CN1010681B - Anisotropy compound of cellulose esters and method of preparing this compound and cellulose esters or cellulose fibres - Google Patents

Abstract

The present invention relates to a composition (M) which uses formate based cellulose ester as a main body. The composition is an anisotropic solution which contains the following components: cellulose ester, formic acid and at least one phosphoric acid. The present invention also relates to a method for obtaining the composition by dissolving cellulose, and relates to a method for processing the composition into products and regenerating the cellulose in the products. The present invention also relates to cellulose fiber. The cellulose in the fiber can be replaced by formate base more than 2%, or 0 or below 2%.

Description

Anisotropy compound of cellulose esters and method of preparing this compound and cellulose esters or cellulose fibres

The present invention relates to cellulosic material.So-called " cellulosic material " is meant the vegetable material that contains Mierocrystalline cellulose and other material (for example xylogen) or refers to process by the whole bag of tricks the Mierocrystalline cellulose of gained, especially be the Mierocrystalline cellulose that raw material is processed into the plant.

The derivatived cellulose (having a part of ester group at least is the formic acid ester group) that the invention particularly relates at least with a kind of cellulose ester group is the anisotropy composition that main body is made.The invention still further relates to the goods by these composition gained, the cellulose formiate in these goods can be reproduced into Mierocrystalline cellulose.The invention still further relates to the method that may obtain these compositions and goods (and the goods with high degree of mechanical character), these goods are with Mierocrystalline cellulose and/or to have the defined derivatived cellulose in a kind of front at least be that main body is made.These goods can be fiber or film etc.

German Patent the 189836th, 189837 and No. 561119, French Patent the 638431st and No. 541048, English Patent the 260650th and No. 275641 and United States Patent (USP) the 1656119th and discussed for No. 1900599 at various mineral compound (hydrochloric acid especially, sulfuric acid or phosphoric anhydride) existence under, Mierocrystalline cellulose is transformed into the method for cellulose formiate by the effect of formic acid.But there are more following shortcomings at least in method described in the above-mentioned patent:

1 can not obtain a kind of solution of formic acid fiber.

During 2 esterifications or when storage, serious Degradation can take place in Mierocrystalline cellulose, especially when temperature during above 0 ℃ more very, the polymerization degree of cellulose formiate is lower than the cellulosic degree of polymerization before the esterification significantly.

3 can not obtain having the goods of high mechanical properties.

United States Patent (USP) discussed for No. 2363091 catalyzer (can be phosphoric acid or phosphoric anhydride etc., its amount should not surpass cellulose 30%) existence under, by mixing the method for first-diacetyl oxide to cellulosic effect manufacturing mixing formic acid-typel element.But the described method of this patent, and can not make cellulose dissolution.

German Patent was discussed work by acetate and phosphoric acid for No. 227198 in order to the method for dissolving cellulos.But this patent is not pointed out the method for making of cellulose formiate solution.And described method can not obtain being enough to obtain the rhodia concentration of anisotropic solution.

No. the 263810th, English Patent is discussed work by phosphoric acid and organic acid (can be acetate, propionic acid or butyric acid) in order to the method for dissolving cellulos.But this patent is not discussed the method for making of cellulose formiate solution.And in the solution that this patent is touched upon, cellulose ester concentration is not enough to obtain anisotropic solution.

English Patent 309(1911) and 29246(1910), and No. the 56146th, Swiss Patent and German Patent discussed Mierocrystalline cellulose and dense formic acid and phosphate mixture phase reaction method for No. 249535.But the example described in these patents shows that they do not obtain cellulose solution or anisotropic solution.

German patent application (OS) was discussed for No. 3035084 cellulose ester was dissolved in the method for making anisotropic solution in the inorganic acid aqueous solution.But this method is not used to make cellulose formiate.In addition, this method is because of being to use cellulose ester but not uses Mierocrystalline cellulose to be raw material, so cost costliness.And the polymerization degree of these cellulose ester will be lower than the cellulosic degree of polymerization of making raw material usually.In addition, goods described in this application and the products machinery performance produced by these esters are all lower.At last, the application did not discuss any method by the cellulose ester solution regenerated cellulose.And it will be very slow carrying out this regeneration with above-mentioned solution, in fact can not carry out continuously.

Purpose of the present invention will be avoided the generation of these shortcomings just.

Therefore, the derivatived cellulose that the present invention relates to and have a kind of cellulose ester group at least (some is the manthanoate group in these ester groups at least) is the composition of main body, and the notable feature of this composition is: it is a kind of anisotropic solution of producing fiber and film.This composition comprises:

A) a kind of derivatived cellulose or all kinds of derivative, the concentration of the plain derivative of a kind of derivatived cellulose or all fibres in solution is at least 10.2%(weight), and the cellulosic degree of polymerization (DP) in derivatived cellulose or all derivatives should be greater than 150 and less than 1500.

B) formic acid or at least two kinds have a kind of formic acid that is by the compound of choosing in monocarboxylic acid and these sour acid anhydrides and the carboxylic acid halides in these compounds;

C) has a kind of phosphoric acid at least.

The invention still further relates to by dissolving cellulos and obtain this method for compositions, this kind solvency action can not cause cellulosic degree of polymerization to reduce in fact.

This law (being commonly referred to as " dissolution method ") has following feature:

A) form a kind of mixture by at least three kinds of materials, that is:

(I) cellulosic material;

(II) contains a kind of by selected compound in monocarboxylic acid and these sour acid anhydrides and the carboxylic acid halides at least, contains some formic acid and/or formic acid and other organic acid acid anhydrides in this material at least;

(III) contains phosphoric anhydride or has a kind of phosphoric acid substance at least, or the material of being made up of phosphoric anhydride and at least a phosphoric acid.

B) forming the existing water yield of mixture is zero or ratio in the case

R _wr= (P _w-P _wr)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

Less than 15.0% and greater than-7.5%, R _WrWith per-cent (%) expression, P _wBe the water weight that possible exist, P _WrFor may with the water weight of material (II) and/or material (III) reaction, P _IBe the cellulose in the material (I), P _IIBe the weight of material (II), P _IIIWeight for material (III);

C) R _IR _II, R _IIIRatio be defined as:

R _I= (P _I)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _Ⅱ= (P _Ⅱ)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _Ⅲ= (P _Ⅲ)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _I, R _II, R _III, R _WrRatio (R _I+ R _II+ R _III+ R _WrSum be decided to be 100%) will satisfy following relationship (its value is represented with %):

If-definite 12.5≤R _Wr＜15.0

Then have:

10.0≤R _I≤ 14.5; 2.0≤R _II≤ 10.0 relations

And R _IAnd R _IIThe pass be: R _II≤ 0.89R _I-2.89;

If-definite 10.0≤R _Wr＜12.5

Then have:

10.0≤R _I≤ 19.5; 2.0≤R _II≤ 17.0 relations

And work as R _I＜14.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 1.78R _I-8.78

Perhaps work as R _I〉=14.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤ 14.0R _I+ 37.30

If-definite 7.5≤R _Wr＜10.0

Then it has:

10.0≤R _I≤ 31.0; 2.0≤R _II≤ 23.0 relations

And work as R _I≤ 12.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 4.40R _I-32.00

Perhaps work as R _I〉=15.5 o'clock,

R then _II≤-1.19R _I+ 41.50

If-definite 5.0≤R _Wr＜7.5

Then have:

10.0≤R _I≤ 37.0; 2.0≤R _II≤ 27.5 relations

And work as R _I≤ 13.0 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 4.17R _I-26.67

Perhaps work as R _I〉=19.0 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.14R _I+ 49.14

If-definite 2.5≤R _Wr＜5.0

Then have:

10.0≤R _I≤ 37.0; 2.0≤R _II≤ 36.5 relations

And work as R _I≤ 14.0 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 4.63R _I-28.25

Perhaps work as R _I〉=15.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.23R _I+ 55.60

If-definite-2.5＜R _Wr＜2.5

Then have:

10.0≤R _I≤ 38.0; 2.0≤R _II≤ 40.0 relations

And work as R _I＜12.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 2.80R _I+ 5.00

Perhaps work as R _I〉=19.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.14R _I+ 62.14

If--5.0＜R _Wr≤-2.5

Then have:

10.0≤R _I≤ 35.0; 2.0≤R _II≤ 45.0 relations

And R _IAnd R _IIThe pass be: R _II≤-1.30 R _I+ 64.50

If--7.5≤R _Wr≤-5.0

Then have:

10.0≤R _I≤ 32.0; 2.0≤R _II≤ 36.0 relations

And if R _I≤ 14.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤ 4.00R _I-22.00;

D) the middle cellulosic degree of polymerization (DP) of material (I) is greater than 150, less than 1500;

E) in mixture, proceed the Mierocrystalline cellulose esterification reaction of for some time again and just be enough to obtain anisotropic solution.

The invention still further relates to composition with this dissolution method gained.

The invention still further relates at least the method for making based on the goods of a kind of derivatived cellulose, its notable feature is that composition of the present invention can be processed to goods, and at least can be from goods reject fall the product of a part of non-cellulose derivative or all derivatives.

The invention still further relates to the goods method for making based on the reproducibility Mierocrystalline cellulose, its distinguishing feature is that the Mierocrystalline cellulose in the goods that make to the aforementioned method of major general gives partial regeneration.

The invention still further relates to the goods of making by these methods.

The invention still further relates to a kind of like this fiber, the monofilament (filament) that this fiber at least a portion is made by main body by the derivatived cellulose of a kind of cellulose ester group (wherein having at least a part to be the manthanoate group) is formed, and it has following characteristic:

A) Mierocrystalline cellulose is at least 2% by the degree (DS) that the manthanoate group is replaced, and cellulosic polymerization degree DP is greater than 150, less than 1500;

B) the intensity T of fiber and initial modulus M _iHas following relation, T and M _iBe with li newton/spy (CN/tex) expression:

T＞20;M _i＞1000;

C) this monofilament has such form; It has a part at least is the laminate structure of embedding each other, and these laminate structure ring copss distribute, and optical direction and crystallization direction are the change of pseudoperiodicity ground along the silk axle in each laminate structure simultaneously.

The invention still further relates to a kind of fiber that is called " reproducibility cellulosic fibre ", it is to be main body and/or to be that the monofilament of main body is processed into by the cellulose-derived of a kind of cellulose ester group (have at least in these ester groups a part for manthanoate group) at least by Mierocrystalline cellulose that this fiber has a part at least.It has following properties:

A) degree (DS) that replaced by the manthanoate group of Mierocrystalline cellulose is zero or less than 2%, and cellulosic extent of polymerization DP is greater than 150, less than 1500;

B) cellulosic polymerization degree DP, the intensity T of fiber and initial modulus M _iBetween have following relation, T and M _iBe with li newton/spy (CN/tex) expression:

In DP＜200 o'clock, T＞20, M _i＞1800;

In 200≤DP＜300 o'clock, T＞30, M _i＞2000;

In 300≤DP＜400 o'clock, T＞40, M _i＞2400;

In 400≤DP≤1500 o'clock, T＞60, M _i＞2600;

C) this monofilament has such form, and it has a part at least is the laminate structure of mutual embedding, and these laminate structure ring copss distribute, and optical direction in each laminate structure and crystallization direction are the change of pseudoperiodicity ground along the silk axle simultaneously.

P _I, P _II, P _IIIHeavily be meant to be assumed to anhydrous Mierocrystalline cellulose and material (II), (III) is heavy, that is, these weight are when the preparation mixture, from a or many parts (I), and existing any water yield of deduction in (II), (III) and recording.P _wHeavily be meant preparation during mixture with material (I), (II), in (III) at least a and or irrelevant with these materials, and any water yield of introducing.

" Mierocrystalline cellulose " is the abbreviation of " holocellulose ", and it refers to existing all alpha-celluloses and hemicellulose in the cellulosic material.And refer to that here cellulosic material also may not contain hemicellulose.

Can exist simultaneously with the mixed anhydride of formic acid and/or at least a formic acid and make the non-aromatic acid that material (II) monobasic organic acid is preferably 2 to 5 carbon atoms, acetate for example, propionic acid, butyric acid and valeric acid etc.The monocarboxylic acid acid anhydride that can make material (II) is preferably the acid anhydrides of above-mentioned acid, and can be the mixed anhydride of mixed anhydride class, especially formic acid.The monobasic carboxylic acid halides that can be used as material (II) is preferably the chloride thing.The present invention includes (for example halogen or the alkyl etc.) that contain substituted radical.The acid anhydrides of organic acid and mineral acid and halogenide.

The compound that is used for material of the present invention (III) especially can be phosphoric acid, as ortho-phosphoric acid (H ₃PO ₄) tetra-sodium (H ₄P ₂O ₇), phosphoric anhydride (P ₂O ₅) or these compounds mixture or these compounds and " Nouveau traite ' de chimie min é rale " to each other (issue pascal in editorship of paul, Volume x, Masson Editeur 1956) the mixture described in the book as other phosphoric acid such as Tripyrophosphoric acid.

The R of aforementioned definitions _I, R _II, R _III, R _WrRatio will be explained in following example in detail.When material (II) and/or material (III) can react with water, P then _wValue be not 0.Otherwise, P _WrBe 0.

Desire prepares mixture, can be with material (I), (II), (III) and the water that can add mix or prepare at least earlier a kind of premixture (for example reaching (III) as being pre-mixed thing with material (II)) simultaneously, then its material with remainder are mixed again.

Used " anisotropy composition " reaches " isotropy composition " in the specification sheets following meanings.

The anisotropy composition has optical anisotropy, that is relaxed state does not have to work as under the dynamic stress situation with this composition under room temperature, place between slide glass and the cover glass, when the microscopic examination of cross line polarizing prism is arranged, can find that this composition has depolarization, and light transmission and uniform color pattern are arranged.On the contrary, the isotropy composition presents black in the microscopical visual field.Usually, the concentration of this anisotropy composition is greater than measured Jie's concentration of facing on derivatived cellulose in expression composition viscosity and the composition or all derivatives concentration relation curves.On this curve, when the concentration of derivatived cellulose or all derivatives increased, then the viscosity of composition increased, and this relation continues up to threshold concentration, and (claim this to be " stagnation point " on the time, the rate of curve of this moment demonstrates wide variation.When concentration surpasses threshold concentration, then the viscosity of composition will begin to reduce more lentamente or increase along with the increase of derivatived cellulose or all derivatives concentrations, vertex that this phenomenon especially can be from curve or weight break point and learn.When the concentration of the derivatived cellulose of composition or all derivatives during greater than threshold concentration, this composition is called " anisotropy composition " usually.The curve of this expression composition viscosity and concentration relationship, the back will further be studied.This specification sheets used " viscosity " all refers to dynamic viscosity.

Numerical value from the complete graph table of following non-limiting example and relevant these examples is readily appreciated that the present invention.

In the accompanying drawings:

-Fig. 1 and 2 every figure are the ternary diagram that expression dissolution method application conditions figure of the present invention is situated between.

-Fig. 3 illustrates the ternary diagram of various compositions related to the present invention for figure is situated between.

-Fig. 4 is the relation curve of cellulose-derived substrate concentration in expression composition viscosity and the composition.

-Fig. 5 is for supplying two kinds of used standard substance characteristic spectrum curves of fiber X diffractometry of the present invention.

-Fig. 6 is a monofilament section diagrammatic sketch related to the present invention, and section is got along the silk axis plane.

-Fig. 7 is a monofilament cross-sectional view shown in Figure 6, and this section is taken from the plane perpendicular to the silk axle, and VII among Fig. 6-VII line chart illustrates this planimetric position.

-Fig. 8 and 9 expression intensity T(Fig. 8) and initial modulus M _i(Fig. 9) function relation figure between the cellulosic degree of polymerization DP in the reproducibility fiber related to the present invention.

In order clearly to illustrate following these examples, we are divided into three big topics and discuss:

I. cellulose composition: this big topic is to discuss the method for testing of these preparation of compositions and resulting composition.

II. the goods of derivatived cellulose: this big topic is to discuss the preparation of these goods and the method for testing of resulting product.

III. the cellulosic goods of reproducibility: this big topic is to discuss the preparation of these reproducibility cellulosicss and the method for testing of resulting product.

The described test of these examples can be the test consistent with the present invention or be not to be for the relatively test of usefulness with the test of unanimity of the present invention.

I. cellulose composition

A. eight kinds of cellulosic materials have been used.These cellulosic materials are numbered C ₁To C ₈, its characteristic is shown in Table 1.

Per-cent shown in the table is the weight percent that accounts for the cellulosic material gross weight.The water yield is equivalent to residual water content.Characteristic shown in this table is measured with following method.

A) alpha-cellulose content: according in November, 1977 the Federal Republic of Germany's standard DIN 54355 mensuration.This amount is equivalent to be insoluble to 18%(weight) cellulosic material in the aqueous sodium hydroxide solution.

B) half fibre content: this value calculates by following formula: (hemicellulose %)=100-(alpha-cellulose %)-(resin %)-(water %)-(grey %).

C) holocellulose content: by aforementioned definitions, holocellulose content (holocellulose %)=(alpha-cellulose %)+(hemicellulose %), equation calculates.

D) resin content: this amount be according in November, 1977 the Federal Republic of Germany's standard DlN 54354(be the dichloromethane extraction method) predict.

E) the ash content of coal: the ash content of coal is measured with thermo-gravimetric analysis.Employed instrument is the TG 50 type Mettler thermobalances that Mettler TG 10 MPU are housed.Temperature increases to 950 ℃ gradually by room temperature, and rate of heating is 20 ℃ of per minutes.Originally use nitrogen gas stream, after temperature to 700 ℃, use air.Sample is cooled to room temperature, then weighs.

F) water yield (residual moisture content: measure with thermo-gravimetric analysis.Use under nitrogen gas stream and the identical instrument of (e) described measurement the ash content of coal, this temperature is that the heating rate with 20 ℃ of per minutes increases to 150 ℃ one by one by room temperature.Sample was kept 15 minutes at 150 ℃, and cooling is weighed then.

G) polymerization degree DP: the limiting viscosity lV of cellulosic material records according to Switzerland standard SNV 195598 in 1970, and concentration range is 0.5 to 0.05g/dl.

Limiting viscosity is recorded by following equation

lV＝ (l)/(C) Ln (t)/(to)

Wherein C represents the concentration of dry cellulosic materials, and " t " represents the flowing time of dilute polymer solution, t _oRepresent the flowing time of neat solvent in Unio margarita Lip river moral (Vbbelohde) viscometer, Ln represents the logarithm of Nepierian, measures and carries out under 20 ℃.

When limiting viscosity (η) is extrapolated to zero-dose by limiting viscosity lV and get.

Weight-average molecular weight M _WBy mark-Huo Wenke (Mark-Houwink) equation: (η)=K M ^α _WAnd get constant wherein, K=5.31 * 10 ^-4And α=0.78, these constants are with relevant for measuring the used solvent system of limiting viscosity.

L.Valtasaari is in Tappi 48.627(1965) in provide these constant values,

The polymerization degree (DP) defines with following formula

162 molecular weight that are meant cellulose base our unit wherein.

H) pH of slurries: the DIN of the Federal Republic of Germany 53124 records according to December nineteen sixty.

B. prepare the used device and method of composition

Composition prepares in cylindric glass reactor.The capacity of this reactor is about 50ml, the about 20mm of its internal diameter.This reactor has the constant temperature outer tube, so the product temperature in the reactor can remain in 25 ℃.Stirring action in the reactor is finished by two metal spiral agitators, and one of them is a fixed, and another rotates around the reactor cylinder axle with 15 to 20rpm speed rings approximately, and fixedly spiral stirrer is far away for the distance of this movable spiral stirrer and axle.Therefore whole reactor inside all can reach stirring.Easy for narrating, will prepare the used material of mixture (even comprising the water that has) and be called " base substance ".

Each test is at first kneaded used base substance to become mashed prod in grinding Bowls together, then it is inserted in the cylindrical reactor.Then, in reactor, further stir to promote cellulosic esterification.The sample that takes out mixture at set intervals test under microscope it, one then stops to stir when solution forms.No matter whether solution formed by 8 hours, all stopped to stir.

Final mixture after stirring stops is known as " composition ".

C. the test case during preparation of compositions

1 outline

Following example is made up of test, and the preparation of mixture and the research of resulting composition are discussed in each test.Test can also can be according to the present invention according to the present invention.These test results are shown in greater detail in table 4 in 14, and the equal schematic illustration of these examples is in table 2.Each mixture is all mixed by four kinds of base substances (being water and following material (I), (II), (III)) and gets.

(I) is a kind of by the selected cellulosic material that gets in the described material of above-mentioned A section, and this material should be dry earlier before using, so that can therefrom remove portion water at least.

(II) contains the material that a kind of following product is formed at least: organic acid, organic acid anhydride, organic acyl chlorides.

(III) contains the material that a kind of following product is formed at least: mineral acid, inorganic acid anhydrides, organic acid.

When testing according to the present invention, then material (II) and (III) are consistent with defined material (II) and (III) in the dissolution method of the present invention respectively.

Water can be with material (I), and one of (II) and (III) (for example positive acid solution) brought in the mixture, and/or brings into other material.

Mixture is produced with the device and method described in the above-mentioned B section.

In order to prepare each mixture, definition earlier is routine ratio down:

R _I= (P _I)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _Ⅱ= (P _Ⅱ)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _Ⅲ= (P _Ⅲ)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _wr= (P _w-P _wr)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

And R _I+ P _II+ P _III+ P _Wr=1

In these ratios, P _IHolocellulose in the representative species (I) is heavy, P _IIRepresentative species (II) is heavy, P _IIIRepresentative species (III) is heavy, P _wRepresent water heavy, P _WrRepresentative can be heavy with the water of material (II) and/or (III) reaction.P _I, P _II, P _IIIHeavily be that anhydrous substances is heavy, promptly before the preparation mixture, not with material (I), (II) or (III) bonded water restatement is gone into, this portion water heavily is referred to as P _wFor example, if pass through C ₁To C ₈A kind of cellulosic material mix and when testing P then with aqueous formic acid and positive acid solution _IRepresent anhydrous holocellulose heavy, P _IIRepresent anhydrous formic acid heavy, P _IIIRepresent anhydrous ortho-phosphoric acid heavy, P _wRepresent in the cellulosic material gross weight of existing water in the existing water and formic acid and ortho-phosphoric acid solution.

The water that may introduce from ambient air is not included in P _wIn.The water that the Mierocrystalline cellulose esterification is disengaged when testing certainly also is not included in P _wIn.When testing according to the present invention, R then _I, R _II, R _III, R _WrRatio meet the definite ratio of aforesaid dissolution method of the present invention.

P _WrHeavily be can be heavy with theoretical total water of material (II) and/or material (III) reaction.Therefore, as use dissolution method of the present invention, when this material contains at least a organic acid anhydride and/or at least a organic acid carboxylic acid halides, then water can react with material (II), when above-mentioned substance contained the phosphoric acid of phosphoric anhydride and/or at least a non-ortho-phosphoric acid, then water can react with material (III).

If, material (II), (III) all can not react with water, then P _WrBe zero.

In this case,

R _wr=R _w= (P _w)/(P _I+P _Ⅱ+P _Ⅲ+P _w)

Work as P _WrBe equal to or greater than P _wThe time, R then _WrBe 0 or negative value, that is the heavy P of whole water _wAll can react with material (II) and/or (III).According to the present invention, P _WrLess than 15%, greater than-7.5%.

The measurement of 2 pairs of resulting compositions and observation

Project to resulting composition test and observation is as follows:

A) solubleness: the dropping liquid that takes out from circle shape reactor uses the Olympus BH with 100 x magnifications ₂The type observation by light microscope.

-when can not see cellulosic solia particle, then expression has obtained cellulose solution.

-when observing cellulosic solia particle, represent that then fiber have insolubility.

Each test period, all every interval certain hour carries out this check.Formed under the solution situation as test in the following example, then table 4 is equivalent to show in the above-mentioned test churning time of the cylindrical reactor when solution has formed to the churning time shown in 14.Stop then stirring according to this test.In any case, all stirrings of stopped reaction device by 8 hours.

B) optical isotropy of solution or anisotropy: only be used to observe solution.A solution is placed Olympus optical polarization microscope (BH ₂Between type) crossed-polarizer and analyzer, then observe it.

C) cellulosic replacement degree (DS) in solution of cellulose derivative.This solution is freezing in liquid nitrogen, and the solid product with gained mixes with dry ice again, and smashs to pieces, to obtain meal, it is mixed with acetone, and the gained throw out is filtered, and uses acetone extract (using the Soxlhet extractor) again.With residual powder in air under 70 ℃ dry at least 30 minutes.

Then accurately weigh up the resulting derivatived cellulose of 400mg, place the Erlenmeyer flask that contains 70ml water and 4ml 1N sodium hydroxide.In 100 ℃, reflux half an hour under the nitrogen gas stream, thereby the Mierocrystalline cellulose in the derivatived cellulose obtains regeneration.After the cooling, use 0.1N HCl solution that excessive sodium hydroxide is given residual titration.

Total DS of method gained is the percent of total of the Mierocrystalline cellulose alcohol radical of esterification thus, promptly when three alcohol functional group in the cellulose base our unit complete when esterified, DS=100% then.

When all ester groups of this derivatived cellulose were the formic acid ester group, then measured DS was directly for being converted into the alcohol radical per-cent of formic acid ester group in the Mierocrystalline cellulose.When derivatived cellulose contains several ester groups (for example formic acid ester group and acetate groups), replace degree in order to distinguish each organic acid, after recording total DS, measure by following method again with aforesaid method.Neutral solution during with the total DS of mensuration becomes alkalescence (PH=11) so that make the regenerated Cellulose precipitates, this Mierocrystalline cellulose is filtered again.Filtrate is used hcl acidifying behind evaporating off water and concentrate then.This residue is weighed, then use the organic acid content of the non-formic acid of gas phase chromatography assay determination.For example, if be acetic acid, then the separation condition of gas phase chromatography is as follows: glass column: long 1.5m, internal diameter 2mm; Filler: Poropak Q; Instrument: Pye Unicam; The temperature of syringe: 250 ℃; Furnace temperature: 140 ℃; The temperature of FlD detector: 220 ℃, record thus corresponding to the organic acid DS outside the formic acid, and then according to total DS value by calculating the DS of corresponding formic acid.

D) cellulosic degree of polymerization in the solution of cellulose derivative (DP).Derivatived cellulose is separated, makes its regeneration with this cellulose derivative of standard hydrogen sodium oxide reflow treatment then, this operation of two steps and above-mentioned c) section described in identical.The Mierocrystalline cellulose water of gained is cleaned, and drying is again with aforementioned Ag) method described in the section measures DP.

Esterified cellulose except the DP value, also point out in the following example table and the plain DP of initial fiber between deviation (△ DP) (table 1 listed DP be the DP value of used cellulosic material in the corresponding test).△ DP represents with absolute value with respect to the per-cent of the plain DP of initial fiber.

E) composition of composition: composition is to calculate by the ratio separately of DS that measures in the derivatived cellulose and base substance to obtain.

Under the 2 outline conditions that provided each example of tabulating.In this table, the asterisk of being marked behind some example number represents that this example according to of the invention process other then is not.Table 4 is understood these examples in detail to 14, and uses following abbreviation:

In-" solubleness " row: " SL " refers to " solvable ", and " lNSL " expression is " soluble.”

In-" character of the solution " row: " lS " refers to " isotropy ", " ANlS " expression " anisotropy ".

In these thin tables, only when composition was solution, the side listed the composition (weight %) of resulting composition.

Table 4 is listed base substance in 14, the numerical value of churning time and resulting composition.Each derivatived cellulose that provides, organic acid, the per-cent of mineral acid is meant the per-cent of compound, the respective compound total amount that provides just is meant the gross weight of solution composition shown in the table, for example the solution of table 4 to 14 just is meant that derivatived cellulose adds that organic acid adds that mineral acid (or all kinds of mineral acid) adds the gross weight of water.

Table 4 to 14 in, R _I, R _II, R _III, R _WrAnd R _wRatio is to represent with per-cent, promptly also can be considered weight ratio corresponding to the value shown in these ratio ranks and (gets P _I+ P _II+ P _III+ P _w-P _WrEqual 100 parts of weight).For example, P is used in No. 1 test (table 4) of example I-1 _I=29.8(weight) part holocellulose, P _II=9.9(weight) part formic acid, P _III=59.7(weight) part ortho-phosphoric acid, P _w=0.6(weight) water (P of part _I+ P _II+ P _III+ P _w=100), because P _WrBe 0, i.e. R _WrEqual R _w, be 0.6%(just 0.006), R _wValue represents then to equal 0.6 with per-cent.

Table 4 comprises except that R to 14 note _WrWeight ratio outside, also comprise the weight ratio of aquatic products thing.

The material (II) that uses for example and (III) and their water content tabular are in table 3.

Table 3

(for base substance (II) and (III) used product)

The character water yield (weight %) of the reference number product of product

1 formic acid 0.1

2 ortho-phosphoric acid 0.6

3 acetate 0.2

4 acid anhydrides 0

5 blended first-acetic anhydrides ^*0

6 Acetyl Chloride 98Min.s 1

7 propionic acid 0.1

8 aqueous formic acids 48.3

9 methyl-2-butyric acid 0.1

10 tetra-sodiums 3

11 phosphoric anhydrides 0

12 positive acid solutions 16

13 phosphorous acid 0.4

14 boric acid 0.4

15 Tetrafluoroboric acids 50

16 sulfuric acid 0.3

17 trifluoroacetic acids 2

Table 3(is continuous)

The character water yield (weight %) of the reference number product of product

18 methylsulfonic acids 1

19 dichloro acetic acid 0.4

20 Monochloro Acetic Acids 1

21 trichoroacetic acid(TCA)s 1

22 formic acid 0.7

23 ortho-phosphoric acid 1.3

24 chloros-2-propionic acid 0.4

^*The weight % of composition: mixed anhydride: 35%;

Aceticanhydride: 15%;

Acetic acid: 50%;

Table 10

The inconsistent test of example I-7(and the present invention)

The test number

1 2 3 4 5

Base substance

Ratio (%) R _I2.0 2.5 2.0 2.5 20.0

R _Ⅱ2.4 2.5 10.0 15.0 20.0

R _Ⅲ68.0 80.0 68.0 80.0 50.0

R _wr＝R _w27.5 15.0 20.0 2.5 10.0

Total amount 100.0 100.0 100.0 100.0 100.0

Churning time 8 1.17 8 0.75 5.5

(hour)

Table 10(is continuous)

The composition of gained

Form (weight %) derivatived cellulose 2.6 3.0

Organic acid 2.3 14.2

Mineral acid 80.0 80.0

Water 15.1 2.8

Total amount 100.0 100.0

Characteristic solubleness INSL SL INSL SL INSL

The character IS IS of solution

Mierocrystalline cellulose DS(%)

Formic acid ester group 9.0 36.7

Other group 0.03 1.1

Table 10(is continuous)

The test number

6

Base substance

Ratio (%) R _I40.4

R _Ⅱ10.9

R _Ⅲ53.7

R _wr＝R _w-5.0

Total amount 100.0

Churning time (hour) 8

The composition of gained

Form (weight %) derivatived cellulose

Organic acid

Mineral acid

Water

Total amount

Characteristic solubleness INSL

The character of solution

Cellulosic DS(%)

The formic acid ester group

Other group

The note of table 10

1, base substance:

-material (I): C ₁: test 1,2,5 and 6; C ₆: test 3,4.

-material (II): the mixture of formic acid (table 3, product 1) and acetate (table 3, product 3), formic acid is heavy to be 9 with the heavy ratio of acetate in all tests.

-material (III): ortho-phosphoric acid (table 3, product 2).

In all tests: R _Wr=R _w

2, the composition of gained:

Identical with table 8 note, but notice that test 1,3,5 and 6 does not form solution.

Table 12

The inconsistent test of example I-9(and the present invention)

The test number

1 2 3

Base substance

Ratio (%) R _I2.6 35.0 45.0

R _Ⅱ24.15 30.0 10.0

R _Ⅲ73.25 37.5 50.0

R _wr0.0 -2.5 -5.0

Total amount 100.0 100.0 100.0

Churning time (hour) 0.5 88

The composition of gained

Form (weight %) derivatived cellulose 3.0

Organic acid 21.1

Mineral acid 75.5

Water 0.4

Total amount 100.0

Characteristic solubleness SL INSL INSL

SOLUTION PROPERTIES IS

Cellulosic DS(%) 49.3

The note of table 12

1, base substance

-material (I): C ₁: test 1

C ₈: test 2 and 3

-material (II): formic acid (table 3, product 1)

-material (III): test 1 and 3: the mixture of ortho-phosphoric acid (table 3, product 2) and phosphoric anhydride (table 3, product 11).The ratio that ortho-phosphoric acid is heavy and phosphoric anhydride is heavy is 2.0 in test 1, is 2.44 in test 3.

Test 2: the mixture of ortho-phosphoric acid (table 3, product 2) and tetra-sodium (table 3, product 10).The ratio that ortho-phosphoric acid is heavy and tetra-sodium is heavy is 0.42.

2, the composition of gained

Derivatived cellulose: cellulose formiate.

Organic acid: formic acid.

Mineral acid: the mixture of phosphoric acid.

The conclusion of D. relevant these examples

Can draw as drawing a conclusion by example I-1 to I-11:

1) not consistent with the present invention example: example I-3, I-4, I-7, I-9, I-10 and I-11 are based on following reason, so inconsistent with the present invention:

-or example I-3, I-4, I-7, in the I-9, R _I, R _II, R _III, R _WrRatio in have a ratio that does not meet the definition of the aforementioned dissolution method of the present invention at least.

-or example I-10, in the I-11, material (II) or (III) are inconsistent with above-mentioned dissolution method definition.

In all scenario, not consistent with the present invention example all causes following result:

-or do not produce the cellulose solution of derivatived cellulose form,

-or form solution, but this solution is isotropy.

These two kinds of composition forms all do not meet the definition of the aforementioned present composition.These not consistent with the present invention compositions are unsuitable for making fiber or the film with high mechanical properties.

2) example consistent with the present invention: example I-1, I-2, I-5, I-6, I-8 is consistent with dissolution method of the present invention.These examples all produce the composition consistent with the present invention under all scenario, each composition all forms the anisotropy cellulose solution of derivatived cellulose form, and promptly composition can (its details be as described in the example of following II and the big topic of III for making fiber with high mechanical properties or film.

In dissolution method of the present invention, R _I, R _II, R _III, R _WrBetween relation unexpectedly corresponding with an extremely limited scope, by Fig. 1 and 2 the expression the ternary diagram examples can illustrate this fact.In order to the material (I) that plots these figure, (II), (III) is as follows:

-material (I): cellulosic polymerization degree DP is greater than 150, the cellulosic material less than 1500, and these materials are by the C of table 1 ₁To C ₈Selected in the material.

-material (II): the mixture of formic acid (product 1, table 3) and acetate (product 3, table 3), the heavy ratio (anhydrous heavy ratio) with the acetate weight of formic acid equals 9.

-material (III): ortho-phosphoric acid (product 2, table 3).

The figure of Fig. 1 is equivalent to R _Wr=R _w=0.0%, the figure of Fig. 2 is equivalent to R _Wr=R _w=7.5%, the coordinate of these figures is corresponding to the R with following relationship _I, R _II, R _III

R _Ⅰ+R _Ⅱ+R _Ⅲ+R _w＝1

Among Fig. 1, Polygons A ₁, A ₂, A ₃, A ₄, A ₅, A ₆Or this Polygons limit institute region surrounded is corresponding to R in the aforementioned dissolution method feature of the present invention (C) _Wr=R _w=0.0% o'clock R _I, R _II, R _IIIBetween relation, these passes tie up to-2.5%＜R _WrStill can satisfy in＜2.5% o'clock.

Among Fig. 1, some A ₁, A ₂, A ₃, A ₄, A ₅, and A ₆Coordinate as follows:

A ₁：R _Ⅰ＝10.0%，R _Ⅱ＝2.0%，R _Ⅲ＝88.0%;

A ₂：R _Ⅰ＝38.0%，R _Ⅱ＝2.0%，R _Ⅲ＝60.0%;

A ₃：R _Ⅰ＝38.0%，R _Ⅱ＝19.0%，R _Ⅲ＝43.0%;

A ₄：R _Ⅰ＝19.5%，R _Ⅱ＝40.0%，R _Ⅲ＝40.5%;

A ₅：R _Ⅰ＝12.5%，R _Ⅱ＝40.0%，R _Ⅲ＝47.5%;

A ₆：R _Ⅰ＝10.0%，R _Ⅱ＝33.0%，R _Ⅲ＝57.0%;

Among Fig. 2, Polygons B ₁, B ₂, B ₃, B ₄, B ₅, B ₆Or this Polygons limit institute region surrounded is pointed out characteristic (the c) (R of dissolution method of the present invention _Wr=R _w=7.5%) the aforementioned R in _I, R _II, R _IIIBetween relation, these passes tie up to 7.5%≤R _WrRemain valid for＜10.0%.

Among Fig. 2, some B ₁, B ₂, B ₃, B ₄, B ₅And B ₆Coordinate as follows:

B ₁：R _Ⅰ＝10.0%，R _Ⅱ＝2.0%，R _Ⅲ＝80.5%;

B ₂：R _Ⅰ＝31.0%，R _Ⅱ＝2.0%，R _Ⅲ＝59.5%;

B ₃：R _Ⅰ＝31.0%，R _Ⅱ＝4.5%，R _Ⅲ＝57.0%;

B ₄：R _Ⅰ＝15.5%，R _Ⅱ＝23.0%，R _Ⅲ＝54.0%;

B ₅：R _Ⅰ＝12.5%，R _Ⅱ＝23.0%，R _Ⅲ＝57.0%;

B ₆：R _Ⅰ＝10.0%，R _Ⅱ＝12.0%，R _Ⅲ＝70.5%;

These zones are little than corresponding ternary figure (with in question triangular plot representative) all.Work as R _wBe timing, this zone is littler, then R _WrHigher.

Some E among Fig. 1 _I-1, 1 is equivalent to the test 1 of example I-1, the some E among Fig. 2 _I-1, 12 are equivalent to the test 12 of example I-1.

Can find to have a kind of material (I) at least, less than 1500, like this, the relation that dissolution method characteristic of the present invention (c) is provided can produce the composition consistent with the present invention to its cellulosic polymerization degree DP greater than 150.

Cellulosic degree of polymerization DP in the cellulosic material (I) preferably is at least 200, is at most 1200, and its R _I, R _II, R _III, R _WrBetween have a following relationship (representing) with %:

If-definite 10.0≤R _Wr＜12.5

Then it has following relation:

13.0≤R _Ⅰ≤19.0;4.0≤R _Ⅱ≤11.0

And work as R _I＜18.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤ 0.73 R _I-2.45,

Perhaps R _I〉=18.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-2.00 R _I+ 48.00;

If-definite 7.5≤R _Wr＜10.0

Then it has following relationship:

12.25≤R _Ⅰ≤23.0;4.0≤R _Ⅱ≤19.5

And work as R _I＜18.0,

R then _IAnd R _IIThe pass be: R _II≤ 1.65 R _I-10.24,

Perhaps R _I〉=18.0 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.40 R _I+ 44.70;

If-definite 5.0≤R _Wr＜7.5,

Then it has following relationship:

11.5≤R _Ⅰ≤27.5;4.0≤R _Ⅱ≤24.0

And work as R _I＜19.5,

R then _IAnd R _IIThe pass be: R _II≤ 1.38R _I-2.81

Perhaps R _I〉=19.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.56 R _I+ 54.47;

If-definite 2.5≤R _Wr＜5.0,

Then it has following relationship:

10.75≤R _Ⅰ≤32.0;4.0≤R _Ⅱ≤30.0

And work as R _I≤ 17.5,

R then _IAnd R _IIThe pass be: R _II≤ 2.07R _I-5.80

Perhaps R _I〉=20.5,

R then _IAnd R _IIThe pass be: R _II≤-1.30 R _I+ 56.74

If-definite-2.5＜R _Wr＜2.5

Then it has following relationship:

10.0≤R _Ⅰ≤33.5;4.0≤R _Ⅱ≤35.0

And work as R _I≤ 15.0,

R then _IAnd R _IIThe pass be: R _II≤ 3.20 R _I-13.00,

Perhaps R _I〉=23.0 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.76 R _I+ 75.52;

If-definite-5.0≤R _Wr≤-2.5,

Then it has following relationship:

10.0≤R _Ⅰ≤33.5;4.0≤R _Ⅱ≤35.0，

And work as R _I≤ 15.0,

R then _IAnd R _IIThe pass be: R _II≤ 3.20 R _I-13.00,

Perhaps R _I〉=20.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.85 R _I+ 72.85.

In this case, as long as show 200≤1200 DP scope before the polymerization degree DP of cellulosic material (I) has, then can obtain anisotropic solution.The cellulosic degree of polymerization DP of cellulosic material (I) is required to be 200 at least, and is at most 1200, and its R _I, R _II, R _III, R _WrBetween relation following (representing) with %:

If-definite 7.5＜R _Wr≤ 10.0,

Then it has following relationship:

13.0≤R _Ⅰ≤19.0;4.0≤R _Ⅱ≤11.0，

And work as R _I＜18.5,

R then _IAnd R _IIThe pass be: R _II≤ 0.73R _I-2.45

Perhaps R _I〉=18.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-2.00R _I+ 48.00

If-definite 5.0＜R _Wr≤ 7.5

Then it has following relationship:

12.25≤R _Ⅰ≤23.0;4.0≤R _Ⅱ≤19.5，

And work as R _I＜18.0,

R then _IAnd R _IIThe pass be: R _II≤ 1.65 R _I-10.24,

Perhaps R _I〉=18.0 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.40 R _I+ 44.70;

If-definite 2.5＜R _Wr≤ 5.0,

Then it has following relationship:

11.5≤R _Ⅰ≤27.5;4.0≤R _Ⅱ≤24.0，

And work as R _I＜19.5,

R then _IAnd R _IIThe pass be: R _II≤ 1.38 R _I-2.81

Perhaps R _I〉=19.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.56 R _I+ 54.47;

If-definite 0.0＜R _Wr≤ 2.5,

Then it has following relationship:

10.75≤R _Ⅰ≤32.0;4.0≤R _Ⅱ≤30.0，

R then _IAnd R _IIThe pass be: R _II≤ 2.07 R _I-5.80,

Perhaps R _I〉=20.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.30 R _I+ 56.74;

If-definite-2.5≤R _Wr≤ 0.0

Then it has following relationship:

10.0≤R _Ⅰ≤33.5;4.0≤R _Ⅱ≤35.0

And work as R _I≤ 15.0,

R then _IAnd R _IIThe pass be: R _II≤ 3.20 R _I-13.00

Perhaps R _I〉=20.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.85 R _I+ 72.85.

It is a kind of solution of cellulose derivative that contains cellulose formiate at least by the present composition of dissolution method gained of the present invention, and is a kind of anisotropic solution.Both of these case unexpectedly meets the utmost point limited range shown in the following note.

In the present composition, r _I, r _II, r _III, r _wWeight percent is defined as follows:

r _I: the per-cent of derivatived cellulose or all derivatives;

r _II: the per-cent of so-called " organic acid " phase, this comprise mutually might be present in organic acid, organic acid anhydride and organic acid carboxylic acid halides in the composition.

r _III: the per-cent of so-called " phosphoric acid " phase, this comprise mutually might be present in phosphoric acid and phosphoric anhydride in the composition.

r _w: the per-cent that may be present in the water in the composition.

r _I, r _II, r _III, r _wThese per-cents by following total weight it: derivatived cellulose or all derivatives be heavy+" organic acid " mutually heavy+" phosphoric acid " water of heavy+any existence is heavy mutually.

These per-cent r _I, r _II, r _III, r _wPer-cent for shown in the table that meets the present invention's test meets following condition:

r _I: at the per-cent shown in the derivatived cellulose row.

r _II: the per-cent shown in the organic acid row.

r _III: the per-cent shown in the mineral acid row.

r _w: the per-cent shown in the water row.

Per-cent r _I, r _II, r _III, r _wCan satisfy following relationship: r _I+ r _II+ r _III+ r _w=1.When composition is not moisture, r _wCertainly equal 0.In the composition of the present invention, r _IBe at least 10.2%.

Can utilize per-cent r _I, r _II, r _III, r _wDefine quaternary figure.

With r _wValue is divided into several at interval.Each every in, r _Wi≤ r _w＜r _Wj, and r _WiAnd r _WjBe fixed value.At each r _WiValue is promptly worked as r down _I+ r _II+ r _III=1-r _WiThe time, it is defined as the polygon that contains a plurality of summits (it can change in another interval at interval by one), and each summit is usually all with C _kIndicate (k is a parameter) and can pass through r _WiValue (is r at ternary diagram _WiThe ternary diagram on plane) the coordinate r in _{I k}, r _{II k}, r _{III k}Defined.Each is every r _Wi≤ r _w＜r _WjIn, with the coordinate r among the corresponding quaternary figure of the present composition _I, r _II, r _III, r _wEvery bit be projected to plane r _WiOn, and perpendicular to this plane (drop shadow spread is at all summit C _kIn the formed polygon, or on this polygonal limit).

These r _Wi≤ r _w＜r _WjInterval and these C _kThe formed all polygons in summit have following relationship, r _Wi, r _w, r _WjAnd summit C _kCoordinate values all represent with %:

-0.0≤r _w＜1.4 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝10.8，r _Ⅱ1＝0.4，r _Ⅲ1＝88.8）

C ₂（r _Ⅰ2＝36.1，r _Ⅱ2＝0.2，r _Ⅲ2＝60.9）

C ₃（r _Ⅰ3＝43.6，r _Ⅱ3＝9.8，r _Ⅲ3＝45.6）

C ₄（r _Ⅰ4＝19.0，r _Ⅱ4＝38.5，r _Ⅲ4＝42.5）

C ₅（r _Ⅰ5＝12.8，r _Ⅱ5＝40.3，r _Ⅲ5＝46.9）

-1.4≤r _w＜3.8 o'clock, this polygon was the septangle with following summit:

C ₁（r _Ⅰ1＝10.8，r _Ⅱ1＝0.5，r _Ⅲ1＝87.3）

C ₂（r _Ⅰ2＝38.9，r _Ⅱ2＝0.1，r _Ⅲ2＝59.6）

C ₃（r _Ⅰ3＝43.1，r _Ⅱ3＝1.4，r _Ⅲ3＝51.7）

C ₄（r _Ⅰ4＝43.6，r _Ⅱ4＝9.8，r _Ⅲ4＝45.2）

C ₅（r _Ⅰ5＝23.6，r _Ⅱ5＝33.3，r _Ⅲ5＝41.7）

C ₆（r _Ⅰ6＝15.2，r _Ⅱ6＝35.5，r _Ⅲ6＝47.9）

C ₇（r _Ⅰ7＝12.7，r _Ⅱ7＝28.6，r _Ⅲ7＝57.3）

-3.8≤r _w＜6.2 o'clock, this polygon was the septangle with following summit:

C ₁（r _Ⅰ1＝10.9，r _Ⅱ1＝0.5，r _Ⅲ1＝84.8）

C ₂（r _Ⅰ2＝37.9，r _Ⅱ2＝0.2，r _Ⅲ2＝58.1）

C ₃（r _Ⅰ3＝43.1，r _Ⅱ3＝1.4，r _Ⅲ3＝51.7）

C ₄（r _Ⅰ4＝43.0，r _Ⅱ4＝10.5，r _Ⅲ4＝57.3）

C ₅（r _Ⅰ5＝19.3，r _Ⅱ5＝30.9，r _Ⅲ5＝46.0）

C ₆（r _Ⅰ6＝17.4，r _Ⅱ6＝31.4，r _Ⅲ6＝47.4）

C ₇（r _Ⅰ7＝12.4，r _Ⅱ7＝14.2，r _Ⅲ7＝69.6）

-6.2≤r _w＜8.6 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝10.6，r _Ⅱ1＝1.1，r _Ⅲ1＝82.1）

C ₂（r _Ⅰ2＝38.1，r _Ⅱ2＝0.2，r _Ⅲ2＝55.5）

C ₃（r _Ⅰ3＝43.0，r _Ⅱ3＝1.5，r _Ⅲ3＝49.3）

C ₄（r _Ⅰ4＝22.7，r _Ⅱ4＝22.0，r _Ⅲ4＝49.0）

C ₅（r _Ⅰ5＝15.6，r _Ⅱ5＝23.5，r _Ⅲ5＝54.7）

C ₆（r _Ⅰ6＝11.7，r _Ⅱ6＝12.2，r _Ⅲ6＝69.9）

-8.6≤r _w＜11.0 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝10.5，r _Ⅱ1＝1.2，r _Ⅲ1＝79.7）

C ₂（r _Ⅰ2＝32.1，r _Ⅱ2＝0.2，r _Ⅲ2＝59.1）

C ₃（r _Ⅰ3＝32.8，r _Ⅱ3＝1.6，r _Ⅲ3＝57.0）

C ₄（r _Ⅰ4＝17.7，r _Ⅱ4＝19.4，r _Ⅲ4＝54.3）

C ₅（r _Ⅰ5＝14.2，r _Ⅱ5＝20.2，r _Ⅲ5＝57.0）

-11.0≤r _w＜13.4 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝10.4，r _Ⅱ1＝1.3，r _Ⅲ1＝77.3）

C ₂（r _Ⅰ2＝20.1，r _Ⅱ2＝1.0，r _Ⅲ2＝67.9）

C ₃（r _Ⅰ3＝21.5，r _Ⅱ3＝6.7，r _Ⅲ3＝60.8）

C ₄（r _Ⅰ4＝16.2，r _Ⅱ4＝14.1，r _Ⅲ4＝58.7）

C ₅（r _Ⅰ5＝10.9，r _Ⅱ5＝7.5，r _Ⅲ5＝70.6）

By example, ternary diagram shown in Figure 3 can be illustrated this fact.As follows for the material that this figure is used:

-derivatived cellulose: contain the mixed cellulose ester of formic acid ester group and acetate groups, the cellulosic degree of polymerization DP in this derivative is greater than 150, less than 1500.

-" organic acid " phase: formic acid, also may contain acetate.

-" phosphoric acid " phase: ortho-phosphoric acid.

Fig. 3 is equivalent to r _Wi=1.4%.Corresponding to this r _WiThe polygon of value is a sexangle, its summit C ₁, C ₂, C ₃, C ₄, C ₅And C ₆With aforementioned r _Wi=1.4% to define consistent also be that the coordinate on this summit is as follows:

C ₁（r _Ⅰ＝10.8%，r _Ⅱ＝0.5%，r _Ⅲ＝87.3%）

C ₂（r _Ⅰ＝38.9%，r _Ⅱ＝0.1%，r _Ⅲ＝59.6%）

C ₃（r _Ⅰ＝43.6%，r _Ⅱ＝9.8%，r _Ⅲ＝45.2%）

C ₄（r _Ⅰ＝23.6%，r _Ⅱ＝33.3%，r _Ⅲ＝41.7%）

This polygonal zone is less than the ternary figure of Fig. 3 trilateral representative.1.4%≤r _wIn＜3.8% interval, can provide the coordinate r of present composition quaternary figure _I, r _II, r _III, r _wEvery bit all be projected on Fig. 3 plane and perpendicular on this plane (in polygon, or in this polygon C ₁, C ₂, C ₃, C ₄, C ₅And C ₆The limit on).

By example, some F _1-6,2Be equivalent to the composition in the test 2 of example I-6.

Cellulosic degree of polymerization DP preferably is at least 200 and is at most 1200 in derivatived cellulose or all derivatives, and is spaced apart r _Wi≤ r _w＜r _WjAnd it is at interval relevant therewith and be positioned at plane r _WiThe summit C of ternary diagram _kFormed polygon has following relationship (r _Wi, r _wr _WjValue and C _kThe coordinate values on summit is represented with %).

-0.0≤r _w＜1.4 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.5，r _Ⅱ1＝1.9，r _Ⅲ1＝86.6）

C ₂（r _Ⅰ2＝35.5，r _Ⅱ2＝0.4，r _Ⅲ2＝64.1）

C ₃（r _Ⅰ3＝37.3，r _Ⅱ3＝4.7，r _Ⅲ3＝58.0）

C ₄（r _Ⅰ4＝24.9，r _Ⅱ4＝27.8，r _Ⅲ4＝47.3）

C ₅（r _Ⅰ5＝18.7，r _Ⅱ5＝28.9，r _Ⅲ5＝52.4）

C ₆（r _Ⅰ6＝12.5，r _Ⅱ6＝14.9，r _Ⅲ6＝72.6）

-1.4≤r _w＜3.8 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.0，r _Ⅱ1＝2.4，r _Ⅲ1＝85.2）

C ₂（r _Ⅰ2＝35.8，r _Ⅱ2＝0.3，r _Ⅲ2＝62.5）

C ₃（r _Ⅰ3＝37.8，r _Ⅱ3＝9.4，r _Ⅲ3＝51.4）

C ₄（r _Ⅰ4＝27.5，r _Ⅱ4＝27.6，r _Ⅲ4＝43.5）

C ₅（r _Ⅰ5＝18.3，r _Ⅱ5＝29.6，r _Ⅲ5＝50.7）

C ₆（r _Ⅰ6＝12.5，r _Ⅱ6＝14.8，r _Ⅲ6＝71.3）

-3.8≤r _w＜6.2 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.8，r _Ⅱ1＝2.4，r _Ⅲ1＝82.0）

C ₂（r _Ⅰ2＝34.0，r _Ⅱ2＝0.7，r _Ⅲ2＝61.5）

C ₃（r _Ⅰ3＝36.6，r _Ⅱ3＝7.4，r _Ⅲ3＝52.2）

C ₄（r _Ⅰ4＝23.9，r _Ⅱ4＝24.4，r _Ⅲ4＝47.9）

C ₅（r _Ⅰ5＝20.7，r _Ⅱ5＝24.8，r _Ⅲ5＝50.7）

C ₆（r _Ⅰ6＝13.2，r _Ⅱ6＝11.9，r _Ⅲ6＝71.1）

-6.2≤r _w＜8.6 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝13.1，r _Ⅱ1＝1.4，r _Ⅲ1＝79.3）

C ₂（r _Ⅰ2＝29.1，r _Ⅱ2＝1.4，r _Ⅲ2＝63.3）

C ₃（r _Ⅰ3＝31.1，r _Ⅱ3＝5.6，r _Ⅲ3＝57.1）

C ₄（r _Ⅰ4＝22.7，r _Ⅱ4＝18.7，r _Ⅲ4＝52.4）

C ₅（r _Ⅰ5＝13.3，r _Ⅱ5＝10.1，r _Ⅲ5＝70.4）

-8.6≤r _w＜11.0 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝12.9，r _Ⅱ1＝3.0，r _Ⅲ1＝75.6）

C ₂（r _Ⅰ2＝24.1，r _Ⅱ2＝2.2，r _Ⅲ2＝65.1）

C ₃（r _Ⅰ3＝24.8，r _Ⅱ3＝9.6，r _Ⅲ3＝57.0）

C ₄（r _Ⅰ4＝20.1，r _Ⅱ4＝16.0，r _Ⅲ4＝55.0）

C ₅（r _Ⅰ5＝13.6，r _Ⅱ5＝7.7，r _Ⅲ5＝70.1）

-11.0≤r _w＜13.4, this polygon is the pentagon with following summit:

C ₁（r _Ⅰ1＝13.6，r _Ⅱ1＝3.0，r _Ⅲ1＝72.4）

C ₂（r _Ⅰ2＝19.9，r _Ⅱ2＝2.5，r _Ⅲ2＝66.6）

C ₃（r _Ⅰ3＝21.0，r _Ⅱ3＝6.8，r _Ⅲ3＝61.2）

C ₄（r _Ⅰ4＝20.1，r _Ⅱ4＝8.3，r _Ⅲ4＝60.6）

C ₅（r _Ⅰ5＝14.1，r _Ⅱ5＝5.2，r _Ⅲ5＝69.7）

Cellulosic degree of polymerization DP preferably is at least 200 in derivatived cellulose or all derivatives, and is at most 1200, at r _Wi＜r _w≤ r _WjEach every in each r _WjValue is promptly worked as r _I+ r _II+ r _III=1-r _WjThe time, polygon is defined as containing a plurality of summits, and can change to another at interval by an interval, and each summit is usually all with C _qSign (q is a parameter) also can be by corresponding r _WjThe ternary diagram of value (is r _WjThe planar ternary diagram) the coordinate r in _{I q}, r _{II q}, r _{III q}Defined.

Each is every r _Wi＜r _w＜r _WjIn, the coordinate r among the quaternary figure relevant with the present composition _I, r _II, r _III, r _wIn every bit for being projected to plane r _WjGo up and perpendicular to this plane (drop shadow spread is in the formed polygon in all summits or on this polygonal limit).

These r _Wi＜r _w≤ r _WjThe interval and these are by summit C _qFormed polygon has following relationship (r _Wi, r _w, r _Wj, and vertex coordinate C _qAll represent with %):

-0.0＜r _w≤ 1.4 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.0，r _Ⅱ1＝2.4，r _Ⅲ1＝85.2）

C ₂（r _Ⅰ2＝35.8，r _Ⅱ2＝0.3，r _Ⅲ2＝62.5）

C ₃（r _Ⅰ3＝37.8，r _Ⅱ3＝9.4，r _Ⅲ3＝51.4）

C ₄（r _Ⅰ4＝27.5，r _Ⅱ4＝27.6，r _Ⅲ4＝43.5）

C ₅（r _Ⅰ5＝18.3，r _Ⅱ5＝29.6，r _Ⅲ5＝50.7）

C ₆（r _Ⅰ6＝12.5，r _Ⅱ6＝14.8，r _Ⅲ6＝71.3）

-1.4＜r _w≤ 3.8 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.8，r _Ⅱ1＝2.4，r _Ⅲ1＝82.0）

C ₂（r _Ⅰ2＝34.0，r _Ⅱ2＝0.7，r _Ⅲ2＝61.5）

C ₃（r _Ⅰ3＝36.6，r _Ⅱ3＝7.4，r _Ⅲ3＝52.2）

C ₄（r _Ⅰ4＝23.9，r _Ⅱ4＝24.4，r _Ⅲ4＝47.9）

C ₅（r _Ⅰ5＝20.7，r _Ⅱ5＝24.8，r _Ⅲ5＝50.7）

C ₆（r _Ⅰ6＝13.2，r _Ⅱ6＝11.9，r _Ⅲ6＝71.1）

-3.8＜r _w≤ 6.2 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝13.1，r _Ⅱ1＝1.4，r _Ⅲ1＝79.3）

C ₂（r _Ⅰ2＝29.1，r _Ⅱ2＝1.4，r _Ⅲ2＝63.3）

C ₃（r _Ⅰ3＝31.1，r _Ⅱ3＝5.6，r _Ⅲ3＝57.1）

C ₄（r _Ⅰ4＝22.7，r _Ⅱ4＝18.7，r _Ⅲ4＝52.4）

C ₅（r _Ⅰ5＝13.3，r _Ⅱ5＝10.1，r _Ⅲ5＝70.4）

-6.2＜r _w≤ 8.6 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝12.9，r _Ⅱ1＝3.0，r _Ⅲ1＝75.6）

C ₂（r _Ⅰ2＝24.1，r _Ⅱ2＝2.2，r _Ⅲ2＝65.1）

C ₃（r _Ⅰ3＝24.8，r _Ⅱ3＝9.6，r _Ⅲ3＝57.0）

C ₄（r _Ⅰ4＝20.1，r _Ⅱ4＝16.0，r _Ⅲ4＝55.0）

C ₅（r _Ⅰ5＝13.6，r _Ⅱ5＝7.7，r _Ⅲ5＝70.1）

-8.6＜r _w≤ 11.0 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝13.6，r _Ⅱ1＝3.0，r _Ⅲ1＝72.4）

C ₂（r _Ⅰ2＝19.9，r _Ⅱ2＝2.5，r _Ⅲ2＝66.6）

C ₃（r _Ⅰ3＝21.0，r _Ⅱ3＝6.8，r _Ⅲ3＝61.2）

C ₄（r _Ⅰ4＝20.1，r _Ⅱ4＝8.3，r _Ⅲ4＝60.6）

C ₅（r _Ⅰ5＝14.1，r _Ⅱ5＝5.2，r _Ⅲ5＝69.7）.

More than shown in quaternary figure all be equivalent to regular tetrahedron (not being shown among the figure) in the currently known methods in order to simplify.

The concentration of the present composition is usually greater than threshold concentration.For example, the curve of Fig. 4 for concerning between cellulose-derived substrate concentration and this soltion viscosity in the expression solution.Derivatived cellulose is a cellulose formiate, and its concentration (being c) in solution is represented with the weight percent of relative solution gross weight.Dynamic viscosity (η) is then shown with pascal-stopwatch.When the concentration of derivative less than threshold concentration C _cWhen (a-quadrant), then viscosity increases with concentration, and when derivatives concentration during greater than threshold concentration (B zone), then viscosity begins to reduce along with the increase of concentration, and this B zone is relevant with anisotropy, in this B zone, at C _mDuring concentration, it is minimum that viscosity reaches.

On this curve, reference point M is equivalent to the composition (table 4) in the test 7 of example I-1, and it is arranged in the B zone.

Method of the present invention can obtain a kind of only make the initial fiber element degrade a little and composition, for example, in previous examples, the relative deviation of DP (△ DP) is usually less than 20%.In solution of the present invention, preferably the formic acid ester group replaces degree DS and equals 5.0% at least in derivatived cellulose or all derivatives, and the replacement degree DS of other ester group is 0 or less than 15.0%.

II. the goods of derivatived cellulose

A. production unit and method

1. the preparation of spinning solution: this solution can any available proper method carry out thermostatic control and the mixing tank that allows in vacuum, to operate in make.If mixing tank can not obtain vacuum, then must follow and spinning solution is outgased by some proper method.

Desire to make the spinning solution of method of the present invention, then can use the following working method that exemplifies.The strap clamp cover reactor that available space is about 4 liters is at first put into this reactor with material (II) and material (III), stirs, then, do not open under the stirring state material (I) is added, reactor is vacuumized, vacuum tightness is about 5 to 10mbar(500 to 1000P _a).Stir then, begin esterification and solvency action this moment.During the stirring, mixture temperature preferably is maintained between 5 to 20 ℃.

Note that other method also can use, for example people can make a kind of pre-solution earlier with following process, are about to material (I) and impregnated in the material (II), cool off this mixture (optimum temps then;-15 to 0 ℃), add solid matter (III) again, then, mix the pre-solution that obtains solid form.In order to finish esterification and solvency action.Again with this pre-solution to stir between in 5 to 20 ℃ of aforementioned methods.

Also can use single screw rod or multiple screw extruder to prepare solution.Soon base substance is added in the forcing machine continuously, is better than most under the vacuum to be prepared.

2. solvent spinning is produced fiber

The 1st solution that saves described method gained directly in order to make fiber, be need not to carry out derivatived cellulose and extracts in advance.Employed spining technology is (dryjet-wet) technology of the what is called " air-gap method " (dry-jet wet-spinning) discussed of No. the 3414645th, United States Patent (USP).To directly add toothed gear pump from the solution in the dissolution reactor.Then this solution is extruded by the nozzle that orifice is arranged.Nozzle face flatly is positioned at precipitation bath liquid level top certain distance, (several millimeters to several centimetres).Before entering precipitation bath, earlier nozzle is dialed out in the gas cloud so that make the spinning molecular orientation make it that mechanical property is arranged before solidifying simultaneously.The fiber of derivatived cellulose forms in precipitation bath.Solidification liquid is essential in the bath can the precipitated cellulose material and solubilized is organic and the mineral acid material.The most handy acetone of solidification liquid is base substance, and the coagulation bath temperature scope is between 10 ℃ to-20 ℃.In the exit of precipitation bath, the spinning product of being made up of many monofilament is wound on the transmission mechanism.The spinning product is defined as spin-drawing factor (S.S.F.) at the ratio of the speed of the winding speed of transmission mechanism and spinning jet ejection.

It should be noted that the present invention is suitable for the non-condensable fluid (for example, nitrogen or other gas) outside the deacration used in so-called " air gap " technology.The present invention simultaneously also is suitable for other spining technology (for example wet spinning silk technology).

B. the mensuration of article characteristic

1. the mechanical property of spinning goods

So-called herein " spinning goods " are meant that buzzword " spun yam " (Spun Yarn) then only refers to by the monofilament aggregate of spinning jet with various spinning technique gained by prepared all the various goods of spin processes.

So-called herein " modulation " (Conditioning) is meant the July according to the standard DIN 53802-20/65(1979 of the Federal Republic of Germany) handle the spinning goods.

The fiber number of spun yam is the standard DIN of the Federal Republic of Germany 53830 mensuration (spun yam is given earlier through modulation) according to June nineteen sixty-five.Measure to use three samples, each sample to take by weighing at least to be equivalent to the long spun yam of 50m and heavily measure.

The fiber number of monofilament is to predict at the resonant frequency that bears under the specific tensile (under the 0.5CN/tex level) by the check single monofilament.Absolute error is less than 0.01.

The mechanical properties of spun yam is to use Zwick Gm bH ﹠amp; Co(the Federal Republic of Germany) 1435 type drawing machines of being made (being equivalent to the standard DIN of the Federal Republic of Germany 51220 in October, 1976 and the DIN 51221 in August, 1976) and record according to the federal standard DIN of the Germany 53834 described working method in January, 1979.Add 100 protectiveness sth. made by twisting for every meter of spun yam in order to measure people, stretch with the spun yam of initial length then above 400mm.All results all are as the criterion with the mean value of 10 measurements.

The mechanical property of monofilament is to use the Textechno(the Federal Republic of Germany of FAFEGRAPH-T type) drawing machine, and using the working method shown in June, 1976 the Federal Republic of Germany's standard DIN 53816 to record, its result is 10 mean values of measuring.

Intensity (T) and initial modulus (Mi) are represented with CN/tex.Elongation (Ar) under the fracture is represented with per-cent.Initial modulus (Mi) is defined as and just applies the slope that 0.5CN/tex gives the straight line portion of the pulling force/extension curve that produces behind the stress.

The mensuration of sound wave modulus.

The speed of sound transmission is used the PPM-5R type dynamic modulus survey meter of Univ Cambridge Tech of Morgan company manufacturing in the fiber " measure.

Measure sample is given synthetic spun yam earlier for process.This measures and is carrying out under the chopping phase envrionment conditions together therewith.On this about 2 meters long spun yam, apply the pre-load of 5CN/tex.Then two MORGAN-WTRT-5FB type transmitters are discharged on the spun yam that slight constant axial power is arranged.The resonant frequency of the piezoelectricity pottery of transmitter is 5KHz.L is the distance (representing with rice) between two sensors.The absolute error of measuring distance is less than 1 millimeter; " t " arrives the required travel-time (showing with stopwatch) of receiving sensor for making emission sensor emit pulse.

The relative error that travel-time " t " is measured is less than 3%.Sound wave modulus Ms is defined as with following formula: Ms=V ²* 10 ^-4CN/tex, V(meter per second) be the velocity of sound of the inverse of the measured straight-line regression slope of different L and " t " being obtained by N, N is at least 3.

2. the chemical property of spinning goods

The replacement degree (DS) and the polymerization degree (DP)

The spinning goods in room temperature (for example about 22 ℃) and relative humidity modulated, and are carried out the measurement of DS and DP with this understanding.The water-content of spinning goods is measured with thermo-gravimetric analysis.

The Mierocrystalline cellulose of derivatived cellulose replaces degree DS and polymerization degree DP mensuration is the same with the method for above-mentioned I.C section, but without acetone extract.

3. the physical properties of spinning goods

3.1 optical property

Use Olympus BH ₂The optical anisotropy of spinning goods is observed and measured to the type polarization microscope.Especially, double refraction is to use Bei Ruike (Berek) compensating prism method to predict.

3.2X-diffraction structure

A) laboratory apparatus and device

-instrument: mensuration is that the instrument with two kinds of patterns carries out.

-superpower producer (producer A).This is for being equipped with rotating anode Japan (Rigaku) RU-200 PL of science system, and operational condition is: 40kV, 200mA; Focus 0.5 * 10mm on the anode ²; The apparent focus 0.5 * 1mm of point ²; Differentiate the K β line radiation of eliminating copper with filtration of nickel sheet and energy.

The general producer of Siemens system (producer B, sealed tube) operational condition is: 40KV, 30mA; Fine rule focus 0.04 * 8mm ²; The K α of copper ₁Radiation can obtain through the CGR monochromator of arc xln (R=1400mm); Focusing distance D=510mm, the Compagnie Generale de Radiologie of CGR=France.

This two speciogenesis device has been used for four kinds of different devices.

-experimental installation

-device 1: the Rigaku SG-R wide-angle protractor (radius 250mm) that has an Euler (Euler) circle and a scintillometer; Sweep velocity in 2 θ: 2 °/minute; The speed of rotation of Euler (Euler) circle: under fixed 2 θ, be 2 °/minute.

The target plane of selected X-ray bundle.

Disperse: some point instrumentation diameter 1mm;

Analyze: be positioned at intersection seam 0.9 * 0.9mm apart from sample plane 110mm ²(0.5 ° * 0.5 ° in hole, angle).

-device 2:

(the Rigaku SG-9R protractor of speed of rotation a: 100rpm and a scintillometer, 2 θ are with 0.1 ° of increment step-by-step operation to be equipped with a Rotary Specimen Rack.

The target plane of-selected X-ray bundle: disperse 1/6 ° of seam; Diffusion seam: 1 °; Analyze seam 0.15mm(and be positioned at place) apart from sample 250mm.

-device 3:

-the Siemens wide-angle protractor of an Euler (Euler) circle and a scintillometer is housed, the sweep velocity of 2 θ is 0.1 °/minute.

-CGR monochromator, focal length 510mm.

-be 0.4mm apart from the analysis seam at sample 155mm place.

-device 4:

-have a Rigaku SASG central authorities scattering protractor of a Leti molded lines detector and an Ortec multiple-grooved analyzer.

The target plane of-selected X-ray bundle: first stitches 15 * 0.1mm ², second seam 15 * 0.05mm ²(under 250mm).

The distance of-sample and detector: 360mm.

The distance of-sample and second seam: 105mm.

Table 15 provides suitable device, angular range and used producer and the funtcional relationship between measured parameter.

Table 15

The producer that the device X-ray angle of diffraction that measuring parameter is suitable for is used

Crystalline orientation index (I-O) 1 extensive angle A

Crystallinity index (I.C.) 2 extensive angle A

Apparent crystallite size

-vertical (T ₁)

-horizontal (T _t) 3 extensive angle B

(L.P.) 4 Small angle A between long-term

Halfwidth degree (△ φ) 4 Small angle A

Integrated intensity (I.I.) 4 Small angle A

B) be used for the reflex action of angle diffraction measurement different structure parameter

The photo of the X-ray diffraction phenomena of fiber demonstrates on meridian, and there are some camber lines on the equator and these two outsides.The characteristic of these camber lines is relevant with the structure of matter.

The aperture angle that is positioned at the about 34.7 ° of meridian camber lines located of diffraction angle 2 θ is relevant with respect to the statistical orientation of fibre axis with crystallite.So the selected apparent vertical size that is used for measuring orientation index I-O and crystallite of the about 34.7 ° of this reflections located of 2 θ, T ₁

2 θ are positioned at the apparent widthwise size (T that 11 ° camber line is used for measuring crystallite on the equator _t).

Measure above-mentioned designated parameters and use specific reflection, but when measuring crystallinity index, need to consider whole diffractogram.

C) in order to measure the method for different parameters

All measurements are carried out with one or more fiber samples, and each fiber sample is formed by the monofilament of some be parallel to each other (promptly not reversing).

-crystalline orientation index (I-O)

Crystalline orientation can characterize with the angle of the normal of fibre axis and crystal face.

Measurement is positioned at the aperture angle that 2 θ are about 34.7 ° of meridian camber lines of locating can directly indicate the crystalline orientation degree relevant with fibre axis.

Orientation index can be defined by following formula:

I.O.＝ (180-α)/180 ×100

Wherein α is by half of angle sweep gained curve high total width; α represents with the number of degrees.

-crystallinity index (I-C)

The relative crystallinity index is to predict according to the method for Wei Kelin (Wakelin) (Jour nal of Applied Physics.Vol.30.No.11.Page 1654.November 1959).

With the X-ray diffractogram of any sample and two standard diffractograms (one be regarded as 100% amorphous, another is considered as 100% crystallization) relatively before, rough experimental value earlier will be through various parameters, count rate, the diffusion that X-ray beam stability, air cause, the correction of polarization and absorption effect.

Before with so-called " correlation method " research, earlier figure is given stdn.

Certainly, gained crystallinity index and selected amorphous standard substance and crystallization standard substance have substantial connection.This two standard substance is made by following method:

Crystallization standard substance: get (under 60 ℃, processing is 24 hours in the standard salt aqueous acid) through acid treatment with the fiber after the cellulose formiate regeneration that has had high-crystallinity very.

Amorphous standard substance: unbodied cellulose formiate.

The characteristic spectrum of this two standard substance is shown in Fig. 5.Among Fig. 5, corresponding to the spectrum S of crystallization standard substance ₁Represent with solid line, corresponding to the spectrum S of amorphous standard substance ₂Then be represented by dotted lines.In these spectrograms, axis of abscissas is that 2 θ angles are represented with the number of degrees), axis of ordinates is that corrected intensity 1(is with vps (C.P.S.) expression).

Spectrum be " rotary sample " from 2 θ=10 the transmission record ° to 2 θ=38 °.Because " rotary sample " can be regarded as a continuous parallel layer of fibers, be exposed to layer of fibers threaded shaft translocation and perpendicular under the situation of X-ray.

The apparent size of-crystallite

Can calculate the crystallite apparent size at reflection direction scanning back debye-Xie Er (Debye-Scherrer) equation of choosing.Then can obtain diffracted intensity and 2 θ angle function relation curves along being the about 34.7 ° meridian reflection scanning of being positioned at of funtcional relationship with 2 θ.Utilizing outside view halfwidth degree is β ₀(representing), can obtain vertical apparent size of crystallite by following equation with radian

${\mathrm{<figure-callout\; id="1"\; label="T"\; filenames="85108974\_DRIMG2.png,85108974\_DRIMG3.png"\; state="\{\{state\}\}">T</figure-callout>}}_1=\frac{\mathrm{<figure-callout\; id="2"\; label="\lambda \; \beta "\; filenames="85108974\_DRIMG2.png,85108974\_DRIMG4.png"\; state="\{\{state\}\}">\lambda </figure-callout>}}{\sqrt{{\beta }^{}}}$

β is equivalent to measured " the instrument width " of urotropin powdery diffractometry.

Angle θ is half of outside view maximum angular 2 θ.λ is the wavelength of used X-ray radioactive rays.

Same steps as (promptly carrying out equator scanning at the plane of reflection that is positioned at about 11 ° of 2 θ of equator) can obtain the horizontal apparent size (T of crystallite _t).The increase of crystallite apparent size must be regarded as the result that actual size increases and/or internal arrangement is improved.

-long period

The X-ray central authorities scattering experiment photo of organic fibre demonstrates, and it has around the scattering of incident ray (extending along the equator) and is positioned at (in central scattering both sides) two very low-angle scatter points on the meridian.This kind small-angle diffraction phenomenon is because due to the periodicity of the electron density in the material of studying.We can characterize this periodically with L.P.=λ/sin ε equation, and wherein λ is the X-ray radiation wavelength, and ε (along 2 θ angles of meridian) is equivalent to the maximum strength of this diffraction.

Note diffracted intensity under the meridian Small angle and the funtcional relationship of ε and can obtain a curve, the halfwidth degree △ φ representative of curve is periodic regular, the following area (integrated intensity) of curve is then represented the amplitude of periodic phenomena, and the possible long period phenomenon of this kind is with parameter L .P.

△ φ .I.I. characterizes.

3.3 morphology

The morphological properties of spinning goods is to predict with opticmicroscope and scanning electronic microscope.

C. example

The narration of following example by the front A.1 the described method of section make esterify cellobiose cellulose fiber (can with reference to above table 1 and 3).In all these examples, R _I, R _II, R _III, R _WrHave identical implication, and calculate with aforementioned same method.Spinning is also finished with above-mentioned A.2 phase method.

Example II .1

Mixture is formed by following base substance:

-material (I): contain 99.3(weight) cellulosic material % holocellulose (45.7 weight % alpha-celluloses and 53.6(weight) % hemicellulose).

-material (II): formic acid (table 3, product 22).

-material (III): ortho-phosphoric acid (table 3, product 23).

Preparation is during mixture, according to following ratio:

R _Ⅰ＝19.8%;R _Ⅱ＝18.1%;R _Ⅲ＝61.05%;

R _wr＝R _w＝1.05%。

After 20 minutes, can have the solution of following component:

Derivatived cellulose (cellulose formiate): 23.65(weight) %; Organic acid (formic acid): 11.8(weight) %; Mineral acid (ortho-phosphoric acid): 61.05(weight) %; Water: 3.5(weight) %.This solution is anisotropy.

Solution is directly inserted in the spinning pump by dissolution reactor.

Solution through pump is extruded by the nozzle with 100 orifices (diameter in every hole is 0.05cm).This nozzle is positioned at-17 ℃ precipitation bath (containing acetone) and goes up on the 2cm place transmission mechanism.This fiber has 90 meters/minute speed, and it is equivalent to 4.5 S.S.F.The yarn tube of gained is cleaned with water, then in air drying.Can contain the spun yam of 100 monofilament with this method, fiber then thus spun yam constitute.

Example II-2

Mixture is to be made by following base substance:

-material (I): contain 99.3(weight) % holocellulose (52.2(weight) % alpha-cellulose and 47.1(weight) the % hemicellulose) cellulosic material.

-material (II) and (III): identical with example II-1.

When preparing this mixture, according to following relationship:

R _Ⅰ＝19.8%;R _Ⅱ＝18.1%;R _Ⅲ＝61.05%;

R _wr＝R _w＝1.05%。

After 20 minutes, can have the anisotropic solution of following component: cellulose formiate 24.05(weight) %; Formic acid: 11.1(weight) %; Ortho-phosphoric acid: 61.05(weight) %; Water: 3.8(weight) %.

Use this solution to be spun into fiber by above example II-1 process.

Example II-3

Mixture is with 368.6g part exsiccant substance C ₁(table 1), 442.6g formic acid (table 3, product 22) and 1500g ortho-phosphoric acid (table 3, product 23) are inserted in the reactor and are made.

When preparing this mixture according to following relationship:

R _Ⅰ＝15.85%;R _Ⅱ＝19.0%;R _Ⅲ＝64.05%;

R _wr＝R _w＝1.1%。

After 20 minutes, can have the anisotropic solution of following component (weight %): cellulose formiate: 19.6%; Formic acid: 12.85%; Ortho-phosphoric acid: 64.05%; Water: 3.5%.

Use this solution and make fiber according to above-mentioned example II-1 process.

Example II-4

The method for making of this solution and example II-2 roughly the same but when making this mixture, have following relationship:

R _Ⅰ＝23.75%;R _Ⅱ＝17.2%;R _Ⅲ＝58.0%;

R _wr＝R _w＝1.05%。

After 20 minutes, promptly get anisotropic solution: cellulose formiate (28.5%) with following component (weight %); Formic acid: 9.4%; Ortho-phosphoric acid: 58.0%; Water: 4.1%.Use this solution and make fiber according to above example II-1 process.But following difference is arranged in the spinning process: the winding speed on transmission mechanism is 81 meters/minute; S.S.F=5.4.

Example II-5

Mixture is made by following base substance:

Material (I): contain 99.4(weight) % holocellulose (91.3(weight) % alpha-cellulose and 8.1(weight) the % hemicellulose) cellulosic material.

Material (II) and (III): identical with example II-1.

When preparing this mixture, following relationship is arranged:

R _Ⅰ＝15.85%;R _Ⅱ＝19.0%;R _Ⅲ＝64.05%;

R _wr＝R _w＝1.1%。

After 90 minutes, promptly get anisotropic solution: cellulose formiate 19.35% with following component (weight %); Formic acid: 13.25%; Ortho-phosphoric acid: 64.05%; Water: 3.35%.Use this solution and make fiber according to the method spinning process of above example II-1.But following difference is arranged: transmission mechanism speed: 90 meters/minute; S.S.F=3.6.

Example II-6

Mixture is made by following base substance:

Material (I): contain 99.1(weight) % holocellulose (89.4(weight) % alpha-cellulose and 9.7(weight) the % hemicellulose) cellulosic material.

Material (II) and (III): identical with example II-1.

When preparing this mixture, following relationship is arranged:

R _Ⅰ＝19.75%;R _Ⅱ＝18.1%;R _Ⅲ＝61.05%;

R _wr＝R _w＝1.1%。

After 90 minutes, promptly get anisotropic solution: cellulose formiate 24.95% with following component (weight %); Formic acid: 9.6%; Ortho-phosphoric acid: 61.05%; Water: 4.4%.Fiber then uses this solution and makes according to the method for example II-1.

Example II-7

Solution use with example II-2 the same terms under make, but employed material (II) is the mixture of formic acid and acetate (table 3, product 22 and 3), formic acid heavy with the heavy ratio of acetate be 9, ratio R _IIIdentical with test II-2 value.Promptly get anisotropic solution after 30 minutes: acetate cellulose formiate: 23.45% with following component (weight %); The mixture of formic acid and acetate: 12.1%; Ortho-phosphoric acid: 61.05%; Water: 3.4%." acetate cellulose formiate " comprises the mixed cellulose ester with formic acid ester group and acetate groups.Use this solution and get fiber according to the legal system of example II-1.

Example II-8

Mixture is formed by following base substance:

Material (I): contain 97.4(weight) % holocellulose (95.1(weight) % alpha-cellulose and 2.3(weight) the % hemicellulose) cellulosic material.

Material (II) and (III): identical with example II-1.

When preparing this mixture, following relation is arranged:

R _Ⅰ＝15.55%;R _Ⅱ＝19.0%;R _Ⅲ＝64.05%;R _wr＝R _w＝1.4%。

By behind the twin-spiral mixer 30 minutes, promptly get the anisotropic solution of (weight %) with following composition: cellulose formiate: 18.85%; Formic acid: 13.6%; Ortho-phosphoric acid: 64.05%; Water: 3.5%.Fiber then uses this solution and makes according to the method for example II-1, and solution is in advance prior to the degassing under the vacuum 30 minutes.

Example II-9

Mixture is made by following base substance:

Material (I): contain 98.7(weight) % holocellulose (89(weight) % alpha-cellulose and 9.7(weight) the % hemicellulose) cellulosic material.

Material (II) and (III): identical with example II-1.

When preparing this mixture, following relation is arranged:

R _Ⅰ＝19.7%;R _Ⅱ＝18.1%;R _Ⅲ＝61.05%;R _wr＝R _w＝1.15%。

After 90 minutes, promptly get the anisotropic solution of (weight %) with following composition: cellulose formiate: 23.75%; Formic acid: 11.4%; Ortho-phosphoric acid: 61.05%; Water: 3.8%.Fiber then is a solution and make according to the method for example II-1 thus.

Above example II-1 is to II-9, and the cellulosic polymerization degree DP of material (I) is all greater than 150, and less than 1500, and the DP deviation is always less than 20% during the preparation composition.

The mechanical properties of spinning goods and chemical property are listed in the following table 16.All carry out T in all tests, Ar, Mi, DP and DS performance measurement, and in the great majority test, measure Ms.

Used abbreviation is as follows in the table: the F=spun yam; The Ft=monofilament; The Ti=fiber number; T=intensity; Elongation during the Ar=fracture; The Mi=initial modulus; Ms=sound wave modulus; The cellulosic total replacement degree of Ds=; The cellulosic polymerization degree in the Dp=derivatived cellulose.

Test the note of II-1 to II-9:

All tests are all consistent with the present invention.The monofilament that constitutes spun yam by gained in these examples shows that via the polarized light microscope observing result each monofilament all has complicated form (being changed to central authorities by the edge).Wherein monofilament 1 is illustrated in Fig. 6 and 7.

Fig. 6 is for also passing through the sectional view of this fiber 1 along containing certain plane of this kind monofilament axle XX ' (being assumed to linear pattern).Fig. 7 is along the cross-sectional view that also passes through this fiber 1 in Fig. 7 perpendicular to above-mentioned axle certain plane of XX ' (representing with alphabetical O).This monofilament has external region 2 that is called " cortex " and the interior region 3 that is called " heart ".Under polarizing microscope, cortex 2 shows the uniform texture form similar to artificial silk.The heart 3 of the similar centre of the palm in aspect is made up of series of layers 4 in addition.These layers be actually with perpendicular to the plane of axle XX ' concentric (as shown in Figure 7).Therefore, monofilament 1 has at least a part to be formed by mutual embedding between layer and the layer.These layers are around the axle of monofilament.Thickness less than one micron the layer 4 in being parallel to Fig. 6 plane of XX ' direction undulate.Optic axis in each layer (optical direction) and crystallization direction are the variation of pseudoperiodicity ground in the direction of axle XX '.For simplicity, these directions are not shown among the figure.

The T of gained fiber and Mi value can satisfy the equation of being given by in the derivatived cellulose definition of the present invention.

Its relation is as follows: DS 〉=2%; 150＜DP＜1500; T＞20; M _i＞1000, T and M _iRepresent with CN/tex.

Therefore, these fibers have high-mechanical property, and this performance is arranged after the typing immediately, need not drawing-off separately after the spinning.

To be at least this DS value of 2%(be to be given partial regeneration and got by Mierocrystalline cellulose in the derivatived cellulose as long as the formic acid ester group in the Mierocrystalline cellulose replaces degree DS), then these conclusions exist.

The following fact finds expression in example II-1 to II-9:

-double refraction △ n is greater than 0.03, so be high.

-after the X-ray fiber analysis, show to there is no the long period phenomenon.

In-the fiber of the present invention, cellulosic formic acid ester group replaces degree DS and is at least 30.0% better, at most only equals 70.0%, and it then is 0 or less than 10.0% that cellulosic other ester group replaces degree.

In the Mierocrystalline cellulose of the present invention, the cellulosic degree of polymerization DP in derivatived cellulose or all derivatives is at least 200, and at most only 1200.

Can make cellulose derivative film with currently known methods (for example spin processes of gap nozzle or teeming practice) with composition of the present invention.

When the replacement degree DS of cellulose formate base less than 2% the time, then these fibers being called " reproducibility cellulosic fibre " back big topic of III provides these reproducibilities cellulosic example.

III. the reproducibility fibre product

A. preparation facilities and method

The preparation of solution and the spinning of these solution are undertaken by above-mentioned second largest topic, but when expectation makes film, then use the nozzle that a slit is arranged.Make by spinning goods partly-hydrolysed cellulose regeneratedly can be intermittently fiber tube or manthanoate cellulosefilm to be impregnated in regeneration and carry out in bathing, also serially these fibers or film are led to regeneration bathe in and finish.This bathes the most handy sodium hydroxide (NaOH) aqueous solution, and the hydroxide concentration in this solution is a 4-5%(weight).In the periodical operation, the recovery time is the function of barrel thickness, can be a few hours to a couple of days.In the operate continuously, the recovery time is quite short, is one minute or below one minute.The regeneration soln temperature is room temperature under two kinds of situations.

B. the mensuration of product properties

Method therefor is identical with aforementioned II-B section, and following difference is only arranged:

The horizontal apparent size T of-crystallite _tMensuration to be to use 2 θ be that 12.3 ° of camber lines of locating carry out.

The mechanical property of-film is to use the used identical strength test machine of staple fibre of measuring (according to the Federal Republic of Germany's standard DIN 53455 in April nineteen sixty-eight) to record.

The replacement degree DS of-spinning goods is recorded by following method: as II-described room temperature of B section and envrionment temperature modulated spinning goods, and finish DS with this understanding and measure.The water yield of spinning goods records with CALVER petty official (Karl Fisher) technology.Then, weigh up 2g spinning goods, clean it with 50ml distilled water, this spinning goods material is continuous wash 15 minutes under agitation.Take out this material, use again the rinsing of 10ml distilled water and centrifugal it.Then 10ml distilled water and 10ml aqueous sodium hydroxide solution (0.1N NaOH) and 10ml water are added in this spinning goods material.This material stirred 15 minutes under nitrogen gas stream and room temperature under this medium.Take out this thing then, centrifugal, clean again with the 160ml alcohol flushing with 20ml water, obtain about 80: 20 ethanol/water solution, thereby this solution no longer contains spinning goods material.Then with ten/monovalent hydrochloric acid (0.1N HCl) ethanol liquid this solution is carried out potential measurement by means of the electrode that is suitable in the ethanol/water medium.Peculiar increase by the sodium formiate electromotive force can record formed manthanoate amount, thereby obtains according to I and the defined DS value of the big topic of II.

C. example

Example III-1

The cellulosic fiber of manthanoate forms identical with example II-1.The gained fiber is wound on the porous yarn tube, again with them in containing 4%(weight) dipping saponification and the cellulosic regeneration to finish manthanoate in 24 hours in the aqueous solution of sodium hydroxide, then this yarn tube is cleaned in water, and on tube with fiber drying.

Example III-2

The manthanoate cellulosic fibre is to make by example II-2, and the Mierocrystalline cellulose of this fiber is then regenerated with the described method of example III-1, but this fiber is from the yarn tube it to be untied, and allows its circulation constantly in the warm air air channel make it exsiccant.After the modulation, the water yield in the fiber is 10.3%, and this water yield is according to ASTM standard D 2654-76(1976) record.

Example III-3

The manthanoate cellulosic fibre is to make by example II-3, and the Mierocrystalline cellulose of this fiber is regenerated with the method for example III-2.

Example III-4

The manthanoate cellulosic fibre is to make by example II-4, and the Mierocrystalline cellulose of this fiber is with the described method regeneration of example III-2.

Example III-5

The manthanoate cellulosic fibre is to make by example II-5, but the speed of its transmission mechanism is 90 meters of per minutes, and S.S.F is equivalent to 4.5.The Mierocrystalline cellulose of this fiber is with the described method regeneration of example III-2.

Example III-6

The manthanoate cellulosic fibre is to make by example II-6, and the Mierocrystalline cellulose of this fiber is with the described method regeneration of example III-2.

Example III-7

Follow the step of example III-6, but the speed of transmission mechanism is 80 meters of per minutes, S.S.F is equivalent to 8.

Example III-8

Mixture forms with example II-1 same procedure, but its material (I) is for containing 97.5(weight) % holocellulose (95.2(weight) % alpha-cellulose and 2.3(weight) the % hemicellulose) and cellulosic material; Material (II) is then identical with example II-1 with material (III).

When preparing this material, following relationship is arranged:

R _Ⅰ＝15.5%;R _Ⅱ＝19%;R _Ⅲ＝64.05%;R _wr＝R _w＝1.4%。

After 30 minutes, promptly get anisotropic solution: manthanoate Mierocrystalline cellulose: 18.95% with following composition (weight) %; Formic acid: 13.4%; Ortho-phosphoric acid: 64.05%; Water: 3.6%.

Fiber makes by example II-1, but the speed of its transmission mechanism is 90 meters of per minutes, and S.S.F is 6.6.

The Mierocrystalline cellulose of this fiber then gives regeneration according to the described method of example III-2.

Example III-9

The manthanoate cellulosic fibre is by making according to example II-9, but the speed of its transmission mechanism is 90 meters of per minutes, and S.S.F is 9.The Mierocrystalline cellulose of this fiber is then with the described method regeneration of example III-2.

Example III-10

Mixture makes with the method that is analogous to example II-1, but its material (I) is for containing 97.4(weight) % holocellulose (95.1(weight) % alpha-cellulose and 2.3(weight) the % hemicellulose) and cellulosic material.Material (II) and (III) are then identical with example II-1.When preparing this mixture, it should have following relationship:

R _Ⅰ＝6.2%;r _Ⅱ＝21.2%;R _Ⅲ＝71.35%;R _wr＝R _w＝1.25%

Therefore this example is not consistent with the present invention.After 90 minutes, promptly get isotropic aqueous solution: manthanoate Mierocrystalline cellulose: 7.45% with following composition (weight %); Formic acid: 19.15%; Ortho-phosphoric acid: 71.35%; Water: 2.05%, fiber makes by example II-1, but the speed of its transmission mechanism is 93 meters of per minutes, and S.S.F is 1.5, and the Mierocrystalline cellulose of this fiber is regenerated with the method for example III-2.

Example III-11

The possibility of film is made in this example explanation by the present invention.Solution makes by example II-4.Use is equipped with the rectangle slit, and (nozzle of 10mm * 0.15mm) makes this solvent spinning.Transmission mechanism is 20 meters of per minutes, and S.S.F is 8.This film-based fibre element is with the described method regeneration of example III-1.

Example III-12

Acetate cellulose formiate fiber is to make by example II-7.With this fiber in 5(weight) in the % sodium hydroxide solution cyclic regeneration 20 seconds to finish manthanoate but not the saponification of acetic ester according to example III-2 the yarn tube of gained is cleaned again and is dry.

Example III-13

Mixture makes with the method that is similar to example II-1, but material (I) is for containing 97.3(weight) % holocellulose (95.0(weight) % alpha-cellulose and 2.3(weight) the % hemicellulose) and cellulosic material.Material (II) and (III) are then identical with example II-1.When preparing this mixture, should have following relationship: R _I=17.85%; R _II=18.5%; R _III=62.2%; R _Wr=R _w=1.45%.

After 30 minutes, obtain having the anisotropic solution of following composition (weight %): manthanoate Mierocrystalline cellulose: 21.4%; Formic acid 12.7%; Ortho-phosphoric acid: 62.2%; Water: 37.0%.Fiber makes by example II-1, but the speed of its transmission mechanism is 80 meters of per minutes, and S.S.F is 14, and the Mierocrystalline cellulose of this fiber is then regenerated with the method for example III-2.

Example III-14

Mixture makes with the method that is similar to example II-1, but its material (I) is for containing 99.0(weight) % holocellulose (97.5(weight) % alpha-cellulose and 1.5(weight) the % hemicellulose) and cellulosic material.Material (II) and (III) are then identical with example II-1.When preparing this material, should have following relationship:

R _Ⅰ＝19.8%;R _Ⅱ＝17.8%;R _Ⅲ＝61.4%;R _wr＝R _w＝1.0%。

After 30 minutes, obtain having the anisotropic solution of following composition (weight %): manthanoate Mierocrystalline cellulose: 23.7%; Formic acid: 11.4%; Ortho-phosphoric acid: 61.4%; Water: 3.5%.

Fiber makes by example II-1, but the speed of its transmission mechanism is 45 meters of per minutes, and S.S.F is 5.6.The Mierocrystalline cellulose of this fiber is then regenerated with the described method of example III-2.

Except that test III-10, all tests are all consistent with the present invention.List in the following table 18 to the fiber of III-14 gained and the mechanical property and the chemical property of film by example III-1, the abbreviation of this table with on show that table 16 is identical, Fm represents film in addition.In the table 18, characteristic T, Ar, Mi, DP, DS all measures characteristic M in all tests _SThen in the great majority test, measure.

Table 18

Character

Instance number ink recorder tool chemistry

^*Ac=is relevant with the DS of acetate groups;

F=is relevant with the DS of formic acid ester group.

Example III-1 is consistent with the present invention to the reproducibility cellulosic fibre of III-14 gained to III-9 and III-12, and the reproducibility cellulosic fibre of example III-10 gained is then inconsistent with the present invention.The formic acid ester group of all these fibers replaces degree less than 2%.

Example III-1 of the present invention to III-9 and III-12 to III-14, the cellulosic degree of polymerization DP of all substances (I) and fiber is all greater than 150 less than 1500, and in all scenario DP deviation during the preparation composition less than 20%.

Fig. 8 represents the funtcional relationship between the cellulosic degree of polymerization DP of fibre strength T and these fibers.Fig. 9 represents the funtcional relationship between the cellulosic degree of polymerization DP of fiber initial modulus Mi and these fibers.Fig. 8, in 9, axis of abscissas is to being equivalent to DPs, axis of ordinates is equivalent to T(Fig. 8 of representing with CN/tex), or be equivalent to Mi(Fig. 9 of representing with CN/tex), DP, T and Mi value are listed in the above table 18.At Fig. 8, in 9, the fiber of gained is expressed as simplification with cross according to the present invention, does not mark each fiber numbering on the figure.Then represent with the inconsistent fiber of the present invention (example III-10) with the black triangle that indicates III-10.Among Fig. 8, also express two kinds of known regenerated fibers with point, these two kinds of known fiber are with F on figure ₁And F ₂Indicate.The character of these known fiber is listed in the following table 20.

Table 20

Character F ₁Fiber F ₂Fiber

DP 560 630

T 42 48

Mi 800 1000

Measure T and Mi character (representing) for these known fiber by staple with CN/tex.

Fig. 8,9 show that the reproducibility cellulosic fibre consistent with the present invention has following relation: if DP＜200, then T＞20 and Mi＞1800;

If 200≤DP＜300, then T＞30 and Mi＞2000;

If 300≤DP＜400, then T＞40 and Mi＞2400;

If 400≤DP＜1500, then T＞60 and Mi＞2600.

T and Mi represent with CN/tex.

By Fig. 8 and 9 further as can be known, all have following relationship by reproducibility cellulosic fibre of the present invention (except the example III-12):

If 150＜DP＜250, then T 〉=1/3DP-26 and Mi 〉=2300;

If 250≤DP＜1500, then T 〉=-18675/DP+132 and Mi 〉=-502250/DP+4309;

T and Mi represent with CN/tex.

Fig. 8 represents to have the linear portions D of equation T=1/3DP-26 ₈, and have the hyperbolic line section H of equation T=-18675/DP+132 ₈, be 250 by the DP value of these part gained.

Fig. 9 represents to have the straight line portion D of equation Mi=2300 ₉, and have the hyperbolic line section H of equation Mi=-502250/DP+4309 ₉, be 250 by the DP value of these part gained.

At Fig. 8, in 9, then do not have above-mentioned all relations with the inconsistent fiber of the present invention.

As follows according to reproducibility cellulosic fibre of the present invention and the interfibrous essence difference of the inconsistent example III-10 of the present invention gained:

-obtaining by anisotropic solution by fiber of the present invention, the concentration of its derivatived cellulose is greater than threshold concentration;

The fiber of-example III-10 is by the isotropic aqueous solution gained, the concentration subcritical concentration of its derivatived cellulose.

So-called " threshold concentration " is in preceding addressing.

On the other hand, research table 18 shows that reproducibility cellulosic fibre according to the present invention has the high pitch mode amount greater than 3000CN/tex.Must note after setting, reaching immediately, need not in addition through drawing-off by the high degree of mechanical character of reproducibility cellulosics of the present invention.

Show also behind the research table 19 that reproducibility cellulosic fibre of the present invention has following characteristic:

-orientation index I.O. is greater than 95.5%, and is very high.

-it has the unexpected T of relation ₁The long period phenomenon of 〉=L.P. exists.

Do not have these characteristics with the inconsistent fiber of the present invention.

Showing behind opticmicroscope or the scanning electron microscopy study reproducibility cellulosic fibre of the present invention, in these fiber form and the big topic of aforementioned II, the replacement degree DS of formic acid ester group is more than or equal to 2% cellulose derivative fibres homomorphosis.

The present invention of the manufacturing reproducibility cellulosic fibre that the front has been discussed has following overall merit:

-need not to begin by derivatived cellulose, but but directly not only fast but also at an easy rate cellulose dissolution is made the solution of spinning;

-use cheapness and avirulent product are as the reagent of cellulose dissolution.

The rare Degradation of Mierocrystalline cellulose between-breaking-in period;

-spinning goods are regenerated easily;

The reproducibility cellulosic fibre of-gained has high strength and two kinds of overall characteristics of high-modulus.

In the reproducibility cellulosic fibre of the present invention, preferably in the Mierocrystalline cellulose ester group of non-manthanoate to replace degree DS be 0 or less than 1.5%.

In the reproducibility cellulosic fibre of the present invention, best, cellulosic DP is at least 200, and is at most 1200.

Certainly, the present invention is not limited to above-described all examples.Especially composition of the present invention also can comprise the material that some had not been addressed, pigment for example, filler and can esterified non-cellulosic polymer during the manufacturing of composition etc.In this case, preferably can make mixture, have aforementioned component basically by composition of the present invention by aforesaid base substance with dissolution method of the present invention.The present invention also comprises composition and the goods of being made up of the derivatived cellulose mixture.

Claims (27)

1, be the composition that main body is made with the derivatived cellulose of a kind of cellulose ester group (having a part in these ester groups at least is the formic acid ester group) at least, it is characterized in that this composition is a kind of for supplying to make the anisotropic solution of fiber and film, it contains:

A) derivatived cellulose or all derivatives, the concentration of the plain derivative of derivatived cellulose or all fibres in solution is at least 10.2% (weight), and the cellulosic degree of polymerization DP in derivatived cellulose or all derivatives is greater than 150 less than 1500,

B) formic acid or at least two kinds of compounds that are selected from unary organic carboxylic acid and these sour acid anhydrides and carboxylic acid halides have a kind of formic acid that is in these compounds,

C) has a kind of phosphoric acid at least.

2, according to the composition of claim 1 regulation, characterize with following properties:

-determine r with following relationship _I, r _II, r _III, r _wWeight percent:

r _I: the per-cent of derivatived cellulose or all derivatives;

r _II: the per-cent of so-called " organic acid " phase, this comprise mutually might be present in organic acid in the composition, organic acid anhydride and organic acid carboxylic acid halides,

r _III: the per-cent of so-called " phosphoric acid " phase, this comprise mutually might be present in phosphoric acid and phosphoric anhydride in the composition,

r _w: may be present in the moisture content per-cent in the composition,

These r _I, r _II, r _III, r _wPer-cent be according to total amount=derivatived cellulose or all derivatives heavy+" organic acid " mutually heavy+" phosphoric acid " water of heavy+any existence is heavy mutually, the per-cent r of calculating _I, r _II, r _III, r _wThese per-cents can determine to have r _I+ r _II+ r _III+ r _wThe quaternary figure of=1 relation,

-with r _wValue is divided into several at interval, each every in, r _Wi≤ r _w＜r _Wj, r wherein _WiAnd r _WjBe fixed value, just say each r _WiWorthwhile r _I+ r _II+ r _III=l-r _WiThe time, the polygon that contains a plurality of summits (can by changing at interval another at interval) can determine that each summit is all with C _kIndicate (k is a parameter) and can be by corresponding r _WiThe ternary diagram of value (is r _WiThe planar ternary diagram) determines the coordinate V on each summit in _{I K}, V _{II K}, V _{III K},

-each is every r _Wi≤ r _m＜r _WjIn, coordinate is r among the corresponding quaternary figure of composition of claim 1 regulation _I, r _II, r _III, r _wEvery bit be projected to plane r _WiOn, and perpendicular to this plane (its scope is at all summit C _kIn the formed polygon, or on this polygonal limit),

-these intervals r _Wi≤ r _w＜r _WjAnd these C _kThe formed all polygons in summit have following relationship, (r _Wi, r _w, r _WjValue and summit C _kCoordinate values all represent with %):

-0.0≤r _w＜1.4 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝10.8，r _Ⅱ1＝0.4，r _Ⅲ1＝88.8）

C ₂（r _Ⅰ2＝36.1，r _Ⅱ2＝0.2，r _Ⅲ2＝60.9）

C ₃（r _Ⅰ3＝43.6，r _Ⅱ3＝9.8，r _Ⅲ3＝45.6）

C ₄（r _Ⅰ4＝19.0，r _Ⅱ4＝38.5，r _Ⅲ4＝42.5）

C ₅（r _Ⅰ5＝12.8，r _Ⅱ5＝40.3，r _Ⅲ5＝46.9）

-1.4≤r _w＜3.8 o'clock, this polygon was the septangle with following summit:

C ₁（r _Ⅰ1＝10.8，r _Ⅱ1＝0.5，r _Ⅲ1＝87.3）

C ₂（r _Ⅰ2＝38.9，r _Ⅱ2＝0.1，r _Ⅲ2＝59.6）

C ₃（r _Ⅰ3＝43.1，r _Ⅱ3＝1.4，r _Ⅲ3＝51.7）

C ₄（r _Ⅰ4＝43.6，r _Ⅱ4＝9.8，r _Ⅲ4＝45.2）

C ₅（r _Ⅰ5＝23.6，r _Ⅱ5＝33.3，r _Ⅲ5＝41.7）

C ₆（r _Ⅰ6＝15.2，r _Ⅱ6＝35.5，r _Ⅲ6＝47.9）

C ₇（r _Ⅰ7＝12.7，r _Ⅱ7＝28.6，r _Ⅲ7＝57.3）

-3.8≤r _w＜6.2 o'clock, this polygon was the septangle with following summit:

C ₁（r _Ⅰ1＝10.9，r _Ⅱ1＝0.5，r _Ⅲ1＝84.8）

C ₂（r _Ⅰ2＝37.9，r _Ⅱ2＝0.2，r _Ⅲ2＝58.1）

C ₃（r _Ⅰ3＝43.1，r _Ⅱ3＝1.4，r _Ⅲ3＝51.7）

C ₄（r _Ⅰ4＝43.0，r _Ⅱ4＝10.5，r _Ⅲ4＝57.3）

C ₅（r _Ⅰ5＝19.3，r _Ⅱ5＝30.9，r _Ⅲ5＝46.0）

C ₆（r _Ⅰ6＝17.4，r _Ⅱ6＝31.4，r _Ⅲ6＝47.4）

C ₇（r _Ⅰ7＝12.4，r _Ⅱ7＝14.2，r _Ⅲ7＝69.6）

-6.2≤r _w＜8.6 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝10.6，r _Ⅱ1＝1.1，r _Ⅲ1＝82.1）

C ₂（r _Ⅰ2＝38.1，r _Ⅱ2＝0.2，r _Ⅲ2＝55.5）

C ₃（r _Ⅰ3＝43.0，r _Ⅱ3＝1.5，r _Ⅲ3＝49.3）

C ₄（r _Ⅰ4＝22.7，r _Ⅱ4＝22.0，r _Ⅲ4＝49.0）

C ₅（r _Ⅰ5＝15.6，r _Ⅱ5＝23.5，r _Ⅲ5＝54.7）

C ₆（r _Ⅰ6＝11.7，r _Ⅱ6＝12.2，r _Ⅲ6＝69.9）

-8.6≤r _w＜11.0 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝10.5，r _Ⅱ1＝1.2，r _Ⅲ1＝79.7）

C ₂（r _Ⅰ2＝32.1，r _Ⅱ2＝0.2，r _Ⅲ2＝59.1）

C ₃（r _Ⅰ3＝32.8，r _Ⅱ3＝1.6，r _Ⅲ3＝57.0）

C ₄（r _Ⅰ4＝17.7，r _Ⅱ4＝19.4，r _Ⅲ4＝54.3）

C ₅（r _Ⅰ5＝14.2，r _Ⅱ5＝20.2，r _Ⅲ5＝57.0）

-11.0≤r _w＜13.4 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝10.4，r _Ⅱ1＝1.3，r _Ⅲ1＝77.3）

C ₂（r _Ⅰ2＝20.1，r _Ⅱ2＝1.0，r _Ⅲ2＝67.9）

C ₃（r _Ⅰ3＝21.5，r _Ⅱ3＝6.7，r _Ⅲ3＝60.8）

C ₄（r _Ⅰ4＝16.2，r _Ⅱ4＝14.1，r _Ⅲ4＝58.7）

C ₅（r _Ⅰ5＝10.9，r _Ⅱ5＝7.5，r _Ⅲ5＝70.6）

3, according to the composition of claim 2 regulation, it is characterized in that cellulosic polymerization degree DP is at least 200 in derivatived cellulose or all derivatives, be at most 1200, r _Wi≤ r _w＜r _WjInterval and corresponding these intervals also are positioned at r _WiSummit C in the planar ternary diagram _kFormed polygon has following relation (r wherein _Wi, r _w, r _WjValue and summit C _kCoordinate values is represented with %):

-0.0≤r _w＜1.4 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.5，r _Ⅱ1＝1.9，r _Ⅲ1＝86.6）

C ₂（r _Ⅰ2＝35.5，r _Ⅱ2＝0.4，r _Ⅲ2＝64.1）

C ₃（r _Ⅰ3＝37.3，r _Ⅱ3＝4.7，r _Ⅲ3＝58.0）

C ₄（r _Ⅰ4＝24.9，r _Ⅱ4＝27.8，r _Ⅲ4＝47.3）

C ₅（r _Ⅰ5＝18.7，r _Ⅱ5＝28.9，r _Ⅲ5＝52.4）

C ₆（r _Ⅰ6＝12.5，r _Ⅱ6＝14.9，r _Ⅲ6＝72.6）

-1.4≤r _w＜3.8 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.0，r _Ⅱ1＝2.4，r _Ⅲ1＝85.2）

C ₂（r _Ⅰ2＝35.8，r _Ⅱ2＝0.3，r _Ⅲ2＝62.5）

C ₃（r _Ⅰ3＝37.8，r _Ⅱ3＝9.4，r _Ⅲ3＝51.4）

C ₄（r _Ⅰ4＝27.5，r _Ⅱ4＝27.6，r _Ⅲ4＝43.5）

C ₅（r _Ⅰ5＝18.3，r _Ⅱ5＝29.6，r _Ⅲ5＝50.7）

C ₆（r _Ⅰ6＝12.5，r _Ⅱ6＝14.8，r _Ⅲ6＝71.3）

-3.8≤r _w＜6.2 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.8，r _Ⅱ1＝2.4，r _Ⅲ1＝82.0）

C ₂（r _Ⅰ2＝34.0，r _Ⅱ2＝0.7，r _Ⅲ2＝61.5）

C ₃（r _Ⅰ3＝36.6，r _Ⅱ3＝7.4，r _Ⅲ3＝52.2）

C ₄（r _Ⅰ4＝23.9，r _Ⅱ4＝24.4，r _Ⅲ4＝47.9）

C ₅（r _Ⅰ5＝20.7，r _Ⅱ5＝24.8，r _Ⅲ5＝50.7）

C ₆（r _Ⅰ6＝13.2，r _Ⅱ6＝11.9，r _Ⅲ6＝71.1）

-6.2≤r _w＜8.6 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝13.1，r _Ⅱ1＝1.4，r _Ⅲ1＝79.3）

C ₂（r _Ⅰ2＝29.1，r _Ⅱ2＝1.4，r _Ⅲ2＝63.3）

C ₃（r _Ⅰ3＝31.1，r _Ⅱ3＝5.6，r _Ⅲ3＝57.1）

C ₄（r _Ⅰ4＝22.7，r _Ⅱ4＝18.7，r _Ⅲ4＝52.4）

C ₅（r _Ⅰ5＝13.3，r _Ⅱ5＝10.1，r _Ⅲ5＝70.4）

-8.6≤r _w＜11.0 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝12.9，r _Ⅱ1＝3.0，r _Ⅲ1＝75.6）

C ₂（r _Ⅰ2＝24.1，r _Ⅱ2＝2.2，r _Ⅲ2＝65.1）

C ₃（r _Ⅰ3＝24.8，r _Ⅱ3＝9.6，r _Ⅲ3＝57.0）

C ₄（r _Ⅰ4＝20.1，r _Ⅱ4＝16.0，r _Ⅲ4＝55.0）

C ₅（r _Ⅰ5＝13.6，r _Ⅱ5＝7.7，r _Ⅲ5＝70.1）

-11.0≤r _w＜13.4 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝13.6，r _Ⅱ1＝3.0，r _Ⅲ1＝72.4）

C ₂（r _Ⅰ2＝19.9，r _Ⅱ2＝2.5，r _Ⅲ2＝66.6）

C ₃（r _Ⅰ3＝21.0，r _Ⅱ3＝6.8，r _Ⅲ3＝61.2）

C ₄（r _Ⅰ4＝20.1，r _Ⅱ4＝8.3，r _Ⅲ4＝60.6）

C ₅（r _Ⅰ5＝14.1，r _Ⅱ5＝5.2，r _Ⅲ5＝69.7）

4, according to the composition of claim 3 regulation, it is characterized in that at each r _WjThe r of value _Wi＜r _w≤ r _WjAt interval, promptly work as r _I+ r _II+ r _III=l-r _WjThe time, just can determine to contain the polygon of a plurality of summits (can change to another at interval at interval) by one, (q is a parameter) and can be by corresponding to r be represented with Cq in each summit _WjThe ternary diagram of value (is r _WjThe planar ternary diagram) determines every point coordinates V in _{I q}, V _{II q}, V _{III q}, be divided into r at each _Wi＜r _w≤ r _WjIn, the quaternary figure coordinate of the corresponding present composition is r _I, r _II, r _III, r _wEvery bit be projected to plane r _WjOn, and perpendicular to this plane (drop shadow spread is in the formed polygon of all summit Cq or on polygonal limit), these r _Wi＜r _w≤ r _WjInterval and these formed polygons in Cq summit have following relationship, r _Wi, r _w, r _WjThe coordinate values of value and summit Cq is all represented with %:

-0.0＜r _w≤ 1.4 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.0，r _Ⅱ1＝2.4，r _Ⅲ1＝85.2）

C ₂（r _Ⅰ2＝35.8，r _Ⅱ2＝0.3，r _Ⅲ2＝62.2）

C ₃（r _Ⅰ3＝37.8，r _Ⅱ3＝9.4，r _Ⅲ3＝51.4）

C ₄（r _Ⅰ4＝27.5，r _Ⅱ4＝27.6，r _Ⅲ4＝43.5）

C ₅（r _Ⅰ5＝18.3，r _Ⅱ5＝29.6，r _Ⅲ5＝50.7）

C ₆（r _Ⅰ6＝12.5，r _Ⅱ6＝14.8，r _Ⅲ6＝71.3）

-1.4＜r _w≤ 3.8 o'clock, this polygon was the sexangle with following summit:

C ₁（r _Ⅰ1＝11.8，r _Ⅱ1＝2.4，r _Ⅲ1＝82.0）

C ₂（r _Ⅰ2＝34.0，r _Ⅱ2＝0.7，r _Ⅲ2＝61.5）

C ₃（r _Ⅰ3＝36.6，r _Ⅱ3＝7.4，r _Ⅲ3＝52.2）

C ₄（r _Ⅰ4＝23.9，r _Ⅱ4＝24.4，r _Ⅲ4＝47.9）

C ₅（r _Ⅰ5＝20.7，r _Ⅱ5＝24.8，r _Ⅲ5＝50.7）

C ₆（r _Ⅰ6＝13.2，r _Ⅱ6＝11.9，r _Ⅲ6＝71.1）

-3.8＜r _w≤ 6.2 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝13.1，r _Ⅱ1＝1.4，r _Ⅲ1＝79.3）

C ₂（r _Ⅰ2＝29.1，r _Ⅱ2＝1.4，r _Ⅲ2＝63.3）

C ₃（r _Ⅰ3＝31.1，r _Ⅱ3＝5.6，r _Ⅲ3＝57.1）

C ₄（r _Ⅰ4＝22.7，r _Ⅱ4＝18.7，r _Ⅲ4＝52.4）

C ₅（r _Ⅰ5＝13.3，r _Ⅱ5＝10.1，r _Ⅲ5＝70.4）

-6.2＜r _w≤ 8.6 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝12.9，r _Ⅱ1＝3.0，r _Ⅲ1＝75.6）

C ₂（r _Ⅰ2＝24.1，r _Ⅱ2＝2.2，r _Ⅲ2＝65.1）

C ₃（r _Ⅰ3＝24.8，r _Ⅱ3＝9.6，r _Ⅲ3＝57.0）

C ₄（r _Ⅰ4＝20.1，r _Ⅱ4＝16.0，r _Ⅲ4＝55.0）

C ₅（r _Ⅰ5＝13.6，r _Ⅱ5＝7.7，r _Ⅲ5＝70.1）

-8.6＜r _w≤ 11.0 o'clock, this polygon was the pentagon with following summit:

C ₁（r _Ⅰ1＝13.6，r _Ⅱ1＝3.0，r _Ⅲ1＝72.4）

C ₂（r _Ⅰ2＝19.9，r _Ⅱ2＝2.5，r _Ⅲ2＝66.6）

C ₃（r _Ⅰ3＝21.0，r _Ⅱ3＝6.8，r _Ⅲ3＝61.2）

C ₄（r _Ⅰ4＝20.1，r _Ⅱ4＝8.3，r _Ⅲ4＝60.6）

C ₅（r _Ⅰ5＝14.1，r _Ⅱ5＝5.2，r _Ⅲ5＝69.7）。

5, obtain the method for compositions of each regulation of claim 1-4, with following characteristic present:

A) mixture is formed by following three kinds of materials at least,

(I) cellulosic material,

A kind of material that (II) is made up of at least a compound that is selected from unary organic carboxylic acid and these sour acid anhydrides and carboxylic acid halides has at least a part to be formic acid and/or formic acid or other organic acid acid anhydrides in this material;

(III) by phosphoric anhydride or at least a phosphoric acid, the perhaps material formed of phosphoric anhydride and at least a phosphoric acid,

The existing water yield is zero or ratio in the case when b) forming mixture:

R _wr= (P _W-P _wr)/(P _I+P _Ⅱ+P _Ⅲ+P _W-P _wr)

Less than 15.0% greater than-7.5%, P _wFor the water that may exist weighs P _WrFor weighing P with the water of material (II) and/or material (III) reaction _IFor the Mierocrystalline cellulose in the material (I) is heavy, P _IIFor material (II) is heavy, P _IIIFor material (III) is heavy,

C) R _I, R _II, R _IIIRatio be defined as:

R _I= (P _I)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _Ⅱ= (P _Ⅱ)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _Ⅲ= (P _Ⅲ)/(P _I+P _Ⅱ+P _Ⅲ+P _w-P _wr)

R _I, R _II, R _III, R _wRatio (R _I+ R _II+ R _III+ R _WrTotal amount be decided to be 100%) will meet following relationship, its value is represented with %:

If-be defined as 12.5≤R _Wr＜15.0

Then have

10.0≤R _I≤ 14.5,2.0≤R _II≤ 10.0 relations,

And R _IAnd R _IIThe pass be: R _II≤ 0.89 R _I-2.89,

If-definite 10.0≤R _Wr＜12.5,

Then have

10.0≤R _I≤ 19.5,2.0≤R _II≤ 17.0 relation,

And work as R _I＜14.5 o'clock,

R _IAnd R _IIThe pass be R _II≤ 1.78R _I-8.78 or work as R _I〉=14.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.40R _I+ 37.30

If-definite 7.5≤R _Wr＜10.0

Then have

10.0≤R _I≤ 31.0,2.0≤R _II≤ 23.0 relations

And work as R _I≤ 12.5 o'clock,

R _IWith R _IIThe pass be R _II≤ 4.40R _I-32.00

Perhaps work as R _I〉=15.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.19R _I+ 41.50

If-definite 5.0≤R _Wr＜7.5,

Then have

10.0≤R _I≤ 37.0,2.0≤R _II≤ 27.5 relations

And work as R _I≤ 13.0 o'clock,

R _IAnd R _IIThe pass be:

R _II≤ 4.17 R _I-26.67 or work as R _I〉=19.0 o'clock,

R then _IAnd R _IIThe pass be:

R _Ⅱ≤-1.14 R _Ⅰ+49.14

If-definite 2.5≤R _Wr＜5.0,

Then have

10.0≤R _I≤ 37.0,2.0≤R _II≤ 36.5 relations,

And work as R _I≤ 14.0 o'clock,

R _IAnd R _IIThe pass be:

R _II≤ 4.63 R ₁-28.25 or work as R _I〉=15.5 o'clock,

R then _IAnd R _IIThe pass be:

R _Ⅱ≤-1.23R _Ⅰ-55.60

If-definite-2.5＜R _Wr＜2.5

Then have

10.0≤R _I≤ 38.0,2.0≤R _II≤ 40.0 relations,

And work as R _I≤ 12.5 o'clock,

R _IAnd R _IIThe pass be:

R _II≤ 2.80 R ₁+ 5.00 or work as R _I〉=19.5 o'clock,

R then _IAnd R _IIThe pass be:

R _Ⅱ≤-1.14 R ₁+62.14

If-definite-5.0＜R _Wr≤ 2.5

Then have

10.0≤R _I≤ 35.0,2.0≤R _II≤ 45.0 relations,

And R _IAnd R _IIThe pass be: R _II≤-1.30 R ₁+ 64.50

If-definite-7.5＜R _Wr＜-5.0

Then have

10.0≤R _I≤ 32.0,2.0≤R _II≤ 36.0 relations,

And work as R _I≤ 14.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 4.00R _I-22.00

D) the cellulosic degree of polymerization DP of material (I) is greater than 150, less than 1500,

E) cellulosic esterification carries out for some time again and just is enough to obtain anisotropic solution in this mixture.

6, according to the method for claim 5 regulation, it is characterized in that the cellulosic degree of polymerization DP in the cellulosic material (I) is at least 200, be at most 1200, simultaneously R _I, R _II, R _III, R _WrBetween have following relationship (R _I, R _II, R _III, R _WrAll represent with %):

If-definite 10.≤R _Wr＜12.5,

Then have

13.0≤R _I≤ 19.0,4.0≤R _II≤ 11.0 relations,

And work as R _I＜18.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 0.73R _I-2.45

Perhaps work as R _I〉=18.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-2.00R _I+ 48.00

If-definite 7.5≤R _Wr＜10.0,

Then have

12.25≤R _I≤ 23.0,4.0≤R _II≤ 19.5 relations,

And work as R _I＜18.0 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 1.65R _I-10.24

Perhaps work as R _I〉=18.0 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.40R _I+ 44.70

If-definite 5.0≤R _Wr＜7.5,

Then have

11.5≤R _I≤ 27.5,4.0≤R _II≤ 24.0 relations

And work as R _I＜19.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 1.38R _I-2.81 or work as R _I〉=19.5 o'clock,

R then _IAnd R _IIThe pass be R _II≤ 1.56R _I+ 54.47

If-definite 2.5≤R _Wr＜5.0,

Then have

10.75≤R _I≤ 32.0,4.0≤R _II≤ 30.0 relations

And work as R _I≤ 17.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 2.07R _I-5.80

Perhaps work as R _I〉=20.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.30R _I+ 56.74

If-definite-2.5＜R _Wr＜2.5

Then have

10.0≤R _I≤ 33.5,4.0≤R _II≤ 35.0 relations

And work as R _I≤ 15.0 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 3.20R _I-13.00

Perhaps work as R _I〉=23.0 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.76R _I+ 75.52

If-definite-5.0＜R _Wr≤-2.5

Then have

10.0≤R _I≤ 33.5,4.0≤R _II≤ 35.0 relations

And work as R _I≤ 15.0 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 3.20R _I-13.00

Perhaps work as R _I〉=20.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.85R _I+ 72.85

7, according to the method for claim 6 regulation, it is characterized in that R _I, R _II, R _III, R _WrBetween have a following relationship (these values are all represented with %):

If-definite 7.5＜R _Wr≤ 10.0,

Then have

13.0≤R _I≤ 19.0,4.0≤R _II≤ 11.0 relations,

And work as R _I＜18.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 0.73R _I-2.45

Perhaps work as R _I〉=18.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-2.00R _I+ 48.00

If-definite 5.0＜R _Wr≤ 7.5

Then have

12.25≤R _I≤ 23.0,4.0≤R _II≤ 19.5 relations

And work as R _I＜18.0 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 1.65R _I-10.24

Perhaps work as R _I〉=18.0 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.40R _I+ 44.70

If-definite 2.5＜R _Wr≤ 5.0

Then have

11.5≤R _I≤ 27.5,4.0≤R _II≤ 24.0 relations

And work as R _I＜19.5 o'clock,

R _IAnd R _IIThe pass be: R _II≤ 1.38R _I-2.81

Perhaps work as R _I〉=19.5 o'clock

R then _IAnd R _IIThe pass be: R _II≤ 1.56R _I+ 54.47

If-definite 0.0＜R _Wr≤ 2.5

Then have

10.75≤R _I≤ 32.0,4.0≤R _II≤ 30.0 relations

And work as R _I≤ 17.5 o'clock

R _IAnd R _IIThe pass be: R _II≤ 2.07R _I-5.80

Perhaps work as R _I〉=20.5 o'clock

R then _IAnd R _IIThe pass be: R _II≤ 1.30R _I+ 56.74

If-definite-2.5≤R _Wr≤ 0.0

Then have

10.0≤R _I≤ 33.5,4.0≤R _II≤ 35.0 relations

And work as R _I≤ 15.0 o'clock,

R _IAnd R _IIThe pass be R _II≤ 3.20R _I-13.00 or work as

R _I〉=20.5 o'clock,

R then _IAnd R _IIThe pass be: R _II≤-1.85R _I+ 72.85.

8, according to the composition of each method gained among the claim 5-7.

9, at least based on the manufacture method of the goods of a kind of derivatived cellulose, it is characterized in that and to be processed into goods according to the composition of claim 1-4 and 8 each gained, from these goods, discard a part of product except that derivatived cellulose or all derivatives simultaneously at least.

10,, it is characterized by in the processing of composition and use precipitation bath according to the method for claim 9 regulation.

11,, it is characterized by that solidification liquid is base substance with acetone in the precipitation bath according to the method for claim 10 regulation.

12, according to the method for claim 10 and 11, it is minimum for-20 ℃ to it is characterized by coagulation bath temperature, is up to 10 ℃.

13,, it is characterized by and use spining technology (dry-jet wet spinning) with non-solidification liquid gap according to each method of claim 9-12.

14, produce manufacture method, it is characterized by according to the Mierocrystalline cellulose in each method resulting product of claim 9-13 and have at least a part to be regenerated cellulose based on the goods of regenerated fibre.

15,, it is characterized by and use alkaline aqueous solution to finish regeneration according to the method for claim 14.

16, the goods that make according to each method among the claim 9-15.

17, according to the goods of claim 16, it is characterized by it is a kind of fiber or film.

18, be that derivatived cellulose with a kind of cellulose ester group (wherein having a part at least is the formic acid ester group) is a kind of fiber that monofilament that main body is made is formed to small part, it is with following property representation.

A) Mierocrystalline cellulose is at least 2% by the degree DS that the formic acid ester group replaces, and cellulosic polymerization degree DP is greater than 150 less than 1500,

B) the intensity T of fiber and initial modulus M _iHave following relationship (T and M _iRepresent with CN/tex): T＞20; M _i＞1000;

C) this monofilament have such form it to have a part at least be by mutually embedding and forming between layer and the layer, these layer ring copss, optical direction of each layer and crystallization direction are the change of pseudoperiodicity ground along the silk axle.

19,, need not drawing-off after it is characterized by shaping according to claim 18 specific fibre.

20,, it is characterized by double refraction △ n greater than 0.03 according to claim 18 or 19 specific fibre.

21,, it is characterized by cellulosic degree of polymerization DP in derivatived cellulose or all derivatives and be at least 200 and be at most 1200 according to each specific fibre of claim 18-20.

22, to small part be based on the Mierocrystalline cellulose of a kind of cellulose ester group (wherein having the part ester group at least is the formic acid ester group) and or a kind of fiber of being formed of the monofilament of derivatived cellulose, it is with following property representation:

A) the degree DS that replaced by the formic acid ester group of Mierocrystalline cellulose is zero or less than 2%, and cellulosic polymerization degree DP is greater than 150 less than 1500,

B) cellulosic polymerization degree DP, cellulosic intensity T and initial modulus M _jBetween have following relationship, (T and M _iRepresent with CN/tex):

If DP＜200, then T＞20 and M _j＞1800,

If 200≤DP＜300, then T＞30 and M _i＞2000,

If 300≤DP＜400, then T＞40 and M _i＞2400,

If 400≤DP＜1500, then T＞60, and M _i＞2600,

C) this monofilament has a kind of like this form, and it has a part at least is by mutually embedding and forming between layer and the layer, these layer ring copss, and the optical direction of each layer and crystallization direction are the change of pseudoperiodicity ground along the silk axle.

23,, it is characterized by wherein DP, T and M according to claim 22 specific fibre _iHave following relationship (T and M _iRepresent with CN/tex): if 150＜DP≤250, then T 〉=1/3DP-26 and M _i〉=2300, if 250≤DP＜1500, then T 〉=18675/DP+132 and M _i〉=-502250/DP+4309.

24,, it is characterized by its sound wave modulus M according to claim 22 or 23 specific fibre _SGreater than 3000CN/tex.

25, according to each specific fibre of claim 22-24, it is characterized by orientation index＞95.5%.

26,, need not drawing-off after it is characterized by moulding according to each specific fibre of claim 22-25.

27,, it is characterized by wherein cellulosic polymerization degree DP and be at least 200 and be at most 1200 according to each specific fibre of claim 22-26.

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