DESC:FIELD
The present disclosure relates to an emulsion polymer composition and a process for its preparation. Particularly, the present disclosure relates to an emulsion polymer composition suitable for providing water-resistant properties to paints.
Definitions:
Yellowness Index: Yellowness Index refers to a number calculated from spectrophotometric data that describes the change in color of a test sample from clear or white to yellow.
Sheen: Sheen refers to a measure of the reflected light (glossiness) from a paint finish.
Tappi brightness: Tappi brightness refers to the measurement of brightness of the coated film.
Whiteness: Whiteness refers to the whiteness of the coated film.
Resultant: Resultant refers to a mixture of complex, compound, mixture and product.
BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.
The emulsion polymer compositions generally utilize acrylic monomers such as styrene, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, n-butyl methacrylate, methacrylic acid, and acrylic acid as the building blocks for polymers. The emulsion is processed by the emulsion polymerization process. The performance of the resulting polymer for waterproofing is determined by water resistance and cross-linking.
Conventionally surfactants and emulsifiers based on sulphates, sulfonates, and succinates are commonly used, however, these do not bind to the polymer backbone and tend to leach out over time. These surfactants are mobile and migrate within the emulsion or paint film, impacting water sensitivity and water absorption. Additionally, these surfactants have a relatively low molecular weight, making their migration easier. Controlling emulsion particle size is critical in maintaining the stability of the composition, which is achieved by precise dosing of surfactants in the initial emulsification and continuous phases. Further, the conventional process adds sodium bicarbonate as a buffer in the emulsification phase to maintain the initial pH for facilitating the desired action. However, excessive addition can affect particle size and distribution.
Further, conventional emulsions consist of a neutralizer based on liquid ammonia, which emits a strong odour, surfactants based on alkyl phenol ethylene oxide (APEO), and biocides that release formaldehyde. The APEO based surfactants are hazardous to aquatic life.
There is, therefore, felt a need to provide an emulsion polymer composition that mitigates the drawbacks mentioned hereinabove and provides at least an alternative solution.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows.
An object of the present disclosure is to ameliorate one or more problems of the background or to at least provide a useful alternative.
Another object of the present disclosure is to provide an emulsion polymer composition.
Yet another object of the present disclosure is to provide an emulsion polymer composition for providing water-resistant properties to paints.
Still another object of the present disclosure is to provide an emulsion polymer composition that uses alkyl phenol ethylene oxide (APEO) free surfactants and formaldehyde-free biocides.
Yet another object of the present disclosure is to provide a process for the preparation of an emulsion polymer composition.
Still another object of the present disclosure is to provide a process for the preparation of an emulsion polymer composition that is economical and environment-friendly.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.
SUMMARY
The present disclosure relates to an emulsion polymer composition and a process of its preparation.
In an aspect the present disclosure provides an emulsion polymer composition.
The emulsion polymer composition comprises a reaction product of 40 mass% to 60 mass% of a plurality of monomers, 0.5 mass% to 2 mass% of at least one polymerizable surfactant, 0.1 mass% to 1 mass% of at least one initiator, 0.01 mass% to 0.5 mass% of at least one coupling agent, 0.05 mass% to 0.3 mass% of a plurality of reducing agents, 0.1 mass% to 2 mass% of at least one pH stabilizer; and 0.05 mass% to 0.2 mass% of at least one buffer, 0.5 mass% to 2 mass% of a plurality of additives and q.s. water, wherein the mass% of each ingredient is with respect to the total mass of said emulsion polymer composition.
The plurality of monomers are selected from the group consisting of styrene, butyl acrylate, methacrylic acid, n-butyl methacrylate, diacetone acrylamide (DAAM), ethylene glycol dimethylacrylate (EGDMA), 2-ethylhexyl acrylate and vinyl trimethoxy silane.
The polymerizable surfactant is selected from the group consisting of alcohols, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid, alkyl diphenyl oxide disulfonate, phosphate ester based polymerizable surfactants and reactive anionic emulsifier.
The initiator is selected from the group consisting of potassium persulphate, sodium persulphate and ammonium persulphate.
The coupling agent is selected from the group consisting of adipic acid dihydrazide (ADH), ethylene glycol dimethylacrylate (EGDMA) and succinic acid dihydrazide.
The plurality of reducing agents are selected from a combination of tert-butyl hydroperoxide and sodium formaldehydesulfoxylate, tert-butyl hydroperoxide and sodium acetone bisulphite, tert-butyl hydroperoxide and L-ascorbic acid and tert-butyl hydroperoxide and sodium meta bisulphate.
The pH stabilizer is at least one selected from the group consisting of 95% of 2-amino-2-methyl-1-propanol solution, 2-amino ethanol, alkanolamine and potassium methylsiliconate.
The buffer is selected from the group consisting of sodium bicarbonate, sodium acetate, sodium carbonate and ethylene diaminetetraacetic acid (EDTA).
The plurality of additives comprises a plurality of preservatives, at least one non-polymerizable surfactant and at least one defoamer. The plurality of additives comprise plurality of preservatives in an amount in the range of 0.1 mass% to 0.5 mass%, the non-polymerizable surfactant in an amount in the range of 0.1 mass% to 1 mass% and the defoamer in an amount in the range of 0.002 mass% to 0.01 mass%, wherein the mass% of each ingredient is with respect to the total mass of the emulsion polymer composition.
The plurality of preservatives at least one selected from the group consisting of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (CIT/CMIT) and benzisothiazolinone (BIT).
The non-polymerizable surfactant is at least one selected from the group consisting of non-ionic fatty alcohol ethoxylates, sodium dodecylbenzenesulfonate, alkyl polyethylene glycol ether and secondary alcohol ethoxylate.
The defoamer is selected from the group consisting of fumed silica, polyether siloxane emulsion and mineral oil based defoamers.
The mass ratio of said monomers to said polymerizable surfactant is in the range of 35:1 to 45:1.
The emulsion polymer composition comprises a reaction product of diacetone acrylamide, styrene, 2-ethylhexyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as plurality of monomers, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, potassium persulphate as the initiator, adipic acid dihydrazide as the coupling agent, tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as the plurality of reducing agents, 2-amino ethanol as the pH stabilizer and sodium bicarbonate as the buffer, the plurality of additives comprising a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), benzisothiazolinone as the plurality of preservatives, non-ionic fatty alcohol ethoxylates and sodium dodecylbenzene sulfonate as the plurality of non-polymerizable surfactants and fumed silica as the defoamer and q.s. water.
The emulsion polymer composition comprises a reaction product of 0.10 mass% to 0.15 mass% of diacetone acrylamide, 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of 2-ethylhexyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.2 mass% to 0.8 mass% of vinyl trimethoxy silane as the plurality of monomers, 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, 0.3 mass% to 0.4 mass% of potassium persulphate as the initiator, 0.02 mass% to 0.08 mass% of adipic acid dihydrazide as the coupling agent, 0.05 mass% to 0.10 mass% of tert-butyl hydroperoxide and 0.05 mass% to 0.10 mass% of sodium formaldehydesulfoxylate as the plurality of reducing agents, 0.5 mass% to 1 mass% of 2-amino ethanol as the pH stabilizer and 0.05 mass% to 0.15 mass% of sodium bicarbonate as the buffer, the plurality of additives comprises 0.05 mass% to 0.15 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.15 mass% of benzisothiazolinone as the plurality of preservatives, 0.2 mass% to 0.4 mass% of non-ionic fatty alcohol ethoxylates and 0.1 mass% to 0.3 mass% of sodium dodecylbenzene sulfonate as the plurality of non-polymerizable surfactants, 0.004 mass% to 0.008 mass% of fumed silica as the defoamer and q.s. water.
The polymer emulsion composition comprises a reaction product of diacetone acrylamide, styrene, butyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as the plurality of monomers, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, potassium persulphate as the initiator, adipic acid dihydrazide as the coupling agent, tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as the plurality of reducing agents, 2-amino ethanol and potassium methylsiliconate as the plurality of pH stabilizers and sodium bicarbonate as the buffer, the plurality of additives comprises a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), benzisothiazolinone as the plurality of preservatives, non-ionic fatty alcohol ethoxylates and sodium dodecylbenzene sulfonate as the plurality of non-polymerizable surfactants and fumed silica as the defoamer and q.s. water.
The emulsion polymer composition comprises a reaction product of 0.05 mass% to 0.15 mass% of diacetone acrylamide, 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of butyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.2 mass% to 0.6 mass% of vinyl trimethoxy silane as the plurality of monomers, 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, 0.3 mass% to 0.4 mass% of potassium persulphate as the initiator, 0.02 mass% of adipic acid dihydrazide as the coupling agent, 0.08 mass% of tert-butyl hydroperoxide and 0.08 mass% of sodium formaldehydesulfoxylate as the plurality of reducing agents, 0.4 mass% of 2-amino ethanol and 0.4 mass% of potassium methylsiliconate as pH stabilizers and 0.1 mass% of sodium bicarbonate as the buffer. The plurality of additives comprises 0.2 mass% to 0.6 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.2 mass% of benzisothiazolinone as the plurality of preservatives, 0.2 mass% to 0.4 mass% of non-ionic fatty alcohol ethoxylates and 0.1 mass% to 0.3 mass% of sodium dodecylbenzene sulfonate as the plurality of non-polymerizable surfactants and 0.002 mass% to 0.008 mass% of fumed silica as said defoamer and q.s. water.
The emulsion polymer composition comprises a reaction product of styrene, butyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as the plurality of monomers, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, potassium persulphate as the initiator, ethylene glycol dimethylacrylate as the coupling agent, tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as the plurality of reducing agents, 2-amino ethanol and potassium methylsiliconate as the plurality of pH stabilizers and sodium bicarbonate as the buffer. The plurality of additives comprise a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and benzisothiazolinone as the plurality of preservatives, non-ionic fatty alcohol ethoxylates as the non-polymerizable surfactant and fumed silica as the defoamer and q.s. water.
The emulsion polymer composition comprises a reaction product of 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of butyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.3 mass% to 0.5 mass% of vinyl trimethoxy silane as the plurality of monomers, 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, 0.3 mass% to 0.4 mass% of potassium persulphate as the initiator, 0.1 mass% to 0.3 mass% of ethylene glycol dimethylacrylate as the coupling agent, 0.04 mass% to 0.12 mass% of tert-butyl hydroperoxide and 0.04 mass% to 0.12 mass% of sodium formaldehydesulfoxylate as the plurality of reducing agents, 0.2 mass% to 0.6 mass% of 2-amino ethanol and 0.2 mass% to 0.6 mass% of potassium methylsiliconate as pH stabilizers and 0.05 to 0.15 mass% of sodium bicarbonate as the buffer. The plurality of additives comprises 0.05 mass% to 0.15 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.15 mass% of benzisothiazolinone as the plurality of preservatives, 0.2 mass% to 0.4 mass% of a non-ionic fatty alcohol ethoxylates as the non-polymerizable surfactant and 0.002 mass% to 0.008 mass% of fumed silica as the defoamer and q.s. water.
In a second aspect, the process for the preparation of an emulsion polymer composition comprises separately heating a first predetermined amount of a polymerizable surfactant and a predetermined amount of a buffer at a first predetermined temperature followed by mixing under stirring to obtain a mixture. Separately a second predetermined amount of the polymerizable surfactant is heated to the first predetermined temperature and cooled to a temperature in the range of 25 °C to 40 °C and sequentially adding predetermined amounts of a plurality of monomers under stirring to obtain a pre-emulsion. 2 mass% to 15 mass% of the pre-emulsion is added to the mixture followed by adding a first predetermined amount of an initiator at a second predetermined temperature to obtain a first resultant. 85 mass% to 98 mass% of the pre-emulsion is added to the first resultant followed by adding a second predetermined amount of the initiator at the second predetermined temperature to obtain a second resultant. The second resultant is cooled to a third predetermined temperature and predetermined amounts of a plurality of reducing agents are added to obtain a third resultant. The third resultant is cooled to a temperature in the range of 40 °C to 50 °C followed by adding a predetermined amount of at least one pH stabilizer and stirring followed by adding a predetermined amount of a coupling agent solution under stirring to obtain a fourth resultant having a pH in the range of 8.5 to 9.5. Predetermined amounts of plurality of preservatives and a predetermined amount of a defoamer are added to the fourth resultant at a temperature in the range of 40 °C to 50 °C followed by the addition of water under stirring to obtain the emulsion polymer composition.

The polymerizable surfactant is selected from the group consisting of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid, alkyl diphenyl oxide disulfonate solution, phosphate ester based polymerizable surfactant solution and reactive anionic emulsifier solution.

The buffer is selected from the group consisting of sodium bicarbonate, sodium acetate, sodium carbonate solution and ethylene diaminetetraacetic acid (EDTA).

The plurality of monomers comprises first monomer selected from the group consisting of diacetone acrylamide and ethylene glycol dimethylacrylate (EGDMA). The second monomer is selected from the group consisting of styrene, butyl acrylate, n-butyl methacrylate, vinyl trimethoxy silane and 2-ethylhexyl acrylate. The third monomer is methacrylic acid.

The initiator is selected from the group consisting of potassium persulphate, sodium persulphate and ammonium persulphate.

The plurality of reducing agents comprise first reducing agent and second reducing agent independently selected from the group consisting of a mixture of tert-butyl hydroperoxide and a non-polymerizable surfactant, a mixture of sodium formaldehyde sulfoxylate and a non-polymerizable surfactant, a mixture of sodium acetone bisulphite and a non-polymerizable surfactant, a mixture of L-ascorbic acid and a non-polymerizable surfactant and a mixture of sodium meta bisulphate and a non-polymerizable surfactant.

The pH stabilizer solution is at least one selected from the group consisting of aqueous 95% of 2-amino-2-methyl-1-propanol solution (AMP 95), 2-amino ethanol, alkanolamine and potassium methylsiliconate.

The coupling agent is selected from the group consisting of a mixture of adipic acid dihydrazide (ADH) and a non-polymerizable surfactant, a mixture of ethylene glycol dimethylacrylate (EGDMA) and a non-polymerizable surfactant and a mixture of succinic acid dihydrazide and a non-polymerizable surfactant.
The plurality of preservatives are selected from the group consisting of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and benzisothiazolinone (BIT).
The defoamer is selected from the group consisting of fumed silica, polyether siloxane emulsion and mineral oil based defoamer.
The non-polymerizable surfactant is selected from the group consisting of non-ionic fatty alcohol ethoxylates, sodium dodecylbenzenesulfonate, alkyl polyethylene glycol ether and secondary alcohol ethoxylate.
The first predetermined temperature is in the range of 75 °C to 85 °C. The second predetermined temperature is in the range of 80 °C to 90 °C. The third predetermined temperature is in the range of 70 °C to 78 °C.
The first predetermined amount of a polymerizable surfactant is in the range of 0.05 mass% to 0.3 mass% with respect to the total mass of the emulsion polymer composition.
The second predetermined amount of the polymerizable surfactant is in the range of 0.5 mass% to 2 mass% with respect to the total mass of the emulsion polymer composition.

The predetermined amount of a buffer is in the range of 0.05 mass% to 0.2 mass% with respect to the total mass of the emulsion polymer composition.

The plurality of monomers comprise first monomer in an amount in the range of 0.05 mass% to 0.5 mass%, with respect to the total mass of the emulsion polymer composition second monomer in an amount in the range of 40 mass% to 55 mass% with respect to the total mass of the emulsion polymer composition and third monomer in an amount in the range of 0.2 mass% to 2 mass% with respect to the total mass of the emulsion polymer composition.

The first predetermined amount of the initiator is in the range of 0.05 mass% to 0.3 mass% with respect to the total mass of mass of said the emulsion polymer composition.

The second predetermined amount of the initiator is in the range of 0.1 mass% to 0.4 mass% with respect to the total mass of the emulsion polymer composition.

The plurality of reducing agents comprise a first reducing agent and a second reducing agent independently in an amount in the range of 0.02 mass% to 0.2 mass% with respect to the total mass of the emulsion polymer composition.

The predetermined amount of pH stabilizer is in the range of 0.2 mass% to 1.5 mass% with respect to the total mass of the emulsion polymer composition.

The predetermined amount of coupling agent is in the range of 0.02 mass% to 0.1 mass% with respect to the total mass of the emulsion polymer composition.

The plurality of preservatives are in an amount in the range of 0.1 mass% to 0.5 mass% with respect to the total mass of the emulsion polymer composition.

The predetermined amount of defoamer is in the range of 0.002 mass% to 0.01 mass% with respect to the total mass of the emulsion polymer composition.

The non-polymerizable surfactant is independently in an amount in the range of 0.05 mass% to 0.2 mass% in the first reducing agent and second reducing agent and the non-polymerizable surfactant is in an amount in the range of 0.1 mass% to 0.5 mass% in the coupling agent.

The polymerizable surfactant, the non-polymerizable surfactant, the buffer, the coupling agent, the initiator, the first reducing agent, the second reducing agent, the pH stabilizer, the plurality of preservatives and the defoamer are aqueous solutions.

The mass ratio of the monomer to the polymerizable surfactant is in the range of 35:1 to 45:1.

DETAILED DESCRIPTION
The present disclosure relates to an emulsion polymer composition and a process for its preparation. Particularly, the present disclosure relates to emulsion polymer composition suitable for providing water-resistant properties to paints.
Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components and methods to provide a complete understanding of the embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.
The terminology used in the present disclosure is only for the purpose of explaining a particular embodiment, and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well unless the context clearly suggests otherwise. The terms "comprises," "comprising," “including,” and “having” are open-ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.
The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
Conventionally surfactants and emulsifiers based on sulphates, sulfonates, and succinates are commonly used, however, these don’t bind to the polymer backbone and tend to leach out over time. These surfactants are mobile and migrate within the emulsion or paint film, impacting water sensitivity and absorption. Additionally, these surfactants have a relatively low molecular weight, making their migration easier. Controlling emulsion particle size is important, requiring precise dosing of surfactants in the initial emulsification and continuous phases. Further, the conventional process adds sodium bicarbonate as a buffer in the emulsification phase to maintain the initial pH for facilitating the desired action. However, excessive addition can affect particle size and distribution.
Further, conventional emulsions consist of a neutralizer based on liquid ammonia, which emits a strong odour, surfactants based on alkyl phenol ethylene oxide (APEO), and biocides that release formaldehyde. The APEO based surfactants are hazardous to aquatic life.
The present disclosure provides an emulsion polymer composition and a process for preparing the emulsion polymer composition. The emulsion polymer composition of the present disclosure imparts water-resistant properties to paints and is free of alkyl phenol ethylene oxide (APEO) surfactants and biocides that release formaldehyde.
In an aspect, the present disclosure relates to an emulsion polymer composition and a process for its preparation.
In an embodiment of the present disclosure, the emulsion polymer composition comprises a reaction product of 40 mass% to 60 mass% of a plurality of monomers, 0.5 mass% to 2 mass% of at least one polymerizable surfactant, 0.1 mass% to 1 mass% of at least one initiator, 0.01 mass% to 0.5 mass% of at least one coupling agent, 0.05 mass% to 0.3 mass% of a plurality of reducing agents, 0.1 mass% to 2 mass% of at least one pH stabilizer; and 0.05 mass% to 0.2 mass% of at least one buffer, 0.5 mass% to 2 mass% of a plurality of additives and q.s. water; wherein mass% of each ingredient is with respect to the total mass of the emulsion polymer composition.
In an exemplary embodiment, the emulsion polymer composition comprises a reaction product of 48.42 mass% of a plurality of monomers, 1.15 mass% of a polymerizable surfactant, 0.43 mass% of initiator, 0.06 mass% of coupling agent, 0.08 mass% of a plurality of reducing agents, 0.8 mass% of pH stabilizer, 0.1 mass% of buffer and 0.71 mass% of a plurality of additives and q.s water; wherein the mass% of each ingredient is with respect to the total mass of the emulsion polymer composition. In another exemplary embodiment, the emulsion polymer composition comprises a reaction product of 48.2 mass% of plurality of monomers, 1.2 mass% of polymerizable surfactant, 0.43 mass% initiator, 0.2 mass% coupling agent, 0.08 mass% of reducing agents, 0.8 mass% of pH stabilizer, 0.1 mass% of buffer and 0.41 mass% of a plurality of additives; wherein the mass% of each ingredient is with respect to the total mass of the emulsion polymer composition. In yet another exemplary embodiment of the present disclosure, the emulsion polymer composition comprises a reaction product of 48.3 mass% of a plurality of monomers, 1.2 mass% of a polymerizable surfactant, 0.43 mass% of initiator, 0.06 mass% of coupling agent, 0.08 mass% of reducing agents, 0.8 mass% of pH stabilizer, 0.1 mass% of buffer and 0.71 mass% of a plurality of additives and q.s water; wherein the mass% of each ingredient is with respect to the total mass of the emulsion polymer composition. In still another exemplary embodiment, the emulsion polymer composition comprises a reaction product of 48.4 mass% of plurality of monomers, 1.2 mass% of a polymerizable surfactant, 0.43 mass% of initiator, 0.05 mass% of coupling agent, 0.08 mass% of reducing agents, 0.8 mass% of pH stabilizers, 0.1 mass% of buffer, 0.61 mass% of a plurality of additives and q.s water; wherein the mass% of each ingredient is with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the plurality of monomers are selected from the group consisting of styrene, butyl acrylate, methacrylic acid, n-butyl methacrylate, diacetone acrylamide (DAAM), ethylene glycol dimethylacrylate (EGDMA), 2-ethylhexyl acrylate and vinyl trimethoxy silane. In an exemplary embodiment, the plurality of monomers is diacetone acrylamide, styrene, 2-ethylhexyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane. In another exemplary embodiment, the plurality of monomers is diacetone acrylamide, styrene, butyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane. In yet another exemplary embodiment, the plurality of monomers is ethylene glycol dimethylacrylate styrene, butyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane.
In an embodiment of the present disclosure, the polymerizable surfactant is selected from the group consisting of alcohols, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid , alkyl diphenyl oxide disulfonate, phosphate ester based polymerizable surfactants and reactive anionic emulsifier. In an exemplary embodiment, the polymerizable surfactant is alcohols, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka SR10).
In an embodiment of the present disclosure, the initiator is selected from the group consisting of potassium persulphate, sodium persulphate and ammonium persulphate. In an exemplary embodiment, the initiator is potassium persulphate.
In an embodiment of the present disclosure, the coupling agent is selected from the group consisting of adipic acid dihydrazide (ADH), ethylene glycol dimethylacrylate (EGDMA) and succinic acid dihydrazide. In an exemplary embodiment, the coupling agent is adipic acid dihydrazide (ADH). In another exemplary embodiment, the coupling agent is ethylene glycol dimethylacrylate (EGDMA).
In an embodiment of the present disclosure, the plurality of reducing agents are selected from a combination of tert-butyl hydroperoxide and sodium formaldehydesulfoxylate, tert-butyl hydroperoxide and sodium acetone bisulphite, tert-butyl hydroperoxide and L-ascorbic acid and tert-butyl hydroperoxide and sodium meta bisulphate. In an exemplary embodiment, the plurality of reducing agent is a combination of tert-butyl hydroperoxide and sodium formaldehydesulfoxylate.
In an embodiment of the present disclosure, the pH stabilizer is at least one selected from the group consisting of 95% 2-amino-2-methyl-1-propanol solution (AMP 95), 2-amino ethanol (phlex 110), alkanolamine and potassium methylsiliconate (Silres BS 168). In an exemplary embodiment, the pH stabilizer is 2-amino ethanol (phlex 110). In another exemplary embodiment, the pH stabilizer is a mixture of 2-amino ethanol (phlex 110) and potassium methylsiliconate (Silres BS 168).
The silicone -based pH stabilizer (Silres BS 168) not only helps in maintaining the pH of emulsions but also enhances water resistance. By forming three-dimensional hydrophobic networks, the silicone -based neutralizer effectively self-crosslinks, resulting in improved water resistance of water-borne coatings, thus preventing water from infiltrating the coating. Further, a mixture of organic amines and inorganic silicones -based neutralizers is used to neutralize the emulsion of the present disclosure in order to obtain the desired water resistance properties.
In an embodiment of the present disclosure, the buffer is selected from the group consisting of sodium bicarbonate, sodium acetate, sodium carbonate and ethylene diaminetetraacetic acid (EDTA).
In an embodiment of the present disclosure, the additives comprise a plurality of preservatives, at least one non-polymerizable surfactant and at least one defoamer.
In an embodiment of the present disclosure, the additives comprise a plurality of preservatives in an amount in the range of 0.1 mass% to 0.5 mass%, a non-polymerizable surfactant in an amount in the range of 0.1 mass% to 1 mass% and a defoamer in an amount in the range of 0.002 mass% to 0.01 mass%, wherein mass% of each ingredient is with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the additives comprise preservatives in an amount of 0.2 mass%, non-polymerizable surfactant in an amount of 0.5 mass% and defoamer in an amount of 0.006 mass% wherein the mass% of each ingredient is with respect to the total mass of the emulsion polymer composition. In another exemplary embodiment, the additives comprise preservatives in an amount of 0.3 mass%, non-polymerizable surfactant in an amount of 0.5 mass% and defoamer in an amount of 0.006 mass% wherein the mass% of each ingredient is with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the plurality of preservatives is selected from the group consisting of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), (Sanitized Cl15) and benzisothiazolinone (BIT) (Sanitized BT 10A). In an exemplary embodiment, the preservative is a mixture of sanitized Cl15 (mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT)) and sanitized BT 10A (benzisothiazolinone).
In an embodiment of the present disclosure, the non-polymerizable surfactant is at least one selected from the group consisting of non-ionic fatty alcohol ethoxylates (Teric 463), sodium dodecylbenzenesulfonate, alkyl polyethylene glycol ether (Emulsogen LCN 407) and secondary alcohol ethoxylate (Tergitol 15S40). In an exemplary embodiment, the non-polymerizable surfactants are a mixture of non-ionic fatty alcohol ethoxylates (Teric 463) and sodium dodecylbenzenesulfonate.
In an embodiment of the present disclosure, the defoamer is selected from the group consisting of fumed silica, polyether siloxane emulsion and mineral oil based defoamers. In an exemplary embodiment, the defoamer is mineral oil based defoamer (tegofoamex K3).
In an embodiment of the present disclosure, the mass ratio of the monomers to the polymerizable surfactant is in the range of 35:1 to 45:1. In an exemplary embodiment, the mass ratio of the monomers to the polymerizable surfactant is 42.10:1. In another exemplary embodiment, the mass ratio of the monomers to the polymerizable surfactant is 40.25:1.
In an embodiment of the present disclosure, the emulsion polymer composition comprises a reaction product of diacetone acrylamide, styrene, 2-ethylhexyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as plurality of monomers, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, potassium persulphate as the initiator, adipic acid dihydrazide as the coupling agent, tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as the plurality of reducing agents, 2-amino ethanol as the pH stabilizer and sodium bicarbonate as the buffer, the plurality of additives comprising a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), benzisothiazolinone as the plurality of preservatives, non-ionic fatty alcohol ethoxylates and sodium dodecylbenzene sulfonate as the plurality of non-polymerizable surfactants and fumed silica as the defoamer and q.s. water.
In an embodiment of the present disclosure, the emulsion polymer composition comprises a reaction product of 0.10 mass% to 0.15 mass% of diacetone acrylamide, 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of 2-ethylhexyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.2 mass% to 0.8 mass% of vinyl trimethoxy silane as the plurality of monomers, 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, 0.3 mass% to 0.4 mass% of potassium persulphate as the initiator, 0.02 mass% to 0.08 mass% of adipic acid dihydrazide as the coupling agent, 0.05 mass% to 0.10 mass% of tert-butyl hydroperoxide and 0.05 mass% to 0.10 mass% of sodium formaldehydesulfoxylate as the plurality of reducing agents, 0.5 mass% to 1 mass% of 2-amino ethanol as the pH stabilizer and 0.05 mass% to 0.15 mass% of sodium bicarbonate as the buffer. The plurality of additives comprising 0.05 mass% to 0.15 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.15 mass% of benzisothiazolinone as the plurality of preservatives, 0.2 mass% to 0.4 mass% of non-ionic fatty alcohol ethoxylates and 0.1 mass% to 0.3 mass% of sodium dodecylbenzene sulfonate as the plurality of non-polymerizable surfactants, 0.004 mass% to 0.008 mass% of fumed silica as the defoamer and q.s. water.
In an exemplary embodiment of the present disclosure, the emulsion polymer composition comprises a reaction product of 0.12 mass% of diacetone acrylamide, 22.7 mass% of styrene, 19.6 mass% of 2-ethylhexyl acrylate, 4.5 mass% of n-butyl methacrylate, 1 mass% of methacrylic acid and 0.5 mass% of vinyl trimethoxy silane, 1.15 mass% of poly(oxy-1,2-ethanediyl), alpha-sulfo-omega-[1-(hydroxymethyl)-2-(2-propenyloxy)ethoxy]- C11-rich C10-C14-branched alkyl ethers ammonium salt, 0.35 mass% of potassium persulphate, 0.06 mass% of adipic acid dihydrazide, 0.08 mass% of tert-butyl hydroperoxide and 0.08 mass% of sodium formaldehydesulfoxylate, 0.8 mass% of 2-amino ethanol and 0.1 mass% of sodium bicarbonate. 0.1 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), 0.1 mass% of benzisothiazolinone, 0.3 mass% of non-ionic fatty alcohol ethoxylates, 0.2 mass% of sodium dodecylbenzene sulfonate and 0.006 mass% of fumed silica and q.s. water.
In an embodiment of the present disclosure, the polymer emulsion composition comprises a reaction product of diacetone acrylamide, styrene, butyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as the plurality of monomers, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, potassium persulphate as the initiator, adipic acid dihydrazide as the coupling agent, tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as the plurality of reducing agents, 2-amino ethanol and potassium methylsiliconate as the plurality of pH stabilizers and sodium bicarbonate as the buffer, the plurality of additives comprising mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), benzisothiazolinone as said plurality of preservatives, non-ionic fatty alcohol ethoxylates and sodium dodecylbenzene sulfonate as the plurality of non-polymerizable surfactants and fumed silica as the defoamer and q.s. water.
In an embodiment of the present disclosure, the emulsion polymer composition comprises a reaction product of 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of butyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.2 mass% to 0.6 mass% of vinyl trimethoxy silane as the plurality of monomers, 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, 0.3 mass% to 0.4 mass% of potassium persulphate as the initiator, 0.02 mass% of adipic acid dihydrazide as the coupling agent, 0.08 mass% of tert-butyl hydroperoxide and 0.08 mass% of sodium formaldehydesulfoxylate as the plurality of reducing agents, 0.4 mass% of 2-amino ethanol and 0.4 mass% of potassium methylsiliconate as the plurality of pH stabilizers and 0.1 mass% of sodium bicarbonate as the buffer. The plurality of additives comprises 0.2 mass% to 0.6 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.2 mass% of benzisothiazolinone as the plurality of preservatives, 0.2 mass% to 0.4 mass% of non-ionic fatty alcohol ethoxylates and 0.1 mass% to 0.3 mass% of sodium dodecylbenzene sulfonate as the plurality of non-polymerizable surfactants and 0.002 mass% to 0.008 mass% of fumed silica as said defoamer and q.s. water.
In an exemplary embodiment, the emulsion polymer composition comprises a reaction product of 0.10 mass% of diacetone acrylamide, 23 mass% of styrene, 19.3 mass% of butyl acrylate, 4.5 mass% of n-butyl methacrylate, 1 mass% of methacrylic acid and 0.4 mass% of vinyl trimethoxy silane as plurality of monomers, 1.2 mass% of poly(oxy-1,2-ethanediyl), alpha-sulfo-omega-[1-(hydroxymethyl)-2-(2-propenyloxy)ethoxy]- C11-rich C10-C14-branched alkyl ethers ammonium salt as polymerizable surfactant, 0.35 mass% of potassium persulphate as initiator, 0.05 mass% of adipic acid dihydrazide as coupling agent, 0.08 mass% of tert-butyl hydroperoxide and 0.08 mass% of sodium formaldehydesulfoxylate as plurality of reducing agents, 0.4 mass% of 95% 2-amino-ethanol and 0.4 mass% of potassium methylsiliconate as pH stabilizers and 0.1 mass% of sodium bicarbonate as buffer. The plurality of additives comprises 0.1 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), 0.1 mass% of benzisothiazolinone as plurality of preservatives, 0.3 mass% of non-ionic fatty alcohol ethoxylates, 0.2 mass% of sodium dodecylbenzene sulfonate as non-polymerizable surfactant and 0.006 mass% of fumed silica as defoamer and q.s. water.
In an embodiment of the present disclosure, the emulsion polymer composition comprising a reaction product of styrene, butyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as the plurality of monomers, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, potassium persulphate as the initiator, ethylene glycol dimethylacrylate as the coupling agent, tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as the plurality of reducing agents, 2-amino ethanol and potassium methylsiliconate as the plurality of pH stabilizers and sodium bicarbonate as the buffer. The plurality of additives comprise a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and benzisothiazolinone as the plurality of preservatives, non-ionic fatty alcohol ethoxylates as the non-polymerizable surfactant and fumed silica as the defoamer and q.s. water.
In an embodiment of the present disclosure, the emulsion polymer composition comprises a reaction product of 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of butyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.3 mass% to 0.5 mass% of vinyl trimethoxy silane as the plurality of monomers, 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as the polymerizable surfactant, 0.3 mass% to 0.4 mass% of potassium persulphate as the initiator, 0.1 mass% to 0.3 mass% of ethylene glycol dimethylacrylate as the coupling agent, 0.04 mass% to 0.12 mass% of tert-butyl hydroperoxide and 0.04 mass% to 0.12 mass% of sodium formaldehydesulfoxylate as the plurality of reducing agents, 0.2 mass% to 0.6 mass% of 2-amino ethanol and 0.2 mass% to 0.6 mass% of potassium methylsiliconate as the plurality of pH stabilizers and 0.05 to 0.15 mass% of sodium bicarbonate as the buffer. The plurality of additives comprises 0.05 mass% to 0.15 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.15 mass% of benzisothiazolinone as the plurality of preservatives, 0.2 mass% to 0.4 mass% of a non-ionic fatty alcohol ethoxylates as the non-polymerizable surfactant and 0.002 mass% to 0.008 mass% of fumed silica as the defoamer and q.s. water.
In an exemplary embodiment, the emulsion polymer composition comprises a reaction product of 23 mass% of styrene, 19.3 mass% of butyl acrylate, 4.5 mass% of n-butyl methacrylate, 1 mass% of methacrylic acid and 0.4 mass% of vinyl trimethoxy silane, 1.2 mass% of poly(oxy-1,2-ethanediyl), alpha-sulfo-omega-[1-(hydroxymethyl)-2-(2-propenyloxy)ethoxy]- C11-rich C10-C14-branched alkyl ethers ammonium salt, 0.35 mass% of potassium persulphate, 0.2 mass% of ethylene glycol dimethylacrylate, 0.08 mass% of tert-butyl hydroperoxide and 0.08 mass% of sodium formaldehydesulfoxylate as plurality of reducing agents, 0.4 mass% of 2-amino ethanol and 0.4 mass% of potassium methylsiliconate and 0.1 mass% of sodium bicarbonate. The plurality of additives comprises 0.1 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), 0.1 mass% of benzisothiazolinone as plurality of preservatives, 0.3 mass% of a non-ionic fatty alcohol ethoxylates as non-polymerizable surfactant and 0.006 mass% of fumed silica as defoamer and q.s. water.
In accordance with the embodiment of the present disclosure, the composition of the monomer is adjusted to obtain a hard and strong film. The strength of the film is improved by keto-imine crosslinking.
The keto–imine crosslinking is introduced in the polymer by using diacetone acrylamide (DAAM) as a polymerizable monomer and adipic acid dihydrazide (ADH) as crosslinking or coupling agent. The crosslinking monomer DAAM has two carbonyl groups which can undergo reaction with NH2 groups from ADH.
A schematic representation for the crosslinking reaction of the diacetone acrylamide and adipic acid dihydrazide is given as scheme A:

SCHEME A
The polymer backbone is represented by the solid black sections, with diacetone acrylamide (DAAM) attached to it. During the crosslinking process, water molecules (H2O) are released. Release of high amount of water slows down crosslinking, but it progresses favourably when water evaporation occurs. The remaining carbonyl groups from the monomer enhance adhesion and the pull-off strength of both the emulsion and the paint film. Further, the coupling agents (cross-linkers) containing two allylic groups or double bonds (bi-functional monomers) increase the molecular weight of the emulsion polymer and enhance the tensile strength of the final emulsion polymer. The hardness can be adjusted by varying the monomer combination and the resulting minimum film-forming temperature (MFFT) of the polymer, potentially influencing the tackiness of the film obtained by applying the emulsion polymer composition of the present disclosure.
In an embodiment of the present disclosure, the polymerizable surfactants augment the waterproofing performance.
In an embodiment of the present disclosure, the polymerizable surfactants of the present disclosure bind to the polymer backbone, thus avoid leaching out for a prolonged period of time.
The polymerizable surfactants have a relatively high molecular weight which has an allylic group located between the hydrophobic part and hydrophilic part, enabling easy accessibility for acrylic or styrene monomers to react. Thus, the surfactants will have a bigger hydrophobic part and the allylic group participates in the additional polymerization reaction. The polymer film formed by using the emulsion polymer composition of the present disclosure will have excellent water resistance and film clarity.
The use of polymerizable surfactant in combination with the coupling agent (crosslinking agent), enhances the water resistance of the emulsion polymer (backbone) and the paint prepared by using the emulsion polymer composition.
In an embodiment of the present disclosure, the emulsion polymer formulated provides high-strength films, uses APEO-free surfactants, and employs formaldehyde free biocides.
In an embodiment of the present disclosure, the emulsion polymer of the present disclosure is well-suited for creating high-quality interior paint that offers prolonged durability.
In another aspect of the present disclosure, there is provided a process for the preparation of an emulsion polymer composition. The process comprises the following steps:
i. separately heating a first predetermined amount of a polymerizable surfactant and a predetermined amount of a buffer at a first predetermined temperature followed by mixing under stirring to obtain a mixture;
ii. separately a second predetermined amount of the polymerizable surfactant is heated to the first predetermined temperature and cooled to a temperature in the range of 25 °C to 40 °C and sequentially adding predetermined amounts of a plurality of monomers, under stirring to obtain a pre-emulsion;
iii. adding 2 mass% to 15 mass% of the pre-emulsion to the mixture followed by adding a first predetermined amount of an initiator at a second predetermined temperature to obtain a first resultant;
iv. adding 85 mass% to 98 mass% of the pre-emulsion to the first resultant followed by adding a second predetermined amount of the initiator at the second predetermined temperature to obtain a second resultant;
v. cooling the second resultant to a third predetermined temperature and adding predetermined amounts of a plurality of reducing agents to obtain a third resultant;
vi. cooling the third resultant to a temperature in the range of 40 °C to 50°C followed by adding a predetermined amount of at least one pH stabilizer and stirring followed by adding a predetermined amount of a coupling agent under stirring to obtain a fourth resultant having a pH in the range of 8.5 to 9.5; and
vii. adding predetermined amounts of a plurality of preservatives and a predetermined amount of a defoamer to the fourth resultant at a temperature in the range of 40 °C to 50 °C followed by adding water under stirring to obtain the emulsion polymer composition.
The process is described in detail below:
In accordance with the present disclosure, the emulsion polymerization process is divided into four stages:
I. Reactor charge;
II. Pre Emulsion;
III. Chaser catalyst and
IV. Additives addition
Stage I. Reactor charge
In an embodiment of the present disclosure, in this stage, DM water, surfactants and buffer are mixed in a reactor and heated at a first predetermined temperature.
In a first step, separately a first predetermined amount of a polymerizable surfactant and a predetermined amount of a buffer are heated at a first predetermined temperature followed by mixing under stirring to obtain a mixture.
In an embodiment of the present disclosure the polymerizable surfactant is selected from the group consisting of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka REASOAP SR 10), alkyl diphenyl oxide disulfonate, phosphate ester based polymerizable surfactant and reactive anionic emulsifier. In an exemplary embodiment, the polymerizable surfactant is C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka REASOAP SR 10).
In an embodiment of the present disclosure, the buffer is selected from the group consisting of sodium bicarbonate, sodium acetate, sodium carbonate and ethylene diaminetetraacetic acid (EDTA). In an exemplary embodiment, the buffer is sodium bicarbonate.
In an embodiment of the present disclosure, the first predetermined temperature is in the range of 75 °C to 85 °C. In the exemplary embodiments, the first predetermined temperature is 80 °C.
In an embodiment of the present disclosure, the time period of mixing of first predetermined amount of a polymerizable surfactant and a predetermined amount of a buffer is in the range of 20 minutes to 30 minutes. In an exemplary embodiment, the time period of mixing of first predetermined amount of a polymerizable surfactant and a predetermined amount of a buffer is 25 minutes.
In an embodiment of the present disclosure, the first predetermined amount of polymerizable surfactant is in the range of 0.05 mass% to 0.3 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the first predetermined amount of polymerizable surfactant is 0.15 mass% with respect to the total mass of the emulsion polymer composition. In another exemplary embodiment, the first predetermined amount of polymerizable surfactant is 0.2 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the predetermined amount of buffer is in the range of 0.05 mass% to 0.2 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the predetermined amount of buffer is 0.1 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the polymerizable surfactant and the buffer are aqueous solutions.
In an embodiment of the present disclosure, the amount of the polymerizable surfactant in the polymerizable surfactant solution is in the range of 0.05 mass% to 0.3 mass%. In an exemplary embodiment, the amount of the polymerizable surfactant in the polymerizable surfactant solution is 0.15 mass%. In another exemplary embodiment, the amount of the polymerizable surfactant in the polymerizable surfactant solution is 0.2 mass%.
In an embodiment of the present disclosure, the amount of the buffer in the buffer solution is in the range of 2 mass% to 6 mass%. In an exemplary embodiment, the amount of the buffer in the buffer solution is 4 mass%. In another exemplary embodiment, the amount of the buffer in the buffer solution is 3 mass% in the buffer solution.
The buffer maintains the pH of the mixture, which facilitates the polymerization reaction.
Stage II: Pre Emulsion:
In an embodiment of the present disclosure, in this stage, monomer emulsification is carried out.
In an embodiment of the present disclosure, DM water, surfactants and monomers are mixed at a temperature in the range of 25 °C to 40 °C to form a monomer preemulsion.
In a second step, separately a second predetermined amount of the polymerizable surfactant is heated to the first predetermined temperature and cooled to a temperature in the range of 25 °C to 40 °C and sequentially predetermined amounts of a plurality of monomers are sequentially added under stirring to obtain a pre-emulsion.
In an embodiment of the present disclosure, the polymerizable surfactant is selected from the group consisting of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka REASOAP SR 10), alkyl diphenyl oxide disulfonate, phosphate ester based polymerizable surfactant and reactive anionic emulsifier. In an exemplary embodiment, the polymerizable surfactant is C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka REASOAP SR 10).
In an embodiment of the present disclosure, the second predetermined amount of polymerizable surfactant is in the range of 0.5 mass% to 2 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the second predetermined amount of polymerizable surfactant is 1 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the polymerizable surfactant is prepared as an aqueous solution.
In an embodiment of the present disclosure, the second predetermined amount of the polymerizable surfactant in the second polymerizable surfactant solution is in the range of 0.5 mass% to 2 mass%. In an exemplary embodiment, the second predetermined amount of the polymerizable surfactant is 1 mass% in the second polymerizable surfactant solution.
In an embodiment of the present disclosure, the first predetermined temperature is in the range of 75 °C to 85 °C. In an exemplary embodiment, the first predetermined temperature is 80 °C.
In an embodiment of the present disclosure, the plurality of monomers comprise first monomer selected from the group consisting of diacetone acrylamide and ethylene glycol dimethylacrylate (EGDMA), second monomer selected from the group consisting of styrene, butyl acrylate, n-butyl methacrylate, vinyl trimethoxy silane and 2-ethylhexyl acrylate; and third monomer is methacrylic acid.
In an exemplary embodiment, the first monomer is diacetone acrylamide (DAAM), the second monomer is a mixture of styrene, 2-ethylhexyl acrylate, butyl methacrylate and vinyl trimethoxy silane and the third monomer is methacrylic acid. In yet another exemplary embodiment, the first monomer is diacetone acrylamide (DAAM), the second monomer is a mixture of styrene, butyl acrylate, n-butyl methacrylate and vinyl trimethoxy silane and the third monomer is methacrylic acid. In still another exemplary embodiment, the first monomer is ethylene glycol dimethylacrylate (EGDMA), the second monomer is a mixture of styrene, butyl acrylate, n-butyl methacrylate and vinyl trimethoxy silane and the third monomer is methacrylic acid.
In an embodiment of the present disclosure, the first monomer is dissolved in water to obtain a first monomer solution.
In an exemplary embodiment, the second predetermined amount of a polymerizable surfactant is mixed with plurality of monomers at a temperature of 35 °C.
In an embodiment of the present disclosure, the predetermined amount of first monomer is in the range of 0.05 mass% to 0.5 mass%, with respect to the total emulsion polymer composition. In an exemplary embodiment, the predetermined amount of first monomer is 0.12 mass% with respect to the total mass of the emulsion polymer composition. In another exemplary embodiment, the predetermined amount of first monomer is 0.1 mass% with respect to the total mass of the emulsion polymer composition. In yet another exemplary embodiment, the predetermined amount of first monomer is 0.2 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the predetermined amount of second monomer is in the range of 40 mass% to 55 mass% with respect to the total emulsion polymer composition. In an exemplary embodiment, the predetermined amount of second monomer is 46.8 mass% with respect to the total emulsion polymer composition. In another exemplary embodiment, the predetermined amount of second monomer is 46.9 mass% with respect to the total emulsion polymer composition. In yet another exemplary embodiment, the predetermined amount of second monomer is with respect to the total emulsion polymer composition is 47 mass% with respect to the total emulsion polymer composition.
In an embodiment of the present disclosure, the predetermined amount of the third monomer is in the range of 0.5 mass% to 2 mass% with respect to the total emulsion polymer composition. In an exemplary embodiment, the predetermined amount of third monomer is 1 mass% with respect to the total emulsion polymer composition.
In an embodiment of the present disclosure, the second predetermined amount of a polymerizable surfactant and plurality of monomers are stirred for a time period is in the range of 5 minutes to 25 minutes. In an exemplary embodiment, the second predetermined amount of a polymerizable surfactant and plurality of monomers are stirred for 15 minutes.
In an embodiment of the present disclosure, the third monomer is added just before the addition of the first portion of the pre-emulsion to the mixture.
In a third step, 2 mass% to 15 mass% of the pre-emulsion is added to the mixture followed by adding a first predetermined amount of an initiator at a second predetermined temperature to obtain a first resultant.
In an exemplary embodiment, 5 mass% to 8 mass% of the pre-emulsion is added to the mixture.
In an embodiment of the present disclosure, the initiator is selected from potassium persulphate (PPS) and sodium formaldehydesulfoxylate (SFS). In an exemplary embodiment, the initiator is potassium persulphate (PPS).
In an embodiment of the present disclosure, the first predetermined amount of initiator is in the range of 0.05 mass% to 0.3 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the initiator is potassium persulphate and the first predetermined amount of initiator is 0.17 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the initiator is an aqueous solution.
In an embodiment of the present disclosure, the amount of the initiator in the first predetermined amount of initiator solution is in the range of 3 mass% to 10 mass%. In an exemplary embodiment, the amount of the initiator is 6.3 mass% in the first predetermined amount of the initiator solution.
In an embodiment of the present disclosure, the second predetermined temperature is in the range of 80 °C to 90 °C. In an exemplary embodiment, the second predetermined temperature is 82 °C.
In an embodiment of the present disclosure, a first portion of the pre-emulsion is added to the mixture followed by immediately adding a first predetermined amount of an initiator.
In accordance with the present disclosure, the temperature of the reactor drops after the addition of initiator and then will increase due to reaction exotherm. The exotherm is allowed to settle. The exotherm is upto 83 °C. Once the exotherm subsides and temperature is dropped by 0.2 °C, remaining portion of preemulsion and initiator is added to the first resultant.
In a fourth step, 85 mass% to 98 mass% of the pre-emulsion is added to the first resultant followed by adding a second predetermined amount of the initiator at the second predetermined temperature to obtain a second resultant.
In an embodiment of the present disclosure, the second predetermined amount of the initiator is in the range of 0.1 mass% to 0.4 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the second predetermined amount of the initiator is 0.18 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the initiator is an aqueous solution.
In an embodiment of the present disclosure, the amount of the initiator in the second predetermined amount of the initiator solution is in the range of 2 mass% to 10 mass%. In an exemplary embodiment, the amount of initiator is 4.5 mass% in the second predetermined amount of initiator solution.
In an embodiment of the present disclosure, the second predetermined temperature is in the range of 80 °C to 90 °C. In an exemplary embodiment, the second predetermined temperature is 85 °C.
In an embodiment of the present disclosure, 85 mass% to 98 mass% of the pre-emulsion is added to the first resultant followed by adding a second predetermined amount of the initiator and stirred for a time period in the range of 1 hour to 10 hours. In an exemplary embodiment, 85 mass% to 98 mass% of the pre-emulsion is added to the first resultant mixture followed by adding a second predetermined amount of the initiator and stirred for 4.5 hours.
Stage III: Chaser catalyst stage:
In a fifth step, the second resultant is cooled to a third predetermined temperature and predetermined amounts of a plurality of reducing agents are added to obtain a third resultant.
In an embodiment of the present disclosure, the third predetermined temperature is in the range of 70 °C to 78 °C. In an exemplary embodiment, the third predetermined temperature is below 78 °C.
In an embodiment of the present disclosure, the plurality of reducing agents comprise first reducing agent and second reducing agents independently selected from the group consisting of a mixture of tert-butyl hydroperoxide and a non-polymerizable surfactant, a mixture of sodium formaldehyde sulfoxylate and a non-polymerizable surfactant, a mixture of sodium acetone bisulphite and a non-polymerizable surfactant, a mixture of L-ascorbic acid and a non-polymerizable surfactant and a mixture of sodium meta bisulphate and a non-polymerizable surfactant.
In an embodiment of the present disclosure, the second resultant is cooled to a third predetermined temperature and a plurality of reducing agents are added and stirred for a time period in the range of 60 minutes to 120 minutes. In an exemplary embodiment, the second resultant is cooled to a temperature below 78 °C and a plurality of reducing agents are added and stirred for a time period of 90 minutes.
In an embodiment of the present disclosure, the predetermined amount of a first reducing agent comprises an aqueous solution of a first predetermined amount of a non-polymerizable surfactant and a predetermined amount of a first reducing agent.
In an embodiment of the present disclosure, the non-polymerizable surfactant is selected from the group consisting of non-ionic fatty alcohol ethoxylates solution, sodium dodecylbenzenesulfonate, alkyl polyethylene glycol ether and secondary alcohol ethoxylate. In an exemplary embodiment, the non-polymerizable surfactant is non-ionic fatty alcohol ethoxylates (Teric 463).
In an embodiment of the present disclosure, the predetermined amount of a first reducing agent is in the range of 0.01 mass% to 0.08 with respect to the total mass of the emulsion composition. In an exemplary embodiment, the predetermined amount of first reducing agent is 0.04 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the first predetermined amount of a non-polymerizable surfactant is in the range of 0.05 mass% to 0.3 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the first predetermined amount of the non-polymerizable surfactant is 0.15 mass% of the total mass of the emulsion polymer composition.
The predetermined amount of second reducing agent is in the range of 0.01 mass% to 0.08 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the predetermined amount of second reducing agent is 0.04 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the reducing agent is an aqueous solution.
In an embodiment of the present disclosure, the amount of the first reducing agent in the first reducing agent solution is in the range of 5 mass% to 15 mass%. In an exemplary embodiment, the amount of first reducing agent in the first reducing agent solution is 8 mass%.
In an embodiment of the present disclosure, the amount of non-polymerizable surfactant in the first reducing agent solution is in the range of 20 mass% to 40 mass%. In an exemplary embodiment, the amount of non-polymerizable surfactant in the first reducing agent solution is 30 mass%.
In an embodiment of the present disclosure, the amount of the second reducing agent in the second reducing agent solution is in the range of 5 mass% to 15 mass%. In an exemplary embodiment, the amount of the second reducing agent in the second reducing agent solution is 8 mass%.
The reducing agent is added at a lower temperature to reduce the free monomer content of polymerization reaction effectively.
The reducing agent generates free radicals for polymerization.
Stage IV: Additives stage:
In a sixth step, the third resultant is cooled to a temperature in the range of 40 °C to 50 °C followed by adding a predetermined amount of a pH stabilizer and stirring followed by adding a predetermined amount of a coupling agent under stirring to obtain a fourth resultant having a pH in the range of 8.5 to 9.5.
In an exemplary embodiment, the third resultant is cooled to a temperature of 45 °C.
In an embodiment of the present disclosure, the pH stabilizer is selected from the group consisting of 95% 2-amino-2-methyl-1-propanol (AMP 95), 2-amino ethanol (Phlex 110), alkanolamine and potassium methylsiliconate (Silres BS 168). In an exemplary embodiment, the pH stabilizer is 2-amino ethanol (Phlex 110) and potassium methylsiliconate (Silres BS 168). In another exemplary embodiment, the pH stabilizer is 2-amino ethanol (Phlex 110).
In an embodiment of the present disclosure, the predetermined amount of pH stabilizer is in the range of 0.2 mass% to 1 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment the predetermined amount of pH stabilizer is 0.8 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the pH stabilizer is an aqueous solution.
In an embodiment of the present disclosure, the amount of the pH stabilizer in the pH stabilizer solution is in the range of 0.5 mass% to 2 mass%. In an exemplary embodiment, the amount of pH stabilizer in the pH stabilizer solution is 1 mass%.
In an embodiment of the present disclosure, the pH of third resultant which is cooled changes after addition of pH stabilizers.
In an embodiment of the present disclosure, the coupling agent comprises a mixture of a pre-determined amount of coupling agent and a predetermined amount of a non-polymerizable surfactant.
In an embodiment of the present disclosure, the coupling agent solution is an aqueous solution of a mixture of coupling agent and a non-polymerizable surfactant.
In an embodiment of the present disclosure, the coupling agent is selected from the group consisting of adipic acid dihydrazide (ADH), ethylene glycol dimethyl acrylate (EGDMA) and succinic acid dihydrazide.
In an embodiment of the present disclosure, the predetermined amount of coupling agent is in the range of 0.02 mass% to 0.1 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the predetermined amount of the coupling agent is 0.06 mass% with respect to the total mass of the emulsion polymer composition. In another exemplary embodiment, the predetermined amount of the coupling agent is 0.05 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the non-polymerizable surfactant is selected from the group consisting of non-ionic fatty alcohol ethoxylates solution, sodium dodecylbenzenesulfonate solution, alkyl polyethylene glycol ether solution and secondary alcohol ethoxylate solution. In an exemplary embodiment, the non-polymerizable surfactant is sodium dodecyl benzene.
In an embodiment of the present disclosure, the predetermined amount of non-polymerizable surfactant is in the range of 0.1 mass% to 0.5 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment the second predetermined amount of non-polymerizable surfactant is 0.2 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the amount of the coupling agent in the coupling agent solution is in the range of 5 mass% to 15 mass%. In an exemplary embodiment, the amount of the coupling agent in the coupling agent solution is 7.5 mass%. In another exemplary embodiment, the amount of coupling agent in the coupling agent solution is 6.25 mass%.
In an embodiment of the present disclosure, the amount of non-polymerizable surfactant in the coupling agent solution is in the range of 20 mass% to 30 mass% with respect to the total amount of coupling agent solution. In the exemplary embodiments, the amount of non-polymerizable surfactant in the coupling agent solution is 25 mass% in the coupling agent solution.
In a seventh step, predetermined amounts of plurality of preservatives and a predetermined amount of a defoamer are added to the fourth resultant at a temperature in the range of 40 °C to 50 °C followed by adding water under stirring to obtain the emulsion polymer composition.
In an embodiment of the present disclosure, each of the preservatives and a defoamer are added to the fourth resultant and mixed for a time period in the range of 5 minutes to 15 minutes. In an exemplary embodiment, each of the preservatives and a defoamer are added to the fourth resultant and mixed for a time period of 10 minutes.
In an embodiment of the present disclosure, the plurality of preservatives are selected from the group consisting of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MCIT/CMIT) (Sanitized Cl15) and benzisothiazolinone (BIT) (Sanitized BT 10A). In an exemplary embodiment, the plurality of preservatives are a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MCIT/CMIT) (Sanitized Cl15) and benzisothiazolinone (BIT) (Sanitized BT 10A).
In an embodiment of the present disclosure, the predetermined amount of preservative is in the range of 0.1 mass% to 0.5 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment the predetermined amount of preservative is 0.2 mass% with respect to the total mass of the emulsion polymer composition.
In an embodiment of the present disclosure, the plurality of preservatives is prepared as an aqueous solution.
In an embodiment of the present disclosure, the amount of the preservative in the preservative solution is in the range of 40 mass% to 60 mass%. In an exemplary embodiment, the amount of preservative in the preservative solution is 50 mass%.
In an embodiment of the present disclosure, the defoamer is selected from the group consisting of fumed silica, polyether siloxane emulsion and mineral oil based defoamer.
In an embodiment of the present disclosure, the predetermined amount of defoamer is in an amount in the range of 0.002 mass% to 0.01 mass% with respect to the total mass of the emulsion polymer composition. In an exemplary embodiment, the predetermined amount of defoamer is 0.006 mass with respect to the total mass of the emulsion polymer composition.

In an embodiment of the present disclosure, the defoamer is an aqueous solution.

In an embodiment of the present disclosure, the amount of defoamer in the defoamer solution is in the range of 1 mass% to 8 mass%. In an exemplary embodiment, the amount of defoamer in the defoamer solution is 3 mass%.

In an exemplary embodiment, the predetermined amounts of plurality of preservatives and a predetermined amount of defoamer are added to the fourth resultant at a temperature of 45 °C.

In an embodiment of the present disclosure, the predetermined amounts of plurality of preservatives and a defoamer is added to the fourth resultant followed by adding water and stirred for a time period is in the range of 20 minutes to 40 minutes. In an exemplary embodiment, the time period is 30 minutes.

In an embodiment of the present disclosure, the water is added in an amount in the range of 45 mass% to 55 mass% with respect to the total mass of the emulsion polymer composition.

The foregoing description of the embodiments has been provided for purposes of illustration and is not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment but are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.
Experiment 1: Process for the preparation of emulsion polymer composition in accordance with the present disclosure:
Example 1:
Stage I: Reactor charge
0.15 g of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka SR10) was dissolved in 100 ml water by heating to 80 °C to obtain a C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka SR10) solution. 0.1g of sodium bicarbonate was dissolved in 2.5 ml water by heating to 80 °C to obtain a sodium bicarbonate solution. Mixing Adeka SR10 solution and sodium bicarbonate solution at 80 °C for 25 minutes to obtain a mixture.

Stage II: Pre Emulsion
1g of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka SR10) was added to 100ml water were mixed and heated to 80 °C to obtain a Adeka SR10 solution and cooled to 35 °C (room temperature) and sequentially DAAM solution (0.12 g of DAAM was dissolved in 2ml of water to obtain a DAAM solution), 22.7 g of styrene, 19.6 g of 2-ethylhexyl acrylate, and 4.5 g of n-butyl methacrylate, 0.5g of Silane A171 and 1 g of methacrylic acid was added at 35 °C under stirring and mixed for 15 minutes to obtain a pre-emulsion(Methacrylic acid was added just before the addition of pre-emulsion to the mixture).

5% to 8% of pre-emulsion (first portion of pre-emulsion) was added to the mixture followed by adding potassium persulphate solution (0.17 g of potassium persulphate (first predetermined amount of initiator) was dissolved in 2.7 ml of water to obtain potassium persulphate solution) at 82 °C to obtain a first resultant.

It was observed that the temperature of reactor drops initially and then was increased due to reaction exotherm. The exotherm was allowed to settle. The exotherm observed was 83 °C. Once the exotherm subsides and temperature was dropped by 0.2 °C remaining 92 % to 95% of preemulsion solution (second portion of pre-emulsion) along with/followed by addition of potassium persulphate solution (0.18 g of potassium persulfate (second predetermined amount of initiator) in 4 ml water) was added while maintaining the temperature during addition at 85 °C to obtain a second resultant. The addition of 92 % to 95% pre-emulsion was completed in 4 hours to 4 hours 15 minutes. Addition of PPS simultaneously was completed in 4 hours 15 minutes to 4 hours 30 minutes.

Stage III: Chaser catalyst
The second resultant was cooled to 73 °C followed by the addition of tBHP solution (0.04 g of tetra butyl hydroperoxide (tBHP) and 0.15 g of Terric 461 was dissolved in 0.5 ml of water to obtain tBHP solution) over 10 minutes and stirred for 10 minutes followed by the addition of SFS solution (0.04g of SFS was dissolved in 0.5 ml water to obtain a SFS solution) over 10 minutes and was maintained for 40 minutes to obtain a third resultant.

Stage IV: Additives addition
The third resultant was cooled to 45 °C followed by addition of phlex solution (0.4 g of phlex 110 was dissolved in 0.4 ml of water to obtain a phlex 110 solution) over a period of 5 minutes and further stirred for 10 minutes followed by addition of ADH solution, (0.06 g of Adipic dihydrazide (ADH) and 0.2 g of sodium dodecylbenzenesulfonate were mixed to obtain a paste. The paste was dissolved in 0.8 ml water to obtain an ADH solution) under stirring over 20 minutes and further stirred for 10 minutes to obtain a fourth resultant having a pH of about 9.

0.1g of Sanitized Cl15 was dissolved in 0.2 ml water and stirred for 10 minutes to obtain Sanitized Cl15 solution. 0.1g of Sanitized BT 10A was dissolved in 0.2 ml water and stirred for 10 minutes to obtain Sanitized BT 10A solution. 0.006g of tegofoamex was dissolved in 0.2 ml water and stirred for 10 minutes to obtain a tegofoamex solution. Sanitized Cl15 solution was added to the fourth resultant at 45 °C and mixed for 10 minutes followed by addition of Sanitized BT 10A solution at 45 °C and mixed for 10 minutes followed by addition of tegofoamex K3 solution at 45 °C and mixed well for 10 minutes followed by adding remaining amount of water i.e. 50% of water to obtain emulsion polymer composition.

Example 2:
Stage I: Reactor charge
0.2 g of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka SR10) was dissolved in 100 ml water by heating to 80 °C to obtain a C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid Adeka SR10 solution. 0.1g of sodium bicarbonate was dissolved in 2.7 ml water by heating to 80 °C to obtain a sodium bicarbonate solution. Mixing Adeka SR10 solution and sodium bicarbonate solution at 80 °C for 25 minutes to obtain a mixture.
Stage II: Pre Emulsion
1g of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid (Adeka SR10) and 100ml water were mixed and heated to 80 °C to obtain a Adeka SR10 solution and cooled at 35 °C (room temperature) and sequentially DAAM solution (0.1 g of DAAM was dissolved in 1.5 ml of water to obtain a DAAM solution), 23 g of styrene, 19.3 g of butyl acrylate, and 4.5 g of n-butyl methacrylate, 0.4 g of Silane A171 and 1 g of methacrylic acid at 35 °C was added under stirring and mixed for 15 minutes to obtain a pre-emulsion(Methacrylic acid was added just before the addition of pre-emulsion to the mixture).

5% to 8% of pre-emulsion was added to the mixture followed by addition of potassium persulphate solution (0.17 g of potassium persulphate (first predetermined amount of initiator) was dissolved in 2.7 ml of water to obtain potassium persulphate solution) at 82 °C to obtain a first resultant.

It was observed that the temperature of reactor drops initially and then was increased due to reaction exotherm. The exotherm was allowed to settle. The exotherm observed was 83 °C. Once the exotherm subsides and temperature was dropped by 0.2 °C remaining 92 % to 95% of preemulsion solution followed by/ along with potassium persulphate solution (0.18 g of potassium persulphate (second predetermined amount of initiator) in 4 ml water) was added while maintaining the temperature during addition at 85 °C to obtain a second resultant. The addition of 92 % to 95% pre-emulsion was completed in 4 hours to 4 hours 15 minutes. Addition of PPS simultaneously was completed in 4 hours 15 minutes to 4 hours 30 minutes.

Stage III: Chaser catalyst
The second resultant was cooled to 73 °C followed by the addition of tBHP solution (0.04 g of tetra butyl hydroperoxide (tBHP) and 0.15 g of Terric 461 was dissolved in 0.5 ml of water to obtain tBHP solution) over 10 minutes and stirred for 10 minutes followed by the addition of SFS solution (0.04g of SFS was dissolved in 0.5 ml water to obtain a SFS solution) over 10 minutes and was maintained for 40 minutes to obtain a third resultant.

Stage IV: Additives addition
The third resultant was cooled to 45 °C followed by addition of phlex solution (0.8 g of phlex 110 was dissolved in 0.4 ml of water to obtain a phlex 110 solution). over a period of 5 minutes and further stirred for 10 minutes followed by addition of silres solution (0.4 g of Silres in 1.2 ml water) over a period of 20 minutes and mixed well for 10 minutes followed by addition of ADH solution (0.05 g of Adipic dihydrazide (ADH) and 0.2 g of sodium dodecylbenzenesulfonate were mixed to obtain a paste. The paste was dissolved in 0.8 ml water to obtain an ADH solution) under stirring over 20 minutes and further stirred for 10 minutes to obtain a fourth resultant having a pH of about 9.

0.1g of Sanitized Cl15 was dissolved in 0.2 ml water and stirred for 10 minutes to obtain Sanitized Cl15 solution. 0.1g of Sanitized BT 10A was dissolved in 0.2 ml water and stirred for 10 minutes to obtain Sanitized BT 10A solution. 0.006g of tegofoamex was dissolved in 0.2 ml water and stirred for 10 minutes to obtain a tegofoamex solution. Sanitized Cl15 solution was added to the fourth resultant mixture at 45 °C and mixed for 10 minutes followed by addition of Sanitized BT 10A at 45 °C and mixed for 10 minutes followed by addition of tegofoamex solution at 45 °C and mixed well for 10 minutes followed by adding remaining amount of water i.e. 50% of water to obtain emulsion polymer composition.

Examples 3 and 4:
Examples 3 and 4 were carried out in the same way as example 2 except that in example 4 EGDMA was used as a first monomer instead of DAAM as well as varying the amounts of ingredients as tabulated in table 1.
Example 5 (Comparative example)
0.1g of sodium bicarbonate was dissolved in 2.5 ml water by heating to 80 °C to obtain a sodium bicarbonate solution.

0.10 g of DAAM was dissolved in 2 ml of water to obtain a DAAM solution. To this 23 g of styrene, 19.3 g of butyl acrylate, 4.5 g of n-butyl methacrylate and mixed for 15 minutes followed by the addition of 1 g of methacrylic acid and 0.5g of Silane A171 at 30 °C to obtain a pre-emulsion.

0.17 g of potassium persulphate was dissolved in 2.7 ml of water to obtain potassium persulphate solution. 5% of pre-emulsion was added to sodium bicarbonate solution at 82 °C followed by addition of potassium persulphate solution to obtain a first resultant.

It was observed that the temperature of reactor drops initially and then was increased due to reaction exotherm. The exotherm was allowed to settle. The exotherm observed was 83 °C. Once the exotherm subsides and temperature was dropped by 0.2 °C remaining 95% of preemulsion solution along with potassium persulphate solution was added while maintaining the temperature during addition at 85 °C to obtain a second resultant.

0.04g of tBHP and 0.15 g of Terric 461 was dissolved in 0.5 ml of water to obtain tBHP solution. 0.04g of SFS was dissolved in 0.5 ml water to obtain a SFS solution.

The second resultant was cooled to 75 °C followed by the addition of tBHP solution over 10 minutes and stirred for 10 minutes followed by the addition of SFS solution over 10 minutes and was maintained for 40 minutes to obtain a third resultant.

0.05g of ADH and 0.2 g of sodium dodecyl benzene sulfonate (LDS 25R) were mixed to obtain a paste. The paste was dissolved in 0.8 ml water to obtain an ADH solution.

0.4 g of phlex 110 was dissolved in 0.4 ml of water to obtain a phlex 110 solution. 0.4 g of Silres BS 168 was dissolved in 1.2 ml water to obtain Silres BS 168 solution. The third resultant mixture was cooled to 45 °C followed by addition of pHlex solution over a period of 5 minutes and stirred for 10 minutes. Silres BS168 solution was added over 20 minutes and stirred for 10 minutes followed by addition of ADH solution under stirring for 20 minutes and stirred for 10 minutes to obtain a fourth resultant having a pH of about 9.

0.1g of Sanitized Cl15 was dissolved in 0.2 ml water and stirred for 10 minutes to obtain Sanitized Cl15 solution. 0.1g of Sanitized BT 10A was dissolved in 0.2 ml water and stirred for 10 minutes to obtain Sanitized BT 10A solution. 0.006g of tegofoamex K3 was dissolved in 0.2 ml water and stirred for 10 minutes to obtain a tegofoamex solution. Sanitized Cl15 solution, Sanitized BT 10A solution and tegofoamex solution were added to the fourth resultant mixture followed by adding remaining amount of water i.e. 50% of water to obtain emulsion polymer composition.

The amounts of the ingredients in examples 1-4 and comparative example are summarized in table 1 below:
Table 1: Amounts of the ingredients in examples 1-4 and comparative example

Ingredients Role of ingredient Example 1 Example 2 Example 3 Example 4 Example 5
(Comparative example)
gm gm gm gm gm
Reactor charge
DM water Fluid medium 15.55 16.00 16.00 16.00 16.00
SLS Non-polymerizable surfactant - - - - 0.2
Adeka SR10 Polymerizable surfactant 0.15 0.2 0.2 0.2 -
Sodium bicarbonate Buffer 0.1 0.1 0.1 0.1 0.1
DM water Fluid medium 2.7 2.7 2.7 2.7 2.7
Pre Emulsion
DM water Fluid medium 18.1 18.1 18.1 19.6 18.0
Sodium lauryl sulfate SLS (10%) Non-polymerizable surfactant - - - - 1.00
Adeka SR10 (10%) Polymerizable surfactant 1.00 1.00 1.00 1.00 -
DM water Fluid medium 2 1.5 1.5 1.5 -
DAAM First Monomer 0.120 0.1 0.2 - 0.1
EGDMA First Monomer/Coupling agent - - - 0.2 -
Styrene Second Monomer 22.7 23.00 23.00 23.00 23.00
Butyl Acrylate Second Monomer - 19.3 19.3 19.3 19.3
2- EHA (2-Ethylhexyl acrylate) Second Monomer 19.6 - - - -
n-BMA (N-butyl methacrylate) Second Monomer 4.5 4.5 4.5 4.5 4.5
MAA-Methacrylic acid Third Monomer 1.00 1.00 1.00 1.00 1.00
Silane A171 Second Monomer 0.5 0.4 0.4 0.4 0.4
PPS 1 (Potassium persulfate) Initiator 0.17 0.17 0.17 0.17 0.17
PPS 2(Potassium persulfate) Initiator 0.18 0.18 0.18 0.18 0.18
DM water Fluid medium 4 3.5 3.5 3.5 3.5
DM water (flushing) Fluid medium 0.5 0.534 0.534 0.534 0.534
Chaser catalyst
tBHP (tert-butyl hydroperoxide) Reducing agent 0.04 0.04 0.04 0.04 0.04
Terric 461 Non-polymerizable surfactant 0.15 0.15 0.15 0.15 0.15
DM water Fluid medium 0.5 0.5 0.5 0.5 0.5
SFS (Sodium formaldehydesulfoxylate) Reducing agent 0.04 0.04 0.04 0.04 0.04
DM water Fluid medium 0.5 0.5 0.5 0.5 0.5
tBHP Reducing agent 0.04 0.04 0.04 0.04 0.04
Terric 461 Non-polymerizable surfactant 0.15 0.15 0.15 0.15 0.15
DM water Fluid medium 0.5 0.5 0.5 0.5 0.5
SFS (Sodium formaldehydesulfoxylate) Reducing agent 0.04 0.04 0.04 0.04 0.04
DM water Fluid medium 0.5 0.5 0.5 0.5 0.5
Additives addition
Phlex 110 pH stabilizer 0.8 0.4 0.4 0.4 0.4
DM water Fluid medium 0.4 0.4 0.4 0.4 0.4
Silres BS168 pH stabilizer - 0.4 0.4 0.4 0.4
DM water Fluid medium 1.2 1.2 1.2 1.2 1.2
Sanitized CI15 Preservative 0.1 0.1 0.1 0.1 0.1
DM water Fluid medium 0.2 0.2 0.2 0.2 0.2
Sanitized BIT 10A Preservative 0.1 0.1 0.1 0.1 0.1
DM water Fluid medium 0.2 0.2 0.2 0.2 0.2
Adipic acid dihydrazide Coupling agent 0.06 0.05 0.05 - 0.05
Sodium dodecyl benzene sulfonate Non-polymerizable surfactant 0.2 0.2 0.2 - 0.2
DM water Fluid medium 0.8 0.8 0.8 0.8 0.8
Tegofoamex K3 Defoamer 0.006 0.006 0.006 0.006 0.006
DM water Fluid medium 0.2 0.2 0.2 0.2 0.2
DM water Fluid medium 0.5 1.00 1.1 0.9 1.15
*In example 4, EGDMA is used as a monomer, instead of DAAM. EGDMA works as a monomer as well as a coupling agent. Therefore, no coupling agent is used in example 4.
Experiment 2: Test Parameters for the emulsion composition prepared in accordance with the present disclosure.
Example 1: Water resistance
Water resistance of emulsion films prepared in accordance with the present disclosure and conventional emulsions were measured
The average particle size, viscosity and MFFT of the emulsion films prepared in accordance with the present disclosure and the conventional emulsions were measured. The particle size of emulsions was measured using Horiba - Light scattering particle size distribution analyzer LA 950. The viscosity of emulsions was measured using Brookfield Viscometer DV1- Using Spindle 3 at 60 rpm. The MFFT of emulsions was measured using Rhopoint MFFT Bar using 76µ applicator under Nitrogen atmosphere.
A glass plate was taken and test emulsion using 4 mill applicator was applied such that the dry film thickness of emulsion film was 40 to 50 microns. The film was dried at room temperature (27 °C and 60 % RH) for 1 day. Then the film was dipped into water such that 40 to 50% film was dipped in water. The film was observed for water resistance after 24 hours visually. The results are summarized in Table 2 below:
Table 2: Measurement of average particle size, viscosity and MFFT and water resistance for emulsion films prepared in accordance with the present disclosure and conventional emulsions

Example 1 Example 2 Example 3 Example 4 Example 5 (Comparative Example)
Average particle size (nm) 100 80 80 80 78
Viscosity in cps 650 705 638 700 688
MFFT (Minimum Film Formation Temperature) in deg C 24 23.0
26.6
27.3
25.5
Water resistance after curing emulsion film
for 24 hrs
R=5 Excellent
R=1 Poor 4 4 3 4 2

From Table 2 it is seen that the particle size of the polymer emulsions prepared in accordance with the present disclosure have a desired particle size in the range of 70 nm to 110 nm, desired viscosity in the range of 300 cps to 700 cps, desired MFFT in the range of 20 °C to 27 °C. Higher MFFT value is observed in example 4 due to different coupling agent EGDMA. EGDMA acts as a monomer as well as a coupling agent and provides water resistant properties when used along with non-polymerizable surfactant Adeka SR10.
The comparative example 5 with conventional emulsions did not show desirable water resistant properties irrespective of other parameters which are within the desired ranges.
Example 2: Application on Paper panel at 100 micron wet film thickness (Mic WFT)
The emulsion polymer compositions prepared in accordance with the present disclosure and conventional emulsions were applied on a paper panel to obtain a coating film. The optical properties of the coating film were measured. The results are summarized in Table 3 below:
Table 3: Optical properties of emulsion polymer compositions prepared in accordance with the present disclosure and conventional emulsions
Example 1 Example 2 Example 3 Example 4 Comparative Example
Odour Acceptable but very low fishy odour Acceptable very low Acceptable very low Acceptable very low Acceptable very low
a. Contrast ratio 94.6 95.24 93.81 94.95 92.51
b. Tappi brightness 89.4 89.93 89.2 90.52 90.23
c. Whiteness index 86.53 87.17 86.56 90.08 87.85

The contrast ratio of comparative example is lesser than the emulsion polymer compositions prepared in accordance with the present disclosure.
Yellowness Index & Whiteness Index are calculated as per ASTM E313-15.
Tappi brightness measures brightness of the coated film. The higher value is better indicating better brightness. Yellowness Index is a number calculated from spectrophotometric data that describes the change in color of a test sample from clear or white to yellow. Lower value is better indicating lower yellowness in film, better whiteness, and shade acceptance. Whiteness measures the whiteness of the film. Higher value is better indicating the improved or better white film. The contrast ratio, tappi brightness and whiteness index values of the coating films of the emulsions in examples 1-4 prepared in accordance with the present disclosure are within acceptable limits.
From Table 3 it is seen that the polymer emulsions prepared in accordance with the present disclosure have high water resistance along with desirable contrast ratio, tappi brightness and whiteness index.
Example 3: Sheen on glass plate:
Method for measuring the gloss on glass panel
Sheen is a measure of the reflected light (glossiness) from a paint finish. A glass plate was taken and the test paint comprising emulsion polymer composition of the present disclosure or conventional emulsions was applied using 4 mill applicator such that the dry film thickness of the paint was close to 50 microns. The film was dried at room temperature (27 °C and 60 %RH) for 1 day. The gloss was measured using glossometer. Gloss indicates shininess of the paint film. The results are summarized in table 4 below:
Table 4: Measurement of sheen on glass plate coated with paint comprising emulsion prepared in accordance with the present disclosure and glass plate coated with conventional paints comprising conventional emulsion composition

Example 1 Example 2 Example 3 Example 4 Comparative Example
60 ° 18.8 20.4 19.4 12 14.9
* The gloss value at 60 degrees is important in architectural paint coating, so the gloss values are measured at 60 °
From Table 4 it is seen that the gloss values of the polymer emulsions in examples 1-3 prepared in accordance with the present disclosure are higher as desired. Whereas the gloss value of polymer emulsion in example 4 prepared in accordance with the present disclosure is lower as different cross-linking system (EGDMA) is used in example 4 instead of DAAM and ADH of examples 1-3 of the present disclosure.
Example 4: Method for measuring the wet scrub resistance of paint on laneta panel
A laneta paper was taken and the test paint comprising emulsion polymer composition of the present disclosure and conventional emulsions was applied using 46mill applicator such that the dry film thickness of the paint was close to 50 microns. The film was dried at RT (27 °C and 60 %RH) for 7 days. The results were measured using wet scrub apparatus and are tabulated in Table 5 below:
(Wet Scrub is tested as per ASTM -D2486).
Table 5: Wet scrub resistance after 7 days in cycles
Example 1 Example 2 Example 3 Example 4 Comparative Example
Wet scrub resistance after 7 days in cycles 550 600 450 500 700

From Table 5 it is seen that the test paints comprising emulsion polymer compositions of the present disclosure show better wet scrub resistance as compared to paints comprising conventional emulsions.
Method for Evaluation for Stain Removability - The test paint comprising emulsion polymer composition of the present disclosure and the test paint comprising conventional emulsions were applied on laneta paper using 4 mill applicator resulting into dry film thickness of 50 microns. The film was dried at RT (27 °C and 60 %RH) for 7 days. Then following stains were applied one below other along the length of paper and kept for 4 hours for drying. The stains were removed using 5% detergent solution by running 100 cycles. The film was dried and checked visually to give the rating.
(Ratings 1 to 10, 10= good and 1 = worst)
The results are summarized in Table 6 below:
Table 6: Method for Evaluation for Stain Removability using paint compositions comprising emulsion composition prepared in accordance with the present disclosure and conventional paints with conventional emulsions
Example 1 Example 2 Example 3 Example 4 Comparative Example
Turmeric 5 7 5 6 5
Grease 8 8 8 8 8
Oil crayons 8 8 8 8 8
Wax crayons 6 8 8 8 7
Pen 6 7 6 7 8
Marker 7 7 4 3 5
Pencil 5 7 6 7 6
Total 45 52 45 47 47

From Table 6 it is seen that the total sum of evaluation for stain removability for the emulsions in examples 1 to 4 prepared in accordance with the present disclosure has desired values indicating better stain removability. Further, it is seen that the emulsion polymer compositions prepared in accordance with the present disclosure have higher water resistance values along with higher stain removability.
Example 5: Method for testing water proofing performance- The emulsion polymer prepared in accordance with the present disclosure is evaluated in High End Interior Paint.
The details of the paint are as follows.
The paint was mid to low PVC interior paint with PVC in the range of 25 % to 30 %. The paint composition comprises emulsion in an amount in the range of 30 % to 50 %, TiO2 in the range of 15 % to 20 %, extenders like calcium carbonate and talc in the range of 15 % to 25%. The paint formulation is based on mixed thickener system to manage and control the flow of the paint.
The paint formulation was free from liquid ammonia and has combination of the incan as well as dry film preservatives to prevent the microbial growth. Natural citrus based biocides were used as incan preservative and synthetic biocides are used as dry film preservative in the paint formulation. There were different silane-based additives in the paint formulation to impart improved interior water proofing performance along with improved adhesion and scuffing resistance. Combination of other set of additives was used to block the pores on the masonry surface and prevent the capillary action in the paint formulation.
1 feet by1 feet porous concrete panel of thickness 1 inch was taken. 1:1 dilute coat of the test paint comprising emulsion polymer composition prepared in accordance with the present disclosure (test paint was diluted with water in a ratio of 1:1) was applied and allowed to dry for 4 hours to 6 hours. Then 2 coats of cement putty were applied. An interval of 4 to 6 hours was kept between the application of two coats of cement putty. Then 1:1 dilute coat of test paint was applied and allowed to dry for 4 to 6 hours. Then test paint was diluted to 40% and two coats were applied with a time interval of 4 to 6 hours. After complete application of the paint, the paint was allowed to dry for 7 days. The test panels coated with paint were kept in the tray filled with water in such a way that 70% of the panel height is dipped in water. The results of rising dampness were observed. The results are summarized in Table 7 below:
Table 7: Method for testing water proofing performance using paint compositions comprising emulsion composition prepared in accordance with the present disclosure and conventional paints with conventional emulsions
Example 1 Example 2 Example 3 Example 4 Comparative Example
(Results for samples kept in water tray and removed) No Blisters
R = 9 No Blisters
R = 9 Blisters Observed after 48 hrs
R= 6 Blisters not observed R=9 Blisters observed in 2 hrs

From Table 7, it is seen that blisters were observed after 2 hours for the paint comprising conventional emulsions whereas the paint comprising emulsion polymer composition of the present disclosure, showed no blisters even after a long time i.e. after 48 hours.
TECHNICAL ADVANCEMENTS
The present disclosure described hereinabove has several technical advantages including, but not limited to, the realization of an emulsion polymer composition that:
• uses polymerizable surfactants which bind to the polymer backbone;
• uses alkyl phenol ethylene oxide (APEO) free surfactants;
• uses biocides that do not release any formaldehyde;
• is free of ammonia;
• forms low odour emulsions;
• improve the waterproofing performance for interior application; and
• is economical and environment friendly;
a process for preparing emulsion polymer composition that:
• is simple, environment friendly and cost-efficient.
The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the following description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.
The foregoing description of the specific embodiments so fully reveals the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results.
Any discussion of documents, acts, materials, devices, articles or the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.
The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations, and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions, or quantities fall within the scope of the disclosure unless there is a statement in the specification specific to the contrary.
While considerable emphasis has been placed herein on the components and component parts of the preferred embodiments, it will be appreciated that many embodiments can be made and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and other changes in the preferred embodiment, as well as other embodiments of the disclosure, will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation. ,CLAIMS:WE CLAIM:

1. An emulsion polymer composition comprising:
A. a reaction product of
i. 40 mass% to 60 mass% of a plurality of monomers;
ii. 0.5 mass% to 2 mass% of at least one polymerizable surfactant;
iii. 0.1 mass% to 1 mass% of at least one initiator;
iv. 0.01 mass% to 0.5 mass% of at least one coupling agent;
v. 0.05 mass% to 0.3 mass% of a plurality of reducing agents;
vi. 0.1 mass% to 2 mass% of at least one pH stabilizer; and
vii. 0.05 mass% to 0.2 mass% of at least one buffer;
B. 0.5 mass% to 2 mass% of a plurality of additives; and
C. q.s. water
wherein said mass% of each ingredient is with respect to the total mass of said emulsion polymer composition.

2. The composition as claimed in claim 1, wherein said plurality of monomers are selected from the group consisting of styrene, butyl acrylate, methacrylic acid, n-butyl methacrylate, diacetone acrylamide (DAAM), ethylene glycol dimethylacrylate (EGDMA), 2-ethylhexyl acrylate and vinyl trimethoxy silane.

3. The composition as claimed in claim 1, wherein said polymerizable surfactant is selected from the group consisting of alcohols, C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid, alkyl diphenyl oxide disulfonate, phosphate ester based polymerizable surfactants and reactive anionic emulsifier.

4. The composition as claimed in claim 1, wherein said initiator is selected from the group consisting of potassium persulphate, sodium persulphate and ammonium persulphate.

5. The composition as claimed in claim 1, wherein said coupling agent is selected from the group consisting of adipic acid dihydrazide (ADH), ethylene glycol dimethylacrylate (EGDMA) and succinic acid dihydrazide.

6. The composition as claimed in claim 1, wherein said plurality of reducing agents are selected from a combination of
• tert-butyl hydroperoxide and sodium formaldehydesulfoxylate;
• tert-butyl hydroperoxide and sodium acetone bisulphite;
• tert-butyl hydroperoxide and L-ascorbic acid; and
• tert-butyl hydroperoxide and sodium meta bisulphate.

7. The composition as claimed in claim 1, wherein said pH stabilizer is at least one selected from the group consisting of 95% 2-amino-2-methyl-1-propanol solution, 2-amino ethanol, alkanolamine and potassium methylsiliconate.

8. The composition as claimed in claim 1, wherein said buffer is selected from the group consisting of sodium bicarbonate, sodium acetate, sodium carbonate and ethylene diaminetetraacetic acid (EDTA).

9. The composition as claimed in claim 1, wherein said plurality of additives comprises a plurality of preservatives, at least one non-polymerizable surfactant and at least one defoamer.

10. The composition as claimed in claim 9, wherein
• said plurality of preservatives are in an amount in the range of 0.1 mass% to 0.5 mass%;
• said non-polymerizable surfactant is in an amount in the range of 0.1 mass% to 1 mass%; and
• said defoamer is in an amount in the range of 0.002 mass% to 0.01 mass%;
wherein said mass% of each ingredient is with respect to the total mass of said emulsion polymer composition.

11. The composition as claimed in claim 9, wherein said plurality of preservatives are at least one selected from the group consisting of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and benzisothiazolinone (BIT).

12. The composition as claimed in claim 9, wherein said non-polymerizable surfactant is at least one selected from the group consisting of non-ionic fatty alcohol ethoxylates, sodium dodecylbenzenesulfonate, alkyl polyethylene glycol ether and secondary alcohol ethoxylate.

13. The composition as claimed in claim 9, wherein said defoamer is selected from the group consisting of fumed silica, polyether siloxane emulsion and mineral oil based defoamers.

14. The composition as claimed in claim 1, wherein a mass ratio of said monomers to said polymerizable surfactant is in the range of 35:1 to 45:1.

15. The composition as claimed in claims 1 and 9, comprising
A. a reaction product of
i. diacetone acrylamide, styrene, 2-ethylhexyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as said plurality of monomers;
ii. C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as said polymerizable surfactant;
iii. potassium persulphate as said initiator;
iv. adipic acid dihydrazide as said coupling agent;
v. tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as said plurality of reducing agents;
vi. 2-amino ethanol as said pH stabilizer; and
vii. sodium bicarbonate as said buffer.
B. said plurality of additives comprising
I. a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), benzisothiazolinone as said plurality of preservatives;
II. non-ionic fatty alcohol ethoxylates and sodium dodecylbenzene sulfonate as non-polymerizable surfactants; and
III. fumed silica as said defoamer; and
C. q.s. water.

16. The composition as claimed in claim 15, comprising
A. a reaction product of
i. 0.10 mass% to 0.15 mass% of diacetone acrylamide, 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of 2-ethylhexyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.2 mass% to 0.8 mass% of vinyl trimethoxy silane as said plurality of monomers;
ii. 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as said polymerizable surfactant;
iii. 0.3 mass% to 0.4 mass% of potassium persulphate as said initiator;
iv. 0.02 mass% to 0.08 mass% of adipic acid dihydrazide as said coupling agent;
v. 0.05 mass% to 0.10 mass% of tert-butyl hydroperoxide and 0.05 mass% to 0.10 mass% of sodium formaldehydesulfoxylate as said plurality of reducing agents;
vi. 0.5 mass% to 1 mass% of 2-amino ethanol as said pH stabilizer; and
vii. 0.05 mass% to 0.15 mass% of sodium bicarbonate as said buffer.
B. said plurality of additives comprising
I. 0.05 mass% to 0.15 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.15 mass% of benzisothiazolinone as said plurality of preservatives;
II. 0.2 mass% to 0.4 mass% of non-ionic fatty alcohol ethoxylates and 0.1 mass% to 0.3 mass% of sodium dodecylbenzene sulfonate as said non-polymerizable surfactants;
III. 0.004 mass% to 0.008 mass% of fumed silica as said defoamer; and
C. q.s. water.

17. The composition as claimed in claims 1 and 9, comprising
A. a reaction product of
i. diacetone acrylamide, styrene, butyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as said plurality of monomers;
ii. C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as said polymerizable surfactant;
iii. potassium persulphate as said initiator;
iv. adipic acid dihydrazide as said coupling agent;
v. tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as said plurality of reducing agents;
vi. 2-amino ethanol and potassium methylsiliconate as said plurality of pH stabilizers; and
vii. sodium bicarbonate as said buffer.
B. said plurality of additives comprising
I. mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT), benzisothiazolinone as said plurality of preservatives;
II. non-ionic fatty alcohol ethoxylates and sodium dodecylbenzene sulfonate as said non-polymerizable surfactants; and
III. fumed silica as said defoamer; and
C. q.s. water.

18. The composition as claimed in claim 17, comprising
A. a reaction product of
i. 0.05 mass% to 0.15 mass% of diacetone acrylamide, 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of butyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.2 mass% to 0.6 mass% of vinyl trimethoxy silane as said plurality of monomers;
ii. 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as said polymerizable surfactant;
iii. 0.3 mass% to 0.4 mass% of potassium persulphate as said initiator;
iv. 0.02 mass% of adipic acid dihydrazide as said coupling agent;
v. 0.08 mass% of tert-butyl hydroperoxide and 0.08 mass% of sodium formaldehydesulfoxylate as said plurality of reducing agents;
vi. 0.4 mass% of 2-amino ethanol and 0.4 mass% of potassium methylsiliconate as said pH stabilizers; and
vii. 0.1 mass% of sodium bicarbonate as said buffer.
B. said plurality of additives comprising
I. 0.2 mass% to 0.6 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.2 mass% of benzisothiazolinone as said plurality of preservatives;
II. 0.2 mass% to 0.4 mass% of non-ionic fatty alcohol ethoxylates and 0.1 mass% to 0.3 mass% of sodium dodecylbenzene sulfonate as said non-polymerizable surfactants; and
III. 0.002 mass% to 0.008 mass% of fumed silica as said defoamer; and
C. q.s. water.

19. The composition as claimed in claims 1 and 9, comprising
A. a reaction product of
i. styrene, butyl acrylate, n-butyl methacrylate, methacrylic acid and vinyl trimethoxy silane as said plurality of monomers;
ii. C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as said polymerizable surfactant;
iii. potassium persulphate as said initiator;
iv. ethylene glycol dimethylacrylate as said coupling agent;
v. tert-butyl hydroperoxide and sodium formaldehydesulfoxylate as said plurality of reducing agents;
vi. 2-amino ethanol and potassium methylsiliconate as said pH stabilizers; and
vii. sodium bicarbonate as said buffer.
B. said plurality of additives comprising
I. a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and benzisothiazolinone as said plurality of preservatives;
II. non-ionic fatty alcohol ethoxylates as said non-polymerizable surfactant; and
III. fumed silica as said defoamer ; and
C. q.s. water.

20. The composition as claimed in claim 19, comprising
A. a reaction product of
i. 22 mass% to 24 mass% of styrene, 19 mass% to 20 mass% of butyl acrylate, 4 mass% to 5 mass% of n-butyl methacrylate, 0.5 mass% to 1.5 mass% of methacrylic acid and 0.3 mass% to 0.5 mass% of vinyl trimethoxy silane as said plurality of monomers;
ii. 0.5 mass% to 1.5 mass% of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid as said polymerizable surfactant;
iii. 0.3 mass% to 0.4 mass% of potassium persulphate as said initiator;
iv. 0.1 mass% to 0.3 mass% of ethylene glycol dimethylacrylate as said coupling agent;
v. 0.04 mass% to 0.12 mass% of tert-butyl hydroperoxide and 0.04 mass% to 0.12 mass% of sodium formaldehydesulfoxylate as said plurality of reducing agents;
vi. 0.2 mass% to 0.6 mass% of 2-amino ethanol and 0.2 mass% to 0.6 mass% of potassium methylsiliconate as said pH stabilizers; and
vii. 0.05 to 0.15 mass% of sodium bicarbonate as said buffer.
B. said plurality of additives comprising
I. 0.05 mass% to 0.15 mass% of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and 0.05 mass% to 0.15 mass% of benzisothiazolinone as said plurality of preservatives;
II. 0.2 mass% to 0.4 mass% of a non-ionic fatty alcohol ethoxylates as said non-polymerizable surfactant; and
III. 0.002 mass% to 0.008 mass% of fumed silica as said defoamer; and
C. q.s. water.

21. A process for the preparation of an emulsion polymer composition, said process comprising the following steps:
i. separately heating a first predetermined amount of a polymerizable surfactant and a predetermined amount of a buffer at a first predetermined temperature followed by mixing under stirring to obtain a mixture;
ii. separately a second predetermined amount of said polymerizable surfactant is heated to said first predetermined temperature and cooled to a temperature in the range of 25 °C to 40 °C and sequentially adding predetermined amounts of a plurality of monomers, under stirring to obtain a pre-emulsion;
iii. adding 2 mass% to 15 mass% of said pre-emulsion to said mixture followed by adding a first predetermined amount of an initiator at a second predetermined temperature to obtain a first resultant;
iv. adding 85 mass% to 98 mass% of said pre-emulsion to said first resultant followed by adding a second predetermined amount of said initiator at said second predetermined temperature to obtain a second resultant;
v. cooling said second resultant to a third predetermined temperature and adding predetermined amounts of a plurality of reducing agents to obtain a third resultant;
vi. cooling said third resultant to a temperature in the range of 40 °C to 50°C followed by adding a predetermined amount of at least one pH stabilizer and stirring followed by adding a predetermined amount of a coupling agent under stirring to obtain a fourth resultant having a pH in the range of 8.5 to 9.5; and
vii. adding predetermined amounts of a plurality of preservatives and a predetermined amount of a defoamer to said fourth resultant at a temperature in the range of 40 °C to 50 °C followed by adding water under stirring to obtain said emulsion polymer composition.
22. The process as claimed in claim 21, wherein said polymerizable surfactant is selected from the group consisting of C10-14-branched, C11-rich, reaction products with ethylene oxide, [(2-propenyloxy)methyl]oxirane and sulfamic acid, alkyl diphenyl oxide disulfonate, phosphate ester based polymerizable surfactant and reactive anionic emulsifier.

23. The process as claimed in claim 21, wherein said buffer is selected from the group consisting of sodium bicarbonate, sodium acetate, sodium carbonate and ethylene diaminetetraacetic acid (EDTA).

24. The process as claimed in claim 21, wherein said plurality of monomers comprise
• first monomer selected from the group consisting of diacetone acrylamide and ethylene glycol dimethylacrylate (EGDMA);
• second monomer selected from the group consisting of styrene, butyl acrylate, n-butyl methacrylate, vinyl trimethoxy silane and 2-ethylhexyl acrylate; and
• third monomer is methacrylic acid.

25. The process as claimed in claim 21, wherein said initiator is selected from the group consisting of potassium persulphate, sodium persulphate and ammonium persulphate.

26. The process as claimed in claim 21, wherein said plurality of reducing agents comprise first reducing agent and second reducing agent independently selected from the group consisting of:
• a mixture of tert-butyl hydroperoxide and a non-polymerizable surfactant;
• a mixture of sodium formaldehyde sulfoxylate and a non-polymerizable surfactant;
• a mixture of sodium acetone bisulphite and a non-polymerizable surfactant;
• a mixture of L-ascorbic acid and a non-polymerizable surfactant; and
• a mixture of sodium meta bisulphate and a non-polymerizable surfactant.

27. The process as claimed in claim 21, wherein said pH stabilizer is at least one selected from the group consisting of 95% 2-amino-2-methyl-1-propanol, 2-amino ethanol, alkanolamine and potassium methylsiliconate.

28. The process as claimed in claim 21, wherein said coupling agent is selected from the group consisting of
• a mixture of adipic acid dihydrazide (ADH) and a non-polymerizable surfactant;
• a mixture of ethylene glycol dimethylacrylate (EGDMA) and a non-polymerizable surfactant; and
• a mixture of succinic acid dihydrazide and a non-polymerizable surfactant.

29. The process as claimed in claim 21, wherein said plurality of preservatives are selected from the group consisting of a mixture of 5-chloro-2-methylisothiazol-3(2H)-one and 2-methylisothiazol-3(2H)-one (MIT/CMIT) and benzisothiazolinone (BIT).

30. The process as claimed in claim 21, wherein said defoamer is selected from the group consisting of fumed silica, polyether siloxane emulsion and mineral oil based defoamer.

31. The process as claimed in claims 26 and 28, wherein said non-polymerizable surfactant is selected from the group consisting of non-ionic fatty alcohol ethoxylates, sodium dodecylbenzenesulfonate, alkyl polyethylene glycol ether and secondary alcohol ethoxylate.

32. The process as claimed in claim 21, wherein
• said first predetermined temperature is in the range of 75 °C to 85 °C;
• said second predetermined temperature is in the range of 80 °C to 90 °C; and
• said third predetermined temperature is in the range of 70 °C to 78 °C.
33. The process as claimed in claims 21, 24 and 26 wherein
• said first predetermined amount of said polymerizable surfactant is in the range of 0.05 mass% to 0.3 mass% and said second predetermined amount of said polymerizable surfactant is in the range of 0.5 mass% to 2 mass% ;
• said predetermined amount of buffer is in the range of 0.05 mass% to 0.2 mass%;
• said predetermined amount of plurality of monomers comprise first monomer in an amount in the range of 0.05 mass% to 0.5 mass%, second monomer in an amount in the range of 40 mass% to 55 mass% and third monomer in an amount in the range of 0.2 mass% to 2 mass%;
• said first predetermined amount of an initiator is in the range of 0.05 mass% to 0.3 mass% and said second predetermined amount of initiator is in the range of 0.1 mass% to 0.4 mass%;
• said predetermined amounts of plurality of reducing agents comprise a first reducing agent and a second reducing agent independently in the range of 0.02 mass% to 0.2 mass%;
• said predetermined amount of pH stabilizer is in the range of 0.2 mass% to 1.5 mass%;
• said predetermined amount of coupling agent is in the range of 0.02 mass% to 0.1 mass%;
• said predetermined amount of plurality of preservatives are in the range of 0.1 mass% to 0.5 mass%; and
• said predetermined amount of defoamer is in the range of 0.002 mass% to 0.01 mass%;
wherein said mass% of each ingredient is with respect to the total mass of said emulsion polymer composition.

34. The process as claimed in claims 26 and 28 wherein said non-polymerizable surfactant is independently in an amount in the range of 0.05 mass% to 0.2 mass% in said first reducing agent and second reducing agent and said non-polymerizable surfactant is in an amount in the range of 0.1 mass% to 0.5 mass% in said coupling agent.

35. The process as claimed in claims 21, 26 and 28, wherein said polymerizable surfactant, said non-polymerizable surfactant, said buffer, said coupling agent, said initiator, said first reducing agent, said second reducing agent, said pH stabilizer, said plurality of preservatives and said defoamer are aqueous solutions.

36. The process as claimed in claim 21, wherein a mass ratio of said monomer to said polymerizable surfactant is in the range of 35:1 to 45:1.

Dated this 26th day of July, 2024

_______________________________
MOHAN RAJKUMAR DEWAN, IN/PA – 25
of R.K.DEWAN & CO.
Authorized Agent of Applicant

TO,
THE CONTROLLER OF PATENTS
THE PATENT OFFICE, MUMBAI