Title of Invention	"BLOCKY HYDROXYETHYLCELLULOSE, DERIVATIVES THEREOF, PROCESS OF MAKING AND USES THEREOF"
Abstract	: This invention relates to non-uniformly substituted ("blocky") hydroxyethylcelluloses (HECs) and derivatives thereof that exhibit associative behavior in both neat solutions and In filled systems. The HECs and derivatives thereof exhibit unique and highly desirable rheology and are more efficient In thickening aqueous systems than prior art HEC products. These blocky HBCs can be distinguished from prior art and commercial HEC products by having an unsubitlruted anhydroglucose trimer ratio (U3R) greater than 0.21 and the hydroxcthyl molar substitution greater than about 1.3 and less than about S. This invention also relates to processes for making blocky HEC and uses thereof in functional systems.

Title of Invention

"BLOCKY HYDROXYETHYLCELLULOSE, DERIVATIVES THEREOF, PROCESS OF MAKING AND USES THEREOF"

Abstract

: This invention relates to non-uniformly substituted ("blocky") hydroxyethylcelluloses (HECs) and derivatives thereof that exhibit associative behavior in both neat solutions and In filled systems. The HECs and derivatives thereof exhibit unique and highly desirable rheology and are more efficient In thickening aqueous systems than prior art HEC products. These blocky HBCs can be distinguished from prior art and commercial HEC products by having an unsubitlruted anhydroglucose trimer ratio (U3R) greater than 0.21 and the hydroxcthyl molar substitution greater than about 1.3 and less than about S. This invention also relates to processes for making blocky HEC and uses thereof in functional systems.

Full Text	BLOCKY HYDROXYETHYLCELLULOSE, DERIVATIVES THEREOF, PROCESS OF MAKING, AND USES THEREOF [0001] This application claims the benefit of U.S. Provisional Application No. 60/653,864, filed February 17, 2006. FIELD OF INVENTION [0002] The present Invention relates to cellulose ether compositions, derivatives thereof, processes for making the composition and uses thereof in functional systems, More specifically, this Invention relates to non-uniformly substituted ("blocky) hydroxyethylcelluloses (HECs) and derivatives thereof. This invention also relates to processes for making blocky HEC and uses thereof in functional systems, BACKGROUND OF THE INVENTION [0003] Hydroxyethylcellulose (HEC) is a cellulose ether usually mada by reacting alkali cellulose with ethylene oxide (EO). In general, the molar ratio of EO to the anhydroglucose units of cellulose Is higher than 1.5 to provide adequate water-solubility to the cellulose backbone. HEC is a water-8oiubie/water-3wellable polymer that generally is used to viscosity aqueous madia of functional systems such as personal care and household products, paints, construction material products, paper coatings, oilfield media, emulsions, latex components, etc. Furthermore, high molecular weight HEC is used In the pharmaceutical industry as an exciplent to provide a swellable diffusion barrier In controlled release applications. [0004] In commercial HECs that are made by a single-stage ethoxylatlon of cellulose, the hydroxyethylene substltuents are nearly randomly distributed among the anhydroglucoae segments of the polymer. Examples of prior art that disclose the preparation of HEC are US Patents 2,572,039, 2,682,535, 2,744,694, and 3,131,177. Another commercial HEC product Is a more highly substituted HEC in which the ethylene oxide Is reacted In two-steps thereby reducing the amount of unsubstituted anhydroglucose units, This results In the formation of a cellulose derivative that Is less susceptible to enzymatic degradation, i.e, enhanced resistance to blodegradatlon. Examples of prior art that disclose the preparation of this type of HEC are US Patent 3,131,176, Canadian Patent 1014280, and US Patent Application US 2005/0139130 A1. The solution viscosities of HECs with these types of EO substitution patterns usually depend on the molecular weight of the cellulose backbone. [0005] Furthermore, HECs can be modified with additional substltuents to improve functionality. For example, US Patent No, 4,228,277 discloses the use of long chain alkyl modifiers having 10 to 24 carbon atoms, Another example of B modified HEC is disclosed In US Patent No, 4,826,970 that describes a carboxymethyi hydrophoblcally modified hydroxyethyl cellulose ether derivative (CMHMHEC) that Is used aa thickeners and protective colloids In water based protective coating compositions, US Patent No 4,904,772 discloses a water-soluble HEC derivative that has a mixed hydrophobe having two or more hydrophoblc radicals having 6 to 20 carbons whereby one of thd hydrophoblc radicals has a carbon chain length that Is at least two carbon atoms longer than that of the other hydrophoblc radical. US Patent 4,683,159 discloses a water-aoiuble, cationlc hydroxyethyl cellulose, [0006] Commercial HEC products are the thickeners of choice in many Industries because they provide the desired rheology and thickening efficiency. Notwithstanding, a need still exists for an HEC-based rheology modifier that would be more efficient In thickening aqueous systems and Interact more strongly with componanta In the system and/or with Itself so that additional desired Theological properties can be achieved. SUMMARY OF THE INVENTION [0007] The present Invention Is related to "blocky" HEC products that have unique thickening efficiency In neat solutions and functional systems. In other words, the HECe of the instant Invention show associative properties that are unknown In commercial HEC products. An advantage of this product Is that It provides a much higher solution viscosity than regular commercial HEC at simllar concentrations and molecular weight. Consequently, a lesser amount of the HEC of the present Invention can produce comparable or better viscosity relative to analogous commercial HECs of similar molecular weight. The HECs and HEC derivatives of the present Invention form solutions that have a high elasticity that la characteristic of a strongly associative polymer network as well as unique adsorption characteristics and Interaction with media components, The gelling properties and suspending.properties of the present Invention are better than similar HEC products of the prior art. [0008] The present Invention Is directed to HECe that have hydroxyethyl groups that are non-uniformiy distributed on the cellulose backbone, wherein the ratio of unsubstltuted anhydroglucoae trimers to the most frequently occurring substituted anhydroglucose trimers (U3R) Is greater than 0.21 and the hydroxyethyl molar substitution is greater than about 1.3 and less than about 5.0. [0009] The present Invention Is further directed to a slurry process for making the above mentioned HEC composition comprising A) mixing and reacting cellulose, water and a base reagent In an organic solvent for a sufficient time and at a sufficient temperature In order to form a first base reagent cellulose mixture, wherein the water to anhydroglucose (AGU) molar ratio Is In the range of about 5 to 35 and (a) the base reagent to AGU molar ratio Is greater than about 1.6 or (b) the base reagent to AGU molar ratio I's lass than about 0.4 B) (i) when (a) la used from Step A, then sufficient acid is added In order to reduce the base reagent concentration to a baae reagent to AGU molar ratio of no lesa than about 0,6 to form a second base reagent cellulose mixture, or (II) when (b) la used from Step A, then sufficient ethylene oxide Is added and reacted at a sufficient temperature and for a sufficient time to form a HEC product with a hydroxyethyl molar substitution of less than 1.3, followed by additional base reagent to adjust the base reagent to AGU molar ratio to greater than about 1.0 to form a baae reagent HEC mixture, and C) tnen adding to the second base reagent cellulose mixture from B(i) or to the base reagent HEC cellulose mixture from D(ll) a sufficient amount of ethyiene oxide and reacting at a sufficient temperature and for a sufficient time In order to form the final HEC composition. [00010] The HEC product prepared by the above mentioned process can optionally be further reacted with at least one other derlvatlzlng reagent to form a modified HEC product. [00011] Likewise, the HEC or modified HEC product, optionally, can further be reacted with a viscosity reducing agent, [00012] The present invention ls also related to a functional system composition Including the non-unlformly substituted HEC composition or derivatives thereof. BRIEF DESCRIPTION OF THE DRAWING [00013] Figure 1 shows a bar graph of the ethylene oxide distribution profile of a HEC polymer. DETAILED DESCRIPTION OF THE INVENTION [00014] it has been surprisingly found that a HEC or derivatives thereof having a non-unlformiy or blocky substitution pattern can produce unique rheology that has not been noted prior to this Invention. [00016] The present Invention Is directed to blocky HECs and modified HECs (nonlonlc, anlonic, and catlonlc) In which a large fraction of the anhydroglucose units (AGU) in the cellulose backbone are not substituted with ethylene oxide (EO). Upon degradation, these unsubstituted anhydroglucose units exist as monomers and oligomers. The characteristic that makes these blocky HECs unique is an unaubstltuted trlmer ratio (U3R) that Is greater than 0.21, preferably greater than 0.235, and e hydroxyethyl molar substitution that is greater than about 1,3 and less than about 5.0, This unique class of HECs shows associative behavior through hydrogen bonding and exhibits significantly higher solution viscosities as compared to other classes of HECs with similar hydroxyethyl molar substitution (HE MS) and cellulos'8 molecular weight. Furthermore, this non-unlformly substituted HEC provides a unique template for reacting hydrophobes that are concentrated In the EO-rlch regions in a non-uniform manner to achieve novel rheologlcai properties, Post addition of nonionlc or Ionic substituents may be necessary to Improve water-solubility or functionality, [00016] In accordance with the present invention, the blocky HEC composition can be further modified with one or more nonionlc, anlonlc, and catlonlc substituents or mixtures thereof, The substituents are attached to the HEC backbone via an ether, ester, or urethane linkage. When the aubstituents have nonionic chemical functionality, the substituents have the formula; -R, or --A-R, wherein A ls CH2-CH(OH)1 CH2-CH(OH)-CH2, (CH2-CH2-O)n- where n " 1-100, CH2-CH(OH)-CH2-0-(CH2-CH2-0)n where n = 1-100, CH(R)-C(0)-CH2l and R Is selected from one of the following groups: i) an acyclic or cyclic, saturated or unsatureted, branched or linear hydrocarbon moiety having 1 to 30 carbon atoms, ii) an acyclic or cyclic, saturated or unsaturated, branched or linear heterohydrocarbon moiety having 1 to 30 carbon atoms and one of more oxygen, nitrogen, orsliicone atoms, III) an acyclic or cyclic, saturated or unsaturated, branched or linear hydrocarbon moiety having 1 to 30 carbon atoms and one or more aromatic hydrocarbon groupsi iv) an acyclic or cyclic, saturated or unsaturated, branched or linear heterohydrocarbon moiety having 1 to 30 carbon atoms and one or more oxygen, nitrogen, or sliicone atoms and one or more aromatic groups, and \t) an acyclic or cyclic, saturated or unsaturated, branched or linear, heterohydrocarbon moiety having 1 to 30.carbon atoms and one or more oxygen, nitrogen, or silicons atoms and one or more heteroaromatlc groups containing one or more oxygen, nitrogen, or sliicone groups, [00017] Based on the formula R above, the subatltuents may be selected from alkyi, aikenyl, alkynyl, aryl, alkyl aryl, aryl alkyl, alkenyl aryl, aryl alkenyi, or mixtures thereof having, when possible, from 1 to 3'0 carbon atoms, [00018] When the substltuents have anlonic chemical functionality, the anlonlc chemical functionality can be carboxylate, sulfate, sulfonate, phosphate, phospnonate or mixtures thereof, More specific examples of this functionality are carboxyrnathyi, eulfoethyl, phosphonomethyl, and mixtures thereof, [0001BJ When the subatltuents have catlonlc chemical functionality, the substituents have the formula R1R2R3R4N+ (A"), where R1 ls [00020] -CH2-CHOH-CH2- or-CH2-CH2-, and R2, R3, R4 are each independently selected from an alkyl or aryl alkyl group having 1 to 20 carbon atoms, and A' is a hallde, sulfate, phosphate, or tetrafluoroborate Ion. [00021] More specifically, the cationlc subatltuents can be selected from 2-hydroxpropyltrlmethylammonlum chloride, 2-hydroxypropyldodecyldlmethylammonIum chloride, 2-hydroxypropylcocoalkyldimethylammonium chloride, 2-hydroxypropyioctadecyldlmethylammonium chloride and mixtures thereof. [00022] Another Important catlonlc group that catfbe used In this invention Is the group derived from the grafting reaction of dlallyldlmethylammonium chloride with HEC or its derivatives, [00023] in accordance with the present Invention, more specific modified hydroxyethyiceiluiose examples are methyl hydroxyethylcelluloae, ethyl nyoroxyethyicaliulose, octy! hydroxyethylcellulose, cetyl hydroxyethylcellullose, cetoxy-2-hydraxypropyl hydroxyethylcelluloae, butoxy-2-hydroxypropyl hydroxyethyicalluloae, butoxy-2-hydroxypropyl cetyl hydroxyethylcellulose, butoxy-2-hydroxypropyl cetoxy-2-hydroxyethylcellulose, carboxymethyi hydroxyethylcellulose, carboxymethyi ethyl hydroxyethylcellulose, carboxymethyi octyl hydroxyethylcelluloae, carboxymethyi cetyl hydroxyethylcellulose, carboxymethyi cetoxy-2-hydroxypropylcellulose, carboxymethyi butoxy-2-hydroxyethylcellulose, aulfoethyl hydroxyethylcelluloae, aulfoethyl ethyl hydroxyethylcellulose, aulfoethyl cetyl hydroxyethylcellulose, aulfoethyl cetoxy-2-hydroxypropylcelluloae, 2- hydroxypropyltrlmethylammonium chloride hydroxyethyicelluloae, 2-hydroxypropyltrlm'ethylammonlum chloride ethyl hydroxyethylcellulose, 2-hydroxypropyltrlmethylammonlum chloride butoxy-2-hydroxypropyl hydroxyethylcelluloae, 2-hydroxypropyltrlmethylammonlum chloride octyl hydrdxyethylcelluloae, 2-hydroxypropyltrlmethylammonlum chloride caty! hydroxyethylcelluloae, 2-hydroxypropyltrlmethylammonlum chloride cetoxy-2-hydroxypropyl hydroxyethylcellulose, 2-hydroxypropyllauryldlmethylammonlum chloride hydroxyethylcellulose, 2- hydroxypropyltrlmethyiammonlum chloride 2-hydroxypropyllauryldlmethylammonlum chloride hydroxyethylcelluloae, diallyldlmethyiammonlum chloride grafted hydroxyethylcelluloae, and dlallyldimethylammonlum chloride grafted cetyi hydroxyethylcelluloae. [00024] in accordance with the preaent Invention, the preferred process for making a non-unlformly substituted HEC product requires a two-step alkalization of the cellulose, while only a single-stage hydroxyethylatlon Is necessary. This differs from the two-step hydroxyethylatlon that has been described In prior art to Improve the enzyme reaistance of HECs. The initial alkalization atep is performed at an alkali to AGU molar ratio higher than 1.6 and at a water to AGU molar ratio In the range of about 5 to 35. Next, the alkali cellulose Is neutralized with an acid to an alkali to AGU molar ratio greater than 0.6, preferably between 1,2 and 1,0. The alkali neutralization step may be done as a single addition, multiple additions, or a continuous addition of the neutralizing aid, with or without the presence of ethylene oxide. Upon completion of the hydroxyethylatlon, the product can be viscosity reduced, purified, dried, and ground as known to those skilled In the art, [00025] Also, in accordance with the present Invention, non-unlformly substituted HEC can be produced using a "reverse" two-step alkallzatlan process as herein described. In this case, the cellulose Is partly alkalized at a caustic to AGU molar ratio that la Insufficient to open up the cellulose fibers. Typical alkali to AGU molar ratios are between 0,2 and 0.4 and water to AGU molar ratios are In the range of about 5 to 35. The cellulose is first hydroxyethylated to less than 1 3 at this stage before more alkali Is added in the second stage to reach alkali to AGU molar ratios between 1.0 to 2,0, preferably between 1.0 and 1.4. After sufficient time, the intermediate HEC Is further hydroxyethylated to achieve the final HE MS [00028] In the slurry process of the present Invention, organic solvent used In this process is selected from ethanol', Isopropanol, tert-butanol, acetone, methyl ethyl ketone, dlmethoxyethane, and mixtures thereof. This slurry process uses alkalis that aro selected from lithium hydroxide, sodium hydroxide, potassium nydroxlde, and mixtures thereof. The raw cellulose starting material used In the process for making the.blocky HECs can be cotton (inters, wood pulps or mixtures thereof. [00027] The blocky HEC compositions mentioned above can be optionally further reacted with at least another derivatizlng reagent to form a modified hydroxyethylcellulose composition. The d,erlvatlzlng reagent used to make this modified hydroxyethylceiluiose composition can be nonlonlc, catlonic, or anlonic organic compounds or mixtures thereof. These organic compounds capable of reacting with the hydroxyls groups of the HEC can be halldea, epoxldes, glycldyl ethers, carboxyllc aclda, Isocyanates, or mixtures thereof. [00028] The biocky HEC or derivatives thereof made by the slurry processes mentioned above can be further reacted with a viscosity reducing agent, such as paroxide, persulfate, peracid, salt of hallde oxo acids, oxygen, or ozone, This enables a person using this process to modify the final product to the desired viscosity or other properties for the desired end use. [00029] The process and process conditions determine how the EO is distributed along the cellulose backbone. Products of the Invention are characterized and can be differentiated from HECs made by prior art by reducing the polymer down to monomers and oilgomers and measuring the degree of unsubstltuted oligomers, more specifically unsubstituted trimers . A novel parameter called the unsubstltuted trimer ratio (U3R) can be defined as the ratio of the molar fraction of unaubstltuted trimers to the molar fraction of the most abundant class of (hydroxyethyl-substltuted) trlmers, with 0 £ U3R £ 1 .0, U3R Is measured by a mass spectrometric technique that is described below. The U3R of the HECs of present Invention are equal to or more than about 0.21, preferably greater than 0,235, [00030] Trlmers, oligomers with a degree of polymerization (DP) of 3 anhydrogtucose units, and other compounds of structure 1 are made by partial methanolysls of permethylated HEC derivatives. It Is assumed that the cleavage of the permethylated H EC-backbone is a random process and that the formed oligomars of structure 1 have an EO-dlstrlbutlon that la representative for the EO-dlstrlbutlon of the whole sample. (Formula Removed) [00031] in general, permethylated derivatives of HEC polymers can be prepared by the methylatlon reaction that Is applied In the methytatlon analysis procedure for polysaccharldas. (See publications of F.-G. Hanlach, Biological Mass Spectrometry, 23 (1994) 309-312; B. Llndberg, U, Llndqulst and O. Stenberg, Carbohydrate Research, 170 (1987) 207-214; and P.W. Arisz, J.A. Lomax, and j.j. Boon, Carbohydrate Research, 243 (1993) 99-114.) UNSUBSTJTUTED TRIMER RATIO (U3R) DETERMINATION [00032] More specifically, In the present Invention, the Investigated HEC polymers are dissolved or swollen in dimethyl aulphoxlde (DMSO). The hydroxyl groups In the polymer ere deprotonated using a lithium methyisulphlnyi carbenlon solution In DMSO and they are converted to methoxyl groups by the reaction with methyl iodide. [00033] The obtained permethylated HEC polymer Is purified. More specifically, the permethylated HEC polyrrier la extracted In three extraction steps with chloroform from an aqueous DMSO layer that Is acidified to pH 100034] The permethylated polymer Is partially degraded by methanolyeia, More specifically, the permethylated polymer Is dissolved / swollen In methanol, Sufficient hydrochloric acid in methanol la added to get a hydrochloric acid concentration of about 0.50 molar. The sample Is dissolved completely at 50°C for 15 minutes. Partial methanolysls Is done at 70"C for 2.5 hours. The reaction Is quenched by the addition of 2-methyl-2:propanol and all solvents are evaporated, yielding a residue that Is composed of a mixture of ollgomers of structure 1. [00038] The residue Is dissolved In methanol and a fraction of this sample Is mixed with 2,5-dlhydroxybenzolc add solution that Is spiked with sodium Iodide. Mass spectra of the ollgomer mixture are recorded with a Bruker Reflex II MAuDl-TOF-MS (matrix assisted laser desorptlon lonlzatlon - time of flight -mass spectrometer), which Instrument la equipped with a mlcrochannel plate detector. The compounds 1 are measured as their sodium Ion adducts. The mass numbers of the monoisotopic mass peaks of the trlmers arem/z2607.32, 711,34, 755.35, 799,38, etc. It Is assumed that all trlmers are measured with equal probability, Independent of their molar HE-substltutlon, chain length of the substltuents and their positions In the anhydroglucose residues. [00036] Trlmer fractions are derived by two data processing steps from the measured peak intensities of their monoisotopic maaa peaks. First the background signal of the MALDi spectrum is subtracted from the measured peak intensities Secondly, mainly due to 13C-laotopes that are Incorporated In structure 1 the monoisotopic mass peaks make up only 70.6, 68.9, 87.2, 65,6%, etc of all isotopes of trlmera having 0,1,2, 3, etc attached EO-unlts, respectively, Unfortunately, the^peak Intensities of 13C-lsotopes can not be measured accurately by MALDI-TOF-MS because of the recovery time that Is needed for the mlcrochannel plate detector after an Intense mass peak has been recorded. In order to compensate the signal for the missing contribution of 13C-isotope peaks, the background corrected monoisotopic mass peak Intensities are multiplied by a correction factor that lscalculated from the theoretical isotope composition of the trimers. This factor Increases with Increasing number of C atoms in 1, and values have been used of 1.417,1.452, 1.488, 1,525, etc for turners having 0, 1, 2, 3, etc attached EO-unlts, respectively, [00037] Figure 1 shows an example of the EO-dlstrlbutlon profile of trimers that are derived from a HEC polymer. The fraction qf unsubstltuted trlmers Is Indicated In gray. The moat abundant class of trlmers In this example Is that of trlmers with 7 attached EO-unlts. This class Is Indicated In white. The unaubstituted trlmer ratio, I.e. the gray fraction divided by the white fraction, Is calculated to be 0,121 for this example. It should be noted that the number of EO-units in the most abundant class of trlmers varies, depending on factors as the molar substitution of the HEC and the process type by which the HEC was made, for example [00038] HEC derivatives that contain secondary aubstltuents such as nonlonlc, cationic and anlonlc substltuents and mixtures thereof are analyzed similarly as non-modified HECa. in the case of modification levels smaller than 3.5 sub8t(tuent6 per 100 monomer units, such as associative hydrophoblc reagents for example, less than 10% of the trimera are modified and consequently the fraction of modified trimers can be neglected. [00039] The fraction of unmodified trlmers decreases with Increasing degree of substitution (DS) of the modifying agent. If the secondary substltuent distribution is at random along the cellulose backbone, than only half of the trimers would remain unmodified at a DS level of 0.21, The carboxymethyl (CM)-modlfied HMHECs listed in Tables 2a, 3a and 4a ail have CM-DS values In this order of magnitude and It ls concluded for these samples that the fraction of CM-modified trimerB cannot be neglected, [00040] Furthermore, CM-groups that are attached to the HEC-backbone are converted Into their methylesters by the derlvatlzatlon procedure. The sodium ion adduct of dlmers with two attached Eo-units and two attached CM-groups has m/z 667,28. The mass resolution of MALDI-TOF-MS Is Insufficient to separate this mass peak from rn/z 667.32, I.e. the mass peak of unsubstltuted trimers, so that an accurate U3R-value for carboxymethylated HEC-derivatives Is not applicable (N/A). APPLICATIONS: [00041] Many of these HEC samples exhibit novel and highly desirable rheology and performance properties In end use systems. [00042] in accordance with the present Invention, the viscosity builds up not only by means conventional to HEC, but also is boosted significantly by molecular association. The association leads to network formation and gel-like Theological properties In water and aqueous based functional systems that are shear reversible. The HECa and derivatives of the present Invention have been shown to lower the HEC use-level needed and to provide unique Theological attributes as compared to commercial HECs available today, [00043] Furthermore, these HECs and derivatives thereof may be used In applications where there Is a need for a specific rheology characteristic, e.g., viscosity., thlxotropy, yield stress, elasticity, or solid state characteristics such as thermoplastlclty and film flexibility. Examples of functional systems Includes aqueous based coatings (e.g., latex paints), building and construction materials (e.g., cements, plasters), personal care products (e.g., skin care, hair care, oral care, nail care, and personal hygiene products), household care products (e.g., Industrial cleaning liquids, pet care products), Pharmaceuticals (e.g., exclpients for tablets capsules, and granules), oilfield applications (e.g., drilling fluids, completion fluids, and fracturing fluids), civil engineering, printing Inks, adhesives, paper coating formulations, and retention and drainage aids in paper making. [00044] In accordance with the present Invention, the functional system can either be prepared In a continuous or batch process and either In a stepwlse addition of the Ingredients or a simple mixing of all of the Ingredients at once. The order of addition of the Ingredients can also vary over a wide range of additions. For example, the functional Ingredients can be Individually added one at a time to the formulation or all at once or the blocky HEC products can be added directly to the formulated Ingredients in a single step. Hence, the process of thickening an aqueous based functional system (e.g., personal care products, household care products, oil field servicing, fluids, civil engineering servicing fluids, paper coating products, paper making compositions, building and construction fluids, mineral processing products, and water based protective coatings such as architectural and Industrial coatings), Includes adding and mixing a sufficient amount of the blocky HEC polymer of the present Invention that Is compatible with the aqueous baaed functional system to thicken the functional system. The resulting functional system has comparable or better rheology and viscosity properties as compared to when using similar thickening agents Including commercial HECs. PERSONAL CARE [00045] in accordance with the present Invention, when the composition Is a personal care composition, It Includes (a) from about 0.1 % to about 99,0 % by weight of the vehicle component and (b) at lead one active personal care ingredient. [00046] In accordance with the present invention, the personal care active Ingredient must provide some benefit to the user's body. Personal care products include hair care, skin care, oral care, nail care, and personal hygiene products. Examples of substances that may suitably be Included In the personal care products according to the present Invention are as follows: 1) Perfumes, which give rise to an olfactory response in the form of a fragrance and deodorant perfumes which In addition to providing a fragrance response can also reduce body malodor; 2) Skin coolants, such as menthol, methyl acetate, methyl pyrrolidone carboxylate N-ethyl-p-menthane-3-carboxamlde and other derivatives of menthol, which give rise to a tactile response In the form of a cooling sensation on the skin; 3) Emollients, such as Isopropyl myristate, sllicone oils, mineral oils and vegetable oils which give rise to a tactile response In the form of an Increase In skin lubricity; 4) Deodorants other than perfumes, whose function Is to reduce the level of or eliminate micro flora at the skin surface, especially those responsible for the development of body malodor. Precursors of deodorants other than perfume can also be used; 5) Antipersplrflnt actives, whose function Is to reduce or eliminate the appearance of perspiration at the skin surface; 6} Moisturizing agents that keep the skin moist by either adding moisture or praventlng moisture from evaporating from the skin; 7} Cleansing agents that remove dirt and oil from the skin; 8) Sunscreen active Ingredients that protect the skin and hair from UV and other harmful light rays from the sun. In accordance with this Invention a therapeutlcally effective amount will normally be from 0.01 to 10% by weight, preferably 0.1 to 5% by weight of the composition; 9) Hair treatment agents that condition the hair, cleans the hair, detangles hair, act as styling agents, volumlzlng and gloss agents, anti-dandruff agent, hair growth promoters, hair dyes and pigments, hair perfumes, hair relaxer, hair bleaching agent, hair moisturizer, hair oil treatment agent, and antl-frlzzlng agent; 10) Shaving products, such as creams, gels and lotions and razor blade lubricating strips; 11) Tissue paper products, such ae moisturizing or cleansing tissues; 12) Beauty aids, such as foundation powders, lipsticks, and eye care; and 13) Textile products, such as moisturizing or cleansing wipes, [00047] in personal care compositions, the rheology modifiers of the present invention can be used either alone or may also be used in combination with other known Theology modifiers Including, but not limited to, polysaccharldes (e.g., carrageenan, pectin, aiglnate), cellulose ethers, blopolymers (e.g., xanthan gum), synthetic polymers, and abrasive/thickening silicas, HOUSEHOLD CARE [00048] In accordance with the present Invention, when the composition is a household care composition, It Includss (a) from about 0.1 % to about 99,0 % by weight of the vehicle component and (b) at least one active household care Ingredient [00048] In accordance with the present Invention, the household care active Ingredient must provide some benefit to the user, Hou3ehold care products include fabric care, laundry detergent, hard surface cleaner, Industrial institutional liquid soaps, and dish detergents. Examples of active Ingredients or substances that may suitably be Included according to the present Invention are as follows: I) Perfumes, that give rise to an olfactory response In the form of a fragrance and deodorant perfumes that In addition to providing a fragrance response can also reduce odor; 2} Insect repellent agent whose function Is to keep Insects from a particular area or attacking skin; 3) Bubble generating agent, such as surfactants which generates foam or lather; 4) Pet deodorizer such as pyrethrlns that reduce pet odor; 5) Pet shampoo agents and actives, whose function Is to remove dirt, foreign material and germs from the 3kln and hair surfaces; 6) industrial grade bar, shower gel, and liquid soap actives that remove germs, dirt, grease and oil from skin, sanftlze skin, and condition the skin; 7) All purpose cleaning agents that remove dirt, oil, grease, and gorms from the surfaces in areas such as kitchens, bathroom, and public facilities; 8) Disinfecting Ingredients that kill or prevent growth of germs In a house or public facility; 9) Rug and Upholstery cleaning actives that lift, and remove dirt and foreign particles from the surfaces and also deliver softening and perfumes; 10) Laundry softener actives that reduce static and makes fabric feel softer;, I1) Laundry detergent ingredients that remove dirt, oil, grease, and stains and kill germs; 12) Dishwashing detergents that remove stains, food, germs; 13) Toilet bowl cleaning agents that remove stains, kill germs, and deodorize; 14) Laundry prespotter actives that help In removing atalns from clothes; 15) Fabric sizing agents that enhance appearance of the fabric; 16) Vehicle cleaning actives that remove dirt, grease, etc, from vehicles and equipment; 17) Lubricating agents that reduce friction between parts; and 18) Textile products, such aa dusting or disinfecting wipes, [00060] In household care compositions, the rheology modifiers of the present Invention can be used'either alone or may also be used In combination with other known rheology modifiers Including, but not limited to, polysaccharides (e.g., carregeenan, pectin, alglnate), cellulose ethers, blopoiymers (e.g., xanthan gum), synthetic polymers, and abrasive/thickening silicas. [00061] The above are only limited examples of personal care and household active ingredients and are not a complete list of active Ingredients that can be used. Other ingredients that are used in these types of products are well known in the industry. In addition to the above Ingredients conventionally used, the composition, according to the present Invention can optionally also include ingredients such as colorants, preservatives, antloxldants, nutritional supplements, activity enhancers, emuleiflers, viacosifying agents (such as salts, e.g., sodium chloride, ammonium chloride and potassium chloride), water-soluble polymers (e.g., HEC, modified HEC, carboxymethylcellulose), and fatty alcohols (e.g., cetyl alcohol), alcohols having 1-6 carbons, and fats and oils, PROTECTIVE COATINGS [00062] Water-based protective coating compositions (commonly referred to aa paints) in which cellulose ether derivatives are commonly used Include latex paints or dispersion paints, of which the principal Ingredient Is the film-forming binders that Include latlces such as styrene-butadiene copolymers, vinyl acetate hornopolymers and copolymers, and acrylic homopolymers and copolymers. Other binders that are typically used in paints Include alkyd resins, and epoxy resins. Typically, paints also contain opaclfylng pigments, dispersing agents and water-soluble protective colloids, the proportions being, by weight of the total composition, about 10 parts to about 50 parts of a latex, about 10 parts to about agent, and about .0.1 part to about 2 parta of a water-soluble protective colloid. These protective coatings can be either aqueous baaed architectural or Industrial coating compositions. Architectural coatings are Intended for on-slte application to interior or exterior surfaces of residential, commercial, Institutional or Industrial buildings, industrial coatings are applied to factory-made articles before or after fabrication, usually with the aid of epeclal techniques for application and drying. [00063] Water-soluble polymers conventionally used in the manufacture of latex paints include casein, methyl cellulose, hydroxyethylcellulose (HEC), sodium carboxymethyl cellulose (CMC), polyvinyl alcohol, starch, and sodium polyacrylate. The HECs of the present Invention can be used as rheology modifiers for water-based protective coating compositions. PAPER COATINGS AND PAPER MAKING [00064] Paper coating Is a process In which the surface structure of paper or board Is Improved by applying a mineral coating that Is subsequently dried. Coating process IS the application of a water-borne pigment slurry, which b bound at the surface by one of several binders. Other coating components can be added to obtain a suitable rheology, and to Impart properties such as brightness or water resistance. [00066] A coating process can generally b© divided into three different phases: (1) preparation of the coating formulation (known as called coating color), (2) coating and (3) drying. The genera! principles of formulating paper coating are mostly well known. Moreover, each paper maker has his own tailor-made recipes for his specific requirements, Therefore, it would not be possible to give a "recipe" for a specific coating process, coating type or printing process. However, a generic coating formulation recipe contains 75 - 90 % pigment (such as clay, satin white, calcium carbonate, titanium dioxide, talc, aluminum hydroxide, calcium sulfate, barium sulfate, synthetics, etc.), 0.10 - 0.50 % dlspersant, 0,05 - 0.30 % alkali, 5 - 20 % binders (such as styrene-butadlene latlcea, acrylics, polyylnyl acetate, starch and atarch derivatives, proteins such as compounds, However, without the clay, joint compounds have poor sag resistance and less body. Examples 2 and 20 were tested at 0.5 wt % as the sale rheoiogy modifier In the clay-free Joint compound system with reduced mica levels as shown, These were compared with Natrosol 260 HHXR product. Table 10 shows the joint compound containing the Natroaol 250 HHXR product had poor sag resistance, open time, and workability, confirming the need for a structure builder like clay. On the other hand, Examples 2 and 20 produced axcellent joint compounds with properties that are typically obtained with thickener and & fullcomplement of attapulglte clay. Typical All-Purpose Joint Compound Formulation with and without Clay Tsable 10; All-Purpote Clay-free Joint Compound Properties (Table Remvoed) Example 30 Paper [000101] Blocky NEC Is a highly efficient water retention agent In paper coatings, Blocky HEC Example 3, commercial samples Aqualon 7L1T CMC, and Natrosol 25OGR were evaluated as thickeners and water retention aids in the paper coating formulation as shown below. The amount of rheology modifier necessary to maintain the BrooKfleld viscosity at 1500 +/-50 cps, the water loss, and Hercules high f hear viscosity are shown In Table 11. BlocKy HEC Example 3 and HEC 250GR are of similar molecular weights and solution viscosities; however, the blocky product has e significantly higher dosage efficiency than HEC 250GR while maintaining Its low water loss rate. In addition, blocky HEC Example 3 has much lower water loss and higher dosage efficiency than Aqualon 7L1T CMC yet similar desirable high shear rrteology, Paper coating formulation (Table Removed) 'Ground Oalalum Carbonate (HydroO«rt) frcm OMYA Ino. Table 11; Paper Coating Properties (Table Removed) Example 31 Pergonai Care [000102] Blocky HEC shows enhanced viscosity In personal care formulations, Natrosol® hydroxytthyl cellulose type 250HHR and blocky HEC Example 2 were compared at 0 J wt% for thickening efficiency in the hair conditioner formulation shown below. Hair Conditioner 90.94g Deionized water 00,70g Thickening polymer (Natrbsol® 250HHR, blocky HEC example 2) 02.00g Cetyl alcohol oo.5Qg Potassium Chloride 02.00g Isopropyl Myrlatate As required - citric add to adjust pH As required - Sodium hydroxide to adjust pH OO.5Og Germaben II Procedure: [000103] The thickening polymer was added to water under agitation. Next, the pH was adjusted to 8.0 to 8.5. The slurry was stirred for at least 30 minutes or until the polymer dissolved, the solution was heated to about 65oC and cetyl alcohol was added and mixed until homogeneous. The mixture was cooled to about 50°C and potassium chloride was added. Isopropyl myrlstate was added and mixed until the mixture looked homogeneous. The pH of the mixture was adjusted to 5.3 - 5,5 with citric add and/or NaOH solution. The conditioner was preserved with 0.5 g Germaben II and mixed until the mixture reached room temperature, [000104] The viscosity of the conditioning formulation containing blocky HEC Example 2 was 1,550 cP, as compared to the control containing Natrosol® 250HHR at 910 cPs, a 70% improvement In thickening effldency. [000106] Hydrophoblcally modified blocky HECs show enhanced viscosity stability In o\|[-ln-water emulsions. They were evaluated as a polymeric emulsifier / stabilizer in a typical emulsion formulation shown. Examples 20 and 21 were compared against commercial polymeric emulslfiera (Natrosol Plus 330,331, and PolySurf 67). In addition, PemulenTR-1, Pemulen TR-2 and Carboppl ETD 2020 products, commonly used hydrophoblcady modified acrylate cross-polymers, were included in the comparison. Table 12 and 13 show the viscosity data for one-month storage at room temperature and 40° 0, respectively. Examples 20 and 21 have dramatically Improved emulsifying and stabilizing properties over the commercial hydrophobically modified HECs. Furthermore, the emulsifying/stabilizing effldency Is near that of Pemulen TR-1, Pemulen TR- 2, and Garbopol ETD 2020, which are extremely efficient emulsifying/stabilizing polymers In the market. The thickening efficiency Is even better than that of Pemulen TR-2, (Table Removed) Composition of Barto Emulalon Formulation Procedure: - Prepare •took solution of polymeric emulslfler/stablllzer - Add mineral oil to the aqueous phtee and Germaben II - Mix the formulation with Braun ratohen mixer for 3 minutes at speed 5, - (All emuliioni prepared had a pH 5-7) Table 12: Viscosity stability of olMn-water emulsions upon 4 weeks storage at room temperature(Table Removed) Table 13: Viscosity stability of oll-ln-water emulsions upon 4 weeks storage at 40°C (Table Removed)[000106] Examples 20 and 21 were evaluated in the surfactant formulation shown to investigate compatibility In general personal care and household applications. Example 20 and 21 were compared against commercial rheology modifiers Natrosol Plus 330, and PolySurf 67 products. In addition, Carbopol ETD 2020 product was Included In the comparison. Table 14 shows that the hydrophoblcally modified blocky HEC Examples 20 and 21 are very efficient cellulosic thickeners. Example 21 resulted In clear solutions unlike any of the others tested. composition of basic surfactant formulation (Table Removed) - Dissolve thickener In damlnerallzed water. - Add Texapon 28 to thickener solution and mix homogeneoualy. - Add Plantaoare 2000 Up to tnlckener solution and mix homogeneously. • - Add Tegobetalne L7 to thickener solution and mix homogeneously, - Adjust pH wfth ottrto add to 5.5 - 6,5. - Add Qemwben II, Table 14: Viscosity and appearance of surfactant formulation with thickener (Table Removed) [000107] Examples 20 and 21 ware evaluated as a gelling agent In an aqueous solution for hair styling gels. In addition, Carbopol Ultrez 10 (carbomer) and Carbopol ETD 2020 (C10-C3C modified aery I ate), Natrcsol 250 HHR, Natroeol 250 HR and Klucel H, commonly used gelling agents were Included In the comparison, [000108] The thickening efficiency and suspending power of Examples 20 and 21 was better than that of commercial HECa and HPC. Furthermore, example 21 showed a carbopol Hke texture (stiff and elastic gel), while the others were considered as flowable gels. The electrolyte tolerance of examples 20 and 21 was better compared to Carbopol Ultrez 10 and Carbopol ETD 2020. Example 32 Completion/Workoverflulds[000109) The HEC of the Invention exhibits novel thickening of heavy brines. Completion fluids are composed of a variety of brines of different salinity characterized by a density ranging from 8.5 ppg (pound per gallon) for seawater up to 19.2 ppg for heavy brines containing zinc and calcium bromide salts. Standard high viscosity MEG Is commonly used as a vlscoslflerfor brines ranging from 6-13 ppg. There presently Is not an efficient vrscosifier for heavy brines with a density ranging from 14 ppg (CaBr2) to 19,2 ppg (ZnBr2/CaBr2). These brines have a very low level of free water content available, and therefore, do not promote optimum hydratlon of standard HECs. These brines are characterized by a very low pH (pH [000110] Blocky HEC Example 2 was evaluated in 4 different brine systems (freshwater, salt-saturated water, CaBr2 and 2nBr2/CaBr2) at 0.57 wt %. These were compared to a standard HEC widely used In completion fluids (Natrosol MI-VIS). The viscosity and fluid loss properties were measured after static aging overnight at room temperature (Tables 15a-d). [000111] Blocky HEC Example 2 showed exceptional thickening In the high density, heavy brine solutions (characterized by low water activity) as detailed by the high apparent viscosities (Y.V.) and yield values (Yv) that developed in these systems (Tables 15 c-d). In contrast, commercial HI-VIS did not go Into solution In these low water activity systems. Additionally, the blocky HEC sample developed appreciable low-end rheology as reflected by the 6 and 3- rpm Fann dial readings (DR), and showed appropriate fluid loss (F.L.) values. (Table Removed) Example 33 Pharmaceuticals [000112] Blocky HEC excipients provide superior tablet hardness. HEC is used In the pharmaceutical industry as an exciplentto provide a ewellable diffusion barrier in controlled release applications. The gel matrix It forms limits the diffusion of aqueous fluids Into a system and dissolved actives out of the system. Currently, HEC produced by Aqualon (Natrosol® 250 series of pharmaceutical grade polymers) holds the majority share of HEC used in the pharmaceutical Industry. [000113] HEC has some unique modified release properties not duplicated by hydroxypropyimethyl cellulose (HPMC) and hydroxypropyl cellulose (HPC). However, current knowledge Is that current commercial grades of HEC show significantly inferior compression properties when compared to HPMC and HPC, The poor compactlblllty of this polymer generally makes the polymer suitable for only wet granulation processing, rather than direct compression processing which is frequently the Industry preference. [000114] In order to improve this limitation, scientists at Astra Zeneca in International Patent Application, WO 02/18990 A1 describe a procedure whereby HEC Is purified by dissolution in water before precipitation via addition of organic solvent. The precipitate Is washed end then milled In a specific manner. The purified HEC has markedly Improved tablet compactiblllty. [000115] in accordance with the present Invention ia the use of blocky HEC material that Is highly compressible for making direct compressible tablets for use in compaction applications such as sustained release tablets for pharmaceutical, household, and agricultural applications. [000116] Table 16 shows the strength of pure polymer tablets (with 1% stearlc acid for lubrication) made from regular HEC, blocky HEC and commercial Natrosol 250 HHX Pharm HEC. Blocky hydroxyethylcellulose with HE-MS 1.7 achieves a 7-fold increase In tablet hardness as compered to regular Natrosol 250 HHX Pharm, The highly substituted blocky HEC (HE-MS 3.0) achieves a remarkable 12-fold Increase in tablet strength. In the typical modified release formulation, these materials all showed excellent direct compression performance and drug release kinetics as compared to commercial Natrosol 250 HHX Pharm. [000117] The data suggest that regions of unsubstituted cellulose backbone appear to be critical for Improved HEC compactlblllty. In the case of the highly substituted, blocky HEC Example 19, the highly substituted ethylene oxide regions may act as a plaaticizer resulting In extremely ductile material that is resistant to fracture. Table 18: Hardntss of 19 wt% HEC with 1 vut% Stearic Acid Tablets (Table Removed) [000118] While this invention has been described with respect to specific embodiments, it should be understood that these embodiments are not intended to be limiting and that many variations and modifications are possible without departing from the scope and spirit of this invention. WHAT IS CLAIMED; 1. A composition comprising hydroxyethylcelluloae (HEC) having hydroxyethyl groups that are non-uniformly distributed on the cellulose backbone wherein the unsubstltuted trlmer ratio (U3R) Is greater than 0.21 and the hydroxyethyl molar substitution Is greater than about 1.3 and less than about 5,0. 2. The composition of claim 1, wherein the hydroxyethylcellulose is further modified with one or more substltuents having chemical functionality selected from the group consisting of nonlonlc, anlonic, and catlonlc and mixtures thereof, 3. The composition of claim 2, wherein the substituents are attached to the hydroxyethylcellulose backbone via an ether, ester, or urethane linkage moiety 4. The composition of claim 2, wherein the substituents present have nontonic chemical functionality. 5. The composition of claim 4, wherein the substituents have the formula -R1or-A-R, wherein A Is selected from the group consisting of CH2-CH(OH), CH2-CH(OH)-CH2, (CH2-CH2-O)n where n = 1-100, CH2CH(OH)-CH2O-(CH2-CH2-0)n where n = 1-100, and CH(R)-C(0)-CH2, and R is selected from the group consisting of I) an acyclic or cyclic, saturated or unsaturated, branched or linear hydrocarbon molsty having 1 to 30 carbon atoms,

Full Text

BLOCKY HYDROXYETHYLCELLULOSE, DERIVATIVES THEREOF, PROCESS OF MAKING, AND USES THEREOF
[0001] This application claims the benefit of U.S. Provisional Application No. 60/653,864, filed February 17, 2006.
FIELD OF INVENTION
[0002] The present Invention relates to cellulose ether compositions, derivatives thereof, processes for making the composition and uses thereof in functional systems, More specifically, this Invention relates to non-uniformly substituted ("blocky) hydroxyethylcelluloses (HECs) and derivatives thereof. This invention also relates to processes for making blocky HEC and uses thereof in functional systems,
BACKGROUND OF THE INVENTION
[0003] Hydroxyethylcellulose (HEC) is a cellulose ether usually mada by reacting alkali cellulose with ethylene oxide (EO). In general, the molar ratio of EO to the anhydroglucose units of cellulose Is higher than 1.5 to provide adequate water-solubility to the cellulose backbone. HEC is a water-8oiubie/water-3wellable polymer that generally is used to viscosity aqueous madia of functional systems such as personal care and household products, paints, construction material products, paper coatings, oilfield media, emulsions, latex components, etc. Furthermore, high molecular weight HEC is used In the pharmaceutical industry as an exciplent to provide a swellable diffusion barrier In controlled release applications.
[0004] In commercial HECs that are made by a single-stage ethoxylatlon of cellulose, the hydroxyethylene substltuents are nearly randomly distributed among the anhydroglucoae segments of the polymer. Examples of prior art that disclose the preparation of HEC are US Patents 2,572,039, 2,682,535, 2,744,694, and 3,131,177. Another commercial HEC product Is a more highly
substituted HEC in which the ethylene oxide Is reacted In two-steps thereby reducing the amount of unsubstituted anhydroglucose units, This results In the formation of a cellulose derivative that Is less susceptible to enzymatic degradation, i.e, enhanced resistance to blodegradatlon. Examples of prior art that disclose the preparation of this type of HEC are US Patent 3,131,176, Canadian Patent 1014280, and US Patent Application US 2005/0139130 A1. The solution viscosities of HECs with these types of EO substitution patterns usually depend on the molecular weight of the cellulose backbone.
[0005] Furthermore, HECs can be modified with additional substltuents to improve functionality. For example, US Patent No, 4,228,277 discloses the use of long chain alkyl modifiers having 10 to 24 carbon atoms, Another example of B modified HEC is disclosed In US Patent No, 4,826,970 that describes a carboxymethyi hydrophoblcally modified hydroxyethyl cellulose ether derivative (CMHMHEC) that Is used aa thickeners and protective colloids In water based protective coating compositions, US Patent No 4,904,772 discloses a water-soluble HEC derivative that has a mixed hydrophobe having two or more hydrophoblc radicals having 6 to 20 carbons whereby one of thd hydrophoblc radicals has a carbon chain length that Is at least two carbon atoms longer than that of the other hydrophoblc radical. US Patent 4,683,159 discloses a water-aoiuble, cationlc hydroxyethyl cellulose,
[0006] Commercial HEC products are the thickeners of choice in many Industries because they provide the desired rheology and thickening efficiency. Notwithstanding, a need still exists for an HEC-based rheology modifier that would be more efficient In thickening aqueous systems and Interact more strongly with componanta In the system and/or with Itself so that additional desired Theological properties can be achieved.
SUMMARY OF THE INVENTION
[0007] The present Invention Is related to "blocky" HEC products that have unique thickening efficiency In neat solutions and functional systems. In other words, the HECe of the instant Invention show associative properties that are
unknown In commercial HEC products. An advantage of this product Is that It provides a much higher solution viscosity than regular commercial HEC at simllar concentrations and molecular weight. Consequently, a lesser amount of the HEC of the present Invention can produce comparable or better viscosity relative to analogous commercial HECs of similar molecular weight. The HECs and HEC derivatives of the present Invention form solutions that have a high elasticity that la characteristic of a strongly associative polymer network as well as unique adsorption characteristics and Interaction with media components, The gelling properties and suspending.properties of the present Invention are better than similar HEC products of the prior art.
[0008] The present Invention Is directed to HECe that have hydroxyethyl groups that are non-uniformiy distributed on the cellulose backbone, wherein the ratio of unsubstltuted anhydroglucoae trimers to the most frequently occurring substituted anhydroglucose trimers (U3R) Is greater than 0.21 and the hydroxyethyl molar substitution is greater than about 1.3 and less than about 5.0.
[0009] The present Invention Is further directed to a slurry process for making the above mentioned HEC composition comprising
A) mixing and reacting cellulose, water and a base reagent In an
organic solvent for a sufficient time and at a sufficient temperature In order to
form a first base reagent cellulose mixture, wherein the water to anhydroglucose
(AGU) molar ratio Is In the range of about 5 to 35 and (a) the base reagent to
AGU molar ratio Is greater than about 1.6 or (b) the base reagent to AGU molar
ratio I's lass than about 0.4
B) (i) when (a) la used from Step A, then sufficient acid is added In
order to reduce the base reagent concentration to a baae reagent to AGU molar
ratio of no lesa than about 0,6 to form a second base reagent cellulose mixture,
or
(II) when (b) la used from Step A, then sufficient ethylene oxide Is added and reacted at a sufficient temperature and for a sufficient time to form a HEC product with a hydroxyethyl molar substitution of less than 1.3, followed by

additional base reagent to adjust the base reagent to AGU molar ratio to greater than about 1.0 to form a baae reagent HEC mixture, and
C) tnen adding to the second base reagent cellulose mixture from B(i) or to the base reagent HEC cellulose mixture from D(ll) a sufficient amount of ethyiene oxide and reacting at a sufficient temperature and for a sufficient time In order to form the final HEC composition.
[00010] The HEC product prepared by the above mentioned process can optionally be further reacted with at least one other derlvatlzlng reagent to form a modified HEC product.
[00011] Likewise, the HEC or modified HEC product, optionally, can further be reacted with a viscosity reducing agent,
[00012] The present invention ls also related to a functional system composition Including the non-unlformly substituted HEC composition or
derivatives thereof.
BRIEF DESCRIPTION OF THE DRAWING
[00013] Figure 1 shows a bar graph of the ethylene oxide distribution profile of
a HEC polymer.
DETAILED DESCRIPTION OF THE INVENTION
[00014] it has been surprisingly found that a HEC or derivatives thereof having a non-unlformiy or blocky substitution pattern can produce unique rheology that has not been noted prior to this Invention.
[00016] The present Invention Is directed to blocky HECs and modified HECs (nonlonlc, anlonic, and catlonlc) In which a large fraction of the anhydroglucose units (AGU) in the cellulose backbone are not substituted with ethylene oxide (EO). Upon degradation, these unsubstituted anhydroglucose units exist as monomers and oligomers. The characteristic that makes these blocky HECs unique is an unaubstltuted trlmer ratio (U3R) that Is greater than 0.21, preferably
greater than 0.235, and e hydroxyethyl molar substitution that is greater than about 1,3 and less than about 5.0, This unique class of HECs shows associative behavior through hydrogen bonding and exhibits significantly higher solution viscosities as compared to other classes of HECs with similar hydroxyethyl molar substitution (HE MS) and cellulos'8 molecular weight. Furthermore, this non-unlformly substituted HEC provides a unique template for reacting hydrophobes that are concentrated In the EO-rlch regions in a non-uniform manner to achieve novel rheologlcai properties, Post addition of nonionlc or Ionic substituents may be necessary to Improve water-solubility or functionality,
[00016] In accordance with the present invention, the blocky HEC composition can be further modified with one or more nonionlc, anlonlc, and catlonlc substituents or mixtures thereof, The substituents are attached to the HEC backbone via an ether, ester, or urethane linkage.
When the aubstituents have nonionic chemical functionality, the substituents
have the formula;
-R, or --A-R, wherein A ls
CH2-CH(OH)1
CH2-CH(OH)-CH2,
(CH2-CH2-O)n- where n " 1-100,
CH2-CH(OH)-CH2-0-(CH2-CH2-0)n where n = 1-100,
CH(R)-C(0)-CH2l and
R Is selected from one of the following groups:
i) an acyclic or cyclic, saturated or unsatureted, branched or linear hydrocarbon moiety having 1 to 30 carbon atoms,
ii) an acyclic or cyclic, saturated or unsaturated, branched or linear heterohydrocarbon moiety having 1 to 30 carbon atoms and one of more oxygen, nitrogen, orsliicone atoms,
III) an acyclic or cyclic, saturated or unsaturated, branched or linear hydrocarbon moiety having 1 to 30 carbon atoms and one or more aromatic hydrocarbon groupsi
iv) an acyclic or cyclic, saturated or unsaturated, branched or linear heterohydrocarbon moiety having 1 to 30 carbon atoms and one or more oxygen, nitrogen, or sliicone atoms and one or more aromatic groups, and \t) an acyclic or cyclic, saturated or unsaturated, branched or linear, heterohydrocarbon moiety having 1 to 30.carbon atoms and one or more oxygen, nitrogen, or silicons atoms and one or more heteroaromatlc groups containing one or more oxygen, nitrogen, or sliicone groups,
[00017] Based on the formula R above, the subatltuents may be selected from alkyi, aikenyl, alkynyl, aryl, alkyl aryl, aryl alkyl, alkenyl aryl, aryl alkenyi, or mixtures thereof having, when possible, from 1 to 3'0 carbon atoms,
[00018] When the substltuents have anlonic chemical functionality, the anlonlc chemical functionality can be carboxylate, sulfate, sulfonate, phosphate, phospnonate or mixtures thereof, More specific examples of this functionality are carboxyrnathyi, eulfoethyl, phosphonomethyl, and mixtures thereof,
[0001BJ When the subatltuents have catlonlc chemical functionality, the substituents have the formula R1R2R3R4N+ (A"), where R1 ls [00020] -CH2-CHOH-CH2- or-CH2-CH2-, and R2, R3, R4 are each independently selected from an alkyl or aryl alkyl group having 1 to 20 carbon atoms, and A' is a hallde, sulfate, phosphate, or tetrafluoroborate Ion.
[00021] More specifically, the cationlc subatltuents can be selected from 2-hydroxpropyltrlmethylammonlum chloride, 2-hydroxypropyldodecyldlmethylammonIum chloride, 2-hydroxypropylcocoalkyldimethylammonium chloride, 2-hydroxypropyioctadecyldlmethylammonium chloride and mixtures thereof.
[00022] Another Important catlonlc group that catfbe used In this invention Is the group derived from the grafting reaction of dlallyldlmethylammonium chloride with HEC or its derivatives,
[00023] in accordance with the present Invention, more specific modified hydroxyethyiceiluiose examples are methyl hydroxyethylcelluloae, ethyl nyoroxyethyicaliulose, octy! hydroxyethylcellulose, cetyl hydroxyethylcellullose, cetoxy-2-hydraxypropyl hydroxyethylcelluloae, butoxy-2-hydroxypropyl hydroxyethyicalluloae, butoxy-2-hydroxypropyl cetyl hydroxyethylcellulose, butoxy-2-hydroxypropyl cetoxy-2-hydroxyethylcellulose, carboxymethyi hydroxyethylcellulose, carboxymethyi ethyl hydroxyethylcellulose, carboxymethyi octyl hydroxyethylcelluloae, carboxymethyi cetyl hydroxyethylcellulose, carboxymethyi cetoxy-2-hydroxypropylcellulose, carboxymethyi butoxy-2-hydroxyethylcellulose, aulfoethyl hydroxyethylcelluloae, aulfoethyl ethyl hydroxyethylcellulose, aulfoethyl cetyl hydroxyethylcellulose, aulfoethyl cetoxy-2-hydroxypropylcelluloae, 2- hydroxypropyltrlmethylammonium chloride hydroxyethyicelluloae, 2-hydroxypropyltrlm'ethylammonlum chloride ethyl hydroxyethylcellulose, 2-hydroxypropyltrlmethylammonlum chloride butoxy-2-hydroxypropyl hydroxyethylcelluloae, 2-hydroxypropyltrlmethylammonlum chloride octyl hydrdxyethylcelluloae, 2-hydroxypropyltrlmethylammonlum chloride caty! hydroxyethylcelluloae, 2-hydroxypropyltrlmethylammonlum chloride cetoxy-2-hydroxypropyl hydroxyethylcellulose, 2-hydroxypropyllauryldlmethylammonlum chloride hydroxyethylcellulose, 2- hydroxypropyltrlmethyiammonlum chloride 2-hydroxypropyllauryldlmethylammonlum chloride hydroxyethylcelluloae, diallyldlmethyiammonlum chloride grafted hydroxyethylcelluloae, and dlallyldimethylammonlum chloride grafted cetyi hydroxyethylcelluloae.
[00024] in accordance with the preaent Invention, the preferred process for making a non-unlformly substituted HEC product requires a two-step alkalization of the cellulose, while only a single-stage hydroxyethylatlon Is necessary. This differs from the two-step hydroxyethylatlon that has been described In prior art to Improve the enzyme reaistance of HECs. The initial alkalization atep is performed at an alkali to AGU molar ratio higher than 1.6 and at a water to AGU molar ratio In the range of about 5 to 35. Next, the alkali cellulose Is neutralized with an acid to an alkali to AGU molar ratio greater than 0.6, preferably between 1,2 and 1,0. The alkali neutralization step may be done as a single addition,
multiple additions, or a continuous addition of the neutralizing aid, with or without the presence of ethylene oxide. Upon completion of the hydroxyethylatlon, the product can be viscosity reduced, purified, dried, and ground as known to those
skilled In the art,
[00025] Also, in accordance with the present Invention, non-unlformly substituted HEC can be produced using a "reverse" two-step alkallzatlan process as herein described. In this case, the cellulose Is partly alkalized at a caustic to AGU molar ratio that la Insufficient to open up the cellulose fibers. Typical alkali to AGU molar ratios are between 0,2 and 0.4 and water to AGU molar ratios are In the range of about 5 to 35. The cellulose is first hydroxyethylated to less than 1 3 at this stage before more alkali Is added in the second stage to reach alkali to AGU molar ratios between 1.0 to 2,0, preferably between 1.0 and 1.4. After sufficient time, the intermediate HEC Is further hydroxyethylated to achieve the final HE MS
[00028] In the slurry process of the present Invention, organic solvent used In this process is selected from ethanol', Isopropanol, tert-butanol, acetone, methyl ethyl ketone, dlmethoxyethane, and mixtures thereof. This slurry process uses alkalis that aro selected from lithium hydroxide, sodium hydroxide, potassium nydroxlde, and mixtures thereof. The raw cellulose starting material used In the process for making the.blocky HECs can be cotton (inters, wood pulps or mixtures thereof.
[00027] The blocky HEC compositions mentioned above can be optionally further reacted with at least another derivatizlng reagent to form a modified hydroxyethylcellulose composition. The d,erlvatlzlng reagent used to make this modified hydroxyethylceiluiose composition can be nonlonlc, catlonic, or anlonic organic compounds or mixtures thereof. These organic compounds capable of reacting with the hydroxyls groups of the HEC can be halldea, epoxldes, glycldyl ethers, carboxyllc aclda, Isocyanates, or mixtures thereof.
[00028] The biocky HEC or derivatives thereof made by the slurry processes mentioned above can be further reacted with a viscosity reducing agent, such as paroxide, persulfate, peracid, salt of hallde oxo acids, oxygen, or ozone, This enables a person using this process to modify the final product to the desired viscosity or other properties for the desired end use.
[00029] The process and process conditions determine how the EO is distributed along the cellulose backbone. Products of the Invention are characterized and can be differentiated from HECs made by prior art by reducing the polymer down to monomers and oilgomers and measuring the degree of unsubstltuted oligomers, more specifically unsubstituted trimers . A novel parameter called the unsubstltuted trimer ratio (U3R) can be defined as the ratio of the molar fraction of unaubstltuted trimers to the molar fraction of the most abundant class of (hydroxyethyl-substltuted) trlmers, with 0 £ U3R £ 1 .0, U3R Is measured by a mass spectrometric technique that is described below. The U3R of the HECs of present Invention are equal to or more than about 0.21, preferably greater than 0,235,
[00030] Trlmers, oligomers with a degree of polymerization (DP) of 3 anhydrogtucose units, and other compounds of structure 1 are made by partial methanolysls of permethylated HEC derivatives. It Is assumed that the cleavage of the permethylated H EC-backbone is a random process and that the formed oligomars of structure 1 have an EO-dlstrlbutlon that la representative for the EO-dlstrlbutlon of the whole sample.
(Formula Removed)

[00031] in general, permethylated derivatives of HEC polymers can be prepared by the methylatlon reaction that Is applied In the methytatlon analysis procedure for polysaccharldas. (See publications of F.-G. Hanlach, Biological Mass Spectrometry, 23 (1994) 309-312; B. Llndberg, U, Llndqulst and O. Stenberg, Carbohydrate Research, 170 (1987) 207-214; and P.W. Arisz, J.A. Lomax, and j.j. Boon, Carbohydrate Research, 243 (1993) 99-114.)
UNSUBSTJTUTED TRIMER RATIO (U3R) DETERMINATION [00032] More specifically, In the present Invention, the Investigated HEC polymers are dissolved or swollen in dimethyl aulphoxlde (DMSO). The hydroxyl groups In the polymer ere deprotonated using a lithium methyisulphlnyi carbenlon solution In DMSO and they are converted to methoxyl groups by the reaction with methyl iodide.
[00033] The obtained permethylated HEC polymer Is purified. More specifically, the permethylated HEC polyrrier la extracted In three extraction steps with chloroform from an aqueous DMSO layer that Is acidified to pH 100034] The permethylated polymer Is partially degraded by methanolyeia, More specifically, the permethylated polymer Is dissolved / swollen In methanol, Sufficient hydrochloric acid in methanol la added to get a hydrochloric acid concentration of about 0.50 molar. The sample Is dissolved completely at 50°C for 15 minutes. Partial methanolysls Is done at 70"C for 2.5 hours. The reaction Is quenched by the addition of 2-methyl-2:propanol and all solvents are evaporated, yielding a residue that Is composed of a mixture of ollgomers of structure 1.
[00038] The residue Is dissolved In methanol and a fraction of this sample Is mixed with 2,5-dlhydroxybenzolc add solution that Is spiked with sodium Iodide.

Mass spectra of the ollgomer mixture are recorded with a Bruker Reflex II MAuDl-TOF-MS (matrix assisted laser desorptlon lonlzatlon - time of flight -mass spectrometer), which Instrument la equipped with a mlcrochannel plate detector. The compounds 1 are measured as their sodium Ion adducts. The mass numbers of the monoisotopic mass peaks of the trlmers arem/z2607.32, 711,34, 755.35, 799,38, etc. It Is assumed that all trlmers are measured with equal probability, Independent of their molar HE-substltutlon, chain length of the substltuents and their positions In the anhydroglucose residues.
[00036] Trlmer fractions are derived by two data processing steps from the measured peak intensities of their monoisotopic maaa peaks. First the background signal of the MALDi spectrum is subtracted from the measured peak intensities Secondly, mainly due to 13C-laotopes that are Incorporated In structure 1 the monoisotopic mass peaks make up only 70.6, 68.9, 87.2, 65,6%, etc of all isotopes of trlmera having 0,1,2, 3, etc attached EO-unlts, respectively, Unfortunately, the^peak Intensities of 13C-lsotopes can not be measured accurately by MALDI-TOF-MS because of the recovery time that Is needed for the mlcrochannel plate detector after an Intense mass peak has been recorded. In order to compensate the signal for the missing contribution of 13C-isotope peaks, the background corrected monoisotopic mass peak Intensities are multiplied by a correction factor that lscalculated from the theoretical isotope composition of the trimers. This factor Increases with Increasing number of C atoms in 1, and values have been used of 1.417,1.452, 1.488, 1,525, etc for turners having 0, 1, 2, 3, etc attached EO-unlts, respectively,
[00037] Figure 1 shows an example of the EO-dlstrlbutlon profile of trimers that are derived from a HEC polymer. The fraction qf unsubstltuted trlmers Is Indicated In gray. The moat abundant class of trlmers In this example Is that of trlmers with 7 attached EO-unlts. This class Is Indicated In white. The unaubstituted trlmer ratio, I.e. the gray fraction divided by the white fraction, Is calculated to be 0,121 for this example. It should be noted that the number of EO-units in the most abundant class of trlmers varies, depending on factors as
the molar substitution of the HEC and the process type by which the HEC was made, for example
[00038] HEC derivatives that contain secondary aubstltuents such as nonlonlc, cationic and anlonlc substltuents and mixtures thereof are analyzed similarly as non-modified HECa. in the case of modification levels smaller than 3.5 sub8t(tuent6 per 100 monomer units, such as associative hydrophoblc reagents for example, less than 10% of the trimera are modified and consequently the fraction of modified trimers can be neglected.
[00039] The fraction of unmodified trlmers decreases with Increasing degree of substitution (DS) of the modifying agent. If the secondary substltuent distribution is at random along the cellulose backbone, than only half of the trimers would remain unmodified at a DS level of 0.21, The carboxymethyl (CM)-modlfied HMHECs listed in Tables 2a, 3a and 4a ail have CM-DS values In this order of magnitude and It ls concluded for these samples that the fraction of CM-modified trimerB cannot be neglected,
[00040] Furthermore, CM-groups that are attached to the HEC-backbone are converted Into their methylesters by the derlvatlzatlon procedure. The sodium ion adduct of dlmers with two attached Eo-units and two attached CM-groups has m/z 667,28. The mass resolution of MALDI-TOF-MS Is Insufficient to separate this mass peak from rn/z 667.32, I.e. the mass peak of unsubstltuted trimers, so that an accurate U3R-value for carboxymethylated HEC-derivatives Is not applicable (N/A).
APPLICATIONS:
[00041] Many of these HEC samples exhibit novel and highly desirable
rheology and performance properties In end use systems.
[00042] in accordance with the present Invention, the viscosity builds up not only by means conventional to HEC, but also is boosted significantly by molecular association. The association leads to network formation and gel-like

Theological properties In water and aqueous based functional systems that are shear reversible. The HECa and derivatives of the present Invention have been shown to lower the HEC use-level needed and to provide unique Theological attributes as compared to commercial HECs available today,
[00043] Furthermore, these HECs and derivatives thereof may be used In applications where there Is a need for a specific rheology characteristic, e.g., viscosity., thlxotropy, yield stress, elasticity, or solid state characteristics such as thermoplastlclty and film flexibility. Examples of functional systems Includes aqueous based coatings (e.g., latex paints), building and construction materials (e.g., cements, plasters), personal care products (e.g., skin care, hair care, oral care, nail care, and personal hygiene products), household care products (e.g., Industrial cleaning liquids, pet care products), Pharmaceuticals (e.g., exclpients for tablets capsules, and granules), oilfield applications (e.g., drilling fluids, completion fluids, and fracturing fluids), civil engineering, printing Inks, adhesives, paper coating formulations, and retention and drainage aids in paper making.
[00044] In accordance with the present Invention, the functional system can either be prepared In a continuous or batch process and either In a stepwlse addition of the Ingredients or a simple mixing of all of the Ingredients at once. The order of addition of the Ingredients can also vary over a wide range of additions. For example, the functional Ingredients can be Individually added one at a time to the formulation or all at once or the blocky HEC products can be added directly to the formulated Ingredients in a single step. Hence, the process of thickening an aqueous based functional system (e.g., personal care products, household care products, oil field servicing, fluids, civil engineering servicing fluids, paper coating products, paper making compositions, building and construction fluids, mineral processing products, and water based protective coatings such as architectural and Industrial coatings), Includes adding and mixing a sufficient amount of the blocky HEC polymer of the present Invention that Is compatible with the aqueous baaed functional system to thicken the functional system. The resulting functional system has comparable or better

rheology and viscosity properties as compared to when using similar thickening agents Including commercial HECs.
PERSONAL CARE
[00045] in accordance with the present Invention, when the composition Is a personal care composition, It Includes (a) from about 0.1 % to about 99,0 % by weight of the vehicle component and (b) at lead one active personal care
ingredient.
[00046] In accordance with the present invention, the personal care active Ingredient must provide some benefit to the user's body. Personal care products include hair care, skin care, oral care, nail care, and personal hygiene products. Examples of substances that may suitably be Included In the personal care products according to the present Invention are as follows:
1) Perfumes, which give rise to an olfactory response in the form of a
fragrance and deodorant perfumes which In addition to providing a
fragrance response can also reduce body malodor;
2) Skin coolants, such as menthol, methyl acetate, methyl pyrrolidone
carboxylate N-ethyl-p-menthane-3-carboxamlde and other
derivatives of menthol, which give rise to a tactile response In the
form of a cooling sensation on the skin;
3) Emollients, such as Isopropyl myristate, sllicone oils, mineral oils
and vegetable oils which give rise to a tactile response In the form
of an Increase In skin lubricity;
4) Deodorants other than perfumes, whose function Is to reduce the
level of or eliminate micro flora at the skin surface, especially those
responsible for the development of body malodor. Precursors of
deodorants other than perfume can also be used;
5) Antipersplrflnt actives, whose function Is to reduce or eliminate the
appearance of perspiration at the skin surface;
6} Moisturizing agents that keep the skin moist by either adding
moisture or praventlng moisture from evaporating from the skin; 7} Cleansing agents that remove dirt and oil from the skin;
8) Sunscreen active Ingredients that protect the skin and hair from UV
and other harmful light rays from the sun. In accordance with this
Invention a therapeutlcally effective amount will normally be from
0.01 to 10% by weight, preferably 0.1 to 5% by weight of the
composition;
9) Hair treatment agents that condition the hair, cleans the hair,
detangles hair, act as styling agents, volumlzlng and gloss agents,
anti-dandruff agent, hair growth promoters, hair dyes and
pigments, hair perfumes, hair relaxer, hair bleaching agent, hair
moisturizer, hair oil treatment agent, and antl-frlzzlng agent;
10) Shaving products, such as creams, gels and lotions and razor
blade lubricating strips;
11) Tissue paper products, such ae moisturizing or cleansing tissues;
12) Beauty aids, such as foundation powders, lipsticks, and eye care;
and
13) Textile products, such as moisturizing or cleansing wipes,
[00047] in personal care compositions, the rheology modifiers of the present invention can be used either alone or may also be used in combination with other known Theology modifiers Including, but not limited to, polysaccharldes (e.g., carrageenan, pectin, aiglnate), cellulose ethers, blopolymers (e.g., xanthan gum), synthetic polymers, and abrasive/thickening silicas,
HOUSEHOLD CARE
[00048] In accordance with the present Invention, when the composition is a household care composition, It Includss (a) from about 0.1 % to about 99,0 % by weight of the vehicle component and (b) at least one active household care
Ingredient

[00048] In accordance with the present Invention, the household care active Ingredient must provide some benefit to the user, Hou3ehold care products include fabric care, laundry detergent, hard surface cleaner, Industrial institutional liquid soaps, and dish detergents. Examples of active Ingredients or substances that may suitably be Included according to the present Invention are as follows:
I) Perfumes, that give rise to an olfactory response In the form of a
fragrance and deodorant perfumes that In addition to providing a fragrance
response can also reduce odor;
2} Insect repellent agent whose function Is to keep Insects from a particular area or attacking skin;
3) Bubble generating agent, such as surfactants which generates foam
or lather;
4) Pet deodorizer such as pyrethrlns that reduce pet odor;
5) Pet shampoo agents and actives, whose function Is to remove dirt,
foreign material and germs from the 3kln and hair surfaces;
6) industrial grade bar, shower gel, and liquid soap actives that remove
germs, dirt, grease and oil from skin, sanftlze skin, and condition the skin;
7) All purpose cleaning agents that remove dirt, oil, grease, and gorms
from the surfaces in areas such as kitchens, bathroom, and public facilities;
8) Disinfecting Ingredients that kill or prevent growth of germs In a
house or public facility;
9) Rug and Upholstery cleaning actives that lift, and remove dirt and
foreign particles from the surfaces and also deliver softening and perfumes;
10) Laundry softener actives that reduce static and makes fabric feel
softer;,
I1) Laundry detergent ingredients that remove dirt, oil, grease, and
stains and kill germs;
12) Dishwashing detergents that remove stains, food, germs;
13) Toilet bowl cleaning agents that remove stains, kill germs, and
deodorize;
14) Laundry prespotter actives that help In removing atalns from clothes;
15) Fabric sizing agents that enhance appearance of the fabric;
16) Vehicle cleaning actives that remove dirt, grease, etc, from vehicles
and equipment;
17) Lubricating agents that reduce friction between parts; and
18) Textile products, such aa dusting or disinfecting wipes,
[00060] In household care compositions, the rheology modifiers of the present Invention can be used'either alone or may also be used In combination with other known rheology modifiers Including, but not limited to, polysaccharides (e.g., carregeenan, pectin, alglnate), cellulose ethers, blopoiymers (e.g., xanthan gum), synthetic polymers, and abrasive/thickening silicas.
[00061] The above are only limited examples of personal care and household active ingredients and are not a complete list of active Ingredients that can be used. Other ingredients that are used in these types of products are well known in the industry. In addition to the above Ingredients conventionally used, the composition, according to the present Invention can optionally also include ingredients such as colorants, preservatives, antloxldants, nutritional supplements, activity enhancers, emuleiflers, viacosifying agents (such as salts, e.g., sodium chloride, ammonium chloride and potassium chloride), water-soluble polymers (e.g., HEC, modified HEC, carboxymethylcellulose), and fatty alcohols (e.g., cetyl alcohol), alcohols having 1-6 carbons, and fats and oils,
PROTECTIVE COATINGS
[00062] Water-based protective coating compositions (commonly referred to aa paints) in which cellulose ether derivatives are commonly used Include latex paints or dispersion paints, of which the principal Ingredient Is the film-forming binders that Include latlces such as styrene-butadiene copolymers, vinyl acetate hornopolymers and copolymers, and acrylic homopolymers and copolymers. Other binders that are typically used in paints Include alkyd resins, and epoxy resins. Typically, paints also contain opaclfylng pigments, dispersing agents and water-soluble protective colloids, the proportions being, by weight of the total composition, about 10 parts to about 50 parts of a latex, about 10 parts to about

agent, and about .0.1 part to about 2 parta of a water-soluble protective colloid. These protective coatings can be either aqueous baaed architectural or Industrial coating compositions. Architectural coatings are Intended for on-slte application to interior or exterior surfaces of residential, commercial, Institutional or Industrial buildings, industrial coatings are applied to factory-made articles before or after fabrication, usually with the aid of epeclal techniques for application and drying.
[00063] Water-soluble polymers conventionally used in the manufacture of latex paints include casein, methyl cellulose, hydroxyethylcellulose (HEC), sodium carboxymethyl cellulose (CMC), polyvinyl alcohol, starch, and sodium polyacrylate. The HECs of the present Invention can be used as rheology modifiers for water-based protective coating compositions.
PAPER COATINGS AND PAPER MAKING
[00064] Paper coating Is a process In which the surface structure of paper or board Is Improved by applying a mineral coating that Is subsequently dried. Coating process IS the application of a water-borne pigment slurry, which b bound at the surface by one of several binders. Other coating components can be added to obtain a suitable rheology, and to Impart properties such as brightness or water resistance.
[00066] A coating process can generally b© divided into three different phases: (1) preparation of the coating formulation (known as called coating color), (2) coating and (3) drying. The genera! principles of formulating paper coating are mostly well known. Moreover, each paper maker has his own tailor-made recipes for his specific requirements, Therefore, it would not be possible to give a "recipe" for a specific coating process, coating type or printing process. However, a generic coating formulation recipe contains 75 - 90 % pigment (such as clay, satin white, calcium carbonate, titanium dioxide, talc, aluminum hydroxide, calcium sulfate, barium sulfate, synthetics, etc.), 0.10 - 0.50 % dlspersant, 0,05 - 0.30 % alkali, 5 - 20 % binders (such as styrene-butadlene latlcea, acrylics, polyylnyl acetate, starch and atarch derivatives, proteins such as

compounds, However, without the clay, joint compounds have poor sag resistance and less body. Examples 2 and 20 were tested at 0.5 wt % as the sale rheoiogy modifier In the clay-free Joint compound system with reduced mica levels as shown, These were compared with Natrosol 260 HHXR product. Table 10 shows the joint compound containing the Natroaol 250 HHXR product had poor sag resistance, open time, and workability, confirming the need for a structure builder like clay. On the other hand, Examples 2 and 20 produced axcellent joint compounds with properties that are typically obtained with thickener and & fullcomplement of attapulglte clay.
Typical All-Purpose Joint Compound Formulation with and without Clay

Tsable 10; All-Purpote Clay-free Joint Compound Properties
(Table Remvoed)
Example 30
Paper
[000101] Blocky NEC Is a highly efficient water retention agent In paper coatings, Blocky HEC Example 3, commercial samples Aqualon 7L1T CMC, and Natrosol 25OGR were evaluated as thickeners and water retention aids in the paper coating formulation as shown below. The amount of rheology modifier necessary to maintain the BrooKfleld viscosity at 1500 +/-50 cps, the water loss,

and Hercules high f hear viscosity are shown In Table 11. BlocKy HEC Example 3 and HEC 250GR are of similar molecular weights and solution viscosities; however, the blocky product has e significantly higher dosage efficiency than HEC 250GR while maintaining Its low water loss rate. In addition, blocky HEC Example 3 has much lower water loss and higher dosage efficiency than Aqualon 7L1T CMC yet similar desirable high shear rrteology,
Paper coating formulation
(Table Removed)

'Ground Oalalum Carbonate (HydroO«rt) frcm OMYA Ino.
Table 11; Paper Coating Properties
(Table Removed)

Example 31
Pergonai Care
[000102] Blocky HEC shows enhanced viscosity In personal care formulations, Natrosol® hydroxytthyl cellulose type 250HHR and blocky HEC Example 2 were compared at 0 J wt% for thickening efficiency in the hair conditioner formulation shown below.
Hair Conditioner
90.94g Deionized water
00,70g Thickening polymer (Natrbsol® 250HHR, blocky HEC example 2)
02.00g Cetyl alcohol
oo.5Qg Potassium Chloride
02.00g Isopropyl Myrlatate
As required - citric add to adjust pH
As required - Sodium hydroxide to adjust pH
OO.5Og Germaben II
Procedure:
[000103] The thickening polymer was added to water under agitation. Next, the pH was adjusted to 8.0 to 8.5. The slurry was stirred for at least 30 minutes or until the polymer dissolved, the solution was heated to about 65oC and cetyl alcohol was added and mixed until homogeneous. The mixture was cooled to about 50°C and potassium chloride was added. Isopropyl myrlstate was added and mixed until the mixture looked homogeneous. The pH of the mixture was adjusted to 5.3 - 5,5 with citric add and/or NaOH solution. The conditioner was preserved with 0.5 g Germaben II and mixed until the mixture reached room temperature,
[000104] The viscosity of the conditioning formulation containing blocky HEC Example 2 was 1,550 cP, as compared to the control containing Natrosol® 250HHR at 910 cPs, a 70% improvement In thickening effldency.
[000106] Hydrophoblcally modified blocky HECs show enhanced viscosity stability In o|[-ln-water emulsions. They were evaluated as a polymeric emulsifier / stabilizer in a typical emulsion formulation shown. Examples 20 and 21 were compared against commercial polymeric emulslfiera (Natrosol Plus 330,331, and PolySurf 67). In addition, PemulenTR-1, Pemulen TR-2 and Carboppl ETD 2020 products, commonly used hydrophoblcady modified acrylate cross-polymers, were included in the comparison. Table 12 and 13 show the viscosity data for one-month storage at room temperature and 40° 0, respectively. Examples 20 and 21 have dramatically Improved emulsifying and stabilizing properties over the commercial hydrophobically modified HECs. Furthermore, the emulsifying/stabilizing effldency Is near that of Pemulen TR-1, Pemulen TR-
2, and Garbopol ETD 2020, which are extremely efficient emulsifying/stabilizing polymers In the market. The thickening efficiency Is even better than that of Pemulen TR-2,
(Table Removed)

Composition of Barto Emulalon Formulation
Procedure:
- Prepare •took solution of polymeric emulslfler/stablllzer
- Add mineral oil to the aqueous phtee and Germaben II
- Mix the formulation with Braun ratohen mixer for 3 minutes at speed 5,
- (All emuliioni prepared had a pH 5-7)
Table 12: Viscosity stability of olMn-water emulsions upon 4 weeks storage at room temperature(Table Removed)

Table 13: Viscosity stability of oll-ln-water emulsions upon 4 weeks storage at 40°C
(Table Removed)[000106] Examples 20 and 21 were evaluated in the surfactant formulation shown to investigate compatibility In general personal care and household applications. Example 20 and 21 were compared against commercial rheology modifiers Natrosol Plus 330, and PolySurf 67 products. In addition, Carbopol ETD 2020 product was Included In the comparison. Table 14 shows that the hydrophoblcally modified blocky HEC Examples 20 and 21 are very efficient cellulosic thickeners. Example 21 resulted In clear solutions unlike any of the others tested.
composition of basic surfactant formulation
(Table Removed)

- Dissolve thickener In damlnerallzed water.
- Add Texapon 28 to thickener solution and mix homogeneoualy.
- Add Plantaoare 2000 Up to tnlckener solution and mix homogeneously.
• - Add Tegobetalne L7 to thickener solution and mix homogeneously,
- Adjust pH wfth ottrto add to 5.5 - 6,5.
- Add Qemwben II,
Table 14: Viscosity and appearance of surfactant formulation with thickener
(Table Removed)
[000107] Examples 20 and 21 ware evaluated as a gelling agent In an aqueous solution for hair styling gels. In addition, Carbopol Ultrez 10 (carbomer) and Carbopol ETD 2020 (C10-C3C modified aery I ate), Natrcsol 250 HHR, Natroeol 250 HR and Klucel H, commonly used gelling agents were Included In the comparison,
[000108] The thickening efficiency and suspending power of Examples 20 and 21 was better than that of commercial HECa and HPC. Furthermore, example 21 showed a carbopol Hke texture (stiff and elastic gel), while the others were considered as flowable gels. The electrolyte tolerance of examples 20 and 21 was better compared to Carbopol Ultrez 10 and Carbopol ETD 2020.
Example 32
Completion/Workoverflulds[000109) The HEC of the Invention exhibits novel thickening of heavy brines. Completion fluids are composed of a variety of brines of different salinity characterized by a density ranging from 8.5 ppg (pound per gallon) for seawater up to 19.2 ppg for heavy brines containing zinc and calcium bromide salts. Standard high viscosity MEG Is commonly used as a vlscoslflerfor brines ranging from 6-13 ppg. There presently Is not an efficient vrscosifier for heavy brines with a density ranging from 14 ppg (CaBr2) to 19,2 ppg (ZnBr2/CaBr2). These brines have a very low level of free water content available, and therefore, do not promote optimum hydratlon of standard HECs. These brines are characterized by a very low pH (pH [000110] Blocky HEC Example 2 was evaluated in 4 different brine systems (freshwater, salt-saturated water, CaBr2 and 2nBr2/CaBr2) at 0.57 wt %. These were compared to a standard HEC widely used In completion fluids (Natrosol MI-VIS). The viscosity and fluid loss properties were measured after static aging overnight at room temperature (Tables 15a-d).

[000111] Blocky HEC Example 2 showed exceptional thickening In the high density, heavy brine solutions (characterized by low water activity) as detailed by the high apparent viscosities (Y.V.) and yield values (Yv) that developed in these systems (Tables 15 c-d). In contrast, commercial HI-VIS did not go Into solution In these low water activity systems. Additionally, the blocky HEC sample developed appreciable low-end rheology as reflected by the 6 and 3- rpm Fann dial readings (DR), and showed appropriate fluid loss (F.L.) values.
(Table Removed)
Example 33
Pharmaceuticals
[000112] Blocky HEC excipients provide superior tablet hardness. HEC is used In the pharmaceutical industry as an exciplentto provide a ewellable diffusion barrier in controlled release applications. The gel matrix It forms limits the diffusion of aqueous fluids Into a system and dissolved actives out of the system. Currently, HEC produced by Aqualon (Natrosol® 250 series of pharmaceutical grade polymers) holds the majority share of HEC used in the pharmaceutical Industry.
[000113] HEC has some unique modified release properties not duplicated by hydroxypropyimethyl cellulose (HPMC) and hydroxypropyl cellulose (HPC). However, current knowledge Is that current commercial grades of HEC show significantly inferior compression properties when compared to HPMC and HPC, The poor compactlblllty of this polymer generally makes the polymer suitable for only wet granulation processing, rather than direct compression processing which is frequently the Industry preference.
[000114] In order to improve this limitation, scientists at Astra Zeneca in International Patent Application, WO 02/18990 A1 describe a procedure whereby HEC Is purified by dissolution in water before precipitation via addition of organic solvent. The precipitate Is washed end then milled In a specific manner. The purified HEC has markedly Improved tablet compactiblllty.
[000115] in accordance with the present Invention ia the use of blocky HEC material that Is highly compressible for making direct compressible tablets for use in compaction applications such as sustained release tablets for pharmaceutical, household, and agricultural applications.
[000116] Table 16 shows the strength of pure polymer tablets (with 1% stearlc acid for lubrication) made from regular HEC, blocky HEC and commercial Natrosol 250 HHX Pharm HEC. Blocky hydroxyethylcellulose with HE-MS 1.7

achieves a 7-fold increase In tablet hardness as compered to regular Natrosol 250 HHX Pharm, The highly substituted blocky HEC (HE-MS 3.0) achieves a remarkable 12-fold Increase in tablet strength. In the typical modified release formulation, these materials all showed excellent direct compression performance and drug release kinetics as compared to commercial Natrosol 250 HHX Pharm.
[000117] The data suggest that regions of unsubstituted cellulose backbone appear to be critical for Improved HEC compactlblllty. In the case of the highly substituted, blocky HEC Example 19, the highly substituted ethylene oxide regions may act as a plaaticizer resulting In extremely ductile material that is resistant to fracture.
Table 18: Hardntss of 19 wt% HEC with 1 vut% Stearic Acid Tablets
(Table Removed)

[000118] While this invention has been described with respect to specific embodiments, it should be understood that these embodiments are not intended to be limiting and that many variations and modifications are possible without departing from the scope and spirit of this invention.

WHAT IS CLAIMED;
1. A composition comprising hydroxyethylcelluloae (HEC) having
hydroxyethyl groups that are non-uniformly distributed on the cellulose backbone
wherein the unsubstltuted trlmer ratio (U3R) Is greater than 0.21 and the
hydroxyethyl molar substitution Is greater than about 1.3 and less than about 5,0.
2. The composition of claim 1, wherein the hydroxyethylcellulose is
further modified with one or more substltuents having chemical functionality
selected from the group consisting of nonlonlc, anlonic, and catlonlc and
mixtures thereof,
3. The composition of claim 2, wherein the substituents are attached
to the hydroxyethylcellulose backbone via an ether, ester, or urethane linkage
moiety
4. The composition of claim 2, wherein the substituents present have
nontonic chemical functionality.
5. The composition of claim 4, wherein the substituents have the formula
-R1or-A-R,
wherein
A Is selected from the group consisting of
CH2-CH(OH),
CH2-CH(OH)-CH2,
(CH2-CH2-O)n where n = 1-100, CH2CH(OH)-CH2O-(CH2-CH2-0)n where n = 1-100, and CH(R)-C(0)-CH2, and
R is selected from the group consisting of I) an acyclic or cyclic, saturated or unsaturated, branched or linear hydrocarbon molsty having 1 to 30 carbon atoms,

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http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=Z/Ha9mcaLgP86m6xEsweBw==&loc=+mN2fYxnTC4l0fUd8W4CAA==

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Patent Number

270947

Indian Patent Application Number

6390/DELNP/2007

PG Journal Number

05/2016

Publication Date

29-Jan-2016

Grant Date

28-Jan-2016

Date of Filing

17-Aug-2007

Name of Patentee

HERCULES INCORPORATED

Applicant Address

1313 NORTH MARKET STREET, HERCULES PLAZA, WILMINGTON, DELAWARE 19894-0001, USA

Inventors:

#	Inventor's Name	Inventor's Address
1	PETRUS WILHELMUS FRANCLSCUS ARLSZ ARISZ	MENADOSTRAAT 33C, NL-1095 TH AMSTERDAM, NETHERLANDS,
2	KATE M. LUSVARDI	3 CARDINAL LANE, CHADDS PORD, PENNSYLVANIA 19317, USA
3	TUYEN T. NGUYEN	41 CELESTIAL WAY, NEWARK, DELAWARE 19711, USA

PCT International Classification Number

C08L 1/28

PCT International Application Number

PCT/US2006/005320

PCT International Filing date

2006-02-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/653,864	2005-02-17	U.S.A.