CN107604476A - A kind of polysaccharide fiber and preparation method thereof - Google Patents

Abstract

The present invention relates to the method for preparing polysaccharide fiber and the fiber thus prepared and application thereof, the polysaccharide fiber contains the mixture of cellulose and α (1 → 3) glucan as the material for forming fiber.

Description

A kind of polysaccharide fiber and preparation method thereof

Technical field

The present invention relates to the method for preparing polysaccharide fiber and the fiber thus prepared and application thereof, the polysaccharide fiber conduct The material for forming fiber contains the mixture of cellulose and α (1 → 3)-glucan.

Background technology

Polysaccharide is just becoming more and more important, because they are can be from the material that renewable raw materials obtain.It is most common more One of sugar is cellulose.The cotton fiber being almost made up of completely cellulose is an example of the importance of polysaccharide.It is however, same The material obtained from other cellulosic materials, such as cellulose-regeneratfasern, also become more and more important.

Species title " lyocell (Lyocell) fiber " by BISFA (staple fibre standardization international office) distribute to from Cellulose fibre in organic solvent without forming the solution of derivative and preparing.

However, so far, only a kind of method of the fiber for the lyocell type for being used to mass produce has obtained extensively General accreditation, i.e. amine oxide method.In the method, tertiary amine oxide, preferably N-methylmorpholine-N- oxides (NMMO), are used as Solvent.

Tertiary amine oxide is already known as cellulose and substitutes solvent.For example known from US2179181, tertiary amine oxide can be molten Cellulose is solved without derivatization occurs, and cellulosic molded body can be prepared from the solution, such as fiber. US3447939 describes solvent of the ring-type amine oxide as cellulose.

From numerous patent documents and other publications, those skilled in the art are for a long time substantially it is known how real Apply the method.For example, the preparation of solution is especially described in EP356419B1, and EP584318B1 describes such fiber The spinning of solution of the element in aqueous tertiary amine oxide.

The cellulosic material mainly used in amine oxide method is the cellulose obtained from timber.Timber and Cellulosic molecule present in the cellulose origin (such as velveteen, straw etc.) of other plants forms very long chain, i.e., they have There is the high degree of polymerization.In order to which the cellulose spinning solution for obtaining industrially processing very well divides, it is necessary to specially adjust cellulose The degree of polymerization of son, wherein inevitably shortening a part of polymer molecule.This occurs in common cellulose preparation method In and in single pre-treatment step, such as bleaching, acid treatment or irradiation are carried out by splitting originally long cellulosic molecule.Remove There is the relatively short chain of the required degree of polymerization, this also results in significantly shorter fragment, such as oligomer or even monomer, and it is the latest Retain in the solution during the precipitation of the spinning solution in precipitating bath, do not advantageously form fiber and therefore be lost in.Raw material is at this The loss occurred during individual is probably huge, and can influence the economy of whole amine oxide method.

US7000000 describes fiber made from the polysaccharide solution being substantially made up of spinning hexose repeat unit, Wherein these hexose repeat units are connected by α (1 → 3)-glycosidic bond.These polysaccharide can by make the aqueous solution of sucrose with GtfJ glucosyltransferases (being isolated from streptococcus salivarius (Streptococcussalivarius)) are contacted to prepare (Simpson etc., Microbiology, vol.41, pp1451-1460 (1995)).As in this context, " substantially " refer to The individual defects position that other key configurations occur is there may exist in the polysaccharide chain.For the purpose of the present invention, these glycocalixs Referred to as " α (1 → 3)-glucan ".

US700000 discloses the possibility that α (1 → 3)-glucan is prepared by monose enzyme process first.By this way, phase The polysaccharide of short chain can be produced in the case where no monomeric unit loses, because polymer chain is formed from monomeric unit.With The preparation of short chain cellulose molecule is on the contrary, polymer chain is shorter, and the preparation of α (1 → 3)-glucan is cheaper, because so anti- Residence time required for answering in device will be short.

According to US7000000, α (1 → the 3)-glucan should be derivatization, preferably acetylation.Preferably, it is molten Agent is the mixture of organic acid, organohalogen compound, fluorinated alohol or these components.These solvents are expensive and are difficult to regenerate 's.

Therefore, attempted to use α (1 → 3)-Portugal under the conditions of the Large scale processes in amine oxide method for commercial applications Glycan replaces cellulose.But result is shown, unsatisfactorily α (1 → 3)-glucan is processed under these conditions Fiber.

The content of the invention

It is a primary object of the present invention to provide a kind of polysaccharide fiber and preparation method thereof, it does not have the shortcomings that above-mentioned. The polysaccharide raw material should manufacture marked downly, and processing method should be known and can be economically and existing Implement in equipment.

The solution of above-mentioned purpose is, there is provided prepares a kind of method of Lyocell fibers, wherein spinning solution contains Water-based amine oxide and cellulose and the mixture of α (1 → 3)-glucan as the material for forming fiber.For the mesh of the present invention , such fiber is also referred to as Lyocell fibers, although they are except polysaccharide of the cellulose also containing other formation fibers, i.e. α (1 → 3)-glucan.

For the purpose of the present invention, term " fiber " includes chopped fiber and long fibre with specific sheared length.Under All principles of the invention of face description are applied basically for chopped fiber and long fibre.

The single fiber titre (Einzelfasertiter) of fiber of the present invention can be 0.1 to 10dtex.It is preferred that 0.5 to 6.5dtex and more preferably 0.9 to 3.0dtex.In the case of chopped fiber, sheared length is usually 0.5 to 120mm, preferably 20 To 70mm and more preferably 35 to 60mm.In the case of long fibre, the single fiber number in fiber yarn is 50 to 10,000, It is preferred that 50 to 3,000.

α (1 → the 3)-glucan can by by the aqueous solution of sucrose with from the GtfJ Portugals that streptococcus salivarius is isolated Glycosyl transferase is contacted and prepared (Simpson etc., Microbiology, vol.41, pp1451-1460 (1995)).

In a preferred embodiment of the inventive method, at least 90% α (1 → 3)-glucan is by hexose Unit is formed to be connected with least 50% hexose by α (1 → 3)-glycosidic bond.

The method for preparing fiber of the present invention is made up of following steps：

1. prepare the spinning solution containing following material：Water-based amine oxide and cellulose as the material for forming fiber and The mixture of α (1 → 3)-glucan, according to one of following two method：

A. α (1 → 3)-glucan can be added to according to known method in the form of the solution in water-based amine oxide The cellulose solution of preparation；

B. before being contacted with water-based amine oxide, it is already possible to which α (1 → 3)-glucan is mixed into cellulose.

2. the spinning solution is expressed into the spinning bath containing water-based amine oxide by nozzle by the air gap, rush Regenerated fiber is washed to remove amine oxide and drying.

The concentration that the material of fiber is formed in spinning solution can be 5 to 20 weight %, preferably 8 to 15 weight % and more It is preferred that 10 to 14 weight %.

In the method for the invention, α (1 → 3)-Portugal that the material for forming fiber can be containing 1 to 99 weight % gathers Sugar.Particularly preferred 5 to 30 weight % α (1 → 3)-beta-dextran content and very particularly preferably 10 to 20 weight % α (1 → 3)-beta-dextran content.When less than 5%, the routine of the economic effect of α (1 → 3)-glucan additive for fiber of the present invention It is too low for；When higher than 30%, occurs the fiber bonding of more degree in spinning process.However, in special bar Particular utility under part or for fiber of the present invention, can more than two limiting values；The scope of the present invention also clearly includes The fiber of α (1 → 3)-beta-dextran content with 1 to the 5 weight weight of % or 30 to 99 %.For example, in the low of spinning-nozzle Shot density, i.e., between the single fiber in the air gap it is big apart from when, the possibility of bonding is substantially lower.

The degree of polymerization (being expressed as weighed average DPw) of α (1 → 3) glucan used in the methods of the invention can be 200 to 2000；It is preferred that 500 to 1000 value.Preferred N-methylmorpholine-N- the oxides of amine oxide.

Further preferably following method parameter in the method for the invention：Spinning solution from the extrusion temperature in nozzle be 90 to 135 DEG C, preferably 120 to 130 DEG C；Depending on desired single fiber titre, the spray volume of spinning-nozzle is 0.01 to 0.2g/ Perforation * min, preferably 0.02 to 0.1g/ perforation * min；The length of the air gap is 7 to 70mm, preferably 20 to 35mm；Water-based NMMO concentration in spinning bath is 0 to 35 weight %, preferably 0 to 25 weight %.

Subject of the present invention still contains the Lyocell fibers of cellulose and α (1 → 3)-glucan.

According to the present invention, α (1 → 3)-Portugal that the material of the formation fiber of fiber of the present invention can be containing 1 to 99 weight % Glycan.α (1 → 3)-glucan of particularly preferred α (1 → the 3)-beta-dextran content for 5 to 30 weight % and very particularly preferably Content is 10 to 20 weight %.When less than 5%, the economic effect of α (1 → 3)-glucan additive is for routinely applying It is too low；When higher than 30%, there is the fiber bonding of more degree.However, under conditions of special or for of the invention fine The particular utility of dimension, can more than two limiting values；The scope of the present invention also clearly includes having 1 to 5 weight % or 30 To the fiber of 99 weight % α (1 → 3)-beta-dextran content.

In a preferred embodiment, at least the 90% of the α (1 → 3)-glucan of Lyocell fibers of the present invention It is made up of hexose and at least 50% hexose is connected by α (1 → 3)-glycosidic bond.

Subject of the present invention also reside in fiber of the present invention be used for manufacture textile product for example yarn, woven fabric, braid or The purposes of person's knitted fabric.

It has surprisingly been found that the fiber of the present invention is (more fine than the common lyocell purchased in market without α (1 → 3)-glucan Dimension is preferably) very well fit through those skilled in the art substantially known processing side from the processing of Lyocell fibers Spinning of method (for example, see SchmidtM., LenzingerBerichte9 (1994), the pp95-97) manufacture with peach face effect Fabric.High fibrillation tendency of the applicability based on fiber of the present invention.

In order to remove the fibril occurred in the various processing steps of weaving chain of fiber surface, usually using so-called machine Tool polishing step or enzyme polishing step (see, for example, SchmidtM., LenzingerBerichte9 (1994), pp95-97). The fiber of the present invention has substantially very well been suitable for use with the manufacture of the textile of such machinery or enzyme polishing step In method.Therefore such purposes of fiber of the present invention is equally subject of the present invention.The dyeing manufactured by fiber of the present invention Plane formation (textile) has preferably white abrasiveness (Weissscheuerung), and showing after wash in addition Go out relatively low ashing and less balling-up.

The fiber of the present invention is especially suitable for all products that can be manufactured in dry method-or wet-laid method.Example Such as include all paper purposes and supatex fabric, i.e., so-called non-thermoplastic product.Pass through the sheet disperseed in the liquid of such as water The strong mechanical stress of invention fiber, can equally cause the fibrillation.Suitable equipment is e.g. also in paper industry The refiner used.Relative to the Lyocell fibers formed by 100% cellulose, fiber of the invention forms thicker fibril, Thus the fiber of these fibrillation is made to be particularly well suited to above-mentioned non-thermoplastic purposes.

In addition, the present invention fiber very well be applied to it is all in the form of acutely shortening be used for other formed bodys or The purposes of the surface treatment of plane body.Mainly include face coat and flocking.The fiber of the present invention is this for example by cutting The length that shearing or Grinding manufacturing in machine are 10 to about 500 μm.

Embodiment

Describe to be used to disclose the present invention below so that those skilled in the art can realize the present invention.It is excellent in describing below Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.

The degree of polymerization of α (1 → 3)-glucan determines by GPC in DMAc/LiCl.Hereafter always provide the weight of the degree of polymerization Measure average value (DPw).

By the N-methylmorpholine of solid (cellulose+α (1 → 3) glucan)/77 weight % respectively containing 13 weight %- The spinning solution of the weight % of N- oxides/10 water at 130 DEG C from nozzle by the air gap (length 30mm) in water Spinning.In the air gap, blown at room temperature using dry air (i.e. humidity=0% is relative).The spray volume of spinning-nozzle For 0.05g/ perforation * min.The cellulosic material used is the Saiccor celluloses of the SCAN viscosity with 450ml/g.Use α (1 → 3) glucan with two kinds of different polymerization degrees.Glucan amount refers to that α (1 → 3)-Portugal gathers in the material for forming fiber The content of sugar.

General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry For personnel it should be appreciated that the present invention is not limited to the above embodiments, that described in above-described embodiment and specification is the present invention Principle, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these change and Improvement is both fallen within the range of claimed invention.The protection domain of application claims by appended claims and its Equivalent defines.

Claims (10)

1. prepare the method for Lyocell fibers, it is characterised in that spinning solution contains water-based amine oxide and as forming fiber The mixture of cellulose and α (1 → 3)-glucan of material.

2. the method for claim 1 wherein it is described formation fiber material contain 1 to 99 weight %, preferably 5 to 30 weight %'s α (1 → 3)-glucan.

3. the method for claim 1 wherein the amine oxide is N-methylmorpholine-N- oxides.

4. the method for claim 1 wherein at least 90% α (1 → 3)-glucan is made up of and at least hexose 50% hexose is connected by α (1 → 3)-glycosidic bond.

5. the method for preceding claims, wherein the fiber is chopped fiber or long fibre.

6. Lyocell fibers, it is characterised in that it contains cellulose and α (1 → 3)-glucan.

7. the Lyocell fibers of claim 6, wherein the material for forming fiber contains 1 to 99 weight %, preferably 5 to 30 weights Measure % α (1 → 3)-glucan.

8. the Lyocell fibers of claim 6, wherein at least 90% α (1 → 3)-glucan be made up of hexose and At least 50% hexose is connected by α (1 → 3)-glycosidic bond.

9. the fiber of preceding claims, wherein the fiber is chopped fiber or long fibre.

10. the fiber of claim 6 is used for the purposes for manufacturing textile product such as yarn, woven fabric, braid or knitted fabric.