ALGINATE FIBER AND PREPARATION METHOD THEREOF

Abstract

An alginate fiber and a preparation method thereof are provided. The preparation method of the alginate fiber includes: S10: preparing a spinning solution with a raw material including sodium alginate; S20: extruding the spinning solution obtained in S10 into a solidification bath to allow solidification molding to obtain a primary fiber; S30: drawing and water-washing the primary fiber obtained in S20 to obtain an alginate fiber; and S40: soaking the alginate fiber obtained in S30 in a finishing agent to allow a post-treatment, where at least one of the raw material in S10, the solidification bath in S20, and the finishing agent in S30 includes a five-membered cyclic quaternary ammonium salt polymer. The alginate fiber obtained above has a high dye uptake, a small fiber strength loss, and a high soaping fastness.

Claims

1. A preparation method for an alginate fiber, comprising: S10: mixing sodium alginate with a five-membered cyclic quaternary ammonium salt polymer in water to obtain a spinning solution, wherein a mass ratio of the sodium alginate to the five-membered cyclic quaternary ammonium salt polymer is 100:(0.001-30); S20: allowing the spinning solution obtained in S10 to stand for deaeration, and then extruding the spinning solution into a solidification bath at 40? C. to 70? C. to allow solidification molding to obtain a primary fiber, wherein the solidification bath comprises the five-membered cyclic quaternary ammonium salt polymer with a mass percentage concentration of 0.01% to 2%; S30: drawing and water-washing the primary fiber obtained in S20 to obtain an alginate fiber; and S40: soaking the alginate fiber obtained in S30 in a finishing agent at 20? C. to 70? C. for 5 min to 60 min, wherein the finishing agent comprises the five-membered cyclic quaternary ammonium salt polymer, and a mass of the five-membered cyclic quaternary ammonium salt polymer is 0.5% to 10% of a mass of the alginate fiber obtained in S30; and the five-membered cyclic quaternary ammonium salt polymer is ##STR00004## wherein R.sub.1 is CH.sub.3 or CH.sub.2CH.sub.3 or CH.sub.2(CH.sub.2).sub.4CH.sub.3 or CH.sub.2(CH.sub.2).sub.10CH.sub.3 or CH.sub.2(CH.sub.2).sub.16CH.sub.3 or C.sub.6H.sub.5CH.sub.2, R.sub.2 is CH.sub.3 or CH.sub.2CH.sub.3 or CH.sub.2(CH.sub.2).sub.4CH.sub.3 or CH.sub.2(CH.sub.2).sub.10CH.sub.3 or CH.sub.2(CH.sub.2).sub.16CH.sub.3 or C.sub.6H.sub.5CH.sub.2, and a degree of polymerization (DP) n ranges from 50 to 25,000.

2. The preparation method for the alginate fiber according to claim 1, wherein a mass percentage content of the five-membered cyclic quaternary ammonium salt polymer in the alginate fiber is 0.1% to 10%.

3. The preparation method for the alginate fiber according to claim 1, wherein a mass percentage concentration of the sodium alginate in the spinning solution is 3% to 6%.

4. The preparation method for the alginate fiber according to claim 1, wherein in S20, a pH of the solidification bath is 4.5 to 6.5; and/or in S20, the solidification bath further comprises a calcium chloride aqueous solution with a mass percentage concentration of 1% to 6%.

5. The preparation method for the alginate fiber according to claim 1, wherein after S40, the preparation method further comprises: S50: washing and oven-drying the alginate fiber obtained in S40.

6. An alginate fiber prepared by the preparation method according to claim 1.

7. The preparation method for the alginate fiber according to claim 2, wherein in S20, a pH of the solidification bath is 4.5 to 6.5; and/or in S20, the solidification bath further comprises a calcium chloride aqueous solution with a mass percentage concentration of 1% to 6%.

8. The preparation method for the alginate fiber according to claim 3, wherein in S20, a pH of the solidification bath is 4.5 to 6.5; and/or in S20, the solidification bath further comprises a calcium chloride aqueous solution with a mass percentage concentration of 1% to 6%.

9. The preparation method for the alginate fiber according to claim 2, wherein after S40, the preparation method further comprises: S50: washing and oven-drying the alginate fiber obtained in S40.

10. The preparation method for the alginate fiber according to claim 3, wherein after S40, the preparation method further comprises: S50: washing and oven-drying the alginate fiber obtained in S40.

11. The alginate fiber according to claim 6, wherein in the preparation method, a mass percentage content of the five-membered cyclic quaternary ammonium salt polymer in the alginate fiber is 0.1% to 10%.

12. The alginate fiber according to claim 6, wherein in the preparation method, a mass percentage concentration of the sodium alginate in the spinning solution is 3% to 6%.

13. The alginate fiber according to claim 6, wherein in S20 of the preparation method, a pH of the solidification bath is 4.5 to 6.5; and/or in S20, the solidification bath further comprises a calcium chloride aqueous solution with a mass percentage concentration of 1% to 6%.

14. The alginate fiber according to claim 6, wherein after S40, the preparation method further comprises: S50: washing and oven-drying the alginate fiber obtained in S40.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0042] FIG. 1 is a scanning electron microscopy (SEM) image of an alginate fiber in the prior art; and

[0043] FIG. 2 is an SEM image of the alginate fiber provided in the present application.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0044] The embodiments described below with reference to the accompanying drawings are exemplary, and are merely intended to explain the present application, rather than to limit the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts should fall within the protection scope of the present application.

[0045] An embodiment of the present application provides a preparation method for an alginate fiber, including: [0046] S10: a spinning solution is prepared with a raw material including sodium alginate; [0047] S20: the spinning solution obtained in S10 is extruded into a solidification bath to allow solidification molding to obtain a primary fiber; [0048] S30: the primary fiber obtained in S20 is drawn and water-washed to obtain an alginate fiber; and [0049] S40: the alginate fiber obtained in S30 is soaked in a finishing agent to allow a post-treatment, [0050] where at least one or all of the raw material in S10, the solidification bath in S20, and the finishing agent in S30 include(s) a five-membered cyclic quaternary ammonium salt polymer.

[0051] In the above embodiment, the alginate fiber obtained in the embodiment of the present application may be used to prepare an alginate fiber-containing blended fabric, and the alginate fiber-containing blended fabric is a blended fabric of the alginate fiber with one or more other fibers. For example, the alginate fiber-containing blended fabric can be at least one of an alginate fiber/cotton blended fabric, an alginate fiber/rayon blended fabric, an alginate fiber/wool blended fabric, an alginate fiber/cashmere blended fabric, and an alginate fiber/silk blended fabric.

[0052] In the above embodiment, the alginate fiber obtained in the embodiment of the present application can be easily dyed to have a bright color. One or more of a direct dye, an acidic dye, a reactive dye, a natural dye, and an indigo dye is/are selected for dyeing.

[0053] In the above embodiment, making at least one or all of the raw material in S10, the solidification bath in S20, and the finishing agent in S30 include a five-membered cyclic quaternary ammonium salt polymer is intended to improve a dye uptake of the alginate fiber during dyeing, reduce a loss rate of the alginate fiber, and improve a soaping fastness of the alginate fiber. The alginate fiber-containing blended fabric obtained by the preparation method provided in the embodiment of the present application has a dye uptake of greater than or equal to 85% and a soaping fastness of greater than or equal to grade 4.

[0054] A principle that the embodiment of the present application can allow the above objective is as follows: Sodium alginate is a block linear polysaccharide obtained by linking two uronic acids with different structures through C-1,4 bonds, namely, ?-D-mannuronic acid (referred to as unit M) and ?-L-guluronic acid (referred to as unit G). These two structural units in a sodium alginate molecule are distributed in a molecular chain in the forms of polymannuronic acid (M)n and polyguluronic acid (G)n, and the two structural units are linked through alternative M and G or poly(MG)n and have chemical structures as follows:

##STR00002##

[0055] When encountering a calcium chloride-containing solidification bath, the sodium alginate-containing spinning solution will be quickly transformed into a water-insoluble calcium alginate gel. This process is mainly characterized by the formation of an egg-shell structure by a GG chain segment and Ca.sup.2+ to produce the alginate fiber. Many monovalent salts destroy the stability of the alginate fiber, that is, an egg-shell cross-linked structure of the alginate fiber is destroyed.

[0056] One of the keys to the present application is that at least one or all of the raw material in S10, the solidification bath in S20, and the finishing agent in S30 include(s) a five-membered cyclic quaternary ammonium salt polymer. By adding the five-membered cyclic quaternary ammonium salt polymer during different processes (one or more steps) of spinning, the alginate fiber can be provided with quaternary ammonium-based chromophores. The five-membered cyclic quaternary ammonium salt polymer of the embodiment of the present application has a similar structure to the M unit of the alginate fiber, has excellent planarity, is easy to adsorb and cross-link with the M unit, and has a low probability of replacing Ca.sup.2+. Due to a high cation density, the five-membered cyclic quaternary ammonium salt polymer of the embodiment of the present application can adsorb different alginate fiber macromolecular chains and ultimately assist the egg-shell system to form a stable dyeable alginate fiber system, and can also ensure the stability and mechanical properties of the alginate fiber as much as possible.

[0057] In summary, the alginate fiber of the embodiment of the present application has excellent dyeability, and can be subjected to salt-free dyeing with a commercial direct dye. The dyeable alginate fiber produced by adding the five-membered cyclic quaternary ammonium salt polymer during spinning in the embodiment of the present application can be dyed to have a bright color, with an excellent fastness. During dyeing, the alginate fiber can retain its original morphology, and undergoes no obvious dissolution and no significant mechanical performance degradation.

[0058] In addition, in the preparation method for a dyeable alginate fiber proposed in the related technology such as CN101736440A, a dendritic macromolecule is added to a spinning raw material to provide a chromophore, but the problem of electronegativity of the fiber cannot be solved. However, in the embodiment of the present application, during the spinning and post-treatment, the five-membered cyclic quaternary ammonium salt polymer is added to solve the problems of stable chromophores and electronegativity of the dyeable alginate fiber.

[0059] In some implementations of the embodiment of the present application, the five-membered cyclic quaternary ammonium salt polymer is

##STR00003## [0060] where R.sub.1 is CH.sub.3 or CH.sub.2CH.sub.3 or CH.sub.2(CH.sub.2).sub.4CH.sub.3 or CH.sub.2(CH.sub.2).sub.10CH.sub.3 or CH.sub.2(CH.sub.2).sub.16CH.sub.3 or C.sub.6H.sub.5CH.sub.2, R.sub.2 is CH.sub.3 or CH.sub.2CH.sub.3 or CH.sub.2(CH.sub.2).sub.4CH.sub.3 or CH.sub.2(CH.sub.2).sub.10CH.sub.3 or CH.sub.2(CH.sub.2).sub.16CH.sub.3 or C.sub.6H.sub.5CH.sub.2, and a DP n ranges from 50 to 25,000.

[0061] In some implementations of the embodiment of the present application, the five-membered cyclic quaternary ammonium salt polymer is a water-soluble five-membered cyclic quaternary ammonium salt polymer.

[0062] In some implementations of the embodiment of the present application, a mass percentage content of the five-membered cyclic quaternary ammonium salt polymer in the alginate fiber is 0.1% to 10%.

[0063] In some implementations of the embodiment of the present application, a mass percentage content of the five-membered cyclic quaternary ammonium salt polymer in the alginate fiber is 2% to 8%.

[0064] In some implementations of the embodiment of the present application, a mass percentage content of the five-membered cyclic quaternary ammonium salt polymer in the alginate fiber is 4% to 6%. In some implementations of the embodiment of the present application, a mass percentage content of the five-membered cyclic quaternary ammonium salt polymer in the alginate fiber is 5%.

[0065] In some implementations of the embodiment of the present application, the five-membered cyclic quaternary ammonium salt polymer is prepared by the following method: a five-membered cyclic quaternary ammonium salt monomer, an initiator, and ethylenediaminetetraacetic acid disodium (EDTA-Na.sub.2) are mixed, and a resulting mixture is incubated at 60? C. to 100? C. for 1 h to 5 h to obtain the five-membered cyclic quaternary ammonium salt polymer.

[0066] In some implementations of the embodiment of the present application, the five-membered cyclic quaternary ammonium salt polymer is prepared by the following method: a five-membered cyclic quaternary ammonium salt monomer, an initiator, and EDTA-Na.sub.2 are mixed, and a resulting mixture is incubated at 70? C. to 90? C. for 2 h to 3 h to obtain the five-membered cyclic quaternary ammonium salt polymer.

[0067] In some implementations of the embodiment of the present application, the five-membered cyclic quaternary ammonium salt polymer is prepared by the following method: a five-membered cyclic quaternary ammonium salt monomer, an initiator, and EDTA-Na.sub.2 are mixed, and a resulting mixture is incubated at 80? C. to 85? C. for 2.5 h to obtain the five-membered cyclic quaternary ammonium salt polymer.

[0068] In the above implementations, a reactor equipped with a stirrer, a thermometer, and a nitrogen introduction device is used to prepare the five-membered cyclic quaternary ammonium salt polymer.

[0069] In the above implementations, a concentration of the five-membered cyclic quaternary ammonium salt monomer is 20% to 80%, a concentration of the initiator is 0.1% to 2%, and a concentration of the EDTA-Na.sub.2 is 0.001% to 0.01%.

[0070] In the above implementations, a concentration of the five-membered cyclic quaternary ammonium salt monomer is 40% to 60%, a concentration of the initiator is 1% to 1.5%, and a concentration of the EDTA-Na.sub.2 is 0.004% to 0.006%.

[0071] In the above implementations, the initiator includes any one or more of potassium persulfate, sodium persulfate, ammonium persulfate, azodiisobutamidine hydrochloride, azodiisobutyronitrile, and azobisisoheptonitrile.

[0072] In the above implementations, a specific preparation method for the five-membered cyclic quaternary ammonium salt polymer is as follows: 20% to 80% of the five-membered cyclic quaternary ammonium salt monomer is added to the reactor equipped with a stirrer, a thermometer, and a nitrogen introduction device, and then 0.1% to 2% of the initiator and 0.001% to 0.01% of the EDTA-Na.sub.2 are added successively; and nitrogen is then introduced for 20 min to 40 min, and a resulting mixture is heated to 60? C. to 100? C. and then kept at this temperature for 1 h to 5 h to obtain the five-membered cyclic quaternary ammonium salt polymer.

[0073] In some implementations of the embodiment of the present application, S10 specifically includes: [0074] S101: sodium alginate is mixed with a five-membered cyclic quaternary ammonium salt polymer in water to obtain a spinning solution, where a mass ratio of the sodium alginate to the five-membered cyclic quaternary ammonium salt polymer is 100:(0.001-30).

[0075] In some implementations of the embodiment of the present application, $10 specifically includes: [0076] S101: sodium alginate is mixed with a five-membered cyclic quaternary ammonium salt polymer in water to obtain a spinning solution, where a mass ratio of the sodium alginate to the five-membered cyclic quaternary ammonium salt polymer is 100:(10-20).

[0077] In some implementations of the embodiment of the present application, S10 specifically includes: [0078] S101: sodium alginate is mixed with a five-membered cyclic quaternary ammonium salt polymer in water to obtain a spinning solution, where a mass ratio of the sodium alginate to the five-membered cyclic quaternary ammonium salt polymer is 100:(12-18).

[0079] In some implementations of the embodiment of the present application, a mass percentage concentration of the sodium alginate in the spinning solution is 3% to 6%.

[0080] In some implementations of the embodiment of the present application, a mass percentage concentration of the sodium alginate in the spinning solution is 4% to 5%.

[0081] In some implementations of the embodiment of the present application. S20 specifically includes: [0082] S201: the spinning solution obtained in S10 is allowed to stand for deaeration, and then extruded into a solidification bath at 40? C. to 70? C. to allow solidification molding.

[0083] In some implementations of the embodiment of the present application, S20 specifically includes: [0084] S201: the spinning solution obtained in S10 is allowed to stand for deaeration, and then extruded into a solidification bath at 50? C. to 60? C. to allow solidification molding.

[0085] In some implementations of the embodiment of the present application, the solidification bath includes the five-membered cyclic quaternary ammonium salt polymer with a mass percentage concentration of 0.01% to 2%.

[0086] In some implementations of the embodiment of the present application, the solidification bath includes the five-membered cyclic quaternary ammonium salt polymer with a mass percentage concentration of 0.5% to 1.5%.

[0087] In some implementations of the embodiment of the present application, the solidification bath includes the five-membered cyclic quaternary ammonium salt polymer with a mass percentage concentration of 1%.

[0088] In some implementations of the embodiment of the present application, S40 specifically includes: [0089] S401: the alginate fiber obtained in S30 is soaked in a finishing agent at 20? C. to 70? C. to allow a post-treatment for 5 min to 60 min.

[0090] In some implementations of the embodiment of the present application, $40 specifically includes: [0091] S401: the alginate fiber obtained in S30 is soaked in a finishing agent at 40? C. to 50? C. to allow a post-treatment for 20 min to 40 min.

[0092] In some implementations of the embodiment of the present application, the finishing agent includes the five-membered cyclic quaternary ammonium salt polymer, and a mass of the five-membered cyclic quaternary ammonium salt polymer is 0.5% to 10% of a mass of the alginate fiber obtained in S30.

[0093] In some implementations of the embodiment of the present application, the finishing agent includes the five-membered cyclic quaternary ammonium salt polymer, and a mass of the five-membered cyclic quaternary ammonium salt polymer is 2% to 8% of a mass of the alginate fiber obtained in S30.

[0094] In some implementations of the embodiment of the present application, the finishing agent includes the five-membered cyclic quaternary ammonium salt polymer, and a mass of the five-membered cyclic quaternary ammonium salt polymer is 4% to 6% of a mass of the alginate fiber obtained in S30.

[0095] In some implementations of the embodiment of the present application, in S20, a pH of the solidification bath is 4.5 to 6.5.

[0096] In some implementations of the embodiment of the present application, in S20, a pH of the solidification bath is 5.

[0097] In some implementations of the embodiment of the present application, in S20, the solidification bath is a calcium chloride aqueous solution with a mass percentage concentration of 1% to 6%.

[0098] In some implementations of the embodiment of the present application, in S20, the solidification bath is a calcium chloride aqueous solution with a mass percentage concentration of 2% to 4%.

[0099] In some implementations of the embodiment of the present application, after S40, the preparation method further includes: [0100] S50: an alginate fiber obtained in S40 is washed and oven-dried.

Example 1

[0101] (1) 40 g of sodium alginate and 1 g of a five-membered cyclic quaternary ammonium salt polymer modifier were prepared into 1,000 g of a spinning solution. [0102] (2) An aqueous solution including 5% (mass percentage) of calcium chloride and 1% (mass percentage) of the five-membered cyclic quaternary ammonium salt polymer modifier was prepared as a solidification bath, and a pH of the solidification bath was adjusted with hydrochloric acid to 5; and the spinning solution was allowed to stand for deaeration and then extruded into the solidification bath at 40? C. to allow solidification molding, and a resulting alginate fiber was drawn and rinsed. [0103] (3) 1 g of the five-membered cyclic quaternary ammonium salt polymer modifier was dissolved in water to prepare 1,000 g of a soaking solution; and the alginate fiber obtained in step (2) was soaked in the soaking solution at 30? C. for 20 min, then rinsed, and dried to obtain a post-treated cross-linked alginate fiber.

Example 2

[0104] (1) 100 g of sodium alginate was dissolved in water to prepare 2,000 g of a spinning solution. [0105] (2) An aqueous solution including 6% (mass percentage) of calcium chloride and 1.5% (mass percentage) of the five-membered cyclic quaternary ammonium salt polymer modifier was prepared as a solidification bath, and a pH of the solidification bath was adjusted with hydrochloric acid to 6; and the spinning solution was allowed to stand for deaeration and then extruded into the solidification bath at 40? C. to allow solidification molding, and a resulting alginate fiber was drawn and rinsed. [0106] (3) 6 g of the five-membered cyclic quaternary ammonium salt polymer modifier was dissolved in water to prepare 1,000 g of a soaking solution; and the alginate fiber obtained in step (2) was soaked in the soaking solution at 40? C. for 10 min, then rinsed, and dried to obtain a post-treated cross-linked alginate fiber.

Example 3

[0107] (1) 300 g of sodium alginate was dissolved in water to prepare 4,000 g of a spinning solution. [0108] (2) An aqueous solution including 4.5% (mass percentage) of calcium chloride was prepared as a solidification bath, and a pH of the solidification bath was adjusted with hydrochloric acid to 5; and the spinning solution was allowed to stand for deaeration and then extruded into the solidification bath at 55? C. to allow solidification molding, and a resulting alginate fiber was drawn and rinsed. [0109] (3) 9 g of the five-membered cyclic quaternary ammonium salt polymer modifier was dissolved in water to prepare 6000 g of a soaking solution; and the alginate fiber obtained in step (2) was soaked in the soaking solution at 50? C. for 8 min, then rinsed, and dried to obtain a post-treated cross-linked alginate fiber.

[0110] For comparison, an ordinary polyquaternary ammonium salt compound that does not have a five-membered ring is adopted as an example in the present application.

Example 4

[0111] (1) 40 g of sodium alginate and 1 g of a diaminourea polymer were prepared into 1,000 g of a spinning solution. [0112] (2) An aqueous solution including 5% (mass percentage) of calcium chloride and 1% (mass percentage) of the diaminourea polymer was prepared as a solidification bath, and a pH of the solidification bath was adjusted with hydrochloric acid to 5; and the spinning solution was allowed to stand for deaeration and then extruded into the solidification bath at 40? C. to allow solidification molding, and a resulting alginate fiber was drawn and rinsed. [0113] (3) 1 g of the diaminourea polymer was dissolved in water to prepare 1,000 g of a soaking solution; and the alginate fiber obtained in step (2) was soaked in the soaking solution at 30? C. for 20 min, then rinsed, and dried to obtain a post-treated cross-linked alginate fiber.

[0114] FIG. 1 is an SEM image of the conventional alginate fiber and FIG. 2 is an SEM image of the dyeable alginate fiber. Dyeing properties of the ordinary alginate fiber and the dyeable alginate fibers obtained in Examples 1, 2, 3, and 4 were shown in Table 1.

TABLE-US-00001 TABLE 1 Properties of the ordinary alginate fiber and the dyeable alginate fibers Dye uptake (%) Direct Direct Direct Breaking Sample scarlet 4BS yellow RS blue 3RL strength Ordinary 4.6 5.3 4.2 3.51 alginate fiber Example 1 85.5 86.9 86.3 3.52 Example 2 88.9 87.6 88.5 3.50 Example 3 91.2 90.3 90.4 3.53 Example 4 34.6 36.6 37.6 2.43

[0115] A dyeing process for the alginate fibers in the examples of the present application was as follows: 0.2 g of a direct dye (direct scarlet 4BS, direct yellow RS, or direct blue 3RL) was weighed and added to 400 g of water, a resulting mixture was stirred for dissolution, then 10 g of an alginate fiber was added at room temperature, and a resulting system was heated at 2? C./min to 80? C. to allow dyeing for 40 min; and then the alginate fiber was washed in a 5 g/L neutral detergent aqueous solution at 90? C. for 10 min, then cooled, washed with water, and then oven-dried at 80? C. or air-dried.

[0116] With reference to the national standard GB/T3921-2008 Textile Color Fastness Test-Soaping Fastness, a soaping fastness of a fiber was tested. Soaping fastnesses of the alginate fibers obtained in Examples 1, 2, 3, and 4 to direct scarlet 4BS, direct yellow RS, and direct blue 3RL all reach or exceed grade 4.

[0117] The terms such as first and second used in the specification and claims of the present application may explicitly or implicitly include one or more corresponding features. In the description of the present application, unless otherwise specified, a plurality of means two or more. In addition, and/or in the specification and claims indicates at least one of the connected objects, and the character / generally indicates an or relationship between associated objects.

[0118] In the description of this specification, the description with reference to the terms one embodiment, some embodiments, an illustrative embodiment, an example, a specific example, or some examples means that specific features, structures, materials, or characteristics described with reference to the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. In addition, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0119] Although the embodiments of the present application have been illustrated and described, a person of ordinary skill in the art can understand that various changes, modifications, replacements, and variants may be made to these embodiments without departing from the principle and purpose of the present application, and the scope of the present application is defined by the claims and equivalents thereof.