WO2018013626A1 - Hybrid polymers of poly (vinylpyrrolidone-vinyl acetate-glycidyl methacrylate) grafted to cellulose ethers - Google Patents

Abstract

The present application discloses a hybrid polymer comprising a cellulose ether moiety and one or more polymer moieties comprising (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2-pyrrolidone moiety, and optionally (c) a vinyl acetate moiety, wherein the polymer moiety is grafted to the cellulose ether moiety via the glycidyl methacrylate moiety. Additionally, the present application discloses a process to prepare the hybrid polymer and its applications in various compositions.

Description

HYBRID POLYMERS OF POLY (VINYLPYRROLIDONE- VINYL ACETATE- GLYCIDYL METHACRYLATE) GRAFTED TO CELLULOSE ETHERS

FIELD OF THE INVENTION

[001] The present application relates to a hybrid polymer comprising a cellulose ether moiety and one or more polymer moieties, and a process for preparing the hybrid polymer and compositions thereof.

BACKGROUND OF THE INVENTION

[002] Cellulose ethers and vinylpyrrolidone polymers possess unique functional properties, which make them useful as additives for many applications including pharmaceutical excipients, coatings, shampoos, conditioners, and cement additives. Cellulose ethers such as hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC), and hydroxypropyl cellulose (HPC) are useful as rheology modifiers, tablet binders, tablet controlled release agents, film formers, and conditioners. Vinylpyrrolidone homopolymers and copolymers, such as polyvinylpyrrolidone (PVP) and vinylpyrrolidone- vinyl acetate copolymer(PVP/VA), are useful as dispersives, adhesives, tablet binders, wetting agents, and film-forming agents.

[003] Conventional cellulose grafting polymers used to solubilize poorly water-soluble drugs in hot-melt applications tend to lack anti-nucleation properties needed to prevent recrystallization. Conventional cellulose grafting polymers having anti-nucleating agents and drug solubilizers tend to have high Tg (glass transition) for hot melt extrusions.

[004] Accordingly, it would be desirable to combine the properties of cellulose ethers and vinylpyrrolidone homopolymers and copolymers into a single hybrid polymer that would provide very desirable functional properties having the properties of both cellulose ether and vinylpyrrolidone homopolymers and copolymers. The combination would provide enhanced application performance in many fields such as pharmaceuticals, foods, beverages, coatings, paints, energy sector agents, oral care, skin care, hair care, cosmetics, toiletry, household and cleaning products, industrial and institutional cleaning products, disinfecting products, opthalmics, injectables, sanitary products, agricultural products, textiles, biocides, preservatives, and laundry products.

[005] U.S. Patent no. 5,362,830 discloses a water-soluble crosslinkable copolymer consisting essentially of (i) 80-99% by weight of vinylpyrrolidone and (ii) 1-20% by weight of an epoxide-containing polymerizable monomer, and wherein, the composition is used as an electrolead on a conductive foilbacking, or for bandages and wound dressings, and as a controlled release media for pharmaceuticals.

[006] U.S. Patent Publication 2010/190947A1 and WO2014/160631 discloses terpolymer of (N-vinyl-2-pyrrolidone), vinyl acetate, and (c) a glycidyl methacrylate and its compositions in different end-user applications.

[007] European Patent no. 2,182,931 discloses grafting of glycidyl methacrylate and other monomers on textile materials for antibacterial delivery.

[008] U.S. Patent no. 3,401,049 discloses a method to graft various polymerizable monomers on non-metallic substrates via activated sites of silver oxide or metallic silver.

[009] Ghanshyam S. Chauhan et al., Cellulose 12: 97-110, 2005, discloses grafting of various glycidyl methacrylate and other comonomers on cellulose.

[0010] U.S. Patent Publication 2015/0041089 discloses a method of improving a paper substrate used in a papermaking process, the method comprising the steps of: providing an NCC -polymer, and adding the NCC-polymer to a paper substrate in the wet-end of a papermaking process, wherein the NCC-polymer is substantially distributed throughout the paper substrate, and wherein the NCC polymer comprises an NCC-Core having a crystalline fraction of no less than 80%.

[0011] U.S. Patent Publication 2015/0344767 discloses an amidic polymer comprising a (a) polymer having a hydroxyl group reacted with a (b) compound having an epoxy group and an unsaturated moiety to provide a reactive unsaturated intermediate polymer; wherein the reactive unsaturated intermediate polymer is further reacted with a (c) vinyl amide to provide the amidic polymer, and wherein, the glycidyl methacrylate monomer grafted on a polymer having hydroxyl group. SUMMARY OF THE INVENTION

[0012] The primary objective of the present application is to provide a hybrid polymer comprising a cellulose ether moiety and one or more polymer moieties comprising (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2-pyrrolidone moiety, and optionally (c) a vinyl acetate moiety, wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety.

[0013] Another objective of the present application is to provide a hybrid polymer grafted to cellulose having the structure set out below:

wherein "a" is an integer ranging from 1 to about 20; n and m are percentages of the molar sum, the sum of which equals 100%; and x and y are percentages of the molar sum, the sum of which equals 100%.

[0014] Yet another objective of the present application is to provide a hybrid polymer grafted to cellulose having the structure set out below:

wherein "a" is an integer ranging from 1 to about 20; "n" and "m" are percentages of the molar sum, the sum of which equals 100%; and x, y, and z are percentages of the molar sum, the sum of which equals 100%.

[0015] Still another objective of the present application is to provide a process for preparing a hybrid polymer comprising: (I) (A) dissolving monomers comprising (a) a glycidyl methacrylate moiety; (b) a N-vinyl-2-pyrrolidone moiety; and optionally (c) a vinyl acetate moiety in an organic solvent; (B) charging resultant of (A) in to a reaction container; (C) preparing a feeding solution- 1 by mixing vinyl pyrrolidone and vinyl acetate and preparing feeding solution- 2 by mixing glycidyl methacrylate and organic solvent; (D) preparing an initiator solution; (E) charging feeding solution-1 into resultant of (B); (F) charging (D) into (E); (G) charging feeding solution-2 in to (F), and (H) charging initiator in to (G), stirring the reaction mixture, cooling the reaction mixture, filtering the solvent, re-suspending solid in the solvent, filtering the solvent, and drying the obtained solid; (II) (A) dissolving specific amount of resultant of step (I) and at least one cellulose ether moiety in water, and mixing the reaction solution by adding an acid, and (B) grinding the dried product of (II) (A).

[0016] One important objective of the present application is to provide a composition comprising: (I) about 0.1 wt.% to about 25 wt. % of hybrid polymer comprising: (i) a cellulose ether moiety; and (ii) one or more polymer moiety, wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2-pyrrolidone moiety, and optionally (c) a vinyl acetate moiety; and wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety, and (II) about 75 wt. % to about 99.9 wt. % of one or more additives.

[0017] Another objective of the present application is to provide enhanced application performances of the hybrid polymers in various end-user application(s) based compositions including but not limited to pharmaceutical, food and beverages, coatings, paints, printing & inks, electronics, lamination, lithography, decorated pigments, oil & energy, performance materials, adhesives, biomaterials, oral care, skin care, hair care, cosmetics, toiletry, household and cleaning products, industrial and institutional cleaning products, disinfecting products, ophthalmics, injectables, sanitary products, agricultural products, textiles, biocides, preservatives, consumer products, membrane and laundry products. [0018] One important aspect of the present application is to provide a pharmaceutical composition comprising: (I) about 0.1 wt.% to about 25 wt. % of hybrid polymer comprising: (i) a cellulose ether moiety; and (ii) one or more polymer moieties, wherein the polymer moiety comprises (a) a glycidyl methacrylate moieties, (b) a N-vinyl-2-pyrrolidone moiety, and optionally (c) a vinyl acetate moiety; and wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety, and (II) about 75 wt. % to about 99.9 wt. % of one or more pharmaceutically acceptable additives.

DETAILED DESCRIPTION OF THE INVENTION

[0019] While this specification concludes with claims particularly pointing out and distinctly claiming that which is regarded as the invention, it is anticipated that the invention can be more readily understood through reading the following detailed description of the invention and study of the included examples.

[0020] All percentages, parts, proportions, and ratios as used herein are by weight of the total composition, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and therefore do not include solvents or by-products that can be included in commercially available materials, unless otherwise specified.

[0021] All references to singular characteristics or limitations of the present application shall include the corresponding plural characteristics or limitations, and vice-versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made.

[0022] All publications, articles, papers, patents, patent publications, and other references cited herein are hereby incorporated herein in their entireties for all purposes to the extent consistent with the disclosure herein.

[0023] As used herein, the following terms, unless otherwise stated, have the meanings set out below.

[0024] Numerical ranges as used herein are intended to include every number and subset of numbers contained within that range, whether specifically disclosed or not. Further, these numerical ranges should be construed as providing support for a claim directed to any number or subset of numbers in that range. [0025] The term "a" or "an" when used in conjunction with the term "comprising" can be "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one." The use of the term "or" is used to mean "and/or" unless explicitly indicated to refer to alternatives only if the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and "and/or."

[0026] The term "about" refers to a difference of 10% from the value specified. Numerical ranges as used herein are meant to include every number and subset of numbers enclosed within that range, whether particularly disclosed or not.

[0027] The term "acidic conditions" refers to conditions relating to the pH value of an aqueous solution. Pure water is considered to be neutral, with a pH close to 7.0 at 25°C. Solutions with a pH value less than 7 are considered to be acidic solutions.

[0028] The term "alkyl" refers to a functionalized or unfunctionalized monovalent straight- chain, branched-chain or cyclic C1-C60 group optionally having one or more heteroatoms. Particularly, an alkyl is a C1-C45 group and more particularly, a C1-C30 group. Non- limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, cyclobutyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cyclyheptyl, methylcyclohexyl, n-octyl, 2-ethylhexyl, tert-octyl, iso-norbornyl, n-dodecyl, tert-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl.

[0029] The term "alkyl (alk) acrylate" refers to an alkyl ester of an acrylic acid or an alkyl acrylic acid.

[0030] The term "alkyl (alk) acrylamide" refers to an alkyl amide of an acrylic acid or an alkyl acrylic acid.

[0031] The term "alkylene" refers to a functionalized or unfunctionalized divalent straight- chain, branched-chain or cyclic C1-C40 group optionally having one or more heteroatoms. Particularly, an alkylene is a C1-C45 group and more particularly, a C1-C30 group. Non- limiting examples of alkylene groups include -CH₂- -CH2-CH2-, -CH(CH₃)-CH₂- -CH₂- CH(CH₃)-, -C(CH₃)₂-CH₂-, -CH₂-C(CH₃)₂-, -CH(CH₃)-CH(CH₃)-, -C(CH₃)₂-C(CH₃)₂- -CH2-CH2-CH2-, -CH(CH₃)-CH₂-CH₂- -CH₂-CH(CH₃)-CH₂- -CH2-CH₂-CH(CH₃)-, - CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-CH2-, - CH2-CH2-CH2-CH2-CH2-CH2-CH2-, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, and the like.

[0032] The term "aryl" refers to a functional group derived from an aromatic hydrocarbon. The aromatic hydrocarbon can be mononuclear or polynuclear. Examples of aryl group of the mononuclear type include phenyl, tolyl, xylyl, mesityl, cumenyl, and the like. Examples of aryl group of the polynuclear type include naphthyl, anthryl, phenanthryl, and the like. The aryl group can have at least one substituent selected from halogen, hydroxy, cyano, carboxy, carbamoyl, nitro, amino, aminomethyl, lower alkyl, lower alkoxy, mercapto, trichloroethyl, or trifluoromethyl. Examples of such substituted aryl groups include 2-fluorophenyl, 3- nitrophenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-hydroxyphenyl, and the like.

[0033] The term "branched and unbranched alkyl groups" refers to alkyl groups, which can be straight chained or branched. For example, the alkyl groups have from 1 to about 60 carbon atoms, more particularly, from 1 to about 30 carbon atoms, and yet more particularly from 1 to about 6 carbon atoms. Branched groups include isopropyl, tert-butyl, and the like.

[0034] The term "comprising" (and any form of comprising, such as "comprise", "comprised", and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. The term "or combinations thereof as used herein refers to all permutations and combinations of the listed items preceding the term. For example, "A, BX_n, BX_n+i, or combinations thereof is intended to include at least one of: A, BX_n, BX_n+i, ABX_n, ABX_n+i, BX_nBX_n+i, or ABX_nBX_n+i and, if order is important in a particular context, also BX_nA, BX_n+iA, BX_n+iBX_n, BX_n+iBX_nA, BXnBXn₊iA, ABXn₊iBXn, BX_nABX_n+i, or BX_n+iABX_n. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as

BXnBXn, AAA, MBXn, BXnBXnBXn₊l, AAABXnBXn₊lBXn₊lBXn₊lBXn₊l,

BXn₊i BXnBXnAAA, BXn₊iA BXnABXnBXn, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. The term "comprising" thus encompasses and includes the more restrictive terms "consisting of" and "consisting essentially of" which can be used to characterize the essential ingredients such as cellulose ethers moieties, lactam moieties, polymer moieties, glycidyl methacrylate moieties, acetate moieties, linking groups and/or hybrid polymers.

[0035] The term "cycloalkyl group" refers to a non-aromatic mono- or multicyclo ring system having from about 3 to about 10 carbon atoms. The cycloalkyl group can be partially unsaturated. The cycloalkyl group can also be substituted with an alkyl group substituent as defined herein. The cycloalkyl chain can contain an oxygen, sulfur, or substituted or unsubstituted nitrogen atom, wherein the nitrogen substituent can be hydrogen, alkyl, substituted alkyl, aryl, or substituted aryl, thus providing a heterocyclo group. Representative monocyclo cycloalkyl rings include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like. Further, the cycloalkyl group can be substituted with a linking group, such as an alkyl group, alkylene group, and the like, to form cyclopropylmethyl group, cyclobutylmethyl group, and the like. The cycloalkyl group can also be a multicyclo cycloalkyl rings such as adamantyl, octahydronaphthyl, decalin, camphor, camphane, and noradamantyl.

[0036] The terms "effective amount" and "effective use level" of hybrid polymer refer to amount of hybrid polymer employed in providing desired performance attributes, stability, efficacy, product aesthetics, and the like.

[0037] The term "free radical addition polymerization initiator" refers to a compound used in a catalytic amount to initiate a free radical addition polymerization, and is used herein as simply "initiator". The term "free radical addition polymerization initiator" also refers to thermal and light activated initiators. The choice of "initiator" depends mainly upon its solubility and its decomposition temperature.

[0038] The term "functionalized" refers to the state of a moiety that has one or more functional groups introduced to it by way of one or more functionalization reactions known to a person having ordinary skill in the art. Non-limiting examples of functionalization reactions include epoxidation, sulfonation, hydrolysis, amidation, esterification, hydroxylation, dihyroxylation, amination, ammonolysis, acylation, nitration, oxidation, dehydration, elimination, hydration, dehydrogenation, hydrogenation, acetalization, halogenation, dehydrohalogenation, Michael addition, aldol condensation, Canizzaro reaction, Mannich reaction, Clasien condensation, Suzuki coupling, and the like. Particularly, functionalization of a moiety replaces one or more hydrogens in the moiety with one or more non-hydrogen groups, for e.g., alkyl, alkoxyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, and/or aryl groups. Non-limiting examples of cycloalkyl groups include cyclopentane, cyclohexane, cycloheptane, and the like. Non-limiting examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and the like. Non-limiting examples of aryl groups include benzenes, naphthalenes (2 rings), anthracenes (3 rings), and the like.

[0039] The term "halogen" refers to chloro, bromo, iodo and fluoro, and in one embodiment is bromo and/or chloro.

[0040] The term "heteroatom" refers to atoms such as oxygen, nitrogen, sulfur, silicon, phosphorous, and/or halogen. The heteroatom(s) can be present as a part of one or more heteroatom-containing functional groups and/or as a part of one or more heterocyclic rings. Non-limiting examples of heteroatom-containing functional groups include ether, hydroxy, epoxy, carbonyl, carboxamide, carboxylic ester, carboxylic acid, imine, imide, amine, sulfonic, sulfonamide, phosphonic, and silane groups.

[0041] The term "homopolymer" refers to a molecule that comprises one type of monomer and the term "non-homopolymer" refers to a polymer that comprises more than one type of monomer and includes such polymers wherein a small amount of polymerization solvent may or may not be covalently bonded into the polymer. The non-homopolymer can be a copolymer, terpolymer, tetramer, or the like.

[0042] The term "hybrid polymer" refers to a polymer moiety grafted to a cellulose ether moiety. The term "hybrid polymer" refers to a polymer comprising a cellulose ether moiety and one or more polymer moieties, wherein the polymer moieties comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2-pyrrolidone moiety, and optionally (c) a vinyl acetate moiety, wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety.

[0043] The terms "linking group" and "spacer group" refer to a segment or group of molecules configured to connect two or more molecules to each another. When the linking group or spacer group is defined as being absent, the linking group or spacer group is replaced by a direct bond. [0044] The term "monomer" refers to the repeat units that comprise a polymer. A monomer is a compound that chemically bonds to other molecules, including other monomers, to form a polymer.

[0045] The term "polymer" refers to both linear and branched polymers derived from one or more monomer units, which may or may not be crosslinked or grafted. Non-limiting examples of polymers include copolymers, terpolymers, tetramers, graft copolymer and the like, wherein the polymer is random, block, or alternating polymer.

[0046] The terms "one embodiment," "one aspect", "one version", and "one objective" of the invention/application include one or more such embodiments, aspects, versions, or objectives, unless the context clearly dictates otherwise.

[0047] The term "personal care composition" refers to such illustrative non-limiting compositions as skin, sun, oil, hair, and preservative compositions, including those to alter the color and appearance of the skin.

[0048] The term "pH" refers to a measure of the acidity or basicity of an aqueous solution. Pure water is considered to be neutral, with a pH of about 7.0 at 25 °C. Solutions with a pH less than 7 are considered to be acidic and solutions with a pH greater than 7 are considered to be basic or alkaline.

[0049] The terms "pharmaceutically acceptable" and "cosmetically acceptable" refer to molecular entities and compositions that are generally regarded as safe. Particularly, as used herein, the term "pharmaceutically acceptable" and "cosmetically acceptable" refer to approved by a regulatory agency of the appropriate governmental agency or listed in the U.S. Pharmacopoeia or other generally recognized pharmacopoeia for use in animals, and more particularly in humans.

[0050] The term "pharmaceutically acceptable excipient" refers to an additive included in a solid formulations in the form of powders, granules, capsules, pellets and tablets to increase the bulk of the desired formulation comprising present solid dispersion. The excipients may be added during or after the preparation of solid dispersion using spray drying or hot-melt extrusion or other methods. [0051] As used herein, the term "excipient" or "additive" are interchangeably used and the terms refer to a pharmaceutically acceptable ingredient that is commonly used in the pharmaceutical technology for preparing granulate and/or solid oral dosage formulations. Examples of categories of excipients include, but are not limited to, binders, disintegrants, lubricants, glidants, stabilizers, fillers and diluents. One of ordinary skill in the art may select one or more of the aforementioned excipients with respect to the particular desired properties of the granulate and/or solid oral dosage form by routine experimentation and without any undue burden. The amount of each excipient used may vary within ranges conventional in the art. The following references which are all hereby incorporated by reference discloses techniques and excipients used to formulate oral dosage forms. See The Handbook of Pharmaceutical Excipients, 4th edition, Rowe et al., Eds., American Pharmaceuticals Association (2003); and Remington: the Science and Practice of Pharmacy, 20th edition, Gennaro, Ed., Lippincott Williams & Wilkins (2000).

[0052] The term "pharmaceutically active ingredient" refers to any ingredient considered to have a therapeutic effect when delivered to a subject in need thereof and further being regulated by drug authorities. Pharmaceutically active ingredients may act systemically upon oral consumption, or locally such as when present in the buccal cavity, on the skin, etc. They may also be delivered across the skin as in transdermal drug delivery systems.

[0053] The term "poorly soluble" refers to slightly soluble or very slightly soluble compounds that require from about 100 or more parts of solvent for one part of solute. The poorly soluble compound means that the solubilization of the active pharmaceutical ingredient (API) compound becomes the rate-limiting step for absorption of such API compound.

[0054] The terms "preferred," "preferably", and variants thereof, refer to embodiments of the application that afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the application.

[0055] The hybrid polymers in the present application contain a polymer moiety grafted to cellulose moiety via a covalent bond through glycidyl methacrylate (GMA), a linking group. Glycidyl methacrylate is a polyfunctional monomer and acts as an adhesive promoting cross- linking co-monomer for acrylic and vinyl resins. Glycidyl methacrylate is an ester of methacrylic acid and is often used to prepare epoxy resins. While many epoxy compounds contain diglycidyl ether of bisphenol A (DGEBA), glycidyl methacrylate is used to provide epoxy functionalization to polyolefins and other acrylate resins. Glycidyl methacrylate is soluble in ethanol, acetone, diethyl ether, and benzene.

[0056] The present application provides a hybrid polymer comprising a cellulose ether moieties; and one or more polymer moieties; wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2-pyrrolidone moiety, and optionally (c) a vinyl acetate moiety, wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety.

[0057] In general, the cellulose ether moieties of the present application have the structure set out below:

wherein R is independently selected from the group consisting of hydrogen; C1-C50 straight- or branched-chain, functionalized or unfunctionalized alkyl groups; hydroxyalkyl groups; alkylcarboxy groups; and functionalized and non-functionalized, substituted or unsubstituted carbonyl groups. The functional groups can be with or without heteroatoms; n is 1 to about 2000; and at least one R is substituted with a glycidyl methacrylate linking group.

[0058] Non-limiting examples of the cellulose ether moieties of the present application include hydroxyalkyl celluloses, alkyl celluloses, carboxyalkyl celluloses, for example, methyl cellulose (MC), ethylcellulose (EC), propyl cellulose (PC), methylhydroxyethylcellulose (MHEC), ethyl hydroxyethyl cellulose (EHEC), methylethyl hydroxyethyl cellulose (MEHEC), hydroxypropyl hydroxyethyl cellulose (HPHEC), methyl hydroxypropyl hydroxyethyl cellulose (MHPHEC), hydroxypropyl cellulose (HPC), methyl hydroxypropyl cellulose (MHPC), and ethyl hydroxypropyl cellulose (EHPC), hydroxypropyl methyl cellulose (HPMC), ethylhydroxyethylcellulose (EHEC), carboxyalkylcelluloses, carboxyalkylhydroxyalkylcellulose, carboxymethyl cellulose, carboxymethylcellulose, and carboxypropylcellulose.

[0059] According to another embodiment of the present application, the cellulose ether moieties for the present application are methylcellulose (MC), ethylcellulose (EC), methylhydroxyethylcellulose (MHEC), hydroxypropyl methyl cellulose (HPMC), ethylhydroxyethylcellulose (EHEC), and methylhydroxyethylcellulose (MHEC).

[0060] According to another embodiment of the present application, cellulose ether moieties include hydroxyethyl cellulose (HEC 250 HV, NatrosolTM hydroxyethyl cellulose, Ashland) and hydroxypropyl cellulose (HPC HF pharma, KlucelTM, Ashland).

[0061] While the lactam carbonyl oxygen atom is a strong hydrogen bond acceptor, access to the oxygen atom is hindered due to the closer proximity of the oxygen atom in the polymeric backbone. Applicants have found that extending the lactam group away from the polymeric backbone on a pendant, linking group (glycidyl methacrylate) results in less steric hindrance and better access to the oxygen atom.

[0062] The lactams useful in the present application are those that can generally be classed as higher lactams that contains at least 3 to 8 carbon atoms in the lactam ring, and wherein, the lactam groups may or may not substituted. Illustrative lactams thus can be polyvinylpyrrolidone, 2-pyrrolidone, 2-piperidone, γ-valerolactam, γ-caprolactam, ε- caprolactam, ε-enantholactam, ζ-enantholactam, caprylolactam, θ-nonanolactam, ζ- decanolactam, K-undecanolactam, λ-dodecanolactam, ξ-pentadecanolactam, o- hexadecanolactam, cyclo hexamethyleneadipamide (14 membered ring), dimeric cyclo hexamethyleneadipamide (28 membered ring), 3-aminocyclohexanecarboxylic acid lactam, 4-aminocyclohexanecarboxylic acid lactam, camphoric acid lactam (wherein the two carbonyl groups are converted to form an amide linking group), phthalimidine, carbostyril, 2,2-bis[5-(e-caprolactam)] propane, homologs of the foregoing lactams and other related compounds thereof. The preferred lactam of the present application is substituted and non- substituted 5 or 7 membered lactam moieties. Preferred lactams include vinylpyrrolidone, 1- hydroxymethyl-2-pyrrolidone (HMP), N-glycidyl pyrrolidone (NGP) and ethylpyrrolidone glycidyl ether (EPGE), l-hydroxymethyl-2-caprolactone, epoxypropyl pyrrolidone (EPP) and pyrrolidinonyl ethylglycidyl ether (PEGE). As per one important embodiment of the present application, it is disclosed to employ vinylpyrrolidone as a lactam moiety. [0063] In one aspect of the present application, cellulose ether moieties having a molecular weight range from about 15,000 to about 200,000 g/mol, react with a polymer comprising glycidyl methacrylate moiety to provide cellulose ether polymers containing glycidyl methacrylate moiety functionality with a degree of substitution (DS) ranging from 0.1 to 2.0, dependent on the initial level of ether capping on the starting cellulose ether as well as the stoichiometry of the glycidyl methacrylate moiety containing reagent relative to the level of free hydroxyl groups present on the cellulose ether.

[0064] In another aspect, certain cellulose ethers having a molecular weight range from about 10,000 to 200,000 g/mol, react with a polymer comprising a glycidyl methacrylate moiety containing reagents, for example, l-hydroxymethyl-2-pyrrolidone (HMP), N-glycidyl pyrrolidone (NGP) and ethylpyrrolidone glycidyl ether (EPGE), l-hydroxymethyl-2- caprolactone, epoxypropyl pyrrolidone (EPP) and pyrrolidinonyl ethylglycidyl ether (PEGE) in conjunction with esterifying agents, for example various acyl halides (R-CO-C1) or anhydrides (R-(C=0)-0-(CO)-R), to provide cellulose ether-ester polymers containing pendant pyrrolidone functionality where the sum of the ester and pyrrolidone DS ranges from 0.1 to 2.0, dependent on the initial level of ether capping on the starting cellulose ether as well as the stoichiometry of the esterifying and lactam containing reagents relative to the level of free hydroxyl groups present on the cellulose ether. The esterifying agent can be chosen from reagents which will produce a cellulose alkonate where the alkonate group is chosen from, but not limited to, acetate, proprionate, butyrate, succinate, maleate, phthalate, citrate, and trimellitate. The lactam is selected from the group as described above, particularly, substituted or non-substituted lactam ring having Ci_-8.

[0065] The unexpected properties achieved by combining cellulose ether moieties with a polymer having vinylpyrrolidone moiety include greater amphiphilic properties (if the alkonate group is chosen from acetate, proprionate or butyrate) as well as improved control of pH dependant solubility (if the alkonate group is chosen from phthalate, succinate, maleate, citrate or trimellitate).

[0066] In another embodiment the present application, the amount of the (N-vinyl-2- pyrrolidone) moiety and the amount of the vinyl acetate moiety can be adjusted to provide a hybrid polymer having the desired amount of hydrophilic properties from the (N-vinyl-2- pyrrolidone) moiety and the desired amount of hydrophobic properties from the vinyl acetate moiety. Also, the amount of the (N-vinyl-2-pyrrolidone) moiety and the amount of the glycidyl methacrylate moiety can be adjusted to provide a hybrid polymer having the desired degree of grafting properties.

[0067] Vinyl acetate undergoes many reactions, such as addition of bromine, hydrogen halides and transesterification with many carboxylic acids. Vinyl acetate also undergoes Diels-Alder cycloadditions. Vinyl acetate can be polymerized with other monomers to prepare copolymers such as ethylene- vinyl acetate (EVA), vinyl acetate-acrylic acid (VA/AA), polyvinyl chloride acetate (PVCA), and polyvinylpyrrolidone (VP/VA copolymer).

[0068] According to another embodiment of the present application, the degree of substitution (DS) or molar substitution (MS) of cellulose ethers in hybrid polymer is in the range of from about 0.01 to about 2.0. Other non-limiting DS or MS suitable for the present application is from about 0.01 to about 0.1, about 0.1 to about 0.2, about 0.2 to about 0.4, about 0.4 to about 0.6, about 0.6 to about 0.8, about 0.8 to about 1.0, about 1.0 to about 1.2, about 1.2 to about 1.4, about 1.4 to about 1.6, about 1.6 to about 1.8, or about 1.8 to about 2.0.

[0069] Molecular weight of the hybrid polymer is in the range of from about 10,000 to about 1,000,000. Other preferred molecular weight ranges would include but are not limited to about 10,000 to about 100,000; about 100,000 to about 200,000; about 200,000 to about 300,000; about 300,000 to about 400,000; about 400,000 to about 500,000; about 500,000 to about 600,000; about 600,000 to about 700,000; about 700,000 to about 800,000; about 800,000 to about 900,000; and/or about 900,000 to about 1000,000.

[0070] The present application provides a hybrid polymer comprising a cellulose ether moiety; and one or more polymer moieties, wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, and (b) a N-vinyl-2-pyrrolidone moiety, wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety.

[0071] According to one important embodiment, the hybrid polymer has the structure set out below:

[0072] wherein "a" is an integer ranging from 1 to about 20; "n" and "m" are percentages of the molar sum, the sum of which equals 100%; and x and y are percentages of the molar sum, the sum of which equals 100%. According to another embodiment, "a" is in the range of from 1 to about 5; "n" and "m" independently is in the range of from about 1% to about 99%; "x" is in the range of from about 99% to about 40%, and "y" is in the range of from 1% to about 60%.

[0073] According to one of the embodiment, the polymer moiety of hybrid polymer has the percentages set out below: vinyl pyrrolidone/glycidyl methacrylate (98/2); vinyl pyrrolidone/glycidyl methacrylate (80/20); vinyl pyrrolidone/glycidyl methacrylate (90/10); and vinyl pyrrolidone/glycidyl methacrylate (95/5)

[0074] The present application also provides a composition comprising a hybrid polymer comprising a cellulose ether moiety; and one or more polymer moiety; wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2-pyrrolidone moiety, and (c) a vinyl acetate moiety, and wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety.

[0075] According to one embodiment, the hybrid polymer has the structure set out below:

wherein "a" is an integer ranging from 1 to about 20; "n" and "m" are percentages of the molar sum, the sum of which equals 100%; and x, y, and z are percentages of the molar sum, the sum of which equals 100%.

[0076] In another embodiment, "a" is in the range of from 1 to about 5; "n" and "m" independently is in the range of from about 1% to about 99%; "x" is in the range of from about 35% to about 60%; "y" is in the range of from 1% to about 7%, and "z" is in the range of from about 40% to about 60%.

[0077] According to another embodiment, the polymer moiety of hybrid polymer has the percentages set out below: vinyl pyrrolidone/vinyl acetate/glycidyl methacrylate (58/40/2); vinyl pyrrolidone/vinyl acetate/glycidyl methacrylate (40/55/5); vinyl pyrrolidone/vinyl acetate/glycidyl methacrylate (40/58/2); and vinyl pyrrolidone/vinyl acetate/glycidyl methacrylate (52/45/3).

[0078] The polymer moiety of the present application is prepared by a process selected from the group consisting of solution polymerization, precipitation polymerization, emulsion polymerization and free-radical polymerization, and wherein, the polymer moiety is block copolymer, alternating copolymer, random copolymer or graft copolymer. [0079] According to yet another embodiment, the present application provides a process for preparing a hybrid polymer comprising the steps of:

(I) . (A) dissolving monomers comprising (a) a glycidyl methacrylate moiety; (b) a N- vinyl-2-pyrrolidone moiety; and optionally (c) a vinyl acetate moiety in an organic solvent,

(B) charging resultant of (A) in to a reaction container in nitrogen atmosphere, stirring the reaction mixture and maintaining temperature at 65°C,

(C) preparing a feeding solution- 1 by mixing vinyl pyrrolidone and vinyl acetate and preparing feeding solution- 2 by mixing glycidyl methacrylate and organic solvent,

(D) preparing an initiator solution by mixing initiator in t-butanol,

(E) charging feeding solution- 1 into resultant of (B) at 65°C and maintaining stirring for over 120 minutes,

(F) charging (D) in to three parts to (E) at rate of one part for each 120 minute,

(G) charging feeding solution-2 in to (F) at 65 °C and maintaining stirring for over 300 minutes and maintaining at a temperature 70°C for an hour,

(H) charging initiator in to (G), stirring the reaction mixture for three hours, cooling the reaction mixture, filtering the solvent, re-suspending solid in the solvent, filtering the solvent, and drying the obtained solid;

(II) . (A) dissolving specific amount of resultant step (I) in water, charging specific amount of cellulose, charging specific amount of phosphoric acid, stirring the reaction mixture for an hour at 15-25°C temperature, drying the reaction mixture in an oven at 85 °C for 24 hours;

(B) grinding the dried product of (II) (A) to ~ 500-1000 microns.

[0080] Cellulose is a naturally available polymer of β-glucose linked together via β(1→4) glycosidic bonds. Cellulose is commonly found in plant cell walls and is responsible for cell wall rigidity because enhanced tensile strength of cellulose is derived from strong hydrogen bonding interactions between adjacent polymer chains. Hydrogen bonding between such polysaccharides can be weakened with various chemical modifications. For example, many functional groups (e.g. alkyl groups or ester groups) on cellulose ethers (or esters) can result in a reduced number of hydroxy groups and the physical separation between the chains can cause hydrogen bonding between the polysaccharides to be weakened. Such structurally modified cellulose products can provide a material having different new properties compared to original natural cellulose. Such modified cellulose can be employed in various applications including but not limited to pharmaceuticals, food and beverages, coatings, paints, oil and energy sectors, performance materials, oral care, skin care, hair care, cosmetics, toiletry, household & cleaning products, industrial and institutional cleaning products, disinfecting products, opthalmics, injectables, sanitary products, agricultural products, textiles, biocides, preservatives, consumer products, and/or laundry products. Hybrid polymers can provide very desirable functional properties having both cellulose and lactam chemistries, thus providing enhanced application performance in various fields.

[0081] Polyvinylpyrrolidone (PVP) is a hydrophilic, non-toxic, ecologically friendly, water and organic soluble, film-forming stiff polymer (high Tg), which has excellent adhesion to a variety of substrates, such as metal, hair, skin, porcelain, plastics, polyesters, paper, concrete, and clays. The carbonyl group in polyvinylpyrrolidones has the ability to hydrogen bond/complex both high molecular weight entities such as polyphenols, tannins, polyacids and low molecular weight entities such as active pharmaceutical ingredients (as a drug excipient), inks or dye-mordants, and mycotoxins.

[0082] Polyvinylpyrrolidone can be radical crosslinked by gamma-ray, x-ray, E-beam, UV- cured, and thermally activated by radical species to form an insoluble composite thereby rendering the polyvinylpyrrolidone formulation as a hydrogel, or a surface treatment that is (semi)permanently affixed to the substrate on which it was coated. However, these crosslinking treatments require specialized equipment not readily available and the crosslinking conditions can damage other components in the formulation rendering them useless in the desired application.

[0083] Polyvinylpyrrolidone binds to polar molecules exceptionally well because of its polarity. Accordingly, polyvinylpyrrolidone is used in applications for coatings for photo- quality ink-jet papers and transparencies as well as in inks for inkjet printers. Polyvinylpyrrolidone is also used in personal care products, such as shampoos and toothpastes, in paints, and adhesives that must be moistened, such as old-style postage stamps and envelopes. Polyvinylpyrrolidone has also been used in contact lens solutions and in steel- quenching solutions. Polyvinylpyrrolidone is the basis of the early formulas for hair sprays and hair gels, and continues to be a component of the same. As a food additive, polyvinylpyrrolidone is a stabilizer and is used in the wine industry as a fining agent for white wine or some beers. In molecular biology, polyvinylpyrrolidone can be used as a blocking agent during southern blot analysis as a component of Denhardt's buffer. It is also exceptionally good at absorbing polyphenols during DNA purification. Polyphenols are common in many plant tissues and can deactivate proteins if not removed and therefore inhibit many downstream reactions.

[0084] According to one of the embodiment, the vinyl glycidyl acrylates moiety contains a reactive epoxy-functionality that has the ability to covalently bond to cellulose ether moiety. A preferred vinyl glycidyl acrylate is glycidyl methacrylate. By covalently bonding to the cellulose ether moieties, the polymeric water-soluble or water-dispersible complex will not be readily available to get washed away when exposed to aqueous solution.

[0085] The conditions of the thermal activation of the hybrid polymer by exposure to heat 90-230°C, can be achieved easily by a blow-dryer, flat-iron or curling-iron, or calendaring onto the substrate, do not destroy other useful ingredients in the formulation. The conditions for preparing the crosslinkable compositions are very mild and can be performed without the need for specialized equipment or dangerous radiation sources. Addition of other catalysts, such as thermal or photoacids, or thermal/photogenerating radical species, can catalyze the crosslinking reactions by simple exposure to the sun, heat, or other external sources.

[0086] Radical, thermal, or chemical crosslinking reactions obviate the problems and issues of high viscosity and uneven application of the crosslinked formulation and the disposal and cleaning of the non-biodegradable crosslinked polymer formulations. When the unused or unreacted composition is simply exposed to water or moisture for several weeks, it renders the reactive epoxy-functionality into a stable non-toxic glycerol moiety so it is ecologically friendly to the environment.

[0087] When polydimethylsiloxane is mixed with an aqueous hybrid polymer formulation, the dispersion formed phase-separates into an oily layer and an aqueous layer within minutes. However, when poly-dimethylsiloxane is reacted with the present hybrid polymer, the terminal hydroxyl or amino-functionality of these modified silicones can attach to the epoxy functionality thereby making them more water dispersible and stable as micro-emulsions. [0088] Hair dyes leach from dyed hair over time. The present hybrid polymer can bind hair dyes to hair substrates through covalent bonds that cannot be leached. The present hybrid polymer provides a means to react hair-dyes and printing dyes onto the present copolymers so that when they contain an inorganic or organic OH, SH, NH, or an acidic hydrogen like inorganic and organic acids, or active-hydrogen compounds like Michael-donors or acceptors, or any nucleophilic or electrophilic functionality capable of reacting with the epoxy-functionality, the hair and printing dyes will be permanently bonded to the hybrid polymer. Upon further crosslinking, a crosslinked matrix of active agents and hybrid polymer result in (semi)permanently fixed to the substrate in one step or multiple steps.

[0089] The attachment of suitable active agents include but are not limited to modified silicones, UV-filters, conditioning agents, vitamins, peptides, enzymes, microbiological agents, cleansing agents, fragrances, medical coatings or devices, pharmaceutical actives, oncology agents, therapeutic agents and therapeutic-peptides/polypeptides, dyes, colorants and inks, formation of block-copolymers and hybrid-polymer compositions with other industrially significant polymers and copolymers such as (meth)acrylates and/or (meth)acrylamides, cellulosics, starches, polyesters, polyamides, vinyl-polymers, proteins, guar, poly-olefins and their chemically modified counterparts. Once the active agent is attached to the copolymer, the attachment provides a means to cross-link with other substrates and/or itself, so that it is (semi)permanently attached to the surface of the substrate by a covalent bond, that has a reactive nucleophilic or electrophilic atom within it, and/or can be encased by the crosslinked polymer-active matrix itself.

[0090] According to one of the embodiment, the present application provides a composition comprising:

I. about 0.1 wt.% to about 25 wt. % of hybrid polymer comprising: (i) a cellulose ether moiety; and (ii) one or more polymer moieties, wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2- pyrrolidone moiety, and optionally (c) a vinyl acetate moiety; and wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety, and

II. about 75 wt. % to about 99.9 wt. % of one or more additives. [0091] The present application provides a universal surface modification composition or delivery system comprising the present hybrid polymers. The hybrid polymer compositions are reacted with useful actives and simultaneously or sequentially crosslinked onto a substrate under mild conditions. The application also provides a means to decay the composition into a non-toxic glycerol entity, when not used or reacted with another agent so form environmentally friendly and green compositional by product results.

[0092] According to another embodiment of the present application, the hybrid polymer composition can be employed in various end-user applications including pharmaceutical, food and beverages, coatings, paints, printing & inks, electronics, lamination, lithography, decorated pigments, oil & energy, performance materials, adhesives, biomaterials, oral care, skin care, hair care, cosmetics, toiletry, household and cleaning products, industrial and institutional cleaning products, disinfecting products, opthalmics, injectables, sanitary products, agricultural products, textiles, biocides, preservatives, consumer products, membrane and laundry products.

[0093] Suitable personal care or cosmetic based active ingredients can be selected from the group consisting of allantoin, tocopherol nicotinate, niacinamide, retinyl propionate, palmitoyl-gly-his-lys, phytosterol, isoflavone, dexpanthenol, panthenol, bisabolol, farnesol, phytantriol, salicylic acid, zinc/sodium pyridinethione salts, piroctone olamine, selenium disulfide, tetrahydrocurcumin, glucosamine, N-acteyl glucosamine, vitamin B3, retinoids, peptides, phytosterol, dialkanoyl hydroxyproline, hexamidine, salicylic acid, N-acyl amino acids, escolols, sunscreen actives, UV-A/UV-B protecting agent, water soluble vitamins, oil soluble vitamins, hesperedin, mustard seed extract, glycyrrhizic acid, glycyrrhetinic acid, carnosine, butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA), ergothioneine, vanillin, vanillin derivatives, diethylhexyl syrinylidene malonate, melanostatine, sterol esters, fatty acids, poly-unsaturated fatty acids, zinc pyrithione (ZPT), anti-fungal agents, thiol compounds, N-acetyl cysteine, glutathione, thioglycolate, β-carotene, ubiquinone, amino acids, idebenone, dehydroacetic acid, licohalcone A, creatine, creatinine, feverfew extract, yeast extract, β-glucans, a-glucans, alone or in combination.

[0094] Personal care compositions can be prepared by employing a suitable personal care or cosmetically acceptable excipient selected from the group consisting of fatty substances, gelling agents, thickeners, surfactants, moisturizers, emollients, hydrophilic or lipophilic active agent, antioxidants, sequestering agents, preserving agents, acidifying or basifying agents, fragrances, fillers, dyestuffs, emulsifying agents, solvents, UV-A or UV-B blocker/filters, plant extracts, moisturizers, proteins, peptides, neutralizing agents, solvents, silicones and reducing agents.

[0095] Personal care compositions that can prepared employing agents selected from the group consisting of hair-care products, shampoos, hair conditioners, leave in and rinse off conditioners, styling and treating hair compositions, hair perming products, hair relaxants, hair straighteners, hair sprays and lacquers, permanent hair dyeing systems, hair styling mousses, hair gels, semi-permanent hair dyeing systems, temporary hair dyeing systems, hair bleaching systems, permanent hair wave systems, hair setting formulations, skin-care products, bath products, shower products, liquid soaps, bar soaps, fragrances and/or odoriferous ingredients consisting preparations, dentifrices, deodorizing and antiperspirant preparations, decorative preparations, light protection formulations, shaving lotions, body oils, body lotions, body gels, treatment creams, body cleaning products, skin protection ointments, shaving and aftershave preparations, skin powders, lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents, sun care products, and/or compositions comprising UV blockers and UV protectors.

[0096] The hybrid polymer can be employed in various end-user formulations including but not limited to an emulsion, a suspension, an ointment, a lotion, a gel, a vesicle dispersion, a paste, a cream, a solid stick, a mousse, a shampoo, or a spray.

[0097] According to one of the embodiment, the present application provides a pharmaceutical composition comprising:

I. about 0.1 wt.% to about 25 wt. % of hybrid polymer comprising: (i) a cellulose ether moiety; and (ii) one or more polymer moieties, wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2- pyrrolidone moiety, and optionally (c) a vinyl acetate moiety; and wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety, and

II. about 75 wt. % to about 99.9 wt. % of one or more pharmaceutically acceptable additives. [0098] Non-limiting examples of pharmaceutically acceptable additives include, but are not limited to, binders, disintegrants, lubricants, glidants, stabilizers, fillers and diluents.

[0099] The pharmaceutically acceptable additives include, but are not limited to, plasticizers, disintegrants, surfactants, lubricants, glidants, carriers, anti-adherents, fillers, wetting agents, pH modifiers, binders, solubility modifiers, recrystallization inhibitors, coating agents, diluents, coloring agents, preservatives, antifoaming agent, antioxidants, buffering agents, acidifying agents, alkalizing agents, complexation-enhancing agent, cryoprotectant, electrolytes, gelling agents, emulsifying agents, solubility-enhancing agents, stabilizers, tonicity modifiers, flavors, sweeteners, complexing agents, fragrances, and viscosity modifiers.

[00100] Further, the hybrid polymer can be mixed with one or more pharmaceutical active ingredients to prepare a pharmaceutical composition.

[00101] Pharmaceutical active ingredients can be selected from the group consisting of analgesics, antibacterial, antifungal, antimicrobial, antibiotics, antipyretics, anti-inflammatory drugs, non-steroidal anti-inflammatory drugs (NSAIDS), chemotherapeutic drugs, hormones, anti-diabetic drugs, anti-psychiatric drugs, anti-viral drugs, anesthetic drugs, cardiovascular drugs, anti-asthmatic drugs, monoclonal antibodies, veterinary drugs, antiseptics, antimalerial drugs, mood stabilizers, oral contraceptives, stimulant drugs, tranquilizers, antacids, reflux suppressants, antiflatulents, antidopaminergics, proton pump inhibitors (PPIs), H2-receptor antagonists, cytoprotectants, prostaglandin analogues, laxatives, antispasmodics, antidiarrhoeals, bile acid sequestrants, opioids, β-receptor blockers, calcium channel blockers, diuretics, cardiac glycosides, antiarrhythmics, nitrate, antianginals, vasoconstrictors, vasodilators, ACE inhibitors, angiotensin receptor blockers, a blockers, thiazide diuretics, loop diuretics, aldosterone inhibitors, anticoagulants, heparin, antiplatelet drugs, fibrinolytics, anti-hemophilic factors, haemostatic drugs, HMG-CoA reductase inhibitors, hypolipidaemic drugs, psychedelics, hypnotics, antipsychotics, antidepressants, antiemetics, anticonvulsants, anxiolytics, barbiturates, movement disorder drugs, benzodiazepines, cyclopyrrolones, dopamine antagonists, antihistamines, cholinergics, anticholinergics, emetics, cannabinoids, and 5-HT (serotonin) antagonists, muscle relaxants, neuromuscular drugs, anticholinesterases, astringents, ocular lubricants, topical anesthetics, sympathomimetics, parasympatholytics, mydriatics, cycloplegics, topical antibiotics, sulfa drugs, aminoglycosides, fluoroquinolones, corticosteroids, mast cell inhibitors, adrenergic agonists, carbonic anhydrase inhibitors, hyperosmotics, cholinergics, miotics, parasympathomimetics, prostaglandin agonists/prostaglandin inhibitors, sympathomimetics, antihistamines, local anesthetics, bronchodilators, antitussives, mucolytics, decongestants, systemic corticosteroids, β2- adrenergic agonists, anticholinergics, leukotriene antagonists, androgens, antiandrogens, gonadotropin, corticosteroids, human growth hormone, insulin, thyroid hormones, antithyroid drugs, alkalinizing agents, quinolones, antispasmodics, 5-a-reductase inhibitors, selective alpha- 1 blockers, sildenafils, fertility and anti-fertility drugs, spermicides, haemostatic drugs, hormone replacement therapy (HRT), bone regulators, follicle stimulating hormones, luteinising hormones, gonadotropin release inhibitor, progesterone, dopamine agonists, oestrogen, prostaglandins, gonadorelins, emollients, anti-pruritics, disinfectants, scabicides, pediculicides, tar products, vitamins and their analogues, keratolytics, proteolytics, sunscreens, antiper spirants, corticosteroids, immune modulators, antileprotics, antituberculous drugs, anthelmintics, amoebicides, antiprotozoals, vaccines, immunoglobulins, immunosuppressants, interferons, tonics, electrolytes, mineral preparations, parenteral nutritions, anti-obesity drugs, anabolic drugs, haematopoietic drugs, food product drugs, cytotoxic drugs, therapeutic antibodies, sex hormones, aromatase inhibitors, somatostatin inhibitors, recombinant interleukins, G-CSF, and erythropoietins.

[00102] In one embodiment, the hybrid polymers can be used for enhancing solubility of poorly soluble drugs are described under Biopharmaceutical Classification System (BCS) class II and/or IV. The non-limiting BCS class II and IV drugs can be a free acid, free base or neutral molecules, or in the form of an appropriate pharmaceutically acceptable salt, a pharmaceutically acceptable solvate, a pharmaceutically acceptable co-crystal, a pharmaceutically acceptable enantiomer, a pharmaceutically acceptable derivative, a pharmaceutically acceptable polymorph, pharmaceutically acceptable ester, pharmaceutically acceptable amide, or a pharmaceutically acceptable prodrug thereof.

[00103] The non- limiting BCS Class II drugs can be selected from the group consisting of albendazole, acyclovir, azithromycin, cefdinir, cefuroxime axetil, chloroquine, clarithromycin, clofazimine, diloxanide, efavirenz, fluconazole, griseofulvin, indinavir, itraconazole, ketoconalzole, lopinavir, mebendazole, nelfinavir, nevirapine, niclosamide, praziquantel, pyrantel, pyrimethamine, quinine, ritonavir, bicalutamide, cyproterone, gefitinib, imatinib, tamoxifen, cyclosporine, mycophenolate mofetil, tacrolimus, acetazolamide, atorvastatin, benidipine, candesartan cilexetil, carvedilol, cilostazol, clopidogrel, ethylicosapentate, ezetimibe, fenofibrate, irbesartan, manidipine, nifedipine, nisoldipine, simvastatin, spironolactone, telmisartan, ticlopidine, valsartan, verapamil, warfarin, acetaminophen, amisulpride, aripiprazole, carbamazepine, celecoxib, chlorpromazine, clozapine, diazepam, diclofenac, flurbiprofen, haloperidol, ibuprofen, ketoprofen, lamotrigine, levodopa, lorazepam, meloxicam, metaxalone, methylphenidate, metoclopramide, nicergoline, naproxen, olanzapine, oxcarbazepine, phenyloin, quetiapine, risperidone, rofecoxib, valproic acid, isotretinoin, dexamethasone, danazol, epalrestat, gliclazide, glimepiride, glipizide, glyburide (glibenclamide), levothyroxine sodium, medroxyprogesterone, pioglitazone, raloxifene, mosapride, orlistat, cisapride, rebamipide, sulfasalazine, teprenone, ursodeoxycholic acid, ebastine, hydroxyzine, loratadine, and pranlukast.

[00104] The hybrid polymer products of the present application can have unexpected properties such as employing the polymer to provide lower glass transition temperature (Tg), unique gelation and film properties, and differentiated organic solubility. These changes in physical chemical properties will translate into improved application performance in areas such as pharmaceutical and personal care applications, particularly with regard to pharmaceutical drug solubilization of solid drug dispersions (SDD) formed through spray drying or hot melt extrusion (HME) method of processing ability as well as a can behave as better excipient for tablet binding and tablet coating functions.

[00105] The pharmaceutical composition prepared in accordance with the present application can be administered through enteral/oral, topical, parenteral, and/or inhalation, and wherein, the pharmaceutical composition can be formulated as solids, semi-solids, liquids, gels, powders, granules, lozenges, tablets, patches, capsules, ointments, lotions, creams, suppositories, aerosols, syrups, elixirs, emulsions, non-aqueous suspensions, aqueous suspensions, and/or solutions.

[00106] The hybrid polymers of the present application can be prepared according to the examples set out below. The examples are presented for purposes of demonstrating, but not limiting, the preparation of the hybrid polymers of this application. The following non- limiting examples are provided to illustrate a few of the methods for preparing the hybrid polymer.

EXAMPLES [00107] EXAMPLE 1: Vinyl Pyrrolidone/Vinyl Acetate/Glycidyl Methacrylate (58/40/2) Grafted to Hydroxyethyl Cellulose (HEC 250 HV)

[00108] (VP/VA/GMA) Polymer was first synthesized by precipitation polymerization. In a 1-L Parr reactor, vinyl acetate (VA, 4g), vinyl pyrrolidone (VP 5.8g) and (435g) of cyclohexane were added. The reactor was pressurize/release with nitrogen three times and then heated to 65°C, with vigorous stirring. A monomer feeding solution 1 was prepared by mixing vinyl pyrrolidone (52g) and vinyl acetated (36g). A monomer feed solution 2 was prepared by mixing of glycidyl methacrylate (2g) and cyclohexane (15g). An initiator solution was prepared by mixing 1 g of Vazo 67 and 5g t-butanol. When the temperature reached 65°C, the monomer feeding solution 1 was metered into the reactor over 120 minutes. The monomer feeding solution 2 was metered into the reactor over 300 minutes. Meanwhile three shots of the initiator solution were added every two hours. The reaction was maintained for 1 hour and then increased to 70°C. Two shots of Trigonox 25C75 were added every one hour. The reaction was held for another three hours. The reaction was cooled to room temperature. Then the solvent was filtered off using either a Buchner funnel with filter paper or a fritted funnel and house vacuum. Re-suspend solid in 150 ml dry cyclohexane and filtered. Repeat resuspension and filtration second time. The dry solid was dried in 40oC oven using house vacuum for 3 hours. The residual VP%, GMA, and VA% in the obtained product was less than 1000 ppm.

[00109] 60g of the above product P(VP/VA/GMA) (58/40/2) was transferred into a 1-L kettle and dissolve into 200ml water then stirred into 60g of hydroxyethyl cellulose (HEC 250HV)) with addition of lg phosphoric acid. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan- forced oven at 85°C for 24 hrs. The dried material was grinded into a powder by a grinder to roughly ~ 500-1000 microns. The yield was 90%.

[00110] EXAMPLE 2: (Vinyl Pyrrolidone/Vinyl Acetate/Glycidyl Methacrylate) (40/55/5) Grafted to Hydroxyethyl Cellulose (HEC 250 HV)

[00111] Polymer (VP/VA/GMA) was first synthesized by precipitation polymerization. In a 1- L Parr reactor. Vinyl pyrrolidone (VP lOg) and (450g) of cyclohexane were added. The reactor was pressurize/release with nitrogen three times and then heated to 65°C, with vigorous stirring. A monomer feeding solution 1 was prepared by mixing vinyl pyrrolidone (30g) and vinyl acetated (55g). A monomer feed solution 2 was prepared by mixing 5g of Glycidyl methacrylate and lOg cyclohexane. When the temperature reached 65°C, the monomer feeding solution 1 was metered into the reactor over 300 minutes, the monomer feeding solution 2 was metered into the reactor over 360 minutes. Meanwhile three shots of 0.125g of Trigonox 25C75 were given every two hours. The reaction was maintained for 3 hours and then increased to 70°C. Two shots of Trigonox 25C75, the reaction was held for another three hours. The solvent was filtered off using either a Buchner funnel with filter paper or a fritted funnel and house vacuum. Re-suspend solid in 150 ml dry cyclohexane and filtered. Repeat resuspension and filtration second time. Dry solid over either a Buchner funnel with filter paper or a fritted funnel using house vacuum for 1 hour. The dry solid was dried in 40°C oven using house vacuum for 3 hours. The residual VP%, GMA and VA% in the obtained product was less than 1000 ppm.

[00112] 60g of the above product P(VP/VA/GMA) (40/55/5) was transferred into a 1-L kettle and dissolved into 200ml water and then stirred into 60g of Hydroxyethyl cellulose (HEC 250HV) with addition of lg phosphoric acid. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan- forced oven at 85°C for 24 hrs. The dried material was grinded into a powder by a grinder to roughly 500-1000 microns. The yield was <90%.

[00113] EXAMPLE 3: (Vinyl Pyrrolidone/Vinyl Acetate/Glycidyl Methacrylate) (40/58/2) Grafted to Hydroxyethyl Cellulose (HEC 250 HV)

[00114] (VP/VA/GMA) polymer was first synthesized by precipitation polymerization. In a 1-L Parr reactor, Vinyl Pyrrolidone (VP 15g) and (646g) of cyclohexane were added. The reactor was pressurize/release with nitrogen three times and then heated to 65°C, with vigorous stirring. A monomer feeding solution 1 was prepared by mixing vinyl pyrrolidone (45g) and vinyl acetated (86g). A monomer feed solution 2 was prepared by mixing 2g of Glycidyl methacrylate and 34 g cyclohexane. When the temperature reached 65°C, the monomer feeding solution 1 was metered into the reactor over 300 minutes. The monomer feeding solution 2 was metered into the reactor over 360 minutes. Meanwhile three shots of 0.479g of Trigonox 25C75 very given two hours The reaction was maintained for 3 hours and then increased to 70°C. Two shots of Trigonox 25C75, the reaction was held for another three hours. The solvent is filtered off using either a Buchner funnel with filter paper or a fritted funnel and house vacuum. Re-suspend solid in 150 ml dry cyclohexane and filtered. Repeat resuspension and filtration second time. Dry solid over either a Buchner funnel with filter paper or a fritted funnel using house vacuum for 1 hour. The dry solid was dried in 40°C oven using house vacuum for 3 hours. The residual VP%, GMA, and VA% in the obtained product was less than 0.1%.

[00115] 60g of the above product P(VP/VA/GMA) (40/58/2) was transferred into a 1-L kettle and dissolve into 200ml water and then stirred into 60g of Hydroxyethyl cellulose (HEC 250HV) with addition of lg phosphoric acid. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan- forced oven at 85°C for 24 hrs. The dried material was grinded into a powder by a grinder to roughly 500-1000 microns. The yield was 90%.

[00116] Example 4: (Vinyl Pyrrolidone/Glycidyl Methacrylate) (VP/GMA) (80/20) Grafted to Hydroxyethyl Cellulose (HEC 250 HV)

[00117] In a 1-L resin kettle equipped with an anchor agitator, thermocouple, gas inlet, and reflux condenser, 680 g of Cyclohexane and 9.6g of N-vinyl pyrrolidone, were charged. The reaction mixture was purged with nitrogen for 30 min. With agitation and nitrogen purging, the reactor was heated to 65 °C, then two feeds of 96.4 g of N-vinyl pyrrolidone and of 24g of Glycidyl Methacrylate were fed. N-vinyl pyrrolidone feed was fed over a period of four hours and Glycidyl Methacrylate feed was fed over five hours and 0.25g of Trigonox 25 C75 was charged. After two hours of reaction, 0.25 g of Tirgonox 25 C 75 was charged into the reactor. The reaction was held for 2 hours then 0.25 g of Trigonox 250 C75 was charged into the reactor. At time 6, 10 and 12 hours, charge 0.40g of Trigonox 25 C75 into the reactor respectively. After 14h, the reaction mixture was cooled to room temperature to discharge the product. GC analysis showed the residual N-vinyl pyrrolidone and glycidyl methacrylate was less than lOOOppm.

[00118] Then 60g of P( VP/GMA) ( 80/20) was transferred into a 1-L kettle and dissolve into 200ml water and then stirred into 60g of Hydroxyethyl cellulose (HEC 250HV ) with addition of lg phosphoric acid. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan- forced oven at 85 °C for 24 hrs. The dried material was grinded into a powder by a grinder to roughly 500-1000 microns.

[00119] Example 5: (Vinyl Pyrrolidone/Glycidyl Methacrylate) (VP/GMA) (90/10) Grafted Hydroxyethyl Cellulose (HEC 250 HV) [00120] In a 1-L resin kettle equipped with an anchor agitator, thermocouple, gas inlet and reflux condenser, 680 g of Cyclohexane and 10.8g of N-(VP), were charged. The reaction mixture was purged with nitrogen for 30 min. With agitation and nitrogen purging, the reactor was heated to 65 °C, then two feeds of 97.4 g of N-(VP) and 12g of Glycidyl Methacrylate (GMA) were fed. N-feed was fed over a period of four hours and Glycidyl Methacrylate feed was fed over five hours and 0.25g of trigonox 25 C 75 was charged. After two hours of reaction, 0.25 g of Tirgonox 25 C 75 was charged into the reactor. The reaction was held for 2 hours followed with 0.25 g of Trigonox 250 C75 was charged into the reactor. At time 6, 10 and 12 hours, charge 0.40g of Trigonox 25 C75 into the reactor respectively. After 14h, the reaction mixture was cooled to room temperature to discharge the product. GC analysis showed the residual N- Vinyl Pyrrolidone and Glycidyl Methacrylate was less than 3000ppm.

[00121] Then 60g of P(VP/GMA) (90/10) was transferred into a 1-L kettle and dissolved into 200ml water and then then stirred into 60g of Hydroxy ethyl cellulose (HEC 250HV) with addition of lg phosphoric acid. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan-forced oven at 85°C for 24 hrs. The dried material was grinded into a powder around 500-1000 microns. The yield was <90%.

[00122] Example 6: (Vinyl Pyrrolidone/Glycidyl Methacrylate) (VP/GMA) (95/5) Grafted to Hydroxyethyl Cellulose (HEC 250 HV)

[00123] In a 1-L resin kettle equipped with an anchor agitator, thermocouple, gas inlet and reflux condenser, 680 g of Cyclohexane and 10.8g of N-(VP), were charged. The reaction mixture was purged with nitrogen for 30 min. With agitation and nitrogen purging, the reactor was heated to 65 °C, then two feeds of 97.4 g of N-(VP) and 12g of Glycidyl Methacrylate (GMA) were fed. N- Vinyl Pyrrolidone feed was fed over a period of four hours and Glycidyl Methacrylate feed was fed over five hours and 0.25g of Trigonox 25 C75 was charged. After two hours of reaction, 0.25 g of Tirgonox 25 C 75 was charged into the reactor. The reaction was held for 2 hours followed with 0.25 g of Trigonox 250 C75 was charged into the reactor. At time 6, 10 and 12 hours, charge 0.40g of Trigonox 25 C75 into the reactor respectively. After 14 h, the reaction mixture was cooled to room temperature to discharge the product. GC analysis showed the residual N- Vinyl Pyrrolidone and Glycidyl Methacrylate was less than 3000ppm. [00124] 60g of the above product P(VP/GMA) (95/5) was transferred into a 1-L kettle and dissolve into 200ml water and then stirred into 60g of Hydroxyethyl cellulose (HEC 250HV) with addition of lg phosphoric acid. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan-forced oven at 85°C for 24 hrs. The dried material was grinded into a powder around 500-1000 microns. The yield was 90%.

[00125] Example 7: (Vinyl Pyrrolidone/Glycidyl Methacrylate) (VP/GMA) (98/2) Grafted to Hydroxyethyl Cellulose (HEC 250 HV)

[00126] In a 1-L resin kettle equipped with an anchor agitator, thermocouple, gas inlet and reflux condenser, 680 g of Cyclohexane and 11.76g of N-(VP), were charged. The reaction mixture was purged with nitrogen for 30 min. With agitation and nitrogen purging, the reactor was heated to 65°C, then two feeds of 105.84 g of N- (VP) and of 2.4g of Glycidyl Methacrylate (GMA) were fed. N- Vinyl Pyrrolidone feed was fed over a period of four hours and Glycidyl Methacrylate feed was fed over five hours and 0.25g of Trigonox 25 C75 was charged. After two hours of reaction, 0.25 g of Tirgonox 25 C 75 was charged into the reactor. The reaction was held for 2 hours followed with 0.25 g of Trigonox 250 C75 was charged into the reactor. At time 6, 10 and 12 hours, charge 0.40g of Trigonox 25 C75 into the reactor respectively. After 14 h, the reaction mixture was cooled to room temperature to discharge the product. GC analysis showed the residual N- Vinyl Pyrrolidone and Glycidyl Methacrylate was less than 3000ppm.

[00127] 60g of the above product P(VP/GMA) (98/2) was transferred into a 1-L kettle and dissolve into 200ml water and then added into 60g of Hydroxyethyl cellulose (250HV) with stirring and lg of phosphoric acid was added. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan- forced oven at 85°C for 24 hrs. The dried material was grinded into a powder around 500-1000 microns. The yield was <90%.

[00128] Example 8: (Vinyl Pyrrolidone/Vinyl Acetate/Glycidyl Methacrylate) (58/40/2) Grafted to Hydroxypropyl Cellulose (HPC HF pharma)

[00129] (VP/VA/GMA) polymer was first synthesized by precipitation polymerization. In a 1-L Parr reactor, Vinyl Acetate (VA, 4g), Vinyl Pyrrolidone (VP 5.8g), and 435g of cyclohexane were added. The reactor was pressurize/release with nitrogen three times and then heated to 65 °C, with vigorous stirring. A monomer feeding solution 1 was prepared by mixing vinyl pyrrolidone (52g) and vinyl acetated (36g). A monomer feed solution 2 was prepared by mixing of Glycidyl methacrylate (2g) and cyclohexane (15g). An initiator solution was prepared by mixing 1 g of Vazo 67 and 5g T-butanol. When the temperature reached 65°C, the monomer feeding solution 1 was metered into the reactor over 120 minutes. The monomer feeding solution 2 was metered into the reactor over 300 minutes. Meanwhile three shot of the initiator solution were added every two hours. The reaction was maintained for 1 hour and then increased to 70°C. Two shots of Trigonox 25C75 was added every one hour, the reaction was hold for another three hours. The reaction was cooled down to room temperature. Then the solvent was filtered off using either a Buchner funnel with filter paper or a fritted funnel and house vacuum. Re-suspend solid in 150 ml dry cyclohexane and filtered. Repeat resuspension and filtration second time. The Dry solid was dried in 40°C oven using house vacuum for 3 hours. The residual VP%, GMA and VA% in the obtained product was less than 1000 ppm.

[00130] 50g of P (VP/VA/GMA) (58/40/2) of the above product was transferred into a 1-L kettle and dissolved into 200ml water and then added to 50g of Hydroxypropyl cellulose (HPC HF Pharma) with stirring and lg phosphoric acid was added. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan- forced oven at 85°C for 24 hrs. The solid mass was grinded into a powder by grinder to roughly ~ 500-1000 microns. The yield was 99%.

[00131] lOg of the above product was removed and further reacted with lg of 12-epoxy- stearic acid-methyl ester into 50g of T-butanol at 85°C for 16 hrs. Then the reaction was discharged and dried in a fan- forced oven. The yield was 99%.

[00132] Then 0.5g of this material dissolved in water and generated a homogenous milky dispersion that swelled into a hydrogel.

[00133] EXAMPLE 9: (Vinyl Pyrrolidone/Vinyl Acetate/Glycidyl Methacrylate) (VP/VA/GMA) (40/55/5) Grafted to Hydroxypropyl Cellulose (HPC HF pharma)

[00134] Polymer (VP/VA/GMA) was first synthesized by precipitation polymerization. In a 1-L Parr reactor, Vinyl Pyrrolidone (VP lOg) and 450g of cyclohexane were added. The reactor was pressurize/release with nitrogen three times and then heated to 65°C, with vigorous stirring. A monomer feeding solution 1 was prepared by mixing vinyl pyrrolidone (30g) and vinyl acetated (55g). A monomer feed solution 2 was prepared by mixing 5g of Glycidyl methacrylate and 10 g cyclohexane. When the temperature reached 65 C, the monomer feeding solution 1 was metered into the reactor over 300 minutes, the monomer feeding solution 2 was metered into the reactor over 360 minutes. Meanwhile three shot of 0.125g of Trigonox 25C75 every two hours. The reaction was maintained for 3 hours and then increased to 70°C. Two shots of Trigonox 25C75, the reaction was hold for another three hours. The solvent is filtered off using either a Buchner funnel with filter paper or a fritted funnel and house vacuum. Re-suspend solid in 150 ml dry cyclohexane and filtered. Repeat resuspension and filtration second time. Dry solid over either a Buchner funnel with filter paper or a fritted funnel using house vacuum for 1 hour. The dry solid was dried in 40°C oven using house vacuum for 3 hours. The residual VP%, GMA and VA% in the obtained product were less than 1000 ppm.

[00135] 50g of the above product was transferred into a 1-L kettle and dissolved into 200ml water and then added to 50g of Hydroxypropyl cellulose (HPC HF Pharma) with stirring and lg phosphoric acid was added. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan- forced oven at 85°C for 24 hrs. The solid mass was grinded into a powder by grinder to roughly ~ 500-1000 microns. The yield was 99%.

[00136] lOg of the above product was removed and further reacted with lg of 12- epoxy- stearic acid-methyl ester into 50g of T-butanol at 85°C for 16 hrs. Then the reaction was discharged and dried in a fan- forced oven. The yield was 99%.

[00137] Then 0.5g of this material dissolved in water and generated a homogenous milky dispersion that swelled into a hydrogel.

[00138] Example 10: (Vinyl Pyrrolidone/Vinyl Acetate/Glycidyl Methacrylate) (VP/VA/GMA) (40/58/2) Grafted to Hydroxypropyl Cellulose (HPC HF pharma)

[00139] (VP/VA/GMA) polymer was first synthesized by precipitation polymerization. In a 1-L Parr reactor, Vinyl Pyrrolidone (VP 15g) and 646g of cyclohexane were added. The reactor was pressurize/release with nitrogen three times and then heated to 65°C, with vigorous stirring. A monomer feeding solution 1 was prepared by mixing vinyl pyrrolidone (45g) and vinyl acetated (86g). A monomer feed solution 2 was prepared by mixing 2g of Glycidyl methacrylate and 34 g cyclohexane. When the temperature reached 65 °C, the monomer feeding solution 1 was metered into the reactor over 300 minutes. The monomer feeding solution 2 was metered into the reactor over 360 minutes. Meanwhile three shot of 0.479g of Trigonox 25C75 very two hours The reaction was maintained for 3 hours and then increased to 70°C. Two shots of Trigonox 25C75, the reaction was hold for another three hours. The solvent is filtered off using either a Buchner funnel with filter paper or a fritted funnel and house vacuum. Re-suspend solid in 150 ml dry cyclohexane and filtered. Repeat resuspension and filtration second time. Dry solid over either a Buchner funnel with filter paper or a fritted funnel using house vacuum for 1 hour. The dry solid was dried in 40°C oven using house vacuum for 3 hours. The residual VP%, GMA and VA% in the obtained product was less than 0.1%.

[00140] 50g of the above product was transferred into a 1-L kettle and dissolved into 200ml water and then added to 50g of Hydroxypropyl cellulose (HPC HF Pharma) with stirring and lg phosphoric acid was added. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan- forced oven at 85°C for 24 hrs. The solid mass was grinded into a powder by grinder to roughly ~ 500-1000 microns. The yield was 99%.

[00141] lOg of the above product was removed and further reacted with lg of 12- epoxy- stearic acid-methyl ester into 50g of T-butanol at 85°C for 16 hrs. Then the reaction was discharged and dried in a fan- forced oven. The yield was 99%.

[00142] Then 0.5g of this material dissolved in water and generated a homogenous milky dispersion that swelled into a hydrogel.

[00143] Example 11: (Vinyl Pyrrolidone/Glycidyl Methacrylate) (VP/GMA) (80/20) Grafted to Hydroxypropyl Cellulose (HPC HF pharma)

[00144] In a 1-L resin kettle equipped with an anchor agitator, thermocouple, gas inlet and reflux condenser, 680 g of Cyclohexane and 9.6g of N-(VP), were charged. The reaction mixture was purged with nitrogen for 30 min. With agitation and nitrogen purging, the reactor was heated to 65 °C, then two feeds of 96.4 g of N-(VP) and of 24g of Glycidyl Methacrylate were fed. N-vinyl pyrrolidone feed was fed over a period of four hours and Glycidyl Methacrylate feed was fed over five hours and 0.25g of Trigonox 25 C 75 was charged. After two hours of reaction, 0.25 g of Tirgonox 25 C 75 was charged into the reactor. The reaction was held for 2 hours, then 0.25 g of Trigonox 250 C75 was charged into the reactor. At time 6, 10 and 12 hours, charge 0.40g of Trigonox 25 C75 into the reactor respectively. After 14h, the reaction mixture was cooled to room temperature to discharge the product. GC analysis showed the residual N- vinyl pyrrolidone and Glycidyl Methacrylate was less than lOOOppm.

[00145] 50g of the above product was transferred into a 1-L kettle and dissolve into 200ml water and then added to 50g of Hydroxypropyl cellulose (HPC HF Pharma) with stirring and lg phosphoric acid was added. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan-forced oven at 85 °C for 24 hrs. The solid mass was grinded into a powder by grinder to roughly ~ 500-1000 microns. The yield was 99%

[00146] lOg of the above product was removed and further reacted with lg of 12-epoxy- stearic acid-methyl ester into 50g of T-butanol at 85°C for 16 hrs. Then the reaction was discharged and dried in a fan- forced oven. The yield was 99%.

[00147] Then 0.5g of this material dissolved in water and generated a homogenous milky dispersion that swelled into a hydrogel.

[00148] Example 12: (Vinyl Pyrrolidone/Glycidyl Methacrylate) (VP/GMA) (90/10) Grafted to Hydroxypropyl Cellulose (HPC HF pharma)

[00149] In a 1-L resin kettle equipped with an anchor agitator, thermocouple, gas inlet and reflux condenser, 680 g of Cyclohexane and 10.8g of N-(VP), were charged. The reaction mixture was purged with nitrogen for 30 min. With agitation and nitrogen purging, the reactor was heated to 65 °C, then two feeds of 97.4 g of N- (VP) and 12g of Glycidyl Methacrylate (GMA) were fed. N-(VP) feed was fed over a period of four hours and Glycidyl Methacrylate feed was fed over five hours and 0.25g of trigonox 25 C 75 was charged. After two hours of reaction, 0.25 g of Tirgonox 25 C 75 was charged into the reactor. The reaction was held for 2 hours, then 0.25 g of Trigonox 250 C75 was charged into the reactor. At time 6, 10 and 12 hours, charge 0.40g of Trigonox 25 C75 into the reactor respectively. After 14h, the reaction mixture was cooled to room temperature to discharge the product. GC analysis showed the residual N- Vinyl Pyrrolidone and Glycidyl Methacrylate was less than 3000ppm.

[00150] 50g of the above product was transferred into a 1-L kettle and dissolve into 200ml water and then added to 50g of Hydroxypropyl cellulose (HPC HF Pharma) with stirring and lg phosphoric acid was added. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan-forced oven at 85°C for 24 hrs. The solid mass was grinded into a powder by grinder to roughly ~ 500-1000 microns. The yield was 99%.

[00151] lOg of the above product was removed and further reacted with lg of 12- epoxy- stearic acid-methyl ester into 50g of T-butanol at 85°C for 16 hrs. Then the reaction was discharged and dried in a fan- forced oven. The yield was 99%.

[00152] Then 0.5g of this material dissolved in water and generated a homogenous milky dispersion that swelled into a hydrogel.

[00153] Example 13: (Vinyl Pyrrolidone/Glycidyl Methacrylate) (VP/GMA) (95/5) Grafted to Hydroxypropyl Cellulose (HPC HF pharma)

[00154] In a 1-L resin kettle equipped with an anchor agitator, thermocouple, gas inlet and reflux condenser, 680 g of Cyclohexane and 10.8g of N-(VP), were charged. The reaction mixture was purged with nitrogen for 30 min. With agitation and nitrogen purging, the reactor was heated to 65°C, then two feeds of 97.4 g of N- Vinyl Pyrrolidone (VP) and 12g of Glycidyl Methacrylate (GMA) were fed. N- Vinyl Pyrrolidone feed was fed over a period of four hours and Glycidyl Methacrylate feed was fed over five hours and 0.25g of Trigonox 25 C75 was charged. After two hours of reaction, 0.25 g of Tirgonox 25 C 75 was charged into the reactor. The reaction was held for 2 hours, then 0.25 g of Trigonox 250 C75 was charged into the reactor. At time 6, 10 and 12 hours, charge 0.40g of Trigonox 25 C75 into the reactor respectively. After 14 h, the reaction mixture was cooled to room temperature to discharge the product. GC analysis showed the residual N- Vinyl Pyrrolidone and Glycidyl Methacrylate was less than 3000ppm.

[00155] 50g of the above product was transferred into a 1-L kettle and dissolved into 200ml water and then added to 50g of Hydroxypropyl cellulose (HPC HF Pharma) with stirring and lg phosphoric acid was added. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan-forced oven at 85°C for 24 hrs. The solid mass was grinded into a powder by grinder to roughly ~ 500-1000 microns. The yield was 99%. [00156] lOg of the above product was removed and further reacted with lg of 12-epoxy- stearic acid-methyl ester into 50g of T-butanol at 85°C for 16 hrs. Then the reaction was discharged and dried in a fan- forced oven. The yield was 99%.

[00157] Then 0.5g of this material dissolved in water and generated a homogenous milky dispersion that swelled into a hydrogel.

[00158] Example 14: (Vinyl Pyrrolidone/Glycidyl Methacrylate) (VP/GMA) (98/2) Grafted to Hydroxypropyl Cellulose (HPC HF pharma)

[00159] In a 1-L resin kettle equipped with an anchor agitator, thermocouple, gas inlet and reflux condenser, 680 g of Cyclohexane and 11.76g of N-, were charged. The reaction mixture was purged with nitrogen for 30 min. With agitation and nitrogen purging, the reactor was heated to 65°C, then two feeds of 105.84 g of N- Vinyl Pyrrolidone (VP) and of 2.4g of Glycidyl Methacrylate (GMA) were fed. N- Vinyl Pyrrolidone feed was fed over a period of four hours and Glycidyl Methacrylate feed was fed over five hours and 0.25g of Trigonox 25 C75 was charged. After two hours of reaction, 0.25 g of Tirgonox 25 C 75 was charged into the reactor. The reaction was held for 2 hours, then 0.25 g of Trigonox 250 C75 was charged into the reactor. At time 6, 10 and 12 hours, charge 0.40g of Trigonox 25 C75 into the reactor respectively. After 14h, the reaction mixture was cooled to room temperature to discharge the product. GC analysis showed the residual N- Vinyl Pyrrolidone and Glycidyl Methacrylate was less than 3000ppm.

[00160] 50g of the above product was transferred into a 1-L kettle and dissolved into 200ml water and then added to 50g of Hydroxypropyl cellulose (HPC HF Pharma) with stirring and lg phosphoric acid was added. The reaction mixture was stirred for one hour at room temperature. Then the reaction was discharged and dried in a fan-forced oven at 85°C for 24 hrs. The solid mass was grinded into a powder by grinder to roughly ~ 500-1000 microns. The yield was 99%.

[00161] lOg of the above product was removed and further reacted with lg of 12- epoxy- stearic acid- methyl ester into 50g of t-butanol at 85 °C for 16 hrs. Then the reaction was discharged and dried in a fan- forced oven. The yield was 99%.

[00162] Then 0.5g of this material dissolved in water and generated a homogenous milky dispersion that swelled into a hydrogel. [00163] While this application has been described in detail with reference to certain preferred embodiments, it should be appreciated that the present application is not limited to those precise embodiments. Rather, in view of the present disclosure, which describes the current best mode for practicing the invention, many modifications and variations would present themselves to those skilled in the art without departing from the scope and spirit of this application.

Claims

What is claimed is:

1. A hybrid polymer comprises : i. a cellulose ether moiety; and ii. one or more polymer moiety; wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2- pyrrolidone moiety, and optionally (c) a vinyl acetate moiety, and wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety.

2. The hybrid polymer according to claim 1, wherein the cellulose ether moiety is selected from the group consisting of methyl cellulose (MC), hydroxyethyl cellulose (HEC), ethylcellulose (EC), propyl cellulose (PC), methylhydroxyethylcellulose (MHEC), ethyl hydroxyethyl cellulose (EHEC), methylethyl hydroxyethyl cellulose (MEHEC), hydroxypropyl hydroxyethyl cellulose (HPHEC), methyl hydroxypropyl hydroxyethyl cellulose (MHPHEC), hydroxypropyl cellulose (HPC), methyl hydroxypropyl cellulose (MHPC), and ethyl hydroxypropyl cellulose (EHPC), hydroxypropyl methyl cellulose (HPMC), ethylhydroxyethylcellulose (EHEC), carboxyalkylcelluloses, carboxyalkylhydroxyalkylcellulose, carboxymethyl cellulose, carboxymethylcellulose, and carboxypropylcellulose.

3. The hybrid polymer according to claim 1, wherein the polymer moiety is prepared by a process selected from the group consisting of solution polymerization, precipitation polymerization, emulsion polymerization and free-radical polymerization.

4. The hybrid polymer according to claim 1, wherein the polymer moiety is a block copolymer, alternating copolymer, random copolymer or graft copolymer.

5. The hybrid polymer according to claim 1, wherein the polymer has the structure:

wherein "a" is an integer ranging from 1 to about 20; n and m are percentages of the molar sum, the sum of which equals 100%; and x and y are percentages of the molar sum, the sum of which equals 100%.

6. The hybrid polymer according to claim 5, wherein "a" is in the range of from 1 to about 5; "n" and "m" independently is in the range of from about 1% to about 99%; "x" in the range of from about 99% to about 40%, and "y" is in the range of from 1% to about%.

The hybrid polymer according to claim 1, wherein the polymer moiety has the set out below: vinyl pyrrolidone/glycidyl methacrylate (98/2);

vinyl pyrrolidone/glycidyl methacrylate (80/20);

vinyl pyrrolidone/glycidyl methacrylate (90/10); and

vinyl pyrrolidone/glycidyl methacrylate (95/5).

The hybrid polymer according to claim 1, wherein the polyi

wherein "a" is an integer ranging from 1 to about 20; "n" and "m" are percentages of the molar sum, the sum of which equals 100%; and x, y, and z are percentages of the molar sum, the sum of which equals 100%.

9. The hybrid polymer according to claim 8, wherein "a" is in the range of from 1 to about 5; "n" and "m" independently is in the range of from about 1% to about 99%; "x" is in the range of from about 35% to about 60%; "y" is in the range of from 1% to about 7%, and "z" is in the range of from about 40% to about 60%.

10. The hybrid polymer according to claim 1, wherein the polymer moiety has the percentages set out below: vinyl pyrrolidone/vinyl acetate/glycidyl methacrylate (58/40/2); vinyl pyrrolidone/vinyl acetate/glycidyl methacrylate (40/55/5); vinyl pyrrolidone/vinyl acetate/glycidyl methacrylate (40/58/2); and vinyl pyrrolidone/vinyl acetate/glycidyl methacrylate (52/45/3).

11. A process for preparing a hybrid polymer comprises: I. (A) dissolving monomers comprising (a) a glycidyl methacrylate moiety; (b) a N-vinyl-2-pyrrolidone moiety; and optionally (c) a vinyl acetate moiety in an organic solvent,

(B) charging resultant of (A) in to a reaction container,

(C) preparing a feeding solution- 1 by mixing vinyl pyrrolidone and vinyl acetate and preparing feeding solution- 2 by mixing glycidyl methacrylate and organic solvent,

(D) preparing an initiator solution,

(E) charging feeding solution- 1 into resultant of (B),

(F) charging (D) into (E),

(G) charging feeding solution-2 in to (F),

(H) charging initiator in to (G), stirring the reaction mixture, cooling the reaction mixture, filtering the solvent, re-suspending solid in the solvent, filtering the solvent, and drying the obtained solid;

II. (A) dissolving specific amount of resultant of step (I) and at least one cellulose ether moiety in water, and mixing the reaction solution by adding an acid,

(B) grinding the dried product of (II) (A).

12. A composition comprising:

I. about 0.1 wt.% to about 25 wt. % of hybrid polymer comprising: (i) a cellulose ether moiety; and (ii) one or more polymer moieties, wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2- pyrrolidone moiety, and optionally (c) a vinyl acetate moiety; and wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety, and

II. about 75 wt. % to about 99.9 wt. % of one or more additive.

13. A composition according to claim 12, where in the additive is useful in an application selected from the group consisting of pharmaceutical, food and beverages, coatings, paints, printing & inks, electronics, lamination, lithography, decorated pigments, oil & energy, performance materials, adhesives, biomaterials, oral care, skin care, hair care, cosmetics, toiletry, household and cleaning products, industrial and institutional cleaning products, disinfecting products, opthalmics, injectables, sanitary products, agricultural products, textiles, biocides, preservatives, consumer products, membrane and laundry products.

14. A pharmaceutical composition comprising:

I. about 0.1 wt.% to about 25 wt. % of hybrid polymer comprising: (i) a cellulose ether moiety; and (ii) one or more polymer moieties, wherein the polymer moiety comprises (a) a glycidyl methacrylate moiety, (b) a N-vinyl-2- pyrrolidone moiety, and optionally (c) a vinyl acetate moiety; and wherein the polymer moiety is grafted to cellulose ether moiety via the glycidyl methacrylate moiety, and

II. about 75 wt. % to about 99.9 wt. % of one or more pharmaceutically acceptable additive.