CN101184797A - Method for compounding polymer pellets with functional additives - Google Patents

Abstract

New methods of forming compounded cellulose esters are provided. The methods comprise mixing a cellulose ester, functional additive, and a swelling agent and subsequently removing at least a portion of the swelling agent. The swelling agent is one that assists in causing the functional additive to penetrate into the cellulose ester, while not acting significantly as a solvent for the cellulose ester. Preferred cellulose esters include, but are not limited to, cellulose acetates, cellulose triacetates, cellulose acetate phthalates, and cellulose acetate butyrates. The functional additive can be a plasticizer, stabilizer, or other additive selected to modify a particular property of the cellulose.

Description

The method of compounding polymer pellets and functional additive

Invention field

The present invention relates to widely and forms the novel method can be used for forming such as the mixture of the Mierocrystalline cellulose of the goods of film, fiber and sustained-release matrix and functional additive.

Background technology

Mierocrystalline cellulose can be with various aliphatic series and aromatic carboxylic acid's esterification.Most typical cellulose ester is acetate, propionic acid, cellulose butyrate, and such as the mixed ester of cellulose acetate propionate and cellulose acetate butyrate.Gedon etc. are at " Cellulose Esters ", Kirk-Othmer Encyclopedia ofChemical Technology, the 4th edition, the 5th volume, John Wiley ﹠amp; Sons, New York, 496-529 has summarized cellulose ester and manufacture method thereof in (1993), here with reference to quoting the document.Steinmeier is in Macromolecular Symposia (2004), and 208 (rhodias) have also been described the manufacturing of cellulose ester among the 49-60, here with reference to quoting the document.United States Patent (USP) 2,196,768 and 3,022,287 have also described cellulosic manufacture method, here with reference to quoting this two pieces of documents.

Various cellulose ester can be purchased.For example, one of goods providers of cellulose ester is Eastman Chemical Company, Inc., Kingsport, TN.The plain ester of commercially available typical fibers comprises rhodia, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, propionic acid cellulose butyrate, acetate propionic acid carboxymethyl cellulose and acetate butyric acid carboxymethyl cellulose.

Cellulose ester generally forms with powder, pellet, particle, ball, elongation ball or granular shape.In these shapes, it is desirable to pellet, particle, ball, elongation ball and granular shape, because they are easy to clean, handle and transportation, also because their ash content is low.

The plain ester of known fiber is excellent thermoplastic material, but so cellulose ester widespread adoption.Edgar etc. are in " cellulose ester performance and application progress (Advances in Cellulose EsterPerformance and Application) ", " polymer science progress " (Progress in PolymerScience) 26 (9), described some among the 1605-1688 (2001) and utilized the application of cellulose ester, here with reference to quoting the document.Because its good thermoplastic performance and the most frequently used cellulose ester is rhodia (CA), cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB).Yet the cellulose ester of other type also can be used for some application.

These materials all have higher fusing or softening temperature (being 150-250 ℃) and higher melt viscosity for every kind.Because the combination of high melting temperature and high melt viscosity, the required temperature of these cellulose ester of melt-processed in some cases will near or surpass the decomposition temperature of cellulose ester.The result degrades cellulose ester during processing, thereby reduces its use in some applications.In order to reduce melt processing temperature, can before the cellulose ester melt-processed or during add monomerics.

The composition and the form that can greatly depend on cellulose ester such as the consistency and the dipping of the functional additive of softening agent.For example, Octyl adipate is demonstration and the bad consistency of rhodia usually, but good with the consistency of most of cellulose acetate butyrates.The consistency of softening agent also can change along with substitution value (the substituting group quantity of each anhydroglucose unit), even also like this for the cellulose ester of single type.For example, to can be used as substitution value be 2.5 or the softening agent of lower rhodia to diethyl phthalate (" DEP "); Yet DEP is considered to the bad softening agent that substitution value is the rhodia of 2.8-3.0.

Functional additive mixes with cellulose ester with conventional melt compounded technology usually, these class methods relate to mixes cellulose ester in having the Bitruder of suitable hybrid element with softening agent and other additive under proper temperature and pressure, obtain fused, mixed uniformly cellulose ester mixture when extruded material is left extruding machine.Generally it is desirable to by having the cellulose ester mixture of diameter, so that extrude adhesive tape for the die head extrusion molding melting mixing of about 2-6mm aperture.This adhesive tape of water or air cooling is cut off with the spacing of rule then, obtains uniform desired size and shape, is called " pellet " or " particle ".

Functional additive mixed fully or be impregnated in the cellulose ester very difficult, if particularly cellulose ester or functional additive thermally labile under the typical hybrid temperature.For example, cellulose triacetate and other cellulose ester are sometimes with the pellet form manufacturing.This pellet is quite hard, is not easy to absorb softening agent or additive with its natural form.The standard melt extrusion condition of routine (260-270 ℃ of barrel zone temperature belongs to the twin screw design together) and since the infiltration of softening agent and whole pellet improper with mix inhomogeneously, make the fusion adhesive tape of leaving extruding machine have significantly not melting zone.Temperature raises and to help to make fusing more complete, raises along with temperature and deepens but cost is a color, because the thermal destruction of pure cellulose triacetate occurs in 350-360 ℃.In addition, some additive may can not bear two required heating phases to thermo-responsive, i.e. melt compounded material, and melt-processed forms final plastics then.Pellet itself also can be a required net shape in controlled release matrix product for example.In this case, not to be exposed under the excessive heat may be ideal to various components.Some softening agent and other additive can be reduced to 300 ℃ with the degraded starting point, and their adding can produce other color.Lesser temps helps to reduce color, but the high softening-point of some cellulose ester requires to improve temperature.

In addition, in the plastic applications melting mixing of cellulose triacetate or melt-processed industrial be infeasible, because the fusing point of cellulose triacetate is higher than its decomposition temperature, and add softening very limited behind the softening agent so melt cellulose triacetate and impracticable.Commercial cellulose triacetate film is often by the solvent cast manufacturing.

The temperature-sensitive additive can join in the cellulose ester by solvent.Yet, functional additive solvent melt compounded is also had the ruined shortcoming of form of cellulose ester in the cellulose ester, and mix products must not deposit no longer or the secondary extrusion molding, to obtain form (for example pellet) easily.Useful is the cellulose ester that further utilizes this pellet or particle deposition, and keeps the form of this needs when cellulose ester mixes with functional additive.Therefore, if material has been the shape that needs, " mixing " step just only need be finished functional additive mixing in these pellets.

Need a kind of softening agent and other additive be incorporated into cellulose ester, especially the method in the cellulose triacetate need not heating to provide, and needn't change the cellulose mixture of cellulose ester pellet general shape.

Summary of the invention

The present invention forms mixture by Mierocrystalline cellulose, additive and swelling agent are mixed, and the method for the formation cellulose mixture of novelty is provided widely, has overcome above problem.

In one embodiment, the invention provides the method for the plain pellet of impregnation of fibers, particulate or particle and at least a additive.This method comprises by the additive of mixed cellulose ester, initial amount and swelling agent formation mixture, removes from mixture to the small part swelling agent then, thereby form the blended cellulose ester.Useful is that this mixed cellulose ester comprises the additive at least about 0.01wt% or 0.1wt% or 1wt% or 5wt% or 10wt% or 20wt% or 30wt% or 40wt% or 50wt% or 60wt% or 70wt% or 80wt% or 90wt% initial amount.

In another embodiment, the invention provides a kind of method, wherein additive and the swelling agent mixing with Mierocrystalline cellulose, initial amount obtains mixture, removes from mixture to the small part swelling agent, thereby forms the blended cellulose ester.In this embodiment, swelling agent comprises the composition that is selected from water, benzene, sulfonated castor oil, dimethylbenzene, toluene, Viscotrol C, pine tar, sulfonation pine tar, hexalin, pimelinketone, glyceryl diacetate and 1,2,3,4-tetralin that is lower than about 10 wt%.

The accompanying drawing summary

Fig. 1 is a series of photos that compared control sample and sample of the present invention in 27 hours.

Describe in detail

The invention provides by mixed cellulose ester, additive and sweller and form mixture, thus the novel method of formation mixed cellulose ester. The mixing of these compositions can realize by any known hybrid technology, includes but not limited to that rotation in drum ladle, top formula stir, sigma shape oar formula is mixed and rolling.

Unless otherwise indicated, being used for specification and claim expresses the quantity of composition, is interpreted as modifying with term " about " in all examples such as all numerals of the performance of molecular weight, reaction condition etc. Therefore, unless point out on the contrary, the digital parameters of listing in following specification and the appended claims all is approximation, can attempt the expected performance that obtains according to the present invention and changes. Minimum each numerical parameter should be explained according to the number of the significant digits of reporting and by using the common technology of rounding up at least. In addition, the scope of explaining in present disclosure and the claim is intended comprising whole described scope and is not only end points. For example, the scope that is expressed as 0-10 intends disclosing all numerical value between 0 to 10, such as 1,2,3,4 etc., and all marks between 0 to 10, such as 1.5,2.3,4.57,6.113 etc., and end points 0 and 10. Equally, the scope relevant with chemical substituting group, for example " C₁-C ₅Hydrocarbon " intend particularly including with open C₁And C₅Hydrocarbon, and C₂、C ₃And C₄Hydrocarbon.

Although listing number range and the parameter of wide region of the present invention is approximation, the numerical value that proposes in the specific embodiment is as far as possible accurately reported. Yet any numerical value has all comprised some error of necessity that the standard deviation found causes inherently in experimental measurement separately.

Article used herein (" a ", " an " and " the ") comprises their plural object, unless context statement in addition clearly.For example, relate to " polymkeric substance " or " moulded products " and intend comprising the processing or the manufacturing of many polymkeric substance or goods.Relate to contain or comprise " certain (an) " composition or " certain (a) " polymkeric substance composition except that specified, intend comprising respectively other composition or other polymkeric substance.

" comprise " or " containing " or " comprising " refers to have specified compound, element, particle or method steps etc. at least in composition or goods or the method; but do not get rid of the existence of other compound, catalyzer, material, particle, method steps etc.; even other this compound, material, particle, method steps etc. have and specified identical effect, unless specially get rid of.

It is also noted that the formulation of one or several method steps is not precluded within conjunction with having other method steps before or after the step of mentioning, or insert method steps knowing between those steps of mark.In addition, be the convenient measure of discrete activity of identification or composition to treatment step or composition numbering, mentioned numbering can be by any series arrangement, except as otherwise noted.

Cellulose ester can be any physical form (for example pellet, powder, particle, a fiber), and can comprise other functional group such as ether group in one embodiment.Preferred cellulose ester has the substitution value (being the substituting group quantity of each anhydroglucose unit) of about 0.7-about 3.0.In one embodiment, it is about 3.0 that substitution value is preferably about 2.7-, and more preferably from about 2.8-about 2.95.In another embodiment, it is about 2.0 that substitution value is preferably about 0.7-, and more preferably from about 1.5-about 1.9.In addition, it is about 5 that preferred cellulose ester will have, about 400,000 dalton of 000-, and more preferably from about 100, about 300,000 dalton of 000-, even more preferably from about 125,000-about 250,000 daltonian weight-average molecular weight (measuring as described below).

Preferred cellulose ester comprises cellulosic C ₁-C ₂₀Ester, more preferably cellulosic C ₂-C ₂₀Ester, even more preferably cellulosic C ₂-C ₁₀Ester, also more preferably cellulosic C ₂-C ₄Ester.Also preferred secondary and uncle's cellulose ester.Especially be preferred for cellulose ester of the present invention and be selected from rhodia, cellulose triacetate, Cellacefate, cellulose acetate butyrate, cellulose butyrate, three cellulose butyrates, cellulose propionate, three cellulose propionates, cellulose acetate propionate, acetate carboxymethyl cellulose, acetate propionic acid carboxymethyl cellulose, acetate butyric acid carboxymethyl cellulose, acetate butyric acid succsinic acid Mierocrystalline cellulose and composition thereof.

In one embodiment, cellulose ester has the substitution value of about 1.0-about 3.0.In another embodiment, cellulose ester is that the about 2.5-of substitution value is about 3.0, the rhodia of preferably about 2.7-about 3.0.In another embodiment, cellulose ester is that the about 0.5-of acetyl substitution value is about 2.0, the rhodia of preferably about 1.6-about 1.8.In another embodiment, cellulose ester is that the about 0.1-of acetyl substitution value is about 2.1, the cellulose acetate propionate of the about 0.5-of propionyl substitution value about 2.5.In another embodiment, cellulose ester is that the about 0.3-of acetyl substitution value is about 2.1, the cellulose acetate butyrate of the about 0.75-of butyryl substitution value about 2.6.

The consumption of cellulose ester preferably should be enough to make mixture to comprise the about 95wt% cellulose ester of about 5wt%-, the preferred about 90wt% cellulose ester of about 50wt%-, even the about 85wt% cellulose ester of 70wt%-more preferably from about, get 100wt% based on cellulose ester and additive in conjunction with weight.

Here used swelling agent is swelling or " opening " cellulose ester, but does not dissolve the compound of this cellulose ester.Promptly through about 120 minutes concentration with the 50wt% cellulose ester be dissolved in cellulose ester in the swelling agent generally be lower than about 5%, preferably be lower than about 2%, more preferably less than about 1%.In addition, swelling agent is this cellulose ester of swelling enough, make at least about 0.01wt% or 0.1wt% or 0.5wt% or 1wt% or 2wt% or 3wt% or 4wt% or 5wt% or 10wt% or 20wt% or 30wt% or 40wt% or 50wt% or 60wt% or 70wt% or 80wt% or 90wt% or 92wt% or 93wt% or 94wt% or 95wt% or 96wt% or 97wt% or 98wt%, preferably at least about 99wt%, more preferably from about the additive of 100wt% initial amount mixes with cellulose ester, and is retained in the final blending cellulose ester.

Preferred swelling agent includes but not limited to be selected from those of ketone (for example acetone, methyl ethyl ketone), ester (for example ethyl acetate, methyl acetate), alcohol (for example methyl alcohol, ethanol, Virahol), ether, carboxylic acid (for example acetate), tetrahydrofuran (THF), supercutical fluid (for example supercritical co) and their mixture.In a preferred embodiment, swelling agent comprises and is lower than about 10wt%, preferably be lower than about 5wt%, preferred about 0wt% is selected from water, benzene, sulfonated castor oil (being also referred to as " turkey red oil "), dimethylbenzene, toluene, Viscotrol C, pine tar, sulfonation pine tar, hexalin, pimelinketone, glyceryl diacetate and 1,2,3, the composition of 4-tetraline.If swelling agent comprises one or more water, benzene, sulfonated castor oil (being also referred to as " turkey red oil "), dimethylbenzene, toluene, Viscotrol C, pine tar, sulfonation pine tar, hexalin, pimelinketone, glyceryl diacetate and/or 1,2,3, the mixture of 4-tetraline, then the mixed weight of every kind of these compositions will be lower than about 10wt% of the swelling agent total amount of existence, preferably be lower than about 5wt%, preferably about 0wt%.

The consumption of swelling agent should be enough to fully infiltration and swollen cellulose matrix in the inventive method, thereby additive is well dispersed in the whole cellulose matrix.Equally preferably the consumption of swelling agent is enough low, make with swelling agent with after additive contacts for some time, the swollen Mierocrystalline cellulose is touch dry and free flowing granule rather than slurry.This generally can obtain swelling agent: the cellulose ester weight ratio is about 0.8: about 3: 1 of 1-, more preferably from about 1: about 1.5: 1 of 1-.

The additive that is used for the inventive method is preferably functional additive.Preferably some performance of cellulose ester is regulated or protected to this additive.Preferred additives comprises and is selected from softening agent, thermo-stabilizer, antioxidant, ultraviolet ray (UV) stablizer, sour stablizer, acid scavenger, dyestuff, pigment, spices (comprising deodovization agent), white dyes, fire retardant, agricultural chemicals (for example agricultural chemicals, weedicide, fertilizer, sterilant, trace mineral), bioactive compounds (for example medicine, medicament, nutrition agent), indicator, and composition thereof those.

" softening agent handbook (Handbook of Plasticizers) ", Wypych, George compiles, and ChemTec Publishing has described softening agent in (2004), here with reference to quoting the document.In one embodiment, preferred plasticizer is by replacing some two valence link of polymkeric substance with softening agent-polymer bonds, can promote to contain the product of polymkeric substance processing, increase flexible and/or increase toughness.The example that is suitable as the softening agent of additive among the present invention includes but not limited to be selected from dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate, butyl benzyl phthalate, glycolic acid butyl phthalyl butyl ester, tri trimellitate (2-ethylhexyl) ester, triethyl phosphate, triphenylphosphate, Tritolyl Phosphate, TOPOT 2,2 (diphenyl phosphoester) and other phosphate derivative, diisobutyl adipate, hexanodioic acid two (2-ethylhexyl) ester, triethyl citrate, citric acid acetyl triethyl, softening agent (the Citroflex that provides of Morflex for example that contains citric acid ^TMSoftening agent), triactin, tripropionin (tripropionin), tributyrin, sucrose acetate isobutyrate, glucose five propionic esters, triglycol-2-ethylhexanoate, polyoxyethylene glycol, polypropylene glycol, poly-propylene glycol dibenzoate, poly-pentanedioic acid second diester, poly-succsinic acid second diester, poly-alkylglycoside, 2,2,4-trimethylammonium-1,3-pentanediol isobutyrate, diisobutyrate, the O-phthalic acid copolymer, 1, the 3-butyleneglycol, 1 of aliphatic epoxide end closure, the 4-butyleneglycol, hexanodioic acid two (2-ethylhexyl) ester, those of epoxidised soybean oil and composition thereof.

The example that is suitable as the UV absorption agent of additive among the present invention and UV stablizer includes but not limited to be selected from benzotriazole, triazine, hydroxy benzophenone, benzoxazine ketone, Resorcinol one benzoic ether, (for example Whitfield's ointment 2 for salicylate, 6-dialkyl phenyl organic ester), p-octylphenyl salicylate, cinnamic acid derivative, N, N '-oxalyl pentanoic, hydroxybenzoate, steric hindrance triazine, bulky amine light scavenging agent (HALS) Tinuvin ^, Chimassorb ^, Cyasorb ^(obtaining) and Univul from Ciba ^TMThose of compound (obtaining) series product and composition thereof from BASF.The content of UV absorption agent and stablizer is generally the about 5wt% of about 0.01-, gets 100wt% based on cellulose ester weight.

If require the second melting moulding, then may need thermo-stabilizer.The example that is suitable as the thermo-stabilizer of additive among the present invention includes but not limited to be selected from antioxidant, free-radical scavengers, free radical terminator, metal scavenger, peroxide decomposer and metal-salt.More specifically, thermo-stabilizer can comprise the compound of the epoxide that is selected from sterically hindered phenol, bulky amine, natural oil, organic phosphite and composition thereof.Some preferred thermo-stabilizer comprises with trade(brand)name Irganox ^, Irgafos ^And Irgastab ^Those that sell (obtaining) from Ciba.Antioxidant can comprise organic phosphite, especially available trialkyl (C ₁-C ₁₀, more preferably C ₁-C ₄), alkyl (C ₁-C ₁₀, more preferably C ₁-C ₄) phenyl and/or triphenyl phosphorous acid ester.

The example of suitable metal(lic)stabilizer includes but not limited to be selected from basic metal and alkaline earth salt, comprises those of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium.Inorganic and the organic acid salt of suitable basic metal and alkaline-earth metal includes but not limited to oxyhydroxide, carbonate, supercarbonate, Citrate trianion, lactic acid salt, tartrate, maleate (maltates), oxalate (oxylates), phosphoric acid salt, acetate, propionic salt etc. and composition thereof.The content of thermo-stabilizer is generally the about 5wt% of about 0.05wt%-, and the about 2wt% of preferably about 0.1wt%-is measured 100wt% based on the cellulose ester gross weight.

Dyestuff can be used for providing the toning or the visual effect of expectation.The example of suitable organic dye includes but not limited to be selected from those of C.I. solvent violet 13, C.I. pigment Blue 15, C.I. Pigment blue 28, C.I. 63 ,DIS,PER,SE ,Vio,let, 63 8, C.I. pigment red 122 and composition thereof.The example of fluorescence dye or white dyes dyestuff comprises and is selected from Eccowhite and Eccobright product (from Eastern Color ﹠amp; Chemical Company acquisition), those of Eastobrite OB-1 (obtaining), fluorescein and composition thereof from Eastman ChemicalCompany.Example extraordinary or novel dyestuff comprises thermochromism and photochromic dyes.The inventive method is especially useful, volatility or thermal destruction because the present invention can utilize and can not stand the dyes and dyestuffs that the standard melt compounded is handled.

Suitable spices, refuse the Fabulous Fragrances that flavouring agent (repellant scents), odor neutralizer and mask agent include but not limited to Jan Moran; The Fragrances of the World of Michael Edwards; The The Illustrated Encyclopedia ofEssential Oils of Julia Lawless; The Chemistry of Fragrant Substances of Paul Jose Teisseire; Those disclosed among the The Fragrance Foundation Reference Guide 1999, The FragrancesFoundation (New York, 1999) is here with reference to quoting these documents.Concrete spices can be selected from pennyroyal oil, Vanillin, ester, linalool, geranial, some aldehyde and ester, complicated spice mixt, plant milk extract and composition thereof.The inventive method is especially useful, volatility or thermal destruction because the present invention can utilize and can not stand the spices that the standard melt compounded is handled.

The example that is used for suitable indicator of the present invention includes but not limited to be selected from those of pH indicator, moisture indicator, oxidation-reduction indicator and temperature indicator.The example of suitable pH indicator comprises and is selected from phenolphthalein, reindeer moss, thymolsulfonphthalein, tropeolin OO, p-dimethylamino-azo-benzene, tropeolin-D, tetrabromophenol sulfonphthalein, tetrabromo-mcresolsulfonphthalein, methyl red, dibromothymolsulfonphthalein, phenol red, toluylene red, thymolphthalein, sodium p-nitrobenzene-azo-salicylate, tropeolin O, nitramine and trinitrobenzoic acid.The example of moisture indicator is a cobalt chloride.The example of temperature indicator comprises such as drawing diindyl because of thermochromic dye blue, spiropyran derivatives.The example of suitable oxidation-reduction indicator comprises and is selected from ferroin, iodine/starch, two (4-dialkyl amido phenyl) squaraine dye, KMnO ₄And K ₂Cr ₂O ₇Those.

The example of sterilant comprises those that are selected from organochlorine compound, organic phosphoric acid salt compound, aryl compound, heterogeneous ring compound, organosulfur compound, carbamate compounds, formamidine compound, dinitrobenzene phenolic compound, organo-tin compound, pyrethroid compound, acyl urea compound, vegetalitas spice compound, antifungal compound, fumigant compound, repellent compound, mineral compound and composition thereof.

The example of weedicide comprises those that are selected from ALSase inhibitor, aromatic carboxylic acid, chlor(o)acetamide, triazine, ESPAase inhibitor, ACCase inhibitor, dinitrobenzene amine compound, bentazone, halogen hydroxy benzonitrile, phenyl ether, different  oxazolidone, Paraquat and composition thereof.

The consumption of additive is enough to that preferably mixture the is contained about 95wt% additive of 5wt%-of having an appointment, the about 50wt% additive of preferably about 10wt%-, even the about 30wt% additive of 15wt%-are more preferably from about got 100wt% based on cellulose ester and additive in conjunction with weight.

Cellulose ester, additive and swelling agent are preferably removed swelling agent after mixing the formation mixture then, to obtain the mixture of cellulose ester and additive.Swelling agent can pass through several different methods, comprises by evaporation removing.Even more preferably swelling agent is removed step by the realization of swelling agent recovery system, makes swelling agent recycling.Preferred this removal step can be removed in the mixture at least about 10wt% or 20wt% or 30wt% or 40wt% or 50wt% or 60wt% or 70wt% or 80wt% or 90wt% or 95wt%, preferably at least about 98wt%, and the swelling agent of 100wt% more preferably from about.

The mixed cellulose ester that it should be understood that gained compares with the mixed cellulose ester that the melt compounded of passing through prior art prepares, and has one or more required performances.For example, mix, make mixed cellulose ester of the present invention can not suffer thermal destruction because the inventive method has realized need not pyritous.Thereby the weight-average molecular weight that makes the cellulose ester in the final mixed cellulose ester reach raw cellulose ester weight-average molecular weight at least about 98%, preferably at least about 99%, even more preferably at least about 100%.

In addition, avoid the high temperature of prior art melt compounded method also to avoid the thermal discoloration of problematic mixed cellulose ester in these art methods.Therefore, in a preferred embodiment, mixed cellulose ester of the present invention can form percent transmittancy to the light of the about 400nm of wavelength at least about 85%, preferably at least about 88%, more preferably at least about 91%, even more preferably at least about the film of about 5 mils of 95% thickness.

Mixed cellulose ester of the present invention will have and the plain essentially identical physical aspect of ester material (for example pellet, powdery, particle, fiber) of original fibers.Mixed cellulose ester can be used by " former state ", or carries out the necessary secondary processing step melt of extrusion molding or injection moulding (for example such as), forms the moulded products or the product of expectation.For example, mixed cellulose ester can be made into such as being used for the film that LCD uses.Useful is, in moulded products or the product weight-average molecular weight of cellulose ester will reach the plain ester weight-average molecular weight of original fibers at least about 73%, preferably at least about 77%, even more preferably at least about 80%.

Describe possible procedure of processing below in detail.

The preparation of moulded products

Mixed cellulose ester can be used as that raw material is heated and melt.In one embodiment, mixed cellulose ester is by the melt extrusion method moulding such as profile extrusion, sheet extrusion, film extrusion, film casting, extrusion blow molded and pultrusion.Vlachopoulos, J etc. be at " Materials science and technology " (Materials Science and Technology), and 19 (9), 1161-1169 has described the melt technology in (2003), here with reference to quoting the document." screw rod extrusion molding: Science and Technology (polymer processing progress) " (Screw Extrusion:Science and Technology (Progress in Polymer Processing)) that White etc. compile, HanserGardner Publications has described extrusion process in (2003), here with reference to quoting the document.

In another embodiment, mixed cellulose ester is by the moulding of melt injection moulding process.Injection moulding prepares a large amount of little and big parts by molten polymer being injected die cavity.The example of melt injection moulding comprises injection moulding, injection blow molding, injection stretch blow, material feeding die casting, overmolding and embedding mould." injection moulding handbook (Injection Molding Handbook) (third edition), volumes such as Rosato, Springer (2000) and " injection moulding: introduce " (Injection Molding:An Introduction), Potsch etc., among the Hanser Gardner Publications (1995) the injection moulding process details has been discussed, here with reference to quoting these documents.

The preparation of controllable release matrix system

In another embodiment, mixed cellulose ester can be used for forming allly if can influence for example controllable release matrix system of the controllable release of spices, agricultural additives or medicated premix.Additive is not to be written into simply or to be incorporated in the appearance face of matrix system.On the contrary, the controllable release matrix system is the basic mixture uniformly of cellulose ester and additive.This low release matrix system can comprise the remaining swelling agent of the about 5wt% matrix system of about 0.005wt%-.

Controllable release matrix system of the present invention allows selection and the consumption according to cellulose ester and additive, and the molecular weight of cellulose ester and substitution value, with different speed release additives.Preferably also control rate of diffusion in one embodiment with softening agent.

Importantly, in the present invention, additive does not have chemistry to contact with cellulose ester.Therefore, unlike the controllable release system of some prior art, do not need the chemical bond hydrolysis between additive and polymer supporting material to come release additives.In certain embodiments, cellulose ester can be biodegradable, and the biological degradation that makes additive pass through cellulose ester discharges.Perhaps cellulose ester can be biological nondegradable, makes additive pass through diffusion and discharges.

In a controllable release matrix embodiment, cellulose ester has the substitution value of about 1.0-about 3.0.In another embodiment, cellulose ester is that the about 2.5-of substitution value is about 3.0, the rhodia of preferably about 2.7-about 3.0.In another embodiment, cellulose ester is that the about 0.5-of acetyl substitution value is about 2.0, the rhodia of preferably about 1.6-about 1.8.In another controllable release matrix embodiment, cellulose ester is that the about 0.1-of acetyl substitution value is about 2.1, the cellulose acetate propionate of the about 0.5-of propionyl substitution value about 2.5.In another embodiment, cellulose ester is that the about 0.3-of acetyl substitution value is about 2.1, the cellulose acetate butyrate of the about 0.75-of butyryl substitution value about 2.6.In one embodiment, the controllable release matrix optimization contains the about 99.9wt% cellulose ester of the 50wt%-that has an appointment, and the about 99wt% Mierocrystalline cellulose of preferably about 70wt%-always refetches 100wt% based on matrix system.

Can adopt various spices in the controllable release matrix of the present invention.Can mix any spices or the spices blend that can diffuse in the swollen cellulose ester matrix.Can be used for the Fabulous Fragrances that spices of the present invention comprises Jan Moran; The Fragrances ofthe World of Michael Edwards; The The Illustrated Encyclopedia of EssentialOils of Julia Lawless; The Chemistry of Fragrant Substances of Paul Jose Teisseire; TheFragrance Foundation Reference Guide 1999, disclosed spices among the The Fragrances Foundation (New York, 1999) is here with reference to quoting every piece of these document.Spices can contain the complicated blend of flavor compounds, or mixes extract in the controllable release matrix system.As selection, spice additive can be a mask agent.Softening agent can mix with spices, to regulate the controllable release velocity of diffusion.

Various medicines or biologically active additives can be used in the controllable release matrix system.Any medicated premix compatible with the plain ester of Biodegradable fibers all can be used for the present invention.Can be used for medicated premix of the present invention is disclosed among Physician ' the s Desk Reference.

Mode of administration according to expection, the controllable release matrix system that comprises medicated premix can be the pharmaceutical composition of solid or semisolid dosage form, for example tablet, suppository, pill, capsule, pulvis, liquid, suspension, lotion, paste, gel etc. preferably are suitable for the individually dosed unit dosage of exact dosage desired.In addition, the controllable release matrix system can comprise other medicinal reagent, pharmaceutical agent, carrier, auxiliary agent, thinner etc.

For oral administration, fine powder or particle can contain thinner, dispersion agent and/or tensio-active agent, and can be present in water or the syrup; Be present among the sachet of capsule or drying regime; Be present in anhydrous solution or the suspension; Be present in tablet or be present in water or syrup in suspension in.Under the situation that requires or need, can comprise seasonings, sanitas, suspension agent, thickening material and/or emulsifying agent.Tablet and granule are the preferred oral administration formulations, and they can be dressings.Injection can be used as liquor or suspension, be dissolved or suspended in the solid form in the liquid before being adapted at injecting, or as emulsion, prepares with conventionally form.

The definite consumption of medicated premix has nothing in common with each other, and depends on individual kind, age, weight and general condition; Need the severity of disease, infection or the state of treatment or prevention; Used concrete medicated premix; And mode of administration.Those of ordinary skills can determine appropriate vol.In one embodiment, the amount of controllable release matrix system Chinese traditional medicine additive is the about 50wt% of about 0.1wt%-, and the about 20wt% of preferably about 0.1wt%-always refetches 100wt% based on the controllable release matrix system.This system can be used for treating human and animal (wild with domestic).

The size and dimension of controllable release matrix system can be used to produce the technology of raw pellets of matrix system and difference according to manufacturing.In one embodiment, matrix system can be that exemplary dimensions is the about 50mm of about 0.1mm-, the about 10mm of preferably about 0.1mm-, the more preferably from about particle of the about 5mm of 0.5mm-or sphere.

Various agricultural additives can be used for controllable release matrix system of the present invention.The typical agricultural additive above has been discussed.But the amount of the agricultural additives of doped matrix system can be depending on the rate of release of agricultural additives and additive.In a preferred embodiment, the controllable release matrix system comprises the about 50wt% agricultural additives of about 0.1wt%-, the preferred about 30wt% agricultural additives of about 0.1wt%-, the about 20wt% agricultural additives of 0.1wt%-more preferably from about always refetches 100wt% based on matrix system.

The controllable release matrix system that contains agricultural additives can be by the technology distribution that is used to use agricultural, gardens or lawn chemical product known in this field.This system can be used for treating plant (agricultural, gardens, meadow etc.) and/or soil.

Can be from controllable release matrix system release additives required time according to used cellulose ester with additive and different.In case additive begins to discharge, also can change according to used cellulose ester and additive the deenergized period of additive.Release period (promptly all additives all overflow matrix required time) basically can be from several days to several years.In one embodiment, can mix small amount of plasticizer in the controllable release matrix system or tensio-active agent comes the adjustment release course.In another embodiment, can there be the small portion of residual swelling agent in the controllable release matrix system.

The preparation of indicator matrix system

Mixed cellulose ester also can be used for forming indicator matrix.The typical indicator that is used for temperature, pH value etc. above has been discussed.

Embodiment

Following examples have illustrated according to the preferred method of the present invention.Yet, should understand these embodiment and be used to illustrate and non-limiting overall range of the present invention.

Test method

1, the gel permeation chromatography of determining molecular weight (GPC)

Eluent is the N-Methyl pyrrolidone (NMP) that contains 1wt% acetate.Temperature is 40 ℃, and flow is 0.8ml/min.Used post is Polymer Laboratories 10 μ m PLGel, and one is the anti-guard post of 50 * 7.5mm, and one is 300 * 7.5mm Mixed B analytical column, and detector is a specific refractory power.Sample is by dissolving 25mg polymkeric substance in 10mL NMP+10 μ L toluene and add the preparation of flow marker.The sample injection volume is 20 μ L.Molecular weight is reported as the polystyrene equivalent with the monodisperse polystyrene standard substance.

2, color analysis

Sample is dissolved in 90/10 (vol/vol) methylene chloride with 15% solid content, and curtain coating prepares 5 mil thick films then.The transmission of film sample is measured by Perkin-Elmer Lambda950 UV-visible spectrophotometer, and the percent transmittancy value at 400nm place is as the value of indication sample jaundice.

3, to the analysis of softening agent and additive

Take by weighing sample,, and be dissolved in the methylene dichloride with the internal standard substance enhanced sensitivity of known quantity.From solution, be settled out cellulose ester by adding non-solvent, stayed softening agent and stablizer in the liquid phase.Filtered sample is also passed through gc analysis liquid.

4, gas-chromatography (GC) method

Gas-chromatography is being equipped with DB-1301 (J﹠amp; W) carry out on the HP6890 gas chromatograph of 30M * 0.32mm * 0.25 μ m analytical column and flame ionization detector (FID).Carrier gas is with 150ml/min shunting mobile helium, is warmed up to 250 ℃ with 15 ℃/min from 40 ℃.

5, inductively coupled plasma optical emission spectrography (ICP-OES)

In the method, by at trace-metal level HNO ₃Middle digestion material preparation sample.Add internal standard substance, sample is sucked in the argon gas inductively coupled plasma.Plasma body ionization also excites the element that exists in the sample.Detect the excited state emission obtain then, and based on the comparison of concentration known standard substance response, be used for the concentration of those elements of volumetric soiutions.

6, profile IR method

Profile (profile) infrared spectroscopy (with Nic-Plan IR microscope coupled NicoletNexus 670 spectrophotometers) is used for the additive that the whole pellet of detection by quantitative exists.The pellet sample is imbedded in the epoxy, obtained section from the pellet middle part with slicing machine then.Measure three points, promptly near the edge, the infrared absorption degree of middle road and pellet center.It is 100 that additive level is normalized to high-content duration.

Embodiment 1

Softening agent and the stablizer dipping in pellet

Cellulose triacetate (" CTA ", CA-436-80 is from Eastman ChemicalCompany) (300g) (150g) is mixed in 32 ounces of vials with acetone (300g) and the diethyl phthalate (DEP) that contains 1% tert.-butyl phenol.Bottle was rotated 16 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and pellet swelling and be full of bottle.Pellet is poured in the shallow chassis, and air-dry 78 hours of room temperature.Weighing dry granular material is 446g.Obtained the pellet that theoretical plasticizer loading is 32.8% softening agent like this.But this dry granular material unrestricted flow, shape and raw pellets are similar, but size is bigger and shape is more irregular a little.This pellet is carried out the softening agent analysis, obtain 32.36%DEP and 0.17% tert.-butyl phenol.This shows that softening agent and stablizer all immerse in the pellet.

Embodiment 2

The dipping of softening agent in pellet

(CA-436-80 is from Eastman Chemical Company) (440g) mixes in 32 ounces of vials with acetone (450g) and triphenylphosphate (60g) with cellulose triacetate.Bottle was rotated 24 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and pellet swelling and be full of bottle.Then pellet is poured in the shallow chassis, and at room temperature air-dry, then forced in the air ovens dry 6 hours at 60 ℃.Weighing dry granular material is 506g, and this is consistent with target 12% plasticizer loading.But this dry granular material unrestricted flow, shape and raw pellets are similar, but size is bigger and shape is more irregular a little.

Embodiment 3

The dipping of UV stablizer in pellet

With cellulose triacetate (CA-436-80, from Eastman Chemical Company) (200g) with 200g acetone and 1.0g Tinuvin7 292 (UV stablizer, obtain from Ciba) and 1.0g Tinuvin7 1130 (the UV absorption agent obtains from Ciba) 32 ounces of vials, mix.Bottle was rotated 15 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and granule size obviously increases.Free flowable pellet is poured in the shallow chassis, and air-dry 78 hours of room temperature.

Embodiment 4

Melt has been flooded the pellet of softening agent and stablizer

(CA-436-80 is from Eastman Chemical Company) (400g) mixes in 32 ounces of vials with acetone (300g) and diethyl phthalate (200g) with cellulose triacetate.Bottle was rotated 6 hours, and nearly all during this period liquid all is inhaled in the cellulose triacetate pellet, and pellet swelling and be full of bottle.Pellet is poured in the shallow chassis, and air-dry 24 hours of room temperature.Weighing dry granular material is 600g, shows that pellet contains 33% softening agent.But this dry granular material unrestricted flow, shape and raw pellets are similar, but size is bigger.On the APV extruding machine, should flood pellet, obtain estimating adhesive tape with good color and finish plate in 265 ℃ of extrusion moldings.

Embodiment 5

Melt has been flooded the pellet of CTA/DEP/TPP/ stablizer

With cellulose triacetate (CA-436-80, from Eastman Chemical Company) (500g) stabilizer blend (5g, phosphite antioxidant and epoxidation oil base thermo-stabilizer) with acetone (300g), diethyl phthalate (48g), triphenylphosphate (48g) and blend in 32 ounces of vials, mix.Bottle was rotated 12 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and pellet swelling and be full of bottle.Pellet is poured in the shallow chassis, and air-dry 24 hours of room temperature.Weighing dry granular material is 617g.But this dry granular material unrestricted flow, shape and raw pellets are similar, but size is bigger.On the APV extruding machine, should flood pellet, obtain having the adhesive tape of good color and finish plate in 265 ℃ of extrusion moldings.

Embodiment 6

Melt has been flooded the pellet of CTA/TPP/ stablizer

With cellulose triacetate (CA-436-80, from Eastman Chemical Company) (400g) stabilizer blend (2g, phosphite antioxidant and epoxidation oil base thermo-stabilizer) with acetone (300g), triphenylphosphate (100g) and blend in 32 ounces of vials, mix.Bottle was rotated 12 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and pellet swelling and be full of bottle.Pellet is poured in the shallow chassis, and air-dry 24 hours of room temperature.Weighing dry granular material is 617g.But this dry granular material unrestricted flow, shape and raw pellets are similar, but size is bigger.On the APV extruding machine, should flood pellet, obtain having the adhesive tape of good color and finish plate in 260-265 ℃ of extrusion molding.

Embodiment 7

Film extrusion has flooded the pellet of CTA/DEP/TPP/ stablizer

With cellulose triacetate pellet (CA-436-80, from Eastman ChemicalCompany) (800g) add in the mixture of acetone (800g), diethyl phthalate (50g), triphenylphosphate (150g) and stabilizer blend (8g, phosphite antioxidant and epoxidation oil base thermo-stabilizer) in 64 ounces of vials.Bottle was rotated 24 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and pellet swelling and almost be full of bottle.Finger is touched dried, free flowable pellet pour in the shallow chassis, and air-dry 24 hours of room temperature.Further dry this air-dry pellet 6 hours in 50 ℃ of baking ovens then.This dry granular material is free flowable, and its shape and raw pellets are similar, but size is bigger.Single multiple screw extruder by 6 inches sheeting dies are housed is in 270 ℃ of pellets that extrusion molding is treated then.This film has good color and transparency through range estimation.

Embodiment 8

The evaluation of softening agent among the CTA

In the method, the 40g cellulose triacetate is exposed in the mixture of 30g acetone and 30g softening agent 16 hours.Discharge unnecessary liquid.Blot pellet then and 25 ℃ of dryings 24 hours, then in forcing air oven in 50 ℃ of dryings 24 hours.Dried weight is the indication of plasticizer absorption, therefore can be used for more different softening agent affinity and diffusibleness.Table 1 has been listed the various softening agent and the plasticizer absorption of test.

Table 1

Softening agent	Expose and dried gross weight (g)	Plasticizer absorption (g)	Plasticizer absorption rate wt%
				Triactin	69.62	29.62	99％
Triethyl citrate (TEC)	66.19	26.19	87％
				Triphenylphosphate (TPP)	63.18	23.18	77％
Diethyl phthalate (DEP)	62.53	22.53	75％
				Citric acid acetyl triethyl (ATEC)	61.44	21.44	71％
Tripropionin	59.49	19.49	65％
				Glucose five propionic esters (GPP)	56.57	16.57	55％
Glycolic acid butyl phthalyl butyl ester	53.69	13.69	46％
				PEG400	53.65	13.65	46％
Dibutyl phthalate (DBP)	52.42	12.42	41％
				Diisobutyl adipate (DIBA)	49.33	9.33	31％
PPG425	48.50	8.50	28％
				Texanol isobutyrate TXIB	47.30	7.30	24％
Diisononyl phthalate (DINP)	45.30	5.30	18％
				Hexanodioic acid two (2-ethylhexyl) ester (DOA)	44.72	4.72	16％
Tri trimellitate (2-ethylhexyl) ester (TOTM)	44.16	4.16	14％
				TPP/DEP 1∶2	62.1	22.1	73％
TPP/DEP 1∶1	61.7	21.7	72％
				TPP/DEP 2∶1	61.2	21.2	71％

Embodiment 9

The evaluation of swelling agent among the CTA

In the present embodiment, the 200g cellulose triacetate is exposed in 150g diethyl phthalate (DEP) and the 150g swelling agent 16 hours.Discharge unnecessary liquid.Blot pellet then and 25 ℃ of dryings 24 hours, then in forcing air oven in 50 ℃ of dryings 24 hours.Dried weight is the indication of plasticizer absorption, is used for the different swelling agents of comparison.Table 2 has been listed the various swelling agents and the plasticizer absorption of test.

Table 2

Swelling agent	Expose and dried gross weight (g)	DEP absorbed dose (g) roughly
			Acetate	323.4	123.4
Acetone	322.6	122.6
			Methyl acetate	313.6	113.6
Acetonitrile	274.2	74.2
			Methyl alcohol	227.1	27.1
Methyl ethyl ketone (MEK)	224.3	24.3
			Turkey red oil	205.2	5.2
Ethyl acetate	220.6	20.6
			Tetrahydrofuran (THF) (HF)	204.5	4.5
Diethylene glycol monomethyl ether	201.7	1.7
			Ethanol	200.8	0.8
P-Xylol	200.8	0.8
			Benzene	200.4	0.4
O-Xylol	200.0	0.0
			Toluene	200.0	0.0

To the most effective swelling agent of cellulose triacetate is acetone, methyl acetate and acetate.The effect of acetonitrile in this test is general, and methyl alcohol, methyl ethyl ketone (MEK) and ethyl acetate are very little to the effect of plasticizer absorption.The sample (be equivalent to effective softening agent incorporation and be lower than 3%) that the weight increase is lower than 5g is the swelling agent of non-constant for this cellulose triacetate/DEP system.Some these liquid, for example turkey red oil and DEP, very thickness stays to hang on the pellet easily, makes DEP absorb high untrue of value.Do not have the very poor sample of swelling agent or swelling agent show do not have suitable swelling agent in the presence of additive infiltrate poor.Handle and do not have the profile IR analysis revealed of the pellet of swelling agent through DEP, only there is extremely thin DEP layer in the pellet surface, and pellet inside does not contain DEP.With acetone as the pellet of swelling agent also by profile IR method test, showing on the whole pellet cross section all has softening agent.

Embodiment 10

The CTA/ white dyes

Cellulose triacetate (CA-436-80 is from Eastman ChemicalCompany) (200g) is mixed in 32 ounces of vials with 200g acetone and 1g Eccowhite white dyes (from EastmanChemical Company).Bottle was rotated 7 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and granule size obviously increases.Then pellet is poured in the shallow chassis and room temperature air-dry.Under the UV lamp (wavelength 254nm or 366nm), pellet sends strong blue-fluorescence.

Embodiment 11

The CTA/ banana aldehyde

Cellulose triacetate (CA-436-80 is from Eastman Chemical Company) (40g) is mixed in 8 ounces of vials with 30g acetone and 0.4g fruit flavor enriched material (Universal Fragrance Corporation#557921).Bottle was rotated 16 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and granule size obviously increases.Then pellet is poured in the shallow chassis and air-dry 78 hours of room temperature.Pellet has slight fruity.

Embodiment 12

CTA/ Vanillin (spices)

(CA-436-80 is from Eastman Chemical Company) (200g) mixes in 32 ounces of vials with 200g acetone, 22g DEP and 2.0g Vanillin with cellulose triacetate.Bottle was rotated 15 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and granule size obviously increases.Then free flowable pellet is poured in the shallow chassis, and air-dry 24 hours of room temperature, still had tangible Vanillin smell after air-dry.50 ℃ of further dried granules 4 hours, still have tangible Vanillin smell then.

Embodiment 13

CTA/ frame material

With cellulose triacetate (CA-436-80, from Eastman Chemical Company) (200g) with 200g acetone, 20g DEP and 0.1g alizarin (CAS[72-48-0], from Aldrich33,317-4 technical grade 85% obtains) in 32 ounces of vials, mix.Bottle was rotated 15 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period.The pellet color becomes brick-red, and size obviously increases.Then free flowable pellet is poured in the shallow chassis, and air-dry 24 hours of room temperature, then 50 ℃ of dryings 12 hours.It is brick-red that dried pellet still keeps.With the pellet of acetic acid treatment dipping alizarin, pellet is from the brick-red golden yellow that progressively become.Under the UV lamp (wavelength 366nm), the pellet of dipping sends fluorescent red-orange, and sends orange-yellow fluorescence through acid-treated dipping pellet.

Embodiment 14

The CTA/pH indicator

(CA-436-80 is from Eastman Chemical Company) (200g) mixes in 32 ounces of vials with 200g acetone and 2.0g phenolphthalein with cellulose triacetate.Bottle was rotated 15 hours, and all liquid all is inhaled in the cellulose triacetate pellet during this period, and granule size obviously increases.Free flowable pellet is poured in the shallow chassis, and air-dry 24 hours of room temperature, then 50 ℃ of dryings 12 hours.Put into the 0.05M sodium hydroxide solution when pellet and just become pink.But decantation or filtering mixt should be indicated pellet with recovery and reuse then.

Embodiment 15

CA/ Virahol/DEP

(CA-320S is from Eastman Chemical Company) (14g) mixes in 8 ounces of vials with Virahol (14g) and diethyl phthalate (14g) with rhodia.Bottle was rotated 16 hours, and all liquid all is inhaled in the rhodia pellet during this period, and pellet swelling and be full of bottle.Then pellet is poured in the shallow chassis, and air-dry 24 hours of room temperature, then 50 ℃ of dryings 12 hours.Dry granular material weight is 27.3g.Obtain the pellet of theoretical plasticizer loading 49wt% like this.But unrestricted flow of dry granular material and shape and raw pellets are similar.

Embodiment 16

CA/ acetone/triactin

(CA-320S is from Eastman Chemical Company) (40g) mixes in 8 ounces of vials with acetone (30g) and triactin (30g) with rhodia.Bottle was rotated 16 hours, and all liquid all is inhaled in the rhodia pellet during this period, and pellet swelling and be full of bottle.Then pellet is poured in the shallow chassis, and air-dry 24 hours of room temperature, then 50 ℃ of dryings 12 hours.Dry granular material weight is 58.6g.Obtain the pellet of theoretical plasticizer loading 31wt% like this.But unrestricted flow of dry granular material and shape and raw pellets are similar.

Embodiment 17

CA/ methyl alcohol/DEP

With rhodia (CA-320S, DS _AC～1.7-1.8 is from Eastman ChemicalCompany) (10g) in 8 ounces of vials, mix with methyl alcohol (15g) and diethyl phthalate (10g).Bottle was rotated 16 hours, and pellet dissolves fully during this period.This shows that methyl alcohol is not the suitable swelling agent of CA-320S, because it is too high to the solvating ability of CA-320S.

Embodiment 18

Handled the dissolving of pellet

This process will compare with the art methods for preparing dope prepare dope with the cellulose triacetate pellet of having handled.Be used to prepare under the laboratory scale condition of cellulose triacetate dope in prior art, the solid cellulose triacetate added in the solution of the solvent, softening agent and any other additive that contain requirement.After in bottle, forming mixture, come the mixed content thing by on parallel rollers, rotating bottle.Under representative condition, the triacetate solid dissolved in about 24 hours.In this research, will be by the contrast triacetate pellet of the prior art method preparation with wherein softening agent and additive compare with the pre-soaked treated triacetate pellet of swelling agent.

Set up control sample and test sample simultaneously, make final solution by 90g cellulose triacetate (CA-436-80 is from Eastman Chemical Company), 10g triphenylphosphate, 1 (＜0.05g) blue dyes (phthalocyanine radical dye) and 567g 90/10 (v/v) CH ₂Cl ₂/ CH ₃OH (target 15% solid dope) forms.In solvent, add blue dyes,, but do not wish the influence dissolving so that observe the dissolving process better.

Control sample A makes with cellulose triacetate.Test sample B is with pre-soaked softening agent and stablizer, makes triphenylphosphate content reach 10% 100.0g and handled the pellet preparation.Two kinds of pellets all before solubility test in 60 ℃ of dryings 16 hours.

For control sample A, in quart bottles, 10g triphenylphosphate and 1 blue dyes are dissolved in 567g 90/10 (v/v) CH ₂Cl ₂/ CH ₃Among the OH.For test sample B, the liquid in the quart bottles is 567g 90/10 (v/v) CH ₂Cl ₂/ CH ₃OH and 1 blue dyes.

Pellet is added it, and moment of liquid in bottle is defined as time=0 (referring to accompanying drawing 1a separately; In each two bottle image, control sample A on the left, and test sample B is on the right).Add pellet fast, and after adding pellet, use each bottle of hand rolling immediately, to minimize the caking of pellet.Pellet among the control sample A expands and also sticks on the bottle wall, so Sample A will additionally be fiddled with and with long scraper stirring, to attempt to open caking.The sample B pellet initially just disperses and need not to open by hand.With hand rolling after 5 minutes, photo shown in Fig. 1 a that acquisition time=5 minute are located is transferred to bottle on the parallel rollers then and is mixed, and this is the typical method of mixed cellulose ester dope.Two bottles all mix by rotating in test, and 23 hours time span intercycles remove, thereby the dissolving process is taken a picture.In order to take sample, bottle is removed from mixing roll, and got the same position of built in light and background.Take a picture with about 2 minutes, and in order to compensate unmixed period of this section at every turn, before taking off the back from roller and getting back on the roller, all use 5 seconds of each bottle of hand rolling.

Hour locate in time=1, control sample A has a small amount of bigger caking, and (Fig. 1 a) and test sample B has the little gel of many dispersive.After 6 hours, gel size diminishes, and the small gel in the sample B almost be cannot see (Fig. 1 b).Hour locate in time=9, the gel in the Sample A is about 2cm * 2cm * 5cm, and the gel in the sample B dissolves basically, and gel is invisible to the naked eye.After 12 hours, the gel in the Sample A becomes more transparent.Hour locate in time=24, undissolved gel has almost dissolved and has been about 1cm among the control sample A ³Hour locate in time=27, Sample A and B be dissolving fully, and becomes and contain 90g CTA (CA-436-80), 10g triphenylphosphate, 1 blue dyes and 567g 90/10 (v/v) CH ₂Cl ₂/ CH ₃The same solution of OH.

Control sample A dissolves in about 27 hours as expectedly fully, and it is also like this to prepare the triacetate dope with art methods.Treated preimpregnation pellet dissolving is faster, only just cannot see gel after 9 hours.Treated pellet since easier initial dispersion in solvent, and under a given set condition, keep to disperse and dissolving obviously faster than untreated cellulose triacetate pellet, and show astonishing improvement.This dissolving improves and is used on the dope of spun fibers, solution casting film, coating etc. very useful in preparation.

In two other dissolving comparative studies, the cellulose triacetate pellet of contrast dissolved in 15-24 hour, and treated pellet dissolved in 9-12 hour.Dissolution time is subjected to the initial dispersion influence of temperature, solid/solvent ratio, plasticizer loading and pellet, but in each case, treated softening agent dipping pellet is all compared according to the pellet dissolving fast.

Embodiment 19

The melt-spun of the cellulose triacetate pellet of dipping

Cellulose triacetate pellet (CA436-80 is from Eastman ChemicalCompany) (300g) is added in 64 ounces of bottles that 67g diethyl phthalate (DEP), 33g triphenylphosphate (TPP), 3g patent stabilizer blend (phosphite antioxidant and epoxidation oil base thermo-stabilizer) and 300g acetone are housed.Come blended mixts by on parallel electromotive roller, rotating bottle.Most of liquid was absorbed in about 4 hours, but will the mixture rotation spend the night.With the swollen pellet 25 ℃ air-dry, in 65 ℃ of vacuum drying ovens dry 3 hours then.Pellet is reeled off raw silk from cocoons after the extra dried overnight in 60 ℃ of vacuum drying ovens immediately.Melt-spun carries out being equipped with in the laboratory scale melt-spun system of toothed gear pump and 16 hole draw plates.Barrel zone temperature is set 270 ℃.With fiber traction with do not draw melt-spun and obtain the canescence fiber.

Embodiment 20

The melt-spun of the rhodia pellet of dipping

With rhodia (CA320S is from Eastman Chemical Company) washing, and stable again by in pellet water slurry, adding calcium hydroxide, obtain 99ppm calcium.The content of calcium is measured with inductively coupled plasma emmission spectrum (ICP-OES) in the cellulose ester sample.

The pellet that these are stable again (300g) adding is equipped with in 64 ounces of bottles of 75g triactin (softening agent), 3g patent stabilizer blend (phosphite antioxidant and epoxidation oil base thermo-stabilizer) and 300g acetone.With hand rolling bottle 2 minutes, mix by on parallel electromotive roller, rotating bottle then.Liquid was all absorbed in 15 minutes.Will the bottle rotation spend the night.The pellet of dipping is air-dry under environment (25 ℃) condition, in 65 ℃ of vacuum drying ovens dry 3 hours then.Pellet is reeled off raw silk from cocoons after the extra dried overnight in 60 ℃ of vacuum drying ovens (20mmHg) immediately.Melt-spun carries out being equipped with in the laboratory scale melt-spun system of toothed gear pump and 16 hole draw plates.Barrel zone temperature is set 260 ℃.With fiber traction with do not draw melt-spun and obtain the canescence fiber.

Embodiment 21

Cellacefate with dyestuff and spices

Cellacefate (40g) added 30g ethanol, 10g Virahol, 1g triactin, 4g oranges and tangerines spices (Universal Fra grance Co., " Citrus Melange ") are housed and (＜0.01g) mixture adds in 16 ounces of bottles from the printing ink of yellow marking pen.Shake mix 10 minutes, during all liquid absorb in the pellet.The swollen pellet is light yellow, and wherein some pellet is more transparent, and some is more muddy.Open bottle cap and content is exposed under environment (25 ℃) condition with the evaporation swelling agent.Periodically stir pellet, lump when minimizing drying.Dried granules has the light yellow of pleasant citrus aromes.

Embodiment 22

Cellacefate with dyestuff and spices

17g ethanol, 15g Virahol, 4g grape flavor (" Add a Scent " board spices are equipped with in Cellacefate (40g) adding, obtain from Darice Inc., be used for making the volatile oil of candle and perfumed soap) and from the printing ink of red permanent marker (＜0.01g) mixture adds 16 ounces of bottles.Shake mix 10 minutes, during all liquid absorb in the pellet.The swollen pellet is a pink, and wherein some pellet is more transparent, and some is more muddy.Open bottle cap and content is exposed under environment (25 ℃) condition with the evaporation swelling agent.Periodically stir dried granules, to minimize caking.Dried granules has the pink of pleasant fruit aroma.

Embodiment 23

Reclaim swelling agent

Cellulose triacetate pellet (CA436-80S is from Eastman ChemicalCompany) (90g) is added and is equipped with in 16 ounces of bottles of 80g acetone and 10g diethyl phthalate.The bottle rotation is spent the night.The swollen pellet is placed the 500ml round-bottomed flask, and be placed on the rotary evaporating device (B ü chi Rotavapor RE121 is equipped with frozen water refrigerative condenser, water aspirator (50mmHg) and heating bath).Heating bath is set 65 ℃, and motor is 55rpm.After 30 minutes, reclaim the 31.5g swelling agent, after about 1 hour, the dry granular material is weighed as 108.6g.This test shows, by the condenser with vacuum and water quench, can realize the partially recycled of swelling agent in dried granules.

Embodiment 24

Reclaim swelling agent

Rhodia pellet (CA320S is from Eastman Chemical Company) (90g) is added and is equipped with in 16 ounces of bottles of acetone (100g) and triactin softening agent (10g), and on parallel rollers, rotate bottle.All liquid absorbed in 10 minutes.The bottle rotation is spent the night.The swollen pellet is transferred in the 1000ml round-bottomed flask, and beaker is placed on the rotary evaporating device (B ü chi Rotavapor RE121 is equipped with frozen water refrigerative condenser, water aspirator (50mmHg) and heating bath).Heating bath is set 55 ℃, and motor is 55rpm.After 30 minutes, reclaimed the 51g swelling agent, after about 1 hour, pellet is weighed as 109.6g.This test shows, by the condenser with vacuum and water quench, can realize the partially recycled of swelling agent in dried granules.

Embodiment 25

Reclaim swelling agent from swollen mixing pellet

(800g, CA436-80S) solution with 700g acetone, 100g methyl acetate, 150g triphenylphosphate (TPP) and 50g diethyl phthalate (DEP) mixes in 1 gallon of bottle with cellulose triacetate.Mixture is rotated in bottle spend the night (about 16 hours).Repeat this process and obtain four batches of swollen cellulose triacetate pellets.Remove phase for swelling agent, the swollen pellet is divided into 8 batches, so that they are packed in 3 liters of flasks on the B ü chi rotary evaporating device.Bathe temperature, 20rpm rotating speed and every batch of 1 hour time with water vacuum, 50 ℃ and remove swelling agent.On rotary evaporating device from pellet desorb swelling agent 1 hour, but consuming time being longer than 1 hour evaporated in evaporation fully fully.Altogether the 2123g swelling agent is recovered (theoretical total swelling agent 66.4%).The swelling agent of removing is by directly with in the liquid inject gas chromatograph (GC), measures the ratio of acetone and methyl acetate, and the amount of the softening agent of desorb is analyzed during measuring swelling agent and removing.To the GC of recovering liquid analyze obtain consist of 92.23% acetone (theoretical 87.5%), 7.74% methyl acetate (theoretical 12.5%) and 3.04ppm diethyl phthalate.Do not detect triphenylphosphate.

The GC analysis revealed, acetone increases with the ratio of methyl acetate in the swelling agent of recovery.Should notice that solvent desorption acutely captures and also carries out not thoroughly, these two factors all can influence the ratio of acetone and methyl acetate accurately.Importantly, the low plasticizer content of 3ppm diethyl phthalate and not detect triphenylphosphate very desirable only in the swelling agent of recovery, this shows that softening agent is retained in the polymkeric substance basically.Low plasticiser in the swelling agent of desorb pollutes the content that can predict softening agent in the polymkeric substance more accurately, and swelling agent need not thoroughly to purify just recycling.

Embodiment 26

The recovery and reuse of swelling agent

(CA436-80S, 90g) adding is equipped with in 16 ounces of bottles of 90g acetone and 10g triactin with the cellulose triacetate pellet.Mixture placed on the electrical parallel roller mix.Most of swelling agent was aggregated thing and absorbs after 1 hour.Bottle is rotated spend the night (about 14 hours).

The swollen pellet is placed the 500ml round-bottomed flask, and be placed on the rotary evaporating device (B ü chiRotavapor RE121 is equipped with frozen water refrigerative condenser, water aspirator and heating bath).Heating bath is set 55 ℃, and motor is set 55rpm.After 30 minutes, reclaim the 53g swelling agent, pellet is weighed as 107.3g.Softening agent analysis revealed 9.8% triactin.

In 8 ounces of bottles, mix acetone and the 5g triactin softening agent that 50g reclaims.In this mixture, add 45g cellulose triacetate pellet (CA436-80S), and the mixture that rotates in the bottle mixes.Most of swelling agent was aggregated thing and absorbs after 1 hour.The bottle rotation is spent the night about 14 hours.The swollen pellet is placed the 500ml round-bottomed flask, and be placed on the rotary evaporating device (B ü chi Rotavapor RE121 is equipped with frozen water refrigerative condenser, water aspirator and heating bath).Heating bath is set 55 ℃, and motor is set 55rpm.After 30 minutes, reclaim 21g acetone, pellet is weighed as 52.4g.Softening agent analysis revealed 10.2% triactin.

This test shows that swelling agent is recyclable, and the swelling agent of this recovery can be used as swelling agent and new a collection of polymkeric substance and additive recycles.The recovery and reuse of swelling agent have reduced the expense of the swelling method of impregnated additive in polymkeric substance.

Embodiment 27

On rotary evaporating device, mix simultaneously with swelling agent and reclaim

In the 500ml round-bottomed flask, mix 60g acetone, 8g diethyl phthalate (DEP) and 72g cellulose triacetate pellet (CA436-80S, from Eastman ChemicalCompany), and flask is placed on the rotary evaporating device (B ü chi Rotavapor RE121).In the mixed phase of this test, earlier this unit is set at the above rotary flask of water-bath and does not have vacuum.160rpm is set in this unit reach 5 minutes, be reduced to 80rpm then and reach 10 minutes, be reduced to 60rpm at last and reach 15 minutes.Mix after 30 minutes, pellet is swelling and be rubber-like, then flask is dropped in 55 ℃ of water-baths remix 30 minutes, still under environmental stress.Mixing time after 1 hour, is opened the evaporation stage that vacuum begins this test altogether.Water-bath is set 55 ℃, and 60rpm is set in rotation, and uses water vacuum and water-cooled condenser.The acetone that reclaims of weighing after about 30 minutes is 26.5g, and after about 2 hours, the cellulose triacetate pellet is weighed as 82.7g.Softening agent analysis revealed 10.0%DEP.

Embodiment 28

In matrass, mix simultaneously with swelling agent and reclaim

1000ml three neck round-bottomed flasks are equipped with electronic stirring rake, heating mantles and water-cooled distiller condenser.In this flask, mix 90g acetone, 6g triphenylphosphate (TPP), 6g triactin and 88g cellulose triacetate (CA436-80S is from Eastman Chemical Company).Stirred the mixture 40 minutes, during most of liquid all absorbed by the cellulose triacetate pellet, and pellet does not lump.Open heating mantles with low temperature (about 40 ℃) then, additionally stir the mixture 20 minutes to finish the dipping phase.All free fluids all are inhaled in the pellet during this time, and pellet touches dried rubber-like for referring to, and freely stir.In order to begin swelling agent evaporation phase, keep stirring, heating is elevated to about 55 ℃, opens vacuum valve, and will distill the reception flask and be immersed in the dry ice.Swelling agent is easy to distill from the swollen pellet, and the acetone that reclaims after 2 hours is weighed as 54.8g.Reheat and vacuum are after 1 hour, and the cellulose triacetate pellet is weighed as 100.7g.Softening agent analysis revealed 6.2% triactin and 6.0%TPP.

Embodiment 29

Be used for the screening of the swelling agent of different cellulose ester

In this screening research, three kinds of different cellulose ester: rhodia (CA398-30), cellulose acetate propionate (CAP141-20) and cellulose acetate butyrate (CAB171-15) all obtain from Eastman Chemical Company, all use with its powder commercial form.Candidate's swelling agent comprises alcohol series and ester series.20g candidate swelling agent is equipped with in candidate's cellulose ester (20g) adding to be added in 4 ounces of bottles (is 8 ounces for CAP141-20) of 2g diethyl phthalate as representative softening agent.At room temperature rotate bottle then and mix these components.Observe the interaction of swelling agent and polymkeric substance.Performance to the expectation of suitable swelling agent is swelling and softening polymkeric substance, and dissolve polymer not, thereby promotes the diffusion of additive in polymeric matrix, and the shape of polymkeric substance and form keep similar.Sample is being observed after 16 hours and after 5 days.Observations is shown in following table 3.The volume that measurement is exposed to after the swelling agent provides the swelling indication.Too strong swelling agent often reduces volume owing to being partly dissolved.The ideal swelling is hardness and the outward appearance indication by exposing the post polymerization thing also.Increase as fruit volume, but polymkeric substance keeps hard gravel shape, then swelling agent too a little less than, be not good candidate.Can dissolve very much or the blend of too weak swelling agent also is suitable swelling candidate.For rhodia CA398-30, best candidate is methyl alcohol and propyl acetate.For CAP141-20 and CAB171-15, butylacetate provides best swelling and has softened.Butylacetate or to have admixed a small amount of certain butylacetate than Weak solvent alcohol be potential swelling candidate.

Table 3-screening general introduction

Ester	CA398-30 in 4 ounces of bottles		CAP141-20 in 8 ounces of bottles		CAB171-15 in 4 ounces of bottles
							Solvent or swelling agent	Volume (cm 3)	Note	Volume (cm 3)	Note	Volume (cm 3)	Note
Contrast (solvent-free/swelling agent)	56		84		58
							Water	113	Hard sand type; Softening slightly after shelving	141	Be bonded at the bottle outside; Sand type	90	Be deposited in the bottle outside; The gravel shape is hard
Methyl alcohol	140	Soft powder	136	Soft powder	134	Soft powder
							Ethanol	140	Hardness, sand type increase	128	Harder; The gravel shape	143	Hardness, sand type increase
N-propyl alcohol	138	Hardness, sand type increase	128	Harder; The gravel shape	132	Hardness, sand type increase
							Propyl carbinol	100	The hardest, sand type is the strongest	128	Harder; The gravel shape	132	The hardest, sand type is the strongest
Methyl acetate	72	Be partly dissolved; Softness, balling-up; Shelve the back: rubber-like is retracted to 49cm 3	90	Partly soluble soft ball adds the powder that is bonded at the bottle outside; Shelve the most of dissolving in back (59cm 3)	68	Be partly dissolved; Very soft ball adds bulky powder; Shelve the back and be rubber-like
							Ethyl acetate	72	Be partly dissolved; Spherical; Shelve the back: solid rubber-like	90	Partly soluble soft ball adds not dissolved powders; It after shelving half dissolving	66	Partly soluble soft ball and dissolved powders not; Shelve the back and be rubber-like
N-propyl acetate	140	Softness, fluffy	102	Partly soluble soft ball adds not dissolved powders; Shelve the hard ball of back for having certain transparency	85	Be partly dissolved; Harder rubber-like ball and powder; Shelve the back and be hard rubber-like
							N-butyl acetate	132	Sand type is stronger	218	Be interfused rubber-like powder (115cm at first 3); Wear into fritter and loose fluffy powder (218cm 3); Shelving the back particle keeps separating	151	Be interfused rubber-like powder (94cm at first 3); Wear into fritter and loose fluffy powder (151cm 3); Shelving the back particle keeps separate/can separating

20g cellulose ester and 20g solvent/swelling agent add that the 2g diethyl phthalate increases the prestige agent.Unless indicate in addition, sample has similar outward appearance and shape after shelving 5 days.

Embodiment 30

Comparative Examples

Rhodia (specified type in the 100.0g table 4) is stirred in 16 ounces of bottles that add the mixture that swelling agent shown in 5.0g G ﹠ W or the table 4 is housed.Because its lower tap density can be mixed the CA398-30 sample in 32 ounces of bottles.Control sample is with the 140g water carrier as glycerine, and the utilization of Comparative Examples sample provide rhodia swelling and with the immiscible swelling agent of glycerine.Mixture is rotated spend the night (about 16 hours) in its bottle separately, mix on parallel electromotive roller so that turning-over type to be provided.For per sample (p.s.), discharge any free fluid, and measure the weight that this does not absorb liquid.Remaining solid was absorbed 30 seconds with paper handkerchief, to remove any surface liquid, was dispersed in then in the tray in 25 ℃ of dryings 6 hours.After 25 ℃ of dryings, with sample 50 ℃ of vacuum-dryings 24 hours.The beaker that 10.0g glycerine is housed is placed in the vacuum drying oven with sample, this glycerine in a vacuum in 50 ℃ place 24 hours after its weight still be 10.0g.Glycerine in the beaker not evaporation shows that drying step itself can't cause the loss of glycerine in the sample.The few sample of the theoretical maximum weight 105g of weight ratio may be interpreted as the 5g glycerine that does not mix all acquisitions during exposing step.

The glycerine per-cent that dry weight that each sample obtains and softening agent analysis are learnt is shown in table 4.For every kind of rhodia, water is minimum as the glycerine water regain of the sample of carrier, and adopt as and the sample of the swelling agent of the good swelling agent of given type rhodia coupling in the glycerine water regain higher.Free fluid and insignificant weight increase high in the water sample show that glycerine more comes to the surface in these samples.The swelling method is infiltrated in the particle additive, thereby makes it be not easy to wash off or absorb.Even as if sample B, H and N have kept some remaining swelling agent after drying.Selection has more volatile swelling agent or higher drying temperature can be used for minimizing remaining swelling agent.

Table 4-is used for mixing at various rhodias the comparison of the water and the swelling agent of glycerine

	The CA type	Solvent or swelling agent	Dry weight (% glycerine)	Note
					A	CA436-80S	140g water	99.8g (0.0%)	Discharge the unnecessary liquid of about 120g
B	CA436-80S	80g acetone 5g methyl alcohol	107.5g (4.7%)	Add methyl alcohol and help the glycerine dissolving.No free fluid.The rubber-like swelling refers to touch dried particle
					C	CA398-30	140g water	100.0g (4.4%)	No free fluid, but humidity " damp sand " sense is arranged
D	CA398-30	100g methyl alcohol	101.3g (5.1%)	No free fluid.Slight remollescent damp
					E	CA398-30	84g methyl alcohol/56g ethyl acetate	101.4g (5.0%)	No free fluid.Slightly lump and thickness, but be easy to fragmentation
F	CA394-60	140g water	100.7g (1.2%)	Discharge the unnecessary liquid of about 70g
					G	CA394-60	100g methyl alcohol	101.3g (2.8%)	Discharge the unnecessary liquid of about 20g
H	CA394-60	60g methyl alcohol/40g ethyl acetate	105.9g (2.9%)	All liquid all is absorbed.Particulate fraction is transparent.
					I	PR CA	140g water	98.8g (0.7%)	Discharge the unnecessary liquid of about 95g
J	PR CA	100g methyl alcohol	102.5g (4.6%)	Discharge the unnecessary liquid of 10g
					K	PR CA	The 100g propyl acetate	-	Glycerine and propyl acetate unmixing
L	PR CA	The 100g ethyl acetate	-	Glycerine and ethyl acetate unmixing
					M	PR CA	100g 70/30 methanol/ethyl acetate	104.1g (4.5%)	Absorb about 1g free fluid
N	PR CA	100g 60/40 methanol/ethyl acetate	105.7g (5.6%)	No free fluid.The good translucent rubber shape of swelling

The CA436-80S=cellulose triacetate, DS _AC～2.8-2.9 (Eastman ChemicalCo.); Physical aspect: grain of rice shape pellet.

The CA398-30=rhodia, DS _AC～2.4-2.5 (Eastman Chemical Co.); Physical aspect: powder.

The CA394-60S=rhodia, DS _AC～2.4-2.5 (Eastman Chemical Co.); Physical aspect: the mixture of the irregular particle of powder and overall dimension 5mm.

PR CA=rhodia, DS _AC～2.4-2.5 (" Primester AcetateFlake "); Physical aspect: irregular particle, the about 20mm * 5mm of size.

Embodiment 31

Comparative Examples

For Sample A, C, E and G, rhodia (100g table 5 shown type) is sneaked in the solution of 32 ounces of 30g triactin, 10g camphor and 165g benzene in the bottle.Rotated mixture overnight about 16 hours, any excess liq of decantation, and dated weight then.Remaining wet solid is exposed under environment (25 ℃) condition, and quiet putting dried 48 hours.

For sample B, D, F and H, rhodia (100g table 5 shown type) is sneaked into 32 ounces of 30g triactins in the bottle and is dissolved in the solution of the 10g camphor in the swelling agent shown in the table 5.Rotated mixture overnight about 16 hours, any excess liq of decantation, and dated respectively weight then.Remaining wet solid is exposed under environment (25 ℃) condition, and quiet putting dried 48 hours.

In every pair of Comparative Examples, adopt the weight of the sample of non-swelling agent benzene to increase less.Substitute to adopt swelling the swelling agent of interested rhodia can obtain higher plasticizer absorption rate.In addition, by selecting swelling agent type and the quantity that cellulose ester absorbs fully between exposure period, can remove the procedure of processing of decantation excess liq.Powdery CA398-30 (sample C) has absorbed all benzene liquid really, but this powder is still very hard and the tool sand type, and this shows that liquid-absorbent mainly is the physical effect of powdery sample form, so the softening agent suction is wished more to come to the surface.Dried sample C is inhomogeneous, and duricrust district and powdery district are arranged.The softening agent analysis also shows the softening agent skewness, and the difference of same sample is submitted to and obtained different softening agent percent value (the clauses and subclauses C of table 5).The used acetate fiber of sample F have similar acetyl content, but the surface area platy form is lower, and when using the rhodia of benzene and DS2.4 to 2.5 scope, this swelling lacks and softening agent suction difference is exaggerated.

For one group of embodiment described in the table 5, plasticizer loading higher (is 40g for 100g CA), so the dissolubility property of softening agent is expected to the swelling effect of solvent/additive or swelling agent/additive solution is produced contribution.This can be obvious by sample E and the sample D in the table 5 (100g CA398-30) in the comparison sheet 4.With the compatible relatively poor glycerine of 5g, 140g 60/40 methanol/ethyl acetate is swelling rhodia well just.Yet, when softening agent becomes 30g triactin and 10g camphor (this is the more high-load deliquescent softening agent adulterant that has more), even 70/30 methanol/ethyl acetate also obtains being partly dissolved the mixture of CA398-30.Therefore, for the more compatible softening agent of 40g, become 100% methyl alcohol and obtain the mixture of swelling adulterant more suitably CA398-30.

Table 5-is used for mixing at various rhodias the comparison of the benzene and the swelling agent of camphor and triactin

	The CA type	Solvent or swelling agent	Decanting liq	Solid dry weight (% triactin) (% camphor)	Note
						A	CA436-80S	165g benzene	196g	(0.0%) 100.0g (0.0%)	Discharge excess liq.There is not the swelling sign
B	CA436-80S	80g acetone	0g	(21.5%) 139.6g (6.4%)	The pellet swelling also absorbs all liquid, obtain free flowable, refer to touch dried rubber-like pellet
						C	CA398-30	165g benzene	0g	(18.5-31.6%) 129.2g (2.3-2.5%)	All liquid is retained in the powder; As if powder is slightly sub-translucent, and has the texture of damp sand gravel
D	CA398-30	98g methyl alcohol/42g ethyl acetate	0g	136.2g	Be partly dissolved.Be dried to caking.Triactin is the cold solvent softening agent (pz) of secondary cellulose acetate, so swelling agent needs not too dissolving, to realize swelling but not be dissolved in the pz/ swelling agent mixture
						E	CA398-30	110g methyl alcohol	0g	(21.8%) 133.6g (4.9%)	All liquid is absorbed and powder has swelling and the sense of undissolved sponge.Have some caking, but they are easy to fragmentation
F	PR CA	165g benzene	171g	(5.6%) 106.3g (1.0%)	Discharge excess liq.Minimum swelling
						G	PR CA	100g methyl alcohol/10g ethyl acetate	1.3g	(21.7%) 138.8g (6.4%)	Do not absorb liquid on a small quantity.Granulate fraction is transparent
H	CA320S	165g benzene	80.0g	(14.3%) 121.8g (1.8%)	Discharge excess liq
						I	CA320S	140g acetone	0g	(21.2%) 139.6g (6.5%)	All liquid was absorbed in 1 hour

The CA436-80S=cellulose triacetate, DS _AC～2.8-2.9 (Eastman ChemicalCo.); Physical aspect: grain of rice shape pellet.

The CA398-30=rhodia, DS _AC～2.4-2.5 (Eastman Chemical Co.); Physical aspect: powder.

The CA394-60S=rhodia, DS _AC～2.4-2.5 (Eastman Chemical Co.); Physical aspect: the mixture of the irregular particle of powder and overall dimension 5mm.

PR CA=rhodia, DS _AC～2.4-2.5 (Primester Acetate Flake); Physical aspect: irregular particle, the about 20mm * 5mm of size.

The CA320S=rhodia, DS _AC～1.7-1.8 (Eastman Chemical Co.); Physical aspect: the ball of the about 2mm of diameter.

Embodiment 32

Comparative Examples

Sample 1A is with acetone-insoluble rhodia (CA394-60,50g) slurrying in 1000g water in the pottle bottle, and rotating in 60 ℃ heating cabinet 1 hour.In slurry, add 25g dimethyl phthalate (DMP) and 5g triphenylphosphate (TPP).Solid TPP (mp=48 ℃) is in case add just fusing and dispersion in several seconds in the hot mixt.Continued to stir slurry in 5 hours at 60 ℃ of additional rotation bottles.With sinter funnel isolated by vacuum filtration solid.Solid on funnel dry 1 hour is dispersed in tray then 25 ℃ of dried overnight, at last in vacuum drying oven (about 25mmHg) in 50 ℃ of dryings 24 hours.The liquid of decantation has slight grease sense.The weight of dried rhodia (theoretical maximum 80g) is shown in table 6.

(CA394-60 50g) sneaks in 8 ounces of bottles that 20g methyl alcohol, 5g ethyl acetate, 25g dimethyl phthalate (DMP) and 5g triphenylphosphate (TPP) solution are housed sample 1B with acetone-insoluble rhodia.Bottle is rotated on parallel electromotive roller, in 25 ℃ of mixed content things 5 hours.Acetate fiber crude granule meromixis becomes piece, but is easy to be broken into granular swelling remollescent particle.Granular solids is dispersed in tray 25 ℃ of dried overnight, then in vacuum drying oven (about 25mmHg) in 50 ℃ of dryings 24 hours.Dried rhodia weight (theoretical maximum 80g) is shown in table 6.

(CA394-60 50g) sneaks in 8 ounces of bottles that 30g methyl alcohol, 25g dimethyl phthalate (DMP) and 5g triphenylphosphate (TPP) solution are housed sample 1C with acetone-insoluble rhodia.Bottle is rotated on parallel electromotive roller, in 25 ℃ of mixed content things 5 hours.All liquid all is absorbed during this time, and acetate fiber crude granule partial melting, but is easy to be broken into granular swelling remollescent particle.With solid dispersed in tray 25 ℃ of dried overnight, then in vacuum drying oven (about 25mmHg) in 50 ℃ of dryings 24 hours.Dried rhodia weight (theoretical maximum 80g) is shown in table 6.

Sample 2A will be insoluble to the cellulose triacetate of acetone, and (CA436-80S 50g) is mixed in the 1000g water in the pottle bottle and room temperature was rotated 1 hour, rotates then to make temperature rise to 60 ℃ in 30 minutes in heating cabinet.Adding 10g N-ethyl para toluene sulfonamide (ETS), 5g dimethyl phthalate (DMP), 5g triphenylphosphate (TPP) and 0.3g alizarin in slurry (CAS[72-48-0], Aldrich 33,317-4 technical grade 85%).Heating (60 ℃) was rotated slurry 8 hours.With sinter funnel isolated by vacuum filtration solid, on funnel dry 1 hour, be dispersed in the tray 25 ℃ of dried overnight, at last in vacuum drying oven (about 25mmHg) in 50 ℃ of dryings 24 hours.As if cellulose triacetate does not have swelling, and has mottled rust yellow appearance.The liquid of decantation has slight grease sense.The weight of dried rhodia (theoretical maximum 70g) is shown in table 6.

Sample 2B will be insoluble to the cellulose triacetate of acetone, and (CA436-80S 50g) is mixed in the solution of 40g acetone, 10g N-ethyl para toluene sulfonamide (ETS), 5g dimethyl phthalate (DMP), 5g triphenylphosphate (TPP) and 0.3g alizarin.Bottle is rotated on parallel electromotive roller, in 25 ℃ of mixed content things 5 hours.All liquid is absorbed, and obtains having the swollen rubber-like pellet of even rust.With solid dispersed in tray 25 ℃ of dried overnight, then in vacuum drying oven (about 25mmHg) in 50 ℃ of dryings 24 hours.The weight of dried rhodia (theoretical maximum 70g) is shown in table 6.

Sample 3A will be insoluble to the cellulose triacetate of acetone, and (CA436-80S 50g) is mixed in the 1000g water in the pottle bottle and room temperature was rotated 1 hour, rotates then to make temperature rise to 60 ℃ in 30 minutes in heating cabinet.In slurry, add 10g N-ethyl para toluene sulfonamide (ETS), 5g dimethyl phthalate (DMP) and 5g triphenylphosphate (TPP).Heating (60 ℃) was rotated slurry 8 hours.With sinter funnel isolated by vacuum filtration solid.Swelling does not appear in cellulose triacetate, and the liquid of decantation has slight grease sense.With solid on funnel dry 1 hour, be dispersed in then in the tray 25 ℃ of dried overnight, at last in vacuum drying oven (about 25mmHg) in 50 ℃ of dryings 24 hours.The weight of dried rhodia (theoretical maximum 70g) is shown in table 6.

Sample 3B will be insoluble to the cellulose triacetate of acetone, and (CA436-80S 50g) is mixed in the solution of 40g acetone, 10g N-ethyl para toluene sulfonamide (ETS), 5g dimethyl phthalate (DMP) and 5g triphenylphosphate (TPP).On parallel electromotive roller, rotate the bottle that this mixture is housed, in 25 ℃ of mixed content things 5 hours.All liquid is absorbed, and obtains swollen rubber-like and refers to touch the dry granular material.The weight of dried rhodia (theoretical maximum 70g) is shown in table 6.

For every group of Comparative Examples, the sample of employing water slurry mixes the weight that only shows seldom behind the softening agent to be increased.It is more effective that water law is compared to cellulose triacetate for acetone-insoluble CA394-60, but still all be not so good as to adopt their the Comparative Examples counterpart with the swelling agent of rhodia coupling.The water of decantation has the thickness sense to show that there is softening agent in aqueous phase.The shortcoming of water slurry method is that the water that has produced a large amount of plasticized dose of pollutions need be handled and reclaim.In addition, for the softening agent that is distributed between water and the rhodia, be difficult in and obtain the target plasticizer loading in the cellulose ester.As selection, by adopting a certain amount of swelling agent all liquid is absorbed, the softening agent loading capacity can be simply definite by add-on.Adopt the swelling method, can more softening agent are incorporated in the rhodia.

Table 6-is used for mixing at rhodia the comparison of the water and the swelling agent of softening agent

	The CA type	Additive	Vehicle	Mixing time/temperature	Dry weight (%DMP) is (%ETS) (%TPP)
						1A	CA394-60S50g	25g DMP 5g TPP	1000g water	1 hour 60 ℃ 5 hours 60 ℃	72.6g(25.3％)(5.4％)(-)
1B	CA394-60S50g	25g DMP 5g TPP	20g methyl alcohol 5g ethyl acetate	5 hours 25 ℃	77.6g(29.0％)(5.5％)(-)
						1C	CA394-60S50g	25g DMP 5g TPP	30g methyl alcohol	3 hours 25 ℃	78.4g(29.0％)(5.5％)(-)
2A	CA436-80S50g	10g ETS 5g DMP 5g TPP 0.3g alizarin	1000g water	1 hour 60 ℃ 8 hours 60 ℃	52.8g
						2B	CA436-80S50g	10g ETS 5g DMP 5g TPP 0.3g alizarin	25g acetone 5g methyl acetate	4 hours 25 ℃	70.0g
3A	CA436-80S50g	10g ETS 5g DMP 5g TPP	1000g water	1 hour 25 ℃ 8 hours 60 ℃	52.3g(1.1％)(1.2％)(2.2％)
						3B	CA436-80S50g	10g ETS 5g DMP 5g TPP	40g acetone	5 hours 25 ℃	69.4g(7.0％)(7.2％)(13.8％)
3C	CA436-80S50g	10g ETS 5g DMP 5g TPP	25g acetone 5g methyl acetate	4 hours 25 ℃	69.5g(7.2％)(6.9％)(13.8％)

The CA436-80S=cellulose triacetate, DS _AC～2.8-2.9 (Eastman ChemicalCo.); Physical aspect: grain of rice shape pellet.

The CA394-60S=rhodia, DS _AC～2.4-2.5 (Eastman Chemical Co.); Physical aspect: the mixture of the irregular particle of powder and overall dimension 5mm.

Embodiment 33

Comparative Examples

For sample 1A, 2A and 3A, in 1 gallon of bottle with rhodia (100g table 7 shown type) and 1800g water, 0.5g turkey red oil (sodium salt of sulfonated castor oil is water dispersible oil and the tensio-active agent that obtains from Sigma Aldrich) and the slurrying of 0.5g dimethylbenzene.Rotate bottles after 1 hour at 25 ℃, in slurry, add 50g dimethyl phthalate (DMP) and 10g triphenylphosphate (TPP), and bottle is transferred on the roller in the heating cabinet 60 ℃ of rotations 60 minutes.By with coarse sinter funnel and vacuum filtration, from slurry, isolate solid.Solid is dispersed in the tray in 25 ℃ of dried overnight (about 16 hours), then in vacuum drying oven in 50 ℃ of dryings 24 hours.

For duplicate 1B, 2B and 3B, rhodia (100g table 7 shown type) is stirred adding be equipped with in the 16 ounces of bottles (is 32 ounces of bottles for 1B) that are dissolved in 50g dimethyl phthalate (DMP) in the swelling agent shown in the table 7 and 10g triphenylphosphate (TPP).Came blend mixture in 5 hours by room temperature on the electrical parallel roller (25 ℃) rotation.By design, there is not liquid filtering from solid.Solid is dispersed in the tray in about 16 hours of 25 ℃ of dried overnight, then in vacuum drying oven in 50 ℃ of dryings 24 hours.

For every pair of comparison, water/dimethylbenzene/Turkey red oil mixt is done the weight increase of the sample of softening agent carrier and can be ignored, and by the additive analyzing and testing less than softening agent.On the contrary, each duplicate of the swelling agent of employing and rhodia coupling and additive shows good swelling, better fluid is mixed and significant weight increases.The amount of this softening agent (60g altogether) is for the amount big (generally the softening agent heap(ed) capacity for rhodia is 10-30%) of 100g rhodia, but, can realize being close to the 60g softening agent that quantitatively mixes by every kind of rhodia is adopted suitable swelling agent.Have with the softening agent of rhodia excellent compatibility and the combining of swelling agent that rhodia had a suitable swelling action and make this height of softening agent mix to become possibility.Adopt the embodiment of water to prove, only be not enough to realize good plasticizer absorption with compatible softening agent.

Table 7-contains the comparison of the water and the swelling agent of tensio-active agent

	The CA type	Additive	Vehicle	Mixing time/temperature	Dry weight (%DMP) (%TPP)
						1A	CA398-30 100g	50g DMP 10g TPP	1800g water 0.5g TRO 0.5g dimethylbenzene	1 hour 60 ℃ 5 hours 60 ℃	99.6g(0.0％)(0.0％)
1B	CA398-30 100g	50g DMP 10g TPP	90g methyl alcohol	5 hours 25 ℃	155.5g(30.9％)(6.1％)
						2A	CA394-60S 100g	50g DMP 10g TPP	1800g water 0.5g TRO 0.5g dimethylbenzene	1 hour 60 ℃ 5 hours 60 ℃	100.3g(0.0％)(0.0％)
2B	CA394-60S 50g	50g DMP 10g TPP	60g methyl alcohol	5 hours 25 ℃	156.7g(31.3％)6.3％)
						3A	CA436-80S 100g	50g DMP 10g TPP	1800g water 0.5g TRO 0.5g dimethylbenzene	1 hour 60 ℃ 5 hours 60 ℃	100.7g(0.0％)(0.0％)
3B	CA436-80S 100g	50g DMP 10g TPP	60g acetone		5 hours 25 ℃							158.1g(30.6％)(6.1％)

The CA398-30=rhodia, DS _AC～2.4-2.5 (Eastman Chemical Co.); Physical aspect: powder.

The CA394-60S=rhodia, DS _AC～2.4-2.5 (Eastman Chemical Co.); Physical aspect: the mixture of the irregular particle of powder and overall dimension 5mm.

The CA436-80S=cellulose triacetate, DS _AC～2.8-2.9 (Eastman ChemicalCo.); Physical aspect: grain of rice shape pellet.

Embodiment 34

The cellulose triacetate film of melt extrusion

1, the film of the pellet of melt compounded/fusion curtain coating

Cellulose triacetate (CA436-80S) and triphenylphosphate (TPP), diethyl phthalate (DEP) and epoxy group(ing) thermo-stabilizer 290 ℃ of melt compounded, are obtained comprising the mixing pellet of 80 parts of cellulose triacetates, 15 parts of TPP, 5 parts of DEP and 1 part of stablizer.The softening agent analysis revealed contains 14.2%TPP and 4.8%DEP.With the raw material of this pellet as the film of fusion curtain coating.At the machine barrel design temperature cast film that has on 1 inch Killion film extruder of 6 inches sheeting dies with 280 ℃.

2, the film of the pellet of non-heating power compounding/fusion curtain coating

(800g, CA436-80S) solution with 700g acetone, 100g methyl acetate, 150g triphenylphosphate (TPP), 50g diethyl phthalate (DEP) and 10g epoxy group(ing) thermo-stabilizer mixes with cellulose triacetate.Placing 1 gallon of bottle transfer to move in mixture spends the night, after this removes most of volatile matter by rotary evaporating device (B ü chi Rotavapor RE121).85 ℃ of further dried overnight, obtain comprising the compounding pellet of 80 parts of cellulose triacetates, 15 parts of TPP, 5 parts of DEP and 1 part of stablizer.The softening agent analysis revealed contains 14.7%TPP and 5.1%DEP.With the raw material of this pellet as the film of fusion curtain coating.At the machine barrel design temperature cast film that has on 1 inch Killion film extruder of 6 inches sheeting dies with 280 ℃.

Molecular weight is measured with N-Methyl pyrrolidone (NMP) eluent and polystyrene standards by gel permeation chromatography (GPC).The value (table 8) of the fusion cast film of more original cellulose triacetate, two kinds of compounding pellets and every kind of pellet formation.The weight loss difference table is understood a kind of benefit that adds thermal history on a small quantity that the compounding of non-heating power swelling provides.Film with same sample solvent cast 5 mil thick.Table 8 has been listed the percent transmittancy value of 400nm place film.Transmitance shows the color benefit of swelling compounding than traditional melt compounded with respect to the loss of original cellulose triacetate.The cellulose triacetate of dipping softening agent is the feasible raw material that is used for the fusion cast film, can be used for comprising lining, film and the Application of optical film of packaging film, adhesive tape and adhesive sheet.

Table 8-loss of molecular weight relatively

Sample	Mn	Mw	Mw/Mn	% transmitance (400nm)
					The CA436-80S starting material	82,700	298,400	3.62	91.1
The melt compounded pellet	64,400	219,800	3.41	88.2
					Film with melt compounded pellet fusion curtain coating (280 ℃)	56,100	195,400	3.52	85.2
" the swelling agent compounding " pellet	82,900	320,600	3.86	91.3
					Film with melt compounded pellet fusion curtain coating (280 ℃)	66,300	246,200	3.71	87.8

Claims (28)

1. form the method for mixed cellulose ester, described method comprises:

The additive of mixed cellulose ester, starting quantity and swelling agent produce mixture; With

Remove to the described swelling agent of small part from described mixture, form the blended cellulose ester, wherein said blended cellulose ester comprises the described additive of the described starting quantity of 92wt% at least.

2. the process of claim 1 wherein that described cellulose ester comprises cellulosic C ₁-C ₂₀Ester.

3. the process of claim 1 wherein that described cellulose ester is selected from rhodia, cellulose triacetate, Cellacefate, cellulose acetate butyrate, cellulose butyrate, three cellulose butyrates, cellulose propionate, three cellulose propionates, cellulose acetate propionate, acetate carboxymethyl cellulose, acetate propionic acid carboxymethyl cellulose, acetate butyric acid carboxymethyl cellulose, acetate butyric acid succsinic acid Mierocrystalline cellulose and composition thereof.

4. the process of claim 1 wherein that described additive is selected from softening agent, thermo-stabilizer, antioxidant, UV stablizer, sour stablizer, acid scavenger, dyestuff, pigment, spices, white dyes, fire retardant, agricultural chemicals, bioactive compounds, indicator and composition thereof.

5. the process of claim 1 wherein that described swelling agent is selected from ketone, ester, alcohol, ether, carboxylic acid, tetrahydrofuran (THF), supercutical fluid and composition thereof.

6. the method for claim 5, wherein said swelling agent is selected from acetone, methyl ethyl ketone, ethyl acetate, methyl acetate, methyl alcohol, ethanol, Virahol, acetate, supercritical co and composition thereof.

7. the process of claim 1 wherein that described cellulose ester has initial weight-average molecular weight, and described mixed cellulose ester comprises the cellulose ester with final weight-average molecular weight, wherein said final weight-average molecular weight is at least about 73% of initial weight-average molecular weight.

8. the process of claim 1 wherein that the described mixed cellulose ester of one deck of about 5 mils of thickness has percent transmittancy at least about 85% to the light of the about 400nm of wavelength.

9. the process of claim 1 wherein that described removal step comprises that removal is at least about the described swelling agent of 95wt%.

10. the method for claim 1 further comprises described mixed cellulose ester is formed moulded products.

11. the method for claim 10, wherein said moulded products are selected from film, fiber, sustained-release matrix and indicator matrix.

12. the method for claim 11, wherein said moulded products comprises film, and described moulding comprises that the described mixed cellulose ester of melt forms film.

13. the method for claim 12, wherein said melt comprise extrusion molding processing.

14. the method for claim 10, wherein said moulding comprise that injection moulding processes described mixed cellulose ester and form moulded products.

15. form the method for mixed cellulose ester, described method comprises:

The additive of mixed cellulose ester, starting quantity and swelling agent, obtain mixture, wherein said swelling agent comprises and is lower than about 10wt% and is selected from water, benzene, sulfonated castor oil, dimethylbenzene, toluene, Viscotrol C, pine tar, sulfonation pine tar, hexalin, pimelinketone, glyceryl diacetate and 1,2,3, the composition of 4-tetraline, described weight percent is measured 100wt% based on the swelling agent gross weight; With

Remove to the described swelling agent of small part from described mixture, form mixed cellulose ester.

16. the method for claim 15, wherein said cellulose ester comprises cellulosic C ₁-C ₂₀Ester.

17. the method for claim 15, wherein said cellulose ester are selected from rhodia, cellulose triacetate, Cellacefate, cellulose acetate butyrate, cellulose butyrate, three cellulose butyrates, cellulose propionate, three cellulose propionates, cellulose acetate propionate, acetate carboxymethyl cellulose, acetate propionic acid carboxymethyl cellulose, acetate butyric acid carboxymethyl cellulose, acetate butyric acid succsinic acid Mierocrystalline cellulose and composition thereof.

18. the method for claim 15, wherein said additive are selected from softening agent, thermo-stabilizer, antioxidant, UV stablizer, sour stablizer, acid scavenger, dyestuff, pigment, spices, white dyes, fire retardant, agricultural chemicals, bioactive compounds, indicator and composition thereof.

19. the method for claim 15, wherein said swelling agent is selected from ketone, ester, alcohol, ether, carboxylic acid, tetrahydrofuran (THF), supercutical fluid and composition thereof.

20. the method for claim 19, wherein said swelling agent is selected from acetone, methyl ethyl ketone, ethyl acetate, methyl acetate, methyl alcohol, ethanol, Virahol, acetate, supercritical co and composition thereof.

21. the method for claim 15, wherein said cellulose ester has initial weight-average molecular weight, and described mixed cellulose ester comprises the cellulose ester with final weight-average molecular weight, and wherein said final weight-average molecular weight is at least about 73% of initial weight-average molecular weight.

22. the method for claim 15, wherein the described mixed cellulose ester of one deck of about 5 mils of thickness has percent transmittancy at least about 85% to the light of the about 400nm of wavelength.

23. the method for claim 15, wherein said removal step comprise that removal is at least about the described swelling agent of 90wt%.

24. the method for claim 15 further comprises described mixed cellulose ester is formed moulded products.

25. the method for claim 24, wherein said moulded products are selected from film, fiber, sustained-release matrix and indicator matrix.

26. the method for claim 25, wherein said moulded products comprises film, and described moulding comprises that the described mixed cellulose ester of melt forms film.

27. the method for claim 26, wherein said melt comprise extrusion molding processing.

28. the method for claim 24, wherein said moulding comprise that injection moulding processes described mixed cellulose ester and form moulded products.

Images