Title of Invention	"A PROCESS FOR THE MANUFACTURE OF STABLE LOW PARTICLE SIZE ORGANOPOLYSILOXANE EMULSION"
Abstract	A process for making stable high viscosity organopolysiloxane emulsion having particle size up to 150 nanometer and in particular to an emulsion-polymerization process involving a simple and cost-effective fester completion of emulsification of organopolysiloxane by using standard homogenizer and also subsequent polymerization of the organopolysiloxane at controlled temperature. The process involves a selective combination of non-ionic emulsifier together with an at least one anionic emulsifier to achieve the desired particle size emulsion. Importantly, the selective mix of non-ionic and anionic emulsifiers having HLB value of the mixture near to 12-15 and maintaining a temperature of up to 50°C is found to favour obtaining low particle stable emulsion with any standard homogeniser avoiding need for high pressure homogenizing.

Title of Invention

"A PROCESS FOR THE MANUFACTURE OF STABLE LOW PARTICLE SIZE ORGANOPOLYSILOXANE EMULSION"

Abstract

A process for making stable high viscosity organopolysiloxane emulsion having particle size up to 150 nanometer and in particular to an emulsion-polymerization process involving a simple and cost-effective fester completion of emulsification of organopolysiloxane by using standard homogenizer and also subsequent polymerization of the organopolysiloxane at controlled temperature. The process involves a selective combination of non-ionic emulsifier together with an at least one anionic emulsifier to achieve the desired particle size emulsion. Importantly, the selective mix of non-ionic and anionic emulsifiers having HLB value of the mixture near to 12-15 and maintaining a temperature of up to 50°C is found to favour obtaining low particle stable emulsion with any standard homogeniser avoiding need for high pressure homogenizing.

Full Text	FIELD OF INVENTION The present invention relates to a process for making stable high viscosity organopolysiloxane emulsion and in particular to an emulsion-polymerisation process involving a simple and cost-effective faster completion of emulsification of organopolysiloxane and also subsequent polymerisation of the organopolysiloxane. The process is directed to be simple and cost-effective and can be easily adapted for emulsion production of stable organopolysiloxane emulsions for diverse beneficial end use and application. Importantly, the silicone emulsion produced by the process of the invention is In the range of average (i.e D50 value) up to 150 nanometer with a very narrow particle size distribution which is highly stable and found to have advantageous and beneficial diverse use in various end applications including in personal care, textile -, rubber, paper and other like applications/uses. BACKGOUND ART It is well known to provide organopolysiloxane emulsions with varying partide sizes to suit different end applications. Organopolysiloxane emulsions having low partide size prepared by emulsion polymerisation process are generally preferred which could provide the desired faster and simple production with focus on emulsion stability and quicker organipotysiloxane polymerisation during emulsification. Such emulsion polymerised products are known to be prepared by various methods. For examples, JP-B 34-2041 disclosed a polymerisation process wherein a strong acid and strong base are used as a polymerisation catalyst. US 3697469 used ion-exchange resin as polymerisation catalyst. US 3360491; US 3697469; US 4228054; US 5726270; US 5817714; US 5895794; US 5925469 and US 6071975 disclosed polymerisation using alkyl benzene sulphonic acid, alkyl naphthalene sulphonic acid, aliphatic sulphonic acid, silylalkyl sulphonic acid, aliphatically substituted dipneny! ether sulfonic add or alkyl hydrogen sulphates as a catalyst. However all these processes take longer time for polymerisation and completion of the emulsion making process. Most of the processes are also only restricted to cydosiloxanes. US 6245852, discloses a process of preparation of organopolysiloxane emulsion having improved stability within a short time. The process comprising the steps of emulsifying and dispersing low molecular weight organopolysiloxane in water in presence of essentially at least one anionic surfactant selected from organic sulphonic acid and organic sulphates by using a high pressure homogeniser with a operating pressure range 1 from 700 to 3000 Kg/cm2 and produce an initial emulsion having partide size up to 300 nm, followed by allowing the emulsion for polymerisation and subsequent neutralization of the emulsion at the end. As would be dearly apparent from the disclosure in US'852 the process necessarily involves the use of very sophisticated and highly capital-intensive machine system for reduction of emulsion time in the emulsion polymerisation process. Also since the process uses a high-pressure system, the emulsion machine needs lot of control system for working safely in the production area. Thus while the process according to the above US'852 stated to reduce the time of emuIsification by using a sophisticated high pressure homogeniser but the said process does not seem to address the requirement for faster completion of the total emulsion process including faster polymerisation. Emulsion polymerisation process usually consists of emulsification of organopolysiloxane and subsequent polymerisation of the organopolysifoxane. So, faster emulsification on its own is not sufficient to complete emulsion polymerisation process or make the process faster. Therefore, it is also important to make faster polymerisation in emulsion polymerisation processes. The above state of art reveals the need to develop processes of making faster the total emulsion polymerisation process .Also the reduction in the partide size which is found to be of relevance for variety of end use/applications involving a faster emulsion polymerisation process is desirable for wide scale commercial manufacturing and use of such emulsions for diverse applications. OBJECTS OF THE INVENTION It is thus the basic object of the invention to provide a process of making silicone emulsion having partide size up to 150 nm which would on one hand be simple, cost-effective and fast and on the other hand would provide a simple and cost effective alternative to the need for complex machinery for faster emulsification and also reduce the polymerisation time in the emulsion polymerisation process and thus can be readily adapted for large scale cost-effective commercial manufacture of such low particle size silicone emulsions for diverse applications such as in personnel care and the like. Another object of the invention is directed to provide a simple process of making silicone emulsion having partide size up to 150 nanometer, which would reduce the total "emulsion polymerisation time" significantly. 2 Another object of the present invention Is directed to a process for the manufacture of silicone emulsion having particle size up to 150 nanometer which would assist faster polymer growth of the - organopolysiloxane during emulsion process. Yet further object of the present invention is directed to making stable silicone emulsion involving standard homogenizer having particle size up to 150 nanometer by way of a selective emulsion formulation and avoiding the need for complex machinery to reduce the emulsification and polymerisation stages in such manufacture of silicone emulsion. SUMMARY OF THE INVENTION Thus according to the basic aspect of the present invention, there is provided a process for the manufacture of a stable emulsion having particle size up to 150 nanometer comprising: i) providing a selective formulation comprising (a) organopolysiloxane or mixtures thereof in an amount of 20 to 80 % by .wt (b) water in an amount of 5 to 30 % by wt. (c) selective non-ionic emulsifier(s) having HLB in the range of 10-19 in amounts of 1 to 25% by wt. and (d) selective anionic emulsifier having HLB In the range of 8 - 19 in an amount of 1 to 15 % by. wt.; ii) homogenizing the mix of (i) using standard homognizer and maintaining a temperature of up to 50°C preferably In the range of 10-40°C such as to favour organopolysiloxane polymer growth rate or rise in polymer viscosity to at least 20000 cps; and Hi) neutralising the emulsion by alkali to a pH range 6-8. Importantly, it is found by way of the invention that one of the critical aspects which enable obtaining of emulsion up to 150 nanometer following a simple process is the selective use of a combination of non-ionic emulsifier together with an atleast one anionic emulsifier to achieve the desired particle sized emulsion. For organopolysiloxane emulsion, HLB value near to 12-15 is found to be the optimum value of the emulsifier or a mixture of emulsifiers, which help to make low particle emulsion. It is also found that a mixture of non-ionic and anionic emulsifiers having HLB value of the mixture near to 12-15 shows optimum combinations to make low particle stable emulsion with a standard homogenizer. 3 Also the quantity of the emulsifiers used in the above selective formulation have selective contribution to make the emulsion stable. In particular, in the above process of making low particle organopolysiloxane emulsion, the emulsion is also stabilized by use of surfactants having critical HLB values that help to make faster low particle emulsion by using standard homogenizer without need for complex ultra high pressure homogeniser. Moreover, it is also important to control temperature for achieving low particle size with narrow distribution of the particle. Advantageously making of the emulsion with a temperature up to 50°C, is found to further help faster polymer growth of organopolysiloxane in the emulsion. Temperature during the emulsion preparation is found to have great importance not only to control the particle size but also control the particle size distribution and faster growth of internal phase viscosity. In the above process of invention, preferably, a suitable biocide is added for preventing microbial growth. Since, the process uses a mixture of surfactants for making low particle organopolysiloxane by using standard homogenizer, it is important to maintain the selective formulation involving making a proper recipe of surfactants mix and recipe of organopolisiloxane and surfactants to achieve particle size up to 150 nanometer. In accordance with a preferred aspect the above process for the manufacture of stable and faster production of low particle size emulsion having high internal phase oil viscosity comprises of: (i) providing a selective formulation comprising providing water in an amount of 5 to 30% of the emulsion, 8 to 30% mixed emulsifiers comprising atleast one anionic emulsifier and at least one non-ionic emulsifier having HLB value of the emulsifiers in the range of 10-19 and an organopolysiloxane or mixture of organopolysiloxanes in the range of 20-80% of the emulsion. (ii) homogenising the mix with standard homogenizer while maintaining a temperature in the range up to 50°C, preferably in the range of 20-40°C for a period of 10 minutes to 2 hr depending on the desired characteristics of the emulsion ; (iii) allowing the emulsion to age in the range of 5 to 30°C to favour faster growth of -viscosity of the internal phase oil; 4 (iv) neutralising the emulsion with alkali and finally adding biocide for microbial prevention in the emulsion. The temperature of the material can be controlled during homogenising by passing cool water. In the above process the desired ageing temperature for growth of very high internal oil viscosity is in the range of 5 to 30 °C Generally, 1 to 12 hr is required to achieve very high viscosity internal phase oil viscosity. If internal oil viscosity is needed less than 500,000 cps, then neutralizing of the emulsion is carried out immediately after completion of mixing. Moreover, it is found that desired mixing time also varies for target viscosity of the polymer and distribution of the particles-in the emulsion. Neutralise the emulsion after completion of dilution steps. Generally, water-soluble inorganic alkali hydroxide or organic amine alcohol is used for neutralization. Preferably, sodium hydroxide or potassium hydroxide or triethanol amine is used to neutralise the emulsion. According to the present invention, one of the critical parameters include the selection of the right emulsifiers and combination of the emulsifiers to achieve the desired low particle size emulsion. The present invention thus achieves producing low particle emulsion in a simple way where selective emulsifier combination and temperature of emuIsification and polymerisation which have a critical part to make the process simple and avoiding the use of cost extensive and complex machinery. DETAILED DESCRIPTION OF THE INVENTION The invention thus provides a process for making stable low particle emulsion from a low molecular organopolysiloxane or a mixture of organopolysiloxane, Organopolysiloxanes referred herein for the purpose of the invention include low molecular organopolysiloxane such as alpha omega hydroxy terminated organopotysiloxane; alpha omega alcoxy terminated organopolysiloxane; organocyclopolysiloxanes or mixture thereof... In case of branched potysiloxane emulsion a tri functional or tetra functional or a mixture thereof is used together with above organopolysiloxanes. The alpha omega functional end blocked linear organopolysiloxane used herein are preferably those of the general formula I: 5 Where R1 hydrogen and/or a monovalent hydrocarbon group of 1 to 10 carbon atoms and/or a hydroxyl group and/or an alcoxy group having it 8 carbon atom. Examples of R1 as a monovalent hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl. Isobutyl, tert-butyl, n-pentyl, Isopentyl, neopentyl, tertpentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethyl pentyl, nonyl such as n- nonyl, decyl such as n decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl and methyl cyclohexyl, aryl such as phenyl, napthyl, anthryl and phenanthryl ; alkylaryl such as o-, m-, p-totyl, xylyl and ethylphenyl; aralkyl, such as benzyl, a and ß-phenylathyl; of which methyl, ethyl, n-propyl, isopropyl are preferred and methyl is particularly preferred. Example of R1 as alcoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or a phenoxy group but not limited to the said groups. Where R, which may differ, is a monovalent hydrocarbon radical. Examples of R are alkyl radicals, such as methyl, ethyl, n-propyl, iso propyl, n-butyl, Isobutyl, tertbutyl, n-pentyl, Isopentyl, neopentyl, tertpentyl, hexyl such as n-hexyl, heptyl, such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethyl pentyl, nonyl such as n- nonyl, decyl such as n decyl, dodecvl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl and methyl cyclohexyl, aryl such as phenyl, napthyl, anthryl and phenanthryl ; alkylaryl such as o-, m-, p-totyl, xylyl and ethylphenyl; aralkyl, such as benzyl, a and ß-phenylathyl, of which methyl, ethyl, n-propyl, isopropyl are preferred and methyl is particularly preferred. x is an integer from 1 to 100. The organocyclosiloxanes used herein have the following structure: 6 Where R is the independently hydrogen or monovalent hydrocaqrbon groups of 3 to 10 carbon atoms inducing an alkyl group such methyl, ethyl, n-propyl, iso propyl, n-butyl. Isobutyl, tert-butyl, n-pentyl, Isopentyl, neopentyl, tert pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and fsooctyl such as 2,2,4-trimethyl pentyl, nonyl such as n- nonyl, decyl such as n decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl and methyl cyclohexyl, aryl such as phenyl, napthyl, anthryl and phenanthryl ; aIkylaryl, such as o-, m-, p-totyl, xylyl and ethylphenyl; aralkyl, such as benzyl, a and ß-phenylathyl, of which methyl, ethyl, n-propyl, isopropyl are preferred and methyl is particularly preferred. 'n' is an integer of 3 to 10. Most preferred organocyclosiloxanes are octamethylcydotetrasiloxane; decamethylcyclopentasiloxane; Dodecamethyl cydohexasiloxane; 1,2,3,4- tetramethyl-1,2,3,4-tetravinyl cyclotetrasiloxane; 1,2,3,4- tetramethyl-l,2,3,4-terraphenyl cyclotetrasiloxane. Organopolysiloxane used according to the present invention may be branched by way of incorporation of branching units. Branching units may be introduced to improve the film forming behaviour of organopolysiloxane. Branching unit may be trifunctional silane or tetrafunctional silane or a mixture thereof. Trifuntional silanes (III) and tetrafunctional si lanes (IV) have the following strucrue: R-S1 -(O - R)3 . . III S1 -(O -R)4 IV Where R, which may differ, is a monovafent hydro carbon radical. Examples of R are alkyl radicals, such as methyl, ethyl, n-propyl, iso propyl, n-butyl. Isobutyl, tert-butyl, n-pentyl, Isopentyl, neopentyl, tert pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and isooctyf such as 2,2,4-trimethyl pentyl, nonyl such as n- nonyl, decyl such as n decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl, such as cydopentyl, cyclohexyl, cydoheptyl and 7 methyl cyclohexyl, aryl such as phenyl, napthyl, anthryt and phenanthryl ; alkytaryl, such as o-, nv, p-totyl, xylyl and ethyfphenyl; aralkyl, such as benzyl, a and ß-phenylathyf, of which methyl, ethyl, n-propyl, isopropyl are preferred and methyl is particularly preferred. Depending on the desired requirement of branching of the organopolysiioxane, branching units are adding during the emulsification process. 0.1 to 5% branching units of the emulsion is useful to make an emulsion containing organopolysiioxane having highly branched structure. Quantity used in the emulsion must be controlled carefully, otherwise gellation of the polymer may occur during emulsion process and emulsion destabilizes. If branched polysiloxane is not required, the silane addition is avoided. According to the present invention, anionic emulsifier has an important role for simple and faster emulsion process of high internal phase viscosity emulsion having particle size up to 150 nm. Anionic surfactant is selected from organic sulfonic adds. Most common sulfonic a acids used in the present process are alkyl aryl sulfonic add; alkyl aryl polyoxyethylene sulphonic acid; alkyl sulfonic add and alkyl polyoxyethylene sulfonic acid. Structures of sulfonic adds are as below: R2 C6H4 SO3 H (V) R2 C6H4 O (C2H4O) m SO3 H (VI) R2SO3H (VI) R2O(C2H4O)mSO3H (VIII) Where R2, which may differ, is a monovalent hydrocarbon radial having atfeast 6 carbon atom. Most preferable R2 groups, but not limited to the following groups, are hexyl, octyl, decyl, dodecyl, cetyl, stearyl, myristyl, and oleyl. 'm' is an integer from 1 to 25. Most preferable anionic surfactants used in the present inventions are octyl benzene sulfonic acid; dodecyl benzene sulfonic add; cetyl benzene sulfonic acid; Alpha octyl sulfonic acid; Alpha dodecyl sulfonic acid; alpha cetyl sulfonic add; polyoxyethylene octyl benzene sulfonic acid; polyoxyethylene dodecyl benzene sulfonic add; polyoxyethylene cetyl benzene sulfonic add; polyoxyethylene octyl sulfonic add; polyoxyethylene dodecyl sulfonic acid and polyoxyethylene cetyl sulfonic acid. Generally, 1 to 15% anionic surfactant is used in the present emulsion processing process. Preferably, 3- 10% anionic surfactant is used in the present emulsion to get the optimum result. Anionic surfactant has a dual role in the present emulsion process. Anionic surfactant acts as a condensation/ring opening catalyst in together with as a surfactant for emulsion making. Thus, by using anionic emulsifier, process doesnt need any catalyst for polymer growth of organopolysiloxane during emulsion process. 8 It is also observed according to the present invention, at least one additional emulsifier together with anionic emulsifier is essential alongwith the controlled temperature of emulsification and polymerisation for making the emulsion in a simple faster way. It is specially found by way of the present invention that at least one non-ionic emulsifier in together with anionic surfactant helps for faster simple emulsion production. Non-ionic emulsifiers having HLB value in between 10-19 are suitable to make the emulsion process simpler. Most useful surfactants of this category are polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ethers and polyoxyalkylene sorbitan esters. Some useful surfactants having HLB value in between 10-19 are polyethylene glycol octyl ether; Polyethylene glycol lauryl ether; Polyethylene glycol tridecyl ether;-Polyethylene glycol cetyl ether; Polyethylene glycol stearyl ether; polyethylene glycol nonylphenyl ether; polyethylene glycol dodecylphenyl ether; polyethylene glycol cetylphenyl ether; polyethylene glycol staerylphenyl ether; polyethylene glycol sorbitan mono stearate and polyethylene glycol sorbitan mono oleate. Non-ionic surfactant having HLB value in-between 10-19 has a great importance in the present invention to make process more simpler. Generally, 1 to 25% nonionic surfactant is used in the emulsion processing process. Preferably, 5- 20% nonionic surfactant is used in the present emulsion to get the optimum result. It is well known in the art that Surfactant(s) having HLB value in-between 12-15 is useful to make organopolysiloxane emulsion by using standard homogenizer in shorter period and it is also well known to use a mixture of surfactants that have HLB value in-between 12-15 to get an emulsion of organopolysiloxane having long stability. According to the present invention, it is also important to provide selective formulation of the emulsifiers in a ratio such that the mix has HLB value preferably in-between 12-15 with at least one anionic surfactant and one non-ionic surfactant in the mixture. An important aspect in the present emulsion process is the selective use of a mixture of surfactants, which not only make stable emulsion in faster way by using standard homogenizer but also to produce a low particle emulsion up to 150 nm. Particle size of the emulsion is highly dependent on the ratio of anionic and non-ionic emulsifier (s) having HLB value of the mixture in-between 12-15. 9 It is also well known of the art that polymer growth rate of the orgaoplylsiloxane is also highly dependent on the particle size of the emulsion. So polymer growth rate of the organopolysiloxane during the emulsion process is much higher compared to organopolysiloxane emulsion having particle size above 150 nm. According to the present invention, the temperature during the emulsion process has an important role to control the particle size of the emulsion, distribution of the particle size distribution (i.e polydispersibility, value 1 is poor and value 0.1 or less than 0.1 is very good) and polymer growth rate of the organopolysiloxane during emulsion process. It is also observed in the present emulsion process, particle size, and distribution of the particle and polymer viscosity become out of control if temperature is not maintained within a selective limit. It is found a significant deviation of final emulsion specifications take place where temperature control is not within the said selective range even though emulsion is produced by using an optimum combination of emulsifiers with a proper combination of fluid to emulsifier. Maintaining a temperature below of 50°C is useful to control the particle size, distribution of particle in the emulsion and polymer growth rate of the organopolysiloxane in the emulsion. Further, it is also important to control the emulsion temperature during the ageing of the emulsion in case of ultra high (more than 2 million cps) organopolysiloxane polymer in the emulsion. A temperature below of 30°C is useful to make the polymerisation faster in case of ultra high organopolysiloxane polymer required in the inner phase of the emulsion. Emulsion polymerisation is significantly dropped if temperature is more than 30°C during ageing process, even difficult to achieve ultra high viscosity at high temperature. So, it is dear that faster completion of emulsion process for high organopolysiloxane polymer to ultra high polymer emulsion by emulsion polymerisation process, temperature has great role during the emulsion making process and during the ageing process. So, according to the present process, a combination of mixed emulsifiers having HLB value 12 -15 (contains atleast one anionic emulsifier and atleast one nonionic emulsifiers) in together with temperature control during emulsion making and during ageing helps the emulsion process useful to produce emulsion below 150 nm by standard homogenizer. The components are homogenised by standard homogenizers. Useful standard shear stirring system may be used such as conventional single stage stator-rotor homogeniser or other types of standard homogeniser which are used in the normal homogenising process. Homogenising can be carried out in batch or continuous depend on the design of emulsion process. From the capital investment point of view, it is also clear that the 10 process also needs a economic homogenising system and avoids the use of the expensive very high pressure homogenising system. Importantly, it is found by way of the present invention that the emulsion obtained following the process of the invention was highly stable .In particular, tests revealed that when the emulsion obtained was put in the oven in the range of 45 to 60°C and most preferably, 55°C for one month, no creaming or separation or deformation in the emulsion was observed. A study of 12 hr freeze/thaw cycles in 10°C/50°C temperature for one month also showed no creaming or separation or deformation in the emulsion. The details of the invention, its objects and advantages are explained hereunder in greater detail in relation to non- limiting exemplary illustrations of the process: EXAMPLES : Example I In the emulsion process, transferred 4.5 kg linear alkyl benzene sulfonic acid, 7 Kg tridecyl alcohol ethoxylate having HLB value 14, 4.5 Kg water in a 100 lit mixing tank having cold water jacket. Mixed the components for 5 mm. Added 31.22 Kg Wacker PDM siloxane (a 40 Cps alpha omega hydroxy terminated polydimethyl siloxane) and mixed the component by single stage stator-rotor homogeniser till particle size dropped to 70nm. Mixing was continued for 25 min to reach particle size 70nm. During mixing, temperature of the components were maintained below 30°C. Then, the emulsion was diluted with 30 kg water and the material maintained at temperature below 30°C. Thereafter neutralized the emulsion with 85% triethanol amine and added 4 ppm kathon CG as a biocide. Total process was completed within one hr. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 1,85,000 Cps Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 70.3 nm particle size of the emulsion having 0.09 polydispersibility. 11 Comparative Example IA A milky white emulsion was prepared by following Example I except non-ionic surfactant replaced by linear alkyl benzene sulfonic add. Maintained temperature below 3O°C like Example I and completed total emulsification process within one hr. Finally neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 70,000 Cps Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 168 nm particle size of the emulsion having 0-40 polydispersibility. The above reveals that due to the use of one emulsifier in the comparative example IA, it was not possible to reach the same particle like example I and higher particle size emulsion in IA compared to I hindered the polymer growth. So, after achieving particle size 168nm even, viscosity of the dimethylpolysiloxane was much less than example I. Also Polydispersibility in IA is higher compared to I. Comparative Example IB A milky white emulsion was prepared by following Example I except non-ionic surfactant replaced by linear alkyl benzene sulfonic add and didn't control temperature during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% tnethanol amine and added 4 ppm Kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 8,000 Cps Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 185 nm particle size of the emulsion having 0.80 polydispersibtlity. 12 Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size tike IA. Example IC A milky white emulsion was prepared by following Example I except the temperature was not maintained within the selective range during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanoi amine and added 4 ppm Kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 80,000 Cps Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 125 nm particle size of the emulsion having 0.80 polydispersibility. Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like I. In the emulsion process, transferred the 3.0 kg linear alkyl benzene sutfonic acid, 3 Kg tridecyl alcohol ethoxylate having HLB value 14, 4.5 Kg water in a 100 lit mixing tank having cold water jacket. Mixed the components for 5 min. Added 31.22 Kg Wacker PDM siloxane (a 40 Cps alpha omega hydroxy terminated polydimethyl siloxane) and mixed the component by single stage stator-rotor homogeniser till particle size dropped to 117 nm. Mixing was continued for 25 min to reach particle size 117 nm. During mixing, temperature of the components were maintained below 30°C. Add 0-22 Kg methyl tnethoxy silane and continued the mixing for 10 min. Then, dilute the emulsion with 31 kg water and maintained the material temperature below 30°C. Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG as a biocide. Total process was completed within one hr. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer 13 three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 8,26,000 Cps Emulsion particle size was measured by Malvern Zetaslzer Nano -ZS. Result showed 116 nm particle size of the emulsion having 0.03 polydispersibility. Comparative Example IIA A milky white emulsion was prepared by following Example n except non-ionic surfactant replaced-by linear alkyl benzene sulfonic acid. Maintained temperature below 30°C like example II and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 1,96,000 Cps Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 185 nm particle size of the emulsion having 0.40 polydispersibility- Since, under this example (comparative example IIA) only one emulsifier was used , it was not possible to reach the same particle like example II and higher particle size emulsion in IIA in compared to II hindered the polymer growth. So, after achieving particle size 185nm even, viscosity of the dimethylpolysiloxane was much less than example II. Comparative Example IIB A milky white emulsion was prepared by following Example n except non-ionic surfactant replaced by linear alkyl benzene sulfonic add and did'nt maintain temperature as per the proposed selective range of the invention during the emulsiflcation process. Temperature was increased to 55°C during emulsiflcation process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer 14 three times by isopropanol. Dried the polymer in vacuum oven, viscosity of the polymer was 87,000 Cps Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 235 nm particle size of the emulsion having 0.70 polydispersibility. Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like 1IA. Example IIC A milky white emulsion was prepared as in Example II except didn't maintain the temperature in the selective range as proposed under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum drier. Viscosity of the polymer was 1,80,000 Cps Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 140 nm particle size of the emulsion having 0.80 polydispersibility. Since, temperature was not maintained during the emulsification process it was not possible to achieve the same fluid viscosity and particle size like II. Example III In the emulsion process, transferred the 4.0 kg linear alkyl benzene sulfonic acid, 7 Kg tndecyl alcohol ethoxytate having HLB value 14, 4.5 Kg water in a 100 lit mixing tank having cold water jacket. Mixed the components for 5 min. Added 31.22 Kg Wacker PDM siloxane (a 40 Cps alpha omega hydroxy terminated polydimethyl siloxane) and mixed the component by single stage stator-rotor homogeniser till partide .size dropped to 117 nm. Mixing was continued for 25 min to reach particle size 117nm. During mixing, temperature of the components were maintained below 30°C. Add 0.22 gm tetraethyl orthosificate and continued the mixing for 10 min. Then, dilute the emulsion with 31 kg 15 water and maintained the material temperature below 30°C. Then, kept the emulsion 5 hr below 25°C. Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 45,26,000 Cps Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 117 nm particle size of the emulsion having 0.09 polydispersibility. Comparative Example IIIA A milky white emulsion was prepared by following Example III except non-ionic surfactant replaced by a mixture of 5.5 kg linear alkyl benzene sulfonic acid and 5.5 Kg Sodium lauryl sulphate. Maintained temperature below 30°C like example III. Then, kept the emulsion 5 hr below 25°C. Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 7,50,000 Cps Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 170 nm particle size of the emulsion having 0.50 polydispersibility. Since, uner this comparative example IIIA two anionic emulsifiers were used , it was not possible to reach the same particle like example III and higher particle size emulsion in IIIA compared to III hindered the polymer growth. So, after achieving particle size 170 nm even, viscosity of the dimethylpolysiloxane was much less than example III. 16 Comparative Example HIB A milky white emulsion was prepared as in Example in except non-ionic surfactant replaced by linear alkyl benzene sulfonic add and didn't maintain temperature during the emulsification process. Temperature was increased to 55°C during emulsification process. Then, kept the emulsion 5 hr at 40-45°C Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr. Separated the polymer by adding - isopropanol in the emulsion -in -3 ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 1,50,000 Cps Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 230 nm particle size of the emulsion having 0.78 polydispersibility. Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like IIIA. Example IIIC A milky white emulsion was prepared by following Example III except didn't maintain temperature within the selective range during the emulsification process. Temperature was increased to 55°C during emulsification process. Then, kept the emulsion 5 hr at 40-45°C. Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 9,73,000 Cps Emulsion particle size was measured by Malvem Zetasizer NartoZS. Result showed 138 nm particle size of the emulsion having 0.80 polydispersibility. Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like HI. 17 Example IV In the emulsion process, transferred the 4.5 kg linear alkyl benzene sulfonic add, 7 Kg tridecyl alcohol ethoxylate having HLB value 14, 4.5 Kg water in a 100 lit mixing tank having cold water jacket. Mixed the components for 5 min. Added 31.22 Kg decamethylcydopentasiloxane and mixed the component by single stage stator-rotor homogemser till particle size dropped to 70nm. Mixing was continued for 25 min to reach particle size 70nm. During mixing, temperature of the components were maintained below 30°C. Then, dilute the emulsion with 30 kg water and maintained the material temperature below 30°C. Neutralized the emulsion with 85% tnethanol amine and added 4 ppm Kathon CG as a biotide. Total process was completed within one hr. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was found 1,05,000 Cps Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 90.5 nm particle size of the emulsion having 0.08 polydispersibility. Comparative Example IV A A milky white emulsion was prepared by following Example IV except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid. Maintained temperature below 30°C like example IV and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% Methanol amine and added 4 ppm Kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was found 24,500 Cps Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 180 nm partide size of the emulsion having 0.30 polydispersibility. 18 Since, under this comparative example IV A only one emulsifiers was used , it was not possible to reach the same particle like example IV and higher particle size emulsion in IV A compared to IV hindered the polymer growth. So, after achieving partide size 180nm even , viscosity of the dimethylpolysiloxane was much less than example IV. Comparative Example IVB A milky white emulsion was prepared by following Example IV except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid and didn't maintain the temperature-within the selected range under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was found 6,000 Cps Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 185 nm particle size of the emulsion having 0.80 polydispersibility. Since, temperature was not maintained during the emulsification process, we even didn't able to achieving the same fluid viscosity and particle size like IV A, Example IV C A milky white emulsion was prepared by following Example IV except didn't maintain temperature as per the selective range proposed under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% tnethanol amine and added 4 ppm Kathon CG. Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was found 7,000 Cps 19 Emulsion particle size was measured by Malvem Zetasizer Nano -2S. Result showed 148.5 nm particle size of the emulsion having 0.80 polydispersibility. Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like IV. Above results clearly demonstrate the findings under the invention that organopolysiloxane emulsion having particle size below is only possible to produce by simple single stage stator-rotor homogeniser when emulsifier mixture comprises atleast one anionic emulsifiers and-atfeast one non-ionic emulstfiers.-Anionic emulsifiers or a mixture of anionic emulsifier can not produce an organopolysiloxane emulsion below 150 nm by using simple homogeniser. According to the present invention, it is also clearly understood that temperature control during emulsion process has an important role to control the particle size, polydispersibility of the emulsion particles and polymer growth rate. It also observed in the examples that when same recipe followed with out controlling the temperature, emulsion produced in the process had worse result in compare to the emulsion produced with same recipe at controlled temperature during the emulsion process. It is observed that low ageing temperature for ultra high polymer also enhances the polymer growth rate in-compare to ageing at higher temperature. Also the above results further demonstrate that particle size below 150 nm has a substantial influence in the faster organopolysiloxane polymer growth in compare of silicone emulsion having particle size more than 150 nm. 20 WE CLAIM: 1. A process for the manufacture of a stable emulsion having particle size up to 150 nanometer comprising: i) providing a selective formulation comprising (a) organopolysiloxane or mixtures thereof in an amount of 20 to 80 % by. wt. (b) water in an amount of 5 to 30 % by wt. (c) selective non-ionic emulsifier(s) having HLB in the range of 10-19 in amounts of 1 to 25% by wt. and (d) selective anionic emulsifier having HLB in the range of 8 - 19 in an amount of 1 to 15 % by. wt.; ii) homogenizing the mix of (i) using any standard homogeniser and maintaining a temperature of up to 50°C preferably in the range of 10-40°C such as to favour organopolysiloxane polymer growth rate or rise in polymer viscosity to at least 20000 cps; and iii) neutralising the emulsion by alkali to a pH range 6-8. 2. A process for the manufacture of a stable emulsion according to claim 1 wherein the emulsifier or a mixture of emulsifiers used have HLB value preferably in the range of 12-15 for low particle organopolysiloxane emulsion 3. A process for the manufacture of stable and faster production of low particle size emulsion having high internal phase oil viscosity comprising: (i) providing a selective formulation comprising providing water in an amount of 5 to 30% of the emulsion, 8 to 30% mixed emulsifiers comprising atleast one anionic emulsifier and at least one non-ionic emulsifier having HLB value of the emulsifiers in the range of 10-19 preferably 12-15 and an organopolysiloxane or mixture of organopolysiloxanes in the range of 20-80% of the emulsion. (II) homogenising the mix with standard homogenizer while maintaining a temperature in the range up to 50°C, preferabily in the range of 20-40°C for a period of 10 minutes to 2 hr depending on the desired characteristics of the emulsion ; (iii) allowing the emulsion to age in the range of 5 to 30°C to favour faster growth of -viscosity of the internal phase oil; (iv) neutralising the emulsion with alkali and finally adding biocide for microbial prevention in the emulsion. 21 4. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 3 wherein for internal oil viscosity of less than 500,000 cps, said neutralizing of the emulsion is carried out immediately after completion of the mixing. 5. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 4 wherein said organopotysiloxanes used comprise low molecular organopolysiioxane preferably alpha omega hydroxy terminated organopolysiloxane; alpha omega alcoxy terminated organopolysiioxane; organocyclopolysiloxanes or mixture thereof . 6. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 5 wherein for branched polysiloxane emulsion a tri functional or tetra functional or a mixture thereof is used together with the organopolystloxanes. 7. A process for the manufacture of a stable emulsion according to anyone of claims 5 to 6 wherein the alpha omega functional end blocked linear organopolysiioxane used are preferably those of the general formula I: where Rl hydrogen and/or a monovalent hydrocarbon group of 1 to 10 carbon atoms and/or a hydroxyl group and/or an alcoxy group having Ito 8 carbon atom and where R, which may differ, is a monovalent hydrocarbon radical. x is an integer from 1 to 100. 8. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 7 wherein the organocyclosiloxanes used herein have the following structure: 22 where R is the independently hydrogen or monovalent hydrocaqrbon groups of 3 to 10 carbon atoms including an alkyl group preferably methyl, ethyl, n-propyl, isopropyl 'n' is an integer of 3 to 10, 9. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 8 wherein the organocydosiloxanes used are preferably selected from octamethylcydotetrasiloxane; decamethylcydopentasiloxane; Dodecamethyl cydohexasiloxane; 1,2,3,4- tetramethyl-l,2,3,4-tetravinyl cydotetrasiloxane; 1,2,3,4- tetramethyl-l,2,3,4-tetraphenyl cyclotetrasiloxane. 10. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 8 wherein the organocydosifoxanes used are branched by way of incorporation of branching units preferably trifunctional silane or tetrafunctional silane or a mixture thereof having the following structure: R-S1 - (O - R)3 III S1 -(O -R)4 IV where R, which may differ, is a monovalent hydro carbon radical. 11. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 10 wherein said anionic emulsifier used comprise anionic surfactant preferably organic sulfonic adds selected from alkyl aryl sulfonic acid; alkyl aryl polyoxyethylene sulphonic add; alkyl sulfonic add and alkyl polyoxyethylene sulfonic add. 12. A process for the manufacture of a stable emulsion according to daim llwherein the structures of sulfonic acids used comprise : R2C6H4SO3H (V) R2C6H4O(C2H4O)mSO3H (VI) R2SO3H (VI) R2O(C2H4O)mSO3H (VIII) Where R2, which may differ, is a monovalent hydrocarbon radial having atleast 6 carbon atom most preferable R2 groups, but not limited to the following groups, are hexyl, octyf, decyi, dodecyl, cetyl, stearyl, myristyl, and oleyl. 'm' is an integer from 1 to 25. 23 13. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 12 wherein the anionic surfactants is used in amounts of 1-15% preferably 3-10% and preferably are selected from octyl benzene sulfonic add; dodecyl benzene sulfonic acid; cetyl benzene sulfonic add; Alpha octyl sulfonic acid; Alpha dodecyl sulfonic add; alpha cetyl sulfonic acid; polyoxyethylene octyl benzene sulfonic add; polyoxyethylene dodecyl benzene sulfonic acid; polyoxyethylene cetyl benzene sulfonic acid; polyoxyethylene octyl sulfonic add; polyoxyethylene dodecyl sulfonic add and polyoxyethylene cetyl sulfonic add. 14. A process for the manufacture of a stable emulsion according to anyone of claims 1 to 13 wherein said non-ionic emulsifiers used comprise non-ionic surfactants preferably in an amount of 1 to 25% more preferably, 5- 20% and selected from polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ethers and polyoxyalkylene sorbitan esters preferably selected from polyethylene glycol octyl ether; Polyethylene glycol lauryl ether; Polyethylene glycol tridecyl ether; Polyethylene glycol cetyl ether; Polyethylene glycol stearyl ether; polyethylene glycol nonyiphenyl ether; polyethylene glycol dodecylphenyl ether; polyethylene glycol cetylphenyl ether; polyethylene glycol staerylphenyl ether; polyethylene glycol sorbitan mono stearate and polyethylene glycol sorbitan mono oleate. 15. A process for the manufacture of a stable emulsion having particle size up to 150 nanometer substantially as hereindescribed and illustrated with reference to the accompanying examples. Dated this 2nd day of February 2005 Anjan Sen Of Anjan Sen & Associates (Applicant's Agent) 24 A process for making stable high viscosity organopolysiloxane emulsion having particle size up to 150 nanometer and in particular to an emulsion-polymerization process involving a simple and cost-effective fester completion of emulsification of organopolysiloxane by using standard homogenizer and also subsequent polymerization of the organopolysiloxane at controlled temperature. The process involves a selective combination of non-ionic emulsifier together with an at least one anionic emulsifier to achieve the desired particle size emulsion. Importantly, the selective mix of non-ionic and anionic emulsifiers having HLB value of the mixture near to 12-15 and maintaining a temperature of up to 50°C is found to favour obtaining low particle stable emulsion with any standard homogeniser avoiding need for high pressure homogenizing.

Full Text

FIELD OF INVENTION
The present invention relates to a process for making stable high viscosity organopolysiloxane emulsion and in particular to an emulsion-polymerisation process involving a simple and cost-effective faster completion of emulsification of organopolysiloxane and also subsequent polymerisation of the organopolysiloxane. The process is directed to be simple and cost-effective and can be easily adapted for emulsion production of stable organopolysiloxane emulsions for diverse beneficial end use and application. Importantly, the silicone emulsion produced by the process of the invention is In the range of average (i.e D50 value) up to 150 nanometer with a very narrow particle size distribution which is highly stable and found to have advantageous and beneficial diverse use in various end applications including in personal care, textile -, rubber, paper and other like applications/uses.
BACKGOUND ART
It is well known to provide organopolysiloxane emulsions with varying partide sizes to suit different end applications.
Organopolysiloxane emulsions having low partide size prepared by emulsion polymerisation process are generally preferred which could provide the desired faster and simple production with focus on emulsion stability and quicker organipotysiloxane polymerisation during emulsification. Such emulsion polymerised products are known to be prepared by various methods. For examples, JP-B 34-2041 disclosed a polymerisation process wherein a strong acid and strong base are used as a polymerisation catalyst. US 3697469 used ion-exchange resin as polymerisation catalyst. US 3360491; US 3697469; US 4228054; US 5726270; US 5817714; US 5895794; US 5925469 and US 6071975 disclosed polymerisation using alkyl benzene sulphonic acid, alkyl naphthalene sulphonic acid, aliphatic sulphonic acid, silylalkyl sulphonic acid, aliphatically substituted dipneny! ether sulfonic add or alkyl hydrogen sulphates as a catalyst. However all these processes take longer time for polymerisation and completion of the emulsion making process. Most of the processes are also only restricted to cydosiloxanes.
US 6245852, discloses a process of preparation of organopolysiloxane emulsion having improved stability within a short time. The process comprising the steps of emulsifying and dispersing low molecular weight organopolysiloxane in water in presence of essentially at least one anionic surfactant selected from organic sulphonic acid and organic sulphates by using a high pressure homogeniser with a operating pressure range
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from 700 to 3000 Kg/cm2 and produce an initial emulsion having partide size up to 300 nm, followed by allowing the emulsion for polymerisation and subsequent neutralization of the emulsion at the end.
As would be dearly apparent from the disclosure in US'852 the process necessarily involves the use of very sophisticated and highly capital-intensive machine system for reduction of emulsion time in the emulsion polymerisation process. Also since the process uses a high-pressure system, the emulsion machine needs lot of control system for working safely in the production area.
Thus while the process according to the above US'852 stated to reduce the time of emuIsification by using a sophisticated high pressure homogeniser but the said process does not seem to address the requirement for faster completion of the total emulsion process including faster polymerisation. Emulsion polymerisation process usually consists of emulsification of organopolysiloxane and subsequent polymerisation of the organopolysifoxane. So, faster emulsification on its own is not sufficient to complete emulsion polymerisation process or make the process faster. Therefore, it is also important to make faster polymerisation in emulsion polymerisation processes.
The above state of art reveals the need to develop processes of making faster the total emulsion polymerisation process .Also the reduction in the partide size which is found to be of relevance for variety of end use/applications involving a faster emulsion polymerisation process is desirable for wide scale commercial manufacturing and use of such emulsions for diverse applications.
OBJECTS OF THE INVENTION
It is thus the basic object of the invention to provide a process of making silicone emulsion having partide size up to 150 nm which would on one hand be simple, cost-effective and fast and on the other hand would provide a simple and cost effective alternative to the need for complex machinery for faster emulsification and also reduce the polymerisation time in the emulsion polymerisation process and thus can be readily adapted for large scale cost-effective commercial manufacture of such low particle size silicone emulsions for diverse applications such as in personnel care and the like.
Another object of the invention is directed to provide a simple process of making silicone emulsion having partide size up to 150 nanometer, which would reduce the total "emulsion polymerisation time" significantly.
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Another object of the present invention Is directed to a process for the manufacture of silicone emulsion having particle size up to 150 nanometer which would assist faster polymer growth of the - organopolysiloxane during emulsion process.
Yet further object of the present invention is directed to making stable silicone emulsion involving standard homogenizer having particle size up to 150 nanometer by way of a selective emulsion formulation and avoiding the need for complex machinery to reduce the emulsification and polymerisation stages in such manufacture of silicone emulsion.
SUMMARY OF THE INVENTION
Thus according to the basic aspect of the present invention, there is provided a process for the manufacture of a stable emulsion having particle size up to 150 nanometer comprising:
i) providing a selective formulation comprising (a) organopolysiloxane or mixtures thereof in an amount of 20 to 80 % by .wt (b) water in an amount of 5 to 30 % by wt. (c) selective non-ionic emulsifier(s) having HLB in the range of 10-19 in amounts of 1 to 25% by wt. and (d) selective anionic emulsifier having HLB In the range of 8 - 19 in an amount of 1 to 15 % by. wt.;
ii) homogenizing the mix of (i) using standard homognizer and maintaining a temperature of up to 50°C preferably In the range of 10-40°C such as to favour organopolysiloxane polymer growth rate or rise in polymer viscosity to at least 20000 cps; and Hi) neutralising the emulsion by alkali to a pH range 6-8.
Importantly, it is found by way of the invention that one of the critical aspects which enable obtaining of emulsion up to 150 nanometer following a simple process is the selective use of a combination of non-ionic emulsifier together with an atleast one anionic emulsifier to achieve the desired particle sized emulsion. For organopolysiloxane emulsion, HLB value near to 12-15 is found to be the optimum value of the emulsifier or a mixture of emulsifiers, which help to make low particle emulsion. It is also found that a mixture of non-ionic and anionic emulsifiers having HLB value of the mixture near to 12-15 shows optimum combinations to make low particle stable emulsion with a standard homogenizer.
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Also the quantity of the emulsifiers used in the above selective formulation have selective contribution to make the emulsion stable. In particular, in the above process of making low particle organopolysiloxane emulsion, the emulsion is also stabilized by use of surfactants having critical HLB values that help to make faster low particle emulsion by using standard homogenizer without need for complex ultra high pressure homogeniser.
Moreover, it is also important to control temperature for achieving low particle size with narrow distribution of the particle. Advantageously making of the emulsion with a temperature up to 50°C, is found to further help faster polymer growth of organopolysiloxane in the emulsion. Temperature during the emulsion preparation is found to have great importance not only to control the particle size but also control the particle size distribution and faster growth of internal phase viscosity.
In the above process of invention, preferably, a suitable biocide is added for preventing microbial growth.
Since, the process uses a mixture of surfactants for making low particle organopolysiloxane by using standard homogenizer, it is important to maintain the selective formulation involving making a proper recipe of surfactants mix and recipe of organopolisiloxane and surfactants to achieve particle size up to 150 nanometer.
In accordance with a preferred aspect the above process for the manufacture of stable and faster production of low particle size emulsion having high internal phase oil viscosity comprises of:
(i) providing a selective formulation comprising providing water in an amount of 5 to 30% of the emulsion, 8 to 30% mixed emulsifiers comprising atleast one anionic emulsifier and at least one non-ionic emulsifier having HLB value of the emulsifiers in the range of 10-19 and an organopolysiloxane or mixture of organopolysiloxanes in the range of 20-80% of the emulsion.
(ii) homogenising the mix with standard homogenizer while maintaining a temperature in the range up to 50°C, preferably in the range of 20-40°C for a period of 10 minutes to 2 hr depending on the desired characteristics of the emulsion ;
(iii) allowing the emulsion to age in the range of 5 to 30°C to favour faster growth of -viscosity of the internal phase oil;
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(iv) neutralising the emulsion with alkali and finally adding biocide for microbial prevention in the emulsion.
The temperature of the material can be controlled during homogenising by passing cool water. In the above process the desired ageing temperature for growth of very high internal oil viscosity is in the range of 5 to 30 °C Generally, 1 to 12 hr is required to achieve very high viscosity internal phase oil viscosity. If internal oil viscosity is needed less than 500,000 cps, then neutralizing of the emulsion is carried out immediately after completion of mixing. Moreover, it is found that desired mixing time also varies for target viscosity of the polymer and distribution of the particles-in the emulsion.
Neutralise the emulsion after completion of dilution steps. Generally, water-soluble inorganic alkali hydroxide or organic amine alcohol is used for neutralization. Preferably, sodium hydroxide or potassium hydroxide or triethanol amine is used to neutralise the
emulsion.
According to the present invention, one of the critical parameters include the selection of the right emulsifiers and combination of the emulsifiers to achieve the desired low particle size emulsion. The present invention thus achieves producing low particle emulsion in a simple way where selective emulsifier combination and temperature of emuIsification and polymerisation which have a critical part to make the process simple and avoiding the use of cost extensive and complex machinery.
DETAILED DESCRIPTION OF THE INVENTION
The invention thus provides a process for making stable low particle emulsion from a low molecular organopolysiloxane or a mixture of organopolysiloxane, Organopolysiloxanes referred herein for the purpose of the invention include low molecular organopolysiloxane such as alpha omega hydroxy terminated organopotysiloxane; alpha omega alcoxy terminated organopolysiloxane; organocyclopolysiloxanes or mixture thereof...
In case of branched potysiloxane emulsion a tri functional or tetra functional or a mixture thereof is used together with above organopolysiloxanes.
The alpha omega functional end blocked linear organopolysiloxane used herein are preferably those of the general formula I:
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Where R1 hydrogen and/or a monovalent hydrocarbon group of 1 to 10 carbon atoms and/or a hydroxyl group and/or an alcoxy group having it 8 carbon atom. Examples of R1 as a monovalent hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl. Isobutyl, tert-butyl, n-pentyl, Isopentyl, neopentyl, tertpentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethyl pentyl, nonyl such as n- nonyl, decyl such as n decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl and methyl cyclohexyl, aryl such as phenyl, napthyl, anthryl and phenanthryl ; alkylaryl such as o-, m-, p-totyl, xylyl and ethylphenyl; aralkyl, such as benzyl, a and ß-phenylathyl; of which methyl, ethyl, n-propyl, isopropyl are preferred and methyl is particularly preferred. Example of R1 as alcoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or a phenoxy group but not limited to the said groups.
Where R, which may differ, is a monovalent hydrocarbon radical. Examples of R are alkyl radicals, such as methyl, ethyl, n-propyl, iso propyl, n-butyl, Isobutyl, tertbutyl, n-pentyl, Isopentyl, neopentyl, tertpentyl, hexyl such as n-hexyl, heptyl, such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethyl pentyl, nonyl such as n- nonyl, decyl such as n decyl, dodecvl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl and methyl cyclohexyl, aryl such as phenyl, napthyl, anthryl and phenanthryl ; alkylaryl such as o-, m-, p-totyl, xylyl and ethylphenyl; aralkyl, such as benzyl, a and ß-phenylathyl, of which methyl, ethyl, n-propyl, isopropyl are preferred and methyl is particularly preferred.
x is an integer from 1 to 100.
The organocyclosiloxanes used herein have the following structure:
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Where R is the independently hydrogen or monovalent hydrocaqrbon groups of 3 to 10
carbon atoms inducing an alkyl group such methyl, ethyl, n-propyl, iso propyl, n-butyl.
Isobutyl, tert-butyl, n-pentyl, Isopentyl, neopentyl, tert pentyl, hexyl such as n-hexyl,
heptyl such as n-heptyl, octyl such as n-octyl and fsooctyl such as 2,2,4-trimethyl
pentyl, nonyl such as n- nonyl, decyl such as n decyl, dodecyl such as n-dodecyl,
octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl, such as
cyclopentyl, cyclohexyl, cycloheptyl and methyl cyclohexyl, aryl such as phenyl, napthyl,
anthryl and phenanthryl ; aIkylaryl, such as o-, m-, p-totyl, xylyl and ethylphenyl;
aralkyl, such as benzyl, a and ß-phenylathyl, of which methyl, ethyl, n-propyl, isopropyl
are preferred and methyl is particularly preferred. 'n' is an integer of 3 to 10. Most
preferred organocyclosiloxanes are octamethylcydotetrasiloxane;
decamethylcyclopentasiloxane; Dodecamethyl cydohexasiloxane; 1,2,3,4- tetramethyl-1,2,3,4-tetravinyl cyclotetrasiloxane; 1,2,3,4- tetramethyl-l,2,3,4-terraphenyl cyclotetrasiloxane.
Organopolysiloxane used according to the present invention may be branched by way of incorporation of branching units. Branching units may be introduced to improve the film forming behaviour of organopolysiloxane. Branching unit may be trifunctional silane or tetrafunctional silane or a mixture thereof. Trifuntional silanes (III) and tetrafunctional si lanes (IV) have the following strucrue:
R-S1 -(O - R)3 . . III S1 -(O -R)4 IV
Where R, which may differ, is a monovafent hydro carbon radical. Examples of R are alkyl radicals, such as methyl, ethyl, n-propyl, iso propyl, n-butyl. Isobutyl, tert-butyl, n-pentyl, Isopentyl, neopentyl, tert pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and isooctyf such as 2,2,4-trimethyl pentyl, nonyl such as n- nonyl, decyl such as n decyl, dodecyl such as n-dodecyl, octadecyl such as n-octadecyl; alkenyl such as vinyl and allyl, cycloalkyl, such as cydopentyl, cyclohexyl, cydoheptyl and
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methyl cyclohexyl, aryl such as phenyl, napthyl, anthryt and phenanthryl ; alkytaryl, such as o-, nv, p-totyl, xylyl and ethyfphenyl; aralkyl, such as benzyl, a and ß-phenylathyf, of which methyl, ethyl, n-propyl, isopropyl are preferred and methyl is particularly preferred. Depending on the desired requirement of branching of the organopolysiioxane, branching units are adding during the emulsification process. 0.1 to 5% branching units of the emulsion is useful to make an emulsion containing organopolysiioxane having highly branched structure. Quantity used in the emulsion must be controlled carefully, otherwise gellation of the polymer may occur during emulsion process and emulsion destabilizes. If branched polysiloxane is not required, the silane addition is avoided.
According to the present invention, anionic emulsifier has an important role for simple and faster emulsion process of high internal phase viscosity emulsion having particle size up to 150 nm. Anionic surfactant is selected from organic sulfonic adds. Most common sulfonic a acids used in the present process are alkyl aryl sulfonic add; alkyl aryl polyoxyethylene sulphonic acid; alkyl sulfonic add and alkyl polyoxyethylene sulfonic acid. Structures of sulfonic adds are as below:
R2 C6H4 SO3 H (V) R2 C6H4 O (C2H4O) m SO3 H (VI)
R2SO3H (VI) R2O(C2H4O)mSO3H (VIII)
Where R2, which may differ, is a monovalent hydrocarbon radial having atfeast 6 carbon atom. Most preferable R2 groups, but not limited to the following groups, are hexyl, octyl, decyl, dodecyl, cetyl, stearyl, myristyl, and oleyl. 'm' is an integer from 1 to 25. Most preferable anionic surfactants used in the present inventions are octyl benzene sulfonic acid; dodecyl benzene sulfonic add; cetyl benzene sulfonic acid; Alpha octyl sulfonic acid; Alpha dodecyl sulfonic acid; alpha cetyl sulfonic add; polyoxyethylene octyl benzene sulfonic acid; polyoxyethylene dodecyl benzene sulfonic add; polyoxyethylene cetyl benzene sulfonic add; polyoxyethylene octyl sulfonic add; polyoxyethylene dodecyl sulfonic acid and polyoxyethylene cetyl sulfonic acid. Generally, 1 to 15% anionic surfactant is used in the present emulsion processing process. Preferably, 3- 10% anionic surfactant is used in the present emulsion to get the optimum result. Anionic surfactant has a dual role in the present emulsion process. Anionic surfactant acts as a condensation/ring opening catalyst in together with as a surfactant for emulsion making. Thus, by using anionic emulsifier, process doesnt need any catalyst for polymer growth of organopolysiloxane during emulsion process.
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It is also observed according to the present invention, at least one additional emulsifier together with anionic emulsifier is essential alongwith the controlled temperature of emulsification and polymerisation for making the emulsion in a simple faster way. It is specially found by way of the present invention that at least one non-ionic emulsifier in together with anionic surfactant helps for faster simple emulsion production. Non-ionic emulsifiers having HLB value in between 10-19 are suitable to make the emulsion process simpler. Most useful surfactants of this category are polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ethers and polyoxyalkylene sorbitan esters. Some useful surfactants having HLB value in between 10-19 are polyethylene glycol octyl ether; Polyethylene glycol lauryl ether; Polyethylene glycol tridecyl ether;-Polyethylene glycol cetyl ether; Polyethylene glycol stearyl ether; polyethylene glycol nonylphenyl ether; polyethylene glycol dodecylphenyl ether; polyethylene glycol cetylphenyl ether; polyethylene glycol staerylphenyl ether; polyethylene glycol sorbitan mono stearate and polyethylene glycol sorbitan mono oleate. Non-ionic surfactant having HLB value in-between 10-19 has a great importance in the present invention to make process more simpler.
Generally, 1 to 25% nonionic surfactant is used in the emulsion processing process. Preferably, 5- 20% nonionic surfactant is used in the present emulsion to get the optimum result. It is well known in the art that Surfactant(s) having HLB value in-between 12-15 is useful to make organopolysiloxane emulsion by using standard homogenizer in shorter period and it is also well known to use a mixture of surfactants that have HLB value in-between 12-15 to get an emulsion of organopolysiloxane having long stability.
According to the present invention, it is also important to provide selective formulation of the emulsifiers in a ratio such that the mix has HLB value preferably in-between 12-15 with at least one anionic surfactant and one non-ionic surfactant in the mixture.
An important aspect in the present emulsion process is the selective use of a mixture of surfactants, which not only make stable emulsion in faster way by using standard homogenizer but also to produce a low particle emulsion up to 150 nm. Particle size of the emulsion is highly dependent on the ratio of anionic and non-ionic emulsifier (s) having HLB value of the mixture in-between 12-15.
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It is also well known of the art that polymer growth rate of the orgaoplylsiloxane is also highly dependent on the particle size of the emulsion. So polymer growth rate of the organopolysiloxane during the emulsion process is much higher compared to organopolysiloxane emulsion having particle size above 150 nm.
According to the present invention, the temperature during the emulsion process has an important role to control the particle size of the emulsion, distribution of the particle size distribution (i.e polydispersibility, value 1 is poor and value 0.1 or less than 0.1 is very good) and polymer growth rate of the organopolysiloxane during emulsion process. It is also observed in the present emulsion process, particle size, and distribution of the particle and polymer viscosity become out of control if temperature is not maintained within a selective limit. It is found a significant deviation of final emulsion specifications take place where temperature control is not within the said selective range even though emulsion is produced by using an optimum combination of emulsifiers with a proper combination of fluid to emulsifier. Maintaining a temperature below of 50°C is useful to control the particle size, distribution of particle in the emulsion and polymer growth rate of the organopolysiloxane in the emulsion.
Further, it is also important to control the emulsion temperature during the ageing of the emulsion in case of ultra high (more than 2 million cps) organopolysiloxane polymer in the emulsion. A temperature below of 30°C is useful to make the polymerisation faster in case of ultra high organopolysiloxane polymer required in the inner phase of the emulsion. Emulsion polymerisation is significantly dropped if temperature is more than 30°C during ageing process, even difficult to achieve ultra high viscosity at high temperature. So, it is dear that faster completion of emulsion process for high organopolysiloxane polymer to ultra high polymer emulsion by emulsion polymerisation process, temperature has great role during the emulsion making process and during the ageing process. So, according to the present process, a combination of mixed emulsifiers having HLB value 12 -15 (contains atleast one anionic emulsifier and atleast one nonionic emulsifiers) in together with temperature control during emulsion making and during ageing helps the emulsion process useful to produce emulsion below 150 nm by standard homogenizer.
The components are homogenised by standard homogenizers. Useful standard shear stirring system may be used such as conventional single stage stator-rotor homogeniser or other types of standard homogeniser which are used in the normal homogenising process. Homogenising can be carried out in batch or continuous depend on the design of emulsion process. From the capital investment point of view, it is also clear that the
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process also needs a economic homogenising system and avoids the use of the expensive very high pressure homogenising system.
Importantly, it is found by way of the present invention that the emulsion obtained following the process of the invention was highly stable .In particular, tests revealed that when the emulsion obtained was put in the oven in the range of 45 to 60°C and most preferably, 55°C for one month, no creaming or separation or deformation in the emulsion was observed. A study of 12 hr freeze/thaw cycles in 10°C/50°C temperature for one month also showed no creaming or separation or deformation in the emulsion.
The details of the invention, its objects and advantages are explained hereunder in greater detail in relation to non- limiting exemplary illustrations of the process:
EXAMPLES : Example I
In the emulsion process, transferred 4.5 kg linear alkyl benzene sulfonic acid, 7 Kg tridecyl alcohol ethoxylate having HLB value 14, 4.5 Kg water in a 100 lit mixing tank having cold water jacket. Mixed the components for 5 mm. Added 31.22 Kg Wacker PDM siloxane (a 40 Cps alpha omega hydroxy terminated polydimethyl siloxane) and mixed the component by single stage stator-rotor homogeniser till particle size dropped to 70nm. Mixing was continued for 25 min to reach particle size 70nm. During mixing, temperature of the components were maintained below 30°C. Then, the emulsion was diluted with 30 kg water and the material maintained at temperature below 30°C. Thereafter neutralized the emulsion with 85% triethanol amine and added 4 ppm kathon CG as a biocide. Total process was completed within one hr.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 1,85,000 Cps
Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 70.3 nm particle size of the emulsion having 0.09 polydispersibility.
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Comparative Example IA
A milky white emulsion was prepared by following Example I except non-ionic surfactant replaced by linear alkyl benzene sulfonic add. Maintained temperature below 3O°C like Example I and completed total emulsification process within one hr. Finally neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 70,000 Cps
Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 168 nm particle size of the emulsion having 0-40 polydispersibility.
The above reveals that due to the use of one emulsifier in the comparative example IA, it was not possible to reach the same particle like example I and higher particle size emulsion in IA compared to I hindered the polymer growth. So, after achieving particle size 168nm even, viscosity of the dimethylpolysiloxane was much less than example I. Also Polydispersibility in IA is higher compared to I.
Comparative Example IB
A milky white emulsion was prepared by following Example I except non-ionic surfactant replaced by linear alkyl benzene sulfonic add and didn't control temperature during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% tnethanol amine and added 4 ppm Kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 8,000 Cps
Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 185 nm particle size of the emulsion having 0.80 polydispersibtlity.
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Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size tike IA.
Example IC
A milky white emulsion was prepared by following Example I except the temperature was not maintained within the selective range during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanoi amine and added 4 ppm Kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 80,000 Cps
Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 125 nm particle size of the emulsion having 0.80 polydispersibility.
Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like I.
In the emulsion process, transferred the 3.0 kg linear alkyl benzene sutfonic acid, 3 Kg tridecyl alcohol ethoxylate having HLB value 14, 4.5 Kg water in a 100 lit mixing tank having cold water jacket. Mixed the components for 5 min. Added 31.22 Kg Wacker PDM siloxane (a 40 Cps alpha omega hydroxy terminated polydimethyl siloxane) and mixed the component by single stage stator-rotor homogeniser till particle size dropped to 117 nm. Mixing was continued for 25 min to reach particle size 117 nm. During mixing, temperature of the components were maintained below 30°C. Add 0-22 Kg methyl tnethoxy silane and continued the mixing for 10 min. Then, dilute the emulsion with 31 kg water and maintained the material temperature below 30°C. Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG as a biocide. Total process was completed within one hr.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer
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three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 8,26,000 Cps
Emulsion particle size was measured by Malvern Zetaslzer Nano -ZS. Result showed 116 nm particle size of the emulsion having 0.03 polydispersibility.
Comparative Example IIA
A milky white emulsion was prepared by following Example n except non-ionic surfactant replaced-by linear alkyl benzene sulfonic acid. Maintained temperature below 30°C like example II and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 1,96,000 Cps
Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 185 nm particle size of the emulsion having 0.40 polydispersibility-
Since, under this example (comparative example IIA) only one emulsifier was used , it was not possible to reach the same particle like example II and higher particle size emulsion in IIA in compared to II hindered the polymer growth. So, after achieving particle size 185nm even, viscosity of the dimethylpolysiloxane was much less than example II.
Comparative Example IIB
A milky white emulsion was prepared by following Example n except non-ionic surfactant replaced by linear alkyl benzene sulfonic add and did'nt maintain temperature as per the proposed selective range of the invention during the emulsiflcation process. Temperature was increased to 55°C during emulsiflcation process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer
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three times by isopropanol. Dried the polymer in vacuum oven, viscosity of the polymer was 87,000 Cps
Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 235 nm particle size of the emulsion having 0.70 polydispersibility.
Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like 1IA.
Example IIC
A milky white emulsion was prepared as in Example II except didn't maintain the temperature in the selective range as proposed under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum drier. Viscosity of the polymer was 1,80,000 Cps
Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 140 nm particle size of the emulsion having 0.80 polydispersibility.
Since, temperature was not maintained during the emulsification process it was not possible to achieve the same fluid viscosity and particle size like II.
Example III
In the emulsion process, transferred the 4.0 kg linear alkyl benzene sulfonic acid, 7 Kg tndecyl alcohol ethoxytate having HLB value 14, 4.5 Kg water in a 100 lit mixing tank having cold water jacket. Mixed the components for 5 min. Added 31.22 Kg Wacker PDM siloxane (a 40 Cps alpha omega hydroxy terminated polydimethyl siloxane) and mixed the component by single stage stator-rotor homogeniser till partide .size dropped to 117 nm. Mixing was continued for 25 min to reach particle size 117nm. During mixing, temperature of the components were maintained below 30°C. Add 0.22 gm tetraethyl orthosificate and continued the mixing for 10 min. Then, dilute the emulsion with 31 kg
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water and maintained the material temperature below 30°C. Then, kept the emulsion 5 hr below 25°C. Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 45,26,000 Cps
Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 117 nm particle size of the emulsion having 0.09 polydispersibility.
Comparative Example IIIA
A milky white emulsion was prepared by following Example III except non-ionic surfactant replaced by a mixture of 5.5 kg linear alkyl benzene sulfonic acid and 5.5 Kg Sodium lauryl sulphate. Maintained temperature below 30°C like example III. Then, kept the emulsion 5 hr below 25°C. Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 7,50,000 Cps
Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 170 nm particle size of the emulsion having 0.50 polydispersibility.
Since, uner this comparative example IIIA two anionic emulsifiers were used , it was not possible to reach the same particle like example III and higher particle size emulsion in IIIA compared to III hindered the polymer growth. So, after achieving particle size 170 nm even, viscosity of the dimethylpolysiloxane was much less than example III.
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Comparative Example HIB
A milky white emulsion was prepared as in Example in except non-ionic surfactant replaced by linear alkyl benzene sulfonic add and didn't maintain temperature during the emulsification process. Temperature was increased to 55°C during emulsification process. Then, kept the emulsion 5 hr at 40-45°C Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr.
Separated the polymer by adding - isopropanol in the emulsion -in -3 ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 1,50,000 Cps
Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 230 nm particle size of the emulsion having 0.78 polydispersibility.
Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like IIIA.
Example IIIC
A milky white emulsion was prepared by following Example III except didn't maintain temperature within the selective range during the emulsification process. Temperature was increased to 55°C during emulsification process. Then, kept the emulsion 5 hr at 40-45°C. Neutralized the emulsion with 85% triethanol amine after 5 hr ageing and added 4 ppm Kathon CG as a biocide. Total process including ageing was completed within six hr.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was 9,73,000 Cps
Emulsion particle size was measured by Malvem Zetasizer NartoZS. Result showed 138 nm particle size of the emulsion having 0.80 polydispersibility.
Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like HI.
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Example IV
In the emulsion process, transferred the 4.5 kg linear alkyl benzene sulfonic add, 7 Kg tridecyl alcohol ethoxylate having HLB value 14, 4.5 Kg water in a 100 lit mixing tank having cold water jacket. Mixed the components for 5 min. Added 31.22 Kg decamethylcydopentasiloxane and mixed the component by single stage stator-rotor homogemser till particle size dropped to 70nm. Mixing was continued for 25 min to reach particle size 70nm. During mixing, temperature of the components were maintained below 30°C. Then, dilute the emulsion with 30 kg water and maintained the material temperature below 30°C. Neutralized the emulsion with 85% tnethanol amine and added 4 ppm Kathon CG as a biotide. Total process was completed within one hr.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was found 1,05,000 Cps
Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 90.5 nm particle size of the emulsion having 0.08 polydispersibility.
Comparative Example IV A
A milky white emulsion was prepared by following Example IV except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid. Maintained temperature below 30°C like example IV and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% Methanol amine and added 4 ppm Kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was found 24,500 Cps
Emulsion particle size was measured by Malvern Zetasizer Nano -ZS. Result showed 180 nm partide size of the emulsion having 0.30 polydispersibility.
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Since, under this comparative example IV A only one emulsifiers was used , it was not possible to reach the same particle like example IV and higher particle size emulsion in IV A compared to IV hindered the polymer growth. So, after achieving partide size 180nm even , viscosity of the dimethylpolysiloxane was much less than example IV.
Comparative Example IVB
A milky white emulsion was prepared by following Example IV except non-ionic surfactant replaced by linear alkyl benzene sulfonic acid and didn't maintain the temperature-within the selected range under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% triethanol amine and added 4 ppm Kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was found 6,000 Cps
Emulsion particle size was measured by Malvem Zetasizer Nano -ZS. Result showed 185 nm particle size of the emulsion having 0.80 polydispersibility.
Since, temperature was not maintained during the emulsification process, we even didn't able to achieving the same fluid viscosity and particle size like IV A,
Example IV C
A milky white emulsion was prepared by following Example IV except didn't maintain temperature as per the selective range proposed under the invention during the emulsification process. Temperature was increased to 55°C during emulsification process and completed total emulsification process within one hr. Finally Neutralized the emulsion with 85% tnethanol amine and added 4 ppm Kathon CG.
Separated the polymer by adding isopropanol in the emulsion in a ratio 3:1 of isopropanol to emulsion. Drained out the isopropanol layer and washed the fluid layer three times by isopropanol. Dried the polymer in vacuum oven. Viscosity of the polymer was found 7,000 Cps
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Emulsion particle size was measured by Malvem Zetasizer Nano -2S. Result showed 148.5 nm particle size of the emulsion having 0.80 polydispersibility.
Since, temperature was not maintained during the emulsification process, it was not possible to achieve the same fluid viscosity and particle size like IV.
Above results clearly demonstrate the findings under the invention that organopolysiloxane emulsion having particle size below is only possible to produce by simple single stage stator-rotor homogeniser when emulsifier mixture comprises atleast one anionic emulsifiers and-atfeast one non-ionic emulstfiers.-Anionic emulsifiers or a mixture of anionic emulsifier can not produce an organopolysiloxane emulsion below 150 nm by using simple homogeniser. According to the present invention, it is also clearly understood that temperature control during emulsion process has an important role to control the particle size, polydispersibility of the emulsion particles and polymer growth rate. It also observed in the examples that when same recipe followed with out controlling the temperature, emulsion produced in the process had worse result in compare to the emulsion produced with same recipe at controlled temperature during the emulsion process. It is observed that low ageing temperature for ultra high polymer also enhances the polymer growth rate in-compare to ageing at higher temperature. Also the above results further demonstrate that particle size below 150 nm has a substantial influence in the faster organopolysiloxane polymer growth in compare of silicone emulsion having particle size more than 150 nm.
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WE CLAIM:
1. A process for the manufacture of a stable emulsion having particle size up to 150
nanometer comprising:
i) providing a selective formulation comprising (a) organopolysiloxane or
mixtures thereof in an amount of 20 to 80 % by. wt. (b) water in an amount of 5 to 30 % by wt. (c) selective non-ionic emulsifier(s) having HLB in the range of 10-19 in amounts of 1 to 25% by wt. and (d) selective anionic emulsifier having HLB in the range of 8 - 19 in an amount of 1 to 15 % by. wt.;
ii) homogenizing the mix of (i) using any standard homogeniser and maintaining a temperature of up to 50°C preferably in the range of 10-40°C such as to favour organopolysiloxane polymer growth rate or rise in polymer viscosity to at least 20000 cps; and
iii) neutralising the emulsion by alkali to a pH range 6-8.
2. A process for the manufacture of a stable emulsion according to claim 1 wherein
the emulsifier or a mixture of emulsifiers used have HLB value preferably in the
range of 12-15 for low particle organopolysiloxane emulsion
3. A process for the manufacture of stable and faster production of low particle size
emulsion having high internal phase oil viscosity comprising:
(i) providing a selective formulation comprising providing water in an amount of 5 to 30% of the emulsion, 8 to 30% mixed emulsifiers comprising atleast one anionic emulsifier and at least one non-ionic emulsifier having HLB value of the emulsifiers in the range of 10-19 preferably 12-15 and an organopolysiloxane or mixture of organopolysiloxanes in the range of 20-80% of the emulsion.
(II) homogenising the mix with standard homogenizer while maintaining a temperature in the range up to 50°C, preferabily in the range of 20-40°C for a period of 10 minutes to 2 hr depending on the desired characteristics of the emulsion ;
(iii) allowing the emulsion to age in the range of 5 to 30°C to favour faster growth of -viscosity of the internal phase oil;
(iv) neutralising the emulsion with alkali and finally adding biocide for microbial prevention in the emulsion.
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4. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 3 wherein for internal oil viscosity of less than 500,000 cps, said neutralizing
of the emulsion is carried out immediately after completion of the mixing.
5. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 4 wherein said organopotysiloxanes used comprise low molecular
organopolysiioxane preferably alpha omega hydroxy terminated
organopolysiloxane; alpha omega alcoxy terminated organopolysiioxane;
organocyclopolysiloxanes or mixture thereof .
6. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 5 wherein for branched polysiloxane emulsion a tri functional or tetra
functional or a mixture thereof is used together with the organopolystloxanes.
7. A process for the manufacture of a stable emulsion according to anyone of claims
5 to 6 wherein the alpha omega functional end blocked linear organopolysiioxane
used are preferably those of the general formula I:

where Rl hydrogen and/or a monovalent hydrocarbon group of 1 to 10 carbon atoms and/or a hydroxyl group and/or an alcoxy group having Ito 8 carbon atom and where R, which may differ, is a monovalent hydrocarbon radical. x is an integer from 1 to 100.
8. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 7 wherein the organocyclosiloxanes used herein have the following structure:
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where R is the independently hydrogen or monovalent hydrocaqrbon groups of 3 to 10 carbon atoms including an alkyl group preferably methyl, ethyl, n-propyl, isopropyl 'n' is an integer of 3 to 10,
9. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 8 wherein the organocydosiloxanes used are preferably selected from
octamethylcydotetrasiloxane; decamethylcydopentasiloxane; Dodecamethyl
cydohexasiloxane; 1,2,3,4- tetramethyl-l,2,3,4-tetravinyl cydotetrasiloxane;
1,2,3,4- tetramethyl-l,2,3,4-tetraphenyl cyclotetrasiloxane.
10. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 8 wherein the organocydosifoxanes used are branched by way of
incorporation of branching units preferably trifunctional silane or tetrafunctional
silane or a mixture thereof having the following structure:
R-S1 - (O - R)3 III S1 -(O -R)4 IV
where R, which may differ, is a monovalent hydro carbon radical.
11. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 10 wherein said anionic emulsifier used comprise anionic surfactant
preferably organic sulfonic adds selected from alkyl aryl sulfonic acid; alkyl aryl
polyoxyethylene sulphonic add; alkyl sulfonic add and alkyl polyoxyethylene
sulfonic add.
12. A process for the manufacture of a stable emulsion according to daim llwherein
the structures of sulfonic acids used comprise :
R2C6H4SO3H (V) R2C6H4O(C2H4O)mSO3H (VI)
R2SO3H (VI) R2O(C2H4O)mSO3H (VIII)
Where R2, which may differ, is a monovalent hydrocarbon radial having atleast 6 carbon atom most preferable R2 groups, but not limited to the following groups, are hexyl, octyf, decyi, dodecyl, cetyl, stearyl, myristyl, and oleyl. 'm' is an integer from 1 to 25.
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13. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 12 wherein the anionic surfactants is used in amounts of 1-15% preferably
3-10% and preferably are selected from octyl benzene sulfonic add; dodecyl
benzene sulfonic acid; cetyl benzene sulfonic add; Alpha octyl sulfonic acid; Alpha
dodecyl sulfonic add; alpha cetyl sulfonic acid; polyoxyethylene octyl benzene
sulfonic add; polyoxyethylene dodecyl benzene sulfonic acid; polyoxyethylene
cetyl benzene sulfonic acid; polyoxyethylene octyl sulfonic add; polyoxyethylene
dodecyl sulfonic add and polyoxyethylene cetyl sulfonic add.
14. A process for the manufacture of a stable emulsion according to anyone of claims
1 to 13
wherein said non-ionic emulsifiers used comprise non-ionic surfactants preferably in an amount of 1 to 25% more preferably, 5- 20% and selected from polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ethers and polyoxyalkylene sorbitan esters preferably selected from polyethylene glycol octyl ether; Polyethylene glycol lauryl ether; Polyethylene glycol tridecyl ether; Polyethylene glycol cetyl ether; Polyethylene glycol stearyl ether; polyethylene glycol nonyiphenyl ether; polyethylene glycol dodecylphenyl ether; polyethylene glycol cetylphenyl ether; polyethylene glycol staerylphenyl ether; polyethylene glycol sorbitan mono stearate and polyethylene glycol sorbitan mono oleate.
15. A process for the manufacture of a stable emulsion having particle size up to 150
nanometer substantially as hereindescribed and illustrated with reference to the
accompanying examples.
Dated this 2nd day of February 2005
Anjan Sen
Of Anjan Sen & Associates (Applicant's Agent)
24

A process for making stable high viscosity organopolysiloxane emulsion having particle size up to 150 nanometer and in particular to an emulsion-polymerization process involving a simple and cost-effective fester completion of emulsification of organopolysiloxane by using standard homogenizer and also subsequent polymerization of the organopolysiloxane at controlled temperature. The process involves a selective combination of non-ionic emulsifier together with an at least one anionic emulsifier to achieve the desired particle size emulsion. Importantly, the selective mix of non-ionic and anionic emulsifiers having HLB value of the mixture near to 12-15 and maintaining a temperature of up to 50°C is found to favour obtaining low particle stable emulsion with any standard homogeniser avoiding need for high pressure homogenizing.

Documents:

00063-kol-2005-abstract.pdf

00063-kol-2005-claims.pdf

00063-kol-2005-correspondence-1.1.pdf

00063-kol-2005-correspondence-1.2.pdf

00063-kol-2005-correspondence.pdf

00063-kol-2005-description(complete).pdf

00063-kol-2005-form-1-1.1.pdf

00063-kol-2005-form-1.pdf

00063-kol-2005-form-2.pdf

00063-kol-2005-form-3.pdf

00063-kol-2005-form-9.pdf

00063-kol-2005-pa.pdf

63--KOL-2005-FORM-1.pdf

63--KOL-2005-FORM-2.pdf

63-KOL-2005-(06-06-2014)-CORRESPONDENCE.pdf

63-KOL-2005-(06-12-2013)-CLAIMS.pdf

63-KOL-2005-(06-12-2013)-CORRESPONDENCE.pdf

63-KOL-2005-(06-12-2013)-FORM-3.pdf

63-KOL-2005-(06-12-2013)-OTHERS.pdf

63-KOL-2005-(06-12-2013)-PETITION UNDER RULE 137.pdf

63-KOL-2005-(07-08-2014)-ABSTRACT.pdf

63-KOL-2005-(07-08-2014)-CLAIMS.pdf

63-KOL-2005-(07-08-2014)-CORRESPONDENCE.pdf

63-KOL-2005-(07-08-2014)-DESCRIPTION (COMPLETE).pdf

63-KOL-2005-(07-08-2014)-FORM-2.pdf

63-KOL-2005-(07-08-2014)-OTHERS.pdf

63-KOL-2005-(09-10-2013)-CORRESPONDENCE.pdf

63-KOL-2005-(09-10-2013)-OTHERS.pdf

63-KOL-2005-(21-07-2014)-CORRESPONDENCE.pdf

63-KOL-2005--CORRESPONDENCE.pdf

63-KOL-2005-ABSTRACT.pdf

63-KOL-2005-Amended Pages Of Specification-020315.pdf

63-KOL-2005-Correspondence-020315.pdf

63-KOL-2005-CORRESPONDENCE.pdf

63-kol-2005-form 18.pdf

63-KOL-2005-FORM-3.pdf

63-KOL-2005-OTHERS-020315.pdf

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Patent Number

266154

Indian Patent Application Number

63/KOL/2005

PG Journal Number

15/2015

Publication Date

10-Apr-2015

Grant Date

08-Apr-2015

Date of Filing

02-Feb-2005

Name of Patentee

WACKER METROARK CHEMICALS PVT,LTD.

Applicant Address

VILL & P.O:CHANDI,P.S.-BISHNUPUR,24 PARGANAS(SOUTH),PIN-743503,

Inventors:

#	Inventor's Name	Inventor's Address
1	PAUL,AMIT KUMAR	GENERAL MANAGER(TECHNICAL),WACKER METROARK CHEMICALS PVT,LTD,VILL&P.O:CHANDI,P.S.-BISHNUPUR,24 PARGANAS(SOUTH),PIN-743503,

PCT International Classification Number

A61K8/92

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA