CA1339432C - High polymer content silicone emulsions - Google Patents
High polymer content silicone emulsionsInfo
- Publication number
- CA1339432C CA1339432C CA000587484A CA587484A CA1339432C CA 1339432 C CA1339432 C CA 1339432C CA 000587484 A CA000587484 A CA 000587484A CA 587484 A CA587484 A CA 587484A CA 1339432 C CA1339432 C CA 1339432C
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- CA
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- Prior art keywords
- polymer content
- emulsion
- weight
- microemulsion
- macroemulsion
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Abstract
HIGH POLYMER CONTENT SILICONE EMULSIONS
A polydiorganosiloxane emulsion having a combination of high polymer content and low viscosity can be produced by blending a high polymer content polydiorgano -siloxane macroemulsion, having a polymer content of greater than 60 percent by weight and an average particle size of greater than 0.14 micrometers ant a high polymer content polydiorganosiloxane microemulsion, having a polymer content of from 20 to 30 percent by weight and an average particle size of less than 0.14 micrometers, with the ratio of the average particle size of the macroemulsion to the average size of the microemulsion of from 5 to 15.
A polydiorganosiloxane emulsion having a combination of high polymer content and low viscosity can be produced by blending a high polymer content polydiorgano -siloxane macroemulsion, having a polymer content of greater than 60 percent by weight and an average particle size of greater than 0.14 micrometers ant a high polymer content polydiorganosiloxane microemulsion, having a polymer content of from 20 to 30 percent by weight and an average particle size of less than 0.14 micrometers, with the ratio of the average particle size of the macroemulsion to the average size of the microemulsion of from 5 to 15.
Description
HIGH POLYMER COhl~Nl SILICONE EMULSIONS
This invention relates to the u~e of silicone microemulsions in con~unction with silicone macroemulsions to produce high polymer content emulsions of lower than normal viscosity.
In any of the prior art methods, as the solids content of the emulsion is raised, the viscosity of the emulsion rises. For applications which require a flowable emulsion, the rise in viscosity limits the polymer content which can be achievet.
An emulsion of polydiorganosiloxane having a high polymer content and yet a relatively low viscosity is produced by blending 100 parts by weight of a polydiorgano-siloxane macroemulsion having a high polymer content with from 1 to 70 parts by weight of a polydiorganosiloxane microemulsion having a high polymer content.
This invention relates to a method of producing a polydiorganosilo~ane emulsion having a high polymer content of greater than 40 percent by weight and a relatively low visco~ity of less than 25 Pa-s at 25~C. comprising, mixing 100 parts by weight of a high polymer content polytiorgano-silo~ane macroemulsion having a polymer content of greater than 60 percent by weight and particle diameters greater than 0.14 micrometers with from 1 to 70 parts by weight of a high polymer content polydiorganosilo~ane microemulsion having a polymer content of from 20 to 30 percent by weight and particle diameters less than 0.14 micrometers, with the ratio of the average particle size of the macroemulsion to the average particle size of the microemulsion being from 5 to 15 , ,~s~ ~
and the particle size distribution of each of the parent emulsions being broad.
A high polymer content polydiorganosiloxane macroemulsion is defined as one in which the polymer phase of the emulsion comprises greater than 60 percent by weight of the total weight of the emulsion. The emulsion has a high viscosity under zero shear, such as a viscosity of greater than 25 Pa-s at 25~C. An emulsion having a viscosity of greater than 25 Pa-s is such that it becomes difficult to work with in normal plant mixing equipment such as stirred mixing kettles and in pumping through pipes during transfer of the emulsion to other processing equipment or to storage containers. The preferred polymer content is from 60 to 80 percent by weight. A macroemulsion is one that has particles which scatter appreciable amounts of light. The average diameter of the emulsion particles exceeds 0.14 micrometers.
Preferably the particles exceed diameters of greater than 0.25 micrometers with a preferred range of 0.25 to 0.5 micrometers. The high polymer content polydiorganosiloxane macroemulsion can be prepared by any of the methods known.
Examples of macroemulsions are found in U.S. Patent Nos. 3,294,725, 4,221, 688, 4,244,844 and 4,244,849, all of which show polydiorganosiloxane macroemulsions and means for their preparation.
The high polymer content polydiorganosiloxane macroemulsion is preferably prepared by following the method found in U.S. Patent No. 3,294,725. An organosiloxane is polymerized while in the dispersed state in an aqueous medium in the presence of a surface active sulfonic acid. The siloxane and surface active sulfonic acid catalyst are dispersed in water to form a stable emulsion. The emulsion is then allowed to stand with or without agitation at the i339432 desired temperature until the siloxane has reached the desired state of molecular aggregation.
A high polymer content polydiorganosiloxane microemulsion is an emulsion having from 20 to 30 percent by weight polymer phase based upon the total weight of the emulsion. The emulsion particles do not exceed diameters of 0.14 micrometers. Preferred are emulsions having particle diameters of less than 0.1 micrometers, with diameters of less than 0.05 micrometers most preferred.
The high polymer content polydiorganosiloxane microemulsion can be prepared by following the methods found in U.S. Patent Nos. 3,433,780, 3975,294, 4,052,331, 4,146,499 and 4,620,878, all of which show methods of producing microemulsions and the microemulsions.
A microemulsion of polydiorganosiloxane may be prepared by sequentially adding a precursor emulsion comprised of cyclopolydiorganosiloxane, surfactant and water to a polymerization medium comprised of water and an effective amount of a polymerization catalyst, while mixing, wherein the rate of addition of the precursor emulsion is effective to form a clear, stable microemulsion which has polydiorganosiloxane droplets of less than 0.14 micrometer in diameter and which contains a surfactant to polydiorgano-siloxane weight ratio of 0.15 to 0.65. That is, the weight of surfactant divided by the weight of polymer is between 0.15 and 0.65.
The macroemulsion and the microemulsion used in this invention can be of the cationic, anionic, or nonionic types. The emulsions can be the normal mechanical emulsions which are formed by intense shear of a mixture of polymer, surfactant and water, or they can be of the type where the polymer is prepared in emulsion form. The important point is that the ratio of the average size of the macroemulsion 1339~32 particles to the average size of the particles of the microemulsion is in the range of from 5:1 to 15:1 with a range of about 10:1 preferred. Ideally, each of the parent emulsions should have 8 highly polydisper~ed particle size distribution. Since the purpose of the mixtures of this invention is to produce a high polymer content emulsion with a low viscosity, the viscosity of the macroemulsion must be high enough to be of concern. The polymer content of the macroemulsion has to be high enough such that the dispersed phase creates enough surface area to create significant interference to flow of the continuous phase, thus creating a high viscosity. This depends upon several factors including the average particle diameter and the distribution of the particle diameters. Thus, when a combination of average particle size and polymer content of a macroemulsion leads to a higher viscosity than is desired by the user, a lower viscosity emulsion can be made by diluting the macroemulsion with a microemulsion. For example, a silicone emulsion having a mean diameter in the 0.3 to 0.4 micrometer range and a polymer content in the range of 62 percent has a visco~ity such that the emulsion is non-flowing or very slowly flowing when at rest or under low s'hear. By ~dding a portion of a microemulsion to such a macroemulsion a new emulsion is formed which has a much lower viscosity.
The polydiorganosilo~ane emulsion of this invention, having a high polymer content and a relatively low viscosity, is produced by mi~ing one of the emulsions slowly into the other emulsion with ~tirring. This blending of two emulsions with large differences in the particle mean tiameter~ ant particle size di~tributions creates an emulsion with a bimodal particle ~ize distribution. As shown in Table I, a high viscosity macroemulsion and a high viscosity microemul~ion, when combined in this manner can give a .j f-~
133~3~
viscosity much lower than that of either one alone. The mixture of 470 Pa-s (470,000 cps) viscosity macroemulsion and 1,900 Pa-s (1,900,000 cps) microemulsion gave a mixture having a viscosity of only 23 Pa-s (23,000 cps), while maintaining a high solids content in the final emulsion.
The emulsions of this invention are particularly useful in applications where a high polymer content in combination with a low viscosity, at low shear rates, are de~irable. These emulsions can be used as coatings which will flow out to a smooth surface, yet give a good coating because of the high polymer content. By the addition of fillers, it is possible to produce emulsions having a viscosity like a paste for use as sealants which can be extruded from a storage tube and yet have very little shrinkage on drying because of the high polymer content, i.e., low volatility content.
The method of this invention enables a manufacturer to use high polymer content, high viscosity macroemulsions in a plant in a practical manner. For example, by putting a microemulsion, having a viscosity of less than 25 Pa-s for example, into a mixing kettle first and then pumping a high viscosity macroemulsion into the kettle with stirring, the viscosity of the mixture in the kettle remains low, below 25 Pa-s. Since the high polymer content macroemulsion can approach a non-flowing material when at rest, this procedure allows the production of emulsions having both high polymer content and low vi~cosity at the same time.
The following examples are included for illustrative purposes only and should not be construed as limitinK the invention which is properly set forth in the appendet claims. All parts are parts by weight.
Example 1 A high polymer content polytiorganosiloxane macroemulsion was prepared by first combining 3 parts of surfactant (WAQE, a 30 percent di~persion of sotium lauryl sulphate in water) with 22 parts of distilled water. Then 75 parts of hytroxyl entblocket polydimethylsiloxane having a viscosity of about 0.08 Pa- 8 at Z5~C. was slowly added with stirring. After all of the polytiorganosiloxane was addet, the crute dispersion was homogenizet twice at 6000 p8i in a single stage laboratory homogenizer. The resultant emulsion was a stable emulsion having a polymer content of 75.9 percent ant an average particle size of about 0. 35 micrometers. Its viscosity was about 470 Pa 8 (470,000 cps) at a shear rate of 1 reciprocal secont.
A high polymer content polydiorganosilo~cane microemulsion was prepared by first combining 7.5 parts of dodecylbenzenesulfonic acid and 142. 5 parts of water, then slowly admixing 100 parts of dimethylcyclosiloxane and homogenizing twice at 7500 psi to form a macroemulsion of the timethylcyclosilo~cane(emulsion A). A microemulsion was then formet by 510wly ~ 1ing 100 parts of macroemulsion A to a reaction flask containing 88 parts of water ant 12 parts of todecylbenzenesulfonic acid which wa~ heatet to 85 to 90~C.
and polymerizing for a ~ufficient time to form a polymer microemulsion (emulsion a) having a polymer content of about 20 percent by weight and an average particle size of about 0.03 micrometers. The viscosity of this emulsion was about 1,900 Pa-s (1,900,000 cps) at a shear rate of 1 reciprocal secont.
A similar high polymer content polytiorgano~iloxane microemulsion was preparet by a similar process to give a microemulsion (b) of about 30 percent by weight polymer and an average particle size of about 0.05 micrometers. Its * Tradem_~
~7~ 1~9~32 viscosity was about 2,000 Pa-s (2,000,000 cps) at a shear rate of 1 reciprocal second.
A series of mixtures were prepared by mixing sufficient diluent into the macroemulsion described above to lower the polymer content from 75 percent to 70.5 percent.
The diluents were distilled water, distilled water with 10 percent sodium lauryl sulphate added, microemulsion (a) and microemulsion (b). The viscosity of each mixture was then measured at a shear rate of 1 reciprocal second with the results shown in Table 1.
.,, oq ~ . o o ,~ ~ ,~
Cl ~d ~ co ~ c~l r l tJ p~
v~
~r S~ ~
C
~ ~ O u~
h ~ . . .
r I 11~ 0 0 0 0 O I
O oo 0~ ~ O
~ ~ . .
--I E
00 rl J~
~ ' O l E3 "I
~4 al o ~ o~
r-l r l ~ O
~r ~ ~ ~ u~
C ~
O O
~rl rl o~ r I r~l J~ + k ~ h ~ O O
~r O ~ ~rl ~rl 3 -' Ei ~3 This shows the result of mixing a minor amount of a microemulsion having a viscosity of about 2,000 Pa-s (2,000,000 cps) into a macroemulsion having a viscosity of about 500 Pa-s (500,000 cps). All of these emulsions were non-flowing before mixing. After atdition of the microemulsion, the resulting emulsion mixture was very fluid.
E~ample 2 The macroemulsion of Example 1 was a nonflowing material when it was not under shear. Microemulsion (a) of E~ample 1 was a nonflowing material when not unter shear.
When 5 parts of microemulsion (a) was mixed into 95 parts of the macroemulsion, the mi~ture was an easily flowing material.
E~ample 3 A crude emulsion was prepared by weighing 352.31 g (19.573 moles) of distilled, deionized water into a beaker and 45.19 g of 1.04 molar solution of sodium dotecyl sulfate was added and mi~ed with a stirrer until homogeneous. Then 1102.5 g (0.402 moles) of hydro~yl endblocked polytimethyl-silo~ane having a viscosity of about 0.08 Pa-s was slowly added and stirred at high speed for 30 minutes.
This crude emulsion was homogenized by passing 2 times through a laboratory single stage homogenizer at 6000 psi. The macroemulsion was about 76 percent polymer content and had an average particle size of about 0.35 micrometres.
The viscosity of the emulsion was 519 Pa-s at a shear rate of 0.1380 reciprocal seconds.
A microemulsion was prepared by first making a macroemulsion, then converting it to a microemulsion.
A macroemulsion using a cyclic polydiorganosilo~ane was prepared by 9~ing 570 g (31.76 moles) of distilled, deionized water to a beaker and mi~ing in 30 g (0.861 mole) of dodecylbenzenesulfonic acid and mixing until a homogeneous solution was obtained. Then 400 g (1.3514 moles) of octamethylcyclotetrasiloxane was added and stirred for 30 minutes. This mixture was then homogenized by pas~ing twice through a single stage laboratory homogenizer to give an emulsion having an average particle size of about 0.23 micrometers and a polymer contents of about 40 percent by weight.
A microemulsion was then prepared by first adding 539.5 g (29.97 moles of distilled, deionized water to a reaction flask and mixing in 110.5 g (0.3171 mole) of dodecylbenzenesulfonic acid, then raising the temperature to 90~C. Then 650 g of the above prepared macroemulsion was slowly added to the reaction flask via a dropping funnel at a rate which maintained a clear, transparent emulsion. Once the addition was complete, the reaction was allowed to continue for 1 hour, at which time the flask was cooled and the emulsion bottled. The microemulsion contained 20 weight percent polymer, had an average particle size of about 0.05 micrometers and a viscosity of about 1,927 Pa-s at 25~C.
The grams of macroemulsion and grams of micro-emulsion shown in Table II were then mixed together, deaired and ~heared at a low shear rate. The viscosity of each sample was then measured at a shear rate of 0.1380 reciprocal seconds with the results shown in Table II.
9 ~ ~ ~
Table II
Sample Macroemulsion Microemulsion Viscosity gm gms Wt%Pa-s 1 20.0 0 0 519 2 19.5 0.5 2.5 121 3 19.0 1.0 5.0 110 4 18.0 2.0 10.0 29 16.0 4.0 20.0 12 6 12.0 8.0 40.0 9 7 8.0 12.0 60.0 20 8 4.0 16.0 80.0 578 9 0.0 20.0 100.0 1,927
This invention relates to the u~e of silicone microemulsions in con~unction with silicone macroemulsions to produce high polymer content emulsions of lower than normal viscosity.
In any of the prior art methods, as the solids content of the emulsion is raised, the viscosity of the emulsion rises. For applications which require a flowable emulsion, the rise in viscosity limits the polymer content which can be achievet.
An emulsion of polydiorganosiloxane having a high polymer content and yet a relatively low viscosity is produced by blending 100 parts by weight of a polydiorgano-siloxane macroemulsion having a high polymer content with from 1 to 70 parts by weight of a polydiorganosiloxane microemulsion having a high polymer content.
This invention relates to a method of producing a polydiorganosilo~ane emulsion having a high polymer content of greater than 40 percent by weight and a relatively low visco~ity of less than 25 Pa-s at 25~C. comprising, mixing 100 parts by weight of a high polymer content polytiorgano-silo~ane macroemulsion having a polymer content of greater than 60 percent by weight and particle diameters greater than 0.14 micrometers with from 1 to 70 parts by weight of a high polymer content polydiorganosilo~ane microemulsion having a polymer content of from 20 to 30 percent by weight and particle diameters less than 0.14 micrometers, with the ratio of the average particle size of the macroemulsion to the average particle size of the microemulsion being from 5 to 15 , ,~s~ ~
and the particle size distribution of each of the parent emulsions being broad.
A high polymer content polydiorganosiloxane macroemulsion is defined as one in which the polymer phase of the emulsion comprises greater than 60 percent by weight of the total weight of the emulsion. The emulsion has a high viscosity under zero shear, such as a viscosity of greater than 25 Pa-s at 25~C. An emulsion having a viscosity of greater than 25 Pa-s is such that it becomes difficult to work with in normal plant mixing equipment such as stirred mixing kettles and in pumping through pipes during transfer of the emulsion to other processing equipment or to storage containers. The preferred polymer content is from 60 to 80 percent by weight. A macroemulsion is one that has particles which scatter appreciable amounts of light. The average diameter of the emulsion particles exceeds 0.14 micrometers.
Preferably the particles exceed diameters of greater than 0.25 micrometers with a preferred range of 0.25 to 0.5 micrometers. The high polymer content polydiorganosiloxane macroemulsion can be prepared by any of the methods known.
Examples of macroemulsions are found in U.S. Patent Nos. 3,294,725, 4,221, 688, 4,244,844 and 4,244,849, all of which show polydiorganosiloxane macroemulsions and means for their preparation.
The high polymer content polydiorganosiloxane macroemulsion is preferably prepared by following the method found in U.S. Patent No. 3,294,725. An organosiloxane is polymerized while in the dispersed state in an aqueous medium in the presence of a surface active sulfonic acid. The siloxane and surface active sulfonic acid catalyst are dispersed in water to form a stable emulsion. The emulsion is then allowed to stand with or without agitation at the i339432 desired temperature until the siloxane has reached the desired state of molecular aggregation.
A high polymer content polydiorganosiloxane microemulsion is an emulsion having from 20 to 30 percent by weight polymer phase based upon the total weight of the emulsion. The emulsion particles do not exceed diameters of 0.14 micrometers. Preferred are emulsions having particle diameters of less than 0.1 micrometers, with diameters of less than 0.05 micrometers most preferred.
The high polymer content polydiorganosiloxane microemulsion can be prepared by following the methods found in U.S. Patent Nos. 3,433,780, 3975,294, 4,052,331, 4,146,499 and 4,620,878, all of which show methods of producing microemulsions and the microemulsions.
A microemulsion of polydiorganosiloxane may be prepared by sequentially adding a precursor emulsion comprised of cyclopolydiorganosiloxane, surfactant and water to a polymerization medium comprised of water and an effective amount of a polymerization catalyst, while mixing, wherein the rate of addition of the precursor emulsion is effective to form a clear, stable microemulsion which has polydiorganosiloxane droplets of less than 0.14 micrometer in diameter and which contains a surfactant to polydiorgano-siloxane weight ratio of 0.15 to 0.65. That is, the weight of surfactant divided by the weight of polymer is between 0.15 and 0.65.
The macroemulsion and the microemulsion used in this invention can be of the cationic, anionic, or nonionic types. The emulsions can be the normal mechanical emulsions which are formed by intense shear of a mixture of polymer, surfactant and water, or they can be of the type where the polymer is prepared in emulsion form. The important point is that the ratio of the average size of the macroemulsion 1339~32 particles to the average size of the particles of the microemulsion is in the range of from 5:1 to 15:1 with a range of about 10:1 preferred. Ideally, each of the parent emulsions should have 8 highly polydisper~ed particle size distribution. Since the purpose of the mixtures of this invention is to produce a high polymer content emulsion with a low viscosity, the viscosity of the macroemulsion must be high enough to be of concern. The polymer content of the macroemulsion has to be high enough such that the dispersed phase creates enough surface area to create significant interference to flow of the continuous phase, thus creating a high viscosity. This depends upon several factors including the average particle diameter and the distribution of the particle diameters. Thus, when a combination of average particle size and polymer content of a macroemulsion leads to a higher viscosity than is desired by the user, a lower viscosity emulsion can be made by diluting the macroemulsion with a microemulsion. For example, a silicone emulsion having a mean diameter in the 0.3 to 0.4 micrometer range and a polymer content in the range of 62 percent has a visco~ity such that the emulsion is non-flowing or very slowly flowing when at rest or under low s'hear. By ~dding a portion of a microemulsion to such a macroemulsion a new emulsion is formed which has a much lower viscosity.
The polydiorganosilo~ane emulsion of this invention, having a high polymer content and a relatively low viscosity, is produced by mi~ing one of the emulsions slowly into the other emulsion with ~tirring. This blending of two emulsions with large differences in the particle mean tiameter~ ant particle size di~tributions creates an emulsion with a bimodal particle ~ize distribution. As shown in Table I, a high viscosity macroemulsion and a high viscosity microemul~ion, when combined in this manner can give a .j f-~
133~3~
viscosity much lower than that of either one alone. The mixture of 470 Pa-s (470,000 cps) viscosity macroemulsion and 1,900 Pa-s (1,900,000 cps) microemulsion gave a mixture having a viscosity of only 23 Pa-s (23,000 cps), while maintaining a high solids content in the final emulsion.
The emulsions of this invention are particularly useful in applications where a high polymer content in combination with a low viscosity, at low shear rates, are de~irable. These emulsions can be used as coatings which will flow out to a smooth surface, yet give a good coating because of the high polymer content. By the addition of fillers, it is possible to produce emulsions having a viscosity like a paste for use as sealants which can be extruded from a storage tube and yet have very little shrinkage on drying because of the high polymer content, i.e., low volatility content.
The method of this invention enables a manufacturer to use high polymer content, high viscosity macroemulsions in a plant in a practical manner. For example, by putting a microemulsion, having a viscosity of less than 25 Pa-s for example, into a mixing kettle first and then pumping a high viscosity macroemulsion into the kettle with stirring, the viscosity of the mixture in the kettle remains low, below 25 Pa-s. Since the high polymer content macroemulsion can approach a non-flowing material when at rest, this procedure allows the production of emulsions having both high polymer content and low vi~cosity at the same time.
The following examples are included for illustrative purposes only and should not be construed as limitinK the invention which is properly set forth in the appendet claims. All parts are parts by weight.
Example 1 A high polymer content polytiorganosiloxane macroemulsion was prepared by first combining 3 parts of surfactant (WAQE, a 30 percent di~persion of sotium lauryl sulphate in water) with 22 parts of distilled water. Then 75 parts of hytroxyl entblocket polydimethylsiloxane having a viscosity of about 0.08 Pa- 8 at Z5~C. was slowly added with stirring. After all of the polytiorganosiloxane was addet, the crute dispersion was homogenizet twice at 6000 p8i in a single stage laboratory homogenizer. The resultant emulsion was a stable emulsion having a polymer content of 75.9 percent ant an average particle size of about 0. 35 micrometers. Its viscosity was about 470 Pa 8 (470,000 cps) at a shear rate of 1 reciprocal secont.
A high polymer content polydiorganosilo~cane microemulsion was prepared by first combining 7.5 parts of dodecylbenzenesulfonic acid and 142. 5 parts of water, then slowly admixing 100 parts of dimethylcyclosiloxane and homogenizing twice at 7500 psi to form a macroemulsion of the timethylcyclosilo~cane(emulsion A). A microemulsion was then formet by 510wly ~ 1ing 100 parts of macroemulsion A to a reaction flask containing 88 parts of water ant 12 parts of todecylbenzenesulfonic acid which wa~ heatet to 85 to 90~C.
and polymerizing for a ~ufficient time to form a polymer microemulsion (emulsion a) having a polymer content of about 20 percent by weight and an average particle size of about 0.03 micrometers. The viscosity of this emulsion was about 1,900 Pa-s (1,900,000 cps) at a shear rate of 1 reciprocal secont.
A similar high polymer content polytiorgano~iloxane microemulsion was preparet by a similar process to give a microemulsion (b) of about 30 percent by weight polymer and an average particle size of about 0.05 micrometers. Its * Tradem_~
~7~ 1~9~32 viscosity was about 2,000 Pa-s (2,000,000 cps) at a shear rate of 1 reciprocal second.
A series of mixtures were prepared by mixing sufficient diluent into the macroemulsion described above to lower the polymer content from 75 percent to 70.5 percent.
The diluents were distilled water, distilled water with 10 percent sodium lauryl sulphate added, microemulsion (a) and microemulsion (b). The viscosity of each mixture was then measured at a shear rate of 1 reciprocal second with the results shown in Table 1.
.,, oq ~ . o o ,~ ~ ,~
Cl ~d ~ co ~ c~l r l tJ p~
v~
~r S~ ~
C
~ ~ O u~
h ~ . . .
r I 11~ 0 0 0 0 O I
O oo 0~ ~ O
~ ~ . .
--I E
00 rl J~
~ ' O l E3 "I
~4 al o ~ o~
r-l r l ~ O
~r ~ ~ ~ u~
C ~
O O
~rl rl o~ r I r~l J~ + k ~ h ~ O O
~r O ~ ~rl ~rl 3 -' Ei ~3 This shows the result of mixing a minor amount of a microemulsion having a viscosity of about 2,000 Pa-s (2,000,000 cps) into a macroemulsion having a viscosity of about 500 Pa-s (500,000 cps). All of these emulsions were non-flowing before mixing. After atdition of the microemulsion, the resulting emulsion mixture was very fluid.
E~ample 2 The macroemulsion of Example 1 was a nonflowing material when it was not under shear. Microemulsion (a) of E~ample 1 was a nonflowing material when not unter shear.
When 5 parts of microemulsion (a) was mixed into 95 parts of the macroemulsion, the mi~ture was an easily flowing material.
E~ample 3 A crude emulsion was prepared by weighing 352.31 g (19.573 moles) of distilled, deionized water into a beaker and 45.19 g of 1.04 molar solution of sodium dotecyl sulfate was added and mi~ed with a stirrer until homogeneous. Then 1102.5 g (0.402 moles) of hydro~yl endblocked polytimethyl-silo~ane having a viscosity of about 0.08 Pa-s was slowly added and stirred at high speed for 30 minutes.
This crude emulsion was homogenized by passing 2 times through a laboratory single stage homogenizer at 6000 psi. The macroemulsion was about 76 percent polymer content and had an average particle size of about 0.35 micrometres.
The viscosity of the emulsion was 519 Pa-s at a shear rate of 0.1380 reciprocal seconds.
A microemulsion was prepared by first making a macroemulsion, then converting it to a microemulsion.
A macroemulsion using a cyclic polydiorganosilo~ane was prepared by 9~ing 570 g (31.76 moles) of distilled, deionized water to a beaker and mi~ing in 30 g (0.861 mole) of dodecylbenzenesulfonic acid and mixing until a homogeneous solution was obtained. Then 400 g (1.3514 moles) of octamethylcyclotetrasiloxane was added and stirred for 30 minutes. This mixture was then homogenized by pas~ing twice through a single stage laboratory homogenizer to give an emulsion having an average particle size of about 0.23 micrometers and a polymer contents of about 40 percent by weight.
A microemulsion was then prepared by first adding 539.5 g (29.97 moles of distilled, deionized water to a reaction flask and mixing in 110.5 g (0.3171 mole) of dodecylbenzenesulfonic acid, then raising the temperature to 90~C. Then 650 g of the above prepared macroemulsion was slowly added to the reaction flask via a dropping funnel at a rate which maintained a clear, transparent emulsion. Once the addition was complete, the reaction was allowed to continue for 1 hour, at which time the flask was cooled and the emulsion bottled. The microemulsion contained 20 weight percent polymer, had an average particle size of about 0.05 micrometers and a viscosity of about 1,927 Pa-s at 25~C.
The grams of macroemulsion and grams of micro-emulsion shown in Table II were then mixed together, deaired and ~heared at a low shear rate. The viscosity of each sample was then measured at a shear rate of 0.1380 reciprocal seconds with the results shown in Table II.
9 ~ ~ ~
Table II
Sample Macroemulsion Microemulsion Viscosity gm gms Wt%Pa-s 1 20.0 0 0 519 2 19.5 0.5 2.5 121 3 19.0 1.0 5.0 110 4 18.0 2.0 10.0 29 16.0 4.0 20.0 12 6 12.0 8.0 40.0 9 7 8.0 12.0 60.0 20 8 4.0 16.0 80.0 578 9 0.0 20.0 100.0 1,927
Claims (2)
1. A method of producing a polydiorganosiloxane emulsion having a high polymer content of greater than 40 percent by weight and a relatively low viscosity of less than 25 Pa.s at 25°C. comprising, mixing 100 parts by weight of a high polymer content polydiorganosiloxane macroemulsion having a polymer content of greater than 60 percent by weight and particle diameters greater than 0.14 micrometers with from 1 to 70 parts by weight of a high polymer content polydiorganosiloxane microemulsion having a polymer content of from 20 to 30 percent by weight and particle diameters less than 0.14 micrometers, with the ratio of the average particle size of the macroemulsion to the average particle size of the microemulsion being from 5 to 15 and the particle size distribution of each of the parent emulsions being broad.
2. The method of claim 1 in which the macroemultion is a polydimethylsiloxane emulsion of from 60 to 80 percent by weight polymer and has an average particle size of from 0.25 to 0.5 micrometers, the microemulsion is from 1 to 50 parts by weight of polydimethylsiloxane emulsion having from 20 to 30 percent by weight polymer and particle diameters less than 0.05 micrometers, with the resulting polydiorganosiloxane emulsion having a polymer content of greater than 60 percent by weight and a viscosity of less than 25Pa.s at 25°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/151,686 US4824877A (en) | 1988-02-02 | 1988-02-02 | High polymer content silicone emulsions |
| US151,686 | 1993-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1339432C true CA1339432C (en) | 1997-09-02 |
Family
ID=22539834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000587484A Expired - Fee Related CA1339432C (en) | 1988-02-02 | 1989-01-04 | High polymer content silicone emulsions |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4824877A (en) |
| EP (1) | EP0327321B1 (en) |
| JP (1) | JPH064702B2 (en) |
| KR (1) | KR960011753B1 (en) |
| AU (1) | AU605405B2 (en) |
| BR (1) | BR8900441A (en) |
| CA (1) | CA1339432C (en) |
| DE (1) | DE68911703T2 (en) |
| MX (1) | MX165296B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1328139C (en) * | 1985-12-12 | 1994-03-29 | Daniel Graiver | Methods for making polydiorganosiloxane microemulsions |
| US5973061A (en) * | 1988-08-31 | 1999-10-26 | Rhone-Poulenc Chimie | Aqueous silicone dispersions crosslinkable into elastometric state by dehydration |
| DE3836830A1 (en) * | 1988-10-28 | 1990-05-17 | Wacker Chemie Gmbh | METHOD FOR PRODUCING AQUEOUS EMULSIONS OF HIGH MOLECULAR ORGANOPOLYSILOXANS |
| FR2658094A1 (en) * | 1990-02-14 | 1991-08-16 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF EMULSIONS, OF THE OIL IN WATER TYPE, MONODISPERSES. |
| CA2042693A1 (en) * | 1990-06-07 | 1991-12-08 | Daniel J. Halloran | Silicone mechanical emulsions for hair care |
| US5145898A (en) * | 1990-10-31 | 1992-09-08 | Dow Corning Corporation | Aqueous siliocone-organic hybrids |
| US5556629A (en) * | 1991-09-13 | 1996-09-17 | General Electric Company | Method of preparing microemulsions |
| US5763523A (en) * | 1993-11-24 | 1998-06-09 | Cytec Technology Corp. | Stable emulsion blends and methods for their use |
| ES2139095T3 (en) * | 1993-11-24 | 2000-02-01 | Cytec Tech Corp | MULTIMODAL EMULSIONS AND PROCEDURES FOR PREPARING MULTIMODAL EMULSIONS. |
| US5914366A (en) * | 1993-11-24 | 1999-06-22 | Cytec Technology Corp. | Multimodal emulsions and processes for preparing multimodal emulsions |
| US5518716A (en) * | 1994-03-31 | 1996-05-21 | General Electric Company | Composition and method of preparing microemulsion blends |
| DE9419333U1 (en) * | 1994-12-02 | 1995-01-26 | Lefatex Chemie Gmbh | Coating agents for paper surfaces |
| JP3439860B2 (en) * | 1995-01-24 | 2003-08-25 | 東レ・ダウコーニング・シリコーン株式会社 | Continuous production method of organopolysiloxane emulsion |
| ATE335518T1 (en) | 1997-05-20 | 2006-09-15 | Baxter Int | NEEDLELESS COUPLING PIECE |
| DE10034831A1 (en) | 2000-07-18 | 2002-01-31 | Ciba Sc Pfersee Gmbh | Mixtures of polysiloxane emulsions |
| US6465568B1 (en) | 2000-09-11 | 2002-10-15 | Dow Corning Corporation | Anionic and cationic silicone emulsions |
| JP5393123B2 (en) | 2007-12-12 | 2014-01-22 | 富士フイルム株式会社 | External preparation for skin and method for producing the same |
| US20110308240A1 (en) * | 2010-06-16 | 2011-12-22 | Applied Chemical Laboratories, Inc. | Degradation of biomass by metal-catalyzed peroxide oxidation |
| BR112013022310A2 (en) * | 2011-03-03 | 2019-09-24 | Dow Corning | bimodal emulsions |
| CN103391960B (en) | 2011-03-03 | 2017-05-24 | 道康宁公司 | Bi-modal emulsions |
| KR20150086284A (en) * | 2012-11-21 | 2015-07-27 | 다우 코닝 코포레이션 | Cosmetic composition comprising bi-modal emulsion |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1024024A (en) * | 1963-04-08 | 1966-03-30 | Dow Corning | Improvements in or relating to polymerising or co-polymerising organosilicon compounds |
| NL133796C (en) * | 1965-01-21 | 1900-01-01 | ||
| US4052331A (en) * | 1972-11-03 | 1977-10-04 | Rhone-Poulenc S.A. | Surface active composition |
| FR2205358B1 (en) * | 1972-11-03 | 1976-04-23 | Rhone Poulenc Ind | |
| US3900617A (en) * | 1973-11-27 | 1975-08-19 | Gen Electric | Method of rendering flexible sheet material non-adherent and article produced thereby |
| DE2601159C3 (en) * | 1976-01-14 | 1982-02-04 | Wacker-Chemie GmbH, 8000 München | Process for the production of coatings which repel tacky substances |
| US4146499A (en) * | 1976-09-18 | 1979-03-27 | Rosano Henri L | Method for preparing microemulsions |
| FR2377982A1 (en) * | 1977-01-19 | 1978-08-18 | Saint Gobain | COMPOSITIONS FOR COATING FIBERS OF GLASS AND FIBERS SO OBTAINED |
| US4221688A (en) * | 1978-04-28 | 1980-09-09 | Dow Corning Corporation | Silicone emulsion which provides an elastomeric product and methods for preparation |
| US4244849A (en) * | 1979-08-06 | 1981-01-13 | Dow Corning Corporation | Silicone emulsion which provides an elastomeric product and methods for preparation |
| DE3017543A1 (en) * | 1980-05-08 | 1981-11-26 | Bayer Ag, 5090 Leverkusen | AQUEOUS DISPERSIONS BASED ON (METH) ACRYLIC ACID ALKYLESTER POLYMERISATES WITH TWO EXCELLENT, PRACTICALLY NOT OVERLAPPING MAXIMAS IN PARTICLE SIZE DISTRIBUTION WITHIN SPECIFIC PARTICLE LARGE RANGE |
| DE3036969A1 (en) * | 1980-10-01 | 1982-05-13 | Hoechst Ag, 6000 Frankfurt | PROTECTIVE COLLOID-FREE PLASTIC DISPERSIONS WITH BIMODAL PARTICLE SIZE DISTRIBUTION |
| US4620878A (en) * | 1983-10-17 | 1986-11-04 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
| FR2600660B1 (en) * | 1986-06-24 | 1988-11-18 | Rhone Poulenc Chimie | AQUEOUS EMULSIONS OF ORGANOPOLYSILOXANE POLYADDITION COMPOSITIONS FOR COATING FLEXIBLE MATERIALS |
-
1988
- 1988-02-02 US US07/151,686 patent/US4824877A/en not_active Expired - Fee Related
-
1989
- 1989-01-04 CA CA000587484A patent/CA1339432C/en not_active Expired - Fee Related
- 1989-01-24 MX MX014635A patent/MX165296B/en unknown
- 1989-02-01 DE DE68911703T patent/DE68911703T2/en not_active Expired - Fee Related
- 1989-02-01 AU AU29508/89A patent/AU605405B2/en not_active Ceased
- 1989-02-01 KR KR1019890001145A patent/KR960011753B1/en not_active IP Right Cessation
- 1989-02-01 EP EP89300945A patent/EP0327321B1/en not_active Expired - Lifetime
- 1989-02-01 JP JP1020936A patent/JPH064702B2/en not_active Expired - Lifetime
- 1989-02-01 BR BR898900441A patent/BR8900441A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE68911703T2 (en) | 1994-07-07 |
| EP0327321A2 (en) | 1989-08-09 |
| AU605405B2 (en) | 1991-01-10 |
| KR960011753B1 (en) | 1996-08-30 |
| DE68911703D1 (en) | 1994-02-10 |
| AU2950889A (en) | 1989-08-03 |
| EP0327321A3 (en) | 1990-12-27 |
| US4824877A (en) | 1989-04-25 |
| JPH024837A (en) | 1990-01-09 |
| EP0327321B1 (en) | 1993-12-29 |
| BR8900441A (en) | 1989-09-26 |
| MX165296B (en) | 1992-11-04 |
| JPH064702B2 (en) | 1994-01-19 |
| KR890013093A (en) | 1989-09-21 |
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