阅读说明：本技术 一种光热转换、蓄热调温纤维素纤维及其制备方法 (A kind of photothermal conversion, thermo-regulated fiber cellulose fiber and preparation method thereof ) 是由 李昌垒 刘长军 马君志 齐鲁 于 2019-07-31 设计创作，主要内容包括：本发明提供一种光热转换、蓄热调温纤维素纤维,石墨烯的含量为0.45~1.91wt%,碳化锆的含量为0.47~0.95wt%,相变储能微胶囊的含量为4.7%~9.5wt%；本发明还提供上述纤维的制备方法,所述制备方法,包括石墨烯分散体系的制备、含光热材料-碳化锆的相变储能微胶囊浆料的制备、功能性纤维素纺丝液的制备、纺丝。在相同初始测试条件下和太阳光或者红外灯照射下,15min后,与普通纤维素纤维相比,制备的光热转换、蓄热调温纤维素纤维的温度高9.7℃~29.9℃,可见光吸收率增加30%~55%；纤维焓值为8.1~15.5J/g,纤维相变温度为25.4~36.6℃。(The present invention provides a kind of photothermal conversion, thermo-regulated fiber cellulose fiber, and the content of graphene is 0.45 ~ 1.91wt%, and the content of zirconium carbide is 0.47 ~ 0.95wt%, and the content of microcapsules of storing energy through phase change is 4.7% ~ 9.5wt%；The present invention also provides the preparation method of above-mentioned fiber, the preparation method, the preparation including graphene dispersion system, the preparation of the microcapsules of storing energy through phase change slurry containing optothermal material-zirconium carbide, preparation, the spinning of functional fiber element spinning solution.Under identical initial testing conditions and under sunlight or infrared light irradiation, after 15min, compared with conventional cellulosic fibers, the photothermal conversion of preparation, thermo-regulated fiber cellulose fiber temperature it is 9.7 DEG C high ~ 29.9 DEG C, it is seen that absorptivity increases by 30% ~ 55%；Fiber enthalpy is 8.1 ~ 15.5J/g, and fiber phase transition temperature is 25.4 ~ 36.6 DEG C.)

1. a kind of photothermal conversion, thermo-regulated fiber cellulose fiber, it is characterised in that: the content of graphene is 0.45 ~ 1.91wt%, The content of zirconium carbide is 0.47 ~ 0.95wt%, and the content of microcapsules of storing energy through phase change is 4.7% ~ 9.5wt%.

2. a kind of photothermal conversion according to claim 1, thermo-regulated fiber cellulose fiber, it is characterised in that: the fiber, Enthalpy is 8.1 ~ 15.5J/g, and phase transition temperature is 25.4 ~ 36.6 DEG C, far infrared normal emittance 0.83 ~ 0.92.

3. the preparation method of a kind of photothermal conversion, thermo-regulated fiber cellulose fiber, it is characterised in that: the preparation method, including The preparation of graphene dispersion system, the preparation of the microcapsules of storing energy through phase change slurry containing optothermal material-zirconium carbide, functional fiber element Preparation, the spinning of spinning solution.

4. the preparation method of a kind of photothermal conversion according to claim 3, thermo-regulated fiber cellulose fiber, feature exist In: the hydroxide of 4.0 ~ 5.0wt% is added into neutral alumina graphene dispersion slurry for the preparation of the graphene dispersion system Sodium is stirred to react 2.0 ~ 4.0h at 60 ~ 95 DEG C, then proceedes to the carboxymethyl cellulose that 0.5 ~ 1.5wt% is added under this condition Or polyvinylpyrrolidone, continue 40 ~ 90min of dispersion；Be cooled to 10 ~ 20 DEG C, be prepared mass fraction be 3.0 ~ The graphene dispersion slurry of 5.0wt%.

5. the preparation method of a kind of photothermal conversion according to claim 3, thermo-regulated fiber cellulose fiber, feature exist In: the preparation of the microcapsules of storing energy through phase change slurry containing optothermal material-zirconium carbide, including prepare oily packet zirconium carbide system, system Standby O/W lotion, microcapsule coated；The oily packet zirconium carbide system of the preparation, core materials, cyst material, initiator is mixed, In 30 ~ 60min is stirred at 35 ~ 50 DEG C of temperature, is uniformly mixed；Addition nano-zirconium carbide powder, raising mixing speed to 1500 ~ 2500rpm continues 20 ~ 50min of stirring, forms oily packet zirconium carbide system.

6. the preparation method of a kind of photothermal conversion according to claim 5, thermo-regulated fiber cellulose fiber, feature exist In: the core materials are one or more of n-octadecane, NSC 77136, n-eicosane；

The mass ratio of the core materials and cyst material is (50 ~ 70): (50 ~ 30), and the initiator is the 0.5 of cyst material The mass ratio of ~ 1.0wt%, Zirconium carbide powder and core materials is 1:5 ~ 1:7.

7. the preparation method of a kind of photothermal conversion according to claim 5, thermo-regulated fiber cellulose fiber, feature exist In: oily packet zirconium carbide system is added in emulsifier solution by the preparation O/W lotion, in 35 DEG C~50 DEG C of temperature, stirring 2500~7000rpm of speed stirs 60~180min, obtains O/W lotion；The mass fraction of the emulsifier solution, emulsifier is 5.0~8.0wt%；The mass ratio of the oil packet zirconium carbide system and emulsifier solution is 1:3 ~ 1:4.

8. the preparation method of a kind of photothermal conversion according to claim 7, thermo-regulated fiber cellulose fiber, feature exist In: the emulsifier is the one or two of styrene-maleic anhydride copolymer sodium salt, neopelex, the benzene The molecular weight of ethylene maleic acid anhydride copolymer is 10000 ~ 35000.

9. the preparation method of a kind of photothermal conversion according to claim 5, thermo-regulated fiber cellulose fiber, feature exist In: the microcapsule coated, reduction mixing speed are 500 ~ 900rpm, and 120 ~ 180min is reacted at a temperature of being heated to 75 ~ 85 DEG C Afterwards, cooling to stop stirring, it is obtained after filtering containing optothermal material-zirconium carbide microcapsules of storing energy through phase change slurry, wherein phase-change accumulation energy The content of microcapsules is 20-40wt%.

10. the preparation method of a kind of photothermal conversion according to claim 3, thermo-regulated fiber cellulose fiber, feature exist In: the preparation of the functional fiber element spinning solution, including prepare first blended silk stock solution, prepare final spinning solution；The preparation First blended silk stock solution, is added to fibre for graphene dispersion system and the microcapsules of storing energy through phase change slurry containing optothermal material-zirconium carbide It ties up in plain spinning solution, stirs to get just blended silk stock solution, the just blended silk stock solution, graphene is relative to alpha cellulose Mass fraction is 2.0 ~ 8.0wt%, and microcapsules of storing energy through phase change is 20 ~ 40wt% relative to the mass fraction of alpha cellulose；It is described Final spinning solution is prepared, the ratio of 1:3 in mass ratio of blended ratio liquid at the beginning of the cellulose of preparation is added to cellulose spinning solution Pipeline in, be uniformly mixed, final spinning solution is obtained, wherein graphene is relative to first kind fiber in final spinning solution The mass fraction of element is 0.5 ~ 2.0wt%, and microcapsules of storing energy through phase change is 5.0 ~ 10wt% relative to the mass fraction of alpha cellulose.

Technical field

The invention belongs to chemical fibre technology in textile technology field, a kind of photothermal conversion, accumulation of heat tune are related in particular to Warm cellulose fibre and preparation method thereof.

Background technique

With the aggravation that textile industry competes, entire industry is badly in need of the function that new material and technology realize textile material Change, is differential.In daily life, the warming and frivolous of textile is two contradictory concepts, this needs textile industry scientific The development of technology gives to solve.

Optothermal material can convert light energy into thermal energy under light illumination, be a kind of new type functional material, main to wrap Include four kinds of organic group, Metal Substrate, carbon-based, semiconductor etc..It gains great popularity, is weaving since it can convert light energy into thermal energy Equal fields have been widely used, and are current one of research hotspots.

Comfortable and easy to wear due to good hygroscopicity, spinnability is excellent, so that cellulose fibre is widely used, Chang Yumian, hair or each Kind synthetic fibers are blended, interweave, and are used for all kinds of clothes and decorative textile product.In recent years due to the high intensity of graphene-structured, Good thermal conductivity, the specific surface area of super large and good biocompatibility become domestic and international optical-thermal conversion material research heat Point.Phase-change material can absorb or discharge a large amount of latent heat in phase transition process, be widely used in heat storage and domain of control temperature, One of the key content studied in terms of having become domestic and international material science and energy science.

In view of optothermal material the field of textiles application process the problem of and the superiority of graphene, phase-change material Can, therefore the cellulose fibre of a kind of photothermal conversion, heat-accumulation temperature-adjustment how is obtained, it is particularly suitable for the function of daily field of textiles Energy property cellulose fibre, is always the focus of textile industry especially cellulose fibre enterprise technology personnel extensive concern, has Great practical application meaning.

Chinese patent CN201811000005.9 discloses a kind of preparation method of photothermal conversion heat-accumulation temperature-adjustment cotton fabric.It should Patented technology is that graphene oxide is reduced to graphene after surface of cotton fabric sprays graphene oxide to obtain photothermal conversion storage Hot temperature adjustment cotton fabric.Due to being that surface sprays, so that the persistence and washability of fiber function are greatly reduced.Simultaneously using oxidation Graphene sprays, and becomes graphene after reduction, so that the binding force of graphene and cotton fabric declines, further decreases persistence.

Chinese patent CN201710271232.4 discloses a kind of method for preparing photothermal conversion fabric.The patented technology is Using fabric as matrix, photo-thermal nano material is attached to the surface of fabric substrate.Although this method can obtain preferable light Hot-cast socket effect, but due to being attached to fabric substrate surface, function persistence and functional stabilization are substantially reduced.

Chinese patent CN201610621351.3 discloses a kind of luminous energy fiber and preparation method thereof.The present invention is by caesium tungsten After nanocomposite and fibrous raw material slice mixed melting, luminous energy fiber is obtained by spinning.This technology is suitable only for melting Spinning is not suitable for the spinning of cellulose fibre, and functional weaker.

Chinese patent CN201610066129.1, CN201310750604.3 disclose a kind of near-infrared sunlight thermal storage fiber Preparation and application, a kind of preparation method of accumulation of heat constant temperature fiber and its method for preparing fabric.The patent is will be with paraffin hydrocarbon It is capsule-core, the phase-change material micro-capsule that urea-melamine-formaldehyde copolymer is cyst wall and heat-storage micro mist as function After energy property increases ingredient and polypropylene base melt mixed, spinning is carried out by screw extruder and box assembly, after spinning again Be blowed cool down, oil, winding shaping, obtain near-infrared sunlight thermal storage fiber.The art of this patent is directly by functional component With polypropylene matrix melt mixed, masterbatch method is not used, so that the functional uniformity of fiber is influenced.

Chinese patent CN201510323141.1 discloses a kind of infrared photothermal conversion fiber and preparation method thereof.This is specially Benefit includes polymer matrix, the first infrared photothermal transition material (tungsten oxide particle and/or combined oxidation tungsten particle), second red Outside line optical-thermal conversion material (titanium dioxide fine particles coated by antimony-doped stannic oxide) and third infrared photothermal transition material (antimony-doped stannic oxide particle), the polymer matrix are formed in the way of dry type or wet spinning.The art of this patent uses Three kinds of optical-thermal conversion materials are compound, considerably increase the difficulty of addition and the uniformity of dispersion, while containing a large amount of in fiber Dispersing agent, affect the performance of fibre property.

Chinese patent CN201710691878.8 discloses a kind of preparation method of speed heat warm-keeping cellulose fiber, the patent Technology is addition speed heat material and thermal control material before cellulose fiber spinning forms, so that making the cellulose fibre of preparation has The warming effect of speed heat.The patented technology is only simply by functional component (speed heat slurry and thermal control material etc.) by simple Dispersion is directly added, and the speed heat slurry of preparation still has dispersion unevenly, when system is unstable and spinning viscose is blended, It is easy the technical issues of reuniting；Its preparation method for not disclosing microcapsules of storing energy through phase change, i.e., using common phase in the market Become accumulation energy microcapsule, there is technical issues that, and the addition of said components influences the mechanical performance of fiber.

Summary of the invention

In view of the deficienciess of the prior art, the present invention provide a kind of photothermal conversion, thermo-regulated fiber cellulose fiber and its Preparation method, to realize following goal of the invention:

(1) dispersibility for improving graphene and optical-thermal conversion material is reunited when avoiding being blended with spinning viscose, is dispersed unevenly, Improve the function uniformity of photothermal conversion, thermo-regulated fiber cellulose fiber；

(2) degree of supercooling for reducing microcapsules of storing energy through phase change, improves the performance of its heat-accumulation temperature-adjustment, improves the cellulose fibre of preparation It is functional；

(3) influence of the photothermal conversion, heat-accumulation temperature-adjustment material that are added to fiber mechanical performance is reduced.

In order to solve the above technical problems, the present invention takes following technical scheme:

The content of a kind of photothermal conversion, thermo-regulated fiber cellulose fiber, graphene is 0.45 ~ 1.91wt%, and the content of zirconium carbide is 0.47 ~ 0.95wt%, the content of microcapsules of storing energy through phase change are 4.7% ~ 9.5wt%.

It is further improvement to above-mentioned technical proposal below:

By the compound use of graphene and zirconium carbide, the thermal conductive resin of graphene and the efficient absorption of Zirconium carbide powder are utilized The functions such as visible light, energy storage assign the higher photothermal conversion performance of fiber；By Zirconium carbide powder and phase-changing energy storage material knot It closes and uses, not only increase the dispersibility of Zirconium carbide powder, while using the heterogeneous nucleating effect of Zirconium carbide powder, reducing phase The degree of supercooling for becoming accumulation energy microcapsule, improves the performance of microcapsules of storing energy through phase change, so that the cellulose fibre prepared has more The functionality such as good heat-accumulation temperature-adjustment.Under sunlight or infrared light irradiation, compared with conventional cellulosic fibers, which has Apparent temperature rise effect.Under identical initial testing conditions and under sunlight or infrared light irradiation, after 15min, with common fibre Cellulose fiber is compared, the photothermal conversion of preparation, thermo-regulated fiber cellulose fiber temperature it is 9.7 DEG C high ~ 29.9 DEG C, it is seen that light absorption Rate increases by 30% ~ 55%, and fiber enthalpy is 8.1 ~ 15.5J/g, and fiber phase transition temperature is 25.4 ~ 36.6 DEG C, the transmitting of far infrared normal direction Rate 0.83 ~ 0.92, doing breaking strength is 2.25 ~ 2.41cN/dtex, and wet breaking strength is 1.19 ~ 1.32cN/dtex, does fracture Elongation is 17.2 ~ 19.6%.

A kind of photothermal conversion, thermo-regulated fiber cellulose fiber the preparation method is as follows:

1, the preparation of graphene dispersion system

Since graphene has big specific surface area, disperse when directlying adopt graphene poor.In order to improve the dispersion of graphene Property, hydrophily graphene oxide dispersed paste is prepared first with well known oxidation-reduction method, is then washed with distilled water to molten Liquid is neutrality；And ground with sand mill, partial size D90≤2.135 μm, neutral alumina graphene dispersion slurry is obtained, is aoxidized The mass fraction of graphene is 4.2 ~ 6.5wt%；Cellulose-binding fibre manufacturing technique, using sodium hydroxide as green reducing agent, 4.0 ~ 5.0wt% sodium hydroxide is added into above-mentioned neutral alumina graphene dispersion slurry, in 60 ~ 95 DEG C and 816 ~ 1100r/min 2.0 ~ 4.0h is reacted under mixing speed, then proceedes to the carboxymethyl cellulose that 0.5 ~ 1.5wt% is added under this condition or poly- second Alkene pyrrolidone continues 40 ~ 90min of dispersion；Be cooled to 10 ~ 20 DEG C it is spare, be finally prepared mass fraction be 3.0 ~ The graphene dispersion slurry of 5.0wt%.Since carboxymethyl cellulose or polyvinylpyrrolidonesolution solution have viscosity higher, especially It is that viscosity is higher at low temperature, so that the graphene dispersion system stability with higher of preparation.

2, the preparation of the microcapsules of storing energy through phase change slurry containing optothermal material-zirconium carbide

Core materials, cyst material, initiator are added in mixing kettle, the mass ratio of core materials and cyst material is (50 ~ 70): (50 ~ 30), initiator is 0.5 ~ 1.0wt% of cyst material, in the stirring of 35 ~ 50 DEG C of temperature and 300 ~ 720rpm 30 ~ 60min is stirred under speed, is uniformly mixed.Addition nano-zirconium carbide powder, raising mixing speed to 1500 ~ 2500rpm, after The mass ratio of 20 ~ 50min of continuous stirring, Zirconium carbide powder and core materials is 1:5 ~ 1:7, is uniformly distributed nano-zirconium carbide powder In above-mentioned mixed system, oily packet zirconium carbide system is formed.

The core materials are one or more of n-octadecane, NSC 77136, n-eicosane；

The cyst material is methyl methacrylate；

The initiator is azodiisobutyronitrile or benzoyl peroxide；

Above-mentioned mixed system is added in emulsifier solution, the mass ratio of above-mentioned mixed system and emulsifier solution is 1:3 ~ 1: 4,60~180min is stirred in 35 DEG C~50 DEG C of temperature, 2500~7000rpm of mixing speed, obtains O/W lotion, emulsion particle diameter D90≤1.865μm；Emulsion system is transferred in reaction kettle, reduction mixing speed is 500 ~ 900rpm, is heated to 75 ~ 85 DEG C At a temperature of react 120 ~ 180min after, natural cooling stop stirring, after filtering i.e. obtain containing the phase transformation of optothermal material-zirconium carbide store up It can microcapsules slurry.Zirconium carbide powder and phase-changing energy storage material are used in combination, the dispersibility of Zirconium carbide powder is not only increased, The heterogeneous nucleating effect for utilizing Zirconium carbide powder simultaneously, reduces the degree of supercooling of microcapsules of storing energy through phase change, improves phase-change accumulation energy The performance of microcapsules, degree of supercooling reduce by 3.2 ~ 5.6 DEG C.

The emulsifier is the one or two of styrene-maleic anhydride copolymer sodium salt, neopelex；It is molten The mass fraction of emulsifier is 5.0 ~ 8.0wt% in liquid, and the molecular weight of styrene-maleic anhydride copolymer is 10000 ~ 35000；

Oily packet zirconium carbide system: refer to the preparation of oil-based system, the i.e. mixing of capsule-core, cyst material and initiator, zirconium carbide；By It is organic phase in capsule-core, cyst wall, that is, oily phase, system are formed the dispersion of organic phase and zirconium carbide after mixing System, since organic phase is continuous phase, so being just oily packet zirconium carbide system.

O/W lotion (oil-in-water): being by oily packet zirconium carbide system (can regard oleaginous system as) in the effect of emulsifier Under, it is dispersed in water phase, since water is high compared to oil phase content too many, water phase in low temperature and is vigorously stirred as continuous phase Under, it is dispersed in oil mutually in water phase, forms little particle.

Microcapsule coated process: in the case where stirring and increasing temperature conditions, after reaching certain temperature, initiator releases first Free radical, under Free Radical, cyst material starts to be crosslinked and be constantly precipitated, so that capsule-core and zirconium carbide be coated, is formed Containing optothermal material-zirconium carbide microcapsules of storing energy through phase change slurry.

3, the preparation of functional fiber element spinning solution

1) the just preparation of blended silk stock solution: above-mentioned graphene dispersion system and the phase-change accumulation energy containing optothermal material-zirconium carbide is micro- Capsule slurry is added in the cellulose spinning solution prepared, under the revolving speed of 500r/min ~ 800r/min shear agitation 20 ~ 35min obtains just blended silk stock solution, wherein the mass fraction of graphene is that 2.0 ~ 8.0wt%(is opposite in first blended silk stock solution In alpha cellulose), the mass fraction of microcapsules of storing energy through phase change is 20 ~ 40 wt %(relative to alpha cellulose), deaeration standby With；

2) preparation of the final spinning solution of cellulose fibre: blended ratio liquid at the beginning of the cellulose of preparation is passed through and utilizes injection device before spinning The ratio of 1:3 is added in the pipeline of cellulose spinning solution in mass ratio.Utilize dynamic mixer and static mixing before spinning Device combination, further realizes the mixing of function additive and cellulose spin dope, it is finely dispersed to prepare functional aid Cellulose spinning solution, wherein the mass fraction of graphene is 0.5 ~ 2.0 wt %(relative to first kind in final spinning solution Cellulose), the mass fraction of microcapsules of storing energy through phase change is 5.0 ~ 10.0 wt %(relative to alpha cellulose).

4, the preparation of photothermal conversion, thermo-regulated fiber cellulose fiber

The final cellulose spinning fluid of above-mentioned preparation is subjected to spinning by adjusting good coagulating bath, coagulating bath include sulfuric acid 90~ 110g/L, 290~310g/L of sodium sulphate, nascent tow cut off again after multistage drafting, mitigate sulfur removal technology, finish application bath, After the concise bath such as washing and drying, photothermal conversion, thermo-regulated fiber cellulose fiber are obtained.

The present invention has following beneficial effect compared with prior art:

(1) patented technology passes through the compound use of graphene and zirconium carbide, utilizes the thermal conductive resin and zirconium carbide of graphene The functions such as the efficient absorption visible light of powder, energy storage assign fiber heat-accumulation temperature-adjustment performance in conjunction with microcapsules of storing energy through phase change, make The cellulose fibre that must be prepared has the functionality such as photothermal conversion, heat-accumulation temperature-adjustment.Under identical initial testing conditions and the sun Under light or infrared light irradiation, after 15min, compared with conventional cellulosic fibers, photothermal conversion, the thermo-regulated fiber element of preparation The temperature of fiber is 9.7 DEG C high ~ and 29.9 DEG C, it is seen that absorptivity increases by 30% ~ 55%；Fiber enthalpy is 8.1 ~ 15.5J/g, fiber phase Temperature is 25.4 ~ 36.6 DEG C, far infrared normal emittance 0.83 ~ 0.92.

(2) preparation method of the art of this patent provides photothermal conversion, thermo-regulated fiber cellulose fiber, overcomes existing system Graphene dispersion is irregular, is easy to the problems such as reuniting in standby technical matters；Zirconium carbide powder is used in combination with phase-changing energy storage material, Using the heterogeneous nucleating effect of Zirconium carbide powder, the degree of supercooling of microcapsules of storing energy through phase change is reduced, improves the micro- glue of phase-change accumulation energy The performance of capsule, to lay a good foundation for the excellent functionality of subsequent photothermal conversion, thermo-regulated fiber cellulose fiber.

(2) spinning solution is prepared using two-step method in the patent, so that functional component is mixed with the multiple of viscose glue stoste, The uniform mixing of functional component is realized, to further ensure the functionality and function uniformity of fiber, is reduced simultaneously Influence of the photothermal conversion, heat-accumulation temperature-adjustment material of addition to fiber mechanical performance, the fiber of preparation, do breaking strength be 2.25 ~ 2.41cN/dtex, wet breaking strength are 1.19 ~ 1.32cN/dtex, and dry elongation at break is 17.2 ~ 19.6%.

The following describes the present invention in detail with reference to examples.

Specific embodiment

Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.