensate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Organo-modified silicate heteropolymer metal (Technical field) This invention relates to improved silicic acid heteropolycondensates containing organic groups. This invention It also relates to methods for their production and uses of such condensates.

(Background technology) Silicic acid heteropolycondensates have been known in the art for a considerable period of time. Generally, this These products can be subjected to low or mild temperature treatments including hydrolysis and condensation. Therefore, the method using triethoxysilane as a raw material when performing the manufacturing method is The details are shown below.

In the reaction formula below, R is a non-hydrolyzable organic group such as an alkyl group or an aryl group. be.

(1) nR51 (OCzHs) 3 nR51 (OFI) s +3nCzH sOHnHzO Equation (1) exemplifies the complete hydrolysis of triethoxysilane.

As shown, each mole equivalent of completely hydrolyzed trialkoxysilane is consumes the equivalent of 1 lb of water. This hydrolysis product is relatively unstable and has the formula (2) They tend to undergo the condensation process quickly. The condensation is all three alcohols It is known in the art that xy groups begin to occur before hydrolysis.

Equation (2) is oversimplified. Two silas each formed in step (1) Shows condensation between nol groups. Even between other groups, as shown by incomplete bonds, Further condensation may occur. This series of condensations forms what is known as a sol-gel. It is known in the art to bring about objects. For the purpose of this invention, “sol- The term "gel" includes one or two non-hydrolyzable groups (e.g. R in the above formula). and one or more silas whose residual silicon value is filled by hydrolyzable groups. organically modified silicic acid heteropolycondensates formed by hydrolysis and condensation of Refers to a glassy solid mixture. Generally, these polycondensation products are interconnected network structure of silicon-containing chains (where silicon atoms are bonded to oxygen) It includes structure. These products are polymers, but they are in the solid state Therefore, molecular weight measurement cannot be performed.

As shown in formula (2), each condensation of two silanol groups also dissociates one molecule of water. Tarasu. This will be discussed in more detail below.

Linear polycondensates consist only of silanes with two hydrolyzable groups per molecule. Produced from reactants. On the other hand, one or more types having 3 or 4 hydrolyzable groups Starting materials containing silanes give crosslinked polycondensates.

Groups present in the three-dimensional polymer network do not react easily due to steric hindrance Therefore, cross-linking can make it difficult for complete hydrolysis and/or condensation to occur. There is sex. Therefore, under the conditions used in conventional methods, crosslinked silicic acid condensates remain. may contain hydrolyzable groups (e.g. alkoxy groups) or residual silanol groups. There is sex. In this technical field, silicic acid heteropolymerized metals (non-organically modified, (i.e., those containing no organic groups), liquids exceeding their supercritical temperature may be used. It is known that drying can be done by (Tewari et al. ls Letters, Vol, L No-9+1o, 363-367 pages (July, 1985)] and Laudise et al., Journa of Non-Cr 5 talline Solids 79. Pages 155-164 ( (1986) demonstrated supercritical drying of alkoxide silica gel using an ethanol-containing system. related to. Monolithic non-mature modified silica gel can also be produced using supercritical solvent evacuation method. (Prassas et al., Journal of Materia lsScience 19. pages 1656-1665 (1986)).

(Disclosure of invention) The challenge with conventional silicic acid heteropolycondensates is that they are It contains residual silanol groups and residual hydrolyzable groups. Such groups are traditionally may have a harmful effect on other substances. We believe that this issue is in a supercritical state. The solution is to remove such groups through treatment of heteropolymerized metals with a fluid of I found out what I can do. We also discovered, surprisingly, the use of supercritical fluids is an organic group bonded to the silicon atom in such a condensate through a silicon-carbon bond. It was also found that . With our modification method we also The organically modified silicic acid heteropolycondensate produced also has improved oxygen permeability. I found it. This property is useful for film formation using the above polycondensates in oxygen permeable systems. Make available. We also demonstrated that monolithic glassy porous solids can be organically modified. comprising the step of contacting the silicic acid sol in a mold with a fluid exceeding a critical temperature and pressure. We also discovered that it can be produced by a method.

Accordingly, this invention has several aspects. Firstly, this invention solves the problem of residual silanol Modification of organically modified silicate heteropolymer metals by removal of groups and/or hydrolyzable groups A method for converting the polycondensed metal to be modified into a silanol group or exceeds the critical temperature and pressure of a given fluid for a sufficient time to remove the hydrolyzable groups. 2. A method comprising: contacting a fluid containing a liquid; - In the embodiment, the added The water-decomposable group is an alkoxide group, and the supercritical fluid is attached to the alkoxide group. It is the corresponding alcohol.

The products of this modification method are free or free of silanol and hydrolyzable groups. is virtually non-existent. For purposes of this invention, "substantially absent" means This means that only 5% of the groups attached to the element are hydrolyzable groups or silanol groups. Taste.

In a second aspect, the invention comprises a method of manufacturing. The manufacturing method of this invention is as follows. Hydrolysis/condensation reactions of the type exemplified by reaction formulas (1) and (2), Subsequent removal of residual hydrolyzable groups and silanol groups from the polycondensation intermediate The modification method comprises: This one! Similar modification methods are of the type described above.

The production and modification aspects of this invention include two types of materials constituting the third aspect of this invention. Directed to the production of mechanically modified silicic acid heteropolycondensation products, the first product type is powder It's the end. In these powders, at least about 90% of the repeating silicon-containing units are silicon. It has at least one organic group (R) bonded to an elementary atom.

The second product type in this third embodiment is a porous, glassy monolithic It is a solid solid. For purposes of this invention, "monolithic" means cast or It means that it is formed in a different state. The monolithic body of this invention is rod-shaped. or may take other shapes, such as lenticular shapes.

The monolithic bodies of this invention can be glassy (i.e., amorphous) opaque solids or transparent. It is a bright solid. A typical rod has a diameter of 0°5 to 25 mm and a length of 10 to 125 pus. have It is also possible to produce products outside this size range.

These monolithic bodies have two main types of repeating units, namely the formula Si= and R31E (wherein R is a non-hydrolyzable compound bonded to the silicon atom via carbon) is an organic group). In these monolithic bodies, the anti- About 5-35 mole percent of the repeat units have formula R31E. Therefore, the monolithic structure of this invention The block body is mostly composed of repeating units represented by the formula 3i=. They are Approximately 5% of repeating units of the formula R51= (wherein R has the same meaning as above) It may even last. The monolithic bodies of this invention are It can be used as a substrate for separation of tographs.

The method of this invention involves the use of hydrolyzable groups and/or silanol groups of cross-linked heteropolymerized metals. This method is useful for removing such groups from linear polycondensates. can also be used.

Brief description of the drawing The line drawings in the drawings indicate the oxygen permeability of the non-monolithic products of this invention as proposed herein. This is a graph plotted against the same material that has not been modified by the method provided. Ru. The oxygen permeability values are on the ``y-axis,'' while the oxygen concentration values are plotted along the ``xj-axis.'' has been cut. As shown, (i) contains a phenyl group, (ii) this invention The organically modified silicic acid heteropolycondensate produced by the method of Much higher oxygen permeability than that of the same material without has.

However, the linearity of the response by the products of this invention is limited by the ratio (for practicing the invention). best form) - embodiments, the present invention provides for multiple hydrolyzable groups and/or silanos Including a method for modifying an organically modified silicic acid heteropolycondensate by reducing the number of silicic acid groups. It becomes. This method involves contact with a fluid under high pressure for a sufficient period of time to remove such groups. and heating the condensate at a high temperature. This process involves the use of the above fluid. It is carried out above the critical temperature and pressure. The product is a liquid and a hydrolyzable group. Volatile products formed during removal can be recovered by separation.

As noted above, for purposes of describing this invention, the method of this embodiment is referred to as the "modified" method of this invention. It is called ``Method''. This modification method involves the heteropolycondensation of a wide variety of organically modified silicic acids. It can be carried out on objects. The applicability of the modification method of this invention is that A hydrolyzable group and/or a silanol group that can be removed from the above condensate is independent of the method used to produce the condensate that provides the condensate to be treated containing .

In addition, as described above, the second aspect of the present invention is referred to herein as a "manufacturing method" or [Manufacturing method of the present invention]. The manufacturing method is (a) Organic modification by reactions comprising hydrolysis and condensation of organosilanes Formation of silicic acid condensate, then (b) residual hydrolyzable groups and/or or removal of silanol groups, Contains. Step (b) constitutes the reforming method of the present invention.

A preferred method within the manufacturing aspect of this invention is represented by (i) formula R31E, which formula The free valences in have repeating silicon units interconnected via oxygen and (i i) Characterized by substantially not containing hydrolyzable groups and silanol groups , a method for producing an organically modified silicate heteropolymerized metal, (A) In the presence of a low boiling point solvent for the silane at low to moderate temperatures, the formula RX S　1(OR')　ax　(wherein R is an alkyl group having up to about 20 carbon atoms or an aryl group, R' is an alkyl group of up to about 4 carbon atoms, and by reacting a silane with water (where X is equal to 1 or 2). Step of forming an intermediate silicic acid condensate; (B) substantially all of the intermediate fasteners; The remaining R'O- group and the silanol group are removed, and the alkyl a pressure above the critical temperature and pressure of the solvent for a sufficient time to produce a canol; heating the reaction mixture produced above at a pressure and temperature; and (C) The above-mentioned alkanol and and a step of removing the solvent.

In the specific embodiment shown immediately above, the combination of steps (A) and (B) constitutes a manufacturing method. Step (B) is a modification method in the manner described above. process (C) is a product recovery step. Such a process is desirable and It is not an essential feature of the invention.

A third aspect of the invention is an organic group-containing porous material containing repeating units 3i= and R3E. a monolithic glassy body, wherein R is a stable organic group, and (a) about 5 to about 35% of said units are R31E; and (b) said R3iE units are (C) the repeating unit is substantially uniformly dispersed throughout the body, and (C) the repeating unit is It has a surface area of about 500 to about 800rd/g, and an apparent density of about 0.25 to about 0.40 g/mL, and substantially no residual silanol groups. and an object that does not contain a hydrolyzable group.

As part of this aspect, the invention provides a method for providing a monolithic body of the type described above. The method provides a method in which the precursor decondensation metal is heated in a mold to a certain fluid critical temperature and Substantially all of the sol is removed from the sol by contact with that fluid for a sufficient period of time to exceed the pressure. Remaining silanol groups and hydrolyzable groups are removed, and then the fluid and the precursor are combined. from the volatile by-products produced by removing the above groups from the heavy condensates. evacuating and cooling to separate the objects.

The precursor condensate is a silane mixture represented by the formula SiXa and the formula R31X3. produced by hydrolysis and condensation of the compound. In addition, in the above formula, in the above mixture about 5 to about 35 mole percent of the silane in the above is of formula R31Xs, and In each of the above formulas, X is a hydrolyzable group, and R is a non-hydrolyzable organic group.

The products of this invention are organically modified (i.e., they contain organic groups). nothing). They are polymeric in nature.

The linear polymer produced by this invention is composed of repeating units of the formula It is. The crosslinked polymer has the formula It consists of repeating units indicated by . The cross-linked product is composed only of these groups. You don't need to be there. As shown more fully below, the products of this invention are It may be modified by including other silicon-containing groups, but in relatively small amounts.

Therefore, the products of this invention have the formula RX S i X4-X, where X=0-2 , except when all X of the starting materials are equal or 0) It can be considered as a heteropolycondensate derived from silanes.

As mentioned above, the crosslinked organically modified silicic acid heteropolymer modified by the method of the present invention The metal shrinkage is a repeating unit R51E (where incomplete bonds are connected via oxygen). ). As discussed, these repeating units have the formula c: R is an organic group bonded to silicon via carbon, and the groups represented by X are the same or different, and alkoxides (e.g. the alkoxide groups mentioned above), Aryl oxides, alkyl alkoxides, alkoxy alkoxides and one or more silanes selected from hydrolyzable groups such as can be formed by hydrolysis and condensation reactions. These hetero Polycondensates also have the formula %formula% One or more silanes represented by (wherein X and R have the same meanings as above) It can also include groups derived from.

When a powder is produced with this invention, a small number of silicon-containing units of the powder are of the formula and ■ or mixtures thereof. This is determined by the following consideration. This can be substantiated in more detail.

Referring first to the compounds of formula ■, by adding them to the reaction mixture, The hardness or abrasion resistance of the heteropolycondensate produced can be enhanced. The compound of formula ■ is al It is preferred that the cooxides, i.e. they have the formula Si (OR'), .

In addition, all alkoxide groups may have the same X or (tetra-atom represented by ORI) Rukoxides are generally preferred because they are cheaper and more easily available. Delicious. However, mixed alkoxides, i.e. 2, 3 or 4 Silicon alkoxides with different alkoxide groups are also used in some cases. be able to.

The type of group bonded to the oxygen atom in the alkoxide provided is not limited. However, the alkoxide groups derived from them are hydrolyzed under the reaction conditions used. It is possible.

Therefore, a radical has a short or long alkyl chain, branched or unbranched, unsaturated or groups such as alkoxy, halogen (CI, Br or I) or amines. may be replaced with . More typically they are short, unbranched, or Slightly branched lower hydrocarbon alkyl group, i.e. composed solely of carbon and hydrogen and is an alkyl group containing up to 4 carbon atoms. Therefore, for example, The alkoxide group in the substance of formula ■ is illustrated by the following non-limiting example. explained.

methoxide ethoxide isopropoxide The most preferred alkoxide of this type is tetramethoxysilane; Other compounds of the type can also be used, such as tetraethoxysilane.

Compounds of formula H useful in this invention include aryl oxides. Therefore , compounds like tetraphenoxysilane and jetoxydiphenoxysilane can also be used in this invention. In general, aryloxy groups are carbon progenitors. There can be up to about 14 phenoxy or alkylphenoxy groups. a The alkyl substituent can be of the type discussed above. powder, sand For non-monolithic products, the amount of compound of formula ■ used in this invention is It is shown in Table 1.

One or more substances of formula (■) can be added. Obtained by incorporating these substances Add linearity to the heteropolycondensate or add more organic groups to the final product. can be granted. For example, regarding the use of a substance of formula ■ for the purpose of imparting organic groups, The combination of 1 mole of and 1 mole of )including. In other words, it is desirable to add the substance of formula ■ for the purpose of improving hardness. Sometimes (as the case may be) adding an equimolar amount of compound 2) results in R31X3 formation. endows the final product with the same degree of organic groups as the condensate produced from the compound alone. child This is because the organic groups impart highly desirable properties, such as increased oxygen permeability, to heteropolymerized metals. This would be a useful tool when adding Among the compounds of formula ■, those of formula RzSi(O Alkoxides represented by R')2 are preferred. Regarding non-monolithic products , R, SiX added to the reaction mixture.

Typical amounts of compound(s) are shown in Table 1.

In the table, the column "Normal usage range" indicates the heterogeneous polymer produced by the method of this invention. This shows that it is not necessary to include compounds of formulas (1) and (2) in the condensate. However However, in some cases these ingredients may be used in amounts up to the higher values in column 5. It's okay.

l-yo (II) SiX, 5i (OR') 4 0-10 1-5 (1) R31X s R51 (OR’) 3 60100 Remainder (III) RzSiXz Rz Si(OR’)z 0 25 10 20*mol% Thus, for example, if one or more substances within formula H are used, they are Up to about 10 mole percent of the silane may be used, based on the total amount of silane used in the reaction mixture. Ru. Now, looking at column 5, if one or more compounds of formula ■ are utilized, they should be Preferably, it is used in a range of about 1 to about 5 mole percent. Similarly, the compound 2m is When utilized, it is generally used in amounts up to about 25 mole percent, or It is preferably used within the range of about 10 to about 20 mol%. The table shows that within formula I If one or more silanes other than the molecule are used, the amount of the substance of formula ■ will generally be about 60 mol% or more.

As mentioned above, the amounts shown in Table 1 are generally in the form of a powder or similar finely ground product. It is useful when it is desired to produce an organically modified silicic acid heteropolycondensate in . It is possible to produce sol-gel products in the form of rods or similar non-milled products. If desired, at least 65 mol% of the compound of formula (II), preferably at least A silane starting mixture is used which also contains 70 mol %. The rest of this silane mixture is preferably one or more compounds of formula I. However, a small amount, i.e. Up to about 5 mol% can be selected from compounds 2).

We have prepared a mixture of methoxides, such as those specifically shown in Example ■. A rod-shaped object was made from the material.

The monolithic products of this invention are not limited to rod-like or rod-like shapes. must be understood. The molded article of this invention is prepared in such a way that the reaction mixture is as specified in Example 3. This corresponds to the shape of the vessel subjected to the supercritical drying process shown. Holds reaction mixture Containers (other than tubular shapes) used to carry products of other shapes, e.g. Ras. Products in the form of rods or other shapes may be hammered or polished after production if necessary. It can be finely ground using techniques such as crushing.

As pointed out above, both the silanes of formulas I and The number of organic groups bonded to the ion (contains one). There are no restrictions on size or type. Preferably, the group is "stable", i.e. It is relatively inexpensive. Third, organic groups may suffer from steric hindrance or undesirable side reactions. It is also preferable not to be so bulky that it unduly slows down the process.

One type of organic group that can be provided within the scope of use in this invention is a linear Or a branched alkyl group is representative. More preferably, the alkyl group is a carbon atom. from about 1 to about 20 carbon atoms, most preferably from 1 to about 10 carbon atoms. particularly interesting are groups containing up to about 6 carbon atoms in the alkyl group.

Specific examples of alkyl groups that can be considered within the scope of the silanes used in this invention include methyl ethyl, isopropyl, n-butyl, 5ec-butyl, tert-butyl, n-pentyl and n-hexyl.

The aryl group includes other species that may be bonded to silicon in the silanes used in this invention. It represents the organic group of the class. Of particular interest are those having about 6 to about 20 carbon atoms, preferably preferably 6 to about 14 carbon atoms, more preferably 6 to about 10 carbon atoms. It is a drocarbyl aryl group. Specific examples are phenyl, naphthyl and biphenyls. (hydrocarbyl groups consist only of carbon and hydrogen).

The group represented by R in each of the above formulas can also be an alkenyl group, for example, from 2 to about 2 carbon atoms. Straight or branched chain containing 20 and more preferably 1 carbon-carbon double bond It is the base of the chain. Specific examples of this type of alkyl group are ethylenyl, allyl and vinyl. is a group.

When producing an organically modified silicic acid heteropolycondensate, starting components (or a mixture of starting components) objects) are brought into contact with water. First, dissolve the silane or silane mixture in an organic solvent. It is preferable to do so. Suitable solvents are alcohols, including methanol and ethanol. from 1 to about 1 carbon atom, as exemplified by alcohol, isopropanol, and isobutyl alcohol. 4 lower alcohols are preferred.

The solvent can also be selected from ketones, especially lower dialkyl ketones. Ru. Solvents of this type include acetone and methyl isobutyl ketone. Ru. Additionally, the solvent may be a diethyl ether or other dialkyl ether. The solvent may also be an amide such as diethylamide. Those skilled in the art will appreciate that the above list of solvents is not limiting and that It will be appreciated that other common solvents may also be utilized in this invention. Further solvent mixture Compounds can also be used. Preferably the solvent is a lower alcohol.

Preferably, the starting materials are mixed with water in an organic solvent in order to proceed with the reaction. good Preferably, the amount of water is the minimum amount necessary to hydrolyze the hydrolyzable groups present. Ru.

For example, the silane starting material used in the process of this invention may be a compound of formula I (such as In other words, if there is one or more compounds represented by the formula R51Xs, even if theoretically Although it is necessary to add 1.5 molar equivalents of water, a minimum of 3 molar water is used. Ru. Three moles of water are required for the hydrolysis of each hydrolyzable group, and formula 2 It is shown that one molar equivalent of water is produced during each condensation between each silanol group.

This mole of water produced through the hydrolysis-condensation process is available for the hydrolysis process. Wear.

Therefore, in this example, the amount of water to be added to the reaction mixture is This is 2/3 of the amount required to hydrolyze the hydrolyzable groups within.

It is not necessary to use exactly stoichiometric amounts of water. Therefore, use excess water can. However, since the monomers are not miscible with water, the amount of water added is large. It should not be too much.

Additionally, if the amount of water exceeds the desired amount, less reactive groups have an opportunity to react. This allows highly reactive substances or groups to be more completely hydrolyzed and condensed. It will be combined.

Therefore, if excess water is used, only about a 5-fold molar excess (500 mol%) is preferably used.

Preferably, water is added slowly to the reaction compartment. Therefore, water flows slowly or Preferably it is added in a dropwise manner.

Addition of water in this manner eliminates the indiscriminate distribution of more reactive groups within the raw materials being reacted. Helps inhibit hydrolysis and/or condensation.

The production method of this invention can be carried out in water alone or in the presence of a catalyst. Appropriate Catalysts are acidic or basic substances. Examples of suitable acidic substances include hydrochloric acid, Included are strong, non-oxidizing inorganic acids such as sulfuric acid and acetic acid. These preferred acids are , has a pKa of at least about 5.

The catalyst may also be a non-oxidizing alkaline substance, such as sodium hydroxide or potassium hydroxide. or a lower alkyl amine such as triethylamine which exhibits at least pKb5. It may be

These reactions are preferably carried out in the presence of a catalyst. using acidic catalysts is also preferred. If a catalyst is used, it should be approximately Usually used in amounts up to 5% by weight.

The hydrolysis and condensation reactions according to the production method of this invention are carried out by gentle heating to prevent relaxation. It is usually carried out at a temperature of Generally, the reaction is carried out within the range of about 10'C to about 130°C. It is done at temperature. Preferably, the reaction is carried out at a temperature within the range of about 5°C to about 65°C. It will be done.

Organic modification by hydrolysis/condensation, the formation of silicic acid heteropolycondensates, is preferable under atmospheric pressure. It is done in advance. However, it should be understood that other pressures can also be used. subordinate So, for example, a slightly lower or slightly higher pressure, i.e. about 0.5 to 5 atm. A range of pressures can be used.

The formation of organomodified silicate heteropolymerized metal products of this invention provides the desired conditions for the reaction. It will be a long wait. In a preferred embodiment, the reaction is run for about 1 minute to 24 hours. catalyst is used When used, the reaction is completed in a short time.

After the sol-gel is produced as described above, it is modified using the modification method of the present invention. Can be modified or improved. In this modification, any used in the manufacturing process There is also no need to remove the solvent. In other words, this modification process It is carried out using a prepared reaction mixture.

In order to modify the organically modified silicon heteropolycondensate according to the present invention, the condensation to be modified must be by treating the material with an extractant fluid at supercritical temperatures and pressures above atmospheric pressure. silanol groups and hydrolyzable groups are removed from the polycondensate. Substitute to generate The products, such as water and alcohol, are mixed with the extractant fluid or absorbed or dissolved in Subsequently, vacuum is applied to remove the fluid from the condensate and extractant is removed. Separate fluids and by-products.

The operating temperature is the critical temperature of the fluid used (e.g. methanol or ethanol) or preferably slightly below that temperature. Operating pressure also depends on fluid dynamics. 1 rotation of the field pressure.

The modification is more preferably within the range of about 200°C to the decomposition temperature of the heteropolycondensate. The process is carried out at a temperature of about 250"C to about 350"C. Temperatures outside this range may also be used. Please understand that you can use The operator has an unacceptable amount of undesirable Choose a temperature that is not so hot as to produce decomposition products, but high enough to give the ideal processing speed. Will.

This reforming step is performed under high pressure. Generally, pressures higher than about 1000 psi are used. use Therefore, the modification process is about ioo.

Typically carried out under pressures of ~5000 psi.

Modification is carried out in small amounts for the purpose of removing hydrolyzable groups that may remain in the polycondensate. It can also be carried out in the presence of water. Therefore, generally all of the starting silanes About 0.5 to about 1° of the amount of water theoretically required to hydrolyze the hydrolyzable group. Use 5x. Those skilled in the art will appreciate that more or less water can be used. There will be. Generally, enough water is used to effect the desired amount of hydrolysis, but preferably Do not use so much water that the process proceeds in undesirable conditions.

The modification step is allowed for a sufficient time to provide the desired amount of hydrolysis or condensation. one Generally, reaction times of about 3 to about 20 hours are used. This reaction time is completely independent It cannot be varied, but only slightly depends on the reaction conditions used. for example , higher reaction temperatures generally require shorter reaction times.

Those skilled in the art will appreciate that the method of this invention is subject to numerous method and compositional modifications. You will understand that there is room.

have This makes it possible to produce compositions with preselected performance criteria. Provides considerable advantages if desired.

If a person skilled in the art wishes to prepare a heteropolycondensate according to the teachings of this invention, he or she may She can build on the example above and above.

Implementation blaze Add phenyl to a 250 mL 30 round bottom flask equipped with a mechanical stirrer and reflux condenser. Ethoxysilane 40s+L (0.17 mol), dichlorodiphenylsilane 6. 6 mL (0,031 mol), tetraethoxysilane 2. 3mL (0,010 mol) and 49 mL of ethanol were added. Stir this mixture at a constant temperature of 60°C. While stirring, 0.15 MMC110.8 mL (0.60 mol) was added dropwise. obtained The solution was stirred at 60 °C for 1 h, left at ambient temperature overnight, and then further stirred at 60 °C. The mixture was stirred at C for 4 hours.

The above operations can be carried out to produce various compositions simply by changing the number of ingredients. Seven things can be changed. The amount of ethanol added is the same as the amount of silane monomers. good. The amount of water added in the state of 0.15M HCl is, for example, silane monomer It will be equal to the number of moles of the hydrolyzable group on the class.

In one example, the organically modified silicic acid heteropolycondensate produced by the above procedure is They were isolated from the ethanolic solution in which they were produced. This reduces the above to a large excess of water. This was done by pouring an ethanol solution of the compound. The viscosity that could be collected The condensate separated as a liquid oil was dried in a vacuum oven) and then in methylene chloride. dissolved in.

A suitable amount of time is used to produce a material of sufficient high molecular weight to be isolated by this method. Ru. Generally, 3 hours of stirring at 60°C after addition of the aqueous HCI was sufficient.

The heteropolymerized metal products manufactured by the method specifically shown in this example will be described in the examples below. treating them at high temperatures and pressures as physically indicated (or as described above); It can be modified by

Husband opening 1 Phenyltriethoxysilane (60+nL, 0.25 mol) was added to ethanol 46 ．． According to the procedure shown in Example 1 using 7 mL and 13.4a+L (0.75 mol) of water. Polymerization occurred. No acid catalyst was used.

The ethanol solution of the produced silicic acid heteropolycondensate was transferred to a stainless steel reactor. Then, as in Example 3, drying is performed by heating above the critical temperature of ethanol. It was dry.

This increases the solution temperature to 280°C and pressure 200°C at a rate of 100°C per hour. This was achieved by increasing the pressure from 0 to 2500 psi. At this point, the reactor is evacuated. Nitrogen was passed through it.

The product was gradually cooled to ambient temperature over approximately 16 hours.

After removing the sample tube from the reactor, a powder was obtained. This powder is CHCl and was found to be soluble in organic solvents such as toluene. CD some of this powder C1, to obtain a "Si NMR spectrum. This spectrum shows that silicon atoms It is clear that more than 95% of the silanol is completely condensed and there is no absorption band of residual silanol. clearly shown. Some silicon atoms with one remaining 10R group are few could be detected as noise on the baseline.

"Si NMR spectrum peak position -82 ppm vs. 5i02 to -112 ppm m- indicates that a phenyl group remains. This fact is 3050,2920 ．． 1600,1435°730.690cm-' and due to 5i-0-3i This was confirmed by an infrared absorption spectrum showing a broad absorption band at 1100ce-'. It has been certified. These absorptions clearly indicate the presence of phenyl groups.

The phenyl group-containing silicon heteropolycondensate produced by the operation of this example is: A product of this invention. Organo-modified silicic acid heterogeneous material that yields rod-shaped products The method for modifying the polycondensate will be specifically explained in the following examples.

Implementation ±1 In a 250 mL 30 round bottom flask equipped with a mechanical stirrer and a reflux condenser, add the tetrameter. Toxysilane 30mL, phenyltriethoxysilane 8,6+mL and methanol 30 mL of water was added. This flask was placed in a constant temperature bath of 60°C and distilled. 26.5 mL of water was added dropwise while stirring. After adding H and O, at 60°C for 2 hours. After continued stirring, it was removed from the bath. The reaction mixture contains the total molar group of silanes used. 15 mole percent phenyltriethoxysilane was included.

The solution of this organically modified silicate heteropolymer metal was poured into a glass with an inner diameter of 7 mm and a length of 25.2 an. Added to the tube. This tube was placed in a stainless steel reactor and the N2 was pumped to about 800 psi. filled to the brim. Then, the temperature of the reactor was increased from 240 to 240 °C at a rate of 100 °C per hour. When the temperature rose to 250°C, the pressure was 2000 psi. This is supercritical A fluid (beyond the critical point of methanol) was created.

At this point it was evacuated with N2 and slowly cooled to ambient temperature.

The product was isolated in the form of a rod that was easily separated from the wall of the glass tube. This stick-like object is It was very unclear.

The following starting materials containing about 15 and 5 mole % of phenyltrimethoxysilane, respectively The above procedure was repeated using the composition.

25% phenyl Tetramethoxysilane 23.2mL Phenyltriethoxysilane 12.6mL Tetramethoxysilane 30mL Phenyphenyltriethoxysilane 2.47+wL Methanol 30+oL HzO15, 1mL Utility of the modified organically modified silicic acid heteropolycondensate of this invention in oxygen detection is shown below.

2 construction To demonstrate the utility of the non-monolithic products of this invention, PtOEPlmg Dissolve 1 g of organically modified silicic acid heteropolycondensate in the added CHz Cl, i0n+L. A stock solution was prepared. Light was blocked from the stock solution. In this study, fiber optic spectroscopy Measure the phosphorescence intensity using a meter (GuidedWave Model 200) did. This commercially available device consists of a single input fiber in the central axis that directs light to the sample. six output beams along the edge that collect the light and scattered light and direct it back to the spectrometer. Equipped with a branched fiber with fibers. These fibers Reaching stainless steel probe. polycarbonate or polymethacrylate The barrel was screwed down with dichloromethane. Pump 25 mil thick plate The optical fiber is placed on the dye in the cross section of the optical fiber, and the field of view is determined by the numerical aperture of each optical fiber. The limited and observable phosphorescence was maximized. Pt0EP/Bruge on a circular glass plate The first drop of the liquid was applied. This coating is then treated at 60°C to 120°C for 1 to 4 hours. I understood. After cooling to room temperature, the glass plate was glued to the barrel. throughout the measurement , the fiber was held in a glass bottle connected to two flow meters. two streams The meter is used to adjust the ratio of compressed nitrogen to air partial pressure while maintaining a constant total pressure. used. Transmits dye/polymer to tungsten light source and wavelengths below 550 nm It was excited with an Ea1ing interference filter. Phosphorescence is 64 with a bandwidth of 10 nm. Monitored at 2 nm. The lifetime of phosphorescence is recorded by applying a nonlinear curve. The evaluation was made from the obtained attenuation curve. Visible absorption spectrum is HP-4850AUV-V It was taken with an IS spectrometer.

The slope of the plot of the (1(?b) / I(Oz) 1) pair of Pox is the lifetime λ , and the permeability Pox.

The line drawing in the figure shows that the organically modified silicon heteropolycondensate produced by the method of Example 2 is than polycondensates prepared from orchids not modified by the method of this invention. It shows a significantly higher permeability to oxygen. As shown by the figure In addition, the material produced by the method of Example 2 was found to be free of oxygen over the range tested. It has a somewhat non-linear response in oxygen permeability to concentration.

During the work carried out in the development of this invention, Pt0E in heteropolycondensates The photostability of P is not permanent and changes over time when exposed to light and oxygen. It was noticed that the phosphorescence of incorporated ptOEP decreased. Hetero of Example 2 It was also observed that Pt0EP incorporated into polycondensates has a relatively slow decomposition rate. It was. This shows another advantage of the invention.

Film products and other products made from the materials of this invention may be used for other purposes than oxygen detection. It can also be used on the go. For example, they are used where high oxygen permeability is observed. anywhere, for example in gas separation applications or on animal or human skin or other external could be used to construct devices or materials for application to human membranes. follow As such, they could be used, for example, in the processing of contact lenses.

The substance of this invention must be composed only of the above-mentioned silicic acid heteropolycondensate. It should be understood that there is no They also contain other compounds in the polymer matrix. It may also be modified to include metal oxide units. In such degeneration, this The raw material composition used in the manufacturing method of the invention contains one or more hydrolyzable substances, e.g. titanium alkoxide, molybdenum alkoxide, lead alkoxide, geranium Approximately 80 moles of alkoxide, zircon alkoxide or vanadium alkoxide It may be modified to contain up to 50 mole %, more preferably up to about 50 mole %. denatured shrinkage Compounds derived from such substances having a utility of 1 (1) to those discussed above. The metal oxide unit contains metal oxide units.

The method of this invention removes residual silanol groups and hydrolyzable groups, so silicic acid Improve the properties of condensates. For example, the method of the present invention may reduce the oxygen permeability of such condensates. Acids that require the use of certain substances that are permeable to oxygen to improve making the material more useful in applications such as elementary detection. Also, this invention Since the modification method does not remove organic groups bonded to silicon via 5i-C bonds, , the acidification of organically modified silicic acid heteropolycondensates without decomposition of their organic substituents. Can be used to improve elementary permeability. Furthermore, a seal such as that provided by this invention The use of organically modified heteropolymerized metals and supercritical fluids in molds has led to new types of A glassy porous solid is provided. An element bonded to a silicon atom via a 5i-C bond No such material with a mechanical group has hitherto been produced. They are many It is useful in many applications, including as an absorbent.

Corrected sound translation submission form (Article 184-8 of the Patent Law) July 18, 1991

Claims (8)

[Claims] 1. Residual silanol groups and hydrolyzable groups in organically modified silicic acid heteropolycondensates A method for modifying the polycondensate by removing silanol from the condensate. critical temperature and pressure of a fluid for a period sufficient to remove the group or hydrolyzable group A method comprising contacting the fluid with an excess of force. 2. The residual hydrolyzable group is an alkoxy group, and the fluid is an alkoxy group. 2. The method of claim 1, wherein the alcohol corresponds to a cy group. 3. Claim 2 wherein said fluid is selected from the group consisting of methanol or ethanol. the method of. 4. The organically modified silicic acid heteropolycondensate has the formula RSi≡ (wherein R is a stable organic 2. The method of claim 1, wherein the method consists essentially of repeating units of the group . 5. 5. The method of claim 4, wherein R is phenyl. 6. containing repeating units Si... and RSi≡ (wherein R is a stable organic group) A porous monolithic glassy body containing organic groups, (a) about 5 to about 35 mol% of said units are RSi≡; (b) said RSi≡ mono dispersed substantially uniformly throughout the glassy body; and (c) the repeating units are linked via oxygen; and Surface area of about 500 to about 800 m2/g, about 0.25 to about 0.40 g/mL Hanging density and organic groups substantially free of residual silanol groups and hydrolyzable groups Contains a porous monolithic glassy body. 7. Substantially all remaining silanol groups and silanol groups are removed from the sol in the mold. the critical temperature and pressure of the fluid for a sufficient time to remove the hydrolyzable groups. contact with that fluid and then remove said groups from said fluid and said sol. for separating the monolithic body of claim 6 from the volatile by-products thus produced. A method of manufacturing the monolithic body, comprising: cooling and evacuation of a monolithic body; , the sol is a mixture of silanes represented by the formula SiX4 and the formula RSiX3. from about 5 to about 35 mole percent of the silanes in the mixture have the formula RSiX3; and each X in each of the above formulas is a methoxy group, and R is a non-hydrolyzable organic group. The above-mentioned monomers are produced by hydrolysis and condensation of a mixture of silanes. A method for manufacturing lithic bodies. 8. 8. The method of claim 7, wherein said fluid is methanol.