CN104105416A

CN104105416A - Substituted cellulose acetates and uses thereof

Info

Publication number: CN104105416A
Application number: CN201380006636.0A
Authority: CN
Inventors: M·T·库姆斯; T·S·加利特
Original assignee: Celanese Acetate LLC
Current assignee: Celanese Acetate LLC
Priority date: 2012-01-27
Filing date: 2013-01-23
Publication date: 2014-10-15
Also published as: BR112014018021A2; KR20140116537A; JP2015510395A; EP2811852A4; EP2811852A1; CA2861037A1; BR112014018021A8; WO2013112502A1; MX2014009100A; US20130192613A1

Abstract

The present invention relates to substituted cellulose acetates and methods of use thereof. One embodiment of the present invention provides a cigarette filter material having a filter having a substituted cellulose acetate having a polar substituent that has an oxygen atom covalently bonded to a nonmetal selected from the group of sulfur, phosphorus, boron, and chlorine; wherein the nonmetal is present in at least 0.01% by weight of the substituted cellulose acetate.

Description

Substituted cellulose acetate and uses thereof

Background technology

The present invention relates to synthetic polymer, and relate to especially substituted cellulose acetate and using method thereof.

Cellulose acetate is cellulosic acetate derivative, the natural biological copolymer that comprises β-D-Glucose monomeric unit, and be widely used in and prepare multiple consumption product.Native cellulose is insoluble in water and mostly counts in organic solvent.In cellulose, 3 free hydroxyl groups of each glucose monomer unit can carry out derivatization to change some character, for example solubility in some solvent.Cellulose acetate is considered to cellulosic one of the most business-like useful derivative, and its specific physics and chemical property largely depend on the replacement degree of acetate on 3 free hydroxyl groups of glucose monomer unit conventionally.

After synthesizing first, cellulose acetate has especially been used as the raw material using in the sheet base in photography, the component in adhesive and cigaratte filter preparation.One of determinant attribute of cellulose acetate is that it can be processed to multiple difformity and form, comprising: film, and tow, thin slice, fiber and entity (solid), depend on the demand of application.For example, cellulose acetate tow is mainly for the preparation of cigaratte filter.

The most typically, cellulosic derivatization uses acidic catalyst to carry out under the reaction temperature raising.Synthetic the relating under acetic anhydride and acetic acid existence of cellulose acetate, makes the cellulose acetylation available from wood pulp conventionally.Acetic acid and sulfuric acid are two kinds of acid that conventionally exist during acetylization reaction.In this reaction kind, acetic anhydride serves as main acetylation reagent; Acetic acid is mainly as diluent; Be used as catalyst with a small amount of sulfuric acid.Generally speaking, cellulosic monomeric unit has easy acquisition for replacing 3 hydroxyls of (for example, via acetylation).The monomeric unit of end also has the other hydroxyl that is usually directed to sugared internal key (inter-sugar linkage).

The product of acetylization reaction is primary filament element acetate, and it conventionally contains the acetate of high concentration level or in other words has high acetate replacement degree (DS).As used herein, " the replacement degree of acetate " is often referred to the acetate average number of each glucose monomer unit.The structure of cellulose acetate can characterize by the replacement degree of regulation acetate conventionally.Thoroughly acetylation of cellulose is commonly referred to primary cellulose acetate, and wherein, according to Federal Trade Commission (Federal Trade Commission) guide, at least 92% hydroxyl is replaced by acetyl group.For example, in the time that each cellulose monomeric unit exists at least about 2 acetyl group (i.e. approximately 2 DS), the biodegradability of acetylcellulose can become remarkable reduction, until at least some acetyl group remove via chemistry or enzyme hydrolysis.Can there is by the controlled hydrolysis preparation of primary cellulose acetate the acetylation of cellulose of the acetate DS of reduction.

Next, primary filament element acetate is hydrolyzed the acetate DS to reduce primary filament element acetate under acetic acid and sulfuric acid existence.The hydrolysate of gained normally has similar approximately 2.4 to about 2.6DS cellulose acetate thin slice.

Once obtain cellulose acetate thin slice, it can experience other processing cellulose acetate is machined to its desired form.For example, cellulose acetate tow can form by following: cellulose acetate thin slice is dissolved in acetone, makes cellulose acetate pass through a series of filter process, and make acetone spin liquid dry spinning by the micropore in spinning head.Along with cellulose acetate moves through this extrusion, collect cellulose acetate long filament.These long filaments are conventionally tied up and are curling to guarantee tow band adhesive force and required bulk density (bulk) subsequently.Last result is cellulose acetate tow, its substantially by by crimped bulk the continuous band that forms of thousands of long filaments of keeping together.Cellulose acetate tow long filament very thin (thin) and can be bundled together tightly to produce filter tip conventionally.As used herein, cellulose acetate tow is often referred to the bundle (bundle) through synthetic post processing of cellulose acetate long filament.

Cellulose acetate is also eco-friendly, because it is the material of the easy degraded that mainly makes from renewable source (wood pulp).Although the structure of the cellulose acetate that acetate DS changes is that similarly this variation can produce some effects to the biodegradable of cellulose acetate.Under higher acetyl replacement degree, with respect to native cellulose or have for the cellulose that less acetyl replaces, biodegradable speed can significantly reduce.There is the cellulose acetate of lower acetate DS than the easier biodegradation of the cellulose acetate with higher acetate DS.This trend is considered to stop gradually under lower acetate DS value, is insoluble in water because material becomes.In an example, to having 1.85,2.07 and the biodegradation rate of the cellulose acetate of 2.57DS value, tested their biodegradable (Fig. 1).The cellulose acetate with 1.85DS shows the highest biodegradation rate, and the cellulose acetate with 2.57 acetyl value (acetyl group value) shows the slowest biodegradation rate.

Although cellulose acetate is the compositions for universal use with many commercial uses, also there is no thoroughly to study the character of some cellulose acetate ester derivant.For example, in typical synthesizing, conventionally remove residual sulfate groups to improve heat endurance.Result is that the cellulose acetate synthetic by typical measure will have approximately 0.005% weight or sulphur atom still less.Similarly, exist potential cellulose acetate ester derivant can provide the character of lifting for many consumer applications of cellulose acetate.

Summary of the invention

The present invention relates to synthetic polymer, and especially, relate to substituted cellulose acetate and using method thereof.

In some embodiments, the invention provides diaper (diaper), it comprises: internal layer, described internal layer contains absorbent core, described absorbent core contains substituted cellulose acetate, described substituted cellulose acetate contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate; And skin.

In other embodiments, the invention provides bandage, it comprises: absorber layer, described absorber layer contains substituted cellulose acetate, described substituted cellulose acetate contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate; And band, described strip design is used for making absorber layer to contact with wound.

In other embodiments, the invention provides potting soil (potting soil) composition, it comprises: organic compost; And absorbent composition, described absorbent composition contains substituted cellulose acetate, and described substituted cellulose acetate contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate.

In other embodiments, the invention provides conditioned soil (amended soil) composition, it comprises: association of soil thing; With water conservation additive, described water conservation additive contains substituted cellulose acetate, and described substituted cellulose acetate contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate.

In other embodiments, the invention provides goods, it contains: non-woven layer, described non-woven layer contains the fiber from substituted cellulose acetate, described substituted cellulose acetate contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate.

In other embodiments, the invention provides method, it comprises: substituted cellulose acetate is provided, and described substituted cellulose acetate contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate; With substituted cellulose acetate is placed in absorbent article.

In other embodiments, the invention provides method, it comprises: absorber material is provided, described absorber material contains substituted cellulose acetate, described substituted cellulose acetate contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate; With absorber material is placed in diaper.

By reading the below description of preferred embodiment, the person skilled in the art will easily understand the features and advantages of the present invention.

Brief description of the drawings

The following drawings is included to illustrate some aspect of the present invention, and should not be considered as unique embodiment.Disclosed theme can have considerable amendment, variation and equivalent in form and function, as those skilled in the art and benefited present disclosure are expected.

Fig. 1 has shown the biodegradable figure of the cellulose acetate of the vicissitudinous replacement degree of tool.

Fig. 2 has shown the water imbibition data of describing in embodiment 3.

Fig. 3 has shown the water imbibition data of describing in embodiment 3.

Fig. 4 has shown the water imbibition data of describing in embodiment 3.

Fig. 5 has shown the water imbibition data of describing in embodiment 3.

Detailed description of the invention

The invention provides the composition, the Method and Process that relate to the substituted cellulose acetate with multiple advantage and/or required character.Substituted cellulose acetate of the present invention can use in multiple application, comprises multiple consumption product, in the situation that particularly wherein absorbability, cohesive and/or degradability come in handy.

As used herein, term " substituted cellulose acetate " refers generally to have the cellulose acetate that is substituted at least one polar substituent on cellulosic polymer hydroxyl.As used herein, " polar substituent " be contain be bonded to nonmetal (for example, sulphur, phosphorus, boron, and chlorine) atom electronegative atom (for example, oxygen) non--acetyl group chemical part.

Against expectation find, according to the present invention, can provide the substituted cellulose acetate composition with at least one non-metallic atom corresponding to polar substituent relatively high replacement degree, that there is relatively high percentage by weight.In addition, also against expectation find, can regulate and/or adjust the weight percent of non-metallic atom to obtain or to improve the multiple character of substituted cellulose acetate as herein described.

In some embodiments, substituted cellulose acetate of the present invention be suitable for using in multiple consumption product general (, there are many different required chemistry and physical propertys) and eco-friendly (, prepared by renewable source, degradable, biodegradable, etc.) material.

As used herein, " degradable " refers to material breakdown and/or is broken into the ability of simpler part.As used herein, " biodegradable " refers to that material is by the ability of biological effect degraded.Depend on application, the definition of " biodegradable " can be obeyed the result of standard testing (for example Organization of Economy and Cooperation Development (OECD) test protocol).

Not bound by theory, thinks that, by adjusting the weight percent of non-metallic atom of polar substituent, substituted cellulose acetate of the present invention can provide chemistry and/or physical property new or that promote.For example, think that some polar substituent (for example, sulfate radical) can improve the hydrophily of substituted cellulose acetate and strengthen the potentiality of electrostatic interaction.

Substituted cellulose acetate composition, in more detailed description below, has the weight percent of non-metallic atom that can be based on existing and gives or some character of strengthening and commercial function (for example, as adhesive, chemical stabilizer, absorbent).In some embodiments, the weight percent of adjustment non-metallic atom can remove or reduce undesirable quality or character in substituted cellulose acetate.

Substituted cellulose acetate can be described by the concentration of its polar substituent, this so can specify (about the replacement degree of polar substituent, the substituting group average number of each glucose monomer unit) or as with respect to substituted cellulose acetate gross weight exist nonmetal (for example, sulphur, phosphorus, boron, and chlorine) atomic percent weight and specifying.In fact, the replacement degree that changes polar substituent also will change the weight percent of the non-metallic atom on substituted cellulose acetate by predictable amount, and vice versa.Therefore, can suppose that increasing substituent replacement degree will increase the weight percent of the non-metallic atom existing on substituted cellulose acetate conventionally.On the contrary, reduce substituent replacement degree and will conventionally reduce the weight percent of the non-metallic atom existing in substituted cellulose acetate by predictable amount.

In theory, the weight percent of the non-metallic atom in substituted cellulose acetate can be approximately 0.01% to approximately 25%, this is corresponding to having the cellulose acetate (significantly and being against expectation greater than in some cases, the cellulose acetate of common preparation) of a small amount of polar substituent and the cellulose acetate thoroughly having been replaced.Although the present invention preferably implements by the substituent nonmetal weight percent of specified polarity, the present invention also can implement by other similar tolerance of the substituent replacement degree of specified polarity or concentration.Substituent replacement degree can be approximately 0.005 to approximately 3.

Multiple embodiment described herein is utilized the substituted cellulose acetate with polar substituent in multiple consumption product.By regulating the weight percent of non-metallic atom of polar substituent, think that substituted cellulose acetate composition of the present invention can especially be used as effective absorbent, adhesive, chemical stabilizer, and be stable into membrane reagent (stabilizing film forming agent).For example, for example, by regulating the weight percent of sulphur atom (, the substituent sulphur atom of sulfate radical), substituted cellulose acetate of the present invention can become water swollen material from water-soluble material.In some embodiments, water-soluble swollen substituted cellulose acetate composition can postpone the release of pharmaceutical composition to encapsulate for example pharmaceutical composition as biodegradable coating in vivo.Other character that can regulate includes but not limited to: the solubility in some solvent, and the ability of stable emulsion, to the cohesive of kinds of surface, and biodegradable.These character can be as required by regulate the polar substituent existing in substituted cellulose acetate non-metallic atom weight percent and further regulate.Those skilled in the art should regulate nonmetallic weight percent to implement multiple embodiments of the present invention as required.

In some embodiments, the replacement degree of change acetate also can obtain or strengthen some character of substituted cellulose acetate.In some embodiments, the replacement degree of the acetate of water-soluble substituted cellulose acetate is approximately 0.4 to approximately 1.In some embodiments, the replacement degree of the acetate of water-soluble swollen substituted cellulose acetate is approximately 1 to approximately 2.Along with the replacement degree of acetate changes between 0.05 to 3, can change suitable dicyandiamide solution.In some embodiments, under the replacement degree of relatively low acetate, water is suitable solvent.In some embodiments, under the replacement degree of relatively high acetate, need organic solvent.Can change replacement degree, make can select to be suitable for the dicyandiamide solution of target final use.

In some embodiments, substituent replacement degree can keep relatively fixing, and regulates the replacement degree of acetate.In some embodiments, regulate the combination of the replacement degree of polar substituent and the replacement degree of acetate that the substituted cellulose acetate with required character is provided.In some embodiments, the replacement extent and scope of polar substituent can affect provides the replacement extent and scope with the required acetate of the substituted cellulose acetate of required character.In some embodiments, the replacement extent and scope of acetate can affect provides the replacement extent and scope with the required polar substituent of the substituted cellulose acetate of required character.

The potential commercial use of substituted cellulose acetate of the present invention is extensively to extend, and includes but not limited to such as button of family's goods, glass, liner, (lady's) shirt, clothes, wedding and party clothes, Household ornament product, cloth, upholstery, cover for furniture, etc.Other commercial use comprises that filter tip comprises cigarette, ink housing tube, and playing cards, etc., and for example diaper of high-absorbable product and surgical product.

In some embodiments, as absorbent, substituted cellulose acetate of the present invention at water-based fluid (for example, water, saline solution, Deng) in water absorption capacity be the several times (for example, approximately 8 times to approximately 24 times) of its weight, depend on the weight percent of the non-metallic atom existing on substituted cellulose acetate.

In some embodiments, substituted cellulose acetate of the present invention can be effectively as adhesive, can bonding multiple matrix, include but not limited to: cardboard, plastics, paper, glass, timber, long fibre plant (hemp), wood chip, composite is (for example, fibre reinforced composites), sawdust etc.Also think that substituted cellulose acetate of the present invention can be effective chemistry/deflocculant, can stablize multiple emulsion mixture.

In some embodiments, substituted cellulose acetate of the present invention can be as being stable into membrane reagent to promote the formation of film of given mixture.In some embodiments, the film of formation can be limpid.

Substituted cellulose acetate can multi-formly exist and utilize with multitude of different ways with multiple.In some embodiments, substituted cellulose acetate can be: fiber, fabric, supatex fabric, tow or tow band (unlimited or non-unlimited), thin slice, foam, emulsion, film, gel, dispersion, solution, paste, suspended substance, and their combination.In some embodiments, substituted cellulose acetate can be used making coatings, additive, and film, layer, core, etc.

In some embodiments, the present invention is also provided for substituted cellulose acetate to be formed as the method for multiple substituted cellulose acetate shape (for example, substituted cellulose acetate tow).These methods make substituted cellulose acetate conventionally in better form is applied for some.For example, the fiber of substituted cellulose acetate may have the character of special needs: some organic chemistry that can selectively absorb and remove certain level; Water miscible or water-soluble swollen; There is high surface; With compatible with dyestuff.Also think that the fiber of substituted cellulose acetate can have the tolerance to fungi and mould.Substituted cellulose acetate can be special expectation in textile application.

Although at least some embodiments relate to the cellulose acetate with at least one polar substituent, also can there is according to any use of compatible embodiment of the present invention the derivative of the cellulose acetate of at least one polar substituent.The derivative of cellulose acetate can include but not limited to, cellulose acetate, and cellulose acetate mixed ester, etc.Applicable cellulose acetate example includes but not limited to, cellulose acetate propionate, and cellulose acetate butyrate, etc.The degree of esterification of cellulose acetate will (at least partly) depend on specific application and be obvious to those skilled in the art.

Substituted cellulose acetate of the present invention can be characterized by: have polar substituent, described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus and boron; Wherein nonmetal at least 0.01 % by weight with substituted cellulose acetate exists.In some embodiments, nonmetal can existence with approximately 25 % by weight that are not more than of substituted cellulose acetate.Not bound by theory, thinks that the upper limit of 25 % by weight for example, corresponding to complete substituted cellulose derivative (, sulfate radical).The accurate scope of nonmetal percentage by weight will depend on the especially chemical composition of polar substituent.

Generally speaking, at least a portion hydroxyl on substituted cellulose acetate will be replaced by acetate.In some embodiments, the replacement degree of acetate will be approximately 0.05 to approximately 3, preferred approximately 0.4 to approximately 2.In some embodiments, can regulate the ratio of the replacement degree of acetate and the replacement degree of polar substituent, to produce or to strengthen the required character of substituted cellulose acetate of the present invention.In some embodiments, the DS of acetate is higher than the DS of polar substituent.

Optionally, substituted cellulose acetate can comprise in addition plasticizer or mix with plasticizer.The applicable example of plasticizer includes but not limited to: glycerine; glyceride (comprise list, two or triacetyl glycerine and glyceride); polyethylene glycol, diethylene glycol, propane diols; dimethyl sulfoxide (DMSO); triacetyl glycerine, triethylene glycol diacetate, their derivative; their combination, and their mixture.In some embodiments, plasticizer comprises the plasticizer that is selected from group below: the ester of monounsaturated dicarboxylic acid, the ester of saturated polyol, fatty acid ester, sulphamide resin, their derivative, and their combination.Plasticizer can be added substituted cellulose acetate to reduce glass transition temperature (Tg) and the fusing point of composition.The function of plasticizer normally promotes processing and strengthens flexibility and the toughness of end product.Also think some plasticizer (for example, ether-ether, simple ester class, etc.) can increase substituted cellulose acetate filter tip and remove the capacity of phenol, this is the useful quality of cigaratte filter.

In some embodiments, polar substituent can be selected from sulfate radical, phosphate radical, borate, carbonate, and their combination.In some embodiments, polar substituent existing at least about 0.03 % by weight with substituted cellulose acetate.In some embodiments, nonmetal approximately 75 % by weight that are not more than with substituted cellulose acetate of polar substituent exist.The accurate scope of polar substituent percentage by weight will depend on the especially chemical composition of polar substituent.

In one or more embodiments, substituted cellulose acetate can have the character that can give or strengthen by increasing or reduce the concentration of polar substituent or non-metallic atom.In some embodiments, substituted cellulose acetate can be water miscible.In some embodiments, substituted cellulose acetate can be water-soluble swollen.In some embodiments, substituted cellulose acetate can be water-fast.In some embodiments, may expect that substituted cellulose acetate has relatively high sulphur percentage and replaces degree with relative high acetate.Especially, water swollen material is conventionally by their water absorbing capacity mark with as sealing material, water-keeping material, and material supply, etc.In some embodiments, substituted cellulose acetate can be degradable.In some embodiments, substituted cellulose acetate can be biodegradable.

Substituted cellulose acetate of the present invention can be as absorber material for multiple consumption application.In some embodiments, the invention provides diaper, described diaper bags is containing absorbent core, and described absorbent core contains substituted cellulose acetate of the present invention and skin.Optionally, diaper can comprise in addition and is designed for water transport to the distribution layer of absorbent core and/or covers the shell of at least a portion absorbent core.

In some embodiments, distribution layer is placed between absorbent core and skin.In some embodiments, distribution layer can be waterproof.

In some embodiments, outer around absorbent core.In some embodiments, skin is waterproof.In some embodiments, skin is designed for the insertion that receives absorbent core.Skin can be also painted or feature Art Design, and it strengthens the visual attraction of diaper.In some embodiments, skin is designed with perforate to receive the insertion of absorbent core.In some embodiments, skin can be reusable.

In some embodiments, skin is made by certain material, and this material comprises the material that is selected from polyethylene, nowoven membrane, composite material film, cloth and their combination.

In some embodiments, diaper can be disposable.In some embodiments, at least a portion diaper can be reusable.

In some embodiments, the invention provides bandage, described bandage comprises absorber layer, and described absorber layer contains substituted cellulose acetate of the present invention and maintains with being designed for the band that absorber layer contacts with wound.Optionally, absorber layer also contains active component, and described active component is selected from: antibiotic, anodyne, antipyretic, antiseptic, anticorrisive agent, anti-allergic agent, anti-acne drug, anesthetic, antiphlogistic, styptic, cosmetics, vitamin, vasodilator, softening agent, pH adjusting agent, antipruritic, counterirritant, antihistaminic, steroids, and their combination.

In some embodiments, anticorrisive agent can comprise at least one transition metal.The applicable example of transition metal includes but not limited to, aluminium, nickel, copper, zinc, titanium, iron, and silver.

In some embodiments, wound is otch, breach, and scratch, stabs penetrating wound, or these any combination.

In some embodiments, band can be flexible.In some embodiments, band can be adhesive.In some embodiments, band comprises the material that is selected from group below: fabric, supatex fabric, plastics, latex, and their combination.

In some embodiments, cigarette filter tip material of the present invention comprises the segmentation filter tip that contains substituted cellulose acetate of the present invention or a part for filter tip.In some embodiments, cigarette filter tip material of the present invention also comprises conventional two types (secondary) cellulose diacetate.Optionally, cigarette filter tip material also comprises plasticizer.Not bound by theory, thinks that substituted cellulose acetate should strengthen the degradability of cigarette filter tip material.

The applicable example of the plasticizer that the embodiment relevant to cigarette filter tip material used together comprises: phthalic acid ester; citric acid acetyl three ethyl ester; citric acid triethyl group ester; citric acid acetyl three butyl ester, decanedioic acid dibutyl ester, triacetin; triacetyl glycerine; polyethylene glycol, propane diols, and glycerine.

In some embodiments, substituted cellulose acetate can be tow.In some embodiments, substituted cellulose acetate forms with excellent shape.

In some embodiments, can light suction material and the cigaratte filter that comprises substituted cellulose acetate long filament of the present invention comprising of smoking apparatus of the present invention.As used herein, " can light suction material " comprises and can burn and anything (for example, tobacco) that its cigarette can be tasted or suck.Tobacco can, with the multi-form utilization of arbitrary number, include but not limited to, dry, fermentation, that smoke, cutting, etc.

In some embodiments, smoking apparatus can comprise cigar, tobacco pipe, cigarette, evaporimeter, etc.

In some embodiments, coating seed of the present invention comprises the seed that is coated with the coating that comprises substituted cellulose acetate of the present invention.Optionally, apply seed and also comprise that secondary growth strengthens coating.The applicable example that secondary growth strengthens coating can be selected from: Main Nutrients, secondary nutrient, hormone, pesticide, parasiticide, herbicide, fungicide, bactericide, pigment, adhesive, surfactant, glidant (glidant), and their combination.

The applicable example of the Main Nutrients being used in combination with embodiments more of the present invention can include but not limited to: ammonium nitrate, urea, ammonium phosphate, ammonium sulfate, urea phosphate, ammonium molybdate, potassium nitrate, potassium phosphate, potassium hydroxide, potassium sulfate, and potassium chloride.

The applicable example of secondary nutrient is selected from: magnesium sulfate, calcium nitrate, Boratex, magnesium nitrate, the chelate complexes of copper, calcium, iron, zinc, magnesium, manganese, ammonium molybdate, sodium molybdate, benzoic acid, and salicylic acid.

The applicable example of the adhesive being used in combination with embodiments more of the present invention can include but not limited to: methylcellulose, carboxymethyl cellulose, hydroxy-methyl cellulose, hydroxy propyl cellulose, polyvinyl alcohol, polyvinyl acetate, PVP, copolyvidone (copolyvidone), their derivative, and their combination.

The applicable example of the surfactant being used in combination with embodiments more of the present invention can include but not limited to: lecithin, NaLS, polysorbate60, polysorbate80, polyoxyethylene polyoxypropylene block copolymer, their derivative, and their combination.

The applicable example of the pigment being used in combination with embodiments more of the present invention can include but not limited to: titanium dioxide, iron oxide, natural pigment, natural dye, FD & C colorant, D & C color lake (lake), their derivative, and their combination.

The applicable example of the glidant being used in combination with embodiments more of the present invention can include but not limited to: talcum, cataloid, stearic acid, their derivative, and their combination.

The applicable example of the herbicide being used in combination with embodiments more of the present invention can include but not limited to: glyphosate, Mediben, alachlor, isopropyl methoxalamine, oxabetrinil, thiocarbamate 5-ethyl-N, N-dipropyl-thiocarbamate, Acetochlor, their derivative, and their combination.

The applicable example of the antidotal compound being used in combination with embodiments more of the present invention can include but not limited to: fluorine azoles (fluorazole), cyometrinil, N, N-diallyl dichloro acetamide, their derivative, and their combination.

The applicable example of fungicide, bactericide, pesticide and the parasiticide being used in combination with embodiments more of the present invention can include but not limited to: Inorganic Copper, organic copper, heavy metal compound, acrylic acid, oxime ether (oximine ether), replace oxime ether, their derivative, and their combination.

The applicable example of the plant hormone being used in combination with embodiments more of the present invention can include but not limited to: auxin, gibberellic acid, cell factor, their derivative, and their combination.

In some embodiments, coated medicament composition of the present invention comprises pharmaceutical composition, and described pharmaceutical composition is coated with the coating that comprises substituted cellulose acetate of the present invention.

In some embodiments, the pharmaceutical composition being used in combination with embodiments more of the present invention can include but not limited to: anodyne, antiphlogistic, anti-arrhythmic agents, antiasthmatics, antibacterial agent, Anti-virus agent, anti-coagulants, anti-dull-witted agent, resist melancholy agent, antidiabetic, rescinnamine, Anti-Malarial, treatment migraines medicament, muscarine antagonist, antitumor agent, immunodepressant, antiprotozoan medicament, antithyroid drug, pectoral, anxiolytic, sedative, somnifacient, neuroplegic, neuroprotective medicament, beta-receptor blocking agent, cardiac inotropic drug, cell adhesion inhibiting compounds, corticosteroid, cytokine receptor active regulator, diuretics, antiparkinsonian drug, gastrointestinal drug, histamine H receptor antagonist, keratolytic, lipid regulating, muscle relaxant, nitrate, antifungal agent, antianginal drug, on-steroidal antiasthmatics, nutritional agents, sex hormone, excitant, treatment erectile dysfunction drug, anesthetic, antihistaminic, decongestant, anti-tussive agents, analgestic, expectorant, their derivative, their combination, with their mixture.

In some embodiments, the pharmaceutical composition being used in combination with embodiments more of the present invention can include but not limited to: pseudoephedrine, Super Odrinex, phyenlephrinium, ephedrine, dextromethorphan, chlophedianol (chlorphedianol), carbetapentane citrate, Caramiphen, oscapine, diphenhydramine, codeine, menthol, hydrocodone, hydromorphone, Fominoben, guaiacol glycerol ether, terpini hydras, ammonium chloride, NAC, bromhexine, ambroxol, chloropheniramine, brompheniramine, chlorpheniramine, dexbrompheniramine, triprolidine (tripolidine), azatadine, doxylamine, PBZ, cyproheptadine, hydroxyzine, clemastine (elemastine), carbinoxamine, phenindamine, bromodiphenhydramine, pyrilamine (pyilamine), Acrivastine, AHR-11325, astemizole, azelastine, cetirizine, Ebastine, Ketotifen, Lodoxamide, Loratadine, levocabastine, mequitazine, Oxatomide, Sai Dasiding, tazifylline, SK F-93944, RMI 9918, Terbutaline, atropine, aminophylline, adrenaline, isoprel, orciprenaline, bitolterol, theophylline, salbutamol, aspirin, acetaminophen, brufen, naproxen, phenol, benzocaine, hexyl resorcin, dyclonine, their derivative, their combination, their the acceptable salt of pharmacy, with their mixture.

The invention provides the kit for detection of analyte, it comprises reporter molecule, and described reporter molecule is coated with the coating that comprises substituted cellulose acetate of the present invention.

The reporter molecule being used in combination with embodiments more of the present invention can include but not limited to: antibody, protein, enzyme, peptide, nucleic acid, little molecule, fluorogen, their derivative, and their combination.

In some embodiments, coating is water miscible or water-soluble swollen.Conventionally, coating provided and can postpone or stop the degrade protective layer of (for example, sex change, cracking) of reporter molecule between the storage life.

In some embodiments, drug delivery medical device of the present invention (stent) comprises support, and described support has the external coating that comprises substituted cellulose acetate of the present invention and the undercoating that comprises pharmaceutical composition.

In some embodiments, support comprises shape-memory material.The applicable example of the shape-memory material being used in combination with embodiments more of the present invention can include but not limited to: kirsite, copper alloy, billon, ferroalloy, copper-zinc-aluminum-nickel alloy, copper-aluminum-nickel alloy, and Ni-Ti alloy.

In some embodiments, support comprises polymer.The applicable example of the polymer being used in combination with embodiments more of the present invention can include but not limited to: fibrin, PLA, organosilicon, polyurethane, polyester, Lustrex, ethylenic copolymer, Voncoat R 3310, acrylate copolymer, polyethers, cellulose family, their derivative, and their combination.

In some embodiments, pharmaceutical composition is selected from group below: glucocorticoid, heparin, hirudin, tocopherol, angiopeptin, aspirin, growth factor, oligonucleotides, antiplatelet drug, anti-coagulants, antimitotic drug, antioxidant (anti-oxidant), metabolic antagonist, antiphlogistic, and their combination.

In some embodiments, potting soil composition of the present invention comprises organic compost and absorbent composition, and described absorbent composition contains substituted cellulose acetate of the present invention.Optionally, potting soil composition can comprise at least one component that is selected from fertile soil, diatomite component, perlite component and their combination in addition.

In some embodiments, fertile soil comprises and is selected from sand, mud (silt), clay, and the component of their combination.

In some embodiments, diatomite component comprises and is selected from diatomite, phosphate (phosphate), magnesium, potassium, nitrogen, and at least one component of their combination.

In some embodiments, conditioned soil composition of the present invention comprises association of soil thing and water conservation additive, and described water conservation additive contains substituted cellulose acetate of the present invention.Optionally, conditioned soil composition can comprise in addition and is selected from sand, mud, clay, calcined clay, iron oxide, dried resin, and the additive of these combination.

The applicable dried resin being used in combination with embodiments more of the present invention can include but not limited to: acrylic polymer, polyvinyl acetate polymer, vinyl acetate co-polymer, their derivative, and their combination.

In some embodiments, the tackifier that wellbore fluid of the present invention comprises basic liquid and contains substituted cellulose acetate of the present invention.Optionally, wellbore fluid can comprise in addition and is selected from fluid loss control agent, clay inhibitor, lubricant, weighting agent, tackifier, and the additive of their any combination.

In some embodiments, basic liquid can be liquid, aqueous, oil-based fluid, synthetic fluid, or emulsion.

In some embodiments, the invention provides goods, described goods comprise non-woven layer, and described non-woven layer contains the fiber from substituted cellulose acetate of the present invention.

In some embodiments, non-woven layer can include but not limited to: diaper, feminine hygiene, hygenic towelette, bandage, Disposable tower, disposable slipper, barrier gown, operating coat, operation towel and drop cloth, operation sterilizing clothes, cap, filter (for example, HEPA filter; Water, coffee, tea-bag; Fluid cartridge, vacuum bag; Geotextiles (for example, geomembrane); Carpet backing; And envelope.

In some embodiments, the invention provides the method for the preparation of substituted cellulose acetate tow, it comprises: carry out spinning to spinning liquid, described in spin the solution that liquid comprises cellulose diacetate and substituted cellulose acetate of the present invention and solvent; Reel and just spin substituted cellulose acetate long filament; Form tow by substituted cellulose acetate long filament; Crimped tow; Regulate through curling tow; With packing dry through curling tow.Optionally, described method may further include the step of lubricated substituted cellulose acetate long filament.

In some embodiments, solvent is: water, acetone, methyl ethyl ketone, carrene, dioxane, dimethyl formamide, methyl alcohol, ethanol, glacial acetic acid, supercritical CO ₂, can dissolve any applicable solvent of aforementioned polymer, or their any combination.As non-limiting example, the solvent of cellulose acetate can be acetone/methanol mixture.

In some embodiments, substituted cellulose acetate carries out spinning in spinning head.In some embodiments, spinning head comprises hole.These holes can have any shape compatible with one or more embodiments of the present invention.Nozzle design and/or spinning parameter can affect the speed of solvent from long filament evaporation, and this can affect size, cross sectional shape, intensity and the machinability of long filament.In some embodiments, spinning head can comprise separately multiple holes of at least 0.070 inch, interval.In some embodiments, the spinning head being used in combination with the present invention can comprise the multiple extrusion cavities in circular structure.As used herein, " circular structure " have in the middle of referring to space any shape (circle, Long Circle, polygon, triangle, etc.), wherein space does not have the hole for extruding.As used herein, term " hole " and " extrusion cavities ", in the time being used in combination with nozzle design, can exchange use, is often referred to spin liquid and extrude by perforate wherein.In some embodiments, extrusion cavities can be tapered (tapered), and for example countersinking has capillary outlet.Being tapered can be with constant angle or to be greater than a kind of angle.In some embodiments, the extrusion cavities in single spinning head can have different tapered angles.In some embodiments, extrusion cavities and/or capillary outlet can have the cross sectional shape that produces required filament cross section shape.The example of extrusion cavities and/or capillary outlet shape can include but not limited to: circle, and substantially circular, Long Circle, basic Long Circle, crescent, multi-leaf-shaped, polygon (for example, as tripod-shaped, tetrapod shape, star, triangle, square, trapezoidal, pentagon, hexagon, etc., there is the limit of equal length or variation length), there is the polygon of fillet and their any mixture.In some embodiments, spinning head can comprise extrusion cavities and/or the capillary outlet of at least two kinds of different cross section shapes.In some embodiments, spinning head can comprise extrusion cavities and/or the capillary outlet of at least two kinds of different sizes.In some embodiments, the size of extrusion cavities and/or cross sectional shape can change the size and/or the cross sectional shape that are different from corresponding capillary outlet.

In some embodiments, spinning parameter can comprise with approximately 0.7 to approximately 1.6 spinneret draft ratio (fiber rate of departure is than draw off rate) and extrudes long filament.

Ability and technical staff should be understood that single method or the action extruding and do not mean that for the production of long filament, and should with the exchanges such as at least spinning, squeezing (expel).

In some embodiments, method of the present invention comprises provides substituted cellulose acetate of the present invention and substituted cellulose acetate is placed in absorbent article.In some embodiments, absorbent article can be can utilize any goods of absorber material (for example, clothes, gel, a piece of furniture, etc.).The applicable example of absorbent article can include but not limited to: diaper, incontinence garments, bandage, surgical pad (surgical pad), cold and hot treatment bag, water bed, snowmaking, and their combination.In some embodiments, absorbent article is disposable and/or degradable.

In some embodiments, substituted cellulose acetate can be placed in the inside of absorbent article.In some embodiments, substituted cellulose acetate can be placed on the outside of absorbent article.In some embodiments, substituted cellulose acetate can be a part for absorbent article outside.Any concrete pattern do not intended to limit the invention in term " placement ".

In some embodiments, method of the present invention comprises with the coating coating seed that comprises substituted cellulose acetate of the present invention.Optionally, coating can comprise at least one composition that is selected from plasticizer, adhesive, wax, stabilizing agent and colorant in addition.

In some embodiments, method of the present invention comprises with the coating coated medicament composition that comprises substituted cellulose acetate of the present invention.Optionally, coating can comprise in addition and is selected from plasticizer, annealing agent, emulsifying agent, emulsion stabilizer, and the additive of these combination.

In some embodiments, annealing agent comprises the water-soluble polymer that is selected from group below: hydroxy propyl cellulose, HYDROXY PROPYL METHYLCELLULOSE, methylcellulose, methylethylcellulose, polyvinylpyrrolidone, sodium carboxymethylcellulose, their derivative, and their combination.

In some embodiments, method of the present invention comprises provides the adhesive that comprises substituted cellulose acetate of the present invention, and adhesive is used from the teeth outwards.In some embodiments, surface can be selected from group below: timber, plastics, paper, glass, cardboard, and these combination.In some embodiments, adhesive is dispersion.Optionally, adhesive can comprise solvent and/or additive in addition.

In some embodiments, solvent can be moisture.In some embodiments, solvent can be mixture, for example organic/aqueous solvent.In some embodiments, solvent can exist with approximately 40% of adhesive to approximately 99 % by weight.

In some embodiments, additive comprises the additive that is selected from group below: multivalent salts (for example, zirconates, for example zirconium carbonate), polyamide-epoxy chloropropane resin, aldehyde is (for example, glyoxal, glutaraldehyde, hydroxyl hexandial), formaldehyde crosslinking agent (for example, 0-formaldehyde, low-formaldehyde crosslinking agent), polyvinyl acetate, polyvinyl alcohol, polystyrene, PLA, their derivative, and their combination.

In some embodiments, the invention provides coating (paint) composition, described coating composition comprises pigment and is stable into membrane reagent, described in be stable into membrane reagent and contain substituted cellulose acetate of the present invention, and use coating coating surface.Optionally, coating can comprise at least one composition that is selected from group below in addition: solvent, filler, antifreeze, catalyst, thickener, bonding force promoter, UV stabilizing agent, delustering agent, biocide, and their combination.

The applicable example of solvent includes but not limited to: aliphatic solvents, arsol, alcohol, ketone, hydrocarbon, ester, petroleum distillate, water, their derivative, and their combination.

The applicable example of pigment comprises the pigment that is selected from group below: clay, calcium carbonate, mica, silica, talcum, titanium dioxide, their derivative, and their combination.

The applicable example of filter tip comprises the filler that is selected from group below: diatomite, talcum, lime, barite, clay, their derivative, and these combination.

In some embodiments, the invention provides a kind of method that coating is provided, described coating comprises: pigment; Be stable into membrane reagent, described in be stable into membrane reagent and contain substituted cellulose acetate, described substituted cellulose acetate contains polar substituent, described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate; With use coating coating surface.

Method of the present invention comprises provides the membrane reagent that is stable into that comprises substituted cellulose acetate of the present invention, and will be stable into membrane reagent and add emulsion.The applicable example of emulsion includes but not limited to: cosmetics, hair-dressing article, photographic negative, cutting fluid, skin ointment, paste, balm, oil, wax, washing agent (detergent), beverage, and these combination.

Method of the present invention comprises provides the thickener that comprises substituted cellulose acetate of the present invention, and thickener is added to food composition.Applicable food composition can include but not limited to: soup, and gravy, dessert, jelly, candy, etc.

In order to promote to understand better the present invention, provide the embodiment of preferred embodiment below.The following examples are never understood to restriction or have defined scope of the present invention.

Embodiment 1

Utilize lap shear test (lap shear test) test pack in the multiple matrix that comprises timber and cardboard to contain the adhesive properties of some adhesive compositions of substituted cellulose acetate of the present invention.For example, by these results and commercially available glue (, the glue of ELMER ) compare.The summary of result is shown in following table 1A and 1B.

Table 1A. lap shear test result

Table I B. lap shear test result

The preparation substituted cellulose acetate with high sulfur content (batch cellulose acetate ester adhesive 1-5) utilization according to one or more embodiments of the present invention (Model3366) lap shear test sets it as wood adhesive and tests.The result (mg sulphur/kg sulphur) that comprises the content of sulphur in solution is summarized in table 1A and 1B above.Utilize 10% aqueous solution of adhesive 2 little wooden blocks are bonded together and make them dry.Gained block is difficult to separate (, block does not all break in the tensile test device using).In the time applying enough power with separating bulk, lumber fibre breaks, and this explanation substituted cellulose acetate adhesive is equally strong with lumber fibre.Also substituted cellulose acetate adhesive is used for to bonding cardboard.Cardboard is also difficult to separate.Substituted cellulose acetate adhesive visually clear and have a high gloss, this may expect in business application.Under environmental condition, substituted cellulose acetate adhesive is being less than 30 minutes inner dryings.

This embodiment demonstration, inter alia, the substituted cellulose acetate with high sulfur content is effective as the adhesive in multiple matrix.

Embodiment 2

This embodiment describes the synthetic of sulfate radical substituted cellulose acetate of the present invention.In first step, under acetic anhydride and sulfuric acid existence, make cellulose acetylation.Cellulose, acetic acid, acetic anhydride and sulfuric acid preparation are similar to the production of standard two fiber type element acetate diacetates.Next, composite reaction thing is to cause acetylization reaction.Allow this reaction to reach and pass through subsequently to add water and any excessive anhydride reaction.Can strictly monitor with reacting condition speed and temperature to control some polymer property.

Next, there is no under the condition of precipitation and follow-up dissolving step again acetolysis cellulose under the existence of acetic acid (, cellulose acetate).This falls cellulose acetate by careful control reaction temperature and time and is reduced to target acetate DS level.Optionally add water, to maintain polymer dissolution degree.This generation has the sulfate radical substituted cellulose acetate product of unforeseeable and wonderful high sulfur content.

Finally, utilize suitable diluent from dicyandiamide solution, to be settled out solid.Optionally washed product is to remove excessive solvent and to be dried to required solid level.

Embodiment 3

In this embodiment, utilize the water absorbing capacity of thermogravimetry (TGA) test water swollen cellulose acetate (low sulfur content) and substituted cellulose acetate (high sulfur content).Each sample is placed in TGA system and the following temperature of experience.Make sample be warming up to 110 DEG C with 20 DEG C/min.Temperature is remained at 110 DEG C to 30 minutes.Elevate the temperature to 650 DEG C with 20 DEG C/min subsequently.Subsequently sample gas is switched to air and temperature is remained at 650 DEG C to 30 minutes.In each test run, cellulose acetate sample is limited to and is less than 100mg.

Absorptive multiple TGA of Fig. 2-5 display measurement high sulfate radical substituted cellulose acetate and low sulfate radical substituted cellulose acetate analyze operation.

Fig. 2 has shown water-saturated, and the TGA of water-soluble swollen cellulose acetate (WSCA) 1036RT-16 drying sample analyzes.WSCA 1036 RT-16 are high sulfate radical substituted cellulose acetate particulate samples of about 0.5 % by weight sulphur of containing cellulose acetate.Along with temperature raises and remains at 110 DEG C, along with water is dried away, the gross weight of water-saturated sample reduces.The temperature of TGA system raises subsequently and remains at 650 DEG C, thereby allows high sulfate radical substituted cellulose acetate to decompose.Water or its weight that WSCA 1036 RT-16 can absorb about 1440 % by weight of dry-eye disease exceed the water of 14 times.

Fig. 3 has shown for the TGA of 2 WSCA 1037 RT-16 dry-eye disease and has copied operation.Than WSCA 1036 RT-16, WSCA 1037 RT-16 are low-sulfur substituted cellulose acetate (DS of acetate are similar).The water of two sample detection is absorbed as 76.91% and 81.31%, and this is respectively 3.35 and 4.37 corresponding to water and the ratio of dry WSCA.

Fig. 4 has shown for the TGA of the saturated WSCA 1036 of two salt solution (～0.9%) (high sulfate radical) RT-16 sample and has copied operation.Two samples contain 87.05% and 92.14% salt solution, and this is respectively 7.48 and 13.6 corresponding to water and the ratio of dry WSCA.

Fig. 5 has shown for the TGA of the saturated WSCA 1037 RT-16 samples of salt solution (～0.9%) and has copied operation.Two samples contain 78.31% and 83.91% salt solution, and this is respectively 3.72 and 5.46 corresponding to water and the ratio of dry WSCA.

This embodiment shows, inter alia, the substituted cellulose acetate with high sulfur content can absorb the water (deionized water and salt solution the two) that is several times as much as its weight.When compared with having the substituted cellulose acetate of low sulfur content, high-sulfur substituted cellulose acetate demonstrates excellent water (deionized water and salt solution the two) and absorbs.

Embodiment 4

Multiple additives is added to some adhesive compositions that comprise substituted cellulose acetate of the present invention.Utilize the test of (Model 3366) lap shear is in the adhesive properties of the upper test of wood substrates (1/4 " pine tree band, 1.5 " width) resulting composition.The summary of result is shown in following table 2 and 3.

Table 2. cellulose acetate ester adhesive 6 (620mg/kg sulphur)

* that copies for 6 times is average

* the lap shear of * 1.5 " x1 " adhesive area

Table 3. cellulose acetate ester adhesive 7-8

As shown in table 2, add zirconium and can increase the required intensity of combination of breaking and forming by cellulose acetate adhesive composition (thering is the substituted cellulose acetate of high sulfur content).Table 3 shows cellulose acetate ester adhesive 7 and 8, the MW140 with ammonium zirconium carbonate (0.08%Zr), the result of the lap shear test of 000 polyvinyl acetate (solid 14%) and MW 150,000 polyvinyl alcohol (solid 14%).Cellulose acetate ester adhesive 6,7, and 8 sulfur content is respectively 620mg/kg, 520mg/kg, and 557mg/kg.

Therefore, the present invention is well suitable for obtaining target and advantage and intrinsic those targets and the advantage mentioned herein.Above-disclosed particular is only exemplary, because but the mode different of equal value that the present invention can be obvious with the those skilled in the art for benefiting from instruction is herein modified and implements.In addition,, describing, do not intend to limit the details of the construction or design showing herein in claim hereinafter.Therefore clearly, above-disclosed particular exemplary embodiment can change, combines or revise, and all these modification are considered within scope and spirit of the present invention.Exemplary disclosed the present invention herein can be compatibly implements under the condition that does not have concrete disclosed any key element herein and/or any optional key element disclosed herein.Although described composition and method about " comprising ", " comprising " or " containing " various ingredients or step, composition and method also can " be made up of various ingredients or step " or " being made up of various ingredients or step " substantially.Above-disclosed all numerical value and scope can change with certain amount.No matter when disclose the number range with lower limit and the upper limit, any numerical value and any scope comprising that drop within the scope of this are all specifically disclosed.Especially, any number range disclosed herein (form has: " about a is to about b ", or ground of equal value " approximately a to b ", or ground of equal value " approximately a-b ") be should understand and the each numeral and the scope that in the relative broad range of numerical value, comprise listed.In addition, the term in claim has their usual, its ordinary meaning, unless patentee clearly and is clearly defined.In addition the indefinite article " a " using in claim, or " one " are defined as the key element that refers to or be greater than its introducing in this article.If the use of word or term exists any conflict with being incorporated to by reference one or more patents or other document herein in this description, should adopt the definition consistent with this description.

Claims

1. cigarette filter tip material, it comprises:

Filter tip, described filter tip contains cellulose diacetate and substituted cellulose acetate, and described substituted cellulose acetate contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal at least 0.01 % by weight with substituted cellulose acetate exists.

2. the cigarette filter tip material of claim 1, wherein nonmetal approximately 25 % by weight that are not more than with substituted cellulose acetate exist.

3. the cigarette filter tip material of claim 1, also comprises plasticizer.

4. the cigarette filter tip material of claim 3, wherein said plasticizer also comprises the plasticizer that is selected from group below: the ester of monounsaturated dicarboxylic acid, the ester of saturated polyol, fatty acid ester, and sulphamide resin.

5. the cigarette filter tip material of claim 1, wherein substituted cellulose acetate is tow.

6. smoking apparatus, it comprises:

Can light suction material; With

Cigaratte filter, described cigaratte filter comprises cellulose diacetate and substituted cellulose acetate long filament, described substituted cellulose acetate long filament contains polar substituent, and described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine; Wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate.

7. the smoking apparatus of claim 6, wherein nonmetal approximately 25 % by weight that are not more than with substituted cellulose acetate exist.

8. the smoking apparatus of claim 6, wherein can light suction material is tobacco.

9. the smoking apparatus of claim 8, wherein tobacco has experienced processing, and described processing comprises the processing that is selected from group below: dry, fermentation, smokes, cutting, and these any combination.

10. the smoking apparatus of claim 6, wherein smoking apparatus is cigar, tobacco pipe, cigarette, or evaporimeter.

11. 1 kinds of methods for the preparation of substituted cellulose acetate tow, it comprises:

Carry out spinning to spinning liquid, describedly spin the solution that liquid comprises cellulose diacetate, substituted cellulose acetate and solvent, described substituted cellulose acetate contains polar substituent, described polar substituent contains and is covalently bond to the nonmetallic oxygen atom that is selected from sulphur, phosphorus, boron and chlorine, wherein nonmetal existing at least about 0.01 % by weight with substituted cellulose acetate;

Reel and just spin substituted cellulose acetate long filament;

Form tow by substituted cellulose acetate long filament;

Crimped tow;

Regulate through curling tow; With

Packing dry through curling tow.

The method of 12. claims 11, wherein nonmetal approximately 25 % by weight that are not more than with substituted cellulose acetate exist.

The method of 13. claims 11, wherein solvent is selected from group below: water, acetone, methyl ethyl ketone, carrene, dioxane, dimethyl formamide, methyl alcohol, ethanol, glacial acetic acid, supercritical CO ₂, and their any combination.

The method of 14. claims 11 is wherein carried out spinning to substituted cellulose acetate in spinning head.

The method of 15. claims 14, wherein spinning head comprises hole.

The method of 16. claims 11, also comprises the step of lubricating substituted cellulose acetate long filament.