KR102033268B1 - Functional Regenerated Cellulose Fibers and Manufacturing Method and Application thereof - Google Patents

Abstract

The present invention provides a functional regenerated cellulose fiber, the functional regenerated cellulose fiber comprises a graphene structure and non-carbon non-oxygen element; The non-carbon non-oxygen element includes Fe, Si and Al elements; The non-carbon nonoxygen element accounts for 0.3 to 5 wt% of the composite containing the carbon nanostructure. The functional regenerated cellulose fibers provided by the present invention are introduced into a conventional regenerated cellulose fiber by introducing a substance containing a graphene structure and a non-carbon non-oxygen element, and in the present invention through a composition of the graphene structure, Fe, Si and Al elements. The regenerated cellulose fibers provided have far-infrared performance, antibacterial and fungicidal various performances, and have a relatively high far-infrared and fungicidal effect by controlling a specific addition ratio.

Description

Functional Regenerated Cellulose Fibers and Manufacturing Method and Application thereof

This application is filed with Chinese Patent Application No. 201510817208.7, filed with Nov. 20, 2015, with Chinese Patent Office, and entitled "functional regenerated cellulose fiber and its manufacturing method and application"; Chinese Patent Application No. 201510849113.3, filed on Nov. 26, 2015 with the Chinese Patent Office, and entitled "Functional Regenerated Cellulose Fiber and Its Manufacturing Method and Application"; The application number 201510819312.x, filed with the Chinese Patent Office on November 20, 2015, claims the priority of the Chinese patent application entitled "Compound and its manufacturing method and polymer material and its manufacturing method". Is incorporated herein by reference.

TECHNICAL FIELD The present invention relates to functional regenerated cellulose fibers, and in particular, to functional regenerated cellulose fibers and processes and applications thereof.

Regenerated cellulose fibers are made from natural polymers by chemical methods and are chemical fibers that are substantially identical in chemical composition to the original polymer. In addition, it may be a regenerated fiber manufactured using cellulose as a raw material and having a structure of cellulose II.

The development of regenerated cellulose fibers can be divided into three stages in total to form third generation products. First generation products are common viscose fibers produced to address cotton deficiency in the early 20th century. The second generation product realized high wet modulus viscose fiber produced by realizing industrialization from the 50s of the 20th century.The main products were Toramomen (later named Polynosic) researched and developed in Japan, and research and development in the United States. One modified high humidity modulus fiber, HWM and Lenzing, is a Modal fiber produced by a new process in the late 80's. From the late sixties, the rapid development of synthetic fiber production technology has satisfied the raw material supply and the low production cost, which greatly influenced the market position of regenerated cellulose fiber. Many research institutes and companies have paid more attention to the development and application of new synthetic fibers. Third generation products represent short-fiber Tencel and long-fiber Newcell, which were introduced in the 90s of the 20th century. People have a new understanding of regenerated cellulose fibers under the influence of factors such as awareness of health and environmental protection and respect for nature, and the physical and chemical performance of the new generation regenerated cellulose fibers have been sufficiently improved. Again, there was rapid growth.

Viscose fiber is one of many regenerated cellulose fibers currently commonly used as textile fibers. Soluble cellulose cellulose xanthate is processed through natural cellulose as a raw material, through alkalizing, aging, and sulfonation. To prepare a viscose by dissolving in a dilute alkali solution, and then prepared by wet spinning (wet spinning). Here, the viscose fiber is mainly made of natural cellulose such as cotton linter, corn cob, wood or bamboo, and is used to produce dissolved pulp having very high cellulose purity through a series of processes such as cooking and bleaching. After the preparation, it is manufactured through process steps such as dipping, pressing, grinding, aging, xanthation, dissolution, mixing, filtration, defoaming, filtration, spinning, post-treatment, drying, and packaging.

The reduction of arable land and the depletion of petroleum resources are increasingly limiting the production of natural and synthetic fibers, so that people value environmental protection during the consumption of textiles and also re-understand and explore the value of regenerated cellulose fibers. It became. In particular, recently, regenerated cellulose fibers with different functions, ie functional regenerated cellulose fibers, further expand the width and depth in textile applications of regenerated cellulose fibers, allowing the application of regenerated cellulose fibers to achieve unprecedented development opportunities. .

Therefore, how to develop a multi-functional regenerated cellulose fiber has become a hot issue and a problem to be addressed widely in the current textile field.

In view of this, it is an object of the present invention to provide a functional regenerated cellulose fiber and its manufacturing process and application, wherein the functional regenerated cellulose fiber, that is, the functional viscose fiber, provided in the present invention not only has a good far-infrared function but also has a relatively high It can have antibacterial and fungal performance.

The present invention provides a functional regenerated cellulose fiber, the functional regenerated cellulose fiber comprises a graphene structure and non-carbon non-oxygen element;

The non-carbon non-oxygen element includes Fe, Si and Al elements;

The Fe, Si and Al elements account for 0.018 wt% to 0.8 wt% of the regenerated cellulose fiber.

Preferably, the graphene structure and the material containing the non-carbon non-oxygen element are introduced in the form of a composite containing carbon nanostructures.

Preferably, the composite containing carbon nanostructures contains graphene, amorphous carbon and non-carbon nonoxygen elements;

In the composite containing the non-carbon non-oxygen element, the non-carbon non-oxygen element includes Fe, Si, and Al elements;

The content of the non-carbon non-oxygen element is 0.5wt% to 6wt% of the composite containing the carbon nanostructure.

Preferably, the carbon element content in the composite containing the carbon nanostructure is ≧ 80 wt%.

Preferably, the non-carbon non-oxygen element accounts for 0.3 to 5 wt% of the composite containing the carbon nanostructure, and more preferably 1.5 to 5 wt%.

Preferably, the non-carbon non-oxygen element is adsorbed on the surface or inside of the carbon nanostructure in any one or two or more forms of a simple substance, oxide or carbide.

As option 1 of the alternatives, the method for preparing the composite containing the carbon nanostructures comprises the following steps:

(1) catalyzing the biomass carbon source under the action of a catalyst to obtain a precursor;

(2) warming the precursor at 140 ° C. to 180 ° C. for 1.5 h to 2.5 h under conditions of a protective gas to obtain a first intermediate;

(3) obtaining a second intermediate by heating the first intermediate to 350 ° C. to 450 ° C. and then warming for 3 h to 4 h under conditions of a protective gas;

(4) raising the second intermediate to 1100 ° C. to 1300 ° C. under the condition of the protective gas, and then insulating for 2 h to 4 h to obtain a third intermediate;

(5) sequentially performing alkali washing, acid washing and washing with water on the third intermediate to obtain a composite; Including;

The temperature increase rate in said steps (3) and (4) is 14 degreeC / min-18 degreeC / min.

Preferably, the biomass carbon source is one kind or two or more kinds of Lignocellulose, cellulose, and Lignin.

As option 2 of the alternatives, the method for preparing a composite containing the carbon nanostructures comprises the following steps:

(1) mixing the biomass carbon source and the catalyst, stirring, catalyzing and drying to obtain a precursor;

(2) Insulating the precursor in a protective gas atmosphere at 280 to 350 ° C. for 1.5 to 2.5 h, then performing temperature programming to 950 to 1200 ° C., and then warming it for 3 to 4 h to obtain a crude product. The temperature increase rate of said temperature programming is between 15 and 20 ° C./min;

(3) washing the crude product, then obtaining a composite containing carbon nanostructures; It includes.

In Method 2, the mass ratio of the biomass carbon source and the catalyst is 1: 0.1 to 10, preferably 1: 0.5 to 5, more preferably 1: 1 to 3;

Preferably, the catalyst is any one or at least two selected from manganese compounds, iron containing compounds, cobalt containing compounds and nickel containing compounds; Preferably the iron-containing compound is any one or a combination of at least two selected from halogen compounds of iron, cyanide of iron and ferrite; Preferably the cobalt containing compound is any one or combination of at least two selected from halogen compounds of cobalt, cobaltite; Preferably, the nickel-containing compound is any one or at least two kinds selected from chlorides of nickel and nickelate; Preferably, the catalyst is ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide (potassium) ferrocyanide), potassium trioxalatoferrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate and nickel acetate Species or a combination of at least two species.

The temperature at the time of stirring and catalyzing is 150 to 200 ° C., the time is ≧ 4 h, preferably 4 to 14 h; Preferably the moisture content in the precursor is 10 wt% or less; Preferably, the temperature increase rate for raising the precursor to 280 to 350 ° C is 3 to 5 ° C / min; Preferably the protective gas atmosphere is any one or a combination of at least two of nitrogen gas, helium gas and argon gas, preferably nitrogen gas; Preferably, the crude product is subjected to acid washing and washing sequentially; The acid washing preferably uses hydrochloric acid at a concentration of 3 to 6 wt%, more preferably hydrochloric acid at a concentration of 5 wt%; The water washing preferably uses deionized water and / or distilled water; Preferably the temperature of the said washing | cleaning is 55-65 degreeC, Preferably it is 60 degreeC.

The biomass carbon source is cellulose and / or lignin, preferably cellulose, more preferably porous cellulose;

Preferably, the porous cellulose is obtained by the following method:

Acid hydrolysis of the biomass resources to obtain lignocellulosic and then porous treatment to obtain porous cellulose; Optionally, porous cellulose is used after bleaching;

Preferably, the biomass resource is any one or a combination of at least two selected from plant and / or agricultural and forest wastes; Any one or a combination of at least two of the preferred agricultural wastes; Preferably the agricultural and forest wastes are any selected from corncob, corncob, sorghum, beet pulp, bagasse, furfural residue, xylose dregs, sawdust, cotton stalks and reeds. 1 type or a combination of at least 2 types, Preferably it is a corn cob.

As a solution 3 of option, the method for preparing a composite containing the carbon nanostructure comprises the following steps:

(1 ') acid hydrolysis of the corncob to obtain lignocellulose, followed by porosity treatment to obtain porous cellulose, bleaching the porous cellulose and preliminary;

(1) After mixing the porous cellulose and the catalyst of the step (1 ') according to the mass ratio 1: 0.5 to 1.5 and stirring at 150 to 200 ℃ catalyzed for 4h or more, until the moisture content of the precursor is lower than 10wt% Drying to obtain a precursor;

(2) In a protective gas atmosphere, the precursor is heated to 280 to 350 ° C. at a rate of 3 to 5 ° C./min and warmed for 2 h, followed by temperature programming to 950 to 1050 ° C. and warmed for 3 to 4 h. Obtaining a product, wherein the temperature ramping rate of said temperature programming is 15-20 [deg.] C./min;

(3) washing the crude product with hydrochloric acid having a concentration of 5wt% at 55-65 ° C, followed by washing with water to obtain a composite containing carbon nanostructures; It includes.

Composites containing carbon nanostructures, prepared by the above method, also belong to one case containing biomass graphene.

The composite containing the carbon nanostructures may typically be, but is not limited to, any one or at least two of materials ①, material ②, material ③ or material ④ having the performance shown in Table a.

Table a

In Table a, IG / ID is the ratio of the peak height of the G and D peaks in the Raman spectrum.

The peak height ratio of G peak and D peak in the composite containing the carbon nanostructure of the present invention is preferably ≥2.0, more preferably ≥3.0, most preferably ≥5.0. Optionally, the peak height ratio of G peak and D peak in the composite containing the carbon nanostructure of the present invention is preferably ≤30, for example 27, 25, 20, 18, 15, 12, 10, 8 , 7 and so on.

Those skilled in the art, the performance index of the composite containing the carbon nanostructures exemplified in Table a all refer to the index of the powder of the composite containing the carbon nanostructures, If the composite containing is a slurry, it will be understood that the index is the index of the powder before the slurry is prepared.

When the composite containing the carbon nanostructures is a powder, the composite powder containing the carbon nanostructures may further have the following performance, in addition to having the performance indexes shown in Table a:

It is black powder, the fineness is uniform and there are no sharply large particles, the water content is ≤3.0%, the particle size is D90≤10.0㎛, the pH is 5.0-8.0, and the apparent density is 0.2-0.4g / cm ³ .

When the composite containing the carbon nanostructures is a slurry, this is a product obtained by dispersing the composite containing the carbon nanostructures in a solvent, and the composite slurry containing the carbon nanostructures, in addition to having the performance index shown in Table a, It can also have the following capabilities:

The solid content is 1.0 to 10.0%, the particle size is D50 ≦ 0.7 μm, the pH is 8.0 to 10.0, the Zeta potential is ≦ -10 mV, and the viscosity is 5.0 to 8.0 mpa · s.

Preferably, the mass of the composite containing the carbon nanostructure accounts for 0.1 wt% to 10 wt% of the mass of the functional regenerated cellulose fiber.

Preferably, the thickness of the graphene structure is less than or equal to 100 nanometers.

Preferably, the graphene structure has one or a combination of two or more of carbon six-membered ring honeycomb lamellar structures having 1-10 layers of 1-10 layers of carbon.

Preferably, the Fe, Si and Al elements account for 0.1 wt% to 0.7 wt% of the regenerated cellulose fiber.

Preferably, the non-carbon non-oxygen element accounts for 0.03 wt% to 1 wt% of the regenerated cellulose fiber.

Preferably, the thickness of the graphene structure is less than or equal to 100 nanometers.

Preferably, the graphene structure has one or a combination of two or more of the six-membered honeycomb honeycomb layered structure having 1 to 10 layers of carbon.

Preferably, the non-carbon non-oxygen element further includes one or two or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co.

The non-carbon nonoxygen element accounts for 0.1 wt% to 1 wt% of the regenerated cellulose fiber.

The present invention also provides a method for producing functional regenerated cellulose fibers, wherein the method for producing functional regenerated cellulose fibers is a pulp impregnation, pressing, grinding, aging, sulfiding, dissolving, ripening, filtration and defoaming step. It includes;

The graphene structure and the non-carbon nonoxygen element are introduced at a stage after the sulfidation step.

Preferably, the graphene structure and the non-carbon nonoxygen element are added in the form of a composite containing carbon nanostructures.

The present invention also provides a method of functional regenerated cellulose fibers, which method comprises dissolving cellulose pulp with NMMO (N-methylmorpholine-N-oxide) solution and containing a graphene structure and a non-carbon non-oxygen element. After obtaining the spinning stock solution, and using the spinning stock solution to prepare a regenerated cellulose fiber.

Preferably, the graphene structure and the material containing a non-carbon non-oxygen element include a composite containing a carbon nano structure.

The present invention also provides an article, wherein the article contains a functional regenerated cellulose fiber as described above, or a regenerated cellulose fiber prepared by a manufacturing method as described above.

Such articles include civilian attire, household textiles, sun protection fabrics or industrial special protective clothing.

Preferably, the household fabric comprises a towel, bath towel, bed sheet and duvet cover.

Compared with the prior art, the present invention has the following beneficial effects:

Compared with the prior art, the functional regenerated cellulose fiber provided by the present invention introduces a material containing graphene structure and non-carbon non-oxygen element into the conventional regenerated cellulose fiber, and mixes the graphene structure, Fe, Si and Al elements. Through the regenerated cellulose fibers provided by the present invention to have a variety of far-infrared performance, antibacterial, and fungi, and to control the specified addition ratio to have a relatively high far-infrared and fungi effect. As a result of the experiment, the far-infrared performance of the regenerated cellulose fibers provided in the present invention can reach a maximum of 0.93, and the antibacterial performance can reach a maximum of 99%.

1 is a flow chart of a filament process of viscose fibers.

In order to further understand the present invention, the following describes a preferred embodiment of the present invention in combination with the embodiments, this description is only for further explaining the features and advantages of the present invention, claims of the present invention It should be understood that this is not a limitation.

All raw materials of the present invention are not particularly limited to the source thereof, and may be purchased in the market or manufactured by a general method familiar to those skilled in the art.

All raw materials of the present invention are not particularly limited in terms of purity, and the present invention preferably uses analytical reagents.

The present invention provides a functional regenerated cellulose fiber, the functional regenerated cellulose fiber comprises a graphene structure and non-carbon non-oxygen element; The non-carbon non-oxygen element includes Fe, Si and Al elements; The Fe, Si and Al elements account for 0.018 wt% to 0.8 wt% of the regenerated cellulose fiber. The Fe, Si and Al elements of the present invention preferably occupy 0.018 wt% to 0.8 wt% of the regenerated cellulose fiber, more preferably 0.1 wt% to 0.7 wt%, and more preferably 0.2 wt% to 0.7 wt%, most preferably 0.3wt% to 0.5wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.45wt%, 0.7wt%, 0.72wt%, 0.78wt%, etc. Can be. In the present invention, the mass fraction of the non-carbon non-oxygen non-hydrogen element in the regenerated cellulose fiber means the content of the non-carbon non-oxygen non-hydrogen element in the regenerated cellulose fiber, that is, the content of the element in the fiber. It preferably does not comprise a late spinning process introduced according to the process conditions, for example a process of coating silicone oil on cellulose.

The non-carbon nonoxygen element accounts for 0.03 wt% to 1 wt% of the regenerated cellulose fiber. The non-carbon non-oxygen element of the present invention preferably accounts for 0.03 wt% to 1 wt% of the regenerated cellulose fiber, more preferably 0.1 wt% to 0.8 wt%, and more preferably 0.2 wt% to 0.7 wt%. %, Most preferably 0.3wt% to 0.5wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.45wt%, 0.7wt%, 0.82wt%, 0.93wt % Etc. can be occupied. In the present invention, the mass fraction of the non-carbon non-oxygen element described above in the regenerated cellulose fiber means the content of the non-carbon non-oxygen element in the regenerated cellulose fiber, ie, a mixture of elements.

The non-carbon non-oxygen element of the present invention preferably comprises a non-carbon non-oxygen non-hydrogen element, and the non-carbon non-oxygen element referred to in the present invention means a mineral element, in particular, referring to the non-carbon non-oxygen element. This is to increase the basis of quotation. The regenerated cellulose fiber contains a certain amount of hydrogen element and the ratio of the non-carbon non-oxygen element to the regenerated cellulose fiber is not limited to 0.03wt% to 1wt and can be appropriately enlarged, for example, to 0.03 to 5wt%. It will be apparent to those skilled in the art.

The present invention is not particularly limited to the graphene structure, and it is only a definition familiar to those skilled in the art, and the graphene structure of the present invention is a combination of various structures including a single layer graphene structure or a multilayer graphene structure. More preferably a combination between monolayer graphene and graphene of different layers; The graphene structure of the present invention is preferably any one or a combination of at least two of the six-membered honeycomb honeycomb layered structure having 1 to 10 layers of carbon, more preferably a single layer, a double layer, or a 3 to 10 layer. Any one or a combination of two or more of the structures. In general, a six-membered honeycomb layered structure of carbon having more than 10 layers and a thickness of 100 nm or less is called graphene nano layered structure, and carbon having more than 10 layers and a thickness of 100 nm or less is manufactured using biomass as a carbon source. The 6-membered ring honeycomb layered structure is called biomass graphene nano layered structure, and the 6-membered ring honeycomb layered structure of carbon with 1-10 layers is called graphene, and the number of layers produced using biomass as carbon source The six-membered honeycomb layered structure of carbon with 1 to 10 layers is called biomass graphene.

In the graphene structure of the present invention, in the microscopic shape, it is preferable that the six-membered honeycomb layered structure of carbon is any one or at least two kinds of microscopically twisted, bent, and folded forms. . The microscopic morphology of the layered structure of the composite is typically obtained by observing using an electron microscope, and may be a transmission electron microscope or a scanning electron microscope. The thickness of the graphene structure of the present invention is preferably less than or equal to 100 nanometers, more preferably less than or equal to 50 nanometers, and most preferably less than or equal to 20 nanometers.

In the functional regenerated cellulose fiber of the present invention, the non-carbon non-oxygen element includes any one or two or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co, more preferably Preferably include P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co; The non-carbon nonoxygen element is present in the form of a single element material and any one or a combination of two or more of the compounds. In the above-mentioned preferred method, the ratio of the non-carbon non-oxygen element to the regenerated cellulose fiber is preferably 0.1 wt% to 1 wt% of the non-carbon non-oxygen element in the regenerated cellulose fiber. It is more preferable that it is 0.8 wt%, It is more preferable that it is 0.3 wt%-0.7 wt%, It is most preferable that it is 0.4 wt%-0.5 wt%.

By way of example, in the regenerated cellulose fiber of the present invention, the non-carbon non-oxygen element is a combination of P, Ca and Na; A combination of Ni, Mn, K and Co; A combination of Mg, Cr, S and Mn; A combination of P, Ca, Na, Ni, Mn, K and Cr; A combination of P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co; And the like. The non-carbon non-oxygen content in the regenerated cellulose fiber is illustratively 0.21 wt%, 0.24 wt%, 0.27 wt%, 0.29 wt%, 0.33 wt%, 0.36 wt%, 0.38 wt%, 0.45 wt%, 0.48 wt % And the like.

The present invention can use the introduction method familiar to those skilled in the art without particular limitation on how to introduce the non-carbon non-oxygen element and the graphene structure into the regenerated cellulose fiber, the present invention is a regenerated cellulose fiber In order to improve the performance, the material containing the non-carbon non-oxygen element and the graphene structure are preferably introduced in the form of a composite containing the carbon nanostructure. The material containing the non-carbon non-oxygen element of the present invention is preferably a nanoscale material of the element, more preferably one or two or more of nanoscale single element materials, nanoscale oxides and nanoscale inorganic compounds.

The mass of the composite containing the carbon nanostructure of the present invention is preferably 0.1wt% to 10wt% of the mass of the regenerated cellulose fiber, more preferably 1wt% to 8wt%, most preferably 3wt% to 5wt% %to be; In the composite containing the carbon nanostructures, the content of the carbon element is preferably greater than or equal to 80 wt%, more preferably 85 wt% to 97 wt%, most preferably 90 wt% to 95 wt%; In the composite containing the carbon nanostructures, the content of the non-carbon non-oxygen element is preferably 0.5 wt% to 6 wt%, more preferably 1 wt% to 5 wt%, and most preferably 2 wt% to 4 wt%. ; In the composite containing the carbon nanostructure, the ratio of the peak height of the G peak to the D peak of the carbon element in the Raman spectrum is preferably 1 to 20, more preferably 3 to 20.

In the composite containing the carbon nanostructure of the present invention, the graphene structure preferably has a six-membered honeycomb layered structure of carbon having a thickness of 100 nm or less, and preferably a six-membered honeycomb shape of carbon having a thickness of 20 nm or less. It has a layered structure, More preferably, it has any 1 type or at least 2 types of combination of the carbon 6-membered honeycomb layered structure of 1-10 layers, Preferably it is a single layer, a double layer, or a 3-10 layer structure. Having any one or a combination of at least two kinds thereof; Preferably, the six-membered honeycomb layered structure of carbon in the composite exhibits any one or at least two combinations of microscopically twisted, bent, folded forms.

The composite containing the carbon nanostructure of the present invention preferably comprises a graphene structure and amorphous carbon; The non-carbon nonoxygen element is adsorbed on the surface or inside of the carbon nanostructure in the form of any one or a combination of two or more of a single element material, an oxide and a carbide. The amorphous carbon further contains two-dimensional graphite layers or three-dimensional graphite microcrystals, and there are a large amount of irregular bonds at the edges of the microcrystals, and in addition to a large amount of sp2 carbons, it further includes a few sp3 carbons. In fact, their internal structure is not really amorphous but crystals having a structure like graphite, except that the layered structure formed by the hexagonal cyclic plane of carbon atoms is messy and irregular, defects are formed in crystals, and mostly amorphous carbon The molecular fragments of the graphite layered structure may be abbreviated as "turbostratic structures" because they are irregularly accumulated in parallel with each other. Between the layers or the pieces are connected by carbon atom bonds of tetrahedral bond method of diamond structure.

Preferably, the graphene structure is not activated or modified with respect to the material introducing the graphene structure in the process of introducing the graphene structure in the preparation of the modified regenerated cellulose fibers.

There is no particular limitation on the manufacturing method of the composite containing the carbon nanostructure of the present invention.

Preferably, the composite containing carbon nanostructures contains graphene, amorphous carbon and non-carbon nonoxygen elements; The non-carbon non-oxygen element in the composite containing the carbon nanostructure includes Fe, Si and Al elements; The non-carbon nonoxygen element content is 0.5wt%-6wt% of the composite containing a carbon nanostructure.

The content of the carbon element in the composite containing the carbon nanostructure of the present invention is ≥80wt%, for example 82wt%, 86wt%, 89wt%, 91wt%, 94wt%, 97wt%, 99wt% and the like, preferably 85 to 97 wt%, more preferably 90 to 95 wt%.

Preferably, the non-carbon non-oxygen element accounts for 0.3 wt% to 5 wt% of the composite containing the carbon nanostructure, preferably accounts for 0.5 to 5 wt%, and more preferably 1.5 to 5 wt%. In some specific embodiments of the present invention, the non-carbon non-oxygen element is 0.7 wt%, 1.1 wt%, 1.3 wt%, 1.6 wt%, 2 wt%, 2.8 wt%, 3.5 wt% of the composite containing carbon nanostructures. , 4.2 wt%, 5.3 wt% or 5.8 wt%.

Preferably, the non-carbon non-oxygen element is adsorbed on the surface or inside of the carbon nanostructure in any one or two or more forms of a simple substance, oxide or carbide.

The present invention is not particularly limited to a method for producing a composite containing the carbon nanostructure, and may be similar to the method for preparing a composite familiar to those skilled in the art.

As Method 1 of the alternatives, the method for preparing a composite containing carbon nanostructures comprises the following steps (indicated by Method (1)):

(1) catalyzing the biomass carbon source under the action of a catalyst to obtain a precursor;

(2) warming the precursor at 140 ° C. to 180 ° C. for 1.5 h to 2.5 h under conditions of a protective gas to obtain a first intermediate;

(3) obtaining a second intermediate by heating the first intermediate to 350 ° C. to 450 ° C. and then warming for 3 h to 4 h under conditions of a protective gas;

(4) raising the second intermediate to 1100 ° C. to 1300 ° C. under the condition of the protective gas, and then insulating for 2 h to 4 h to obtain a third intermediate;

(5) sequentially performing alkali washing, acid washing and washing with respect to the third intermediate to obtain a composite; Including;

The temperature increase rate in the said (3) and (4) is 14 degreeC / min-18 degreeC / min.

The carbon source is preferably a biomass carbon source, and the biomass resource is any one or a combination of at least two selected from plant and / or agricultural and forest wastes; Preferably any one or a combination of at least two of conifers, hardwoods, hardwoods and agricultural wastes; The agricultural and forest waste is preferably any one selected from corncob, corncob, tree, beet pulp, bagasse, furfural dregs, xylose dregs, sawdust, cotton rods, fruit husks and reeds. Or a combination of at least two species, preferably corncobs. The biomass carbon source is selected from lignocellulose, cellulose and / or lignin, preferably cellulose and / or lignin, more preferably cellulose, and more preferably porous cellulose.

Preferably, the graphene structure is not activated or modified with respect to the material into which the graphene structure is introduced during the production of regenerated cellulose fibers.

The mass ratio of the biomass carbon source and the catalyst is 1: 0.1 to 10, for example 1: 0.2, 1: 0.5, 1: 0.8, 1: 1.1, 1: 1.5, 1: 2, 1: 3, 1: 4 , 1: 5, 1: 6, 1: 7, 1: 8, 1: 9, and the like, preferably 1: 0.5 to 5, and more preferably 1: 1 to 3.

Preferably, the catalyst is any one or at least two selected from manganese compounds, iron containing compounds, cobalt containing compounds and nickel containing compounds; The iron-containing compound is any one or a combination of at least two selected from a halogen compound of iron, a cyanide of iron and a ferrite; The cobalt-containing compound is any one or a combination of at least two selected from a cobalt halogen compound and cobaltite; The nickel-containing compound is any one or a combination of at least two selected from the salts of nickel and nickelate; More preferably, the catalyst is ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide ( potassium ferrocyanide), potassium trioxalatoferrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate and nickel acetate 1 type or a combination of at least 2 types. Illustratively, the catalyst is a combination of ferric chloride and ferric nitrate, ferrous nitrate, a combination of ferric sulfate and cobalt chloride, a combination of cobalt acetate, nickel chloride and nickel sulfate, potassium ferricyanide, ferro A combination of potassium cyanide, potassium trioxalate (III) acid and ferrous nitrate, a combination of cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate.

Preferably, the temperature at the time of stirring and catalyzing in step (1) is 150 to 200 ° C., time is ≧ 4 h, preferably 4 to 14 h; The moisture content in the precursor is preferably 10 wt% or less; The temperature increase rate for raising the precursor in step (2) to 280 to 350 ° C. is preferably 3 to 5 ° C./min; The protective gas atmosphere is any one or a combination of at least two of nitrogen gas, helium gas and argon gas, preferably nitrogen gas; Washing the crude product in step (3) is proceeding with acid washing and washing sequentially; The acid wash preferably uses hydrochloric acid at a concentration of 3 to 6 wt% and more preferably hydrochloric acid at a concentration of 5 wt%; The water washing preferably uses deionized water and / or distilled water; The temperature of the said washing | cleaning is 55-65 degreeC, Preferably it is 60 degreeC.

The preparation step of the present invention preferably includes the following steps specifically:

First, the biomass carbon source and the catalyst are mixed, stirred and catalyzed, and then dried to obtain a precursor.

Next, in a protective gas atmosphere, the precursor was kept at 140 to 180 ° C. for 1.5 to 2.5 h to obtain a first intermediate; In some specific embodiments of the present invention, the temperature is 142 ° C, 148 ° C, 155 ° C, 160 ° C, 172 ° C or 178 ° C; The heat retention time is 1.6h, 1.8h, 2h, 2.2h or 2.4h.

Thereafter, temperature programming is performed from 350 ° C. to 450 ° C., followed by warming for 3 h to 4 h to obtain a second intermediate. In some specific embodiments of the invention, the temperature is 360 ° C., 370 ° C., 380 ° C., 390 ° C., 410 ° C., 420 ° C., 430 ° C. or 440 ° C .; The warming time is 3.1 h, 3.3 h, 3.5 h, 3.8 h or 3.9 h.

Then warming to 1100-1300 ° C. and warming for 2 h-4 h to obtain a third intermediate, ie, a crude product; In some specific embodiments of the invention the temperature is 1130 ° C., 1170 ° C., 1210 ° C. or 1280 ° C .; The time is 2.2h, 2.4h, 2.6h, 2.8h, 3.0h, 3.2h, 3.4h, 3.6h or 3.8h.

The temperature increase rate of the temperature programming is 14 ° C./min to 18 ° C./min, and in some specific embodiments of the invention the room temperature rate is 15 ° C./min, 16 ° C./min or 17 ° C./min.

Finally, the third intermediate (ie, the crude product) is subjected to alkali washing, acid washing, and washing to obtain a composite.

In the present invention, the biomass carbon source is preferably one or two or more of lignocellulose, cellulose and lignin, more preferably lignocellulose, cellulose or lignin.

In the present invention, the mass ratio of the biomass carbon source and the catalyst is 1: (0.5 to 5), preferably 1: (1 to 3); In some specific embodiments of the invention the ratio is 1: 0.5, 1: 1 or 1: 3.

In the present invention, the catalyst is any one or a combination of at least two selected from halogen compounds of manganese, iron-containing compounds, cobalt-containing compounds and nickel-containing compounds.

Preferably, the iron-containing compound is any one or a combination of at least two selected from halogen compounds of iron, cyanide of iron and ferrite. The ferrite is a salt of an organic acid containing iron or a salt of an inorganic acid containing iron. The halogen compound of iron may be ferric chloride and / or iron bromide.

Preferably, the cobalt-containing compound is any one or a combination of at least two selected from halogen compounds of cobalt and cobaltite. The cobaltite is a salt of an organic acid containing a cobalt element or a salt of an inorganic acid containing a cobalt element. The cobalt-containing halogen compound may be cobalt chloride and / or cobalt bromide.

Preferably, the cobalt-containing compound is any one or a combination of at least two selected from the salts of cobalt and cobaltite. The cobaltite is a salt of an organic acid containing a cobalt element or a salt of an inorganic acid containing a cobalt element. The nickel-containing halogen compound may be nickel chloride and / or nickel bromide.

More preferably, the catalyst is ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, trioxalato iron (III) any one or a combination of at least two selected from potassium acid, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate and nickel acetate.

Typical examples of the combination of the catalysts of the present invention include a combination of ferrous chloride and ferric sulfate, a combination of potassium ferricyanide and potassium trioxalato iron (III) acid, cobalt chloride, cobalt nitrate and ferric chloride. Combinations of cobalt sulfate, cobalt acetate and nickel nitrate, and combinations of ferric chloride, cobalt chloride and cobalt acetate.

The temperature at which the catalyzing treatment is carried out while stirring is 150 to 200 ° C, for example, 160 ° C, 170 ° C, 180 ° C, 190 ° C, and the like, and the time is ≥4h, preferably 4h to 14h, In some specific embodiments the time is 4.2h, 7h, 9h, 12h, 16h, 19h, 23h and the like.

Preferably, the moisture content in the precursor is 10 wt% or less, and in some specific embodiments of the invention the moisture content is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%. %, 10 wt%, and the like.

Preferably, the protective gas atmosphere is any one or a combination of at least two of nitrogen gas, helium gas, and argon gas, and preferably nitrogen gas.

Preferably, the acid wash uses an aqueous hydrochloric acid solution having a concentration of 3 wt% to 6 wt%, more preferably an aqueous hydrochloric acid solution having a concentration of 5 wt%; The water washing preferably uses deionized water and / or distilled water; The alkali wash is used in an aqueous sodium hydroxide solution having a concentration of 5wt% to 15wt%, more preferably using an aqueous sodium hydroxide solution having a concentration of 10wt%.

Preferably, the said washing temperature is 55-65 degreeC, for example, 56 degreeC, 57 degreeC, 58 degreeC, 60 degreeC, 63 degreeC, etc., Preferably it is 60 degreeC.

The biomass carbon source is cellulose and / or lignin, preferably cellulose, more preferably porous cellulose.

The porous cellulose of the present invention can be obtained through the existing technology, the conventional technology to obtain a typical porous cellulose, for example, there is a porous cellulose prepared by the method disclosed in the patent publication number CN104016341A, cellulose prepared by the method disclosed in CN103898782A It is not limited to this.

Preferably, the porous cellulose is obtained in the following way:

Acid hydrolysis of the biomass resources to obtain lignocellulosic and then porous treatment to obtain porous cellulose; Optionally, porous cellulose is used after bleaching.

The biomass resource is any one or a combination of at least two selected from plant and / or agricultural and forest wastes; Preferably any one or a combination of at least two of the agricultural and forest wastes.

Preferably, the agricultural and forest wastes may be any one selected from corn cob, corn cob, corn cob, beet pulp, bagasse, furfural dregs, xylose dregs, sawdust, cotton rods and reeds. It is a combination of at least two species, preferably corn cobs.

Typical examples of the combination of the above biomass resources of the present invention include a combination of corncob and corncob, bagasse, a combination of sawdust and sawdust, a combination of beetroot, bagasse and corncob, sorghum, beetroot and xylose waste. Combinations and the like, but are not limited thereto.

Composites containing the carbon nanostructures of the present invention may be prepared by a variety of methods, including:

As Method 2 of the alternatives, the method for preparing the composite containing the carbon nanostructures comprises the following steps (indicated by Method (2)):

(1) mixing the biomass carbon source and the catalyst, stirring, catalyzing and drying to obtain a precursor;

(2) In the protective gas atmosphere, the precursor was kept at 280 to 350 ° C. for 1.5 to 2.5 h, followed by temperature programming to 950 to 1200 ° C., and then at 3 to 4 h to obtain a crude product. A temperature increase rate of 15 to 20 ° C / min;

(3) washing the crude product, then obtaining a composite containing carbon nanostructures; It includes.

Method 2 of the selectable options, wherein the mass ratio of the biomass carbon source and the catalyst is 1: 0.1 to 10, preferably 1: 0.5 to 5, more preferably 1: 1 to 3;

Preferably, the catalyst is any one or at least two selected from manganese compounds, iron containing compounds, cobalt containing compounds and nickel containing compounds; Preferably the iron-containing compound is any one or a combination of at least two selected from halogen compounds of iron, cyanide of iron and ferrite; Preferably, the cobalt containing compound is any one or a combination of at least two selected from halogen compounds of cobalt and cobaltite; Preferably, the nickel-containing compound is any one or at least two kinds selected from chlorides of nickel and nickelate; Preferably, the catalyst is ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide (potassium) ferrocyanide), potassium trioxalatoferrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate and nickel acetate Species or a combination of at least two species.

The temperature at the time of stirring and catalyzing is 150 to 200 ° C., and the time is ≧ 4 h, preferably 4 to 14 h; Preferably the moisture content in the precursor is 10 wt% or less; Preferably, the temperature increase rate for raising the precursor to 280 to 350 ° C is 3 to 5 ° C / min; Preferably the protective gas atmosphere is any one or a combination of at least two of nitrogen gas, helium gas and argon gas, preferably nitrogen gas; Preferably, the crude product is subjected to acid washing and washing sequentially; The acid washing preferably uses hydrochloric acid at a concentration of 3 to 6 wt%, more preferably hydrochloric acid at a concentration of 5 wt%; The water washing preferably uses deionized water and / or distilled water; Preferably the temperature of the said washing | cleaning is 55-65 degreeC, Preferably it is 60 degreeC.

The biomass carbon source is cellulose and / or lignin, preferably cellulose, more preferably porous cellulose.

Preferably, the porous cellulose is obtained by the following method:

Acid hydrolysis of the biomass resources to obtain lignocellulosic and then porous treatment to obtain porous cellulose; Optionally, porous cellulose is used after bleaching.

Preferably, the biomass resource is any one or a combination of at least two selected from plant and / or agricultural and forest wastes; Any one or a combination of at least two of the preferred agricultural wastes; Preferably the agricultural and forest wastes are any one or at least one selected from corncob, corncob, sorghum, beet pulp, bagasse, furfural dregs, xylose dregs, sawdust, cotton rods and reeds. It is a combination of 2 types, Preferably it is corn cobs.

As Method 3 of the alternatives, the method for preparing the composite containing the carbon nanostructures comprises the following steps (indicated by Method (3)):

(1 ') acid hydrolysis of the corncob to obtain lignocellulose, followed by porosity treatment to obtain porous cellulose, bleaching the porous cellulose and preliminary;

(1) After mixing the porous cellulose and the catalyst of the step (1 ') according to the mass ratio 1: 0.5 to 1.5 and stirring at 150 to 200 ℃ catalyzed for 4h or more, until the moisture content of the precursor is lower than 10wt% Drying to obtain a precursor;

(2) In a protective gas atmosphere, the precursor is heated to 280 to 350 ° C. at a rate of 3 to 5 ° C./min and warmed for 2 h, followed by temperature programming to 950 to 1050 ° C. and warmed for 3 to 4 h. Obtaining a product, wherein the temperature ramping rate of said temperature programming is 15-20 [deg.] C./min;

(3) washing the crude product with hydrochloric acid having a concentration of 5wt% at 55-65 DEG C, followed by washing with water to obtain a composite containing carbon nanostructures; It includes.

Composites containing carbon nanostructures produced by the above methods (methods (1), (2), and (3)) also belong to one case containing biomass graphene.

Composites containing carbon nanostructures, prepared by the above method, also belong to one case including biomass graphene.

Composites containing the carbon nanostructures of the present invention may also be prepared by a variety of methods, including:

Method (4): Activated carbon is obtained by the conventional process using biomass resources, and the type and content of trace elements in different plants are very different. The content is controlled and graphene is introduced on the basis so that the non-carbon non-oxygen element occupies 0.5wt% to 6wt% of the composite.

Method (5): purchase lignin on the market, carbonize in an inert gas or proceed with insufficient graphitization reaction, and then add graphene, followed by nano P, Si, Ca, Al, Na, A combination of any three or more of Fe, Ni, Mn, K, Mg, Cr, S, or Co is introduced to control the content to 0.5wt% to 6wt%.

Method (6): Graphene is introduced after carbonization of some organic wastes, such as phenolic resin foam boards, followed by nano P, Si, Ca, Al, Na, Fe, Ni, Mn A combination of any three or more of any of K, Mg, Cr, S or Co and more elements is introduced to control the content to 0.5wt% to 6wt%.

Method (7): Activated carbon and graphene are added to nanographite, followed by any three of nanoP, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or Co And a combination of more elements to control the content to 0.5wt% to 6wt%.

The composite containing carbon nanostructures, as claimed in the present invention, is not limited to the above production method. In the product of the composite containing the carbon nanostructure to be claimed in the present invention manufactured by the above method, far infrared rays performance and antimicrobial performance were obtained by the methods (1) to (3) than those obtained by the methods (4) to (7). Although excellent in all downstream products, they can be uniformly dispersed in functional regenerated cellulose fibers without the need for activating or modifying composites containing carbon nanostructures, thereby achieving a certain effect, in particular, methods (1) to ( 3) is more so obtained.

The present invention introduces a material containing a non-carbon non-oxygen element and a graphene structure through a method of a composite containing carbon nanostructures, and does not need to pretreat (eg, activate, modify, etc.) materials introduced during the introduction process. It can be effectively combined with regenerated cellulose, which can lead to improved far-infrared and bactericidal effect separately.

Method 1 for measuring the content of non-carbon nonoxygen element

Composites containing carbon nanostructures are decomposed into nitric acid (ρ = 1.42 g / mL), perchloric acid (ρ = 1.67 g / mL), hydrofluoric acid (ρ = 1.16 g / mL), insulated in nitric acid medium, and purified After quantitative analysis of the P, Si, Ca, Al, Na, etc. in the composite containing the carbon nanostructure using a standard curve method with an inductively coupled plasma atomic emission spectrometer.

Method 2: measuring the content of non-carbon nonoxygen element

The national standard GB / T17359-1998, the electronic probe and the scanning electron microscope general rules of X-ray energy spectrum quantitation are used.

The present invention is not limited to the measurement method of the non-carbon non-oxygen element, all known or new measurement methods in the art can be applied to the present invention, the present invention provides a method for measuring the content of two non-carbon non-oxygen element. Preferably, it is measured by "Method 1 for measuring non-carbon non-oxygen element content", and in Example of the present invention, "Method 1 for measuring non-carbon non-oxygen element content".

Infrared detection data of the composite containing the carbon nanostructure is in accordance with GBT7286.1-1987 <Test method for total normal emittance of metals and nometallic metetials.

The fungal detection data of the composite containing the carbon nanostructure is according to the GB / T20944.3-2008 verification method ( Staphylococcus aureus as an example).

The present invention also provides a method for producing functional regenerated cellulose fibers, wherein the method for producing functional regenerated cellulose fibers comprises pulp dipping, pressing, grinding, aging, sulfiding, dissolving, ripening, filtration and defoaming steps;

The material containing the graphene structure and the non-carbon nonoxygen element is introduced after the sulfidation step.

The graphene structure of the present invention is preferably introduced in the form of a mixture, where it preferably comprises a non-graphene structural component, such as an amorphous carbon component. Preferably, the graphene structure and the non-carbon nonoxygen element are added in the form of a composite containing carbon nanostructures.

More preferably, the material containing the graphene structure and the non-carbon non-hydrogen element is introduced in the dissolution step, more preferably a dilute alkali solution for dissolving cellulose xanthate in advance. Dissolved in.

The composite containing the carbon nanostructures may typically be, but is not limited to, any one or at least two of materials ①, material ②, material ③ or material ④ having the performance shown in Table a.

Table a

In Table a, IG / ID is the ratio of the peak height of the G and D peaks in the Raman spectrum.

Those skilled in the art, the performance index of the composite containing the carbon nanostructures exemplified in Table a all refer to the index of the powder of the composite containing the carbon nanostructures, If the composite containing is a slurry, it will be understood that the index is the index of the powder before the slurry is prepared.

When the composite containing the carbon nanostructures is a powder, the composite powder containing the carbon nanostructures may further have the following performance, in addition to having the performance indexes shown in Table a:

It is black powder, the fineness is uniform and there are no sharply large particles, the water content is ≤3.0%, the particle size is D90≤10.0㎛, the pH is 5.0-8.0, and the apparent density is 0.2-0.4g / cm ³ .

When the composite containing the carbon nanostructures is a slurry, this is a product obtained by dispersing the composite containing the carbon nanostructures in a solvent, and the composite slurry containing the carbon nanostructures, in addition to having the performance index shown in Table a, It can also have the following capabilities:

The solid content is 1.0 to 10.0%, the particle size is D50 ≦ 0.7 μm, the pH is 8.0 to 10.0, the Zeta potential is ≦ -10 mV, and the viscosity is 5.0 to 8.0 mpa · s.

The present invention dissolves cellulose pulp with an N-Methylmorpholine-N-oxide (NMMO) solution, and introduces a graphene structure and a substance containing a non-carbon non-oxygen element to form a spinning stock solution. After the obtained, there is provided a method of functional regenerated cellulose fibers comprising the step of producing regenerated cellulose fibers using the spinning stock solution.

The regenerated cellulose fiber production process is a spinning process using an N-methylmorpholine-N-oxide (NMMO) solvent. A specific method involves the direct mixing of cellulose pulp with N-methylmorpholine-N-oxide (NMMO) and the addition of additives (eg CaCl ₂ ) and antioxidants (eg PG) to oxidatively decompose the fibers during dissolution. To control the viscosity of the solution and improve the performance of the fibers. The moisture content is controlled to less than 133% to reach the most desirable solubility. After dissolving at 85-125 ° C. to obtain a relatively high concentration of the solution, the solution was filtered and defoamed, wet or dry spun at 88-125 ° C. to solidify in a low temperature aqueous solution or water / NMMO system, and then stretch. Fibers are prepared by the following steps: washing, washing, degreasing, drying and solvent recovery. Into the cellulose pulp, a substance containing a graphene structure and a non-carbon nonoxygen element is introduced.

The article provided by the present invention contains a functional regenerated cellulose fiber according to any one of the above technical solutions, or a regenerated cellulose fiber prepared by a manufacturing method according to any one of the above technical solutions; Preferably the article is characterized in that it comprises civilian clothing, household textiles, sun protection fabrics or industrial special protective clothing.

The functional regenerated cellulose fiber and its manufacturing process and applied article provided by the present invention, by introducing a graphene structure and a non-carbon non-oxygen element into the conventional regenerated cellulose fiber, and through the composition of the graphene structure, Fe, Si and Al elements The regenerated cellulose fibers provided by the present invention have far-infrared performance, antibacterial and fungicidal various performances, and have a relatively high far-infrared and fungicidal effect by controlling a specific addition ratio. In addition, the present invention introduces a material containing a graphene structure and a non-carbon non-oxygen element through the method of a composite containing a carbon nanostructure, and pretreatment (eg, activation, modification, etc.) to the material introduced during the introduction process It can be effectively combined with the regenerated cellulose without having to do so, it can bring about improved far-infrared and bactericidal effect separately.

Method for measuring the content of non-carbon non-oxygen and non-hydrogen element of the functional fiber of the present invention 1:

The fiber was decomposed into nitric acid (ρ = 1.42g / mL), perchloric acid (ρ = 1.67g / mL), hydrofluoric acid (ρ = 1.16g / mL), insulated in nitric acid medium, defined, and then inductively coupled A plasma atomic emission spectrometer is used to quantitatively analyze elemental contents such as P, Si, Ca, Al, and Na in composites containing carbon nanostructures using the standard curve method.

It should be noted that before detecting the fibers, the effects of the process such as oiling are removed at a later stage. The influences mainly include silicone oil, and the removal method is water boiling or washing several times. .

Method 2 for measuring the content of non-carbon non-oxygen non-hydrogen elements

The national standard GB / T17359-1998, the electronic probe and the scanning electron microscope general rules of X-ray energy spectrum quantitation are used.

The present invention is not limited to the measurement method of the non-carbon non-oxygen non-hydrogen element, any known or new measurement method of the art can be applied to the present invention, in the present invention a method for measuring the non-carbon non-oxygen non-hydrogen element It is provided in two ways and is preferably measured by "Method 1 for measuring non-carbon non-oxygen and non-hydrogen element content", and in Example of the present invention, "Method 1 for measuring non-carbon non-oxygen and non-hydrogen element content".

The non-carbon non-oxygen element of the present invention is an element whose fiber inside cannot be removed by simple washing several times.

The present invention detects the far infrared and antimicrobial performance of the functional fiber and the detection standard is as follows:

Herein, the infrared detection data is verified according to the FZ / T64010-2000 verification method of the National Quality Supervision and Inspection Center of textile products;

Antimicrobial data are as follows: GB / T20944.3-2008 Verification method of the National Textile Products Supervision and Inspection Center.

As a result of the experiment, the far-infrared performance of the regenerated cellulose fibers provided in the present invention can reach a maximum of 0.93, and the antibacterial performance can reach a maximum of 99%.

In order to further explain the present invention, in the following, the functional regenerated cellulose fiber provided by the present invention in combination with the embodiment and its manufacturing process and application will be described in detail, but the protection scope of the present invention is described in the following examples. It is not limited.

Example 1

Composites containing carbon nanostructures are as follows:

(1) mixing corncob cellulose and ferrous chloride according to a mass ratio of 1: 1, stirring at 150 ° C., catalyzing for 4 h, and drying the precursor moisture content to 10 wt% to obtain a precursor;

(2) In the protective gas atmosphere, the precursor was heated to 170 ° C. at a rate of 3 ° C./min and warmed for 2 h, followed by temperature programming to 400 ° C. and warmed for 3 h, and then heated up to 1200 ° C. and warmed for 3 h. Obtaining a crude product, wherein the temperature increase rate of the temperature programming is 15 ° C./min;

(3) washing the crude product with a sodium hydroxide solution having a concentration of 10% and hydrochloric acid at 4 wt% at 55-65 ° C., followed by washing with water to obtain a carbon nanostructured composite; Get through

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 1 showed that the peak height ratio of G peak and D peak was 3;

As a result of detection by the measurement method 1 of non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains P, Si, Ca, Al, Fe, Mg elements and the content is 3.2wt%.

Example 2

The corncob cellulose of Example 1 is replaced with reed cellulose.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 2 showed that the peak height ratio of G peak and D peak was 4.8;

As a result of detection by the measurement method 1 of the non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains Si, Ca, Al, Fe, Mg and S elements and the content was 2.5wt%.

Example 3

The corncob cellulose of Example 1 is replaced with poplar cellulose.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 3 showed that the peak height ratio of the G peak and the D peak was found to be 4.6;

As a result of detection by the measurement method 1 of non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains P, Si, Al, Na, Fe, and Ni elements, and its content is 3.5wt%.

Example 4

Corncob cellulose of Example 1 is replaced with corncob lignin.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 4 showed that the peak height ratio of G peak and D peak was 2.8;

As a result of detection by the measurement method 1 of the non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, K elements and the content is 2.7wt%. to be.

Example 5

Corn cob spare material is added to three times 44% zinc chloride solution (adjusted to pH = 1 with hydrochloric acid), stirred and impregnated sufficiently, and allowed to stand for 5 hours for absorption. After letting it stand to absorb for a while to absorb all the zinc chloride, transfer to an open and wide-bottomized carbonization furnace, seal and carbonize, carbonize at 400 ℃ for 3 hours and thoroughly stir once every 30 minutes, before stirring The temperature of the carbonization furnace is lowered to 100 ° C or lower. After stirring, the temperature is again raised and sealed to proceed with carbonization. The carbonization process is carried out until black cokes are burned. The material is taken out and cooled, impregnated with twice the amount of zinc chloride solution (pH = 1) and stirred sufficiently to allow the zinc chloride solution to be absorbed, transferred to an activation furnace and activated at 650 ° C. for 70 minutes before Remove and cool, transfer to wooden barrel and add equivalent 40% ammonium chloride solution. Then thoroughly stirred, washed and left to purify, aspirate the supernatant by siphoning, sequentially wash with 30%, 12% and 3% ammonium chloride and then again equilibrate with 30% hydrochloric acid Stir and wash, filter the carbon particles and place in a pot, add equal volume of water, boil and wash until ammonium chloride is gone. The mixture was heated, evaporated and roasted with stirring to remove moisture, dried and pulverized to obtain activated carbon through a 120 mesh sieve. Graphene is introduced on the basis, and nanomaterials containing P, Si, Ca, Al, Fe, and Mg are added, and the content is 3.5wt%, specifically, nano pentoxide, nano silicon powder (Silicon Power), nano carbonate Materials containing calcium, nano aluminum oxide, nano iron and nano magnesium powders are added to obtain a composite containing carbonate nanostructures.

Example 6

The lignin is sealed and carbonized in a carbonization furnace, carbonized at 400 ° C. for 3 hours, and thoroughly stirred once every 30 minutes. The temperature of the carbonization furnace is lowered below 100 ° C. before stirring. After stirring, the temperature was again raised to 2200 ° C. under argon gas and sealed to graphitize for 2 h, and the material was taken out and cooled. Then, the mixture was washed with 30%, 12%, and 3% ammonium chloride solution, and then washed again in an equivalent amount. Stirred with 30% hydrochloric acid, washed, dried and pulverized to obtain a mixed carbon material of graphite and activated carbon via a 120 mesh sieve. On the basis, graphene is introduced and nanomaterial containing P, Si, Ca, Al, Fe, Mg is added, and the content is 3.3wt%. Specifically, composites containing carbon nanostructures are obtained by introducing nanomaterials such as nanodioxide, nano silica, nano calcium carbonate, nano aluminum powder, nano iron and nano magnesium carbonate.

Example 7

Primary carbonization at 330 ° C. to remove hydrogen and oxygen elements using a phenol resin foam board, followed by high temperature carbonization at 700 ° C., and introduction of graphene on the basis of P, Si, Ca, Al, Fe, and Mg A nanomaterial is added, but the content is 3.4 wt% to obtain a composite containing carbon nanostructures.

Example 8

Activated carbon and graphene are added to the nanographite, and a nanomaterial including P, Si, Ca, Al, Fe, and Mg is added, and the content thereof is 3.3 wt%, specifically, nano pentoxide, nano silicon powder, nano aluminum powder, Nano iron and nano magnesium powder are added to obtain a composite containing carbon nano structures.

Example 9

(1) Preparation of Porous Cellulose:

The aqueous solution of corncob was adjusted to pH = 3 with sulfuric acid at 90 ° C. and deposited for 10 min and hydrolyzed to obtain lignocellulosic, the mass of sulfuric acid being 3% of the mass of corncob. Next, the obtained lignocellulosic was deposited at 70 ° C. in acid sulfite for 1 h to obtain porous cellulose, wherein the acid is sulfuric acid and the sulfite is magnesium sulfite, and the mass of sulfuric acid is 4% of the lignocellulosic mass and the liquid- The solids ratio is 2: 1 and is prepared for preliminary use (see the patent document of publication number CN104016341A for this step).

(2) The porous cellulose obtained in step (1) was mixed with ferric chloride according to the mass ratio 1: 1, stirred at 200 ° C. for 8 h, catalyzed, and dried until the precursor moisture content reached 4 wt%. Get; Next, the precursor was heated to 350 ° C. at a rate of 5 ° C./min in a protective gas atmosphere to warm for 2 h, followed by temperature programming up to 1000 ° C., and warmed for 4 h to obtain a crude product; The temperature increase rate of the temperature programming is 20 ° C / min. The crude product is acid washed with hydrochloric acid having a concentration of 4wt% at 55-65 ° C and washed with water to obtain a composite containing carbon nanostructures.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 9 showed a peak height ratio of G peak and D peak as 6.8;

The composite containing carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg, Fe, Mg, K elements, and the content is 3.5wt%. to be.

Example 10

In distinction from Example 9, in step (2):

The porous cellulose obtained in step (1) of Example 9 according to the mass ratio 1: 5 was mixed with manganese chloride, stirred at 180 ° C. for 5 h, catalyzed, and dried until the precursor moisture content was 6 wt% to obtain a precursor. ; Next, the precursor was warmed up to 300 ° C. at a rate of 4 ° C./min in a protective gas atmosphere to warm for 3 h, followed by temperature programming up to 1000 ° C., and warmed for 4 h to obtain crude product; The temperature increase rate of the temperature programming is 17 ° C / min. The crude product was acid washed with hydrochloric acid having a concentration of 5 wt% at 60 ° C. and washed with water to obtain a composite containing carbon nanostructures.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 10 showed that the peak height ratio of G peak and D peak was 15;

As a result of detection by the measurement method 1 of non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg, Mn, S elements, and the content is 5.7 wt%.

Example 11

(1) The straw was pulverized and pretreated, and the treated straw was cooked with an organic acid solution of formic acid and acetic acid having a total acid concentration of 80 wt%. The mass ratio of acetic acid and formic acid in the organic acid solution of the present example was 1:12, and the raw material was prepared. Before the addition, hydrogen peroxide (H ₂ O ₂ ), which accounts for 1 wt% of the straw material, is added as a catalyst, and the reaction solution is controlled to have a reaction temperature of 120 ° C., a reaction of 30 min, and a solid-liquid mass ratio of 1:10. Remove the tea liquid. The solid obtained by the first solid-liquid separation was added to an organic acid solution of formic acid and acetic acid having a total acid concentration of 75 wt%, followed by acid washing. Here, hydrogen peroxide occupying 8 wt% of a straw raw material in an organic acid solution having a total acid concentration of 75 wt%. (H ₂ O ₂ ) is added as a catalyst, and the mass ratio of acetic acid and formic acid is 1:12. The reaction solution was separated into a second solid solution by controlling the temperature to 90 ° C., the washing time of 1 h, and the solid-liquid mass ratio of 1: 9. Collect the liquid obtained by primary and secondary solid-liquid separation, evaporate at high temperature and high pressure until evaporated to dryness at 301 kPa at 120 ° C., and then cool the steam of formic acid and acetic acid obtained above, and then cook it in the reaction kettle of step (1). It is refluxed as a liquid and used for cooking in step (1). The solid obtained by the secondary solid-liquid separation is collected and washed, and the washing slurry obtained by controlling the washing temperature is 80 ° C and the concentration of the washing slurry is 6wt%, thereby separating the solid washing liquid. Collect the liquid obtained by the third solid-liquid separation and proceed with water and acid distillation, and the mixed acid solution obtained through this is refluxed as a cooking liquor in the reaction kettle of step (1) and used for cooking in step (1). The water obtained is recycled as washing water in step (5). The solid obtained by tertiary solid-liquid separation is collected and the required fine pulp cellulose is selected and obtained (see the patent document of Publication No. CN103898782A for this step).

(2) The cellulose obtained in Preparation Example (2) was mixed with ferrous chloride according to the mass ratio 1: 0.1, stirred at 150 ° C. for 4 h, catalyzed, and dried until the precursor moisture content was 10 wt%, thereby precipitating the precursor. Get; Next, the precursor was heated to 280 ° C. at a rate of 3 ° C./min in a protective gas atmosphere to warm for 2 h, followed by temperature programming to 950 ° C., and warmed for 3 h to obtain a crude product; The temperature increase rate of the temperature programming is 15 ° C / min. The crude product is acid washed with hydrochloric acid having a concentration of 4wt% at 55-65 ° C and washed with water to obtain a composite containing carbon nanostructures.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 11 showed that the peak height ratio of G peak and D peak was 3;

The composite containing carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg elements, and the content is 0.7wt%.

Example 12

In distinction from Example 11, in step (2):

According to the mass ratio 1: 1, the cellulose obtained in step (1) of Example 11 was mixed with ferric chloride, stirred at 200 ° C. for 8 h, catalyzed, and dried until the precursor moisture content was 8 wt%. Get; Next, the precursor was heated to 350 ° C. at a rate of 5 ° C./min in a protective gas atmosphere to warm for 2 h, followed by temperature programming up to 1050 ° C., and warmed for 4 h to obtain a crude product; The temperature increase rate of the temperature programming is 20 ° C / min. The crude product is acid washed with hydrochloric acid having a concentration of 6 wt% at 55 to 65 ° C. and washed with water to obtain a composite containing carbon nanostructures.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 12 showed a peak height ratio of G peak and D peak as 4.8;

As a result of detection by the method 1 of measuring the non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg elements and the content is 3.1 wt%.

Example 13

(1) After pulverizing the poplar or eucalyptus branches and leaves, pretreatment of the treated lignocellulosic biomass with an acid solution of 90% formic acid, 5% acetic acid and 5% water in organic acid However, the reaction temperature is controlled to 165 ℃, the reaction 10min, where the liquid-solid mass ratio of the mixed acid solution of formic acid and acetic acid and the biomass raw material is 1:20, the reaction solution obtained through this is subjected to the first solid-liquid separation; (2) The solid obtained in step (1) was added to a solution of formic acid having a concentration of 90%, acetic acid having a concentration of 5%, and an organic acid solution of 5% water, followed by acid washing with a temperature of 60 to 80 ° C. and a washing time. It is for 0.5 to 1 h, the reaction solution is subjected to secondary solid-liquid separation, and the solid obtained by separation is washed with water to obtain the required cellulose; (3) the liquid obtained by solid-liquid separation in steps (1) and (2) was collected and subjected to reduced pressure distillation and concentration to obtain formic acid and acetic acid, and a concentrated liquid whose concentration was 4-5 times the original liquid concentration; (4) the formic acid obtained by distillation in step (3) and steam of acetic acid are cooled and refluxed in the reaction kettle of step (1) to be used for acid decomposition of step (1); (5) dilution by adding water to the concentrate obtained in step (3), the mass ratio of the preparation and the concentrate is 2: 1, the third solid-liquid separation by controlling to stir 0.5-1 h at 60-70 ℃, Water is added to the obtained solid (mass ratio of water and the solid is 3: 1), stirred at 75-80 ° C. for 2-3 h, washed with water, and then de-esterified to obtain the necessary lignin. (For this step, reference may be made to "Comprehensive Use of Lignocellulose Biomass" of Publication No. CN103131018A).

(2) The poplar cellulose obtained in Preparation Example (3) was mixed with ferric chloride according to mass ratio 1: 1, stirred at 200 ° C. for 8 h, catalyzed, and dried until the precursor moisture content reached 8 wt%. To obtain a precursor; Next, the precursor was heated to 350 ° C. at a rate of 5 ° C./min in a protective gas atmosphere to warm for 2 h, followed by temperature programming up to 1050 ° C., and warmed for 4 h to obtain a crude product; The temperature increase rate of the temperature programming is 20 ° C./min; The crude product is acid washed with hydrochloric acid having a concentration of 6 wt% at 55 to 65 ° C. and washed with water to obtain a composite containing carbon nanostructures.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 13 showed a peak height ratio of G peak and D peak as 4.6;

As a result of detection by the measurement method 1 of non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg, Ni and K elements and the content is 3.6 wt%.

Example 14

In distinction from Example 13, in step (2):

The eucalyptus cellulose obtained in step (1) of Example 13 was mixed with nickel chloride according to the mass ratio 1: 0.5, stirred at 170 ° C. for 5 h, catalyzed, and dried until the precursor moisture content reached 6 wt%. Get; Next, the precursor was warmed up to 300 ° C. at a rate of 4 ° C./min in a protective gas atmosphere to warm for 3 h, followed by temperature programming up to 1000 ° C., and warmed for 4 h to obtain crude product; The temperature increase rate of the temperature programming is 17 ° C / min. The crude product was acid washed with hydrochloric acid having a concentration of 5 wt% at 60 ° C. and washed with water to obtain a composite containing carbon nanostructures.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 14 showed that the peak height ratio of the G peak and the D peak was 2.1;

As a result of detection by the method 1 of measuring the non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg, Ni, and K elements, and the content is 1.6wt%.

Example 15

In distinction from Example 13, in step (2):

The poplar cellulose obtained in Preparation Example (3) was mixed with ferrous chloride according to the mass ratio 1: 3, stirred at 180 ° C. for 5 h, catalyzed, and dried until the precursor moisture content was 6 wt% to obtain a precursor. ; Next, the precursor was warmed up to 300 ° C. at a rate of 4 ° C./min in a protective gas atmosphere to warm for 3 h, followed by temperature programming up to 1000 ° C., and warmed for 4 h to obtain crude product; The temperature increase rate of the temperature programming is 17 ° C / min. The crude product was acid washed with hydrochloric acid having a concentration of 5 wt% at 60 ° C. and washed with water to obtain a composite containing carbon nanostructures.

Raman spectrum detection of the composite containing the carbon nanostructures prepared in Example 15 showed a peak height ratio of G peak and D peak as 2.1;

As a result of detection by the measurement method 1 of non-carbon non-oxygen element content, the composite containing the carbon nanostructure mainly contains P, Si, Ca, Al, Na, Fe, Mg, Ni, and K elements, and the content is 4.7wt%.

Comparative Example 1

Graphene obtained according to Example 7 disclosed in CN104016341A, which is named "Method for Producing Porous Graphene," is referred to as Comparative Example 1. As a result of Raman spectrum detection of the graphene prepared in the comparative example, the ratio of the peak height of the G peak and the D peak is 13.

Comparative Example 2

Phosphorous doped graphene prepared by the method disclosed in CN103508444A and its preparation method are specifically used as follows:

1 g of 95% pure graphite is added to 24 ml of mass fraction of 65% concentrated nitric acid and 90 ml of mass fraction of 98% of concentrated sulfuric acid, and the mixture is stirred for 20 minutes in an iced mixed bath environment, Potassium permanganate is slowly added to the mixture, where the mass ratio of potassium permanganate to graphite is 5: 1. After stirring for 1 hour the mixture is heated to 85 ° C. and maintained for 30 min. Then deionized water was added and continued at 85 ° C. for 30 min, where the liquid-solid ratio of deionized water and graphite was 90 mL: 1 g, and finally a hydrogen peroxide solution having a mass fraction of 30%. Wherein the liquid-solid ratio of hydrogen peroxide solution to graphite is 10 mL: 1 g. After stirring for 10 min and suction filtration of the mixture, the mixture is washed sequentially with dilute hydrochloric acid and deionized water, where the solid-liquid ratio of dilute hydrochloric acid, deionized water and graphite is 100 mL: 150 mL: 1 g. Washed three times, and finally, the solid material was dried in a vacuum oven at 60 ° C. for 12 hours to obtain graphite oxide; The mixture of graphite oxide and diphosphorous pentoxide is uniformly mixed at a mass ratio of 1: 2, and the temperature is raised to 900 ° C. at a temperature rising rate of 15 ° C./min and maintained for 2 h in an argon gas atmosphere having a flow rate of 300 ml / min. Phosphorus doped graphene is prepared by lowering to room temperature in an argon gas atmosphere.

Raman spectrum detection of the phosphorus-doped graphene prepared in Comparative Example 2 showed that the peak height ratio of the G peak and the D peak was 5;

As a result of detection by the method 1 of measuring the non-carbon non-oxygen element content, the composite containing a carbon nanostructure mainly contains P element.

Comparative Example 3

Parallel comparison experiment

The activated carbon including graphene prepared in Example 1 of the activated carbon / graphene composite disclosed in CN104118874A and the preparation method thereof includes P, Si, Ca, Fe, Mg, and Mn elements.

Raman spectrum detection was performed on the activated carbon / graphene composite prepared in Comparative Example 3, and the peak height ratio of G peak and D peak was 0.5;

As a result of detection by the method 1 of measuring the non-carbon non-oxygen non-hydrogen element content, the activated carbon / graphene composite obtained above contains S, N, and Cl elements.

Functional regenerated cellulose fibers are prepared using the composite containing the carbon nanostructures prepared in Examples 1-15 and Comparative Examples 1-3.

For example, the viscose liquid used in the present invention is a viscose liquid used in the prior art, and the manufacturing method is immersed, compressed, pulverized, aged, sulfided, dissolved, aged, filtered, defoamed, etc. as a raw material. It's a step forward. The pulp is immersed in an aqueous sodium hydroxide solution having a concentration of about 18% to convert cellulose to alkaline cellulose, eluting hemicellulose to partially lower the degree of polymerization; Pressing removes the excess alkaline solution. Lump-shaped alkali cellulose is loosely floc after being crushed in the mill, and the increase in surface area improves the uniformity of subsequent chemical reactions. Alkali cellulose produces an oxidative cleavage under the action of oxygen, which lowers the average degree of polymerization. This process is called aging. After aging, alkali cellulose is reacted with carbon disulfide to produce cellulose xanthate (sulphide), further weakening hydrogen bonds between polymers, and cellulose xanthate in dilute alkaline solution due to hydrophilicity of xanthic acid group. Can greatly improve the solubility. Solid cellulose xanthate is dissolved in dilute alkaline solution, ie viscose. Viscose, which has just been prepared, has a relatively high viscosity and salinity, which makes it difficult to mold, and by leaving it at a constant temperature for a certain time (aging), sodium cellulose xanthate in viscose gradually becomes hydrolyzed and saponified, The degree of esterification is reduced and the viscosity and stability of the action on the electrolyte change accordingly. After aging, defoaming and filtration are performed to remove bubbles and impurities. Specifically as follows:

(1) Viscose fiber filament process flow refers to FIG. 1 which shows a flow chart of the filament process of viscose fiber.

(2) alkali immersion process conditions

Alkaline solution (NaOH): concentration 240g / L, temperature 20 ℃

Immersion time: 120min

(3) aging process conditions

Temperature 25 ℃, time 34h

(4) xanthation process conditions

Sulfide Method: Wet Sulfide

Basicization: time 30min, temperature 21.0 ± 0.5 ℃

Sulfurization: Time 120min, Temperature First 21.0 ± 0.5 ℃, Final 30.0 ± 0.5 ℃

CS ₂ addition amount: 34.5% (per α-cellulose)

Pre melt: 120min, temperature 16.5 ± 0.5 ℃

After dissolution: time 180min, temperature 16.5 ± 0.5 ℃

(5) Prepared Viscose Stock Solution Composition:

α-cellulose 8.30 ± 0.10%

NaOH 5.80 ± 0.10%

S 2.25 ± 0.1%

(6) Viscose ripening conditions

Time 36-38h

Temperature 19.0 ± 0.5 ℃

(7) manufactured spinning glue condition

Viscosity 30-40 s (20 ° C, falling ball method)

Aging degree 7.8-8.6 ml (10% NH ₄ Cl value)

(8) spinning process conditions:

Spinning Speed: 82m / min

Draft: 25%

Tension draft: 4.12%

(9) coagulation bath conditions

Acid bath ingredients:

H ₂ SO ₄ 132.0 ± 1.0g / L

ZnSO ₄ 10.5 ± 0.5g / L

Na ₂ SO ₄ 265.0 ± 5.0g / L

Temperature: 52.0 ± 1.0 ℃

Specific gravity: 1.270 ± 0.005

Temperature: 45-50 ℃

In general, a graphene structure and a non-carbon non-oxygen element may be introduced into a plurality of steps of preparing the above-described viscose liquid, for example, before grinding, before aging, before sulfiding, or before aging. It is not usually introduced after a filtration or defoaming step. The present invention is preferably introduced after aging and before filtration, and the inventors at this time have a higher mixing efficiency by adding a graphene structure with a material containing a non-carbon non-oxygen element (for example, a composite containing carbon nanostructures), It has been found that the mixing time can be shortened by more than half and can usually be shortened by 1/3.

In the present invention, preferably, the material containing the non-carbon non-oxygen element and the graphene structure are first made into a dispersion system, and then the dispersion solution is uniformly mixed with the viscose solution. Preferred dispersion solvents are water. Preferably, the composite containing the graphene structure is prepared in a dispersion system with a solid content of 0.1 to 10%.

A more preferred method is first to disperse the composite containing the graphene structure in a dilute alkaline solution for dissolving cellulose xanthate, and then to disperse the cellulose xylated, ie cellulose xanthate. This method does not need to introduce water separately due to the introduction of the graphene structure, and since the cellulose is combined with the graphene structure immediately after dissolution, it has the advantage of being more uniformly mixed. In this embodiment, when dispersing the graphene structure in a dilute alkali solution and after adding cellulose xanthate, it is not necessary to stir for a long time, but after stirring, the dispersion efficiency of the graphene structure can be greatly increased. Can be improved.

Next, after filtration and defoaming, spinning, desulfurization, washing, oiling and drying are performed to obtain the final viscose fiber. They belong to the traditional method and are not described in detail in the text.

Specifically, a viscose liquid having a solid content of 8% is prepared by using corn cob as a raw material and undergoing impregnation basicization, compression, grinding, aging, sulfidation, dissolution, and aging; After dispersing the raw material containing the carbon nanostructures prepared in Examples 1-8 and Comparative Examples 1-3 with 5 times mass of water, the dispersion of graphene structure and viscose solution were mixed and stirred for 1 h with a high speed stirrer to mix solution The amount of the composite containing the carbon nanostructures is 0.7%, 1.5%, 3%, 5% and 10% of the cellulose mass. Filtration and defoaming are performed, and functional viscose fibers are produced by spinning, desulfurization, washing with water and drying. Here, the coagulation bath is composed of: 105 g / l sulfuric acid, 200 g / l sodium sulfate, and 12 g / l zinc sulfate. The far infrared and antimicrobial performance of the functional fiber is detected and the detection standards are as follows:

Herein, the infrared detection data is verified according to the FZ / T64010-2000 verification method of the National Quality Supervision and Inspection Center of textile products;

Antimicrobial data are as follows: GB / T20944.3-2008 Verification method of the National Textile Products Supervision and Inspection Center.

Detection result:

The raw material containing the graphene structure and the non-carbon non-oxygen element prepared in Examples 1-15 and Comparative Examples 1-3 are added.

When the addition amount is 0.7%, the functional viscose fiber produced is as follows:

When the addition amount is 1.5%, the functional viscose fiber produced is as follows:

When the addition amount is 3%, the functional viscose fiber produced is as follows:

When the addition amount is 5%, the functional viscose fiber produced is as follows:

When the addition amount is 10%, the functional viscose fiber produced is as follows:

As can be seen from the above examples and comparative examples, since there are many trace elements in the plant itself, the plant itself can be used to prepare a material containing graphene structure and trace elements to further add each component of the product (for example, trace elements). It can be uniformly dispersed, and the effect when combined with a material such as the next polymer material is better, and the effect is more obvious when mixed uniformly by introducing a trace element subsequently, and the effect is slightly smaller than a naturally formed effect. Falls.

When the addition amount of the composite containing the carbon nanostructure is more than 5wt%, especially more than 10wt%, coagulation easily occurs. Therefore, the composite containing the carbon nanostructure is non-uniformly dispersed in the fiber, resulting in the reduction of far infrared rays and antibacterial effect. do. As long as the composite containing the carbon nanostructure has a good dispersibility in the fiber, it can be added continuously.

In the above, the functional regenerated cellulose fiber provided by the present invention, a method for producing the same, and an applied article have been described in detail. Herein, the principles and embodiments of the present invention have been described with specific examples, and the description of the above examples is merely to help understand the method and the central idea of the present invention. For those skilled in the art, it should be understood that certain improvements and modifications may be made to the present invention without departing from the principles thereof, and such improvements and modifications fall within the protection scope of the claims of the present invention.

Claims (17)

In the functional regenerated cellulose fiber,
The functional regenerated cellulose fiber comprises a graphene structure and a non-carbon nonoxygen element;
The non-carbon non-oxygen element includes Fe, Si and Al elements;
The Fe, Si and Al elements occupy 0.018 wt% to 0.8 wt% of the regenerated cellulose fiber. The method of claim 1,
The material containing the graphene structure and the non-carbon non-oxygen element is a functional regenerated cellulose fiber, characterized in that is introduced in the form of a composite containing carbon nanostructures. The method of claim 2,
The composite containing carbon nanostructures contains graphene, amorphous carbon and non-carbon nonoxygen elements;
In the composite containing the non-carbon non-oxygen element, the non-carbon non-oxygen element includes Fe, Si, and Al elements;
The content of the non-carbon non-oxygen element is a functional regenerated cellulose fiber, characterized in that 0.5wt% to 6wt% of the composite containing the carbon nanostructure. The method of claim 2 or 3,
In the composite containing the carbon nanostructure, the carbon element content is ≥80wt%,
Functional regenerated cellulose fiber, characterized in that. The method of claim 4, wherein
The non-carbon non-oxygen element occupies 0.3 ~ 5wt% of the composite containing the carbon nanostructures. delete The method of claim 4, wherein
The non-carbon non-oxygen element is a functional regenerated cellulose fiber, characterized in that occupies 1.5 ~ 5wt% of the composite containing the carbon nanostructure. The method of claim 2 or 3,
Method for producing a composite containing the carbon nanostructure is:
(1) catalyzing the biomass carbon source under the action of a catalyst to obtain a precursor;
(2) warming the precursor at 140 ° C. to 180 ° C. for 1.5 h to 2.5 h under conditions of a protective gas to obtain a first intermediate;
(3) obtaining a second intermediate by heating the first intermediate to 350 ° C. to 450 ° C. and then warming for 3 h to 4 h under conditions of a protective gas;
(4) raising the second intermediate to 1100 ° C. to 1300 ° C. under the condition of the protective gas, and then insulating for 2 h to 4 h to obtain a third intermediate;
(5) sequentially performing alkali washing, acid washing and washing with respect to the third intermediate to obtain a composite; Including,
Functional regeneration cellulose fiber, characterized in that the temperature increase rate in the step (3), (4) is 14 ℃ / min ~ 18 ℃ / min. The method of claim 8,
The biomass carbon source is a functional regenerated cellulose fiber, characterized in that one or two or more of lignocellulosic, cellulose and lignin.
The method of claim 2 or 3,
The Fe, Si and Al elements occupy 0.1wt% to 0.7wt% of the regenerated cellulose fiber. The method of claim 10,
The non-carbon non-oxygen element accounts for 0.03 wt% to 1 wt% of the regenerated cellulose fiber. The method of claim 2 or 3,
The graphene structure of the functional regenerated cellulose fiber, characterized in that less than or equal to 100 nanometers. The method of claim 12,
The graphene structure is a functional regenerated cellulose fiber, characterized in that it has one or a combination of two or more of the six-membered honeycomb-shaped layered structure of carbon having a layer of 1 to 10 layers. The method of claim 2 or 3,
The non-carbon non-oxygen element further comprises one or two or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S and Co,
The non-carbon non-oxygen element accounts for 0.1 wt% to 1 wt% of the regenerated cellulose fiber. In the method for producing a functional regenerated cellulose fiber,
The method for producing functional regenerated cellulose fibers includes pulp dipping, pressing, grinding, aging, sulfiding, dissolving, ripening, filtration and defoaming;
The graphene structure and the non-carbon nonoxygen element are introduced at a stage after the sulfidation step;
The graphene structure and the non-carbon non-oxygen element is a method for producing a functional regenerated cellulose fiber, characterized in that added in the form of a composite containing carbon nanostructures. In the method for producing a functional regenerated cellulose fiber,
In the method of the functional regenerated cellulose fibers, the cellulose pulp is dissolved in an NMMO solution, a material containing a graphene structure and a non-carbon non-oxygen element is introduced to obtain a spinning dope, and then the regenerated cellulose fiber is prepared using the spinning dope. Including the steps of;
The material containing the graphene structure and the non-carbon non-oxygen element comprises a composite containing a carbon nanostructures method of producing a functional regenerated cellulose fiber. In the article,
The article contains a functional regenerated cellulose fiber according to any one of claims 1 to 3, or a regenerated cellulose fiber prepared by the production method according to any one of claims 15 to 16;
The article comprises a civilian garment, household textile, sunscreen fabric or industrial special protective clothing.

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