CA1150869A - Silicone emulsions for treating silicate particulate matter - Google Patents
Silicone emulsions for treating silicate particulate matterInfo
- Publication number
- CA1150869A CA1150869A CA000331281A CA331281A CA1150869A CA 1150869 A CA1150869 A CA 1150869A CA 000331281 A CA000331281 A CA 000331281A CA 331281 A CA331281 A CA 331281A CA 1150869 A CA1150869 A CA 1150869A
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- CA
- Canada
- Prior art keywords
- silicone
- units
- water
- parts
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1051—Organo-metallic compounds; Organo-silicon compounds, e.g. bentone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2995—Silane, siloxane or silicone coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Abstract
Abstract of the Disclosure A silicone emulsion for treating silicate particulate matter such as perlite and vermiculite, to make it water-resistant comprising a silicone fluid composed of difunctional siloxy units, trifunctional siloxy units and monofunctional siloxy units and as the emulsifier in water there is the reaction product of an aliphatic carboxylic acid with ammonia. The silicon emulsion is applied by spraying it on to the heated silicate particulate matter which is preferably heated to at least 150°C, such that the silicone fluid rapidly cures on the particulate matter.
Description
.~ 8~9 6 0 SI- 17 3 ¦ Background of the Invention The present invention relates to silicone emulsions and more , particularly the present invention relates to silicone emulsions , for rendering silicate particulate matter such as perlite and I vermiculite water-resistant. Perlite and vermiculite are naturall.y !
occurring siliceous roclc. Perlite is a volcanic glassy ash rock while vermiculite is mica.
The distinguishing feature which sets perlite and vermiculite apart from other mineral glasses is when they are heated to a suitable point in their softening range, these rocks expand to 4 to 20 times their origianl volume. This expansion is due to the presence of ¦ two to six percent by weight of combined w~ter in the crude perlite or vermiculite rock. When such ground crude perlite or vermiculite rock is heated to a temperature above 16000 F or 871 C, the crude rock rapidly expands in a manner similar to popcorn as the combined water vaporizes and creates countless tiny bubbles in the heat softened glassy particles. It is these tiny glass_sealed bubbles which account for ,the very light weight and other exceptional physical properties of expanded perlite or vermiculite.
Expanded perlite and vermiculite can be manufactured to weigh as little as two pounds per cubic foot or 32 kilograms per cubic meter making such expanded perlite and vermiculite adaptable for numerous industrial uses. Accordingly, such material as perlite ` 115~3869 60 SI- 17 3 ; `f and vermiculite and specifically the expanded perlite has countless uses as additives in the formulation of abrasives, acoustical plaster, acoustical tile, charcoal barbecue base, concrete aggregate, ~ filteraid, fertilizer extender, foundry ladle covers, foundry sand additive, inert carrier, insulation board, loose fill insulation, pac~caging material, paint texture, pipe insulation, plaster aggregate~
plaster texture, potting soil additives, soil conditioner, tile mortarl aggregate and wallboard core filler.
In the loose fill application for instance, it may be inserted into hollow masonry cavities such as that in concrete blocks or between brick walls and other masonry walls as insulation. It has been found it can also be incorporated in the formulation of insulation boards and other types of wall materials for insulative , propertie s . It has been found that when perlite has been used as loose fill insulation in masonry walls, it has retarded the passage of heat or of cold through the wall by 50~o.
Accordingly, perllte and vermiculite as an insulation have found wide acceptance in the building industry. ~owever, there is one difficulty with perlite and vermiculite as insulation. Due to the large surface area of the particulate matter after it has expanded it will absorb and hold a great deal of moisture. Thus, expanded perlite or expanded vermiculite when manufactured is completely dry, but when exposed to moisture it will pick up 50% of the exposed moisture and absorb it.
:1~5~)869 60 SI-173 1 , , The perlite or vermiculate that has absorbed moisture also tends to keep the moisture in the perlite or vermiculite particle. Such ¦' perlite or vermiculite particulate matter when it has become ~ saturated with moisture functions ineffectively and very poorly as a j thermal insulation barrier. Accordingly, it was highly de sirable to make expanded perlite or expanded vermiculite resistant to the adsorption of water vapor. There are a number of coatings that could be utili2:ed to ma~e vermiculite and perlite resistant to water vapor, however, silicones is one of the basic chemicals in industry that has resistance to weathering and specifically, water vapor.
Silicone solutions for application to masonry walls so as to render them water repellent are well known. Accordingly, it was highly desirable to formulate a silicone coating solution or material for application to perlite or vermiculite so as to render it water resistant. Accordingly, various silicone compositions were formu-lated for this application. One i~uch silicone composition for appli-cation to perlite to render it water repellent is an emulsion of a methyl hydrogen polysiloxane fluid.
It should be noted to maintain the cost of the treated perlite as inexpensive as possible, it was desirable to apply the silicone coating to t~e perlite in as inexpensive a manner as possible.
Accordingly, one process which has been devised and which has been found highly suitable is to produce a solution of emulsion of the silicone and spray it on the heated perlite as it comes from the furna ce .
:115~869 6 0 SI- 17 3 ' ~' `, Accordingly, the water in the water emulsion then is evaporat ed and the silicone is cured onto the perlite. This is a simple and inexpensive way of applying the silicone coating. Accordingly, it was highly desirable to formulate silicone coatings, which could be I applied by a simple spray method onto the expanded perlite or expanded vermiculite. Accordingly, the water emulsions of methyl hydrogen polysiloxane fluid could be applied in such a manner.
However, the trouble with such emulsions and specifically with meth rI
hydrogen polysiloxane fluids, is that they will slowly at time~ libera hydrogen upon standing in the 55 gallon drum~ in which they are packaged. Accoraingly, the drums have to be continually checked to see that the hydrogen gas i6 released to the atmosphere and does not accumulate in the drum and possibly result in a fire or explo sion.
Another type of silicone composition which was found acceptable for coating expanded perlite or expanded vermiculite is an aqueous solution of sodium methyl siliconate. Sodium methyl siliconate is a water repellent compound which when applied to masonry will render it wat er repellent. The difficulty with such sodium methyl siliconate is that it is corrosive and, accordingly, has to be handled carefully by the workers applying the material and handling it.
Another type of silicone that could be utilized is an alkoxy functiona ~ilane such as rnethyltrimethoxy silane dissolved in water or as a dispersion in water. The difficulty with such alkoxy silanes i9 ~5~8f~9 60 SI- 17 3 I~` ( ¦ that unless they are dispersed to quite a low concentration in ! water they are highly flammable materials since the pure material has a flash point of 47 F. Accordingly, all the prior art 1' silicone coatings for silicate particulate matter were found to be ¦ undesirable for one reason of another and basically because of flammability or handling problems. Accordingly, it was highly desirable to find a silicone material or a silicone coating compo-sition which would coat the silicate particulate matter such as expanded perlite or expanded vermiculite and which was not flammable and which was not dangerous to handle by the workers applying the compositions in the field.
It was also desirable to prepare a silicone coating composition which could ~be applied with facility to the expanded perlite and vermiculite as the expanded perlite and vermiculite were manufac-tured in the fact~ry or plant in which they were produced.
It should be noted that in the above description while in some sense specific to expanded perlite and expanded vermiculite applies to other particulate silicate matter. There are other types of particulate silicate matter whi ch is desired to be made water-resistant by applying a silicone coating thereover. That the prior ¦ art silicone compositions which could be applied to such particulate silicate matter to make it water resistant have the disadvantages discussed previously. AccordinglSr, it was highly desirable to be able to formulate a suitable silicone coating for all type 5 of siliG~te ~lS(~869 '~
!
` particulate matter including perlite and vermiculite. It is one ! object of the present invention to provide for a silicone coatlng t ¦ for a silicate particulate matter which is inexpensive, and simple ~ to apply. It is another object of the present invention to provide ¦ for a silicone coating composition for expanded perlite and ver-miculite which is inexpensive and simple to apply.
It is an additional object of the present invention to provide for sllicone coating compositions for perlite and vermiculite which coating compositions are not flammable.
It ts yet an additional object of the present invention to provide for a simple and economic silicone coating emulsion composition for perlite and vermiculite which does not present a problem in handling by the workers applying the composition. These and other objects accomplished by means of the disclosure set forth herein-below.
Summary of the Invention In accordance with the above objects, there is provlded by the present invention a silicone emulsion for treating silicate par-ticulate matter to make the particulate matter water resistant compri,sing (a) from 40 to 60 parts by wefght of a silicone fluid having R Siô units R SiO units and R35iOo 5 units with the ratio of organo siloxy units to dioorganosiloxy units varies from .11 to 1.4, inclusive and the ratio of triorganosiloxy to diorgano siloxy units varies for .02 to about 1, inclusive and the fluid has a silanol content varying from .1 to 8~ by weight and a viscosity varying from 10 to 10,000 centipoise at 25C and where 1 ~15~869 , 60 Si-173 R is a monovalent hydrocarbon radical; (b) from .5 to 5 parts by weight of a aliphatic carboxylic acid having from 6 to 20 carbon atoms; (c) from .1 to .8 parts bv weight of ammonia; and (d) from 20 to 150 parts of water.
The method for preparing the coated silicate particulate matter, such as the coated perlite and vermiculite comprises (1) applying to the surface of silicate particulate matter a silicone emulsion having (a) from 40 to.50 parts by weight of a silicone fluid having R SiO uni.ts, R SiO uni.ts where the foregoing ratio ~f the units is given previously and the fluid has a silanol content varuing from ..1 to 8% by weight and a viscosity varying from 10 to 10,000 centi-poise at 25C,- (b) from .5 to ~ parts by weight of an alTphatic carboxylic acid: of from 6 to 20 carbon etoms; (c) from .1 to .8 ...... parts by weight of ammonia; and (d) from 20 to 150 parts of water;
occurring siliceous roclc. Perlite is a volcanic glassy ash rock while vermiculite is mica.
The distinguishing feature which sets perlite and vermiculite apart from other mineral glasses is when they are heated to a suitable point in their softening range, these rocks expand to 4 to 20 times their origianl volume. This expansion is due to the presence of ¦ two to six percent by weight of combined w~ter in the crude perlite or vermiculite rock. When such ground crude perlite or vermiculite rock is heated to a temperature above 16000 F or 871 C, the crude rock rapidly expands in a manner similar to popcorn as the combined water vaporizes and creates countless tiny bubbles in the heat softened glassy particles. It is these tiny glass_sealed bubbles which account for ,the very light weight and other exceptional physical properties of expanded perlite or vermiculite.
Expanded perlite and vermiculite can be manufactured to weigh as little as two pounds per cubic foot or 32 kilograms per cubic meter making such expanded perlite and vermiculite adaptable for numerous industrial uses. Accordingly, such material as perlite ` 115~3869 60 SI- 17 3 ; `f and vermiculite and specifically the expanded perlite has countless uses as additives in the formulation of abrasives, acoustical plaster, acoustical tile, charcoal barbecue base, concrete aggregate, ~ filteraid, fertilizer extender, foundry ladle covers, foundry sand additive, inert carrier, insulation board, loose fill insulation, pac~caging material, paint texture, pipe insulation, plaster aggregate~
plaster texture, potting soil additives, soil conditioner, tile mortarl aggregate and wallboard core filler.
In the loose fill application for instance, it may be inserted into hollow masonry cavities such as that in concrete blocks or between brick walls and other masonry walls as insulation. It has been found it can also be incorporated in the formulation of insulation boards and other types of wall materials for insulative , propertie s . It has been found that when perlite has been used as loose fill insulation in masonry walls, it has retarded the passage of heat or of cold through the wall by 50~o.
Accordingly, perllte and vermiculite as an insulation have found wide acceptance in the building industry. ~owever, there is one difficulty with perlite and vermiculite as insulation. Due to the large surface area of the particulate matter after it has expanded it will absorb and hold a great deal of moisture. Thus, expanded perlite or expanded vermiculite when manufactured is completely dry, but when exposed to moisture it will pick up 50% of the exposed moisture and absorb it.
:1~5~)869 60 SI-173 1 , , The perlite or vermiculate that has absorbed moisture also tends to keep the moisture in the perlite or vermiculite particle. Such ¦' perlite or vermiculite particulate matter when it has become ~ saturated with moisture functions ineffectively and very poorly as a j thermal insulation barrier. Accordingly, it was highly de sirable to make expanded perlite or expanded vermiculite resistant to the adsorption of water vapor. There are a number of coatings that could be utili2:ed to ma~e vermiculite and perlite resistant to water vapor, however, silicones is one of the basic chemicals in industry that has resistance to weathering and specifically, water vapor.
Silicone solutions for application to masonry walls so as to render them water repellent are well known. Accordingly, it was highly desirable to formulate a silicone coating solution or material for application to perlite or vermiculite so as to render it water resistant. Accordingly, various silicone compositions were formu-lated for this application. One i~uch silicone composition for appli-cation to perlite to render it water repellent is an emulsion of a methyl hydrogen polysiloxane fluid.
It should be noted to maintain the cost of the treated perlite as inexpensive as possible, it was desirable to apply the silicone coating to t~e perlite in as inexpensive a manner as possible.
Accordingly, one process which has been devised and which has been found highly suitable is to produce a solution of emulsion of the silicone and spray it on the heated perlite as it comes from the furna ce .
:115~869 6 0 SI- 17 3 ' ~' `, Accordingly, the water in the water emulsion then is evaporat ed and the silicone is cured onto the perlite. This is a simple and inexpensive way of applying the silicone coating. Accordingly, it was highly desirable to formulate silicone coatings, which could be I applied by a simple spray method onto the expanded perlite or expanded vermiculite. Accordingly, the water emulsions of methyl hydrogen polysiloxane fluid could be applied in such a manner.
However, the trouble with such emulsions and specifically with meth rI
hydrogen polysiloxane fluids, is that they will slowly at time~ libera hydrogen upon standing in the 55 gallon drum~ in which they are packaged. Accoraingly, the drums have to be continually checked to see that the hydrogen gas i6 released to the atmosphere and does not accumulate in the drum and possibly result in a fire or explo sion.
Another type of silicone composition which was found acceptable for coating expanded perlite or expanded vermiculite is an aqueous solution of sodium methyl siliconate. Sodium methyl siliconate is a water repellent compound which when applied to masonry will render it wat er repellent. The difficulty with such sodium methyl siliconate is that it is corrosive and, accordingly, has to be handled carefully by the workers applying the material and handling it.
Another type of silicone that could be utilized is an alkoxy functiona ~ilane such as rnethyltrimethoxy silane dissolved in water or as a dispersion in water. The difficulty with such alkoxy silanes i9 ~5~8f~9 60 SI- 17 3 I~` ( ¦ that unless they are dispersed to quite a low concentration in ! water they are highly flammable materials since the pure material has a flash point of 47 F. Accordingly, all the prior art 1' silicone coatings for silicate particulate matter were found to be ¦ undesirable for one reason of another and basically because of flammability or handling problems. Accordingly, it was highly desirable to find a silicone material or a silicone coating compo-sition which would coat the silicate particulate matter such as expanded perlite or expanded vermiculite and which was not flammable and which was not dangerous to handle by the workers applying the compositions in the field.
It was also desirable to prepare a silicone coating composition which could ~be applied with facility to the expanded perlite and vermiculite as the expanded perlite and vermiculite were manufac-tured in the fact~ry or plant in which they were produced.
It should be noted that in the above description while in some sense specific to expanded perlite and expanded vermiculite applies to other particulate silicate matter. There are other types of particulate silicate matter whi ch is desired to be made water-resistant by applying a silicone coating thereover. That the prior ¦ art silicone compositions which could be applied to such particulate silicate matter to make it water resistant have the disadvantages discussed previously. AccordinglSr, it was highly desirable to be able to formulate a suitable silicone coating for all type 5 of siliG~te ~lS(~869 '~
!
` particulate matter including perlite and vermiculite. It is one ! object of the present invention to provide for a silicone coatlng t ¦ for a silicate particulate matter which is inexpensive, and simple ~ to apply. It is another object of the present invention to provide ¦ for a silicone coating composition for expanded perlite and ver-miculite which is inexpensive and simple to apply.
It is an additional object of the present invention to provide for sllicone coating compositions for perlite and vermiculite which coating compositions are not flammable.
It ts yet an additional object of the present invention to provide for a simple and economic silicone coating emulsion composition for perlite and vermiculite which does not present a problem in handling by the workers applying the composition. These and other objects accomplished by means of the disclosure set forth herein-below.
Summary of the Invention In accordance with the above objects, there is provlded by the present invention a silicone emulsion for treating silicate par-ticulate matter to make the particulate matter water resistant compri,sing (a) from 40 to 60 parts by wefght of a silicone fluid having R Siô units R SiO units and R35iOo 5 units with the ratio of organo siloxy units to dioorganosiloxy units varies from .11 to 1.4, inclusive and the ratio of triorganosiloxy to diorgano siloxy units varies for .02 to about 1, inclusive and the fluid has a silanol content varying from .1 to 8~ by weight and a viscosity varying from 10 to 10,000 centipoise at 25C and where 1 ~15~869 , 60 Si-173 R is a monovalent hydrocarbon radical; (b) from .5 to 5 parts by weight of a aliphatic carboxylic acid having from 6 to 20 carbon atoms; (c) from .1 to .8 parts bv weight of ammonia; and (d) from 20 to 150 parts of water.
The method for preparing the coated silicate particulate matter, such as the coated perlite and vermiculite comprises (1) applying to the surface of silicate particulate matter a silicone emulsion having (a) from 40 to.50 parts by weight of a silicone fluid having R SiO uni.ts, R SiO uni.ts where the foregoing ratio ~f the units is given previously and the fluid has a silanol content varuing from ..1 to 8% by weight and a viscosity varying from 10 to 10,000 centi-poise at 25C,- (b) from .5 to ~ parts by weight of an alTphatic carboxylic acid: of from 6 to 20 carbon etoms; (c) from .1 to .8 ...... parts by weight of ammonia; and (d) from 20 to 150 parts of water;
(2) curing the silicone emulsion and evaporating the water. The best way to cure the s;licone emulsion and evaporate the water Is to apply or spray the silicone emulsion onto the expanded perlite or vermiculite which has been heated to at least 15C.
It should also be noted that in accordance wTth the present inven-tion the foregoing emulsion and concentration of ingredients can be utilized as stated previously except that for the silicone fluid having the trifunctional siloxy units, the difunctlonal siloxy units and the monfunctional siloxy units there can be utilized a silanol endstopped diorganopolysiloxane polymer with the organo groups being monovalent hydrocarbon radicals and the viscosity of ` ~ 8 ~ 9 60 Si-173 ~ .
the polymer varies from lO to lO,000 centipoise at 25C. The -radical R in the above formula is preferably methyl and the aliphatic carboxylic acid is oleic acid. It should be noted that the advan-~ tage of preparing the emulsion in which the emulsifying agent is an ¦ ammonia salt of an aliphatic carboxylic acid is that upon heating and curing of the silicone emulsion, the ammonia will evaporate into the atmosphere leaving behind the aliphatic carboxylic acid, which is an oil and which acts to resist moisture. If there was utilized for instance an alkali metal salt of an aliphatic carboxylic acid, then when the silicone f~uid was cured, the metal salt ~ould remain on the surface of the silicate particulate matter rendering the surface somewhat suceptible to the absorption of moisture and detracting away from the hydrophobic characteristics of the silicone coating. Accordingly, it is desired to utilize a fugitive emulsi-fylng agent so that there will not be any chance of the emulsifying agent remaining on the silicone coating and rendering it suceptible to picking up moisture.
Description of the Preferred Embodiment In t,he silicone emulsion preferably there is utilized a silicone fluid having diorganodifunctional silowy units, mono-organofunctional trifunctTonal siloxy units and triorgano monofunctional siloxy units rather than silanol endstopped diorganopolysiloxane polymer as the sTlicone fluid to provide the silicone coating on the silicate par-ticulate matter since such a fluid is less expensive tban the silanol endstopped diorganopolysiloxane polymer. The radical R in the for-mula of the units may be any monovalent hydrocarbon radical or hal-ogenated monovalent hydrocarbon radical such as for instance alkyl radials of 1 to 8 carbon radicals such as ethyl, methyl, propyl, I ~lS~869 60 si-l73 ,, '.
alkenyl radicals, such as vinyl, allyl; mononuclear aryl radicals i such as phenyl, methylphenyl, ethylphenyl; halogenated monovalent hydrocarbon radicals such as fluoroalkyl radicals for instance 3, ~ 3,3 trifluoropropyl. Most preferably the R radical is methyl since i that is the cheapest silicone fluid that needs silanol groups in order to cure. The silicone fluid w;ll cure by the silanol groups condensing to liberate water and form an SiOSi linkage.
Accordingly, it is generally preferred the silicone fluid trifunc-tionality have from .1% to 8~ by hy~roxy groups attached to the silicone atoms and more preferably anywhere from .1~ to 2% by weight of hydroxy groups attached to the silicone. If the trifunctional silicone fluid disclosed above, has too much silanol in it, it will not cure fully unless a protracted heating step is utilized and If it has too little silanol groups in the trifunctional silicone fluid then the silicone fluid will not cure at all.
With respect`to the ratio of the different units in the polymer, this may vary as indicated previously, in which the ratio of the organo siloxy units to diorgano siloxy units varies from about .11 to 1.4, inclusive and the ratio of the triorgano siloxy units to diorgano siloxy units varies from .02 to about 1, inclusive.
More preferably, the ratio of the organo siloxy units to the diorgano siloxy units has a value of anywhere from .11 to about.36, inclusive and the ratio of said triorganosiloxy units to diorgano siloxy units has a value which varies from .02 to about .04, inclusive. It has been found that the trifunctional silicone fluid with the units with-in the preferred range is the simplest to make and has the most pre-ferred properties. However, the basic advantage of the preferred ratio of units of the diorgano siloxy units to triorgano siloxy units as to mono-organo siloxy units is that within the preferred ~, 60 Si-173 I; range the fluid is simplest to produce. The branched or trifunctional ¦ silicone fluid of the instant case can be produced by hydrolyzing ¦ a mixture of diorganodihalosilanes, R SiX2, organotrihalosilanes, 1 RSiX3, and triorganohalosilane, R35iX, where R is as previously defined and X is a halogen radial such as chloro. It has been found expedient to maintain a concentration of effluent acid formed during the hydrolysis of the above ingredients to below about 31% by weight of acid and preferably in the range of between about 28 to 32~ of acid.
If the hydrolysis is accomplished at a pH of 5 to about 7 by use of buffering agents such as alkali bicarbonates, the trifunctional sili-cone fluid can be made by having 8~ or more by weight of hydroxy groups attached to silicone. Preferably the hydrolysis is performed at a temperature below 30 but a temperature between 20 to 40C will provide for effective results. The hydrolyzate is then recovered from the acid layer and neutralized with a standard neutralizing agent such as alkali bicarbonate for example sodium bicarbonate or ammonium. There are various ways in which the branchchained tri-¦ functional silicone fluid can be produced other than the above in-¦ dicated. For instance instead of chlorosilanes that can be hydrol-yzed, alkoxy-containing silanes to yield a trifunctional silicone fluid with possibly some alkoxy groups. Such alkoxy groups wlll not interfere with the cure of the branch-chained sTlicone fluid.
Accordingly, the procedure for prepartng such a fluid can be as follows: The triorganochlorosilane can be blended wlth the organ-otrichloro silane and analyzed for monofunctional to trifunctional unit ratio by ~ass spectrometer. Then the difunctional silane can be added and the ratio of the trifunctional to difunctional ratio can be determined so that it is in accordance with the above descrtp-tion. The reason for this addition is that the relatively small ~1 ~V869 60-Si-173 , ~
amount of monofunctional siloxy cannot be accurately measured in the presence of the large amount of trifunctional siloxy units. The final blend of chlorosilanes must then be free from SiH hydrosilane 1 since the presence of such silanes will cause the mixture to gel f-~ upon hydrolysis. It also important to note that the foregoing ratios of trifunctional chlorosilanes to difunctional chlorosilanes to mono-functional chlorosilsnes must be observed if the mixture is not to gel upon hydrolysis and if the mixture is to have the desired prop-erties in accordance with the disclosure hereinbelow.
Accordingly, preferably the silane blend can then be continuously hydrolyzed, keeping the hydrolyzate effluent, acid concentration at about 20% and the temperature of the hydrolysis under 30C. The silicone hydrolyzate fluid can then be continuously decanted from the water acid phase. Then the silicone fluid which contains some acid can be neutralized with about 1% of a saturated salt solution or it can be treated with sodium bicarbonate to reduce the acidity. The salts that are formed can then be removed by filtration. Then the silicone fluid can be neutralized with 2% of dry Fuller's Earth by stirring it at about 90C. After heating for two hours, the fluid is cooled and tested for acidity. Such a fluid as tested for acidity shouldn't contain more than 25 parts per million of ac~id ini~t.
If it contains more than 25 parts per million of acid in it then the excess acid will cause the fluid to degenerate or revert.
Accordingly, should the branch-chained silicone fluid fail to pass the acidity test then it is reheated to 90C for another hour, and if it still fails to pass the test and another 1% Fuller's Earth is used and the process is continued as before. Finally, when the fluid passes the acidity test, it is filtered to remove all the salts and Fuller's Earth. It should be noted as stated previously that the ~lS~869 60 Si-173 1~ .
I silane blend must be practically free from methylhydrogendichlorosilane ¦ in order that the hydrolyzed product will pass the final product specification. Not more than 0.2~ silicone hydride is allowable in ¦ the starting blend.
~ In addition, concentrations of acid above 29~ in the hydrolyzate effluent is undesirable since it increases the possibility of gelling the silicone fluid in the hydrolyzate vessel and it may increase the volatiles in the product. Lower acid concentration than 28~ in the hydrolyzate increases the tendency of the acid and oil to emulsify ~0 and so prevent efficient separation of oil and water by decantation.It should also be noted that temperatures for the hydrolyzate in ex-cess of over 30 generally are undesirable although temperatures of up to about 50 can be tolerated. However, care has to be utilized in carrying out the hydrolysis at these high temperatures since temper-atures above 30C for the hydrolysis may cause the silicone fluid to gel in the hy`drolyzate mixture. On the other hand, temperatures below room temperatures will not deleterious1y affect the hydrolysis and may be desirable. It should be noted that temperatures O C and below may be utilized without any disadvantageous results. The only undesirable part of such a hydrolysis below room temperature is that it requires additional cooling equipment to carry out the reaction at that temperature.
It should also be noted that the shelf life of the acidic trifunctional sillcone fluid is very short and excess acidity will cause the silicone fluid to gel. Accordingly, the acid specification is very pertinent in the production of the branch-chained silicone fluid.
It should be noted that this presence of water in the silicone fluid for the application of the instant case is not a detriment since a water emulsi s is the form of the ~ilicone fluid as discussed pre-1 115~869 60 Si-173 I` '.
¦ viously. It should be noted that In the instant composition there may be utilized a catalyst to cure the emulsion or the branch-chained ¦ silicone fluid. Such a catalyst would speed up the cure of the i branch-chained silicone fluid. Examples of such cataiysts are metal salts of carboxylic acid such as for instance iron salts of carboxylic acid, such as iron octoate, zinc octoate and other such salts. Such salts will increase the rate of cure of the branch-chained silicone fluid in the emulsions of the instant case at a much faster rate then would be the case without the catalyst. The only trouble with having such a metal salt of carboxylic acid present as a catalyst and even in a small concentration of .01 to .1% by weight of the stlicone fluld is that the metal salt of carboxylic acid may cause back wetting which will be described with respect to the emulsifying agents that may be utillzed with the silicone emulsions of the instant case. Such metal salt of carboxylic acids may take away the water resistance or repellancy of the silicone coating that is put on the silicate par-ticulate matter.
Another material that may be utilized as a silicone fluid for producing a silicone fluid emulsion for being applied to silicate particulate matter, such as expanded perlite and expanded vermicultte is a sill-cone emulsion of a silanol endstopped diorganopolysiloxane polymer, where the polymer has the viscosity of anywhere from 10 to 10,000 centipoise at 25C and more preferably has a viscosity varying any-where from 50 to 5,000 cnntipoise at 25C.
It should be noted that with respect to the previous branch-chained silicone fluid that the foregoing vTscosity limitations for the silanol end-stopped diorgano polysiloxane polymer applies to the branch-chained silicone fluid. Thus the silicone branch-chained fluid desirably has a viscosity that varies anywhere from 10 to 10,000 ~15(~869 60 Si-173 :
` centipoise at 25C and more preferably varies from 50 to 5,000 i centipoise at 25C.
Such silanol terminated diorganopolysiloxane polymer is preferably ~ basically linear with about a maximum of .1~ by wei~ht of combined monofunctionality and trifunctionality. The organo groups of such linear polymer may be selected from any monovalent hydrocarbon radi-cal and halogenated monovalent hydrocarbon radical such as alkyl rad-icals from 1 to 8 carbon atoms, methyl, ethyl, propyl, etc. cycloalkyl radicals such as cyclohexyl, cycloheptyl, cyclooctyl, etc. ; mono-nuclear aryl radicals such as phenyl, methylphenyl, ethylphenyl;
halogenated alkyl radicals such as 3, 3, 3 trifluoropropyl, etc.
Most preferably the organo radical is an alkyl radical of 1 to 8 carbon atoms such as methyl. A preferred formula for these linear silanol endstopped diorganopolysiloxane polymer is as follows:
~ ¦
Where R' Is the same as previously given for the definition of the organo group and ~ varies such that the polymer has generally a viscosity varying from 10 to 10,000 centipoise at 25 C and more preferably has a viscosity varying from 50 to 5,000 centipoise at 25C. A process for producing such a polymer is well known. Such a process generally comproses taking diorganodichlorosilanes and hydrolyzing them in water, then reducing the acidity to less than 25 parts per million by decanting the excess acid water phase and heating the resulting mixture to vent off acid. Finally, there is additionally added a base tr, neutralize the acid. The resulting ~ 869 60 Si-173 i silanol terminated low molecular weight diorganopolysiloxane ', polymer is then filtered to remove the sa1ts and other impurities ~ to yield the relatively pure low molecular silanol endstopped di-¦ organopolysiloxane polymer. For higher molecular weight material, I that is above 1,000 centipoise viscos;ty at 25C, then what is done ~ is to take the hydrolyzate that is obtained and then that is added ¦ to it small quantities of KOH and the hydrolysate is heated at ele-vated temperatures so as to preferentially distill overhead relatively pure octaorganocyclotetrasiloxanes. These cyclotetrasiloxanes are taken and mixed in the desired proportions to obtain the desired substttution in the end polymer. To this cyclotetrasiloxane there is added anywhere from 50 to 500 parts per millTon of KOH again and the desired amounts of water or as an alternative the desired quan-I tities of the low molecular weight silanol diorganopolysiloxane ! polymer hydrolyzate. The amount of the low molecular weight hydrol-¦ yzate which ~was prepared by the hydrolysis of the diorganodichloro-~ silanes as a cha;nstopper will determine the final molecular weight i of the silanol endstopped diorganopolysiloxane polymer that is formed.
I AccordTngly, the hydrolyzate is added to the cyclotetrasTloxanes In ; the desired quantities and the mixture is heated at elevated temper-atures, that is temperatures above 100C for periods of time varying from 1 to 8 hours to ~ a silanol endstopped linear aiorganopoly-¦ siloxane polymer having a viscosity of anywhere from 1,000 to 10,000 I centipoise or more if desired. The KOH may then be neutralized with ~ a mild acid such that the acid concentration in the polymer does not ¦ exceed 10 parts per million and then the excess cyclics can be stopped off to yield the silanol endstopped diorganopolysiloxane polymer. Further details and explanations with respect to the pro-duction o these polymers is to be found in the patent o~ M.D. 8eers Il -15-` i ~15~3869 60 Si-173 1 ~.
¦~ United States Patent 3,838,205 which issued Sept. 24~ 1974.
As pointed out previously, it is preferred that there be utilized in i the compositions of the instant case, the branch-chained silicone fluid since it is cheaper than the silanol endstopped linear diorgano-polysiloxane polymer. Again with such linear silanol endstopped polymer, such a polymer can be preferably cured at a faster rate by the utilization of metal salt of carboxylic acid, such as tin salts or an iron salt. However, as pointed out previously such metal salts of carboxylic acids are undesired in the compositions of the instant case since they may cause back wetting of the silicone coating, that is make the silicone coating have an attraction to moisture.
Such silicone materials may be applied by being dispersed in water and sprayed onto the silicate particulate matter to be coated.
However, as mentioned previously, it is preferred that they be emul-sified since silicones are not soluble in water.
Accordingly,~it is desired that these materials be emulsified in water since they would be more easily sprayed on the silicate par-ticulate matter to form a uniform coating.
Accordingly, per 40 - 60 parts by weight of branch-chained silicone fluid or of the linear diorganopolysiloxane polymer to be emulsified there is generally used from .5 to 5 parts by weight of an aliphatic carboxylic acid having 6 - 20 carbon atoms and from .1 to o.8 parts by weight of ammonia with from 20 - 150 parts of water to form a stable silicone emulsion. The preferred aliphatic carboxylic acid is of course oleic acid. However, any other aliphatic carboxylic acid may be used. The preferred compound for the preferred anion forming the emulsification salt is ammonia because upon heating ammonia will evaporate from the emulsion into the atmosphere. It is desired to have ammonia as the anlon in the emulsl~ication salt in ~15~869 `, 60 Si-173 ~.
the silicone emulsions of the present case to prevent a phenomena known as back wetting. The emulsification salts which are formed with anions which are for instance alkali metal, such as sodium il and potassium cause upon the curing of the silicone fluid and the ! evaporation of the water to leave behind an alkali metal salt on the silicone coating. Such salts will ionize in the presence of moisture, allowing the moisture to penetrate through the silicone coating which is formed about the silicate particulate matter. Accordingly, such back wetting is possible with standard alkali metal emulsification salts. It is desirable that such salts not be present on the surface of the silicone coating or mixed with the silicone coating. For this reason it is desirable that the anion in the emulsification salt be an anion emulsification salt of ammonia.
There only need be present sufficient ammonia so as to form a proper ammonia emulsification salt such that the sllicone fluid can be prop-erly emulsified to form a stable water emulsion. Then when the emulslion is applied to the silicate particulate matter, either by heating the silicate particulate matter or by having the sllicate particulate matter preheated to a temperature of at least 150C or thereabouts, the ammonia will simple evaporate to the atmosphere leaving behind an aliphatic carboxylic acid which is an oil and whTch will add rather than detract from the water repellent properties of the silicone coating.
It should also be noted that while there has been specified in the claims and specification that there be used 40 - 60 parts by weight of the~branch-chained silieone fluid or of the linear diorganopoly-siloxane and from .5 - 5 parts of the aliphatic carboxylic acid and from .1 - . parts by weight of a ~ ;nia .~d 20 - 150 parts water to
It should also be noted that in accordance wTth the present inven-tion the foregoing emulsion and concentration of ingredients can be utilized as stated previously except that for the silicone fluid having the trifunctional siloxy units, the difunctlonal siloxy units and the monfunctional siloxy units there can be utilized a silanol endstopped diorganopolysiloxane polymer with the organo groups being monovalent hydrocarbon radicals and the viscosity of ` ~ 8 ~ 9 60 Si-173 ~ .
the polymer varies from lO to lO,000 centipoise at 25C. The -radical R in the above formula is preferably methyl and the aliphatic carboxylic acid is oleic acid. It should be noted that the advan-~ tage of preparing the emulsion in which the emulsifying agent is an ¦ ammonia salt of an aliphatic carboxylic acid is that upon heating and curing of the silicone emulsion, the ammonia will evaporate into the atmosphere leaving behind the aliphatic carboxylic acid, which is an oil and which acts to resist moisture. If there was utilized for instance an alkali metal salt of an aliphatic carboxylic acid, then when the silicone f~uid was cured, the metal salt ~ould remain on the surface of the silicate particulate matter rendering the surface somewhat suceptible to the absorption of moisture and detracting away from the hydrophobic characteristics of the silicone coating. Accordingly, it is desired to utilize a fugitive emulsi-fylng agent so that there will not be any chance of the emulsifying agent remaining on the silicone coating and rendering it suceptible to picking up moisture.
Description of the Preferred Embodiment In t,he silicone emulsion preferably there is utilized a silicone fluid having diorganodifunctional silowy units, mono-organofunctional trifunctTonal siloxy units and triorgano monofunctional siloxy units rather than silanol endstopped diorganopolysiloxane polymer as the sTlicone fluid to provide the silicone coating on the silicate par-ticulate matter since such a fluid is less expensive tban the silanol endstopped diorganopolysiloxane polymer. The radical R in the for-mula of the units may be any monovalent hydrocarbon radical or hal-ogenated monovalent hydrocarbon radical such as for instance alkyl radials of 1 to 8 carbon radicals such as ethyl, methyl, propyl, I ~lS~869 60 si-l73 ,, '.
alkenyl radicals, such as vinyl, allyl; mononuclear aryl radicals i such as phenyl, methylphenyl, ethylphenyl; halogenated monovalent hydrocarbon radicals such as fluoroalkyl radicals for instance 3, ~ 3,3 trifluoropropyl. Most preferably the R radical is methyl since i that is the cheapest silicone fluid that needs silanol groups in order to cure. The silicone fluid w;ll cure by the silanol groups condensing to liberate water and form an SiOSi linkage.
Accordingly, it is generally preferred the silicone fluid trifunc-tionality have from .1% to 8~ by hy~roxy groups attached to the silicone atoms and more preferably anywhere from .1~ to 2% by weight of hydroxy groups attached to the silicone. If the trifunctional silicone fluid disclosed above, has too much silanol in it, it will not cure fully unless a protracted heating step is utilized and If it has too little silanol groups in the trifunctional silicone fluid then the silicone fluid will not cure at all.
With respect`to the ratio of the different units in the polymer, this may vary as indicated previously, in which the ratio of the organo siloxy units to diorgano siloxy units varies from about .11 to 1.4, inclusive and the ratio of the triorgano siloxy units to diorgano siloxy units varies from .02 to about 1, inclusive.
More preferably, the ratio of the organo siloxy units to the diorgano siloxy units has a value of anywhere from .11 to about.36, inclusive and the ratio of said triorganosiloxy units to diorgano siloxy units has a value which varies from .02 to about .04, inclusive. It has been found that the trifunctional silicone fluid with the units with-in the preferred range is the simplest to make and has the most pre-ferred properties. However, the basic advantage of the preferred ratio of units of the diorgano siloxy units to triorgano siloxy units as to mono-organo siloxy units is that within the preferred ~, 60 Si-173 I; range the fluid is simplest to produce. The branched or trifunctional ¦ silicone fluid of the instant case can be produced by hydrolyzing ¦ a mixture of diorganodihalosilanes, R SiX2, organotrihalosilanes, 1 RSiX3, and triorganohalosilane, R35iX, where R is as previously defined and X is a halogen radial such as chloro. It has been found expedient to maintain a concentration of effluent acid formed during the hydrolysis of the above ingredients to below about 31% by weight of acid and preferably in the range of between about 28 to 32~ of acid.
If the hydrolysis is accomplished at a pH of 5 to about 7 by use of buffering agents such as alkali bicarbonates, the trifunctional sili-cone fluid can be made by having 8~ or more by weight of hydroxy groups attached to silicone. Preferably the hydrolysis is performed at a temperature below 30 but a temperature between 20 to 40C will provide for effective results. The hydrolyzate is then recovered from the acid layer and neutralized with a standard neutralizing agent such as alkali bicarbonate for example sodium bicarbonate or ammonium. There are various ways in which the branchchained tri-¦ functional silicone fluid can be produced other than the above in-¦ dicated. For instance instead of chlorosilanes that can be hydrol-yzed, alkoxy-containing silanes to yield a trifunctional silicone fluid with possibly some alkoxy groups. Such alkoxy groups wlll not interfere with the cure of the branch-chained sTlicone fluid.
Accordingly, the procedure for prepartng such a fluid can be as follows: The triorganochlorosilane can be blended wlth the organ-otrichloro silane and analyzed for monofunctional to trifunctional unit ratio by ~ass spectrometer. Then the difunctional silane can be added and the ratio of the trifunctional to difunctional ratio can be determined so that it is in accordance with the above descrtp-tion. The reason for this addition is that the relatively small ~1 ~V869 60-Si-173 , ~
amount of monofunctional siloxy cannot be accurately measured in the presence of the large amount of trifunctional siloxy units. The final blend of chlorosilanes must then be free from SiH hydrosilane 1 since the presence of such silanes will cause the mixture to gel f-~ upon hydrolysis. It also important to note that the foregoing ratios of trifunctional chlorosilanes to difunctional chlorosilanes to mono-functional chlorosilsnes must be observed if the mixture is not to gel upon hydrolysis and if the mixture is to have the desired prop-erties in accordance with the disclosure hereinbelow.
Accordingly, preferably the silane blend can then be continuously hydrolyzed, keeping the hydrolyzate effluent, acid concentration at about 20% and the temperature of the hydrolysis under 30C. The silicone hydrolyzate fluid can then be continuously decanted from the water acid phase. Then the silicone fluid which contains some acid can be neutralized with about 1% of a saturated salt solution or it can be treated with sodium bicarbonate to reduce the acidity. The salts that are formed can then be removed by filtration. Then the silicone fluid can be neutralized with 2% of dry Fuller's Earth by stirring it at about 90C. After heating for two hours, the fluid is cooled and tested for acidity. Such a fluid as tested for acidity shouldn't contain more than 25 parts per million of ac~id ini~t.
If it contains more than 25 parts per million of acid in it then the excess acid will cause the fluid to degenerate or revert.
Accordingly, should the branch-chained silicone fluid fail to pass the acidity test then it is reheated to 90C for another hour, and if it still fails to pass the test and another 1% Fuller's Earth is used and the process is continued as before. Finally, when the fluid passes the acidity test, it is filtered to remove all the salts and Fuller's Earth. It should be noted as stated previously that the ~lS~869 60 Si-173 1~ .
I silane blend must be practically free from methylhydrogendichlorosilane ¦ in order that the hydrolyzed product will pass the final product specification. Not more than 0.2~ silicone hydride is allowable in ¦ the starting blend.
~ In addition, concentrations of acid above 29~ in the hydrolyzate effluent is undesirable since it increases the possibility of gelling the silicone fluid in the hydrolyzate vessel and it may increase the volatiles in the product. Lower acid concentration than 28~ in the hydrolyzate increases the tendency of the acid and oil to emulsify ~0 and so prevent efficient separation of oil and water by decantation.It should also be noted that temperatures for the hydrolyzate in ex-cess of over 30 generally are undesirable although temperatures of up to about 50 can be tolerated. However, care has to be utilized in carrying out the hydrolysis at these high temperatures since temper-atures above 30C for the hydrolysis may cause the silicone fluid to gel in the hy`drolyzate mixture. On the other hand, temperatures below room temperatures will not deleterious1y affect the hydrolysis and may be desirable. It should be noted that temperatures O C and below may be utilized without any disadvantageous results. The only undesirable part of such a hydrolysis below room temperature is that it requires additional cooling equipment to carry out the reaction at that temperature.
It should also be noted that the shelf life of the acidic trifunctional sillcone fluid is very short and excess acidity will cause the silicone fluid to gel. Accordingly, the acid specification is very pertinent in the production of the branch-chained silicone fluid.
It should be noted that this presence of water in the silicone fluid for the application of the instant case is not a detriment since a water emulsi s is the form of the ~ilicone fluid as discussed pre-1 115~869 60 Si-173 I` '.
¦ viously. It should be noted that In the instant composition there may be utilized a catalyst to cure the emulsion or the branch-chained ¦ silicone fluid. Such a catalyst would speed up the cure of the i branch-chained silicone fluid. Examples of such cataiysts are metal salts of carboxylic acid such as for instance iron salts of carboxylic acid, such as iron octoate, zinc octoate and other such salts. Such salts will increase the rate of cure of the branch-chained silicone fluid in the emulsions of the instant case at a much faster rate then would be the case without the catalyst. The only trouble with having such a metal salt of carboxylic acid present as a catalyst and even in a small concentration of .01 to .1% by weight of the stlicone fluld is that the metal salt of carboxylic acid may cause back wetting which will be described with respect to the emulsifying agents that may be utillzed with the silicone emulsions of the instant case. Such metal salt of carboxylic acids may take away the water resistance or repellancy of the silicone coating that is put on the silicate par-ticulate matter.
Another material that may be utilized as a silicone fluid for producing a silicone fluid emulsion for being applied to silicate particulate matter, such as expanded perlite and expanded vermicultte is a sill-cone emulsion of a silanol endstopped diorganopolysiloxane polymer, where the polymer has the viscosity of anywhere from 10 to 10,000 centipoise at 25C and more preferably has a viscosity varying any-where from 50 to 5,000 cnntipoise at 25C.
It should be noted that with respect to the previous branch-chained silicone fluid that the foregoing vTscosity limitations for the silanol end-stopped diorgano polysiloxane polymer applies to the branch-chained silicone fluid. Thus the silicone branch-chained fluid desirably has a viscosity that varies anywhere from 10 to 10,000 ~15(~869 60 Si-173 :
` centipoise at 25C and more preferably varies from 50 to 5,000 i centipoise at 25C.
Such silanol terminated diorganopolysiloxane polymer is preferably ~ basically linear with about a maximum of .1~ by wei~ht of combined monofunctionality and trifunctionality. The organo groups of such linear polymer may be selected from any monovalent hydrocarbon radi-cal and halogenated monovalent hydrocarbon radical such as alkyl rad-icals from 1 to 8 carbon atoms, methyl, ethyl, propyl, etc. cycloalkyl radicals such as cyclohexyl, cycloheptyl, cyclooctyl, etc. ; mono-nuclear aryl radicals such as phenyl, methylphenyl, ethylphenyl;
halogenated alkyl radicals such as 3, 3, 3 trifluoropropyl, etc.
Most preferably the organo radical is an alkyl radical of 1 to 8 carbon atoms such as methyl. A preferred formula for these linear silanol endstopped diorganopolysiloxane polymer is as follows:
~ ¦
Where R' Is the same as previously given for the definition of the organo group and ~ varies such that the polymer has generally a viscosity varying from 10 to 10,000 centipoise at 25 C and more preferably has a viscosity varying from 50 to 5,000 centipoise at 25C. A process for producing such a polymer is well known. Such a process generally comproses taking diorganodichlorosilanes and hydrolyzing them in water, then reducing the acidity to less than 25 parts per million by decanting the excess acid water phase and heating the resulting mixture to vent off acid. Finally, there is additionally added a base tr, neutralize the acid. The resulting ~ 869 60 Si-173 i silanol terminated low molecular weight diorganopolysiloxane ', polymer is then filtered to remove the sa1ts and other impurities ~ to yield the relatively pure low molecular silanol endstopped di-¦ organopolysiloxane polymer. For higher molecular weight material, I that is above 1,000 centipoise viscos;ty at 25C, then what is done ~ is to take the hydrolyzate that is obtained and then that is added ¦ to it small quantities of KOH and the hydrolysate is heated at ele-vated temperatures so as to preferentially distill overhead relatively pure octaorganocyclotetrasiloxanes. These cyclotetrasiloxanes are taken and mixed in the desired proportions to obtain the desired substttution in the end polymer. To this cyclotetrasiloxane there is added anywhere from 50 to 500 parts per millTon of KOH again and the desired amounts of water or as an alternative the desired quan-I tities of the low molecular weight silanol diorganopolysiloxane ! polymer hydrolyzate. The amount of the low molecular weight hydrol-¦ yzate which ~was prepared by the hydrolysis of the diorganodichloro-~ silanes as a cha;nstopper will determine the final molecular weight i of the silanol endstopped diorganopolysiloxane polymer that is formed.
I AccordTngly, the hydrolyzate is added to the cyclotetrasTloxanes In ; the desired quantities and the mixture is heated at elevated temper-atures, that is temperatures above 100C for periods of time varying from 1 to 8 hours to ~ a silanol endstopped linear aiorganopoly-¦ siloxane polymer having a viscosity of anywhere from 1,000 to 10,000 I centipoise or more if desired. The KOH may then be neutralized with ~ a mild acid such that the acid concentration in the polymer does not ¦ exceed 10 parts per million and then the excess cyclics can be stopped off to yield the silanol endstopped diorganopolysiloxane polymer. Further details and explanations with respect to the pro-duction o these polymers is to be found in the patent o~ M.D. 8eers Il -15-` i ~15~3869 60 Si-173 1 ~.
¦~ United States Patent 3,838,205 which issued Sept. 24~ 1974.
As pointed out previously, it is preferred that there be utilized in i the compositions of the instant case, the branch-chained silicone fluid since it is cheaper than the silanol endstopped linear diorgano-polysiloxane polymer. Again with such linear silanol endstopped polymer, such a polymer can be preferably cured at a faster rate by the utilization of metal salt of carboxylic acid, such as tin salts or an iron salt. However, as pointed out previously such metal salts of carboxylic acids are undesired in the compositions of the instant case since they may cause back wetting of the silicone coating, that is make the silicone coating have an attraction to moisture.
Such silicone materials may be applied by being dispersed in water and sprayed onto the silicate particulate matter to be coated.
However, as mentioned previously, it is preferred that they be emul-sified since silicones are not soluble in water.
Accordingly,~it is desired that these materials be emulsified in water since they would be more easily sprayed on the silicate par-ticulate matter to form a uniform coating.
Accordingly, per 40 - 60 parts by weight of branch-chained silicone fluid or of the linear diorganopolysiloxane polymer to be emulsified there is generally used from .5 to 5 parts by weight of an aliphatic carboxylic acid having 6 - 20 carbon atoms and from .1 to o.8 parts by weight of ammonia with from 20 - 150 parts of water to form a stable silicone emulsion. The preferred aliphatic carboxylic acid is of course oleic acid. However, any other aliphatic carboxylic acid may be used. The preferred compound for the preferred anion forming the emulsification salt is ammonia because upon heating ammonia will evaporate from the emulsion into the atmosphere. It is desired to have ammonia as the anlon in the emulsl~ication salt in ~15~869 `, 60 Si-173 ~.
the silicone emulsions of the present case to prevent a phenomena known as back wetting. The emulsification salts which are formed with anions which are for instance alkali metal, such as sodium il and potassium cause upon the curing of the silicone fluid and the ! evaporation of the water to leave behind an alkali metal salt on the silicone coating. Such salts will ionize in the presence of moisture, allowing the moisture to penetrate through the silicone coating which is formed about the silicate particulate matter. Accordingly, such back wetting is possible with standard alkali metal emulsification salts. It is desirable that such salts not be present on the surface of the silicone coating or mixed with the silicone coating. For this reason it is desirable that the anion in the emulsification salt be an anion emulsification salt of ammonia.
There only need be present sufficient ammonia so as to form a proper ammonia emulsification salt such that the sllicone fluid can be prop-erly emulsified to form a stable water emulsion. Then when the emulslion is applied to the silicate particulate matter, either by heating the silicate particulate matter or by having the sllicate particulate matter preheated to a temperature of at least 150C or thereabouts, the ammonia will simple evaporate to the atmosphere leaving behind an aliphatic carboxylic acid which is an oil and whTch will add rather than detract from the water repellent properties of the silicone coating.
It should also be noted that while there has been specified in the claims and specification that there be used 40 - 60 parts by weight of the~branch-chained silieone fluid or of the linear diorganopoly-siloxane and from .5 - 5 parts of the aliphatic carboxylic acid and from .1 - . parts by weight of a ~ ;nia .~d 20 - 150 parts water to
3 60 Si-173 ~5~8~9 I produce the silicone emulsion, there is nothing critical about any ! of these concentrations. The foregoing ingredients can be utilized 1 and varied as desired to produce a stable emulsion. Thus, amounts j of~the ingredients may be utilized in the above concentrations and ! may be varied as desired. There need be present sufficient amounts of the emulsification salt to form the ammonia carboxylic acid salt so Tt will emulsify the silicone fluid or the linear diorganopoly-siloxane in water. As can he appreciated the concentration of the ammonium salt plus the water plus the silicone fluid that will form a stable emulsion will vary by a great deal It should be also noted that an aliphatic carboxylic acid may be used. However, other car-boxylic acids may be utilized there are emulsifying agents for sili-cone fluids. It is only necessary that the carboxylic acid, whether it be aliphatic or aromatic of the nature of an oil in its pure form, such that it will be hydrophobic so that it will repel or add to the water repellçncy of the silicone coating rather than detract from it, that is rather than attract water to the silicone coating. Examples of carboxylic acid that may be utilized as an emulsifying agents in .
the instant invention are as follows:
Elaidic Acid Arotic Acid Azelaic Acid Gaidic Acid Pelargonic Acid Aleurtic Acid Sebacic Acid Muconic Acid Capryltc Acid Myristic Acid Stearic Acid Isobutyric Acid Stearolic Acid Valeric Acid Copric Acid Caproic Acid Undecanoic Acid Enanthic Acid Lauric Acid Lactaric Acid Erucic Acid Behenic Acid Ricinoleic Acid Agaric Acid Aupanodonic Acid Brassic Acid Behenolic Acid Margaric Acid Melissic Acid Enanthis Acid The most preferred carboxylic acid is oleic Acid since It is found to perform satisfactorily in all respects. It should be noted that ' ~15~869 60 Si-173 aromatic carboxylic acid may be utilized. It should be noted that ¦ in preparing the emulsion as wi11 be explained below, it is preferred ! that there be utilized in the emulsion from .01 to .5 parts of a ~. silicone antifoam compound. Usually such a silicone antifoam compound ~ comprising basically a mixture or emulsion of a polydimethylsiloxane polymer having a viscosity of anywhere from 100 to 10,000 centipoise at 25C which is emulsified by itself or mixed with the usual emulsify-ing agents and mixing in filler such as for instance silazane treated fumed silica. Such a silicone fluid with the foregoing filler alone or with the foregoing filler in emulsion form when added in small quantities in the process of the preparation of an emulsion of the instant case will cut down the amount of foam that is formed during the process for forming the emulsion.
The amount of the emulsifying agent that is present in the relatively small quantity of anti foam compaund, that is added to the emulsion does not detr~act from the water repellent properties of the silicone coating that is formed from the silicone emulsion of the instant case.
The process for forming the emulsion is as follows:
The branch-chained silicone fluid or the silanol endstopped diorgano-polysiloxane polymer is pumped to a premixed tank. Then the aliphatic carboxylic acid which is clean is added to silicone fluld, then the silicone fluid and the aliphatic carboxylic acid are mixed by uslng rapid agitation for anywhere from 10 - 60 minutes. Preferably the mixing is carried out at the temperature of 25 ~ 50 C and more pre-ferably from 25 - 35C. In a separate tank there is blended the ammonia and half the total amount of water in which they are blended or mixed for a period of time varying anywhere from 10 to 60 minutes and preferably varying from 20 to 40 minutes. Then slowly the ammo--19- l ` 1 ~15~869 60 Si-173 .
, nia water blend is added to the premixed tank containing the silicone , fluid and aliphatic carboxylic acid and the mixture is stirred, and the addition taking place anywhere from 10 to 60 minutes with rapid agitation and preferably from 20 to 40 minutes.
~ Then to this concentration of ingredients there is added a small amount of antifoam to reduce or control the foaming of the emulsion, that is formed as it is being agitated. Then the second part of water or the rest of the water is then added to the blend and agitation is continued anywhere from 20 - 60 minutes and more preferably from 30 - 40 minutes. ~he emulsTon will then be analyzed for water-content and if it passes the stability emulsion water content then the emul-sion will be passed through a homogenizer at a pressure of above 500 psig and then passed into the necessary steel drums.
The foregoing emulsion is prepared as indicated above is not flammab~e with only traces of amount of hydrogen gas occasionally being liberated in storage. ~The emulsion for the linear silanol endstopped diorgano-polysiloxane polymer is prepared in much the same way as was the emulsion for the branch-chained silicone fluld. It should be noted that in these emulsions there may be utilized by welght as stated prevlously by weight of the branch-chained sillcone fluid or of the linear diorganopolysiloxane polymer as stated previousty of .01 to .1~ by weight of a metal salt of carboxylic acid as the catalyst for curing the silicone fluid or the linear diorganopolysiloxane polymer.
However, as stated previously, such salts will remain on the sTlTcone coatings after It has curred and are undesirable because they tend to allow moisture to penetrate the silicone coating rather than assist the silicone coating in repellTng moisture. However, if a rapid cure Ts a very basic need in the application of the sTlicone coating and the silicone coating does not have to have maxTmum water reslstance then such salt may be utTlized Tn small quantTtTes to Increase the ~ 869 60 5i-173 ~` rate of cure of the silicone coating.
The emulsion usually contains from anywhere from 30 - 60~ by weight of silicone solids. When it is desired to utilize the emulsion to , apply it to the silicate particulate matter, it is preferably diluted I with water such that there is anywhere from 1 - 5% by weight of silicone solids and then the silicone emulsion is sprayed by normal spraying equipment onto the particulate silicate matter, as it comes from the expanding process, that is the expanded perlite leaves the heated furnace and before~it has reached room temperature, has a temperature of at least 150C and more preferably at least 300C.
The silicone emulsion is sprayed on the heated particles~ The heat in the heated particles then causes the water to evaporate almost instantly and cures the silicone fluid to result in the rapid forma-tion of a silicone coating on the expanded perlite or vermiculite silicate particles, in the same drying and curing step, the ammonia is evaporate`d from the emulsion leaving behind the aliphatic car-boxylic acid as an otl on the silicone coating.
However, while the above is the preferred process for applying the silicone emulsion to particulate silicate matter, it is only exem-plary. Other processes may be utilized such as that for instance the silicone coating may be applied to the perlite and theQ the perlite may be heated at elevated temperatures above 100C to cure the sili-cone coating. It should be noted that elevated temperatures are preferred in the application of the silicone emulsion in accordance with the instant process since if elevated temperatures are not util-ized and no curing catalyst is utilized, the branch-chained silicone fluid and the linear silanol endstopped diorganopolysiloxane will cure slowly over a prolonged period such as a matter of weeks~ Accordingly, without the use of a metal salt of carboxylic acid as a curing catalyst ~ 6 9 60 Si-173 i . it i5 desirable and necessary for the silicone emulsion to be applied j to the expanded perlite particles and such particles be heated, that I is preheated or subsequently heated or simultaneously heated to ~ elevated temperatures above 150C and more preferably above 300C
~ so that the silicone fluid may cure in a short period of time to form a silicone coating.
The examples below are given for the purpose of illustrating the present invention. The Examples below are not given for any purpose of setting limits or bounds to the definition of the present inven-tion as set forth In the specification and the claims.
The Examples below are illustrations of the present invention only.
All parts in the examples are by weight.
Example I
There was prepared an emulsion comprising a silicone fluid having (CH3)3 SiOo 5 units (CH3)2siO units and CH3 Si1.5 unitS with a viscosity of 50 centipoise at 25C. An emulsion was formed from the fluid having 50% by weight of the silicone fluid, 1.40~ by weight of oleic acid, 0.30% by weight ammonia, and the rest being water. One part of this emulsion was diluted with 20 parts of water. The diluted emulslon was sprayed on a dry bed of perlite and the perlite was heated at 300F for 10 minutes. The dried perlite which was composi-tion A was tested for water absorbency.
One part of the 5,0~ solid silicone emulsion previously described was diluted with 3P parts of water. The diluted emulsion was sprayed on a dry bed of perlite and the perlite was heated at 300F for 10 minutes The drTed perlite which was Composition B was tested for water absor-bency.
One part of the 50~ solids emulsion previously descrtbed was diluted with 40 parts of water. The diluted emulsion was sprayed on a dry ' ~i5~869 60 Si-173 ¦ of perlite and the perlite was heated at 3000F for 10 minutes. The ¦` dried perlite which was Composition C, was tested for water absorbency.
One part of the 50~ solid emulsion previously described was diluted 1~ wlth 20 parts of water, the diluted emulsion was sprayed on a dry bed ' of perlite and the perlite was heated at 500F for 10 minutes so as ¦ to assure water evaporation. The dried perlite which was Somposition D was tested for water absorbency.
Water Repellency Test The water repellency of perlite insulation was determined in accord-ance with the following procedure. A rigid plastic tube 2 inch ID
by 12 inches long with a 16 mesh plastic screen covering firmly fastened or adhered to the bottom opening was employed. The tube was marked at 7.77 inches from screen covered end indicating a volume of 400 ml. The plastic tuve was filled with the perlite insulation to level sllghtly above the 400 ml. mark. It was then compacted by dropping the tube from a height of approximate~y 3 inches on a large rubber stopper for 10 drops. As the sample compacted to a level be-low the 400 ml. mark, additional material was added so that after the tenth drop the level of the sample was within 1/8 inch of the 400 ml.
mark. The tube was kept in a vertical position during compactlon.
With the tube supported in a vertical position and a beaker positioned under the tube. There was poured 50 ml. of water onto the perlite insulation. There was allowed 3 minutes for the water to drain through specimen, then the the tube was tilted approximately 45 to drain water collected on screen. There was poured water which was collected in the beaker into graduate and the recorded amount, which was the amount of water which was repelled by the treated perlite loose fill insulation.
115~869 60 Si-173 ~` I
The results are listed below: ~S
Composition ~ Water Repelled A
the instant invention are as follows:
Elaidic Acid Arotic Acid Azelaic Acid Gaidic Acid Pelargonic Acid Aleurtic Acid Sebacic Acid Muconic Acid Capryltc Acid Myristic Acid Stearic Acid Isobutyric Acid Stearolic Acid Valeric Acid Copric Acid Caproic Acid Undecanoic Acid Enanthic Acid Lauric Acid Lactaric Acid Erucic Acid Behenic Acid Ricinoleic Acid Agaric Acid Aupanodonic Acid Brassic Acid Behenolic Acid Margaric Acid Melissic Acid Enanthis Acid The most preferred carboxylic acid is oleic Acid since It is found to perform satisfactorily in all respects. It should be noted that ' ~15~869 60 Si-173 aromatic carboxylic acid may be utilized. It should be noted that ¦ in preparing the emulsion as wi11 be explained below, it is preferred ! that there be utilized in the emulsion from .01 to .5 parts of a ~. silicone antifoam compound. Usually such a silicone antifoam compound ~ comprising basically a mixture or emulsion of a polydimethylsiloxane polymer having a viscosity of anywhere from 100 to 10,000 centipoise at 25C which is emulsified by itself or mixed with the usual emulsify-ing agents and mixing in filler such as for instance silazane treated fumed silica. Such a silicone fluid with the foregoing filler alone or with the foregoing filler in emulsion form when added in small quantities in the process of the preparation of an emulsion of the instant case will cut down the amount of foam that is formed during the process for forming the emulsion.
The amount of the emulsifying agent that is present in the relatively small quantity of anti foam compaund, that is added to the emulsion does not detr~act from the water repellent properties of the silicone coating that is formed from the silicone emulsion of the instant case.
The process for forming the emulsion is as follows:
The branch-chained silicone fluid or the silanol endstopped diorgano-polysiloxane polymer is pumped to a premixed tank. Then the aliphatic carboxylic acid which is clean is added to silicone fluld, then the silicone fluid and the aliphatic carboxylic acid are mixed by uslng rapid agitation for anywhere from 10 - 60 minutes. Preferably the mixing is carried out at the temperature of 25 ~ 50 C and more pre-ferably from 25 - 35C. In a separate tank there is blended the ammonia and half the total amount of water in which they are blended or mixed for a period of time varying anywhere from 10 to 60 minutes and preferably varying from 20 to 40 minutes. Then slowly the ammo--19- l ` 1 ~15~869 60 Si-173 .
, nia water blend is added to the premixed tank containing the silicone , fluid and aliphatic carboxylic acid and the mixture is stirred, and the addition taking place anywhere from 10 to 60 minutes with rapid agitation and preferably from 20 to 40 minutes.
~ Then to this concentration of ingredients there is added a small amount of antifoam to reduce or control the foaming of the emulsion, that is formed as it is being agitated. Then the second part of water or the rest of the water is then added to the blend and agitation is continued anywhere from 20 - 60 minutes and more preferably from 30 - 40 minutes. ~he emulsTon will then be analyzed for water-content and if it passes the stability emulsion water content then the emul-sion will be passed through a homogenizer at a pressure of above 500 psig and then passed into the necessary steel drums.
The foregoing emulsion is prepared as indicated above is not flammab~e with only traces of amount of hydrogen gas occasionally being liberated in storage. ~The emulsion for the linear silanol endstopped diorgano-polysiloxane polymer is prepared in much the same way as was the emulsion for the branch-chained silicone fluld. It should be noted that in these emulsions there may be utilized by welght as stated prevlously by weight of the branch-chained sillcone fluid or of the linear diorganopolysiloxane polymer as stated previousty of .01 to .1~ by weight of a metal salt of carboxylic acid as the catalyst for curing the silicone fluid or the linear diorganopolysiloxane polymer.
However, as stated previously, such salts will remain on the sTlTcone coatings after It has curred and are undesirable because they tend to allow moisture to penetrate the silicone coating rather than assist the silicone coating in repellTng moisture. However, if a rapid cure Ts a very basic need in the application of the sTlicone coating and the silicone coating does not have to have maxTmum water reslstance then such salt may be utTlized Tn small quantTtTes to Increase the ~ 869 60 5i-173 ~` rate of cure of the silicone coating.
The emulsion usually contains from anywhere from 30 - 60~ by weight of silicone solids. When it is desired to utilize the emulsion to , apply it to the silicate particulate matter, it is preferably diluted I with water such that there is anywhere from 1 - 5% by weight of silicone solids and then the silicone emulsion is sprayed by normal spraying equipment onto the particulate silicate matter, as it comes from the expanding process, that is the expanded perlite leaves the heated furnace and before~it has reached room temperature, has a temperature of at least 150C and more preferably at least 300C.
The silicone emulsion is sprayed on the heated particles~ The heat in the heated particles then causes the water to evaporate almost instantly and cures the silicone fluid to result in the rapid forma-tion of a silicone coating on the expanded perlite or vermiculite silicate particles, in the same drying and curing step, the ammonia is evaporate`d from the emulsion leaving behind the aliphatic car-boxylic acid as an otl on the silicone coating.
However, while the above is the preferred process for applying the silicone emulsion to particulate silicate matter, it is only exem-plary. Other processes may be utilized such as that for instance the silicone coating may be applied to the perlite and theQ the perlite may be heated at elevated temperatures above 100C to cure the sili-cone coating. It should be noted that elevated temperatures are preferred in the application of the silicone emulsion in accordance with the instant process since if elevated temperatures are not util-ized and no curing catalyst is utilized, the branch-chained silicone fluid and the linear silanol endstopped diorganopolysiloxane will cure slowly over a prolonged period such as a matter of weeks~ Accordingly, without the use of a metal salt of carboxylic acid as a curing catalyst ~ 6 9 60 Si-173 i . it i5 desirable and necessary for the silicone emulsion to be applied j to the expanded perlite particles and such particles be heated, that I is preheated or subsequently heated or simultaneously heated to ~ elevated temperatures above 150C and more preferably above 300C
~ so that the silicone fluid may cure in a short period of time to form a silicone coating.
The examples below are given for the purpose of illustrating the present invention. The Examples below are not given for any purpose of setting limits or bounds to the definition of the present inven-tion as set forth In the specification and the claims.
The Examples below are illustrations of the present invention only.
All parts in the examples are by weight.
Example I
There was prepared an emulsion comprising a silicone fluid having (CH3)3 SiOo 5 units (CH3)2siO units and CH3 Si1.5 unitS with a viscosity of 50 centipoise at 25C. An emulsion was formed from the fluid having 50% by weight of the silicone fluid, 1.40~ by weight of oleic acid, 0.30% by weight ammonia, and the rest being water. One part of this emulsion was diluted with 20 parts of water. The diluted emulslon was sprayed on a dry bed of perlite and the perlite was heated at 300F for 10 minutes. The dried perlite which was composi-tion A was tested for water absorbency.
One part of the 5,0~ solid silicone emulsion previously described was diluted with 3P parts of water. The diluted emulsion was sprayed on a dry bed of perlite and the perlite was heated at 300F for 10 minutes The drTed perlite which was Composition B was tested for water absor-bency.
One part of the 50~ solids emulsion previously descrtbed was diluted with 40 parts of water. The diluted emulsion was sprayed on a dry ' ~i5~869 60 Si-173 ¦ of perlite and the perlite was heated at 3000F for 10 minutes. The ¦` dried perlite which was Composition C, was tested for water absorbency.
One part of the 50~ solid emulsion previously described was diluted 1~ wlth 20 parts of water, the diluted emulsion was sprayed on a dry bed ' of perlite and the perlite was heated at 500F for 10 minutes so as ¦ to assure water evaporation. The dried perlite which was Somposition D was tested for water absorbency.
Water Repellency Test The water repellency of perlite insulation was determined in accord-ance with the following procedure. A rigid plastic tube 2 inch ID
by 12 inches long with a 16 mesh plastic screen covering firmly fastened or adhered to the bottom opening was employed. The tube was marked at 7.77 inches from screen covered end indicating a volume of 400 ml. The plastic tuve was filled with the perlite insulation to level sllghtly above the 400 ml. mark. It was then compacted by dropping the tube from a height of approximate~y 3 inches on a large rubber stopper for 10 drops. As the sample compacted to a level be-low the 400 ml. mark, additional material was added so that after the tenth drop the level of the sample was within 1/8 inch of the 400 ml.
mark. The tube was kept in a vertical position during compactlon.
With the tube supported in a vertical position and a beaker positioned under the tube. There was poured 50 ml. of water onto the perlite insulation. There was allowed 3 minutes for the water to drain through specimen, then the the tube was tilted approximately 45 to drain water collected on screen. There was poured water which was collected in the beaker into graduate and the recorded amount, which was the amount of water which was repelled by the treated perlite loose fill insulation.
115~869 60 Si-173 ~` I
The results are listed below: ~S
Composition ~ Water Repelled A
Claims (15)
1. A silicone emulsion for treating silicate particu-late matter selected from perlite and vermiculite to make the particulate matter water-resistant comprising (a) from 40 to 60 parts by weight of a silicone fluid having R2SiO units, R SiO1.5 units and R3SiO.5 units where the ratio of organosiloxy units to diorganosiloxy units varies from 0.11 to 1.4 inclusive and the ratio of triorganosiloxy units to diorganosiloxy units varies from 0.02 to about 1 inclusive and the fluid has a silanol content varying from 0.1 to 8 percent by weight and a viscosity varying from 10 to 10,000 centipoise at 25°C. and where R is selected from the class consisting of alkyl radicals of 1 to 8 carbon atoms vinyl radicals and mononuclear aryl radicals; (b) from 0.5 to 5 parts by weight of an aliphatic carboxylic acid having from 6 to 20 carbon atoms; (c) from 0.1 to 0.8 parts by weight of ammonia and (d) from 20 to 150 parts of water.
2. The silicone emulsion of claim 1 wherein said aliphatic carboxylic acid is oleic acid.
3. The silicone emulsion of claim 1 wherein R is methyl.
4. The silicone emulsion of claim 1 wherein there is present from 0.1 to 0.5 parts by weight of a silicone antifoam compound.
5. The silicone emulsion of claim 4 wherein the antifoam compound is a dimethylpolysiloxane of a viscosity varying from 10 to 10,000 centipoise at 25°C. dispersed or emulsified in water.
6. A method for forming a silicone emulsion for treating silicate particulate matter selected from perlite and vermiculite to make the particulate matter water-resistant comprising (a) mixing from 40 to 60 parts by weight of a silicone fluid having R2SiO units, R SiO1.5 units and R3SiO0.5 units where the ratio or organosiloxy units to diorganosiloxy units varies from 0.11 to 1.4 inclusive and the ratio of triorgano-siloxy to diorganosiloxy units varies from 0.02 to 1, inclusive, and the fluid has a silanol content varying from 0.1 to 8 percent by weight and a viscosity varying from 10 to 10,000 centipoise at 25° C., where R is selected from the class consisting of alkyl radicals of 1 to 8 carbon atoms, vinyl radicals, and mononuclear aryl radicals and from 0.5 to 5 parts of an aliphatic carboxylic acid having from 6 to 20 carbon atoms; (b) mixing separately from 20 to 150 parts of water with from 0.1 to 0.8 parts of ammonia; (c) adding with agitation the ammonia-water mixture to the silicone fluid, carboxylic acid mixture; and (d) adding additional water as needed.
7. The method of claim 6 wherein the process is carried out at a temperature in the range of 25°C. to 50°C.
8. The method of claim 6 wherein approximately half of the water is added in step (b) and the rest of the water is added in step (d).
9. The method of claim 6 wherein said aliphatic carboxylic acid is oleic acid.
10. The method of claim 6 wherein R is methyl.
11. The method of claim 6 wherein there is present from 0.01 to 0.5 parts by weight of a silicone antifoam compound.
12. The method of claim 11 wherein the antifoam compound is a dimethylpolysiloxane of a viscosity varying from 10 to 10,000 centipoise at 25°C. dispersed or emulsified in water.
13. A silicone coated particulate matter comprising (1) a silicate particulate matter selected from perlite and vermiculite which is coated with (2) the cured composition of the following mixture of ingredients (a) from 40 to 60 parts by weight of a silicone fluid having R2SiO units, R SiO1.5 units and R3SiO0.5 units where the ratio of organosiloxy units to diorganosiloxy units varies from 0.11 to 1.4 inclusive, the ratio of triorganosiloxy units to diorganosiloxy units varies from 0.02 to about 1, inclusive, and the fluid has a silanol content varying from 0.1 to 8 percent by weight and a viscosity varying from 10 to 10,000 centipoise at 25°C. and where R is selected from the class consisting of alkyl radicals of 1 to 8 carbon atoms, vinyl radicals and mononuclear aryl radicals and (b) from 0.5 to 5 parts by weight of an aliphatic carboxylic acid having from 6 to 20 carbon atoms.
14. The silicone coated matter of claim 13 wherein said aliphatic carboxylic acid is oleic acid.
15. The silicone coated matter of claim 13 wherein R is methyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/929,461 US4175159A (en) | 1978-07-31 | 1978-07-31 | Silicone emulsions for treating silicate particulate matter |
| US929,461 | 1978-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1150869A true CA1150869A (en) | 1983-07-26 |
Family
ID=25457899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000331281A Expired CA1150869A (en) | 1978-07-31 | 1979-07-06 | Silicone emulsions for treating silicate particulate matter |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4175159A (en) |
| JP (1) | JPS5527389A (en) |
| AU (1) | AU528285B2 (en) |
| BE (1) | BE877983A (en) |
| CA (1) | CA1150869A (en) |
| DE (1) | DE2930483A1 (en) |
| ES (1) | ES482769A1 (en) |
| FR (1) | FR2432536A1 (en) |
| GB (1) | GB2031445B (en) |
| GR (1) | GR69228B (en) |
| IT (1) | IT1122258B (en) |
| NL (1) | NL7905890A (en) |
| NO (1) | NO792498L (en) |
| NZ (1) | NZ190718A (en) |
| PH (1) | PH15565A (en) |
| TR (1) | TR20929A (en) |
| ZA (1) | ZA792932B (en) |
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| DE3105860A1 (en) * | 1980-02-18 | 1981-12-10 | Kabushiki Kaisha Toyota Chuo Kenkyusho, Nagakute, Aichi | PLATE OR TABLET-SHAPED MINERAL TONE PRODUCT |
| DE3007089A1 (en) * | 1980-02-26 | 1981-09-03 | Dezsö T. 6749 Schweigen-Rechtenbach Kabai | Sustained-release fertiliser prods. - contg. some components in coated form |
| US4313997A (en) * | 1980-07-14 | 1982-02-02 | Grefco, Inc. | Perlite boards and method for making same |
| US4342796A (en) * | 1980-09-10 | 1982-08-03 | Advanced Chemical Technologies, Inc. | Method for inhibiting corrosion of internal structural members of reinforced concrete |
| DE3115758A1 (en) * | 1981-04-18 | 1982-11-11 | Hoechst Ag, 6000 Frankfurt | "BLOODED MINERAL SHAPED BODY" |
| US4368313A (en) * | 1981-09-18 | 1983-01-11 | General Electric Company | Stabilization of silanol hydrolysates of organosilanes |
| US4439489A (en) * | 1982-02-16 | 1984-03-27 | Acme Resin Corporation | Particles covered with a cured infusible thermoset film and process for their production |
| US4540629A (en) * | 1982-04-08 | 1985-09-10 | Pq Corporation | Hollow microspheres with organosilicon-silicate walls |
| US4424297A (en) | 1982-07-08 | 1984-01-03 | Dow Corning Corporation | Colloidal silesquioxanes |
| US4671973A (en) * | 1985-09-23 | 1987-06-09 | Grefco, Inc. | Method for the treatment of mineral extender fillers |
| JPS6424742A (en) * | 1987-07-21 | 1989-01-26 | Shinetsu Chemical Co | Silicone-mica laminated object and its manufacture |
| US4877654A (en) * | 1988-05-02 | 1989-10-31 | Pcr, Inc. | Buffered silane emulsions for rendering porous substrates water repellent |
| US4990377A (en) * | 1988-05-02 | 1991-02-05 | Pcr Group, Inc. | Buffered silane emulsions having low volatile organic compounds when cured |
| US5096733A (en) * | 1989-10-30 | 1992-03-17 | The United States Of America As Represented By The Secretary Of The Dept. Of Health And Human Services | Prevention of the acute cytotoxicity associated with silica containing minerals |
| US5075103A (en) * | 1990-07-06 | 1991-12-24 | Dow Corning Corporation | Hair fixatives comprising nonpolar silsesquioxanes |
| RU2036213C1 (en) * | 1992-10-14 | 1995-05-27 | Смирнов Александр Витальевич | Composition for solid surface modification |
| US5747561A (en) * | 1992-10-14 | 1998-05-05 | Smirnov; Aleksandr Vitalievich | Solid surface modifier |
| US5449712A (en) * | 1993-01-13 | 1995-09-12 | Thoro System Products, Inc. | Organosilicon emulsions for rendering porous substrates water repellent |
| US5965664A (en) * | 1997-08-27 | 1999-10-12 | Lindley Laboratories, Inc. | High concentration silane emulsions for rendering absorbent substrates water repellent |
| US5964934A (en) * | 1997-12-18 | 1999-10-12 | Usg Interiors, Inc. | Acoustical tile containing treated perlite |
| US7279438B1 (en) | 1999-02-02 | 2007-10-09 | Certainteed Corporation | Coated insulation board or batt |
| US7220470B2 (en) | 2001-02-20 | 2007-05-22 | Certainteed Corporation | Moisture repellent air duct products |
| US6769455B2 (en) * | 2001-02-20 | 2004-08-03 | Certainteed Corporation | Moisture repellent air duct products |
| PE20030419A1 (en) * | 2001-10-10 | 2003-05-31 | Middleway Entpr Ltd | HYDRO-ABSORBENT COMPOUND TO CONDITION SOILS FOR AGRICULTURAL, FOREST AND LANDSCAPE USE |
| US6610782B1 (en) | 2001-11-20 | 2003-08-26 | Lindley Laboratories, Inc. | Binary silane emulsions for rendering absorbent substrates water repellant |
| US7223455B2 (en) * | 2003-01-14 | 2007-05-29 | Certainteed Corporation | Duct board with water repellant mat |
| US6986367B2 (en) | 2003-11-20 | 2006-01-17 | Certainteed Corporation | Faced mineral fiber insulation board with integral glass fabric layer |
| US20050221061A1 (en) * | 2004-04-02 | 2005-10-06 | Toas Murray S | Method and apparatus for forming shiplap edge in air duct board using molding and machining |
| US20060019568A1 (en) | 2004-07-26 | 2006-01-26 | Toas Murray S | Insulation board with air/rain barrier covering and water-repellent covering |
| JP4842571B2 (en) * | 2004-10-08 | 2011-12-21 | Ａｇｃエスアイテック株式会社 | Method for producing water-repellent inorganic powder or water-repellent resin beads |
| WO2007000834A1 (en) * | 2005-06-29 | 2007-01-04 | Agc Si-Teck Co., Ltd. | Process for producing water repellent particulate |
| EP1967553A4 (en) * | 2005-12-28 | 2010-05-19 | Agc Si Tech Co Ltd | Water-repellent inorganic powder and process for production thereof |
| DE102006005899B4 (en) † | 2006-02-09 | 2009-01-08 | Knauf Perlite Gmbh | building board |
| US8343272B2 (en) * | 2009-04-29 | 2013-01-01 | Christine L. Rada, legal representative | Lightweight construction material and methods and device for fabrication thereof |
| US8673393B2 (en) | 2009-06-08 | 2014-03-18 | Innovanano, Inc. | Hydrophobic materials made by vapor deposition coating and applications thereof |
| ES2551952T3 (en) * | 2010-04-15 | 2015-11-24 | Kompoferm Gmbh | Media for jet abrasion (blasting) and procedure for jet abrasion (blasting) |
| KR101003986B1 (en) * | 2010-04-19 | 2010-12-31 | 한국교통연구원 | Perlite concrete, soft-ground arresting pavement for aircraft using perlite concrete and manufacturing method of such pavement |
| US9962809B2 (en) * | 2012-10-12 | 2018-05-08 | Kompoferm Gmbh | Blasting agent and blasting method |
| CN103923493B (en) * | 2014-03-20 | 2016-04-06 | 江苏荣昌新材料科技有限公司 | A kind of method of silicon hydride oil treatment porous material |
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| RU2759942C2 (en) | 2017-01-18 | 2021-11-18 | Эвоник Оперейшенс ГмбХ | Granular heat-insulating material and its production method |
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| CA680839A (en) * | 1964-02-25 | Dow Corning Corporation | Aqueous organopolysiloxane polishes | |
| NL85087C (en) * | 1951-10-09 | |||
| US3362933A (en) * | 1963-10-09 | 1968-01-09 | Dow Corning | Polymers of haloethersilanes and their quaternary salts |
| US3418151A (en) * | 1965-11-26 | 1968-12-24 | Wyandotte Chemicals Corp | Treated soil adjuvant plant-growing product |
| GB1227795A (en) * | 1968-05-13 | 1971-04-07 | ||
| US3963627A (en) * | 1970-02-16 | 1976-06-15 | Imperial Chemical Industries Limited | Surface treatment of particulate solids |
| US3861939A (en) * | 1971-12-22 | 1975-01-21 | Gen Electric | Process for coating substrates using fast curing silanol-containing organopolysiloxane resins |
| US4046941A (en) * | 1972-09-27 | 1977-09-06 | Sanko Chemical Company Ltd. | Support sheet with sensitized coating of organic acid substance and organic high molecular compound particulate mixture |
-
1978
- 1978-07-31 US US05/929,461 patent/US4175159A/en not_active Expired - Lifetime
-
1979
- 1979-06-13 ZA ZA792932A patent/ZA792932B/en unknown
- 1979-06-13 NZ NZ19071879A patent/NZ190718A/en unknown
- 1979-06-14 GB GB7920817A patent/GB2031445B/en not_active Expired
- 1979-06-14 GR GR59338A patent/GR69228B/el unknown
- 1979-07-06 CA CA000331281A patent/CA1150869A/en not_active Expired
- 1979-07-09 AU AU48755/79A patent/AU528285B2/en not_active Expired - Fee Related
- 1979-07-17 PH PH22790A patent/PH15565A/en unknown
- 1979-07-18 JP JP9047879A patent/JPS5527389A/en active Pending
- 1979-07-23 IT IT2455179A patent/IT1122258B/en active
- 1979-07-23 ES ES482769A patent/ES482769A1/en not_active Expired
- 1979-07-26 FR FR7919262A patent/FR2432536A1/en not_active Withdrawn
- 1979-07-26 TR TR2092979A patent/TR20929A/en unknown
- 1979-07-27 DE DE19792930483 patent/DE2930483A1/en not_active Withdrawn
- 1979-07-30 NO NO792498A patent/NO792498L/en unknown
- 1979-07-31 NL NL7905890A patent/NL7905890A/en not_active Application Discontinuation
- 1979-07-31 BE BE0/196527A patent/BE877983A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BE877983A (en) | 1979-11-16 |
| IT7924551A0 (en) | 1979-07-23 |
| AU4875579A (en) | 1980-02-07 |
| GR69228B (en) | 1982-05-10 |
| DE2930483A1 (en) | 1980-02-21 |
| GB2031445B (en) | 1983-05-18 |
| TR20929A (en) | 1983-01-19 |
| ZA792932B (en) | 1980-11-26 |
| ES482769A1 (en) | 1980-04-16 |
| NZ190718A (en) | 1981-10-19 |
| NL7905890A (en) | 1980-02-04 |
| IT1122258B (en) | 1986-04-23 |
| AU528285B2 (en) | 1983-04-21 |
| NO792498L (en) | 1980-02-01 |
| FR2432536A1 (en) | 1980-02-29 |
| JPS5527389A (en) | 1980-02-27 |
| US4175159A (en) | 1979-11-20 |
| PH15565A (en) | 1983-02-11 |
| GB2031445A (en) | 1980-04-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |