Low-energy nanoemulsion polymerization with low levels of surfactants

Abstract

The present invention relates to a low energy process for preparing nanoemulsions and to a process for preparing polymers from said nanoemulsions.The present invention is also directed to aqueous nanoemulsions prepared by the claimed process of the invention.

Description

[Technical field]

[0001] The present invention relates to a low energy method for preparing nanoemulsions. The present invention further relates to a method for preparing polymers from said nanoemulsions. The present invention is also directed to aqueous emulsions prepared by the method of the claimed invention. [Background technology]

[0002] Miniemulsion polymerization is an emulsion polymerization method in which a monomer emulsion is reduced in size to the range of 50-1000 nm and subsequently polymerized. This allows the use of hydrophobic monomers that do not polymerize in conventional emulsion polymerization systems. In addition, additives such as nanoparticles and non-reactive waxes / oils can be incorporated into the final latex. However, the processes disclosed in the prior art require the use of large amounts of surfactants (greater than 20% by weight of the total weight of monomers) or the use of high energy such as homogenization or sonication.

[0003] Due to the high energy required to produce this nanoemulsion, this process has not been commercially successful due to issues with high energy emulsification upon scale-up or the inability to use existing infrastructure. Summary of the Invention [Problem to be solved by the invention]

[0004] It is an object of the present invention to have a method for preparing nanoemulsions that is not only a low energy method, but also uses low amounts of surfactant, fits within existing conventional emulsion polymerization equipment, and does not require special equipment. Another object of the present invention is to have a method for preparing polymers from nanoemulsions that is also applicable to hydrophobic monomers. [Means for solving the problem]

[0005] Surprisingly, we discovered that by utilizing the principle of hydrophilic-lipophilic deviation (HLD), the nanoemulsification process can be achieved under standard stirring (i.e., low energy and low surfactant loading (1–10 wt %) based on the weight of monomer).

[0006] Thus, in one aspect, the invention provides a method for preparing a nanoemulsion, comprising the steps of: (i) forming an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -1 at a temperature between 0°C and 100°C, the emulsion system comprising at least one monomer, at least one surfactant, a salt, and water; (ii) increasing the internal phase of the emulsion system to up to 80% by volume of the emulsion system by adding to the emulsion system at least one monomer used in step (i) or an additional amount of at least one monomer different from that used in step (i); and (iii) mixing the contents of step (ii) at a temperature between 0°C and 100°C to obtain a nanoemulsion having a volume average particle size in the range of 50 nm to 1000 nm as determined according to a dynamic light scattering technique. The present invention relates to a method comprising:

[0007] Another aspect of the claimed invention is directed to an aqueous nanoemulsion prepared by the above-described method.

[0008] In one aspect, the claimed invention is directed to a method of preparing a polymer from the nanoemulsion prepared by the method described herein above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Before describing the compositions, concentrates, and formulations of the present invention, it is to be understood that the invention is not limited to the particular compositions, concentrates, and formulations described, as such compositions, concentrates, and formulations may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the invention will be limited only by the appended claims.

[0010] Hereinafter, when a group is defined as including at least a certain number of embodiments, this preferably means that the group consists of only these embodiments. Furthermore, the terms "first", "second", "third", or "(a)", "(b)", "(c)", "(d)" and the like in this specification and claims are used to distinguish similar components and do not necessarily describe them in sequential or chronological order. Thus, it should be understood that the terms used in this manner are interchangeable under appropriate circumstances and that the embodiments of the invention described herein can be implemented in other orders than those described or illustrated herein. Where the terms "first", "second", "third", or "(A)", "(B)" and "(C)", or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. refer to steps of a method or use or assay, unless otherwise specified in this application, as hereinbefore or hereinafter described, there is no time interval or no consistency between the steps, i.e., the steps may be performed simultaneously or there may be a time interval of seconds, minutes, hours, days, weeks, months or even years between such steps.

[0011] In the text below, various aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects, unless expressly indicated otherwise. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

[0012] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrase "one embodiment" or "an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, although they may.

[0013] Furthermore, particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments, as would be apparent to one of ordinary skill in the art from this disclosure. Additionally, as will be understood by one of ordinary skill in the art, some embodiments described herein may include some features but not others included in other embodiments, meaning that combinations of features from different embodiments are within the scope of the invention and form different embodiments. For example, in the appended claims, any of the claimed embodiments may be used in any combination.

[0014] Furthermore, it should be noted that the terms "at least one," "one or more," or similar expressions indicating that a feature or element may be present one or more times, are typically used only once in introducing each feature or element. In the following, in most cases, when referring to each feature or element, the expressions "at least one" or "one or more" will not be repeated, despite the fact that each feature or element may be present one or more times.

[0015] Furthermore, ranges defined throughout this specification are inclusive of end values, i.e., a range of 1 to 10 means that both 1 and 10 are included in the range. For the avoidance of doubt, Applicant reserves the right to any equivalents pursuant to applicable law.

[0016] One aspect of the invention is a method for preparing a nanoemulsion, comprising the steps of: (i) forming an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -1 at a temperature between 0°C and 100°C, the emulsion system comprising at least one monomer, at least one surfactant, a salt, and water; (ii) increasing the internal phase of the emulsion system to up to 80% by volume of the emulsion system by adding to the emulsion system at least one monomer used in step (i) or an additional amount of at least one monomer different from that used in step (i); and (iii) mixing the contents of step (ii) at a temperature between 0°C and 100°C to obtain a nanoemulsion having a volume average particle size in the range of 50 nm to 1000 nm as determined according to a dynamic light scattering technique. The present invention relates to a method comprising:

[0017] Another aspect of the claimed invention is directed to an aqueous nanoemulsion prepared by the above-described method.

[0018] In one aspect, the claimed invention is directed to a method of preparing a polymer from an emulsion prepared by the method described hereinabove.

[0019] Nanoemulsions are kinetically stable emulsions with a mean particle size of less than 1000 nm. They are thermodynamically unstable.

[0020] Miniemulsions are nanoemulsions prepared by high energy treatment (eg, sonication or homogenization) prior to polymerization.

[0021] The terms nanoemulsion and miniemulsion may be used interchangeably and are meant to have the same meaning throughout the present invention.

[0022] Monomer In certain embodiments, at least one monomer is a hydrophobic monomer, which is a substance that does not dissolve in water or other polar solvents.

[0023] In certain embodiments, the hydrophobic monomer is an α,β-ethylenically unsaturated monomer.

[0024] In an embodiment, the at least one monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-methylheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate. , isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, alkyl crotonate, di-n-butyl maleate, di-octyl maleate, hydroxyethyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate acrylate, cyclohexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxy (meth)acrylate, 2(2ethoxyethoxy)ethyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, caprolactone (meth)acrylate, polypropylene glycol mono (meth)acrylate, polyethylene glycol (meth)acrylate, benzyl (meth)acrylate, hydroxypropyl (meth)acrylate Acrylates, methyl polyglycol (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, styrene, butadiene, vinyl esters, acrylonitrile, (meth)acrylamide, 2-ethylhexyl thioglycolate, 3,5,5-trimethyl-1-hexyl acrylate, 3-butyl mercaptopropionate, acetoacetoxyethyl methacrylate, alpha methylstyrene, C 17-acrylate, diacetone acrylamide, dimethylaminoethyl acrylate, isoamyl acrylate, isobutyl acrylate, isodecyl acrylate, isononyl acrylate, isoprenol acrylate, prenol acrylate, tert-butyl acrylate, tert-butyl methacrylate, vinyl acetate, or combinations thereof. In another embodiment, at least one acid monomer is selected from α,β-ethylenically unsaturated acids. Examples of suitable ethylenically unsaturated acids include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, dimethacrylic acid, ethylacrylic acid, allylacetic acid, vinylacetic acid, vinyllactic acid, mesaconic acid, methylenemalonic acid, citraconic acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, (meth)acrylic phosphate ester, or combinations thereof. The acid group can be partially or completely neutralized with a suitable base as a neutralizing agent (e.g., aqueous solution of sodium hydroxide or potassium hydroxide, or ammonia).

[0025] In a preferred embodiment, the monomer is methyl methacrylate, lauryl acrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 2-ethylhexyl thioglycolate, 2-propylheptyl methacrylate, 3,5,5-trimethyl-1-hexyl acrylate, 3-butyl mercaptopropionate, acetoacetoxyethyl methacrylate, acrylic acid, alpha methylstyrene, methacrylic acid, butyl methacrylate, C 17acrylate, cyclohexyl methacrylate, diacetone acrylamide, dimethylaminoethyl acrylate, ethyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, isoamyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isodecyl acrylate, isononyl acrylate, isoprenol acrylate, lauryl acrylate, prenol acrylate, stearyl acrylate, styrene, tert-butyl acrylate, tert-butyl methacrylate, vinyl acetone, or combinations thereof.

[0026] In one embodiment, the volume percentage of the at least one monomer is between 20 volume percent and 80 volume percent.

[0027] Surfactants The method of the present invention includes at least one surfactant.

[0028] In certain embodiments, the at least one surfactant is selected from cationic surfactants, anionic surfactants, zwitterionic surfactants, nonionic surfactants, and combinations thereof.

[0029] In one embodiment, the anionic surfactant has the following structure: R-(O) n -(D) p -(E) q -SO 3 - -M + (In the formula, R is a straight or branched chain, substituted or unsubstituted C 6 ~C 22 Alkyl, or substituted or unsubstituted C 6 ~C 20 is alkylaryl, D is CH(CH 3 )-CH 2 represents -O-, E is CH 2-CH 2 represents -O-, n is an integer ranging from 0 to 1; p is an integer ranging from 0 to 10; q is an integer ranging from 0 to 20; M is H, or an alkali metal, or an ammonium cation. has.

[0030] In a preferred embodiment, R is a straight or branched unsubstituted C 6 ~C 20 It is an alkyl.

[0031] In a more preferred embodiment, R is a straight or branched unsubstituted C 8 ~C 20 It is an alkyl.

[0032] In the most preferred embodiment, R is a straight-chain unsubstituted C 8 ~C 18 It is an alkyl.

[0033] In another embodiment, R is a straight or branched chain, substituted or unsubstituted C 6 ~C 20 It is an alkylaryl.

[0034] In a preferred embodiment, R is a linear or branched, substituted or unsubstituted C 10 ~C 13 It is an alkylbenzene.

[0035] In the most preferred embodiment, R is a linear C 10 ~C 13 It is an alkylbenzene.

[0036] In a preferred embodiment, the cation M is selected from H, sodium, potassium, and ammonium cations.

[0037] The anionic surfactant of the embodiment (p=0, q=0, R is a linear or branched unsubstituted C 8 ~C 12Alcohols (C 8 ~C 12 (carbon atom) or synthetic alcohol, followed by neutralization with alkali hydroxide. Therefore, the resulting compound also includes reaction by-products, such as free salts (e.g., when the neutralizing agent is sodium hydroxide, sodium chloride is the free salt by the product), free fatty alcohol, and salt of fatty alcohol. Therefore, the solid content of anionic surfactants may be different from the active ingredient. The active ingredient represents the "amount of anionic surfactant" present in the composition, while the solid content represents the "total of anionic surfactant, fatty alcohol, salt of fatty alcohol, and free salt compound" in the composition. "Free" in this specification means that the salt is not bound to the fatty alcohol / anionic surfactant of the formula shown above by any kind of chemical bond.

[0038] Anionic surfactants (wherein p=0, q=1 to 20, R is a straight or branched chain unsubstituted C 6 ~C 22 The alkyl sulfates (which are alkyl groups) are produced by the ethoxylation of fatty alcohols and are therefore generally obtained in the form of mixtures of various alkyl chain lengths and degrees of ethoxylation. Frequently, such mixtures will necessarily also contain some non-ethoxylated alkyl sulfates.

[0039] In a preferred embodiment, p is an integer in the range of 2 to 10, more preferably an integer in the range of 3 to 8, q is an integer in the range of 0.01 to 10, more preferably an integer in the range of 0.05 to 8, and R is a linear or branched unsubstituted C 14 ~C 18 alkyl and M=sodium or H.

[0040] p is an integer ranging from 2 to 10, q is an integer ranging from 0.01 to 10, and R is a linear or branched unsubstituted C 14 ~C 18The anionic surfactant of the preferred embodiment, M is alkyl and M is H, is produced by propoxylation and ethoxylation of fatty alcohols, followed by sulfation of the alcohols, and is therefore generally obtained in the form of a mixture with different alkyl chain lengths and different degrees of propoxylation and ethoxylation.Frequently, such mixtures may also contain some degree of non-ethoxylated / non-propoxylated compounds.These propoxylated and ethoxylated sulfate compounds are neutralized with alkali hydroxide, such as sodium hydroxide, to produce compounds with M=sodium.

[0041] In a preferred embodiment, n is 0, p is 0, q is 0, and R is a straight or branched, unsubstituted or substituted C 10 ~C 13 It is alkylaryl and M=sodium.

[0042] Alpha-olefin sulfonates are generally produced by sulfonation of alpha-olefins. The alpha-olefins sulfonated to form the surfactants used in the claimed compositions of the present invention may contain about 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The alpha-olefins may originate from various processes, such as wax cracking, ethylene built up, or dehydration of the corresponding primary alcohols. Exemplary alpha-olefins are 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and the like, and mixtures thereof. The sulfonation of these long chain olefins is typically carried out utilizing sulfur trioxide mixed with a diluent. After the sulfonation is complete, neutralization and hydrolysis of the acid mixture is carried out to convert the by-product sulfones formed to the corresponding hydroxyalkanesulfonates. Thus, as is known in the art, the term α-olefin sulfonate as used herein includes not only the alkene sulfonates themselves but also mixtures of those formed as a result of the conventional sulfonation neutralization and hydrolysis procedures with a corresponding amount of the corresponding water-soluble hydroxyalkane sulfonate.

[0043] Linear alkylbenzene sulfonates (LABS) are produced by the sulfonation of linear alkylbenzenes (LAB) followed by neutralization of the corresponding sulfonic acids (HLAS). Linear alkylbenzenes are synthesized by the alkylation of benzene with linear olefins. Conventional aromatic alkylation processes use Friedel-Crafts type catalysts, e.g. hydrofluoric acid, aluminum trichloride, etc.

[0044] Anionic surfactants can also be represented by the formula R''CONHR'''OSO 3 M (In the formula, R'' is C 2 ~C 22 represents alkyl; R''' is C 2 ~C3 is an alkyl radical, M is a hydrogen atom, or an alkali metal cation, or their ethoxylated (EO) and / or propoxylated (PO) derivatives, containing an average of 0.5 to 60 EO and / or PO units; Also included may be alkyl amido sulfates of the formula:

[0045] Further anionic surfactants include C 8 ~C 24 of saturated or unsaturated fatty acids, alkyl glyceryl sulfonates, paraffin sulfonates, N-acyl N-alkyl taurates, alkyl phosphates, isethionates, alkylsuccinamates, alkyl sulfosuccinates, sulfosuccinate monoesters or diesters, N-acylsarcosinates, alkyl glycoside sulfates, polyethoxycarboxylates, where the cation is an alkali metal (sodium, potassium, or lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, or tetramethylammonium, dimethylpiperidinium, etc.), or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine, etc.), and an alkyl or alkylaryl phosphate ester.

[0046] Sulfosuccinate esters have the following structure: [ka] (In the formula, R 1 is a straight or branched chain, substituted or unsubstituted C 4 ~C 22 is alkyl, R 2 is H or a straight or branched chain, substituted or unsubstituted C 4 ~C 22 alkyl, M 1 is H or an alkali metal cation. has.

[0047] In a preferred embodiment, R 1 and R 2 are independently linear unsubstituted C 6 ~C 20 It is an alkyl.

[0048] In a more preferred embodiment, R 1 and R 2 are independently linear unsubstituted C 6 ~C 16 It is an alkyl.

[0049] In the most preferred embodiment, R 1 and R 2 are identical and are linear unsubstituted C 6 ~C 12 It is an alkyl.

[0050] In a preferred embodiment, the cation M 1 is selected from H, a sodium cation, a potassium cation, or an ammonium cation.

[0051] In a more preferred embodiment, the cation M 1 is selected from the sodium or potassium cation.

[0052] In the most preferred embodiment, M 1 is sodium.

[0053] In a preferred embodiment, the sulfosuccinate ester is soluble in water.

[0054] In another preferred embodiment, the sulfosuccinate ester is dissolved in a mixture of water and a water-miscible solvent.

[0055] In certain embodiments, the water-miscible solvent is selected from ethylene glycol, propylene glycol, neopentyl glycol, and mixtures thereof.

[0056] In a preferred embodiment, the sulfosuccinate ester is dissolved in a mixture of water and neopentyl glycol.

[0057] Cationic surfactant is a known group of surface active compounds that have at least one active cationic (positive ion) component.As cationic surfactant, quaternary ammonium hydroxide can be exemplified, for example, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow trimethylammonium hydroxide and coconut oil trimethylammonium hydroxide and their salts can be exemplified.

[0058] Examples of amphoteric surfactants include betaines, sulfobetaines, and carboxylates and sulfonates of fatty acids and imidazoles (e.g., alkyl dimethyl betaines, alkyl amidopropyl dimethyl betaines, alkyl dimethyl sulfobetaines, or alkyl amidopropyl dimethyl sulfobetaines).

[0059] Some of the nonionic surfactants that may be mentioned are condensates of alkylene oxides (especially ethylene oxide) with alcohols, polyols, alkylphenols, fatty acid esters, fatty acid amides, and fatty amines; oxide amines, sugar derivatives, such as polyalkylglycosides or fatty acid esters of sugars, in particular sucrose monopalmitate; long-chain tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and polyoxypropylene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly(ethylene oxide), and fatty acid amides modified to impart hydrophobicity (e.g. fatty acid mono- and diethanolamides containing 10 to 18 carbon atoms). In particular, the alkyl substituents are C 6 ~C 12and containing 5 to 25 oxyalkylene units; polyoxyalkylated (polyethoxyethylated, polyoxypropylated, or polyoxybutylated) alkylphenols, glucosamides, glucamides, and glycerol amides; polyoxyalkylenated C containing 1 to 25 oxyalkylene (oxyethylene, oxypropylene) units; 8 ~C 22 Fatty alcohols.

[0060] The above-mentioned surfactants can be used either alone or in combination, so long as the HLD value in the emulsion is appropriately adjusted within the range of 0 to -1.

[0061] In one embodiment, the amount of the at least one surfactant ranges from 1 to 10 weight percent based on the total weight of monomer.

[0062] In one embodiment, the characteristic curvature value (Cc) of at least one surfactant ranges from −10 to 10, calculated as an average on a molar basis for each individual surfactant.

[0063] The characteristic curvature value Cc of a mixture of surfactants is the molar weighted average of the Cc of the surfactants.

[0064] The characteristic curvature is a value assigned to a surfactant to determine its relative hydrophobicity or hydrophilicity compared to other surfactants in the same family. Having this value, one can predict the performance of a surfactant by using the HLD equation.

[0065] The characteristic curvature is typically measured by an HLD tube scan. Known amounts of the surfactant to be measured are placed in several tubes. At a constant temperature, an oil with a known equivalent alkane carbon number (EACN) is added, as well as an equal amount of saline. The amount of salt is increased throughout the tubes, changing the HLD value in each tube. The discovery of Windsor Type III microemulsions is evidence of an HLD of 0 at that salt concentration. The HLD is set to 0, the salt temperature and oil are known, and the Cc value can be solved for.

[0066] salt The methods of the present invention include salts.

[0067] In certain embodiments, the salt is selected from sodium chloride, potassium chloride, sodium hydroxymethanesulfinate hydrate, and tetrasodium pyrophosphate.

[0068] In one embodiment, the amount of salt in the emulsion system ranges from 0.1 to 15 weight percent based on the total weight of monomers.

[0069] In one embodiment, the amount of salt in the emulsion system ranges from 0.1 to 15 weight percent based on the total weight of monomers.

[0070] In another embodiment, the amount of salt in the emulsion system ranges from 0.1 to 10 weight percent based on the total weight of monomers.

[0071] In yet another embodiment, the amount of salt in the emulsion system ranges from 0.1 to 5 weight percent based on the total weight of monomers.

[0072] water In one embodiment, the volume percentage of water is 20 volume % to 80 volume %.

[0073] The total amount of water in the process includes the water present in the surfactant and the water present in the salt solution.

[0074] Additional Ingredients In some embodiments, the method includes an additional component.

[0075] In some embodiments, the additional ingredient is selected from an oil, an oil-soluble compound, or an alcohol.

[0076] Preferably, the additional ingredient is an oil or an oil-soluble compound.

[0077] Examples of oils or oil-soluble compounds include, but are not limited to, hydrocarbons having more than 16 carbon atoms, such as hexadecane, cetyl alcohol, polymethyl methacrylate, polystyrene, polyvinyl acetate, vinyl hexanoate, p-methylstyrene, vinyl 2-ethylhexanoate, vinyl decanoate, vinyl stearate, and mixtures thereof.

[0078] method In one embodiment, the present invention provides a method of preparing a nanoemulsion, comprising the steps of: (i) forming an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -1 at a temperature between 0°C and 100°C, the emulsion system comprising at least one monomer, at least one surfactant, a salt, and water; (ii) increasing the internal phase of the emulsion system by up to 80% by volume by adding to the emulsion system at least one monomer used in step (i) or an additional amount of at least one monomer different from that used in step (i); and (iii) mixing the contents of step (ii) at a temperature between 0°C and 100°C to obtain a nanoemulsion having a volume average particle size in the range of 50 nm to 1000 nm as determined according to a dynamic light scattering technique. A method is disclosed that includes:

[0079] In one embodiment, at temperatures between 0°C and 100°C, an emulsion system is formed having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -0.8.

[0080] In another embodiment, at temperatures between 0°C and 100°C, an emulsion system is formed having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -0.6.

[0081] In another embodiment, an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -0.4 is formed at a temperature between 0°C and 100°C.

[0082] Hydrophilic-Lipophilic Deviation (HLD) is an empirical model that predicts surfactant performance based on the salt concentration, temperature, oil, and surfactant in the system. Due to the method of the present invention, the emulsion system is balanced where all of the surfactant is attracted and therefore located at the interface. At this point, the interfacial tension is fairly low.

[0083] Rapidly moving away from this point by adjusting the HLD parameters is called "quenching". This is done by varying the salt concentration, temperature, oil, and surfactant. As a result, the surfactant remains at the interface and a nanoemulsion of a certain size is obtained, depending on the surfactant concentration in the system. Nanoemulsions (50-1000 nm) of the monomer, and any incorporated additives, can be efficiently produced in this manner, typically requiring only 1-10 wt% surfactant relative to the monomer.

[0084] In a more particular embodiment, the mixing step (iii) is carried out at a temperature between 30°C and 80°C.

[0085] In a most preferred embodiment, the (iii) mixing step is carried out at a temperature of from 40°C to 80°C.

[0086] In a preferred embodiment, the nanoemulsion has a mean particle size in the range of 50 nm to 800 nm, as determined according to dynamic light scattering techniques.

[0087] In a more preferred embodiment, the nanoemulsion has an average particle size in the range of 50 nm to 700 nm as determined according to dynamic light scattering techniques.

[0088] In a most preferred embodiment, the nanoemulsion has a mean particle size in the range of 50 nm to 650 nm as determined according to dynamic light scattering techniques.

[0089] Dynamic Light Scattering (DLS) is a common technique used to determine the size distribution of dispersed nanoparticles. DLS uses the temporal fluctuations of light scattered by nanoparticles to calculate the distribution of translational diffusion coefficients, which are then converted to a distribution of apparent hydrodynamic diameters. Nanoemulsions or polymers (latexes) are diluted with DI water and then placed into a Zetasizer instrument. The instrument emits a laser, which is scattered by the particles. Software can then infer the average particle size of the nanoemulsion or polymer (latex) from the amount of light scattered.

[0090] The mean particle size is expressed as a volume average particle size distribution, which physically represents that each volume of particle larger or smaller than the median volume accounts for 50% of the total particle volume.

[0091] By using many surfactants, nanoemulsions can be obtained in low energy and non-optimized systems. This can be 1 g surfactant to oil, but also 10 g surfactant to oil. The HLD to internal phase ratio applied to the system allows efficient (performance and cost) use of surfactant. Typically, nanoemulsions using HLD to internal phase ratios have 0.01 to 0.1 g surfactant to monomer according to the invention.

[0092] The addition of HLD to the nanoemulsion process provides a robust and scalable method for producing the nanoemulsions required for polymerization. Due to the low energy requirements, the process is scalable and the use of HLD allows for predictable adjustments when system conditions change.

[0093] In one embodiment, the power density in the (iii) mixing step is from 0.1 W / kg to 100 W / kg.

[0094] In a more preferred embodiment, the power density in the (iii) mixing step is 0.1 W / kg to 10 W / kg.

[0095] In a most preferred embodiment, the power density in the (iii) mixing step is from 0.1 W / kg to 1 W / kg.

[0096] In one embodiment, all steps of the method for preparing a nanoemulsion (steps (i) to (iii)) may be automated and performed by computer.

[0097] In one embodiment, the present invention provides a method of preparing a nanoemulsion, comprising the steps of: (i) forming an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -1 at a temperature between 0°C and 100°C, the emulsion system comprising at least one monomer, at least one surfactant, a salt, and water; (ii) increasing the internal phase of the emulsion system by up to 80% by volume by adding to the emulsion system at least one monomer used in step (i) or an additional amount of at least one monomer different from that used in step (i); and (iii) mixing the contents of step (ii) at a temperature between 0°C and 100°C to obtain a nanoemulsion having a volume average particle size in the range of 50 nm to 1000 nm as determined according to a dynamic light scattering technique. Including, (iii) the mixing step has a power density of 0.1 W / kg to 100 W / kg; A method is disclosed.

[0098] In another embodiment, the present invention provides a method for preparing a nanoemulsion, comprising the steps of: (i) forming an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -1 at a temperature between 0°C and 100°C, the emulsion system comprising at least one monomer, at least one surfactant, a salt, and water; (ii) increasing the internal phase of the emulsion system by up to 80% by volume by adding to the emulsion system at least one monomer used in step (i) or an additional amount of at least one monomer different from that used in step (i); and (iii) mixing the contents of step (ii) at a temperature between 0°C and 100°C to obtain a nanoemulsion having a volume average particle size in the range of 50 nm to 1000 nm as determined according to a dynamic light scattering technique. Including, (iii) the mixing step has a power density of 0.1 W / kg to 100 W / kg; The at least one surfactant is selected from a cationic surfactant, an anionic surfactant, a zwitterionic surfactant, a nonionic surfactant, or a combination thereof. A method is disclosed.

[0099] In another embodiment, the present invention provides a method for preparing a nanoemulsion, comprising the steps of: (i) forming an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -1 at a temperature between 0°C and 100°C, the emulsion system comprising at least one monomer, at least one surfactant, a salt, and water; (ii) increasing the internal phase of the emulsion system by up to 80% by volume by adding to the emulsion system at least one monomer used in step (i) or an additional amount of at least one monomer different from that used in step (i); and (iii) mixing the contents of step (ii) at a temperature between 0°C and 100°C to obtain a nanoemulsion having a volume average particle size in the range of 50 nm to 1000 nm as determined according to a dynamic light scattering technique. Including, (iii) the mixing step has a power density of 0.1 W / kg to 100 W / kg; The amount of salt in the emulsion system ranges from 0.1 to 15% by weight based on the total weight of the monomers. A method is disclosed.

[0100] In a particularly preferred embodiment, step (i) is computer-implemented.

[0101] In one embodiment, step (i) comprises: a. receiving, at a computing device, input data selected from at least the parameters salinity, equivalent alkane carbon number (EACN), temperature, and characteristic curvature of a surfactant (Cc); b. Adjusting the parameters of step (a) using equation (I) or (II) to obtain an HLD value between 0 and -1; HLD=F(S)-k.EACN-α(T-25)+Cc (I) HLD=F(S)-k.EACN-α(T-25)+F(A)+Cc (II) (In the formula, EACN: Available alkane carbon number of monomer or oil component T temperature (℃) S is a function of salinity (g / 100ml) Cc Characteristic curvature of surfactant α temperature coefficient; and F(A) is a function of the % of alcohol or other additional ingredients added to the system. and is computer-implemented.

[0102] By applying and solving equation (I) and / or equation (II), the parameters are optimized to obtain a process that operates with lower energy and lower amounts of surfactant.

[0103] "Computer-implemented" or "computing device" refers to the operations and processes of a computer system or similar electronic computing device that manipulate and transform data represented as physical (e.g., electronic) quantities in the computer system's registers and memory into other data similarly represented as physical quantities in the computer system's memory or registers, or other such information storage, transmission, or display device.

[0104] The computer-implemented step (i) may be stored on a computer-readable storage medium (e.g., a non-transitory computer-readable storage medium). The computer-readable storage medium may be a floppy disk, a hard disk, a CD (compact disk), a DVD (digital versatile disk), a USB (universal serial bus) storage device, a RAM (random access memory), a ROM (read-only memory), and an EPROM (erasable programmable read-only memory). The invention may be implemented in digital electronic circuitry, or in computer hardware, firmware, software, or a combination of these, for example in hardware available in conventional mobile devices.

[0105] Equations (I) and (II) are known to those skilled in the art and are disclosed in the prior art, such as the academic paper J Surfact Deterg (2013) 16:449-472.

[0106] In another aspect, the present invention provides a method for preparing a polymer from a nanoemulsion, comprising the steps of: (I) charging a reactor with the nanoemulsion obtained by the method described herein above; (II) adding at least one initiator to step (I); and (III) mixing the contents of step (II) to obtain a polymer having a volume average particle size in the range of 50 nm to 1000 nm as determined according to dynamic light scattering techniques. A method is disclosed that includes:

[0107] As used herein, the term "polymer" generally refers to a molecule having at least four monomer units. Polymers include, but are not limited to, homopolymers, copolymers, such as block copolymers, graft copolymers, random copolymers, and alternating copolymers. Furthermore, unless expressly limited otherwise, the term "polymer" is intended to include all possible isomeric configurations of monomers (e.g., but not limited to, isotactic, syndiotactic, and random symmetric configurations, and combinations thereof). Furthermore, unless specifically limited otherwise, the term "polymer" is intended to include all possible geometric configurations of molecules.

[0108] In this method, the nanoemulsion is polymerized, for example by free radical polymerization, to produce an aqueous polymer dispersion. Each monomeric nanodroplet is converted into a polymeric nanoparticle, and the surfactant remains at the interface between the particle and the continuous phase, stabilizing it against coagulation. Thus, any additives incorporated into the monomeric nanodroplet remain in the polymeric nanoparticle and are uniformly incorporated throughout the final polymer when dried, for example as a coating or adhesive.

[0109] Traditional emulsion polymerization relies on the mechanism of monomer transport from the emulsion droplets through the water phase to the growing latex particles. If low solubility monomers or additives (waxes, nanoparticles) are used, they will not participate in the process. Either the reaction stagnates (hydrophobic monomers) or the additives will not be transported through the water to the latex / polymer (additives).

[0110] Miniemulsion polymerization works by directly polymerizing emulsion droplets, which is traditionally achieved by reducing the size of the emulsion.

[0111] In one embodiment, the method of preparing the polymer of the claimed invention comprises at least one polymerization initiator. At least one polymerization initiator suitable for carrying out the method is capable of thermal decomposition into radicals in a first order reaction.

[0112] In some embodiments, the initiator is an oil- or water-soluble initiator selected from peroxides, persulfates, azo compounds, or mixtures thereof.

[0113] In some embodiments, the at least one oil-soluble initiator is selected from the group consisting of 2,2'-azodi-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), tertiary butyl perbenzoate, tert-amylperoxy 2-ethylhexyl carbonate, 1,1-bis(tert-amylperoxy)cyclohexane, lauryl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, benzoyl peroxide, or mixtures thereof.

[0114] In some embodiments, the at least one water-soluble initiator is selected from succinic acid peroxide, tertbutyl hydroperoxide (TBHP), ammonium persulfate, sodium persulfate, potassium persulfate, or a mixture thereof.

[0115] In some embodiments, the initiator may be added during the process of preparing the nanoemulsion or during the process of preparing the polymer from said nanoemulsion. Preferably, an oil-soluble initiator is added to the nanoemulsion and a water-soluble initiator is added during the process of preparing the polymer.

[0116] In a preferred embodiment, the initiator is an oil soluble initiator selected from tertiary butyl hydroperoxide (TBHP), ammonium persulfate, or a mixture thereof.

[0117] In a preferred embodiment, step (III) is carried out at a temperature of 30 to 100°C.

[0118] In a preferred embodiment, the polymer has an average particle size in the range of 50 nm to 800 nm as determined according to dynamic light scattering techniques.

[0119] In a more preferred embodiment, the polymer has an average particle size in the range of 50 nm to 700 nm as determined according to dynamic light scattering techniques.

[0120] In a most preferred embodiment, the polymer has an average particle size in the range of 50 nm to 650 nm as determined according to dynamic light scattering techniques.

[0121] advantage The methods of the present invention provide one or more of the following advantages.

[0122] 1. The nanoemulsion process is scalable while maintaining low surfactant loading levels.

[0123] 2. The process is cost effective and avoids undesirable latex properties downstream.

[0124] 3. The process of the present invention is compatible with existing industrial equipment used for conventional emulsion polymerization.

[0125] 4. Due to the process according to the present invention, the final particle size of the polymer / latex can be controlled, and the final size should be the same as the initial emulsion size, which is not the case in conventional emulsion polymerization.

[0126] 5. The method allows for the use of hydrophobic monomers, enabling novel polymer / latex properties such as glass transition temperature.

[0127] 6. The method of the present invention facilitates the addition of functional additives to the nanoemulsion, which are then incorporated into the polymer / latex, thus improving the functional properties of the polymer. For example, the addition of wax to the nanoemulsion and thus to the polymer will provide water resistance to the product. Many functional additives can be incorporated by this method.

[0128] 7. The method may be automated and optimized by using a computing device.

[0129] 8. The entire process is facilitated due to automation and computer implementation.

[0130] Embodiment The present invention will be explained in more detail by the following embodiments and combinations of embodiments taken together with reference to and association with the corresponding dependent relationships.

[0131] 1. A method for preparing a nanoemulsion comprising: (i) forming an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -1 at a temperature between 0°C and 100°C, the emulsion system comprising at least one monomer, at least one surfactant, a salt, and water; (ii) increasing the internal phase of the emulsion system by up to 80% by volume by adding to the emulsion system at least one monomer used in step (i) or an additional amount of at least one monomer different from that used in step (i); and (iii) mixing the contents of step (ii) at a temperature between 0°C and 100°C to obtain a nanoemulsion having a volume average particle size in the range of 50 nm to 1000 nm as determined according to a dynamic light scattering technique. The method includes:

[0132] 2. The method of embodiment 1, wherein the power density in the step (iii) of mixing is between 0.1 W / kg and 100 W / kg.

[0133] 3. The method according to embodiment 1 or 2, wherein the power density in the mixing step (iii) is between 0.1 W / kg and 10 W / kg.

[0134] 4. The method of embodiment 1, wherein at least one monomer is a hydrophobic monomer.

[0135] 5. The method of embodiment 4, wherein the hydrophobic monomer is an α,β-ethylenically unsaturated monomer.

[0136] 6. At least one monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-methylheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate , isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, alkyl crotonate, di-n-butyl maleate, di-octyl maleate, hydroxyethyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (Meth)acrylate, cyclohexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxy (meth)acrylate, 2(2ethoxyethoxy)ethyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, caprolactone (meth)acrylate, polypropylene glycol mono (meth)acrylate, polyethylene glycol (meth)acrylate, benzyl (meth)acrylate , Hydroxypropyl (meth)acrylate, Methyl Polyglycol (meth)acrylate, 3,4-Epoxycyclohexylmethyl (meth)acrylate, 1,6-Hexanediol Di(meth)acrylate, 1,4-Butanediol Di(meth)acrylate, Styrene, Butadiene, Vinyl Ester, 2-Ethylhexyl Thioglycolate, 3,5,5-Trimethyl-1-hexyl Acrylate, 3-Butyl Mercaptopropionate, Acetoacetoxyethyl Methacrylate, Alpha Methyl Styrene, C 176. The method of claim 4 or 5, wherein the alkyl group is selected from the group consisting of acrylate, diacetone acrylamide, dimethylaminoethyl acrylate, isoamyl acrylate, isobutyl acrylate, isodecyl acrylate, isononyl acrylate, isoprenol acrylate, prenol acrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylonitrile, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, dimethacrylic acid, ethyl acrylic acid, allyl acetate, vinyl acetate, vinyl lactic acid, mesaconic acid, methylene malonic acid, citraconic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidomethylpropane sulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, (meth)acrylic phosphate esters, vinyl acetate, or combinations thereof.

[0137] 7. The method according to one or more of the preceding embodiments, wherein the volume percent of monomer is between 20% and 80% by volume.

[0138] 8. The method of embodiment 1, wherein steps (i) to (iii) are carried out at a temperature between 20° C. and 80° C.

[0139] 9. The method according to one or more of the preceding embodiments, wherein the amount of the at least one surfactant is in the range of 1 to 10% by weight, based on the total weight of the monomers.

[0140] 10. The method according to one or more of the preceding embodiments, wherein the characteristic curvature value (Cc) of at least one surfactant is in the range of -10 to 10, calculated as an average on a molar basis of each individual surfactant.

[0141] 11. The method according to one or more of the preceding embodiments, wherein the at least one surfactant is selected from cationic surfactants, anionic surfactants, zwitterionic surfactants, nonionic surfactants, and combinations thereof.

[0142] 12. The method of embodiment 11, wherein the at least one surfactant is selected from alkyl sulfates, alkyl benzene sulfonates, alkyl diphenyl oxide disulfonates, alkyl sulfosuccinates, sulfosuccinate esters, alkyl sulfosuccinamates, alkyl ether sulfates, alkyl phenol polyethoxy ether sulfates, alkyl phenol alkyl ether phosphates, quaternary amines, block copolymers containing ethylene oxide, alkyl polyethoxy and / or polypropoxy ethers.

[0143] 13. The method according to one or more of the preceding embodiments, wherein the amount of salt in the emulsion system ranges from 0.1 to 15% by weight, based on the total weight of the monomers.

[0144] 14. The method according to one or more of the preceding embodiments, wherein the amount of salt in the emulsion system ranges from 0.1 to 10% by weight, based on the total weight of the monomers.

[0145] 15. The method according to one or more of the preceding embodiments, wherein the amount of salt in the emulsion system is in the range of 0.1 to 5% by weight, based on the total weight of the monomers.

[0146] 16. The method according to one or more of the preceding embodiments, wherein the salt is selected from sodium chloride, potassium chloride, sodium hydroxymethanesulfinate hydrate, tetrasodium pyrophosphate.

[0147] 17. The method according to one or more of the preceding embodiments, wherein the emulsion system further comprises at least an additional component selected from an oil, an oil-soluble compound, or an alcohol.

[0148] 18. Step (i) is a. receiving, at a computing device, input data selected from at least the parameters salinity, equivalent alkane carbon number (EACN), temperature, and characteristic curvature of a surfactant (Cc); b. Adjusting the parameters of step (a) using equation (I) or (II) to obtain an HLD value between 0 and -1; HLD=F(S)-k.EACN-α(T-25)+Cc (I) HLD=F(S)-k.EACN-α(T-25)+F(A)+Cc (II) (In the formula, EACN: Available alkane carbon number of monomer or oil component T temperature (℃) S is a function of salinity (g / 100ml) Cc Characteristic curvature of surfactant α temperature coefficient; and F(A) is a function of the % of alcohol or other additional ingredients added to the system. 2. The method of embodiment 1, wherein the method is computer-implemented.

[0149] 19. An aqueous nanoemulsion prepared by a method according to one or more of embodiments 1 to 18.

[0150] 20. A method for preparing a polymer from a nanoemulsion, comprising: (I) charging a reactor with the nanoemulsion obtained by the method according to one or more of embodiments 1 to 16; (II) adding at least one initiator to step (I); and (III) mixing the contents of step (II) to obtain a polymer having a volume average particle size in the range of 50 nm to 1000 nm as determined according to dynamic light scattering techniques. The method includes:

[0151] 21. The method of embodiment 20, wherein the initiator is selected from a peroxide, a persulfate, an azo compound, or a mixture thereof.

[0152] 22. The method of embodiment 21, wherein the initiator is selected from tertbutyl hydroperoxide (TBHP), ammonium persulfate, or a mixture thereof.

[0153] 23. The method of embodiment 20, wherein step (III) is carried out at a temperature of 30 to 100°C. EXAMPLES

[0154] compound Surfactants: The surfactants are as follows: Surfactant 1: Sodium dioctyl sulfosuccinate, dissolved in a mixture of water and neopentyl glycol Surfactant 2: an anionic surfactant of the formula: R-(O) n -(D) p -(E) q -SO 3 - -M + n is 1, p is a value ranging from 0 to 8, q is an integer ranging from 00 to 8, and R is a linear or branched, unsubstituted or substituted C 10 ~C 18 Alkyl or C 10 ~C 18 Alkylaryl and M=sodium or H.

[0155] Surfactant 2a: R-(O) n -(D) p -(E) q -SO 3 - -M + n is 1, p is a value ranging from 3 to 8, q is an integer ranging from 0.05 to 8, and R is a linear or branched unsubstituted C 14 ~C 18 alkyl and M=sodium or H.

[0156] Surfactant 2b: R-(O) n -(D) p -(E) q -SO 3 - -M + n is 0, p is 0, q is 0, and R is a straight or branched, unsubstituted or substituted C 10~C 13 It is alkylaryl and M=sodium.

[0157] Monomer: Stearyl Acrylate Lauryl acrylate 2-Ethylhexyl acrylate (2-EHA) Methyl methacrylate (MMA) Azobisisobutyronitrile (AIBN)

[0158] Salt: Sodium chloride (NaCl)

[0159] oil Hexadecane Glissopal 1300

[0160] method thermal analysis The samples were cooled to 100°C for 24 hours using a heat / cool / heat cycle at 10 °C / min. 2 The samples were analyzed by DSC (TA Instruments DSC2500) under vacuum. The samples were first heated from room temperature to 300° C., then cooled to −80° C. and reheated to 300° C. This analysis was repeated with a pinhole lid and cooled before the first heating cycle.

[0161] Dynamic Light Scattering for Particle Size Determination Dynamic Light Scattering (DLS) is a common technique used to determine the size distribution of dispersed nanoparticles. DLS uses the temporal fluctuations of light scattered by nanoparticles to calculate the distribution of translational diffusion coefficients, which are then converted to a distribution of apparent hydrodynamic diameters. Nanoemulsions or polymers (latex) are diluted with DI water and then placed into a Zetasizer instrument. The instrument emits a laser, which is scattered by the particles. Software can then infer the average particle size of the nanoemulsion or polymer (latex) from the amount of light scattered.

[0162] Basic steps The monomer mixture contained 13% hexadecane (oil component) and the following monomers:

[0163] [Table 1]

[0164] The ingredients in vials 1 and 2 are as follows:

[0165] [Table 2]

[0166] The emulsification process for each vial was as follows: 1 mL of salt solution and surfactants 1 and 2 were placed in a vial and emulsified with 3 mL of monomer mixture. An additional 2 mL of salt solution was added and mixed again. The particle size of the resulting pre-emulsion was analyzed before polymerization. The vials were kept in an oven at 80° C. for 16 hours. The vials were cooled to room temperature and analyzed for final latex (polymer) particle size by dynamic light scattering on a Zetasizer (Zetasizer Nano ZS90).

[0167] The average particle sizes of the pre-emulsion and the polymer are as follows:

[0168] [Table 3]

[0169] Particle size analysis shows that the average particle size of the polymer correlates with the size of the starting pre-emulsion.

[0170] DSC results of polymer

[0171] [Table 4]

[0172] The DSC data showed a single peak, indicating that only one product (polymer) was formed and that there was no unreacted monomer present, which also indicates that the method of the present invention works well with hydrophobic monomers since the desired polymer is formed.

[0173] Basic Step 2 The monomer mixture contains 10% hexadecane (oil component) and the following monomers:

[0174] [Table 5]

[0175] The ingredients in the container were as follows:

[0176] [Table 6]

[0177] The emulsification process for each vessel was as follows: The salt solution and surfactants 1 and 2 were placed in a 500 mL round bottom flask. The monomer mixture was added dropwise to the vessel with stirring at 300 rpm to emulsify. The particle size of the resulting pre-emulsion was analyzed prior to polymerization. 200 g of deionized water was placed in a 1 L round bottom flask and heated to 85° C. under nitrogen with stirring at 300 rpm. The monomer emulsion was then pumped from the emulsion vessel to the reaction vessel over 80 minutes. The reaction was allowed to continue for an additional 2 hours. The reaction product was cooled to room temperature and analyzed by optical microscopy.

[0178] The average particle sizes of the pre-emulsion and polymer are as follows:

[0179] [Table 7]

[0180] Microscopic observations showed that the particle size of the polymer correlated with the size of the starting pre-emulsion, as evidenced by inversion upon dilution with water (w / o / w), except for Example 6, where the initial emulsion formed was water-in-oil. The material then phase separated upon reaction.

[0181] Basic Step 3 The monomer mixture contained 10% Glissopal 1300 (oil component) and the following monomers:

[0182] [Table 8]

[0183] The ingredients in the container were as follows:

[0184] [Table 9]

[0185] The emulsification process for each vessel was as follows: The salt solution and surfactants 1 and 2 were placed in a 500 mL round bottom flask. The monomer mixture was added dropwise to the vessel with stirring at 300 rpm to emulsify. The particle size of the resulting pre-emulsion was analyzed prior to polymerization. 100 g of deionized water was placed in a 1 L round bottom flask and heated to 85° C. under nitrogen with stirring at 300 rpm. The monomer emulsion was then pumped from the emulsion vessel to the reaction vessel over 80 minutes. The reaction was allowed to continue for an additional 2 hours. The reaction product was cooled to room temperature and analyzed for final latex (polymer) particle size by dynamic light scattering on a Zetasizer (Zetasizer Nano ZS90).

[0186] The average particle sizes of the pre-emulsion and the polymer are as follows:

[0187] [Table 10]

[0188] Basic Step 4 The monomer mixture contained 10% hexadecane (oil component) and the following monomers:

[0189] [Table 11]

[0190] The ingredients in the container were as follows:

[0191] [Table 12]

[0192] The emulsification process for each vessel is as follows: The salt solution and surfactants 1 and 2 were placed in a 500 mL round bottom flask. The monomer mixture was added dropwise to the vessel with stirring at 300 rpm to emulsify. The particle size of the resulting pre-emulsion was analyzed prior to polymerization. 85 g of deionized water was placed in a 1 L round bottom flask and heated to 85° C. under nitrogen with stirring at 300 rpm. The monomer emulsion was then pumped from the emulsion vessel into the reaction vessel over 80 minutes while co-feeding 0.2 g of potassium persulfate in 15 ml of deionized water. The reaction was allowed to continue for an additional 2 hours. The reaction product was cooled to room temperature and analyzed for final latex (polymer) particle size by dynamic light scattering on a Zetasizer (Zetasizer Nano ZS90).

[0193] The average particle sizes of the pre-emulsion and the polymer are as follows:

[0194] [Table 13]

[0195] Basic Step 5 The monomer mixture contained 10% hexadecane (oil component) and the following monomers:

[0196] [Table 14]

[0197] The ingredients in the container are as follows:

[0198] [Table 15]

[0199] The emulsification process for each vessel was as follows: The salt solution and surfactants 1 and 2 were placed in a 500 mL round bottom flask. The monomer mixture was added dropwise to the vessel with stirring at 300 rpm to emulsify. The particle size of the resulting pre-emulsion was analyzed prior to polymerization. 200 g of deionized water was placed in a 1 L round bottom flask and heated to 85° C. under nitrogen with stirring at 300 rpm. The monomer emulsion was then pumped from the emulsion vessel to the reaction vessel over 80 minutes. The reaction was allowed to continue for an additional 2 hours. The reaction product was cooled to room temperature and analyzed by optical microscopy.

[0200] The average particle sizes of the pre-emulsion and the polymer are as follows:

[0201] [Table 16]

[0202] Microscopic observations showed that the polymer particle size correlated with the particle size of the starting pre-emulsion in Examples 9 and 10 at 0% and 0.25% NaCl, respectively. At 0.5% NaCl (Example 11), multiple emulsions began to form.

Claims

1. A method for preparing a nanoemulsion, comprising: (i) forming an emulsion system having a hydrophilic-lipophilic deviation (HLD) value in the range of 0 to -1 at a temperature of 0°C to 100°C, said emulsion system comprising at least one monomer, at least one surfactant, a salt, and water; (ii) increasing the internal phase of the emulsion system to up to 80% by volume of the emulsion system by adding an additional amount of said at least one monomer used in step (i) or at least one monomer different from that used in step (i); and (iii) mixing the contents of step (ii) at a temperature of 0°C to 100°C to obtain a nanoemulsion having a volume average particle size in the range of 50 nm to 1000 nm as determined by dynamic light scattering technique. A method comprising the above steps.

2. (iii) The mixing step is carried out at a power density of 0.1 W / kg to 100 W / kg. The method according to claim 1.

3. (iii) The mixing step is carried out at a power density of 0.1 W / kg to 10 W / kg. The method according to claim 1.

4. The at least one monomer is a hydrophobic monomer. The method according to any one of claims 1 to 3.

5. The hydrophobic monomer is an α,β-ethylenically unsaturated monomer. The method according to claim 4.

6. The at least one monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-methylheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, alkyl crotonate, di-n-butyl maleate, di-octyl maleate, hydroxyethyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxy (meth)acrylate, 2(2-ethoxyethoxy)ethyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, caprolactone (meth)acrylate, polypropylene glycol mono (meth)acrylate, polyethylene glycol (meth)acrylate, benzyl (meth)acrylate, hydroxypropyl (meth)acrylate, methyl polyglycol (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 1,6-hexanediol di (meth)acrylate, 1,4-butanediol di (meth)acrylate, styrene, butadiene, vinyl ester, 2-ethylhexyl thioglycolate, 3,5,The method according to any one of claims 1 to 3, selected from 5-trimethyl-1-hexyl acrylate, 3-butyl mercaptopropionate, acetoacetoxyethyl methacrylate, alpha-methylstyrene, C17-acrylate, diacetone acrylamide, dimethylaminoethyl acrylate, isoamyl acrylate, isobutyl acrylate, isodecyl acrylate, isononyl acrylate, isoprenol acrylate, prenol acrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylonitrile, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, dimethacrylic acid, ethylacrylic acid, allyl acetic acid, vinyl acetic acid, vinyl lactic acid, mesaconic acid, methylene malonic acid, citraconic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, (meth)acrylic phosphate ester, vinyl acetate, or a combination thereof.,

7. The volume percentage of the monomer is 20% to 80% by volume of the emulsion system. The method according to any one of claims 1 to 3.

8. Steps (i) to (iii) are carried out at a temperature of 20°C to 80°C. The method according to any one of claims 1 to 3.

9. The amount of the at least one surfactant is in the range of 1 to 10% by weight based on the total weight of the monomer. The method according to any one of claims 1 to 3.

10. The at least one surfactant is selected from a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, or a combination thereof. The method according to any one of claims 1 to 3.

11. The amount of the salt in the emulsion system is in the range of 0.1 to 15% by weight based on the total weight of the monomer. The method according to any one of claims 1 to 3.

12. An aqueous nanoemulsion prepared by the method according to any one of claims 1 to 3.

13. A method for preparing a polymer from a nanoemulsion, comprising: (I) filling a reactor with the nanoemulsion obtained by the method according to any one of claims 1 to 3; (II) adding at least one initiator to step (I); and (III) mixing the contents of step (II) to obtain a polymer having a volume average particle diameter in the range of 50 nm to 1000 nm determined according to dynamic light scattering technique A method comprising the steps of:

14. The method according to claim 13, wherein the initiator is selected from peroxides, persulfates, azo compounds, or mixtures thereof.