WO2019061768A1 - Method for preparing functional cellulose capable of increasing effective content of functional materials - Google Patents

Abstract

The present invention provides a method for preparing functional cellulose capable of greatly increasing the effective content of functional materials in fibers. In a cellulose material product obtained according to the method, functional materials account for 5-60% of a relative product mass ratio, or even more, which generally can reach 15% or more or 30% or more. The functional cellulose prepared accordingly can be greatly improved in effects, such as flame retardance, bacteriostasis, moisturizing, skin care, beauty, heat storage and release, aroma, catalysis, and inhibition due to the high content of the functional materials. The method according to the present invention has widely available raw materials, is environmentally friendly during the whole process, is easy to industrial production, and can be applied to fields such as textile manufacturing, medicine, cosmetics, and agriculture.

Description

Method for preparing functional cellulose for improving effective content of functional substance Technical field

The invention relates to a preparation method of a cellulose material, in particular to a preparation method of functional cellulose for improving the effective content of a functional substance, and a functional cellulose long material prepared by the method.

Background technique

Cellulose fibers are especially important among the various types of fibers. Different from fossil energy, cellulose is a renewable resource widely found in nature. It plays an important role in the fields of textile, light industry, petroleum, national defense, metallurgy, biology and medicine. Compared with other spinning methods, cellulose fibers have a low preparation temperature and relatively mild conditions, and are excellent functional substance carriers. Therefore, many attempts have been made to introduce functional materials into fiber materials.

A method of adding polyethylene glycol to hollow fibers is described in U.S. Patent 4,908, 238, and a phase change material is directly mixed with cellulose in EP 1430168. These are methods in which a functional substance such as a flame retardant, a retarding agent, a heat storage material, a bacteriostatic agent, or the like is directly mixed with a spinning liquid phase, followed by crystallization or solidification of the cellulose to obtain a fiber. The fiber has a certain temperature responsiveness and can absorb heat or exotherm in a timely manner, but the functional material therein cannot either be firmly retained in the fiber or cause a decrease in mechanical properties of the fiber to cause leakage of the functional material.

European Patent No. EP 0 306 022 discloses a technique for mixing microspheres containing a phase change material or a plastic crystal material in a polymer to form a fiber having reversible heat storage properties; in CN103225123A, a peppermint oil and an antibacterial agent are disclosed. Encapsulation, mixing the microcapsules with the viscose spinning solution, and wet-spinning to obtain fibers containing functional substances; in CN101942706A, the phase change microcapsules are described in the sulfonation step, the dissolving step, the mixing step or A method of adding a functional fiber to a cellulosic material during spinning to obtain a functional fiber by spinning. These methods adopt a method of microencapsulating a functional substance (menthol oil, antibacterial agent or phase change material) and mixing with a spinning solution. The preparation process of the microspheres of this technology is complicated, and the diameter and resistance of the microspheres are resistant. Thermal stability, solvent stability and the like all affect the preparation and properties of the fiber, such as the size requirements of the microcapsules are relatively strict, otherwise it will cause problems such as clogging of the spinning orifice; Moreover, when the relative addition amount of the functional substance exceeds 5% by mass, the interface area between the microcapsule and the cellulose is greatly increased, which greatly affects the molding process of the cellulose fiber and the physical properties of the product. However, the relative addition amount of the functional substance is lower than the mass ratio of 5%, and the functional effect of the fiber is not good.

In WO 2009/062657 a method is described in which a functional substance is first formed into an emulsion, then the emulsion is mixed with a cellulose solution, and the emulsion is stabilized by adding a viscosity-enhancing hydrophobic agent, and then the nanoparticles are added to form a suspension. The cellulose is then recrystallized to obtain a method of differentiating the fibers. The method effectively increases the content of functional materials in the fiber, but it is found in practical applications that the functional material is in a dispersed state, and the interface energy between it and cellulose is too high, in further processing (such as fiber). The weaving, dyeing and finishing, etc.) the loss of functional materials is very serious, and also has an effect on the mechanical properties of the fibers. Of course, this method can be used for a lot of applications in areas such as drug release.

It can be seen that a method for substantially increasing the effective content of functional materials in the fiber is provided, including the addition of functional materials during fiber preparation, fusion with the fibrous matrix, and still in the post-processing of the fibers. A method of maintaining a high functional material retention rate is extremely necessary.

Summary of the invention

It is an object of the present invention to provide a method for preparing functional cellulose which can substantially increase the effective content of functional materials in fibers in view of the problems in the prior art.

The inventors have noted that the microencapsulation process provides a shell material that effectively protects the functional material. However, the preparation of microcapsules and spinning solution separately, and the method of mixing the two has great limitations. The compatibility and adaptability of the microcapsules, the particle size and shape, etc. all affect the function of the fiber product. Therefore, this method can not accommodate enough functional substances, such as CN10225123A, the peppermint oil does not exceed 1%, the antibacterial agent does not exceed 8%; or the fiber properties such as mechanical strength declines severely or even unable to adapt to further processing, and the functional durability is poor. The loss is serious. EP 1243326 also teaches the preparation of microcapsules for perfumes or other functional substances, likewise taking the steps of microencapsulation and fibrillation separately, which leads to great limitations and uneconomical in high-volume preparation. . The method given in WO 2009/062657, while increasing the content of functional materials, does not maintain a high retention of functional materials during post-processing of the fibers.

The inventors have noticed that the emulsion droplet diameter of the functional additive is very critical in the process of forming the cellulose solution into fibers, and in the subsequent processes such as ripening, collision, etc., the droplets may grow, and the excessively large particles may be caused. The diameter may cause blockage during the spinning process; however, the diameter of the droplet is too small, the specific surface The increase in product means that the relative content of functional substances is severely reduced, essentially resulting in a decrease in the effective content. Therefore, during the preparation of the functional cellulosic material, the droplet diameter of the emulsion needs to be stably maintained in a range. The microcapsule method is often used at this stage to solve this problem. The oil-water interface performance is critical from the formation and growth of droplets. It is also related to the uniform dispersion of functional materials in cellulose solution and the mechanical strength of the bond between functional materials and cellulose. One of the keys. The microcapsule method can stabilize the droplet diameter to a certain size, but the interface of the microcapsule method has been stabilized, and the stable interface has its inherent defects. The present invention, on the other hand, provides a solution in cellulose. A method of adding a functional material and forming an emulsion droplet and curing the oil-water interface in a subsequent process.

The preparation method of the functional cellulose capable of greatly increasing the effective content of the functional material in the fiber according to the present invention comprises the following steps:

1) Configuring a solvent comprising a sodium hydroxide having a mass concentration of 5% to 12%, a zinc oxide having a mass concentration of 0.1% to 9%, and then adding a cellulose having a total mass of 2% to 15% of the solution, and freezing to - a step of obtaining a cellulose solution after thawing at 5 ° C or lower and then not higher than 45 ° C;

2) using the cellulose solution obtained in the step 1) as a continuous phase, and using a functional substance as a dispersed phase to form an emulsion;

3) adding a polymer monomer or prepolymer to the emulsion system obtained in the step 2), initiating polymerization, forming a polymer at the oil-water interface in the emulsion; wherein the monomer or prepolymer is a mass functional substance 0.05%-29.99% of the mass;

4) The cellulose in the system obtained in the step 3) is solidified to obtain functional cellulose in which the functional substance is dispersed in the cellulose matrix.

Compared with the existing cellulose dissolution method, especially the conventional method of industrialization: cellulose dissolution under a strong alkali solution under high temperature and high pressure, or dissolution with NMMO, ionic liquid at a high temperature, the purpose of step 1) is to form The continuous phase of the cellulose solution, which makes it possible to add and cure the functional substance in one step in a subsequent step.

In step 1), the cellulose comprises at least one of cellulose carbamate, lignocellulose, reed, cotton, flax, starch, chitosan or synthetic polysaccharide or any combination thereof; wherein preferably, Cellulose carbamate, lignocellulose, starch, chitosan or synthetic polysaccharides have a degree of polymerization of from 300 to 800.

The solution may be an aqueous solution, an aqueous solution of NMMO (N-methylmorpholine-N oxide), an ionic liquid, or the like, wherein N-methylmorpholine-N-oxidation in an aqueous solution of N-methylmorpholine-N-oxide The material can be mixed with water in any ratio.

Among them, the ionic liquid is newly developed. It is a compound composed entirely of a positive ion and an anion, and is called a ionic liquid, typically such as methylimidazolium hexafluorophosphate.

The study found that the key factor affecting the stability of the emulsion is the composition of the cellulose solution. The cellulose dissolution process is relatively mild, and the too high or too low temperature and pressure are extremely unfavorable. An aqueous solution containing sodium hydroxide or zinc oxide, or further including N-methylmorpholine-N-oxide or an ionic liquid, allows the cellulose dissolution process to be easily controlled. The inventors have noted that it is extremely helpful to have a certain amount of water in the above solution. But the reason for this remains to be further studied and explained.

In step 2), there are many methods for forming the emulsion. Generally, there are at least three methods for forming the emulsion from the mixing method: 1) the normal phase emulsion is generally formed by adding the dispersed phase to the continuous phase and stirring; 2) The reverse conversion method is a typical method of adding a continuous phase to a dispersed phase to form an emulsion, which is characterized by being able to obtain a smaller, more uniform emulsion; 3) adding a continuous phase and a dispersion to the high-pressure shear pump, A typical pressurized emulsification method. Thus step 2) can be carried out by methods commonly used in the art to give an emulsion.

The functional substance is added in an amount of 5% or more relative to the weight ratio of the cellulose, may be 15% or more, or even more, more than 30%, and 50% or more, and currently 5-60% is acceptable; preferably 15- 60%, more preferably 30-60%.

The size of the droplets in the emulsion affects the amount of addition. For example, the preparation of the fibers generally requires that the droplet diameter be less than half the diameter of the single fiber; if less than 3.5 microns is required, even D90 is required to be less than 2 microns.

The functional substances include flame retardants, inhibitors, aromatic plant extracts, proprietary Chinese medicine preparations, vitamin A, vitamin D, vitamin E, aliphatic hydrocarbons, fatty alcohols, fatty acids, fatty acid esters, acid anhydrides, polyols, hydration Salt, paraffin, dibasic acid, fat-soluble protein, vegetable oil, bactericide, insecticide, bacteriostatic agent, insect repellent, catalyst, crosslinking agent, heat stabilizer, light stabilizer, liquid crystal, dye, pigment, sensation At least one of a thermochromic material, a photochromic material, or any combination thereof.

The choice of functional material can be selected based on the intended use and characteristics of the fiber, which can be done with reference to common knowledge in the art.

Further, the functional substance further includes a solution or dispersion of the functional substance in any ratio, a porous material or a layered material to which the functional substance is adsorbed, and a nanotube.

In step 3), the polymer comprises polyurethane, melamine resin, polyacrylate, styrene polymer, ethylene polymer, acrylic polymer, polycarbonate, polyester, polyether, fluorocarbon polymer , epoxy polymer, silicon-containing polymer, polyamide, polyimide, polyol polymer, copolymer or a mixture of any of the above.

The introduction of polymer monomers or prepolymers is mainly to obtain a stable, non-destructible oil-water interface, and the amount of addition and polymerization time can affect the droplets and stability of the emulsion.

The introduction of the polymer monomer or prepolymer will be determined according to factors such as system polarity, compatibility, mechanical strength and the like. The initiation is a common knowledge in the art, and the initiator or initiating condition is determined according to the kind and amount of the polymer. The polymer monomer or prepolymer will form a shell of different molecular weight or degree of reaction to separate the functional substance and The base body also serves as a connection and protection.

The step of adding a polymer monomer or prepolymer to the system may result in a change in thermodynamic or kinetic factors, resulting in a different curing mechanism, and the formation of the shell may be from the outside to the inside, or from the inside to the outside. This will affect the surface properties or particle size of the interface. These properties will lead to the degree of isolation or connection of functional materials to the outside world, such as phase change materials have good thermal storage, more suitable for non-direct contact; plant spices are more suitable for slow release rather than complete isolation. More importantly, the method of the present invention is capable of substantially increasing the effective amount of functional material and has a very low loss rate in subsequent processing.

Further, the step 2) and the step 3) can be simultaneously performed by simultaneously adding a functional substance and a polymer monomer or a prepolymer to the cellulose solution system to initiate polymerization to form an emulsion system. The process includes the step of forming a dispersed phase of the emulsion together with the polymer monomer or prepolymer and the functional material, including the step of adding a polymer monomer or prepolymer after the emulsion is formed or about to form.

In step 4), the fiber curing may be carried out by a method commonly used in the art, such as: 1. Coagulation bath method: spraying cellulose dissolved in a strong alkali aqueous solution into an acid, and precipitating and solidifying the cellulose; 2. Temperature difference method : using a solution of cellulose solution at different concentrations and temperatures, such as a solution of 20% cellulose concentration and heating it to 60 ° C, rapidly passing through a low concentration (such as 20 ° C) low concentration (such as 5%) cellulose solution, A large amount of cellulose is precipitated and solidified; 3. Dry and wet separation method, after the spinning solution is sprayed, it flies in the air for a distance, and then enters the spinning solution, and the cellulose is solidified. After the cellulose is cured, the functional substance is distributed in the fiber At least one part of the interior or surface of the matrix, the functional substance is partially embedded in the matrix when the functional substance is distributed on the surface of the substrate.

The resulting cellulosic material is comprised of a functional material in the cellulosic matrix, and a polymeric layer between the functional material and the cellulosic matrix, which may be continuous or discontinuous.

The cellulose is cured, in addition to forming a fibrous material, and may include a film, a sheet, a massive sponge or a sphere. Fibrous filaments can be used to make yarns of any ratio with other fibers, fabric weaving, as a filler or film material; to make fibers, films, sponges, etc., or to form blocks, porous Objects, sheets, spheres, etc., have important applications in the manufacture of yarns, fabrics, fillers or film materials.

When determining the type of the product of the cellulosic material, the film forming property of the cellulosic material needs to be considered. Therefore, the method of the present invention may further comprise: 4') uniformly coating the cellulose obtained in the step 3) on the glass piece, curing The film formability of the cellulosic material was evaluated by comparison with a control sample; wherein the control sample was a cellulosic material to which no functional material was added (the same materials, formulations, and procedures).

The film forming property explains the spinnability to some extent, and the possibility of obtaining the fiber is obtained. Specifically, the film formation test is to compare the film formation process (the process is as close as possible to the spinning conditions, such as drying temperature, speed, water washing, etc.) to the blank film (ie, non-functional substance). The degree of easy peeling of the film on the glass piece was evaluated, and the easier peeling indicates that the film formability is better. The distribution uniformity of the functional substance on the surface or the cross section of the film is judged by means of a microscope or the like. The corresponding functionality of the film was also tested. If the test passes, it means that the fiber is more likely to be obtained (spinning and film formation are still different, film formation is only a sufficient condition, not a necessary condition), and the strength and washability of the fiber can be obtained by testing the properties of the film. Feedback; if the film forming property is not good, it is possible to prepare other shapes of cellulosic material products such as lumps, sponges, granules and the like.

Step 4') can be performed before or at the same time as step 4).

In addition, in the film formation test, at least two substances are produced: a membrane and a filtrate, and by analyzing the two, the distribution of functional substances in the cellulose material product can be roughly understood.

Experiments have proved that the above method can obtain a cellulosic material product having a high effective content of a functional substance, the functional substance accounting for 5-50%, or even more, preferably 15-60%, more preferably 30-60% of the relative product mass ratio. .

Compared with the existing preparation methods of functional cellulose, the method of the invention has the following characteristics:

1) Different from direct addition of functional materials, such as flame retardants, aromatic extracts, vegetable oils, etc., the solution of the present invention takes into account the strong acid/strong alkali, high temperature, high pressure and other functionalities that may be encountered in fiber production and processing. The excessive loss caused by the substance provides a shell layer for protecting the functional material, which is more conducive to the functionality of the material product (such as flame retardant, endothermic/exothermic, bacteriostatic, etc.) or more durable (such as aroma, bacteriostatic) , drug release, etc.);

2) Compared with the method of microcapsule and fiber forming separately, the method of the invention can greatly increase the content of the functional substance in the cellulose matrix, and the weight content of the functional material in the product can reach 5-60% or even more. ;

3) In the field of functional materials, such as differentiated fibers, functional films or sponges, the present invention provides useful insights. In terms of specific high-volume preparation, the present invention simplifies the process and reduces the operation. Have obvious progress and economic value;

4) In the applicability of the method, it is not limited to the addition of high-content functional substances, and is similar to properties (such as similar surface properties, similar hydrophobic and hydrophobic properties, surface charge, etc.) but limited to the inventors' knowledge and not poor This method also provides some inspiration and reference for the functional substances.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a DSC characterization curve of a fiber prepared in Example 1 of the present invention.

2 is a DSC characterization curve of a fiber prepared in Example 9 of the present invention.

Detailed ways

The invention will be specifically described below by way of examples with reference to the accompanying drawings, and unless otherwise specified

Example 1

A regenerated cellulose filament which increases the effective content of the phase change material is prepared by the following method:

1) by dissolving cellulose of polymerization degree 650 in an aqueous solution containing 6.15% by mass of sodium hydroxide and 8% of zinc oxide, and freezing to below -5 ° C, and then not higher than 45 ° C (25 ° C) Thawing to obtain a cellulose solution;

2) The cellulose solution obtained in the step 1 is used as the continuous phase, and the paraffin wax having a melting point of 28 ° C (10 parts) And calcium stearate (2 parts), diphenylmethane diisocyanate (0.6 parts), toluene diisocyanate (1.5 parts) as a dispersed phase, and formed into an emulsion; high-speed shear 12000r / min to form an emulsion;

3) Inducing the above system prepolymer to form a polymer at the oil-water interface of the emulsion droplet; using 0.02 parts of ethylenediamine as an initiator, the system was uniformly mixed for 1 minute. The initiator is very active and will complete the reaction in a short time.

4) The above system is passed through a spinneret to solidify the cellulose to obtain a cellulose fiber having a temperature-regulating function in which paraffin is dispersed in a cellulose matrix.

The differential thermal scanning calorimetry analysis (instrument model TA Q20, test curve shown in Figure 1), a cellulose fiber having a temperature regulating function prepared in this example, wherein the paraffin content is about 38.99%.

The comparative samples in Table 1 below are functional fibers (commercially available, Clima, 6.67 dtex) prepared by the method described in WO2009/062657, and subjected to functional comparison after baking, alkali shrinking, bleaching, and dyeing, respectively. The functional loss rate of the sample of this example and the comparative sample was compared by the thermal scanning calorimetry.

From the test data, it is known that commercially available comparative fibers (commercially available, Clima, 6.67 dtex) and the fibers obtained in this example can obtain high effective content of functional fibers, but after baking, alkali shrinking, bleaching, and dyeing, comparison The sample exhibited severe loss of functional material, in contrast to the fiber loss of this example.

Table 1

Example 2

A regenerated cellulose filament which increases the effective amount of protein is prepared by the following method:

1) Dissolving cellulose having a polymerization degree of 550 in water and ionic liquid 1-A containing 9% by weight (7%-10%) of sodium hydroxide, 0.25% (0.1%-5%) of zinc oxide a solution of the base-3 butyl imidazolium chloride salt (wherein the amount of water is 20%, the ionic liquid is the balance), is frozen to below -7 ° C, and then thawed at 40 ° C to obtain a cellulose solution;

2) The cellulose solution obtained in the step 1 is used as a continuous phase, and the dispersion is carried out as a dispersion of 35% of silk fibroin and 2% of dispersant Span80 and PEG-grafted cellulose having a molecular weight of about 1300 (ratio 1:3). Phase, the continuous phase was added dropwise to the dispersed phase at a rate of 0.5 ml/min in the reverse transfer method to form an emulsion;

3) after the emulsion is formed, toluene diisocyanate having a cellulose mass ratio of 8.5% is added thereto;

4) The above system was induced with triethylenetetramine having a cellulose mass ratio of 0.09% as an initiator, and the prepolymer was polymerized at the oil-water interface of the emulsion; the system was uniformly mixed for 1 minute.

5) The above system is passed through a spinneret to solidify the cellulose to obtain a protein-rich cellulose filament in which the silk protein is dispersed in the cellulose matrix.

The protein mass ratio in the fiber can be adjusted between 20-40% as needed.

The cellulose filaments are cut to obtain a fibrin-rich cellulose staple fiber.

The above-mentioned protein-rich fiber can be further processed into yarn, various kinds of woven fabrics, knitted fabrics, or masks.

In the existing cellulose dissolution system, the dissolution of proteins, particularly animal proteins, is a problem, and it is difficult to add more than 5%.

Example 3

A regenerated cellulose filament which increases the effective content of the thermochromic material is prepared by the following method:

1) by dissolving bamboo cellulose in an aqueous solution of N-methylmorpholine-N-oxide containing 7% by mass of sodium hydroxide and 4.5% of zinc oxide, and freezing to below -5 ° C, then not Thawing above 40 ° C to obtain a cellulose solution;

2) The cellulose solution obtained in the step 1 is used as the continuous phase, the three-stage thermochromic pigment with a cellulose mass ratio of 10-25% and a critical temperature of 50 ° C and 70 ° C, 15-25% phase change paraffin and 5% Dispersion a styrene-maleic anhydride resin as a dispersed phase and forming an emulsion;

3) during the emulsion formation process, adding 2% nano-kaolin particles and 10% melamine resin aqueous solution in a mass ratio of cellulose to the emulsion;

4) Inducing the above system prepolymer to form a polymer at the oil-water interface of the emulsion droplet, adjusting to a weak acidity (pH about 5), after mixing, standing for 1 hour, and then adjusting to neutral;

5) The above system is passed through a spinneret to solidify the cellulose to obtain a multi-stage thermochromic cellulose filament having a content of up to 10-25%.

The fibers obtained in this example can be displayed in different colors at different temperatures for the production of anti-counterfeiting, warning, decoration, thermal protection and other products.

Compared with commercially available color-changing fibers, such as Egret chemical fiber, the method uses a color-changing microcapsule to add viscose fiber, wherein the color-changing material is added in an amount of only 2% to 5%.

Example 4

A regenerated cellulose filament which increases the effective content of the flame retardant is prepared by the following method:

1) By dissolving the cotton-wood pulp in an aqueous solution containing 12% by mass of sodium hydroxide, 5% zinc oxide and 0.1% urea, freezing to below -5 °C, and then thawing at not higher than 45 °C , obtaining a cellulose solution;

2) using the cellulose solution obtained in the step 1 as a continuous phase, using a cellulose mass ratio of 50% organophosphorus flame retardant and 1% nano silica, 12% toluene diisocyanate as a dispersed phase, and forming an emulsion;

3) Using 0.02 parts of ethylenediamine as an initiator, the prepolymer of the above system was induced to form a polymer at the oil-water interface of the emulsion droplets. The initiator is very active and will complete the reaction in a short time. The general treatment is to let the system mix evenly for a period of time, such as 1 minute.

4) The above system is passed through a spinneret to solidify the cellulose to obtain a cellulose fiber excellent in flame retardancy. The flame retardant content can reach 50%, or even more (currently up to 60%), which can effectively improve the flame retardant performance and even improve the fire rating.

The flame retardant fibers obtained in this example were tested with a fiber strength tester, and the strength modulus thereof is shown in Table 2 below. It can be seen from the data in the table that the flame retardant addition amount of the flame retardant fiber in this example is higher than that of the commercially available flame retardant fiber Visil (indicating the manufacturer Finnish fiber manufacturer Sateri), and the strength modulus is higher than that, and the advantage is obvious.

Table 2 fiber strength modulus

project	Commercial staple viscose staple	Example 4 Flame Retardant Fiber	Commercially available Visil
Dry breaking strength cN/dtex	2.20	2.38	1.52
Wet breaking strength cN/dtex	1.03	1.94	0.69
Flame retardant added amount%	0	50	30

Example 5

A regenerated cellulose filament which increases the effective content of the plant essence is prepared by the following method:

1) by dissolving cellulose having a polymerization degree of 650 in an aqueous solution containing 7% by mass of sodium hydroxide, 4% of zinc oxide, and 0.1% of urea, and freezing to below -5 ° C, and then not higher than 45 ° C. Thawing to obtain a cellulose solution;

2) Adsorption of lavender-type plant essence into porous nano-silica by vacuum adsorption (perfume: silica = 1:1), average particle size of silica of 120 nm, and 50% of the above-mentioned adsorption flavor of cellulose mass Silica and 7.5% toluene diisocyanate as a dispersed phase; the cellulose solution obtained in step 1 as a continuous phase, 5% dispersant styrene-maleic anhydride resin, and an emulsion;

3) Inducing the above system prepolymer to form a polymer at the oil-water interface of the emulsion droplet; using 0.02 parts of ethylenediamine as an initiator.

4) The above system is passed through a spinneret to solidify the cellulose to obtain a cellulose fiber excellent in aromatic properties. Among them, the fragrance content can reach 25% or even more, which can effectively improve the aromatic performance and prolong the aromatic storage period.

Compared with this example, the traditional method is to coat the plant essence with microcapsules, and then add it to the spinning solution for spinning. The microcapsule addition amount is only 5% (or even lower), and the effective flavor content needs to be multiplied by Microcapsule coverage.

Example 6

A regenerated cellulose filament which increases the effective content of the mosquito repellent and the phase change material is prepared by the following method:

1) by dissolving cellulose having a polymerization degree of 550 in a mixed solvent solution containing 9% by mass of sodium hydroxide, 0.35% of zinc oxide, and ionic liquid 1-methyl-3 butylimidazolium chloride. Freezing to below -7 ° C, then thawed at 40 ° C to obtain a cellulose solution;

2) The cellulose solution obtained in step 1 is used as the continuous phase, with a cellulose mass ratio of 35% octadecane and 10% mosquito repellent, 2% benzene-ma resin as the dispersed phase, and a high shear of 10000 r/min. Forming an emulsion at a rate;

3) after the emulsion is formed, a 5% by weight of butyl methacrylate and 1% of allyl methacrylate are added thereto;

4) Inducing the above system prepolymer to form a polymer at the oil-water interface of the emulsion droplet; maintaining the cellulose mass ratio of 0.02% potassium persulfate as an initiator, and incubating at 50 ° C for 2 hours.

5) The above system is passed through a spinneret to solidify the cellulose to obtain a cellulose filament containing a two-component functional substance in which the octadecane and the mosquito repellent are dispersed in the cellulose matrix.

The cellulose filaments are cut to obtain a cellulose staple fiber rich in two-component functional substances.

The above-mentioned fibers rich in two-component functional substances can be further processed into yarns, various kinds of woven fabrics, knitted fabrics, or fillers, as outdoor products or home textile products.

The prior art has no phase change thermostat and mosquito repellent two-component report.

Example 7

A regenerated cellulose filament which increases the effective content of the liquid crystal material is prepared by the following method:

1) by dissolving bamboo cellulose in an aqueous solution of N-methylmorpholine-N-oxide containing 7% by mass of sodium hydroxide and 4.5% of zinc oxide, and freezing to below -5 ° C, then not Thawing above 40 ° C to obtain a cellulose solution;

2) The cellulose solution obtained in the step 1 is used as the continuous phase, and the liquid crystal (cholesteryl phthalate) and the 5% dispersant styrene-maleic anhydride resin are used as the dispersed phase at a critical temperature of 25% of the cellulose mass ratio of 50 ° C. And forming an emulsion;

3) during the emulsion formation process, adding 0.5% graphene particles and 8% styrene, 1% divinylbenzene to the cellulose mass ratio;

4) Inducing the above system prepolymer to form a polymer at the oil-water interface of the emulsion droplet, adding light to initiate Irradiation with ultraviolet light for 30 minutes;

5) The above system is passed through a spinneret to solidify the cellulose to obtain a multi-stage liquid crystal cellulose filament having a content of up to 10-25%.

The fiber obtained in this example, in addition to the liquid crystal, is also provided with a graphene material which enhances heat conduction, and makes the liquid crystal more sensitive to environmental changes. This product can be used in the manufacture of products, signs, trademarks, logos, warning signs, etc., for anti-counterfeiting, warning, decoration, cold and heat protection and other products.

Example 8

A regenerated cellulose membrane that increases the level of mosquito repellent is prepared by the following method:

1) by dissolving cellulose having a polymerization degree of 550 in a mixed solvent solution containing 9% by mass of sodium hydroxide, 0.35% of zinc oxide, and ionic liquid 1-methyl-3 butylimidazolium chloride. Freezing to below -7 ° C, then thawed at 40 ° C to obtain a cellulose solution;

2) using the cellulose solution obtained in the step 1 as a continuous phase, using a mosquito repellent having a cellulose mass ratio of 35%, 2% benzene-ma resin as a dispersed phase, and forming an emulsion at a high shear rate of 10000 r/min;

3) after the emulsion is formed, a 5% by weight of butyl methacrylate and 1% of allyl methacrylate are added thereto; and the prepolymer of the above system is induced to form a polymer at the oil-water interface of the emulsion droplet; Cellulose quality is 0.02% potassium persulfate as initiator, and kept at 50 ° C for 2 hours

4') The above system is uniformly coated on a glass sheet to solidify the cellulose to obtain a cellulose film having a mosquito repellent content dispersed in the cellulose matrix.

The degree of peeling of the obtained film on the glass piece (the easier it is to fall off), the film formation uniformity (especially the distribution of the mosquito repellent) is analyzed and tested, such as observation of the surface and cross section of the film by electron microscopy; mosquito repellent (GB/ T 30126-2013 Textile anti-mosquito performance testing and evaluation) to test.

The test results show that it is easy to peel off. After drying, the film separates from the substrate by itself, peels off naturally, and the peeled film is intact, without cracking or defect during peeling, and the film is uniform, the film is white and opaque, and the surface is smooth and flat. No obvious bubbles. This shows that the process used in this example has good film formability and high spinnability. After repellent test, the repellent rate was 74.3%.

The film obtained in this example can be used for repelling mosquitoes, preventing disease spread, etc., and is suitable for clothing, bedding, outdoor products, automobile interiors, medical supplies, health care products, and the like.

Example 9

A regenerated cellulose membrane for increasing the content of a phase change material is prepared by the following method:

1) by dissolving cellulose having a polymerization degree of 550 in a mixed solvent solution containing 9% by mass of sodium hydroxide, 0.35% of zinc oxide, and ionic liquid 1-methyl-3 butylimidazolium chloride. Freezing to below -7 ° C, then thawed at 40 ° C to obtain a cellulose solution;

2) using the cellulose solution obtained in the first step as a continuous phase, with a cellulose mass ratio of 55% butyl stearate and 2% benzene-horse copolymer resin as a dispersed phase at a high shear rate of 8000 r/min. Forming an emulsion;

3) after the emulsion is formed, a cellulose mass ratio of 5% of dodecyl methacrylate and 1% of allyl methacrylate is added thereto; and the prepolymer of the above system is induced to form a polymer at the oil-water interface of the emulsion droplet; The cellulose was incubated at 50 ° C for 2 hours with a cellulose mass ratio of 0.02% potassium persulfate as an initiator.

4') The above system is uniformly coated on a glass piece to solidify the cellulose to obtain a cellulose film in which the content of the phase change material is increased by dispersing butyl stearate in the cellulose matrix.

The degree of peeling of the obtained film on the glass sheet (the easier it is to fall off), the film formation uniformity (especially the distribution of the mosquito repellent), and the analysis, such as observation by a polarizing microscope, or observation of the surface and cross section of the film by an electron microscope.

The test results show that it is easy to peel off. After drying, the film separates from the substrate by itself, peels off naturally, and the peeled film is intact, without cracking or defect during peeling, and the film formation is uniform, the film is milky white and opaque, and the surface is smooth and flat. No obvious bubbles. It shows that the process used in this example has good film formability and high spinnability. The test using a differential scanning calorimeter (model METTLER DSC822e) is shown in Figure 2, indicating that the phase transition point of the film is about 22 degrees with a 焓 value of 71.49 J/g.

The film obtained in this example can be used for temperature regulation, such as heat dissipation, heat preservation, heat insulation, etc., and is suitable for clothing, bedding, outdoor products, automobile interiors, electronic products, building materials, medical supplies, biological breeding and the like.

The above-described embodiments are merely illustrative of preferred embodiments of the invention and are not intended to limit the scope of the invention. Since the embodiments are not exhaustive, various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should be considered as merely by simply changing the shape without departing from the spirit of the present invention. Within the scope of protection defined by the claims of the present invention.

Claims (10)

1. A method for preparing functional cellulose capable of substantially increasing the effective content of functional materials in fibers, comprising the steps of:

   1) Configuring a solvent comprising a sodium hydroxide having a mass concentration of 5% to 12%, a zinc oxide having a mass concentration of 0.1% to 9%, and then adding a cellulose having a total mass of 2% to 15% of the solution, and freezing to - a step of obtaining a cellulose solution after thawing at 5 ° C or lower and then not higher than 45 ° C;

   2) using the cellulose solution obtained in the step 1) as a continuous phase, and using a functional substance as a dispersed phase to form an emulsion;

   3) adding a polymer monomer or prepolymer to the emulsion system obtained in the step 2), initiating polymerization, forming a polymer at the oil-water interface in the emulsion; wherein the mass of the polymer monomer or prepolymer is 0.05%-29.99% of the mass of the functional substance;

   4) The cellulose in the system obtained in the step 3) is solidified to obtain functional cellulose in which the functional substance is dispersed in the cellulose matrix.
2. The preparation method according to claim 1, wherein in the step 1), the cellulose comprises cellulose carbamate, lignocellulose, reed, cotton, flax, starch, chitosan or synthetic polysaccharide. At least one of or any combination thereof; preferably, the cellulose carbamate, lignocellulose, starch, chitosan or synthetic polysaccharide has a selected degree of polymerization of from 300 to 800.
3. The preparation method according to claim 1, wherein in the step 1), the solution is a mixture of one or more of an aqueous solution, an aqueous solution of N-methylmorpholine-N oxide, and an ionic liquid.
4. The preparation method according to claim 1, wherein in the step 2), the functional substance is added in a mass to cellulose mass ratio of from 5 to 60%, preferably from 15 to 60%, more preferably from 30 to 60%.
5. The preparation method according to claim 1, wherein in the step 2), the functional substance comprises a flame retardant, a inhibitor, an aromatic plant extract, a proprietary Chinese medicine preparation, vitamin A, vitamin D, vitamin E. , aliphatic hydrocarbons, fatty alcohols, fatty acids, fatty acid esters, acid anhydrides, polyols, hydrated salts, paraffin, dibasic acids, fat-soluble proteins, vegetable oils, fungicides, insecticides, bacteriostatic agents, insect repellents, catalysts, At least one of a crosslinking agent, a heat stabilizer, a light stabilizer, a liquid crystal, a dye, a pigment, a thermochromic material, a photochromic material, or any combination thereof.
6. The preparation method according to claim 5, wherein the functional substance is further included A solution or dispersion of any ratio of the functional substance described above, a porous material or a layered material to which the functional substance is adsorbed, or a nanotube.
7. The preparation method according to claim 1, wherein in the step 3), the polymer comprises polyurethane, melamine resin, polyacrylate, styrene polymer, ethylene polymer, acrylic polymer, Polycarbonate, polyester, polyether, fluorocarbon polymer, epoxy polymer, silicon-containing polymer, polyamide, polyimide, polyol polymer, copolymer or a mixture of any of the above.
8. The preparation method according to claim 1, wherein the step 2) and the step 3) are simultaneously performed.
9. The preparation method according to claim 1, wherein the method further comprises: 4') uniformly coating the cellulose obtained in the step 3) on a glass piece, solidifying, and evaluating the cellulose by comparison with a control sample. Film formability of the material; wherein the control sample is a cellulosic material to which no functional material is added.
10. A functional cellulosic material prepared by the process according to any one of claims 1-9, characterized in that the fiber comprises a functional material, and the functional material and the cellulose matrix are also polymerized. The layer, the polymer layer being continuous or discontinuous, wherein the functional material in the fiber has a ratio of effective content to cellulose weight of greater than 5%, preferably from 15 to 60%, more preferably from 30 to 60%.

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