CN101262845A - Personal care products incorporating cellulosic fatty acid esters - Google Patents

Abstract

Cellulose ester compounds and compositions that include such cellulose ester compounds dissolved in lipophilic solvents.

Description

Introduce the personal care product of cellulose fatty acid ester

Invention field

The present invention relates to cellulose esters chemical compound and the compositions that comprises the plain ester compounds of this fibrid.More specifically, the present invention relates to contain the cellulose esters compound compositions that can be dissolved in the lipophilic solvent.

Background of invention

The cellulose esters chemical compound is to replace side joint with ester moiety to form 1 of cellulose polymeric skeleton, the cellulosic molecule of the one or more hydroxyls on 4 '-O-β-bonding anhydroglucose monomeric unit in series connection.They for example can be used as film-forming components in the compositions or thickening agent to give said composition required physical property.Oil base or cosmetics and personal care product with oil phase have limited durability on lip or skin.For example, color make-up is bearing when smearing power, especially being accompanied by when perspiring, consumes behind finite time.Skin nursing products under the situation of for example sunscreen cream, are for example wiped with contact with clothing the time or are washed off when swimming.For durability and the resistance to water of improving this based composition, they preferably contain the oil-soluble film former.Need thickening so that they can spread maybe can pour into and be contained in the hands and with pointing with sticking bar-shaped (stick) form spreads such as the compositions of color make-up, deodorizer, skin nursing frost and emulsion and hair preparation.To be useful so that compositions is stayed the position of placing them can not flow away or drip from intended substrate yet in thickening.The best shear thinning of the compositions of thickening is to provide easy spreadability or thin dripping and uniform distribution is provided when spraying.Correspondingly, personal care articles need have superperformance, and durability, suitable texture also are easy to spread.The cellulose esters chemical compound also need be to be enough to produce favourable physical property, and for example the concentration of thickening and film property is dissolved in oil base cosmetics and the personal care composition.

Summary of the invention

Be dissolved in cellulose esters chemical compound in the lipophilic solvent by providing, solve the problem in this area with concentration that can the realization level before being higher than.In some embodiments, concentration is higher than 10 weight %, 20 weight % or even 50 weight % under room temperature and normal pressure.These higher concentrations can prepare and have desirable physical property, for example the cosmetics of thickening and film property and personal care composition.In some personal care products, improved film property can improve effect and the properties of product of this product as the carrier of other component, for example fouling resistance (smudge resistance), anti-transitivity (transfer resistance); Durability, resistance to water, moisture resistance and as the carrier of additive, active matter and/or pigment.

The present invention further provides the compositions and the purposes of this based composition in personal nursing and cosmetic applications that contain one or more cellulose esters chemical compounds of the present invention and one or more lipophilic solvent.

The present invention further provides the personal care product of containing compositions of the present invention.

Detailed Description Of The Invention

Definition

Used in the whole text " cellulose " of the application should refer to any cellulose from any natural and artificial source.Chemically, cellulose is described to for example contain and multiplely a stringly passes through 1, and 4 '-O-β-glycosidic inkage is the polymer of the anhydroglucose monomeric unit of covalent bonding in series.The example in available cellulose source comprises hard wood pulp, soft wood pulp, velveteen, Bacterial cellulose and regenerated cellulose.Also can use the source material (for example, hemicellulose) that comprises other chemical compound.

The used in the whole text term " cellulosic cpd " of the application should comprise cellulose and based on the cellulosic any chemical compound that replaces the one or more hydroxyls that exist on the cellulose of natural generation with another part.This replacement can be with any part (for example, ester, ether, thioesters, thioether (sulfide), hydroxyl, phosphate ester, carbonic ester, amine, imines, amide, nitrate, nitrile, urethane (carbamate), urea, thiourea, silane, sulfuric ester, sulfonic acid, azoles, phenol, pyridine or pyrimidine part or key, or the combination in any of aforementioned part) carry out.

The used in the whole text term " cellulose esters chemical compound " of the application should refer to have any cellulosic cpd of one or more ester moieties of the one or more free hydroxyl group parts that exist on the cellulose that replaces natural generation.This replacement makes the oxygen in the hydroxylic moiety be substituted by (singly-bound closes) oxygen of ester moiety.Any chemical compound that meets this description all falls into this definition.Therefore, the cellulose esters chemical compound can be the esterification reaction product of unmodified fibers element, esterification reaction product of the cellulosic cpd of modification (comprising this cellulosic cpd as cellulose esters, as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose-acetate propionate, cellulose acetate-butyrate, carboxymethyl cellulose, acetic acid butanoic acid carboxymethyl cellulose etc.) or esterification reaction product modification and combination unmodified cellulose.As a result, this cellulose esters chemical compound can have two or more types replacement or derive, and is included in two or more types that take place on some same monomer.In addition, the cellulose esters chemical compound can be the product with two or more dissimilar ester moiety esterifications, for example uses the product of esterification of the mixture of carboxylic acid and/or acid chloride.As the application is used in the whole text, mention a kind of minute period of the day from 11 p.m. to 1 a.m as " product " of specified reactant, it provides as the mode that makes things convenient for of describing this molecular structure, and is not limited to by concrete grammar or the molecule that uses concrete reactant to make.Therefore, have with reference to product and describe but by other method or all will be in the implication of the used in the whole text term of the application " product " by any molecule of the molecular structure of other reactant acquisition.It is inessential whether the reaction of the opportunity of esterification, order and character and this class is carried out simultaneously, because any cellulosic cpd of ester moiety with one or more types is all in the scope of this definition.Some examples of esterified cellulose chemical compound are: use the acid-catalyzed transesterification reaction of fatty acid; Use the base-catalyzed transesterification reaction of fatty acid; Use the acid catalysis direct esterification reaction of fatty acid anhydride; Use the acid catalysis direct esterification reaction of fatty acid acyl chlorides (fatty acid chlorides); And the acid catalysis direct esterification reaction of using the fatty acid mixed acid anhydride.At Gedon, S.; Fengl, R.: " Cellulose Esters, " Kirk-Othmer Encyclopedia Of Chemical Technology, the 4th edition, the 5th volume, John Wiley ﹠amp; Sons, New York, in 1993, the 496-529 pages or leaves more detailed description be used to prepare the method and the program of cellulose esters chemical compound.

The cellulose esters examples for compounds comprises cellulose caproate, cellulose pelargonate, the lauric acid cellulose, the Palmic acid cellulose, cellulose stearate, mountain Yu acid cellulose, the 2 Ethylbutanoic acid cellulose, the 2 ethyl hexanoic acid cellulose, the isopropylformic acid. cellulose, isovaleric acid cellulose (celluloseiso-pentanoate), different cellulose pelargonate, the isodecyl acid cellulose, the isostearic acid cellulose, trimethylace tonitric cellulose (neopentanoic acid cellulose), new enanthic acid cellulose, the neodecanoic acid cellulose, new hendecanoic acid cellulose, new dodecylic acid cellulose, new cellulose stearate, oleic acid cellulose (vaccenic acid acid cellulose), linoleic acid cellulose (octadecadienoic acid cellulose), linolenic acid cellulose (jeceric acid cellulose); The acetic acid cellulose caproate, the acetic acid cellulose pelargonate, the acetate+lauric acid cellulose, acetic acid Palmic acid cellulose, the acetic acid cellulose stearate, acetic acid mountain Yu acid cellulose, acetic acid 2 Ethylbutanoic acid cellulose, acetic acid 2 ethyl hexanoic acid cellulose, acetic acid isopropylformic acid. cellulose, acetic acid isovaleric acid cellulose (cellulose acetate iso-pentanoate), the different cellulose pelargonate of acetic acid, acetic acid isodecyl acid cellulose, acetic acid isostearic acid cellulose, acetic acid trimethylace tonitric cellulose (acetic acid neopentanoic acid cellulose), the new enanthic acid cellulose of acetic acid, acetic acid neodecanoic acid cellulose, the new hendecanoic acid cellulose of acetic acid, the new dodecylic acid cellulose of acetic acid, the new cellulose stearate of acetic acid, acetic acid oil acid cellulose (acetic acid vaccenic acid acid cellulose), acetic acid linoleic acid cellulose (acetic acid octadecadienoic acid cellulose), acetic acid linolenic acid cellulose (acetic acid jeceric acid cellulose), the propanoic acid cellulose caproate, the propanoic acid cellulose pelargonate, propanoic acid lauric acid cellulose, propanoic acid Palmic acid cellulose, the propanoic acid cellulose stearate, propanoic acid mountain Yu acid cellulose, propanoic acid 2 Ethylbutanoic acid cellulose, propanoic acid 2 ethyl hexanoic acid cellulose, propanoic acid isopropylformic acid. cellulose, isoamyl propionate cellulose (cellulose propionate iso-pentanoate), the different cellulose pelargonate of propanoic acid, propanoic acid isodecyl acid cellulose, propanoic acid isostearic acid cellulose, propanoic acid trimethylace tonitric cellulose (propanoic acid neopentanoic acid cellulose), the new enanthic acid cellulose of propanoic acid, propanoic acid neodecanoic acid cellulose, the new hendecanoic acid cellulose of propanoic acid, the new dodecylic acid cellulose of propanoic acid, the new cellulose stearate of propanoic acid, propanoic acid oleic acid cellulose (propanoic acid vaccenic acid acid cellulose), propanoic acid linoleic acid cellulose (propanoic acid octadecadienoic acid cellulose), propanoic acid linolenic acid cellulose (propanoic acid jeceric acid cellulose); The butanoic acid cellulose caproate, the butanoic acid cellulose pelargonate, butanoic acid lauric acid cellulose, butanoic acid Palmic acid cellulose, the butanoic acid cellulose stearate, butanoic acid mountain Yu acid cellulose, butanoic acid 2 Ethylbutanoic acid cellulose, butanoic acid 2 ethyl hexanoic acid cellulose, butanoic acid isopropylformic acid. cellulose, butanoic acid isovaleric acid cellulose (cellulosebutyrate iso-pentanoate), the different cellulose pelargonate of butanoic acid, butanoic acid isodecyl acid cellulose, butanoic acid isostearic acid cellulose, butanoic acid trimethylace tonitric cellulose (butanoic acid neopentanoic acid cellulose), the new enanthic acid cellulose of butanoic acid, butanoic acid neodecanoic acid cellulose, the new hendecanoic acid cellulose of butanoic acid, the new dodecylic acid cellulose of butanoic acid, the new cellulose stearate of butanoic acid, butanoic acid oleic acid cellulose (butanoic acid vaccenic acid acid cellulose), butanoic acid linoleic acid cellulose (butanoic acid octadecadienoic acid cellulose), butanoic acid linolenic acid cellulose (butanoic acid jeceric acid cellulose); Acetic acid propanoic acid cellulose caproate, acetic acid propanoic acid cellulose pelargonate, acetic acid propanoic acid lauric acid cellulose, acetic acid propanoic acid Palmic acid cellulose, acetic acid propanoic acid cellulose stearate, acetic acid propanoic acid mountain Yu acid cellulose, acetic acid propanoic acid 2 Ethylbutanoic acid cellulose, acetic acid propanoic acid 2 ethyl hexanoic acid cellulose, acetic acid propanoic acid isopropylformic acid. cellulose, acetic acid isoamyl propionate cellulose (cellulose acetate propionate iso-pentanoate), the different cellulose pelargonate of acetic acid propanoic acid, acetic acid propanoic acid isodecyl acid cellulose, acetic acid propanoic acid isostearic acid cellulose, acetic acid propanoic acid trimethylace tonitric cellulose (acetic acid propanoic acid neopentanoic acid cellulose), the new enanthic acid cellulose of acetic acid propanoic acid, acetic acid propanoic acid neodecanoic acid cellulose, the new hendecanoic acid cellulose of acetic acid propanoic acid, the new dodecylic acid cellulose of acetic acid propanoic acid, the new cellulose stearate of acetic acid propanoic acid, acetic acid propanoic acid oleic acid cellulose (acetic acid propanoic acid vaccenic acid acid cellulose), acetic acid propanoic acid linoleic acid cellulose (acetic acid propanoic acid octadecadienoic acid cellulose), acetic acid propanoic acid linolenic acid cellulose (acetic acid propanoic acid jeceric acid cellulose); Acetic acid butanoic acid cellulose caproate, acetic acid butanoic acid cellulose pelargonate, acetic acid butanoic acid lauric acid cellulose, acetic acid butanoic acid Palmic acid cellulose, acetic acid butanoic acid cellulose stearate, acetic acid butanoic acid mountain Yu acid cellulose, acetic acid butanoic acid 2 Ethylbutanoic acid cellulose, acetic acid butanoic acid 2 ethyl hexanoic acid cellulose, acetic acid butanoic acid isopropylformic acid. cellulose, acetic acid butanoic acid isovaleric acid cellulose (cellulose acetatebutyrate iso-pentanoate), the different cellulose pelargonate of acetic acid butanoic acid, acetic acid butanoic acid isodecyl acid cellulose, acetic acid butanoic acid isostearic acid cellulose, acetic acid butanoic acid trimethylace tonitric cellulose (acetic acid butanoic acid neopentanoic acid cellulose), the new enanthic acid cellulose of acetic acid butanoic acid, acetic acid butanoic acid neodecanoic acid cellulose, the new hendecanoic acid cellulose of acetic acid butanoic acid, the new dodecylic acid cellulose of acetic acid butanoic acid, the new cellulose stearate of acetic acid butanoic acid, acetic acid butanoic acid oleic acid cellulose (acetic acid butanoic acid vaccenic acid acid cellulose), acetic acid butanoic acid linoleic acid cellulose (acetic acid butanoic acid octadecadienoic acid cellulose), acetic acid butanoic acid linolenic acid cellulose (acetic acid butanoic acid jeceric acid cellulose) or the like.Also comprise except that with also using the deutero-cellulose esters chemical compound of other parts (for example, carboxymethyl cellulose and acetic acid butanoic acid carboxymethyl cellulose, Cellacefate, hydroxypropyl cellulose etc.) the ester moiety.

Term " ester group " or " ester moiety " that the application is used to describe the group of the free hydroxyl group on the substituted cellulose chemical compound in the whole text should comprise any group or the part with structure-O (C=O)-R, wherein are not that two keys are bonded on the carbon of dewatered grape saccharide residue that oxygen on the carbon is bonded to cellulosic cpd.R can be the organic group of any kind of any size, comprises saturated or undersaturated, branched-chain or straight-chain alkyl or cyclic group, or its combination.R may further include aryl and contains replacement or other structure of any other type of the atom outside de-carbon and the hydrogen.The common example of this type of atom comprises nitrogen, oxygen, aluminum, silicon and sulfur.Therefore, only as an example, R can comprise one or more esters, ether, thioesters, thioether (sulfide), hydroxyl, phosphate ester, carbonic ester, amine, imines, amide, nitrate, nitrile, urethane (carbamate), urea, thiourea, silane, sulfuric ester, sulfonic acid, azoles, phenol, pyridine or pyrimidine part or key, or the combination in any of aforementioned part.

The used in the whole text term " lipophilic solvent " of the application is meant that the dissolubility in water is in " slightly soluble " scope or lower solvent.(one of ordinary skill in the art will appreciate that for the chemical compound of " being slightly soluble in water ", the required water yield of dissolving 1 this chemical compound of gram should be in 30 milliliters to 100 milliliters scope.The chemical compound that dissolubility in water is lower than " slightly soluble " (i.e. " slightly molten ", " atomic molten " or " almost insoluble ") needs the water of more volume to dissolve this chemical compound.

The example of suitable lipophilic solvent comprises hydro carbons, Arrcostab, fat and oil, fatty acid, aliphatic alcohol and silicone oil.The example of hydro carbons comprises isoparaffin, hydrogenation poly-(isobutene .), Fancol ID, Isoeicosane, 2-Methylpentadecane, isopentane, microwax, mineral oil, rosin, paraffin, vaseline, zamene, polyethylene, native paraffin, as Brazil wax and candelilla wax, CTFA InternationalCosmetic Ingredient Handbook, 2004 the 10th edition, listed hydro carbons in the 2136th and 2137 page, and any two or more mixture in the above-mentioned solvent.The example of suitable Arrcostab is that cellulose esters of the present invention dissolves in wherein those, and preferably wherein moieties has at least eight carbon atoms.They comprise alkyl acetate, mountain Yu acid alkyl ester, lactic acid alkyl ester, benzoic acid alkyl ester, alkyl salicylate, representative fatty acids Arrcostab, as stearic acid Arrcostab, Palmic acid Arrcostab, myristic acid Arrcostab and lauric acid Arrcostab, and composition thereof.The example of fat and oil is further defined as the glyceride (triglyceride) of fatty acid, also comprises the synthetic ester of glycerol and fatty acid.Example comprises soybean oil, Semen Maydis oil, Oleum Brassicae campestris, olive oil, sunflower oil, triolein, tristearin, caprylic/capric triglyceride and composition thereof.The example of fatty acid comprises valeric acid, enanthic acid, sad, lauric acid, myristic acid and Palmic acid, mountain Yu acid, capric acid, caproic acid, coconut oil, oleic acid, linoleic acid, Palmic acid, different Palmic acid, stearic acid, isostearic acid and composition thereof.The example of suitable aliphatic alcohol comprises side chain and straight chain C ₉-C ₃₀Alcohol.These comprise for example lauryl alcohol, different lauryl alcohol, spermol, different spermol, stearyl alcohol, isooctadecanol, octyldodecanol, octyl group tetradecanol, dodecyl hexadecanol, cetyl EICOSANOL and composition thereof.The example of suitable silicone oil comprises those compatible with the oil base solution of cellulose esters, comprise straight chain with cyclic volatility and non-volatile silicone oil.Example comprises polydimethylsiloxane, cetyl polymethyl siloxane (methicone), Stearyl dimethicone, cyclopolymethyl siloxane, ring penta siloxanes, phenyl trimethyl polysiloxanes (trimethicone) and composition thereof.

" reference solvent " or " reference lipophilic solvent " that the application is used in the whole text should refer to Fancol ID, CAS No.31807-55-3.

The average of the free hydroxyl group that is replaced by ester moiety of the used in the whole text term " replacement degree " of the application, every anhydroglucose ring that " DS " and " DS/AGU " is meant cellulosic cpd separately.Theoretical maximum DS is 3, because this is the free hydroxyl group number on every anhydroglucose ring on substituted cellulose not.DS can be by proton N MR at the dimethyl sulfoxine-d that contains several trifluoroacetic acids [TFA] ₆[(CD ₃) ₂SO; DMSO-d ₆], oxolane-d ₈[C ₄D ₈O; THF-d ₈], chloroform-d[CDCl ₃] or the middle mensuration of sym-tetrachloroethane-d (TCE-d) (or equivalent solvent).For example, use proton N MR, DS can pass through ¹H NMR is containing the dimethyl sulfoxine-d of several trifluoroacetic acids ₆[(CD ₃) ₂SO; DMSO-d ₆] or oxolane-d ₈[C ₄D ₈O; THF-d ₈] middle measure (so that any free hydroxyl group proton translocation (downfield)).The quantity (for example DS of new heptanoate) that can use " replacement degree " and synonym thereof to describe to replace with specific single part, with the quantity (DS that for example has all esters of branching saturated alkyl chain) or the replacement sum on the cellulose esters chemical compound (i.e. " DS always ") of a plurality of parts replacements.

When measuring total DS of ester, by necessary reprogramming so that NMR result does not comprise the minimizing possibility of residual reactants molal quantity as the part of ester molal quantity.For example, when carrying out esterification with carboxylic acid, correction program is so that deduct the free acid molal quantity from the total acid mole value that comprises free acid and ester value.In this program, the cellulose esters compound sample is dried to do not contain solvent and water substantially.20 milligrams of cellulose esters compound dissolutions also under agitation are heated to up to 80 ℃ with the dissolving cellulos ester in about 1 milliliter of TCE-d where necessary.Make this solution be cooled to room temperature then and in this solution, add at least 0.1 milliliter of isocyanates tribromo-acetyl ester, stirred at least 5 minutes then.In a few hours of preparation, use conventional proton N MR parameter then but with the proton N MR spectrum (at 80 ℃) of 64 scanning test sample.Gained NMR data provide the peak of the free acid that exists and the peak of total acid (acid and ester combination).With these two kinds of peak integrations and the peak that from the total acid peak, deducts free acid so that the value of total esterification acid to be provided.Use this value to calculate DS.Use this method, the molal quantity (use hydroxyl peak) of the hydroxyl by more cellulosic reaction can obtain internal inspection, because derivation agent (derivatizing agent) is all reacted with cellulosic no esterification hydroxyl and no esterification acid.Calculate the hydroxyl molal quantity and divided by the value of skeleton molal quantity with the residual hydroxyl number that produces every anhydroglucose.3.00 deducting this hydroxyl value should produce and the identical esterification acid DS value of using other method to calculate.

Term " extent of polymerization " and " DP " and " DP that the application is used in the whole text _v" be meant the number of monomers in given polymer chain of using following method to calculate separately based on intrinsic viscosity (IV).IV at first uses can be available from Rheotek USA Inc., LaGrange, and the RPV-1 polymer viscosity meter of KY or any equivalent of the apparatus are measured.Rheotek appliance requires sample moisture content carries out its calculating.By the weight before and after relatively drier, the cellulose esters chemical compound is carried out humidity measurement.Placed at least 4 hours in 105 ℃ of stoves by digesting laminate samples, carry out drying 4.0 to 5.0.Sample was cooled off 1 hour in exsiccator (dessicator) before weighing again at least.Humidity percentage based on the weight change calculation sample.In order to calculate IV, with about 0.25 gram sample with 50 ml waters pack into container and on demand magnetic stir 1 to 5 minute to disperse and to use the water-wet sample.Then 50 milliliters of Copper hydrate ethylenediamines (Cuene) are assigned in the container under the nitrogen purging, and stirred at least 1 minute, then sample is added a cover immediately and stirred until sample and dissolve fully.Use 25.0 ℃ of constant temperature mineral oil bath specimen to measure flowing time with the Rheotek viscometer.Software by Rheotek provides uses based on two average flow Time Calculation IV that duplicate experiment the most approaching.The average flow time of each sample of Rheotek instrument test, related software calculates IV on PC.Also can use exact method with aforementioned equivalence.

In case know IV, calculate DP by following formula _vOr extent of polymerization value:

$\stackrel{\‾}{{\mathrm{DP}}_v}=\left(1.65\right)\left({\left[\mathrm{\η}\right]}^{\frac{1}{0.9}}\right)$

Wherein η is to be the IV that records of unit representation with the deciliter/gram by the Rheotek instrument, but it changes into milliliter/gram to be suitable for given formula.

Unless specifically indicate in addition, the used in the whole text word of the application " comprises " and other form (for example " comprising ") of this speech be meant that this list or explanation only provide example rather than restricted or limit when being used to describe the list of item category or illustrating.

Used in the whole text " room temperature and the normal pressure " of the application is meant 25 ℃ temperature and 1 atmospheric pressure.The cellulose esters chemical compound

Cellulose esters chemical compound of the present invention is useful, because they can be dissolved in the lipophilic solvent with favourable high concentration.By point out that whether the cellulose esters chemical compound is dissolved in the Fancol ID reference solvent with specified wt concentration under room temperature and normal pressure this character is described herein.Therefore, in some embodiments, the cellulose esters chemical compound is dissolved in the Fancol ID with the concentration of at least 5 weight % under room temperature and normal pressure.In some embodiments, the cellulose esters chemical compound is dissolved in the Fancol ID with the concentration of at least 10 weight % under room temperature and normal pressure.In some embodiments, the cellulose esters chemical compound is dissolved in the Fancol ID with the concentration of at least 15 weight % under room temperature and normal pressure.In some embodiments, cellulose esters chemical compound concentration with at least 20 weight % under room temperature and normal pressure is dissolved in the Fancol ID, or the like.Thus, can following description embodiment, wherein the cellulose esters chemical compound with higher concentration, is dissolved in the Fancol ID as at least 25 weight %, 30 weight %, 35 weight %, 40 weight %, 45 weight % or 50 weight % under room temperature and normal pressure at least at least at least at least at least.The application in the whole text in, " weight concentration " is meant that cellulose esters chemical compound weight multiply by 100% again divided by whole sample (chemical compound, solvent and any other component) gross weight.

Have been found that, the hydroxyl that use is carried out for the ester moiety that has 6 carbon atoms (comprising the carbon as the part of ester group) with one or more at least replaces and has 2.5 or the cellulose of higher total DS, the cellulose esters chemical compound that can obtain to have excellent solubility character.In some embodiments, ester group has at least 7 carbon atoms, or at least 8 carbon atoms.Carboxylate on the cellulosic cpd can have same structure or two or more different structures fully.

But, the invention is not restricted to concrete DS scope.In some embodiments, total DS of cellulose esters chemical compound is 0.5 to 3.0.Conventionally test (routine testing) be can pass through and the best DS or the minimum DS of required dissolubility easily determined to realize, in this test, manufacturing has the cellulose esters chemical compound of different DS values simply, and tests the dissolubility of each DS value in the reference solvent.Thus, the cellulose esters chemical compound can be described to have the DS value that is higher than specified minimum, for example, following at least any value: 0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8 or 2.9.Perhaps, the cellulose esters chemical compound can be described to have the DS value in specified scope, for example, following at least any value: 0.5-0.6,0.6-0.7,0.7-0.8,0.8-0.9,0.9-1.0,1.0-1.1,1.1-1.2,1.2-1.3,1.3-1.4,1.41-1.5,1.5-1.6,1.6-1.7,1.7-1.8,1.8-1.9,1.9-2.0,2.0-2.1,2.1-2.2,2.2-2.3,2.3-2.4,2.4-2.5,2.5-2.6,2.6-2.7,2.7-2.8,2.8-2.9 or 2.9-3.0.Also can use more wide region in conjunction with above-mentioned any range, for example 0.5-1.0,1.0-1.5,1.0-2.0,1.5-2.0,2.0-3.0,2.0-2.5 or 2.5-3.0, or the scope such as 1.5-1.8,1.6-1.8,1.7-2.0,1.8-2.2,2.0-2.2,2.2-2.6,2.3-2.5,2.4-2.6,2.5-2.7,2.4-2.8.Above-mentioned DS value can be the DS to certain portions or part group separately, or total DS of cellulose esters chemical compound.

Find further that if the ester moiety on this compounds is branching and saturated, not branching and saturated or branching and undersaturated, then above-mentioned cellulose esters chemical compound has especially favourable dissolubility in lipophilic solvent.The example of branched esters part comprises: the ester that has tert-butyl group end (may also be referred to as the quaternary carbon end) on any chain (main chain or side chain); Ester with saturated isoalkyl is with or without further branching; With the ester that has at the alkyl structure of the last branching of α carbon (it is the carbon on the carbon that is bonded directly in the hydroxy-acid group).Some examples with ester moiety of the tert-butyl group comprise new heptanoate, neodecanoic acid ester, new hendecane acid esters, new dodecylate and new stearate.Cellulose esters chemical compound with mixed ester part (it is the residue with the esterification of eo-acid (neo-acid) mixture) also within the scope of the invention.The new base of C9-C28 (neo-based) derivant admixture that the example that contains this type of mixture of eo-acid comprises Neo 910 Acid (ExxonMobil Chemical), Neo 913 (ExxonMobilChemical) and can buy.Some examples with ester of saturated isoalkyl comprise tricaprylate, isodecyl acid esters, 3,5,5-tri-methyl hexanoic acid ester and isostearate.Some examples with ester of the alkyl structure of branching on α carbon comprise 2 methyl valeric acid ester (2-methylvalerate), the 2 methyl caproic acid ester, 2-methyloctanoic acid ester, 2-methyl decanoin, 2-methyl stearate, the 2 Ethylbutanoic acid ester, 2-ethyl valerate (2-ethylvalerate), 2-ethylhexanoate, 2-ethyl caprylate, 2-ethyl decanoin, the 2-ethyl stearate, 2,2-dimethyl butyrate acid esters, 2-ethyl-2-Methyl Butyric Acid ester, 2,2-diethyl butyrate, 2,2-dimethyl-penten acid esters (2,2-dimethylpentanoate), 2-ethyl-2 methyl valeric acid ester (2-ethyl-2 methyl valeric acid ester), 2,2-diethyl valerate (2,2-diethylpentanoate), 2,2-dimethyl alkyl caproate, 2,2-diethyl alkyl caproate, 2,2-dimethyl-octa acid esters, 2-ethyl-2,5-dimethyl alkyl caproate, 2,2-dimethyl-3-hydroxy propionate.Cellulose esters chemical compound with mixed ester part (it is the product with the esterification of branched acids mixture) also within the scope of the invention.Some examples with ester moiety of unsaturated alkyl comprise macene acid esters (myristoleate) (9-tetradecene acid esters), palmitic olefinic acid ester (palmitoleate) (palmitoleic acid ester), oleate (cis-9-vaccenic acid acid esters), elaidic acid ester (elaidic acid ester), Semen Sinapis acid esters (cis-13-docosenoic acid ester), linoleate (9,12-vaccenic acid acid esters), linolenate (9,12,15-jeceric acid ester) or the like.Have as also within the scope of the invention with the cellulose esters chemical compound of the mixed ester part of the residue of unsaturated acids mixture esterification.

The cellulose esters chemical compound also can relate to the esterification reaction product of the mixture of chemical compound, thereby produces the cellulose esters chemical compound with dissimilar ester moieties.This is used in by in several embodiments made from fatty acid esterification, because therefore many commercial fatty acid products also contain the mixture of other sour and possible chemical compound of difference from natural origin.For example, n-nonanoic acid is also referred to as pelargonic acid, is colourless to xanchromatic oil, and can for example pass through nonyl alcohol, nonyl aldehyde or oleic oxidation generation.Therefore, have the cellulose esters chemical compound of pelargonate part and can be for example contain the commodity (Aldrich for example of 96% n-nonanoic acid product and 4%2-methyloctanoic acid by use; Catalog#N29902) esterification is made, and may produce the cellulose esters product with two parts.Similarly, used many products of selling as the isostearic acid product are actually the commercial source (A﹠amp for example of the mixture that contains isomery C18 fatty acid in several derivants are synthetic; E Connock, Perfumery and Cosmetics, LTD).

It being understood that the structure that the present invention relates to the cellulose esters chemical compound, the method and the reactant that are used to prepare ester are all inessential to the present invention.Therefore, for example, when mentioning ester moiety as the residue of carboxylic esterification reaction or product, it is only as the method that makes things convenient for of describing this structure, and the invention is not restricted to by the actual chemical compound of making of the reaction that relates to carboxylic acid.With any chemical compound of this structrual description coupling all in the present invention, no matter be by (for example) and carboxylic acid reaction, with the acid chloride reaction, with anhydride reactant or alternate manner manufacturing.

In some embodiments, the DP of cellulose esters chemical compound _vScope help dissolubility in hydrophilic solvent.In some embodiments, DP _vLess than 4000.In some embodiments, DP _vLess than 3500.Also there is DP _vLess than 3000, less than 2500, less than 2000, less than 1500, less than 1000 or less than 500 embodiment.As for DS, the ideal range in this class embodiment can be determined by the normal experiment method.DP determines molecular weight certainly.Therefore, in some embodiments, cellulose esters chemical compound of the present invention has 20,000 to 8,000, the 000 daltonian weight average molecular weight (Mw) that records by the contrast of the gel permeation chromatography in THF polystyrene standards usually.

In some embodiments, cellulosic cpd of the present invention is the mixed ester chemical compound that also has other ester group on it except side chain or unsaturated group.The example of other ester group comprises acetas, propionic ester, butyrate and valerate.In relating to some embodiments of mixed ester, can obtain high-dissolvability, even the DS of side chain and/or beta-unsaturated esters part less than 2.5, for example at least 0.8, at least 1.0, at least 1.5 or at least 2.0.

Also have been found that in use to comprise in acetas part and another some embodiments, keep the DS of this another part to be lower than a certain threshold value and significantly improved dissolubility than the cellulose esters chemical compound of long-chain ester part.In some embodiments, the cellulose esters chemical compound has the acetyl group replacement degree less than 1.0.In some embodiments, acetyl group replaces degree less than 0.5.Also exist acetyl group DS less than 0.8, less than 0.6, less than 0.4, less than 0.3 or less than 0.2 embodiment.

It being understood that above-mentioned value is available in some embodiments example, the present invention includes and have any train value of going up (for example, for DP _v, DS, other ester is the DS of acetyl base class for example) and their the cellulose esters chemical compound of any combination, as long as they realize required dissolubility under reference solvent and normal pressure and room temperature.For given cellulose esters chemical compound, ideal parameters is determined by normal experiment easily, for example by changing DP _vWith DS and determine to make the dissolubility that reaches optimum separately.

The cellulose compound compositions

Compositions of the present invention contains one or more cellulose esters chemical compounds of the present invention and one or more lipophilic solvent, and wherein at least some cellulose esters compound dissolutions are in solvent.In some embodiments, the cellulose esters chemical compound dissolves being equal to or higher than under the specific concentrations under room temperature and the normal pressure.Example is included in dissolved cellulose esters chemical compound under following at least any percentage ratio (by weight) concentration: 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%.Can make solution by any effective means.In some embodiments, under stirring or other stirring, component is heated to proper temperature.In many cases, this can realize by being heated to up to 90 ℃, but according to chemical compound and related purposes, higher temperature can be necessary or useful.

Said composition can be used in the oil base cosmetics or as the part of oil phase in the emulsion used among cosmetics or the personal care product.Said composition can contain any other suitable component.The example that is useful in the composition among the personal care product comprises, for example, abluent, emollient, wetting agent, pigment, comprise pearlescent pigment, colorant, spice, antimicrobial, antiseptic, antioxidant, antiperspirant, oral cavity nursing agent, exfoliator, hormone, enzyme, medical compound, vitamin, UV absorbent, dihydroxy acetone, Porcelana Skin Bleaching Agent Porcelana, anti-pox agent, plant extract, silicone oil, organic oils, wax, viscosifier, plasticizer, film former comprises hairspray, thickening agent, filler and binding agent, pure and mild other organic solvent, and propellant.The compositions that comprises emulsion can comprise oil-in-water emulsion, water-in-oil emulsion and heterogeneous emulsion, for example Water-In-Oil bag oil and W/O/W emulsion.This type of emulsion can contain emulsifying agent or surfactant, thus for example make one or more oil phases with one or more waters so that one another mixes for the mode that is suspended in the discontinuous phase in the continuous phase with micelle form when consecutive identical mutually.In this type of emulsion, oil phase can contain the cellulose esters chemical compound, and is optional with other composition, and water or contain water and can choose wantonly and contain other composition.In some skin nursing products, for example contain the water chemical compound and can comprise wetting agent, as glycols, saccharide and analog.The example of suitable glycol comprises propylene glycol, Polyethylene Glycol, polypropylene glycol and glycerol.The example of sugar comprises glucose, fructose, inositol and sucrose.Other water soluble ingredient comprises gellant, as water solublity or water-swellable natural gum, with water-soluble polymer, comprises the polymer of acrylic acid and ester thereof.

Although above discussed available compositions in personal nursing and the cosmetics, the invention is not restricted to this based composition and purposes.Other compositions within the scope of the present invention and the example of purposes comprise: the compositions that can be used as polymeric additive (nucleation, clarification, impact-resistant modified, or the like); Binding agent; Paint vehicle and other coating; Printing ink; Lubricant; Electronic device; Display; Polarizing coating; Compensate film; Immobilization compositions (being included in the compositions that is used for fixing microorganism and enzyme in the bioreactor); The inner plastifying moulded products of rheology modifiers or thickening agent; The transdermal delivery of food, edible oil or food base food, material; The film of various uses.

The purposes of compositions

Any purposes of compositions of the present invention all within the scope of the present invention.An example is the personal care product.The example of this series products comprises deodorizer, antiperspirant, deodorization hidroschesis combination agent, product shaves, skin lotion (skin lotion), wetting agent, toner, the shower product, cleaning products, hair care product, shampoo, hair conditioner, mousse, the typing gel, the eruption setting agent, hair dye, the hair-dyeing product, float and send out agent (hair bleach), the curly hair product, hair straighten, fingernail maintenance product, nial polish, nail polish remover, the armor frost, the fingernail washing liquid, keratolytic, protection cream, sunscreen product, anthelmintic, aging products, color make-up, lip pomade, foundation cream, face powder, the informer, eye shadow, kermes, color cosmetic (makeup), mascara, the personal care formulations that adds cellulose components as usual, and the drug delivery system that is used for to be administered to the local application of the pharmaceutical composition on the skin.As mentioned above, this type of purposes is unrestricted, and any purposes all within the scope of the invention.

By the more detailed illustration the present invention of following specific embodiment.It being understood that these embodiment are exemplary, and be not restriction of the present invention but in the scope of claims and content, broadly explain.Unless indicate separately, all umbers among the embodiment and percentage ratio are all by weight.

Embodiment

Comparative Examples 1

Prepare the acetic acid cellulose pelargonate by pyridine-acid chloride method (being similar to people such as C.J.Malm, Industrial andEngineering Chemistry, volume 43, the 684-688 pages or leaves, the method for describing in 1951) by cellulose acetate.

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser/distillation column and be placed in 1 liter of three neck round-bottomed flask in the silicone oil bath: 500 milliliters of N-Methyl pyrrolidone (pyrrolidinone)-(C ₅H ₉NO), (NMP); 17 milliliters of pyridine-(C ₅H ₅N); The cellulose acetate of 30 gram oven dry; this cellulose acetate has the acetyl content of 31.0 to 33.0 weight %; the intrinsic viscosity of about 0.88dL/g and about 47, the 500 daltonian weight average molecular weight (M that in N-Methyl pyrrolidone, record in pyridine by size exclusion chromatography (SEC) _w).To be similar to Gedon, S.; Fengl, R. " Cellulose Esters, " Kirk-Othmer Encyclopedia of ChemicalTechnology, the 4th edition, volume 5, John Wiley ﹠amp; Sons, New York, the mode described in 1993, the 496-529 pages or leaves prepares cellulose acetate.At room temperature stirring this mixture dissolves up to cellulose acetate.Process dropwise added 27 milliliter of 96% pelargonyl group chlorine (C in about 30 minutes in this mixture of clockwise under continuing stirring ₉H ₁₇ClO) (Aldrich; Catalog No.156833).Subsequently whole mixture is warming up to 90-91 ℃, and under this temperature, stirred 24 hours.Adding 35 ml deionized water subsequently in reactant mixture decomposes to guarantee any residual pelargonyl group chlorine.Make gained cellulose esters product precipitation by reactant mixture being admixed methanol.Changing methanol for several times behind the solvent with the eccysis product, in filter bag and whole night with deionized water wash with transferred product.With product in vacuum drying oven under nitrogen purging, 50 ℃ dry 24 hours down, and under 80 ℃ dry 24 hours again.Analyze the gained dry products by NMR, find that it contains 1.7 DS acetyl group and 1.5 DS pelargonyl group.The gel permeation chromatography that employing is used in oxolane, the contrast polystyrene standards is measured weight average molecular weight (M _w) be 1.09 * 10 ⁵Dalton.

Solubility test:In order to be determined at the dissolubility in all kinds of solvents, prepare to contain the independent bottle (" carrying capacity " is meant the amount that produces 1% or 8% solution when respectively being placed in dissolving in given bottle) of 1% carrying capacity or 8% carrying capacity polymer.Subsequently, the range estimation bottle is to determine that whether polymer is as not existing the dissolving shown in any visible solid in the solvent.When observing solid, with solvent heating and stirring so that the solvability maximization.If observe visible solid during heating, to giving concentration, it is soluble that polymer is considered to.This product dissolves in acetone, and at 2-Methylpentadecane (Creasil IH ^TM) in or at Fancol ID (Creasil ID ^TM) at 1% or 8% time soluble (Creasil IH ^TMWith Creasil ID ^TMBe the trade name of Optima Specialty Chemical LLC).Detect dissolubility by solvent-laden independent bottle that the amount of each polymer is packed into.

Comparative Examples 2

Prepare the acetic acid cellulose pelargonate by pyridine-acid chloride method by cellulose acetate.

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser/distillation column and be placed in 1 liter of three neck round-bottomed flask in the silicone oil bath: 292 milliliters of N-Methyl pyrrolidone; 28 milliliters of pyridines; The cellulose acetate of 30 gram oven dry, about 20, the 000 daltonian weight average molecular weight (M that it has the acetyl content of 17.0 to 19.0 weight % and records by size exclusion chromatography (SEC) in N-Methyl pyrrolidone _w), the mode described in the Comparative Examples 1 prepares by being similar to above.At room temperature stirring this mixture dissolves up to cellulose acetate.After the cellulose esters dissolving, distill out 18 milliliters of solvents to guarantee from reaction, removing any residual water.Process dropwise added 73 milliliter of 96% pelargonyl group chlorine (C in about 30 minutes in this mixture of clockwise under continuing stirring ₉H ₁₇ClO) (Aldrich; Catalog No.156833).After adding pelargonyl group chlorine, mixture is warming up to 95 ℃, and under this temperature, stirred 24 hours.Adding deionized water (35 milliliters) subsequently in reactant mixture decomposes to guarantee any residual pelargonyl group chlorine.By reactant mixture being admixed 50/50 deionized water/carbinol mixture, make gained cellulose esters product precipitation.Changing methanol for several times behind the solvent with the eccysis product, with transferred product in filter bag, and whole night with deionized water wash.By said procedure product is dissolved in the acetone, precipitates and washing, make the granule precipitate thus.With product in vacuum drying oven under nitrogen purging, 50 ℃ dry 24 hours down, and under 80 ℃ dry 24 hours again.Analyze the gained dry products and find that it contains 0.7 DS acetyl group and 2.4 DS pelargonyl group by NMR.May be that the DS that always records is greater than 3.0 because this product may contain free acid impurity.In oxolane, pass through gel permeation chromatography measurement weight average molecular weight (M _w), and the contrast polystyrene standards finds that it is 6.5 * 10 ⁴Dalton.Some solvent is used the solubility test program of Comparative Examples 1.Product dissolves in acetone at 8% time, dissolves in toluene at 8% time, but is insoluble to 2-Methylpentadecane or Fancol ID at 1% or 8% time, forms swelling but undissolved solid.

Comparative Examples 3

Prepare acetic acid butanoic acid cellulose pelargonate by pyridine-acid chloride method by cellulose acetate-butyrate.

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser/distillation column and be placed in 1 liter of three neck round-bottomed flask in the silicone oil bath: 438 milliliters of N-Methyl pyrrolidone; 46 milliliters of pyridines; The cellulose acetate-butyrate (CAB) of 30 gram oven dry; it has the bytyry content of the acetyl content of about 4.01 weight %, about 28.37 weight % and the hydroxy radical content of about 1.30 weight %; and about 40, the 600 daltonian weight average molecular weight (M that in N-Methyl pyrrolidone, record by size exclusion chromatography (SEC) _w).To be similar to Gedon, S.; Fengl, R. " Cellulose Esters, " Kirk-Othmer Encyclopedia of Chemical Technology, the 4th edition, volume 5, John Wiley ﹠amp; Sons, New York, the mode described in 1993, the 496-529 pages or leaves prepares CAB.At room temperature stirring this mixture dissolves up to CAB.After the CAB dissolving, from reactant mixture, distill out 30 milliliters of solvents.Under continuing stirring, added 81 milliliter of 96% pelargonyl group chlorine (C in this mixture of clockwise through about 45 minutes ₉H ₁₇ClO) (Aldrich; Catalog No.156833).After adding pelargonyl group chlorine, whole mixture is warming up to 95 ℃, and under this temperature, stirred 24 hours.Adding 35 ml deionized water then in reactant mixture decomposes to guarantee any residual pelargonyl group chlorine.Product is the gel piece in the reaction flask, and precipitates by adding in 50/50 deionized water/carbinol mixture, forms the soft precipitation thing this moment, and it can form piece when leaving standstill again in precipitation liquid.In triplicate dissolving, precipitation with after washing cycle, product forms the solids precipitation thing.Changing methanol for several times behind the solvent with the eccysis product, with transferred product in filter bag, and whole night with deionized water wash.Product is following dry 24 hours at 50 ℃ under nitrogen purging in vacuum drying oven.Because from the interference of bytyry signal, the gained dry products is difficult to analyze by NMR in the pelargonyl group scope.In oxolane, pass through gel permeation chromatography measurement weight average molecular weight (M _w), and the contrast polystyrene standards finds that it is 1.4 * 10 ⁵Dalton.Some solvent is used the solubility test program of Comparative Examples 1.Product even dissolve in acetone at 8% time, even dissolve in toluene at 8% time, and be insoluble to 2-Methylpentadecane or Fancol ID at 1% or 8% time.

Comparative Examples 4

Prepare the acetate+lauric acid cellulose by pyridine-acid chloride method by cellulose acetate.

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser/distillation column and be placed in 1 liter of three neck round-bottomed flask in the silicone oil bath: the cellulose acetate of 324 milliliters of pyridines and 30 gram oven dry; this cellulose acetate has the acetyl content of 31.0 to 33.0 weight %, intrinsic viscosity in pyridine and about 47, the 500 daltonian weight average molecular weight (M of about 0.88dL/g _w).At room temperature stirring this mixture dissolves up to cellulose acetate.After this cellulose acetate dissolving, from reactant mixture, distill out 20 milliliters of solvents.Process dropwise added 43 milliliter 98% lauroyl chloride (C in about 30 minutes in this mixture of clockwise under continuing stirring ₁₂H ₂₃ClO) (Aldrich; Catalog No.156930).After adding lauroyl chloride, whole mixture is warming up to 90-91 ℃, and under this temperature, stirred 24 hours.Adding 25 ml deionized water subsequently in reactant mixture decomposes to guarantee any residual lauroyl chloride.Make gained cellulose esters product precipitation by when stirring, this reactant mixture being added deionized water, and changing methanol for several times behind the solvent with the eccysis product, with transferred product in filter bag, and whole night with deionized water wash.Product is following dry 24 hours at 80 ℃ under nitrogen purging in vacuum drying oven.Analyze products obtained therefrom and find that it contains 1.92 DS acetyl group and 1.42 DS laurate by NMR.May be because this product may contain free acid impurity, the DS that always records is greater than 3.0.In oxolane, pass through gel permeation chromatography measurement weight average molecular weight (M _w), and the contrast polystyrene standards finds that it is 9.2 * 10 ⁴Dalton.Some solvent is used the solubility test program of Comparative Examples 1.Product dissolves in acetone, dichloromethane and n-propyl acetate at 1 and 8% time, is partially soluble in toluene, and is insoluble to 2-Methylpentadecane or Fancol ID, acetic acid or isopropyl alcohol at 1% or 8% time.

Comparative Examples 5

Prepare acetic acid Palmic acid cellulose by pyridine-acid chloride method by cellulose acetate.

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser/distillation column and be placed in 1 liter of three neck round-bottomed flask in the silicone oil bath: 307 milliliters of pyridines; 21 milliliters of N-Methyl pyrrolidone; Cellulose acetate with 30 gram oven dry; it has the acetyl content of 31.0 to 33.0 weight %, the intrinsic viscosity in pyridine of about 0.88dL/g and about 47, the 500 daltonian weight average molecular weight (M that record by the size exclusion chromatography (SEC) in N-Methyl pyrrolidone _w).At room temperature stirring this mixture dissolves up to cellulose acetate.After the cellulose acetate dissolving, from reactant mixture, distill out 31 milliliters of solvents.Process added 56 milliliter 98% Hexadecanoyl chloride (C in about 30 minutes in this mixture of clockwise under continuing stirring ₁₆H ₃₁ClO) (Aldrich; Catalog No.P78).After adding Hexadecanoyl chloride, whole mixture is warming up to 95 ℃ and stirred 24 hours under this temperature.Adding deionized water (25 milliliters) subsequently in reactant mixture decomposes to guarantee any residual Hexadecanoyl chloride.Make gained cellulose esters product precipitation in the deionized water by this reactant mixture is admixed, and from acetone soln redeposition.In methanol wash for several times behind the solvent with the eccysis product, with transferred product in filter bag, and whole night with deionized water wash.With product usefulness methanol Soxhlet (Soxhlet) extraction 12 hours, and following dry 24 hours at 80 ℃ under nitrogen purging in vacuum drying oven.In oxolane, pass through gel permeation chromatography measurement weight average molecular weight (M _w), and the contrast polystyrene standards finds that it is 1.10 * 10 ⁵Dalton.Some solvent is used the solubility test program of Comparative Examples 1.The product of present embodiment 1 and 8% time at 2-Methylpentadecane or Fancol ID, insoluble and only slight swelling in acetic acid or the isopropyl alcohol.

Comparative Examples 6

Adopt as at Morooka T., Norimot, M., Yamada, T., Jour.AppliedPolymer Science, 1984, trifluoroacetic anhydride described in 29,3981, stearic acid method prepare cellulose stearate by alpha-cellulose content greater than the soft wood pulp of 94 weight %.

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser/distillation column and be placed in 1 liter of three neck round-bottomed flask in the silicone oil bath: 78.4 milliliters of (117 gram) trifluoroacetic anhydride (Aldrich; Catalog No.106232) and 194 grams contain stearic compositions (J.T.Baker can obtain Catalog No.JT0340-07 by VWR International; TriplePressed; N.F.; It is believed that and contain two kinds of fatty acid and a kind of fatty acids that have than low carbon content of 8-10% at least) with higher carbon content.Stir this mixture down up to stearic acid dissolving and formation mixed acid anhydride solution at 50 ℃.Under agitation in this solution, add 10 gram wood pulp celluloses, and under lasting the stirring, reactant mixture is kept whole night down at 50 ℃.Add about 200 milliliters of toluene to dilute this mixture.Half of this diluted mixture thing is deposited in the methanol.

Sulphuric acid (0.1 gram) is added in second half mixture.This mixture was stirred about 3 hours down at 50 ℃.With four hydration magnesium acetate neutralisation of sulphuric acid.Subsequently this reactant mixture is deposited in the methanol.

Two parts of this experiment are all at first washed in methanol in deionized water then.Gel permeation chromatography by the contrast polystyrene standards records, from the weight average molecular weight (M of the product ester of two moieties _w) be about 3.5 * 10 ⁶Dalton.Some solvent is used the solubility test program of Comparative Examples 1.Product ester from two moieties all forms turbid gel at 1 and 8% time in Fancol ID, and all forms muddy dispersion at 1 and 8% time in 2-Methylpentadecane.

Embodiment 7

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser/distillation column and be placed in 1 liter of three neck round-bottomed flask in the silicone oil bath: 34.3 milliliters of (51 gram) trifluoroacetic anhydride (Aldrich; Catalog No.106232) and 93 grams contain stearic compositions (J.T.Baker can obtain Catalog No.JT0340-07 by VWR International; Triple Pressed; N.F.; It is believed that and contain two kinds of fatty acid and a kind of fatty acids that have than low carbon content of 8-10% at least with higher carbon content) stir down up to the stearic acid dissolving at 50 ℃, and form mixed acid anhydride solution.Under agitation add the cellulose acetate of 10 gram oven dry in this solution, it has the acetyl content of 17.0 to 19.0 weight % and about 20, the 000 daltonian weight average molecular weight (M that record by the size exclusion chromatography (SEC) in N-Methyl pyrrolidone _w).Continuous stirring remains on 50 ℃ with reactant mixture and descends and make its reaction 5 hours.By being deposited in the methanol (5X volume/volume) with separating obtained product.With sedimentary acetic acid cellulose stearate product methanol wash, use deionized water wash then, and then use methanol wash.Product is dry down at 35 ℃ under nitrogen purging in vacuum drying oven.This product has 2.3 DS stearate and 0.8 DS acetas, and all dissolves in 2-Methylpentadecane and Fancol ID at 1 and 8% time.May be because this product may contain free acid impurity, the DS that always records is greater than 3.0.In oxolane, pass through gel permeation chromatography measurement product weight average molecular weight (M _w), and the contrast polystyrene standards finds that it is 6.5 * 10 ⁴Dalton.

Embodiment 8

Use trifluoroacetic anhydride, the n-nonanoic acid method prepares cellulose pelargonate by wood pulp.

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser and be placed in 500 milliliters the three neck round-bottomed flasks in the silicone oil bath: 44 grams, 96% n-nonanoic acid (Aldrich; Catalog No.N29902; 4% of remnants are considered to the 2-methyloctanoic acid) and 49 gram trifluoroacetic anhydride (Aldrich; Catalog No.106232).This mixture is heated 1 hour down to form mixed acid anhydride at 50 ℃.Under agitation in this solution, add the soft wood pulp of 5 gram alpha-cellulose content greater than 95 weight %.Under lasting the stirring, reactant mixture is kept whole night down at 50 ℃.Then this reactant mixture is deposited in the methanol, at first in deionized water, in methanol, washs then.Then that product is dry down at 50 ℃ under vacuum.Gained cellulose pelargonate ester has 3.0 DS pelargonate, and dissolves in Fancol ID at 1% time, is insoluble to Fancol ID at 8% time; All be insoluble to 2-Methylpentadecane at 1 and 8% time.In oxolane, pass through gel permeation chromatography measurement product weight average molecular weight (M _w), and the contrast polystyrene standards finds that it is 6.3 * 10 ⁵Dalton.

Comparative Examples 9

Use trifluoroacetic anhydride n-nonanoic acid method to prepare the acetic acid cellulose pelargonate by cellulose acetate.

Following reagent added in the following order be furnished with mechanical agitator and water-cooled condenser and be placed in 500 milliliter of three neck round-bottomed flask in the silicone oil bath: 44 grams, 96% n-nonanoic acid (Aldrich; CatalogNo.N29902; 4% of remnants are considered to the 2-methyloctanoic acid) and 49 gram trifluoroacetic anhydride (Aldrich; Catalog No.106232).This mixture is heated 1 hour down to form mixed acid anhydride at 50 ℃.Under agitation in this solution, add 5 gram cellulose acetates, about 20, the 000 daltonian weight average molecular weight (M that it has the acetyl content of 17.0 to 19.0 weight % and records by size exclusion chromatography (SEC) in N-Methyl pyrrolidone _w), and under lasting the stirring, reactant mixture is kept whole night down at 50 ℃.Then this reactant mixture is deposited in the methanol, at first in deionized water, in methanol, washs then.With precipitation and the product washed at 50 ℃ of following vacuum dryings.Gained acetic acid cellulose pelargonate ester has 2.48 DS pelargonate and 0.6 DS acetas, and is insoluble to Fancol ID and 2-Methylpentadecane at 1 and 8% time.May be because this product may contain free acid impurity, the DS that always records is greater than 3.0.In oxolane, pass through gel permeation chromatography measurement product weight average molecular weight (M _w), and the contrast polystyrene standards finds that it is 3.9 * 10 ⁴Dalton.

Embodiment 10-23

Use the trifluoroacetic anhydride carboxyl acid method to prepare compositions of the present invention, comprise mixed ester by velveteen.

Use the amount of reagent shown in the following table 1, the preparation modified cellulose compound.500 milliliter of three neck round-bottomed flask is furnished with mechanical agitator and cold water cooling vacuum distilling apparatus and is placed in the silicone oil bath.In flask, add one or more carboxylic acids to each embodiment batch of material appropriate amount and type.When needs have the cellulosic cpd (for example acetic acid cellulose pelargonate) of the ester moiety of mixed type, add two types carboxylic acid of appropriate amount.After adding carboxylic acid, under agitation dropwise add trifluoroacetic anhydride (the TFAA) (Aldrich of specified amount; Catalog No.106232).In continuous stirring, keep 30 to 45 minutes to form mixed anhydride with mixture heated to 50 ℃ and under this temperature.The lint cellulose that adds specified amount in this solution is (from can be available from BuckeyeTechnologies, Inc. isolated high-purity dissolving grade cellulose in the commercial cotton boll, for raw cellulose, the average degree of polymerization that records by intrinsic viscosity is greater than 3900), and reactant mixture kept down finishing up to reaction in 3 to 4 hours at 50 to 52 ℃ under continuing to stir.In order to make level and smooth (smooth) solution, or if the gelling of product, reactant mixture is diluted to four times of its volume with oxolane or N-Methyl pyrrolidone.Under stirring rapidly, dropwise add the 50/50w/w ethanol/water mixture that is enough to decompose residual acid anhydride but is not enough to cause the sedimentary amount of cellulose esters product.Then solution is cooled to ambient temperature, produces the level and smooth mixture of viscosity that is known as " viscous solution (dope) ".In order to separate the modified cellulose compound product, this viscous solution is transferred in the separatory funnel.In a viscous solution, add solvent mixture (heptane: dichloromethane; 9: 1 (w/w)) and fully sneak in the viscous solution.Divide aliquot to add methanol then and mix until generation and be separated with viscous solution.Between each methanol adds, mixture is left standstill.Liquid phase is rich in discharge.Repeat that methanol adds and the interpolation that is separated up to fraction methanol begins to make the product precipitation.To be stirred to from the gained viscous solution of this extraction in the excessive methanol so that the product precipitation.By filtering with product and precipitation fluid separation applications, with methanol wash for several times, then under vacuum under slight nitrogen purge 50 ℃ of dryings whole night.Measure DS, molecular weight and the heat deflection (thermal transition) of gained cellulose esters by NMR, GPC and DSC respectively, and be presented in the table 2.In table 2, LCE is meant " long-chain ester " (being pelargonate, isostearate, stearate).

Table 1

Embodiment number	The esters type	Cellulose (gram)	TFAA (gram)	Carboxylic acid (gram)	Acetic acid (gram)
						10	Cellulose pelargonate	15	134	137	0
11	Cellulose pelargonate	15	134	137	0
						12	Cellulose pelargonate	15	134	137	0
13	The acetic acid cellulose pelargonate	14	125	104	6
						14	The acetic acid cellulose pelargonate	14	125	104	6
15	The acetic acid cellulose pelargonate	14	125	104	6
						16	The isostearic acid cellulose	15	134	200	0
17	The isostearic acid cellulose	20	179	267	0
						18	The isostearic acid cellulose	20	179	267	0
19	Acetic acid isostearic acid cellulose	20	179	231	8
						20	Cellulose stearate	10	97	162	0
21	Cellulose stearate	10	89	133	0
						22	Cellulose stearate	18	161	240	0
23	The acetic acid cellulose stearate	23	181	204	9

Table 2

^aWith respect to the polystyrene equivalent, the weight average molecular weight in oxolane

^bSample from 3 embodiment is carried out conjoint analysis

^cVb: the melting peak of non-constant width; B: wide melting peak

Table 3 described modified cellulose compound of the present invention (with the bonded cellulose pelargonate of the sample from embodiment 10-12 of equal quantities) mixed with the concentration of 1,2 and 4 weight % with specified used for cosmetic solvent and mixture.For each mixture, solvent and modified cellulose compound are weighed into bottle.Bottle is added a cover, and overturn whole night down at about 65 ℃.At room temperature place and observe this mixture after 1 to 3 months.

In table 3-8, following term and abbreviation have following meanings:

" cl hi-vis liq " is meant limpid high-viscous liquid

" cl med-vis liq " is meant limpid middle slime body

" cl lo-vis liq " is meant limpid thin fluid body

" muddiness " is meant muddiness but do not have solid.Be not meant solution or suspension although know muddiness, do not observe precipitation or solid.

" insoluble " is meant the solid of observing some types, for by solvent swell in various degree but do not absorb the particle of all solvents, or be not subjected to the particle of solvent effect.

" gel " is meant the formation (promptly not having solids or isolating liquid phase) of the even gel that does not move under gravity.Sample can be inverted, material did not move in a few hours.On the contrary, viscous pill is known from experience under action of gravity mobile, but extremely slow.

Use 1 to 5rad/sec shear rate mensuration viscosity, " low viscosity " is meant less than 500 centipoises; " medium viscosity " is meant 500 to 2000 centipoises; " high viscosity " is meant greater than 2000 centipoises.

Table 3

Table 4 described with modified cellulose compound of the present invention (merge equal quantities from the sample of embodiment 13-15 and the acetic acid cellulose pelargonate) mix with the concentration of 1,2 and 4 weight % with specified used for cosmetic solvent and must mixture.For each mixture, solvent and modified cellulose compound are weighed into bottle.Bottle is added a cover, and overturn whole night down at about 65 ℃.The acetic acid cellulose pelargonate has 2.6 DS pelargonate and 0.42 DS acetas.At room temperature place and observe this mixture at least after 1 month to maximum 3 months.

Table 4

^*The bottom gel layer

Table 5 described with modified cellulose compound of the present invention (by merge equal quantities from embodiment 16﹠amp; 17 sample and the isostearic acid cellulose made) mix with the concentration of 1,2 and 4 weight % with specified used for cosmetic solvent and mixture.For each mixture, solvent and modified cellulose compound are weighed into bottle.Bottle is added a cover, overturn whole night down at about 65 ℃.At room temperature place and observe this mixture after 1 to 3 months.

Table 5

^*The bottom gel layer

Table 6 described modified cellulose compound of the present invention (from the acetic acid isostearic acid cellulose sample of embodiment 19) mixed with the concentration of 1,2 and 4 weight % with specified used for cosmetic solvent and mixture.For each mixture, solvent and modified cellulose compound are weighed into bottle.Bottle is added a cover, and overturn whole night down at about 65 ℃.At room temperature place and observe this mixture after 1 to 3 months.

Table 6

Table 7 has been described modified cellulose compound of the present invention (cellulose stearate of making by the sample from embodiment 20-22 that merges equal quantities) has been mixed the mixture that gets with specified used for cosmetic solvent with the concentration of 1 and 4 weight %.For each mixture, solvent and modified cellulose compound are weighed into bottle.Bottle is added a cover, and overturn whole night down at about 65 ℃.At room temperature place and observe this mixture after 1 to 3 months.

Table 7

Table 8 described modified cellulose compound of the present invention (from the acetic acid cellulose stearate sample of embodiment 23) mixed with the concentration of 1,2 and 4 weight % with specified used for cosmetic solvent and mixture.For each mixture, solvent and modified cellulose compound are weighed into bottle.Bottle is added a cover, and overturn whole night down at about 65 ℃.At room temperature place and observe this mixture after 1 to 3 months.

Table 8

Comparative Examples 24

The preparation of isostearoyl chlorine:

Restrain from A﹠amp 80.1; E Connock, Perfumery and Cosmetics, the isostearic acid of LTD (complex mixtures of methyl branch and straight chain C 18 fatty acids) adding is furnished with in the round-bottomed flask of condensation type still head, mechanical agitator and thermostatic control oil bath.The initial temperature of this bath is about 25 ℃.Through 50 minutes, continuing in isostearic acid, dropwise to add thionyl chloride (39 grams, 0.33 mole) (REAGENTPLUS, Aldrich Catalog No.230464) under the stirring.At the about half way that adds, oil bath temperature rises to 35 ℃, will react restir 2 hours.Distillation column is applied vacuum (90mm Hg), oil bath temperature is risen to 50 ℃.Distill out unreacted thionyl chloride (4.5 gram) from product, produce 85 gram isostearoyl chlorine, it is used without further purification.

Trial prepares the cellulose acetate-butyrate sample with isostearoyl ester group according to the program described in the embodiment 1 of pct international patent application No.PCT/FR2004/001202 (publication number WO2005/013926).In batches be among the disclosed embodiment 1 of WO2005/013926 disclosed amount 25%.At room temperature reagent is added by following order and is furnished with mechanical agitator, is discharged into cold water cooler condenser in the drying tube that dead plaster is housed, is furnished with dried nitrogen feed pipe and is placed in 1000 milliliter of three neck round-bottomed flask in the silicone oil bath:

225 gram toluene (Burdick and Jackson--B﹠amp; J High Purity Solvent grade); With

225 gram butanones (Mallinckrodt-analytical-reagent grade).

Under stirring rapidly, slowly add 25 gram cellulose acetate-butyrates (Eastman ChemicalCompany CAB-553-0.4,46.43 weight % bytyries), and dissolved in 1 hour by under continuing to stir, being heated to 50 ℃.This mixture is cooled to room temperature and in this mixture, adds 5.0 gram triethylamines (REAGENTPLUS, Aldrich Catalog No.90340).Continuing under the stirring and doing under the blanket of nitrogen, flask is cooled in ice bath+5 ℃.When mixture reach+5 ℃ the time, through from charging hopper, dropwise adding the isostearoyl chlorine (being dissolved in 25 gram toluene and the 25 gram butanones) that 14.22 grams are as above made in 1 hour 30 minutes.In reinforced process, use handheld electronic thermometer measure temperature for several times.The maximum temperature that reaches in the reactant mixture is 7.1 ℃.Reactant mixture taken out from ice bath and recover room temperature (22 ℃), under continuing slowly to stir, kept 18 hours.The crystal that is considered to triethylamine hydrochloride makes the reactant mixture muddiness, but invisible on the flask side.

The gained mixture is passed through filter paper filtering then with medium sintered glass funnel.The partial reaction mixture is stirred to respectively in methanol, ethanol and the isopropyl alcohol.Do not form filtrable precipitate; But only form the yellow solution or the milky solution of the muddiness that does not have filtering precipitate.To remain reactant mixture and be stirred to methanol, 50/50, among the w/w, form milky solution, form the oily yellow liquid phase that contains the small amount of precipitate thing.The precipitate that reclaims it is found that it is the isostearic acid that is produced by the unreacted isostearoyl chlorine of water decomposition by in the precipitation process, does not therefore separate the cured polymer sample.Therefore, make and successfully to make the cellulosic expection solid sediment of acetic acid butanoic acid isostearic acid in this way.

Embodiment 24A

Prepare the cellulosic sample of acetic acid butanoic acid isostearic acid by the program described in the embodiment 1 of international patent application No.PCT/FR2004/001202 (publication number WO2005/013926), difference just product at heptane but not precipitate in the alcohol.Prepare two batches, in batches be separately among the disclosed embodiment 1 of WO2005/013926 disclosed amount 25%.At room temperature reagent is added by following order and is furnished with agitator, is discharged into cold water cooler condenser in the drying tube that dead plaster is housed, does nitrogen feed pipe and be placed in 1000 milliliter of three neck round-bottomed flask in the silicone oil bath:

Each flask 225 gram toluene--Burdick and Jackson--B﹠amp; J High PuritySolvent grade;

Each flask 225 gram butanone--Mallinckrodt-analytical-reagent grade.

Under stirring rapidly, in each flask, slowly add 25 gram cellulose acetate-butyrates (Eastman Chemical Company CAB-553-0.4,46.43 weight % bytyries), and dissolved in 1 hour by under continuing to stir, being heated to 50 ℃.This mixture is cooled to room temperature and in each flask, adds 7.5 gram triethylamines (REAGENTPLUS, Aldrich Catalog No.90340) (excess of triethylamine is to prevent the HCL degraded of product ester).Continuing under the stirring and doing under the blanket of nitrogen, flask is cooled in ice-water bath+5 ℃.

When mixture reach+5 ℃ the time, dropwise added the isostearoyl chlorine (being dissolved in 25 gram toluene and the 25 gram butanones) that 20.00 grams are as above made from charging hopper to each flask through about 1 hour 30 minutes.In reinforced process, use handheld electronic thermometer measure flask temperature for several times.The maximum temperature that reaches in the reactant mixture is 7.6 ℃.Reactant mixture is taken out and returns to room temperature (22 ℃) from ice bath, under lasting slowly stirring, kept 18 hours.The crystal that is considered to triethylamine hydrochloride makes the reactant mixture muddiness, but invisible on the flask side.

To merge from the gained mixture of two flasks, at first use medium sintered glass funnel to filter,, and in heptane, precipitate then by filter paper filtering.This mixture produces the white plates precipitate, and it is enough big and hard to leach from precipitated liquid.Precipitate is washed twice in heptane, under 55 ℃, be dried to constant weight under nitrogen and the vacuum.The precipitate that reclaims weighs 46.96 grams and has 0.17 isostearate DS by the NMR analysis of spectrum.This product have by gel permeation chromatography contrast polystyrene standards record 3.2 * 10 ⁴Daltonian weight average molecular weight.Product is insoluble to Fancol ID and 2-Methylpentadecane.

Embodiment 25-27

The research all kinds of solvents dissolves cellulose pelargonate (CN), acetic acid cellulose pelargonate (CAN) and isostearic acid cellulose (CIS) so which kind of to be measured with maximum concentration, and purpose is to make solution sprawl (drawdown) and dry with the generation thin film.Used CN is the mixture from the equal quantities product of embodiment 10-12.Used CAN is the mixture from the equal quantities product of embodiment 13-15.Used CIS is the mixture from the equal quantities product of embodiment 16 and 17.

Being tried solvent is methyl acetate, butyl acetate, positive methyl pyrrolidone, white spirits, Ketohexamethylene, isophorone, methanol and Aromatic 100 hydrocarbon fluids (ExxonMobil).The Aromatic100 hydrocarbon fluid it is found that the most suitable, and it dissolves all three kinds of modified cellulose compounds with 15 weight %.Other solvent can not be with the soluble modified cellulosic cpd of the concentration that is higher than 10 weight %.In Aromatic 100 fluids, make the solution of specified modified cellulose compound with 15 weight %.On metallic plate and Leneta drawing, sprawl solution.Thin film is at room temperature dry.The gained thin film is transparent, about 2 mils of average thickness.Pendulum by flex bar test and sense of touch evaluation and test method testing film is surveyed (Pendulum) hardness (ASTM D4366-87), figure health (Tukon) hardness (ASTMD1474), glossiness and flexible.The results are shown in the following table 9.Each result of the test is 3 meansigma methodss of measuring.

Table 9

	CN	CAN	CIS
				Pendulum hardness sec	42	62	8
Figure health hardness knoops	1.0	1.5	＜0.5
				Flex Bar test	By 1/8 inch not fracture	By 1/8 inch not fracture	By 1/8 inch not fracture
Flexible grading *	2	3	1
				Glossiness	80	83	83
Refractive index	1.473	1.472	1.476

^*The 1st, the most soft the most flexible, the 3rd, the hardest and least flexible.All three thin film have good gloss, and if desired, can give the personal care product with gloss.

Embodiment 28-31

In each the following example, use is dissolved in suitable cosmetics and prepares personal care product's (mascara) with the CN in the solvent, CAN or CIS.CN, CAN and CIS are and the described identical product mix of embodiment 25-27 above.Wax, stearic acid, ethylhexyl palmitate and the modified cellulose compound of specified amount are weighed into beaker and are heated to 80 ℃.When fusing, mix each composition to obtain homogeneous mixture.Radix Acaciae senegalis added in the entry and hydrolysis at room temperature whole night.Water/gum mixture under agitation is heated to 50 ℃, slowly adds hydroxyethyl-cellulose simultaneously, add triethanolamine then.Water is heated to 80 ℃; Slowly add wax phase in the blended while to aqueous phase then.This mixture is cooled to 40 ℃, and adds antiseptic.Continue to mix until blend.The results are shown in the following table 10.

Table 10

Composition	Example 28	Comparative Examples 29	Comparative Examples 30	Example 31
					Candelilla wax	4.9 gram	4.9 gram	4.9 gram	3.1 gram
Paraffin	4.3	4.3	4.3	2.7
					Cera Flava	9.2	9.2	9.2	5.8
Stearic acid	6.3	6.3	6.3	4.0
					Ethylhexyl palmitate	10.8	10.8	10.8	6.8
CN	5.4	-	-	-
					CAN	-	5.4	-	-
CIS	-	-	5.4	3.4
					Water	51.5	-	51.5	64.7
Radix Acaciae senegalis	3.7	-	3.7	4.6
					Hydroxyethyl-cellulose	1.0	-	1.0	1.3
Triethanolamine	2.6	-	2.6	3.3
					Antiseptic (Germabem II)	0.3	-	0.3	0.3

Use the embodiment of CN to have cream shape denseness.In the time of on using eyelash, it makes eyelashes root root clearly demarcated (separate and define).The preparation made from CAN is not finished as a comparison case, because CAN is insoluble to the wax phase composition of fusing.Use first embodiment of CIS to form solid, this is not suitable for use in mascara.Second preparation of CIS that use has the wax phase concentration of reduction has cream shape denseness.In the time of on using eyelash, it makes eyelashes root root clearly demarcated.The preparation of this embodiment also spreads and spreads on the skin.It is sprawled easily, feels smooth when spreading out, and stays waterproof membrane on skin.Such as known in the art, can in above-mentioned preparation, add pigment.

Embodiment 32

In the following example, use CIS (from the mixture of the equal quantities product of embodiment 16 and 17) to prepare personal care product's (lip pomade) in solvent in suitable cosmetics.Each composition is weighed into jar and is placed in 95 ℃ the stove.After all the components fusing, they are mixed to evenly.When mixture cools off, be poured into the lip pomade mould.Evaluate and test the gained lip pomade on the skin by using.Specified amount and composition are listed in the following table 11.

Table 11

Composition	Weight %
		Tissuemat E	30.8
CIS	4.7
		Fancol ID	46.1
Parleam	7.7
		Isooctadecanol	2.8
Phenyl trimethyl polysiloxanes	3.6
		C30-39 alkene/isopropyl maleate/MA copolymer	0.9
The pigment wax dispenser	3.2

This lip pomade has poor slip, but deposited colors well.A few minutes after spreading, its sensation is dry and not oily.Color is adhered to fine, can not wiped.

Embodiment 33-35

In the following example, the preparation hair fixing product.Topknot is available from International HairImporters ﹠amp; Products, Inc., Floram Park, NY has following specification: new burnt umber hair; Every bundle 2.2 gram hairs; 20 centimeter length.Before test, be suspended on all topknots on the nail-plate and cut to accurate 6-1/2 inch (26 unit markings on the nail-plate).By merging, moistening and removal excessive water, prepare topknot then.By solution or gel being got on the hair, 4%CN, CAN in each Fancol ID of equal quantities (0.2 gram) and CIS (from above to the described equal mixture of embodiment 25-27) solution or gel are applied on the topknots of great about 2.8 grams with finger.Combing topknot and make its air dried overnight after spreading solution or gel.After the drying, use curler topknot to be done to roll up and after handling 2 hours under the 90%RH, be suspended on the nail-plate.The curling length that compares topknot then.Compare with untreated topknot, the easier combing of the topknot that modified cellulose compound was handled has more gloss, and has better curling fixing under 90% relative humidity under 22 ℃.CN compares with CAN with CIS bigger gloss and better bed knife is provided.It is elastic fixing that CIS provides, and CN provides harder fixing.After spreading, topknot is washed with shampoo.Modified cellulose compound is difficult to wash off from hair.After the hair drying, can on hair, see residual modified cellulose compound as white macula.

Shown in the eccysis of difference, modified cellulose compound obviously has the good substantivity to hair (Substantivity) and therefore can be used as interim hair dye.Incorporate into hair dye in the solution of modified cellulose compound in Fancol ID and be applied on the hair.

In order to make the low VOC product that meets low VOC rule, use 2-Methylpentadecane to replace Fancol ID.Topknot needs to keep its greasy feeling after dry also a few hours at room temperature of more time.But heat treatment is for example handled with hair drier or curler, removes the 2-Methylpentadecane solvent rapidly, stays glossy surface, good property arranged and crimp retention.

Embodiment 36

Preparation has the sunscreen product of specified composition in the following table 12.CN is the admixture from the product of embodiment 10-12 of equal quantities.

Table 12

Composition	Weight %
		Benzoic acid C12-15 Arrcostab (Finsolv TN)	5.0
Ethylhexyl methoxy cinnamate	7.0
		Salicylic acid butyl monooctyl ester	2.0
Octocrilene (Octocrylene)	2.0
		Benzophenone-3	4.0
Butyl methoxydibenzoylmethane	2.0
		Cetearyl alcohol (with) the dicetyl phosphate ester (with) the ceteth-10 phosphate ester	2.0
Myristyl myristate	3.0
		Tristerin	1.0
Cellulose pelargonate	1.0
		Polyester-5	3.0
Water	68.0
		Triethanolamine	0.1

Oil-phase component and water-phase component mix down at 80 ℃ separately, merge then and mix 10 minutes with high shear mixer.Gained low viscosity emulsion has smooth sensation and stays waterproof membrane when being applied on the skin.

Embodiment 37﹠amp; 38

Preparation has the antiperspirant products of specified composition (weight %) in the following table 13.To also under agitation be heated to 85 ℃ except other outer composition of tetrachloro hydration glycine (tetrachlorohydrex-Gly) aluminum/zirconium (AAZG-7167, Summit ResearchLab) is weighed in the beaker.When mixture shows when even, add tetrachloro hydration glycine and also use the high speed dispersion device to disperse.Preparation was mixed 10 minutes down at 82 ℃, then cooling.When temperature reaches 60 ℃, this mixture is poured in hidroschesis rod (antiperspirant stick) container.After at room temperature placing whole night, evaluation and test hidroschesis rod.Both all form the White-opalescent rod.In the time of on being applied to skin, both all have smooth sensation.CIS is the admixture from the product of embodiment 16 and 17 of equal quantities.

Table 13

Composition	Embodiment 37	Comparative Examples 38
			Spermol	20.0	20.0
Encircle penta siloxanes	26.5	30.0
			Fancol ID	26.0	26.0
CIS	3.5	-
			Tetrachloro hydration aluminum glycinate/zirconium	24.0	24.0

Embodiment 37 is deposition rate Comparative Examples 38 more materials on skin according to observations.After drying, the CIS preparation provides more comfortable sensation on skin, does not have the tight sense of skin.When very firmly rubbing, embodiment 37 rolls from skin, show to stay thin film, and the sample that does not contain CIS does not have this effect.

Embodiment 39-42's is general open

Use the trifluoroacetic anhydride carboxyl acid method to prepare compositions of the present invention, comprise mixed ester by velveteen.

Prepare modified cellulose compound via the detailed procedure that provides below.In flask, add the suitable amount of each embodiment batch of material and one or more carboxylic acids of type.When needs have the cellulosic cpd (for example acetic acid cellulose pelargonate) of the ester moiety of mixed type, add two types carboxylic acid of appropriate amount.After forming solution, in assigned temperature downhill reaction mixture, add specified amount lint cellulose (from can be available from Buckeye Technologies, isolated high-purity dissolving grade cellulose in the commercial cotton boll of Inc.; The average degree of polymerization DP that records by intrinsic viscosity is greater than 1300), rise to 50 to 55 ℃ gradually, and under continuing to stir, remain on this temperature and finish until reaction.After reaction was finished, by being deposited under shear conditions in 100% methanol, separating obtained level and smooth mixture was also referred to as " viscous solution ".Analysis and the solubility results of embodiment 39-42 are provided in table 14-19.

Embodiment 39

Synthetic and the purification of cellulose stearate

Mix the preparation of stearic acid/trifluoroacetic anhydride

1000 milliliter of 4 neck round-bottomed flask of flame-dried argon purge; Be furnished with agitator bearing/mechanical agitation axle for vacuum purposes design, have the PTFE that extracts nut and fill in (stopper) (24/40 standard taper joint) and two Claisen adapters, it is furnished with following: a) reflux condenser; B) 125 milliliters have the charging hopper that measures plug, and c) internal thermometer/thermocouple adds stearic acid (166.75 grams, 0.5862 mole) (J.T.Baker in this flask; CatalogNo.JT0340-07; Lot#B0336; Triple Pressed; N.F; 90-100%; Stearic acid; By liquid chromatography, material contains two kinds of fatty acid and a kind of fatty acids with higher carbon content that have than low carbon content of 8-10% at least).Still at room temperature in, for fully dissolved fat acid, under agitation add 150 milliliters of normal heptane (Burdick; Jackson; Catalog No.207-4) and 50 milliliters of dichloromethane (Burdick ﹠amp; Jackson; Catalog No.300-4) and be mixed into the acquisition homogeneous solution.For the color that makes mixed anhydride minimizes, this solution is cooled to 10-15 ℃, and kept 30 minutes.With trifluoroacetic anhydride (TFAA) (111.92 grams, 0.5329 mole; 74.07 (Aldrich milliliter); Catalog No.106232) adds to rapidly in 125 milliliters of charging hoppers of being furnished with meticulous control metering plug.Glass stopper is recalled to charging hopper; Guarantee that the normal pressure that flows through reactor is in possible floor level (the slowest possible bubbling rate in the oily bubbler of silicone oil is housed).Adding TFAA-interpolation speed with moderate speed in refrigerative solution makes the internal temperature of reactant mixture keep below 15 ℃.After trifluoroacetic anhydride adds fully, remove cooling bath and change at room temperature the bath that contains tap water into.(or when the flask interior temperature is recovered 25 ℃) after 25-30 minute, with mixture restir 30 minutes to guarantee to form mixed anhydride.At this moment, reactant mixture evenly also produces very shallow golden yellow tone.

The reaction of the mixed anhydride of cellulose and stearic acid/trifluoroacetic acid-with the cellulosic fragment of velveteen level (about 15 millimeters * 15 mm sizes; Can be available from Buckeye Technologies, Inc.) in vacuum drying oven,＜25 inches Hg predryingly down are no less than 24 hours at 55 ℃.During this period, transfer in the 0% humidity exsiccator cellulose with cooling rapidly and be stored into use.Remove the PTFE plug and via wide mouthful of powder funnel in reactant mixture, add as quickly as possible 15.16 gram (0.0935 mole) exsiccant handss tear up sheet-guarantee when carrying out this operation, flow through this system minimum positive argon pressure so that the steam release of reaction vessel minimize.After adding cellulose fully, recall to stopper; Use the temperature control oil bath, through ensuing 2 hours gradually the reacting by heating mixture to realize 50 ℃ final internal solution temperature.This mixture was kept 5 hours under lasting the stirring under these conditions.At this moment, this mixture complete reaction is to produce the translucent viscous solution that shallow golden brown is transferred.Stop the heating of this mixture during this period.

After the neutralization-viscous solution that will continue to stir is cooled to 30 ℃ internal temperature, by through slowly dropwise adding methanol/Millipore water (3.80 gram and/or 4.80 milliliters of MeOH ﹠amp in 90 minutes; 2.14 gram H ₂O) 50: 50 (w/w) mixture (with respect to excessive TFA, by mole), residual trifluoroacetic anhydride neutralizes.In this case, internal temperature rises to 41.5 ℃ of maximums (11.5 ℃ of risings)-emphasis: add speed and should make internal temperature keep being equal to or less than 50 ℃ to reduce cellulosic degraded as far as possible.After internal temperature returns to 30-35 ℃, determine that neutralization finishes substantially.Make reaction vessel prepare to be used for distillation then.

Distillation-before distillation, remove Claisen adapter, thermocouple/thermometer adapter, charging hopper and condenser, and change lubricated glass stopper into DOW Corning High Vacuum Grease.Add 90 ° of pipe connection adaptor opening the neck of 1000 milliliters of round-bottomed flasks of 4 necks, and be connected in series on two 500 milliliters of vacuum traps via high-vacuum tube and Schlenk menifold.These two traps all cool off with liquid nitrogen cryogenics.When keeping 30 ℃ mixture internal temperature, slowly/incrementally introduce vacuum until the final vacuum that reaches 60mmHg.After balance under this pressure, by the heating crude mixture, the distillation-slowly increase heat that causes residual trifluoroacetic acid, trifluoro-acetate, water and methanol is with the stable distillation of initiation/maintenance.Continue heating and reach 50 ℃ maximum up to internal temperature.Continuing to keep the perfect vacuum 60 minutes down at 50 ℃ under the stirring.At this moment, distill most low boiling pollutant, and remove a large amount of dichloromethane and normal heptane.Stop heating, stop vacuum, with this system of argon backfill.The gained mixture is to show dark amber very heavy-gravity viscous solution

Precipitation/separation-, add 30 milliliters of trichloroethylene (Aldrich in order to prepare precipitation; CatalogNo.372145; Anhydrous) and be stirred in the gained viscous solution 30 minutes.Viscous solution is transferred to the separatory funnel from the primitive reaction device, and it is used for rough viscous solution slowly is metered into 100% methanol solution (the Burdick ﹠amp that vigorous stirring/is highly stirred subsequently; Jackson; Catalog No.230-4; 99.9+%)-ratio that effectively precipitates the required methanol total amount of viscous solution is about 20-25: 1[(v/v); MeOH/ viscous solution].After precipitation is finished, the canescence flocky precipitate stayed slowly stir 60-120 minute in the precipitation vessel again so that hardened material.By water conservancy diversion (course) glass sintering funnel vacuum filtration, catch precipitate thus.Solid instant is transferred in the flask of appropriate size and with 2000 ml methanol slurrying.With gained slurry restir 1 hour and standing sedimentation, and further be no less than 12 hours.Isolating polymer is caught by water conservancy diversion glass sintering funnel vacuum filtration; Stay in the funnel that still applies vacuum with air-dry at least 60 minutes; And transfer in the basin to prepare further drying.In vacuum drying oven,＜25 inches Hg are no less than 24 hours 50 ℃ of following further dryings with air-dry material.This material taken out from vacuum drying oven and transfer in the exsiccator so that the polymer cooling, after this obtain to be used to analyze and/or the sample of dissolubility test.The reaction of making cellulose stearate (and/or three-O-cellulose stearate) produces 81.54 gram (90.7% yield, isolating) canescence to shallow cream color waxy solid.

So that not comprising the residual reactants molal quantity, NMR result do not carry out NMR program and correlation computations as the mode of the minimizing possibility of the part of ester molal quantity.Then with this solution cool to room temperature, and in this solution, add at least 0.1 milliliter of Carbimide. tribromo-acetyl ester, stirred at least 5 minutes then.In a few hours of preparation, use conventional proton N MR parameter then but with the proton N MR spectrum (under 80 ℃) of 64 scanning test sample.Gained NMR data provide the peak of the free acid that exists and the peak of total acid (acid and ester summation).With these two kinds of peak integrations and the peak that from the total acid peak, deducts free acid so that the value of total esterification acid to be provided.Use this value to calculate DS.Use this method, the molal quantity (use hydroxyl peak) of the hydroxyl by more cellulosic reaction can obtain internal inspection, because derivatization agent and cellulosic no esterification hydroxyl and no esterification acid are all reacted.Calculate the hydroxyl molal quantity and divided by the value of skeleton molal quantity with the residual hydroxyl number that produces every anhydroglucose.3.00 deducting this hydroxyl value should produce and the identical esterification acid DS value of using other method to calculate.By ¹H NMR finds that this material has 2.81 stearate DS.This polymer is all solvable in 2-Methylpentadecane and Fancol ID.Listed concentration is carried out the above solubility test rules described in the Comparative Examples 1 in the following table in 2-Methylpentadecane and Fancol ID.After 2 to 1 month, write down the result.Detail analysis and solubility results are provided in the table.

Embodiment 40

The cellulosic synthetic and purification of neodecanoic acid

The 1000 milliliter of 4 neck round-bottomed flask that mixes the preparation-flame-dried argon purge of neodecanoic acid/trifluoroacetic anhydride; Be furnished with agitator bearing/mechanical agitation axle for vacuum purposes design, have the PTFE that extracts nut and fill in (24/40 standard taper joint) and two Claisen adapters, it is furnished with following: a) reflux condenser; B) 125 milliliters have the charging hopper that measures plug, and c) internal thermometer/thermocouple adds 100.97 gram neodecanoic acid Prime in this flask, CAS#26896-20-8, limpid colourless liquid under room temperature/pressure can be available from ExxonMobil ChemicalCompany, ( ¹H NMR, ¹³C NMR ₃And liquid chromatography (LC) provides the evidence by the multicomponent mixture that constitutes more than 6 kinds of chemical compounds).For the color that makes mixed anhydride minimizes, this solution is cooled to 0 ℃, and kept 60 minutes.With trifluoroacetic anhydride (TFAA) (111.92 grams, 0.5329 mole; 74.07 (Aldrich milliliter); Catalog No.106232) adds to rapidly in 125 milliliters of charging hoppers of being furnished with meticulous control metering plug.Glass stopper is recalled to charging hopper; Guarantee that the normal pressure that flows through reactor is in possible floor level (the slowest possible bubbling rate in the oily bubbler of silicone oil is housed).Adding TFAA-interpolation speed with moderate speed through 120-150 minute (2.0-2.5 hour) in refrigerative solution makes the internal temperature of reactant mixture keep below 5 ℃.Meaningly, in TFAA interpolation process, it is purple to the purple tone that solution begins to present powder.After trifluoroacetic anhydride adds fully, remove cooling bath and change at room temperature the bath that contains tap water into.(or when the flask interior temperature is recovered 25 ℃) after 25-30 minute, with mixture at room temperature restir 60 minutes to guarantee to form mixed anhydride.At this moment, reactant mixture evenly also produces very bright purple tone.

The reaction of the mixed anhydride of cellulose and neodecanoic acid/trifluoroacetic acid-with the cellulosic fragment of velveteen level (about 15 millimeters * 15 mm sizes; Can be available from Buckeye Technologies, Inc.) in vacuum drying oven,＜25 inches Hg predryingly down are no less than 24 hours at 55 ℃, and are stored in the 0% humidity exsiccator up to use.Remove the PTFE plug and via wide mouthful of powder funnel in reactant mixture, add as quickly as possible the cellulosic dry hands of velveteen level tear up sheet (15.16 grams, 0.0935 mole)-guarantee when carrying out this operation, flow through this system minimum positive argon pressure so that the steam release of reaction vessel minimize.After adding cellulose fully, recall to stopper; Use the temperature control oil bath, through ensuing 2 hours gradually the reacting by heating mixture to realize 50 ℃ final internal solution temperature.This mixture was kept 18 hours under lasting the stirring under these conditions.Stop the heating of this mixture during this period.

Neutralization-the viscous solution that will continue to stir adds 35 milliliters of trichloroethylene (Aldrich after being cooled to 30 ℃ internal temperature; Catalog No.372145; Anhydrous) with viscosity that reduces viscous solution and the dissolving that helps neutralise mixt.(4.18 restrain and/or 5.28 milliliters of MeOH﹠amp by slowly dropwise adding methanol/Millipore water through 90 minutes; 2.35 gram H ₂O) 50: 50 (w/w) mixture (with respect to 10% molar excess of excessive TFA), residual trifluoroacetic anhydride neutralizes.In this case, internal temperature rises to 42.5 ℃ maximum (12.5 ℃ of risings).Keep adding speed so that internal temperature keeps being equal to or less than 50 ℃ to reduce cellulosic degraded as far as possible.After internal temperature returns to 30-35 ℃, determine that neutralization finishes substantially.Make reaction vessel prepare to be used for distillation then.

Distillation-before distillation, remove Claisen adapter, thermocouple/thermometer adapter, charging hopper and condenser, and change lubricated glass stopper into DOW Corning High Vacuum Grease.Add 90 ° of pipe connection adaptor opening the neck of 1000 milliliters of round-bottomed flasks of 4 necks, and be connected in series on two 500 milliliters of vacuum traps via high-vacuum tube and Schlenk menifold.These two traps all cool off with liquid nitrogen cryogenics.When keeping 30 ℃ mixture internal temperature, slowly/incrementally introduce vacuum until the final vacuum that reaches 60mmHg.After balance under this pressure, by the heating crude mixture, the distillation-slowly increase heat that causes residual trifluoroacetic acid, trifluoro-acetate, water and methanol is with the stable distillation of initiation/maintenance.Continue heating and reach 50 ℃ maximum up to internal temperature.Continuing to keep the perfect vacuum 60 minutes down at 50 ℃ under the stirring.At this moment, distill most low boiling pollutant, and remove a large amount of trichloroethylenes.Stop heating, stop vacuum, with this system of argon backfill.The gained mixture is the very heavy-gravity viscous solution that shows than dark brown red.

Precipitation/separation-, add 50 milliliters of trichloroethylene (Aldrich in order to prepare precipitation; CatalogNo.372145; Anhydrous) and be stirred in the gained viscous solution 30 minutes-trichloroethylene and not only aspect solution viscosity, serve as diluent and also help effectively to remove residual/unreacted fatty acid.Viscous solution is transferred to the separatory funnel of appropriate size from the primitive reaction device.This separatory funnel is used for rough viscous solution slowly is metered into the 100% methanol solution (Burdick﹠amp that vigorous stirring/is highly stirred subsequently; Jackson; Catalog No.230-4) in-ratio that effectively precipitates the required methanol total amount of viscous solution is about 20-25: 1[(v/v); MeOH/ viscous solution].After precipitation is finished, the fine precipitate of canescence stayed slowly stir 60-120 minute in the precipitation vessel again so that hardened material.When stirring termination, all material of very fine sand shape particulate forms is fallen the bottom of precipitation vessel immediately and is condensed into uniform pancake shape, shows that purified material is very dense in nature.By water conservancy diversion glass sintering funnel vacuum filtration, catch precipitate thus.Solid instant is transferred in the flask of appropriate size and with 2000 ml methanol slurrying.Gained slurry restir 1 hour with standing sedimentation, and further is no less than 12 hours.Isolating polymer is caught by water conservancy diversion glass sintering funnel vacuum filtration; Stay in the funnel that still applies vacuum with air-dry at least 60 minutes; Crushing is to granular granularity in mortar and pestle; And transfer in the basin to prepare further to remove solvent and water.In vacuum drying oven,＜25 inches Hg are no less than 24 hours 50 ℃ of following further dryings with air-dry material.This material taken out from vacuum drying oven and transfer in the exsiccator so that the polymer cooling, after this obtain to be used to analyze and/or the sample of dissolubility test.For finishing processing, pass the small-sized Hammermill that is furnished with 1.0 mm sieve filters to reduce the granularity of drying material.The reaction of making neodecanoic acid cellulose (and/or three-O-neodecanoic acid cellulose) produces the fine-powdered granular solids of 49.35 grams (84.4% yield, isolating), and it is dark white.Use above the program described in the embodiment 39 to carry out NMR program and correlation computations, so that NMR result does not comprise the minimizing possibility of residual reactants molal quantity as the part of ester molal quantity.By ¹H NMR finds that this material has 2.53 neodecanoic acid ester DS; This polymer is all solvable in 2-Methylpentadecane and Fancol ID.Listed concentration is carried out the above solubility test rules described in the Comparative Examples 1 in the following table in 2-Methylpentadecane and Fancol ID.After 2 to 1 month, write down the result.About detail analysis and solubility results, please referring to subordinate list (showing down).

Embodiment 41

The cellulosic synthetic and purification of neodecanoic acid

1000 milliliter of 4 neck round-bottomed flask of the preparation of blended neodecanoic acid/trifluoroacetic anhydride-flame-dried argon purge; Be furnished with agitator bearing/mechanical agitation axle for vacuum purposes design, have the PTFE that extracts nut and fill in (24/40 standard taper joint) and two Claisen adapters, it is furnished with following: a) reflux condenser; B) 125 milliliters have the charging hopper that measures plug, and c) internal thermometer/thermocouple adds 100.97 gram neodecanoic acid Prime in this flask, CAS#26896-20-8, can be available from ExxonMobil Chemical Company, neodecanoic acid product (limpid colourless liquid under room temperature/pressure ¹H NMR, ¹³C NMR and liquid chromatography (LC) provide the evidence by the multicomponent mixture that constitutes more than 6 kinds of chemical compounds).For the color that makes mixed anhydride minimizes, this solution is cooled to 0 ℃, and kept 60 minutes.With trifluoroacetic anhydride (TFAA) (111.92 grams, 0.5329 mole; 74.07 (Aldrich milliliter); Catalog No.106232) adds to rapidly in 125 milliliters of charging hoppers of being furnished with meticulous control metering plug.Glass stopper is recalled to charging hopper; Guarantee that the normal pressure that flows through reactor is in possible floor level (the slowest possible bubbling rate in the oily bubbler of silicone oil is housed).Adding TFAA-interpolation speed with moderate speed through 120-150 minute (2.0-2.5 hour) in refrigerative solution makes the internal temperature of reactant mixture keep below 5 ℃.In TFAA interpolation process, it is purple to the purple tone that solution begins to present powder.After trifluoroacetic anhydride adds fully, remove cooling bath and change at room temperature the bath that contains tap water into.(or when the flask interior temperature is recovered 25 ℃) after 25-30 minute, with mixture at room temperature restir 60 minutes to guarantee to form mixed anhydride.At this moment, reactant mixture evenly also produces very bright purple tone.

The reaction of the mixed anhydride of cellulose and neodecanoic acid acid anhydride and trifluoroacetic acid-with the cellulosic fragment of velveteen level (about 15 millimeters * 15 mm sizes; Can be available from Buckeye Technologies, Inc.) in vacuum drying oven,＜25 inches Hg predryingly down are no less than 24 hours at 55 ℃, and are stored in the 0% humidity exsiccator up to use.Remove the PTFE plug and via wide mouthful of powder funnel in reactant mixture, add as quickly as possible the cellulosic dry hands of velveteen level tear up sheet (15.16 grams, 0.0935 mole)-guarantee when carrying out this operation, flow through this system minimum positive argon pressure so that the steam release of reaction vessel minimize.After adding cellulose fully, recall to stopper; Use the temperature control oil bath, through ensuing 5 hours gradually the reacting by heating mixture to realize 53.5 ℃ final internal solution temperature.This mixture was kept 29 hours under lasting the stirring under these conditions.This moment, mixture reaction produced translucent sand shape viscous solution, and it has dark claret-red (burgundy) tone, contains a small amount of light brown light in whole color.In order to drive molecular balance, add 40 milliliters of trifluoro-ethylene (Aldrich towards three esters; Catalog No.372145); Oil bath temperature is reduced to 45 ℃; Reaction was continued 9.5 hours again.But by the physical appearance and the denseness of viscous solution, the replacement degree of ester obviously is lower than the degree that the similar polymer of making among the embodiment 40 is obtained most probably.Even so, stop the heating-total reaction time 38.5 hours of this mixture after during this period.

Neutralization-after cooling, (4.18 restrain and/or 5.28 milliliters of MeOH﹠amp by slowly dropwise adding methanol/Millipore water through 90 minutes; 2.35 gram H ₂O) 50: 50 (w/w) mixture (with respect to 10% molar excess of excessive TFA), residual trifluoroacetic anhydride neutralizes.In this case, internal temperature rises to 42.5 ℃ maximum (12.5 ℃ of risings).Keep adding speed so that internal temperature keeps being equal to or less than 50 ℃ to reduce cellulosic degraded as far as possible.After internal temperature returns to 30-35 ℃, determine that neutralization finishes substantially.Make reaction vessel prepare to be used for distillation then.

Distillation-before distillation, remove Claisen adapter, thermocouple/thermometer adapter, charging hopper and condenser, and change lubricated glass stopper into DOW Corning High Vacuum Grease.Add 90 ° of pipe connection adaptor opening the neck of 1000 milliliters of round-bottomed flasks of 4 necks, and be connected in series on two 500 milliliters of vacuum traps via high-vacuum tube and Schlenk menifold.These two traps all cool off with liquid nitrogen cryogenics.When keeping 30 ℃ mixture internal temperature, slowly/incrementally introduce vacuum until the final vacuum that reaches 60mmHg.After balance under this pressure, by the heating crude mixture, the distillation-slowly increase heat that causes residual trifluoroacetic acid, trifluoro-acetate, water and methanol is with the stable distillation of initiation/maintenance.Continue heating and reach 50 ℃ maximum up to internal temperature.Continuing to keep the perfect vacuum 60 minutes down at 50 ℃ under the stirring.At this moment, distill most low boiling pollutant, and remove a large amount of trichloroethylenes.Stop heating, stop vacuum, with this system of argon backfill.The gained mixture is to show dark henna very heavy-gravity sand shape viscous solution.

Precipitation/separation-, add 60 milliliters of trichloroethylene (Aldrich in order to prepare precipitation; CatalogNo.372145) and be stirred in the gained viscous solution 30 minutes.Viscous solution is transferred to the separatory funnel of appropriate size from the primitive reaction device.Separatory funnel is used for rough viscous solution slowly is metered into 100% methanol solution (the Burdick ﹠amp that vigorous stirring/is highly stirred subsequently; Jackson; CatalogNo.230-4) in-ratio that effectively precipitates the required methanol total amount of viscous solution is about 20-25: 1[(v/v); MeOH/ viscous solution].After precipitation is finished, the fine precipitate of canescence stayed slowly stir 60-120 minute in the precipitation vessel again so that hardened material.When stirring termination, all material of very fine sand shape particulate forms is fallen the bottom of precipitation vessel immediately and is condensed into uniform pancake shape, shows that purified material is very dense in nature.By water conservancy diversion glass sintering funnel vacuum filtration, catch precipitate thus.Solid instant is transferred in the flask of appropriate size and with 2000 ml methanol slurrying.With gained slurry restir 1 hour and standing sedimentation, and further be no less than 12 hours.Isolating polymer is caught by water conservancy diversion glass sintering funnel vacuum filtration; Stay in the funnel that still applies vacuum with air-dry at least 60 minutes; Crushing is to granular granularity in mortar and pestle; And transfer in the basin to prepare further to remove solvent and water.In vacuum drying oven,＜25 inches Hg are no less than 24 hours 50 ℃ of following further dryings with air-dry material.This material taken out from vacuum drying oven and transfer in the exsiccator so that the polymer cooling, after this obtain to be used to analyze and/or the sample of dissolubility test.For finishing processing, pass the small-sized Hammermill that is furnished with 1.0 mm sieve filters to reduce the granularity of drying material.The reaction of making neodecanoic acid cellulose (and/or three-O-neodecanoic acid cellulose) produces the fine-powdered granular solids of 41.97 grams (71.8% yield, isolating), and it is dark white.Use above the program described in the embodiment 39 to carry out NMR program and correlation computations, so that NMR result does not comprise the minimizing possibility of residual reactants molal quantity as the part of ester molal quantity.By ¹H NMR finds that this material has 2.35 neodecanoic acid ester DS.Listed concentration is carried out the above solubility test rules described in the Comparative Examples 1 in the following table in 2-Methylpentadecane and Fancol ID.After 2 to 1 month, write down the result.About detail analysis and solubility results, please referring to subordinate list (showing down).Form sharp contrast ground with the DS2.53 material of being made by identical fatty acid product among the embodiment 40, this polymer all has the dissolubility of extreme difference in 2-Methylpentadecane and Fancol ID.

Embodiment 42

The cellulosic synthetic and purification of new enanthic acid

1000 milliliter of 4 neck round-bottomed flask of the preparation of blended new enanthic acid/trifluoroacetic anhydride-flame-dried argon purge; Be furnished with agitator bearing/mechanical agitation axle for vacuum purposes design, have the PTFE that extracts nut and fill in (24/40 standard taper joint) and two Claisen adapters, it is furnished with following: a) reflux condenser; B) 125 milliliters have the charging hopper that measures plug, c) internal thermometer/thermocouple adds the new enanthic acid Prime of 76.31 grams, CAS#95823-36-2 in this flask, can be available from new enanthic acid product (the limpid colourless liquid under room temperature/pressure of ExxonMobil Chemical Company ¹H NMR, ¹³C NMR and liquid chromatography (LC) provide the evidence of the multicomponent mixture that is made of different chemical compounds of 3-4 kind at least).For the color that makes mixed anhydride minimizes, this solution is cooled to 0 ℃, and kept 60 minutes.With trifluoroacetic anhydride (TFAA) (111.92 grams, 0.5329 mole; 74.07 (Aldrich milliliter); Catalog No.106232) adds to rapidly in 125 milliliters of charging hoppers of being furnished with meticulous control metering plug.Glass stopper is recalled to charging hopper; Guarantee that the normal pressure that flows through reactor is in possible floor level (the slowest possible bubbling rate in the oily bubbler of silicone oil is housed).Adding TFAA-interpolation speed with moderate speed through 120-150 minute (2.0-2.5 hour) in refrigerative solution makes the internal temperature of reactant mixture keep below 5 ℃.In TFAA interpolation process, solution begins to present slightly LightPink tone.After trifluoroacetic anhydride adds fully, remove cooling bath and change at room temperature the bath that contains tap water into.(or when the flask interior temperature is recovered 25 ℃) after 25-30 minute, with mixture at room temperature restir 60 minutes to guarantee to form mixed anhydride.At this moment, reactant mixture evenly and produce general light pink Flos Rosae Rugosae tone.

The reaction of the mixed anhydride of cellulose and new enanthic acid and trifluoroacetic acid-with the cellulosic fragment of velveteen level (about 15 millimeters * 15 mm sizes; Can be available from Buckeye Technologies, Inc.) in vacuum drying oven,＜25 inches Hg predryingly down are no less than 24 hours at 55 ℃, and are stored in the 0% humidity exsiccator up to use.Remove the PTFE plug and via wide mouthful of powder funnel in reactant mixture, add as quickly as possible the cellulosic dry hands of velveteen level tear up sheet (15.17 grams, 0.0936 mole)-guarantee when carrying out this operation, flow through this system minimum positive argon pressure so that the steam release of reaction vessel minimize.After adding cellulose fully, recall to stopper; Use the temperature control oil bath, through ensuing 5 hours gradually the reacting by heating mixture to realize 53.5 ℃ final internal solution temperature.At this moment, stirred mixture for cream-colored to apricot and seeming the extraordinary image Brazil wax aspect the denseness.This mixture was kept 20 hours under lasting the stirring under these conditions.This moment, mixture reaction produced translucent shallow golden brown accent viscous solution.Reduce oil bath temperature to realize 30 ℃ viscous solution internal temperature.For viscous mixture is thinning to prepare being used for neutralization, add 60 milliliters of trifluoro-ethylene (Aldrich; Catalog No.372145).

Neutralization-after cooling, by slowly dropwise added methanol/Millipore water (4.18 gram and/or 5.28 milliliters of MeOH﹠amp through 90 minutes; 2.35 gram H ₂O) 50: 50 (w/w) mixture (with respect to 10% molar excess of excessive TFA), residual trifluoroacetic anhydride neutralizes.In this case, internal temperature rises to 41.5 ℃ of maximums (11.5 ℃ of risings).Keep adding speed so that internal temperature keeps being equal to or less than 50 ℃ to reduce cellulosic degraded as far as possible.After internal temperature returns to 30-35 ℃, determine that neutralization finishes substantially.Make reaction vessel prepare to be used for distillation then.

Distillation-before distillation, remove Claisen adapter, thermocouple/thermometer adapter, charging hopper and condenser, and change lubricated glass stopper into DOW Corning High Vacuum Grease.Add 90 ° of pipe connection adaptor opening the neck of 1000 milliliters of round-bottomed flasks of 4 necks, and be connected in series on two 500 milliliters of vacuum traps via high-vacuum tube and Schlenk menifold.These two traps all cool off with liquid nitrogen cryogenics.When keeping 30 ℃ mixture internal temperature, slowly/incrementally introduce vacuum until the final vacuum that reaches 60mmHg.After balance under this pressure, by the heating crude mixture, the distillation-slowly increase heat that causes residual trifluoroacetic acid, trifluoro-acetate, water and methanol is with the stable distillation of initiation/maintenance.Continue heating and reach 45 ℃ maximum up to internal temperature.Continuing to keep the perfect vacuum 60 minutes down at 45 ℃ under the stirring.At this moment, distill most low boiling pollutant, and remove a large amount of trichloroethylenes.Stop heating, stop vacuum, with this system of argon backfill.The gained mixture is to show more dark brown golden very sticking viscous solution.

Precipitation/separation-, add 60 milliliters of trichloroethylene (Aldrich in order to prepare precipitation; CatalogNo.372145) and be stirred in the gained viscous solution 30 minutes-trichloroethylene and not only aspect solution viscosity, serve as diluent and also help effectively to remove residual/unreacted fatty acid.Viscous solution is transferred to the separatory funnel of appropriate size from the primitive reaction device.Separatory funnel is used for rough viscous solution slowly is metered into 100% methanol solution (the Burdick ﹠amp that vigorous stirring/is highly stirred subsequently; Jackson; Catalog No.230-4) in-ratio that effectively precipitates the required methanol total amount of viscous solution is about 20-25: 1[(v/v); MeOH/ viscous solution].After precipitation is finished, white powdery precipitate stayed slowly stir 60-120 minute in the precipitation vessel again so that hardened material.When stirring termination, all material of extremely fluffy swelling white particles form begins slowly to fall the precipitation vessel bottom and condenses into thick flocculate precipitate.By water conservancy diversion glass sintering funnel vacuum filtration, catch precipitate thus.Solid instant is transferred in the flask of appropriate size and with 2000 ml methanol slurrying.With gained slurry restir 1 hour and standing sedimentation, and further be no less than 12 hours.Even after leaving standstill 12 hours, approximately the 5-10% precipitate still freely is suspended in the main material of the polymer of falling precipitation vessel bottom top.Isolating polymer is caught by water conservancy diversion glass sintering funnel vacuum filtration, stays in the funnel that still applies vacuum with air-dry at least 60 minutes.In vacuum drying oven,＜25 inches Hg are no less than 24 hours 50 ℃ of following further dryings with air-dry material.This material taken out from vacuum drying oven and transfer in the exsiccator so that the polymer cooling, after this obtain to be used to analyze and/or the sample of dissolubility test.The brilliant white that the reaction of making new enanthic acid cellulose (and/or the new enanthic acid cellulose of three-O-) produces 44.77 grams (95.9% yield, isolating) is fluffy to the featheriness solid.Use above the program described in the embodiment 39 to carry out NMR program and correlation computations, so that NMR result does not comprise the minimizing possibility of residual reactants molal quantity as the part of ester molal quantity.By ¹H NMR finds that this material has 2.85 new heptanoate DS; This polymer is all solvable in 2-Methylpentadecane and Fancol ID.Listed concentration is carried out the above solubility test rules described in the Comparative Examples 1 in the following table in 2-Methylpentadecane and Fancol ID.After 2 to 1 month, write down the result.About detail analysis and solubility results, please referring to subordinate list (showing down).

Embodiment 43

(2 ethyl hexanoic acid) cellulosic synthetic and purification

The preparation of blended 2 ethyl hexanoic acid/trifluoroacetic anhydride-with 84.53 gram 2 ethyl hexanoic acid (Aldrich Catalog No.538701, Eastman Chemical Company makes) add in 1000 milliliter of 4 neck round-bottomed flask of flame-dried argon purge, this flask is furnished with for the agitator bearing/mechanical agitation axle of vacuum purposes design, has PTFE plug (24/40 standard taper joint) and two Claisen adapters of extracting nut out, and it is furnished with following: a) reflux condenser; B) 125 milliliters have the charging hopper that measures plug; And c) internal thermometer/thermocouple.It is different to avoid oils and fats and trifluoroacetic acid anhydride reactant that all clouded glass joints all are furnished with the PTFE cover.Being connected to 500 milliliters with the placed in-line floss hole of Claisen adapter via pipeline and containing 350 milliliters of saturated sodium bicarbonate (NaHCO of reaction vessel ₃) in the Dreschel Drexel bottle of aqueous solution.Use the trifluoroacetic acid of selecting in this Drexel bottle eccysis course of reaction.This solution is cooled to 0 ℃, and kept 60 minutes.Then with 111.92 gram (74.07 milliliters) trifluoroacetic anhydride (TFAA) (Aldrich; Catalog#106232, former state is used) add to rapidly in 125 milliliters of charging hoppers of being furnished with meticulous control metering plug.Glass stopper is recalled to charging hopper,, guarantee that carefully the normal pressure that flows through reactor keeps low then by attempting obtaining the slowest possible bubbling rate in the oily bubbler of silicone oil is housed.In refrigerative solution, add TFAA through 120-150 minute (2.0-2.5 hour) with moderate speed, make the internal temperature of reactant mixture keep below 5 ℃ simultaneously.After trifluoroacetic anhydride adds fully, remove cooling bath and change at room temperature the bath that contains tap water into.When the flask interior temperature is recovered 25 ℃, with mixture at room temperature restir 60 minutes to guarantee to form mixed anhydride.

The reaction of the mixed anhydride of cellulose and 2 ethyl hexanoic acid acid anhydride and trifluoroacetic acid-before reaction, (can be with the cellulosic fragment of velveteen level (about 15 millimeters * 15 mm sizes) available from BuckeyeTechnologies, Inc.) in vacuum drying oven,＜25 inches Hg, down predryingly be no less than 24 hours at 55 ℃, transfer in the 0% humidity exsiccator then rapidly and store up to use.Remove the PTFE plug and in reactant mixture, add 15.43 gram fragments rapidly, keep flowing through the minimum positive argon pressure of this system simultaneously via wide mouthful of powder funnel.After adding cellulose fully, recall to stopper, and use the temperature control oil bath, through ensuing 2.5 hours gradually the reacting by heating mixture to realize 50.0 ℃ final internal solution temperature.Can only see one very the cellulose of small pieces do not dissolve.This mixture was kept 6 hours under lasting the stirring under these conditions.Reduce oil bath temperature to realize 35 ℃ internal temperature.Add 35 milliliters of trifluoro-ethylene (Aldrich then; Catalog #372145, former state is used).

Neutralization-after cooling, by slowly dropwise added methanol/Millipore water (4.18 gram MeOH﹠amp through 50 minutes; 2.35 gram H ₂O) mixture (with respect to 10% molar excess of excessive TFA), residual trifluoroacetic anhydride neutralizes.Control is added speed and is risen to 40.5 ℃ maximum so that internal temperature keeps being equal to or less than 50 ℃ and internal temperature.After internal temperature returns to 30-35 ℃, make reaction vessel prepare to be used for distillation.

Distillation-before distillation, remove Claisen adapter, thermocouple/thermometer adapter, charging hopper and condenser, and change into the lubricated glass stopper of high pressure grease.Add 90 ° of pipe connection adaptor opening the neck of 1000 milliliters of round-bottomed flasks of 4 necks, and be connected in series on two 500 milliliters of vacuum traps via high-vacuum tube and Schlenk menifold.These two traps all cool off with liquid nitrogen cryogenics.When keeping 30 ℃ mixture internal temperature, slowly/incrementally introduce vacuum until the final vacuum that reaches 58-61mmHg.After balance under this pressure,, cause the distillation of residual trifluoroacetic acid, trifluoro-acetate, water and methanol by the heating crude mixture.Slowly increase heat with the stable distillation of initiation/maintenance.Continue heating and reach 45.6 ℃ maximum up to internal temperature.Continuing to keep perfect vacuum (54mm Hg) 60 minutes down at 45.6 ℃ under the stirring.Stop heating, stop vacuum, with this system of argon backfill.The gained mixture is to show more dark brown golden very sticking viscous solution.

Precipitation/separation-40 milliliters of trichloroethylene (Aldrich of adding; Catalog # 372145, former state is used) and be stirred in the gained viscous solution 30 minutes to reduce viscosity and to help effectively to remove residual/unreacted fatty acid.Viscous solution is transferred to the separatory funnel of appropriate size from the primitive reaction device.Separatory funnel is used for rough viscous solution slowly is metered into 100% methanol solution (the Burdick ﹠amp that vigorous stirring/is highly stirred subsequently; Jackson; Catalog # 230-4; 99.9+% is by GC) in.The ratio that effectively precipitates the required methanol total amount of viscous solution is about 20-25: 1[(v/v); MeOH/ viscous solution].After precipitation is finished, white powdery precipitate stayed slowly stir 60-120 minute in the precipitation vessel again so that hardened material.When stirring termination, all material of extremely fluffy swelling white particles form begins slowly to fall the precipitation vessel bottom and condenses into thick flocculate precipitate.By water conservancy diversion glass sintering funnel vacuum filtration, catch precipitate thus.Solid instant is transferred in the flask of appropriate size and with 2000 ml methanol slurrying.With gained slurry restir 1 hour and standing sedimentation, and further be no less than 12 hours.Isolating polymer is caught by water conservancy diversion glass sintering funnel vacuum filtration, and stays in the funnel that still applies vacuum with air-dry at least 60 minutes.In vacuum drying oven,＜25 inches Hg are no less than 24 hours 50 ℃ of following further dryings with air-dry material.This material is taken out from vacuum drying oven and transfers in the exsiccator, after this obtain to be used to analyze and/or the sample of dissolubility test.This reaction produces the dark white of 48.36 grams (95.6% yield, isolating) to linen fluffy to the featheriness solid.By ¹H NMR finds that this material has 2.93 2-ethylhexanoate DS; This polymer is all highly solvable in 2-Methylpentadecane and Fancol ID.Detail analysis and solubility results are listed in the table 14,15 and 20.

Table 14

Embodiment number	Cellulose esters (branching type)	The DS ester a	The DS OH that dissociates a	Residual fluoride b (ppm-wt)	Residual TFA b (ppm-wt)	Residual fatty acid c (wt％)
							39	Stearate	2.81	n.o. d	＜5	437	＜0.07
40	The neodecanoic acid ester	2.53	0.28	＜5	343	＜0.05
							41	The neodecanoic acid ester	2.35	0.26	n.a. e	n.a. e	n.a. e
42	New heptanoate	2.85	0.05	＜5	67.3	＜0.04
							43	2-ethylhexanoate	2.93	n.o. d	＜5	181	＜0.04

A) substitution value (DS) that ester moiety and free hydroxyl group (free OH) are all measured.

B) residual fluoride and the trifluoroacetic acid of measuring by the chromatography of ions (IC) (TFA).

C) the residual fatty acid of measuring by liquid chromatography (LC) (being unreacted stearic acid, neodecanoic acid and new enanthic acid).

D) do not observe (n.o.)

E) obtain (n.a)---because can't this polymer of solvation/dissolving in necessary dicyandiamide solution, residue analysis can not be obtained.

Table 15

Embodiment number	Cellulose esters (branching type)	Decompose beginning a (℃)	Relaxation b T g(℃)	Fusion b T m(℃)
					39	Stearate	358	n.o. c	26.8 it is (main; Non-constant width) 105.6 is (inferior; Wide)
40	The neodecanoic acid ester	333	33.7	n.o. c
					41	The neodecanoic acid ester	333	38.7	n.o. c
42	New heptanoate	359	97.6	n.o. c
					43	2-ethylhexanoate	358	31.9	n.o. c

A) measure by thermogravimetry (TGA), and be recorded as that the sweep speed at 20 ℃/minute is issued to the required value of 10% total mass loss under nitrogen.

B) measure by differential scanning calorimetry (DSC).Under 20 ℃/minute sweep speed, in post bake process, obtain the reported values that relaxation events (relaxation event)/glass transition (Tg) and fusion transform (Tm).

C) do not observe (n.o.)---in-140 to 175 ℃ of scopes, do not observe specified incident heat.

In following table, " solvable " is meant the liquid that forms liquid, contains little gel, or gel, is with or without to remove desolvate (irrelevant with clarity or turbidity in all cases); And " soluble " is meant the solids that are separated or stay the cellulose esters chemical compound.

Table 16

The solubility performance of cellulose stearate (embodiment 39) in the related hydrocarbons solvent

^aCellulose esters chemical compound weight is to total solution weight

Table 17

The solubility performance of neodecanoic acid cellulose (embodiment 40) in the related hydrocarbons solvent

^aCellulose esters chemical compound weight is to total solution weight

Table 18

The solubility performance of neodecanoic acid cellulose (embodiment 41) in the related hydrocarbons solvent

^aCellulose esters chemical compound weight is to total solution weight

^*Meet the standard of above-mentioned " solvable " definition, but be very muddy liquid or gel with physics discordance; It is unclear that whether reality is dissolved.

Table 19

The new solubility performance of enanthic acid cellulose (embodiment 42) in the related hydrocarbons solvent

^aCellulose esters chemical compound weight is to total solution weight

Table 20

The solubility performance of 2 ethyl hexanoic acid cellulose (embodiment 43) in the related hydrocarbons solvent

^aCellulose esters chemical compound weight is to total solution weight

Described the present invention in detail, but those of skill in the art will recognize that and under the situation of the scope and spirit of the present invention that do not deviate from this paper disclosure and description, to make change to various aspects of the present invention.Therefore, scope of the present invention is not subjected to a restriction of the specific embodiments that exemplifies and describe, but determines scope of the present invention by claims and counterpart thereof.

Claims (19)

1. compositions comprises:

At least a cellulosic cpd, at least some free hydroxyl groups on it replaced by at least one ester moiety with at least 6 carbon atoms and

At least a lipophilic solvent;

Wherein total replacement degree of ester moiety is at least 2.5 on this at least a cellulosic cpd, and wherein at least some of this at least a cellulosic cpd are dissolved in the described at least a lipophilic solvent.

2. the compositions of claim 1, wherein said at least one ester moiety are selected from saturated branched esters part, saturated not branched esters part, branching and beta-unsaturated esters part and aforementioned two or more combination.

3. the compositions of claim 1, wherein said at least one ester moiety are selected from saturated and unsaturated branched esters part and aforementioned two or more combination.

4. the compositions of claim 1, wherein said at least one ester moiety are selected from ester moiety, the ester with saturated isoalkyl with tert-butyl group end, the ester with alkyl structure of branching on α carbon and aforementioned two or more combination.

5. the compositions of claim 1, wherein said at least one ester moiety are selected from beta-unsaturated esters part and aforementioned two or more combination.

6. the compositions of claim 1, wherein said at least a cellulosic cpd is dissolved in the Fancol ID with the concentration of at least 5 weight % under room temperature and normal pressure.

7. the compositions of claim 1, wherein said at least a cellulosic cpd is dissolved in the Fancol ID with the concentration of at least 30 weight % under room temperature and normal pressure.

8. the compositions of claim 1, wherein said composition is deodorizer, antiperspirant, the product that shaves, skin lotion, the product of preserving moisture, skin toning agent, cleaning products, hair care product, fingernail maintenance product, protection cream, sunscreen product, anthelmintic, aging products, color make-up, lip pomade, foundation cream, face powder, informer, eye shadow, kermes, mascara, medicine is locally applied to system on the skin, or aforementioned two or more combination.

9. the compositions of claim 1, wherein said cellulosic cpd is derived from wood pulp or velveteen.

10. compositions comprises:

At least a cellulosic cpd, at least some free hydroxyl groups on it are replaced by first ester moiety that at least one has 6 carbon atoms at least, at least other free hydroxyl groups replaced by at least one second ester moiety and

At least a lipophilic solvent;

Wherein total replacement degree of first ester moiety is at least 0.8 on this at least a cellulosic cpd, and wherein at least some of this at least a cellulosic cpd are dissolved in the described at least a lipophilic solvent.

11. the compositions of claim 10, total replacement degree of first ester moiety is at least 1.0 on the wherein said at least a cellulosic cpd.

12. the compositions of claim 10, total replacement degree of at least one first ester moiety is at least 1.5 on the wherein said at least a cellulosic cpd.

13. the compositions of claim 10, wherein said at least one first ester moiety are selected from saturated branched esters part, saturated not branching part, branching and unsaturated part and aforementioned two or more combination.

14. the compositions of claim 10, wherein said at least one first ester moiety are selected from saturated and unsaturated branched esters part and aforementioned two or more combination.

15. the compositions of claim 10, wherein said at least one first ester moiety are selected from ester moiety, the ester with saturated isoalkyl with tert-butyl group end, the ester with alkyl structure of branching on α carbon and aforementioned two or more combination.

16. the compositions of claim 10, wherein said at least one first ester moiety are selected from beta-unsaturated esters part and aforementioned two or more combination.

17. the compositions of claim 10, wherein said at least one second ester moiety are selected from acetas, propionic ester, butyrate, valerate and aforementioned two or more combination.

18. the compositions of claim 10, wherein said composition is deodorizer, antiperspirant, the product that shaves, skin lotion, the product of preserving moisture, skin toning agent, cleaning products, hair care product, fingernail maintenance product, protection cream, sunscreen product, anthelmintic, aging products, color make-up, lip pomade, foundation cream, face powder, informer, eye shadow, kermes, mascara, medicine is locally applied to system on the skin, or aforementioned two or more combination.

19. a compositions comprises:

At least a cellulosic cpd, at least some free hydroxyl groups on it had at least 6 carbon atoms by at least one and be selected from saturated branched esters part, saturated not branched esters part, branching and beta-unsaturated esters part and aforementioned two or more the ester moiety of combination replaces and

At least a lipophilic solvent;

Wherein at least some of this at least a cellulosic cpd are dissolved in the described at least a lipophilic solvent.