CN1304650C - Phase change composite spinning solution and its preparation and application - Google Patents
Phase change composite spinning solution and its preparation and application Download PDFInfo
- Publication number
- CN1304650C CN1304650C CN 03129652 CN03129652A CN1304650C CN 1304650 C CN1304650 C CN 1304650C CN 03129652 CN03129652 CN 03129652 CN 03129652 A CN03129652 A CN 03129652A CN 1304650 C CN1304650 C CN 1304650C
- Authority
- CN
- China
- Prior art keywords
- fiber
- phase change
- solvent
- solution
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a phase change composite spinning solution, a preparation method thereof and an application thereof, which belongs to the technical field of preparation and application of spinning solutions. The spinning solution contains solutes and a solvent, wherein the solutes are phase change substances and fiber-forming polymer materials, and the phase change substances are polyalcohols, polyolefins, polyethers or paraffin hydrocarbons; the fiber-forming polymer materials are celluloses and derivatives thereof, chitins and derivatives thereof, polyacrylonitrile or polyvinyl alcohols, and the solvent is a mixed solvent of acetone and DMSO, ketone, organic acids, distilled water or DMF. Ultra-fine phase change fibers and ultra-fine phase change fiber felts can be prepared from using the spinning solution by adopting an electrostatic spinning method of three steps of material feeding, electrostatic spinning and fiber collection on an electrostatic spinning device; the spinning solution is applied in electrostatic spinning, and has favorable spinnability; additionally, the ultra-fine phase change fibers can be made into multifunctional protective suits with good respiratory ability, good protection and favorable temperature comfort.
Description
Technical field
The present invention relates to a kind of phase transformation composite spinning stoste and preparation and application, belong to spinning solution preparation and applied technical field.
Background technology
Utilize heat absorption and the exothermic phenomenon of some material in the phase transition process, can carry out the control of thermal energy storage and adjustment.Utilize these low temperature heat energies store research that phase change materials prepare suitable fiber of temperature and textiles since the eighties just.People such as Vigo begin one's study from the mid-80 and doughnut are immersed in the solution or melt of polyethylene glycol (PEG) or plastic crystal (plastic crystalline) material, make polyethylene glycol or plastic crystal enter fibrous inside, obtain having the fiber of phase-change characteristic-40～60 ℃ of temperature.The internal diameter of this fiber is bigger, and phase change material residues in fiber surface.Commercial at present is microcapsules coated phase-change material or powder, is mainly used in routine and takes fiber.
Method of electrostatic spinning is a polymeric spray static stretch spinning method, is a kind of important method for preparing superfine fibre.The fiber that makes with this method is much thinner than traditional spinning process, fibre diameter generally tens of to thousands of nanometers.This method generally is used to spin superfine fibre and the superfine fibre felt of PEO, PAN, PBI etc., and this method spinning has the superfine fibre of phase-change thermal storage function and the research of superfine fibre felt does not appear in the newspapers so far as yet but use.
Summary of the invention
First technical problem that the present invention will solve is to propose a kind of phase transformation composite spinning stoste, this stoste contains solute and solvent, solute is dissolved in the solvent, it is characterized in that, solute is phase change material and fiber-forming polymer material, phase change material is a TPO, the fiber-forming polymer material is cellulose and derivative, chitin and derivative thereof, polyacrylonitrile or polyvinyl alcohol, phase change material and fiber-forming polymer material are dissolved in respectively after in a kind of solvent and mix, and solvent is the mixture of DMSO, ketone, organic acid, distilled water or DMF and acetone.Utilize this stoste can prepare ultra-fine phase change fiber and ultra-fine phase change fiber felt by method of electrostatic spinning.
Second technical problem that the present invention will solve provides a kind of preparation of phase transformation composite spinning stoste.The present invention makes above-mentioned technical problem be resolved by the following technical programs: by preparation phase change material solution A, be mixed with fine high polymer material solution B, mixed solution A and solution B and make phase transformation composite spinning stoste to even three steps, the solvent of solution A and solution B is identical.
Now describe the preparation of phase transformation composite spinning stoste of the present invention in detail.The preparation of described phase transformation composite spinning stoste is characterized in that operating procedure:
First step obtain solution A
Phase change material is dissolved in the solvent, stirs, be mixed with solution A, concentration is 2～30wt%, and phase change material is TPO, PMA or PA, and solvent is the mixture of DMSO, ketone, organic acid, distilled water or DMF and acetone;
The second step obtain solution B
With the fiber-forming polymer material dissolves in solvent, stir, be mixed with solution B, concentration is at 2～3Owt%, the fiber-forming polymer material is cellulose and derivative, chitin and derivative thereof, polyacrylonitrile or polyvinyl alcohol, solvent is the mixture of DMSO, ketone, organic acid, distilled water or DMF and acetone, and solution A is identical with solvent in the solution B;
The 3rd step mixed solution A and solution B
Solution A is added solution B mix, the weight ratio of phase change material and fiber-forming polymer is 20～70: 80～30, and spinning solution concentration is 8～15wt%.
Of the present invention being further characterized in that, fiber-forming polymer material are microcrystalline cellulose, wood pulps, cellulose diacetate or Triafol T; Solvent is acetone, methyl ethyl ketone or acetic acid.
The 3rd technical problem that the present invention will solve provides a kind of application of phase transformation composite spinning stoste.The present invention solves the problems of the technologies described above by the following technical solutions: utilize phase transformation composite spinning stoste of the present invention, pass through method of electrostatic spinning on electrospinning device: reinforced, electrostatic spinning and three step of fiber collecting ultra-fine phase change fiber of preparation and ultra-fine phase change fiber felt.
Now be described with reference to the accompanying drawings the application of phase transformation composite spinning stoste of the present invention.
The application of described phase transformation composite spinning stoste needs to implement on electrospinning device, it is characterized in that operating procedure:
The first step is reinforced
Described phase transformation composite spinning stoste is injected measuring pump 1 after deaeration, filtration, the pump housing holding temperature of measuring pump 1 is 20～90 ℃;
The second step electrostatic spinning
Stoste is put 3 places by spray silk die orifice 2 Taylor and is accelerated formation injection thread 5 under the high-pressure electrostatic effect, the capillary aperture of spray silk die orifice 2 is 0.2～0.8mm, spinning the air that adopts 20～100 ℃ on the journey is medium, and air velocity is 0～1m/min, and electrostatic field voltage is 10～60kv;
The 3rd step fiber collecting
Spraying thread 5 solvent evaporates in course of injection drops on the fiber receiving device 4 after solidifying, make ultra-fine phase change fiber and ultra-fine phase change fiber felt, the average diameter of fiber is 20～600nm, phase transition temperature was 26～70 ℃ when fiber and fibrofelt heated up, phase transition temperature is 38～14 ℃ during cooling, and enthalpy of phase change is 20～250J/g.
Advantage of the present invention:
One, phase transformation composite spinning stoste of the present invention is applied to electrostatic spinning, has better spinnability.
Two, prepared ultra-fine phase change fiber of application of the present invention and ultra-fine phase change fiber felt have very high specific area and surface-to-volume than, very strong absorption affinity and good filterability, barrier and good adjustment performance.Be applicable to and produce the polymer superfine fibre non-weaving cloth, this product can be used as distinct temperature and requires filtering material, high functional material, shielding material, biology and the medical supplies that use down, the protective articles of accurate miniature components and parts etc., when playing general superfine fibre effect, the temperature of coating object can be remained on certain scope, thereby avoid object when too high or too low for temperature, to sustain damage.But utilize low-density, high porosity, bigger serface and the phase transformation performance of ultra-fine phase change fiber can make the multifunctional protective suit that has respiratory, protective and temperature comfortableness concurrently.
Description of drawings
Fig. 1 is an electrostatic spinning process schematic diagram.Wherein, the 1st, measuring pump, the 2nd, spray silk die orifice, the 3rd, Taylor's point, the 4th, the fiber receiving device, the 5th, spray thread.Electrostatic field voltage is 10～60kv, be applied to+,-between holding.
The specific embodiment
All embodiment are fully according to the preparation of above-mentioned a kind of phase transformation composite spinning stoste and the operating procedure operation of application.
Embodiment 1
The preparation of phase transformation composite spinning stoste:
Phase change material is PMA or PA, and solvent is the mixture of DMF and acetone, and the blend part by weight of DMF and acetone is 50: 50～98: 2; The fiber-forming polymer material is a polyacrylonitrile, and solvent is the mixture of DMF and acetone, and the blend part by weight of DMF and acetone is 50: 50～98: 2; The weight ratio of phase change material and fiber-forming polymer is 50～70: 50～30, and spinning solution concentration is 8～15wt%.
The application of phase transformation composite spinning stoste:
The pump housing holding temperature of measuring pump 1 is 50～90 ℃; The capillary aperture of spray silk die orifice 2 is 0.3～0.8mm, and spinning the air that adopts 50～100 ℃ on the journey is medium, and air velocity is 0～1m/min, and electrostatic field voltage is 10～60kv; The average diameter of the fiber that makes is 100～600nm, and phase transition temperature was 50～70 ℃ when fiber and fibrofelt heated up, and phase transition temperature is 45～38 ℃ during cooling, and enthalpy of phase change is 100～250J/g.
Claims (4)
1. phase transformation composite spinning stoste, contain solute and solvent, solute is dissolved in the solvent, it is characterized in that, solute is phase change material and fiber-forming polymer material, phase change material is a TPO, and the fiber-forming polymer material is cellulose and derivative, chitin and derivative thereof, polyacrylonitrile or polyvinyl alcohol, and solvent is the mixture of DMSO, ketone, organic acid, distilled water or DMF and acetone.
2. the preparation of the described phase transformation composite spinning of claim 1 stoste is characterized in that operating procedure:
First step obtain solution A
Phase change material is dissolved in the solvent, stirs, be mixed with solution A, concentration is 2～30wt%, and phase change material is TPO, PMA or PA, and solvent is the mixture of DMSO, ketone, organic acid, distilled water or DMF and acetone;
The second step obtain solution B
With the fiber-forming polymer material dissolves in solvent, stir, be mixed with solution B, concentration is at 2～30wt%, the fiber-forming polymer material is cellulose and derivative, chitin and derivative thereof, polyacrylonitrile or polyvinyl alcohol, solvent is the mixture of DMSO, ketone, organic acid, distilled water or DMF and acetone, and solution A is identical with solvent in the solution B;
The 3rd step mixed solution A and solution B
Solution A is added solution B mix, the weight ratio of phase change material and fiber-forming polymer is 20～70: 80～30, and spinning solution concentration is 8～15wt%.
3. the preparation of phase transformation composite spinning stoste according to claim 2 is characterized in that, the fiber-forming polymer material is microcrystalline cellulose, wood pulps, cellulose diacetate or Triafol T; Solvent is acetone, methyl ethyl ketone or acetic acid.
4. the application of the described phase transformation composite spinning of claim 1 stoste needs to implement on electrospinning device, it is characterized in that operating procedure:
The first step is reinforced
Described phase transformation composite spinning stoste is injected measuring pump (1) after deaeration, filtration, the pump housing holding temperature of measuring pump (1) is 20～90 ℃;
The pump housing holding temperature of measuring pump (1) is 20～90 ℃;
The second step electrostatic spinning
Stoste is located to be accelerated formation by spray silk die orifice (2) at Taylor's point (3) and is sprayed thread (5) under the high-pressure electrostatic effect, the capillary aperture of spray silk die orifice (2) is 0.2～0.8mm, spinning the air that adopts 20～100 ℃ on the journey is medium, air velocity is 0～1m/min, and electrostatic field voltage is 10～60kv;
The 3rd step fiber collecting
Spraying thread (5) solvent evaporates in course of injection drops on the fiber receiving device (4) after solidifying, make ultra-fine phase change fiber and ultra-fine phase change fiber felt, the average diameter of fiber is 20～600nm, phase transition temperature was 26～70 ℃ when fiber and fibrofelt heated up, phase transition temperature is 38～14 ℃ during cooling, and enthalpy of phase change is 20～250J/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03129652 CN1304650C (en) | 2003-07-02 | 2003-07-02 | Phase change composite spinning solution and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03129652 CN1304650C (en) | 2003-07-02 | 2003-07-02 | Phase change composite spinning solution and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1493720A CN1493720A (en) | 2004-05-05 |
| CN1304650C true CN1304650C (en) | 2007-03-14 |
Family
ID=34239752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03129652 Expired - Fee Related CN1304650C (en) | 2003-07-02 | 2003-07-02 | Phase change composite spinning solution and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1304650C (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7579078B2 (en) * | 2001-09-21 | 2009-08-25 | Outlast Technologies, Inc. | Temperature regulating cellulosic fibers and applications thereof |
| US9434869B2 (en) | 2001-09-21 | 2016-09-06 | Outlast Technologies, LLC | Cellulosic fibers having enhanced reversible thermal properties and methods of forming thereof |
| CN100347348C (en) * | 2004-06-30 | 2007-11-07 | 东华大学 | Static spinning device and its industrial use |
| CN100577720C (en) * | 2005-03-21 | 2010-01-06 | 中国科学院化学研究所 | Biodegradable and absorb polymer nano fibrous membrane materials and method for making and purposes |
| CN100427652C (en) * | 2005-11-11 | 2008-10-22 | 东南大学 | Composite nano fiber endless tow preparing apparatus and its preparing method |
| CN100363542C (en) * | 2006-05-16 | 2008-01-23 | 苏州大学 | Polyvinyl alcohol electrostatic spinning solution |
| CN100447316C (en) * | 2006-08-10 | 2008-12-31 | 中国科学院广州化学研究所 | Phase-change energy-storage ultra-fine composite fiber and preparation method and application thereof |
| CN100447315C (en) * | 2006-08-23 | 2008-12-31 | 中国科学院广州化学研究所 | Super fine composite terylene fibers storing energy through phase change, and preparation method |
| CN101260172B (en) * | 2007-03-07 | 2010-05-19 | 中国科学院化学研究所 | Method for preparing super-high molecular weight polyacrylonitrile-base carbon fiber spinning primary fluid |
| DE102007054702B4 (en) * | 2007-11-14 | 2018-10-18 | Smartpolymer Gmbh | Process for the preparation of cellulosic shaped bodies, cellulosic shaped bodies and their use |
| CN102002342B (en) * | 2010-09-26 | 2013-05-08 | 大连工业大学 | Method for preparing waste acrylic fiber and fatty acid combined phase change material |
| CN102071486B (en) * | 2010-12-06 | 2012-09-05 | 中原工学院 | Method for preparing retardant phase change fiber for protecting thermal insulating layer |
| CN102504186B (en) * | 2011-10-31 | 2013-06-05 | 东北林业大学 | Method for preparing nano-crystalline cellulose compound phase change material in catalysis assisting way |
| CN103205824B (en) * | 2013-03-22 | 2015-02-04 | 中科院广州化学有限公司 | Cyclodextrin supermolecular composite phase-change energy-storage superfine fiber and preparation method and application thereof |
| CN105200559A (en) * | 2014-07-30 | 2015-12-30 | 耿云花 | Phase-change blend fiber |
| CN105249576B (en) * | 2014-07-30 | 2016-10-19 | 汕头市永成隆有限公司 | A kind of manufacture method of multifunctional clothes package material |
| CN104562268B (en) * | 2015-01-13 | 2016-11-30 | 四川大学 | There is phase-change energy-storage fibre of isolation chamber and preparation method thereof |
| CN104746170A (en) * | 2015-02-13 | 2015-07-01 | 南京航空航天大学 | Automatic temperature-regulation polyester composite fiber and preparation method thereof |
| CN106048757B (en) * | 2016-06-20 | 2018-05-29 | 中原工学院 | A kind of preparation method of the phase change fiber with nucleocapsid bead structure |
| CN106192043B (en) * | 2016-07-19 | 2018-07-20 | 宜宾海丝特纤维有限责任公司 | A kind of preparation method of cold silk |
| CN109021344A (en) * | 2018-06-06 | 2018-12-18 | 广西民族大学 | A kind of polyacrylonitrile nanofiber film/polyolefin elastomer composite material and preparation method |
| CN109056106A (en) * | 2018-08-09 | 2018-12-21 | 安徽农业大学 | A kind of thermostabilization, high-intensitive sizing phase transformation superfine fibre preparation method |
| CN109576823B (en) * | 2018-11-08 | 2021-02-19 | 华南理工大学 | Phase change energy storage material with skin-core fiber structure and preparation method thereof |
| CN112587311B (en) * | 2020-12-28 | 2022-07-05 | 福建恒安集团有限公司 | Preparation method of self-temperature-control sanitary towel |
-
2003
- 2003-07-02 CN CN 03129652 patent/CN1304650C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1493720A (en) | 2004-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1304650C (en) | Phase change composite spinning solution and its preparation and application | |
| CN108589048A (en) | Orientation capillary power drive is prepared using electrostatic spinning large area efficiently to catchment the methods of hydrophobic/hydrophilic Janus composite cellulosic membranes | |
| Almetwally et al. | Technology of nano-fibers: Production techniques and properties-Critical review | |
| Luo et al. | Electrospinning versus fibre production methods: from specifics to technological convergence | |
| CN105926161B (en) | A kind of preparation method of the thickness combined nano fiber air filtering material with gradient-structure | |
| Ghorani et al. | Controlled morphology and mechanical characterisation of electrospun cellulose acetate fibre webs | |
| Krishnappa et al. | Morphological study of electrospun polycarbonates as a function of the solvent and processing voltage | |
| CN106283389B (en) | A kind of hydrophobic/hydrophilic infiltration sex differernce composite cellulosic membrane and preparation method thereof | |
| CN103173892B (en) | A kind of preparation method of nano bamboo fiber composite material | |
| CN102277689A (en) | Device and method for preparing cellulose fibrous membrane with nanometer structure | |
| CN1727530A (en) | Superfine fiber membrane material in core/shell structure, and preparation method | |
| CN103625089B (en) | The preparation method of nano fibrous membrane modified cellulose forming paper and application thereof | |
| CN107059150B (en) | A kind of preparation method of high intensity regenerated fibroin fiber | |
| CN103526336A (en) | Preparation method of oriented shell-core structural superfine composite fiber | |
| CN110438666A (en) | A kind of compound melt spraying non-woven fabrics and preparation method thereof | |
| CN103628253A (en) | Preparation method of functionalized tobacco shred bundles for filter stick and application of preparation method | |
| CN101445963A (en) | Polymer superfine fibre wet electrostatic spinning method | |
| CN102619026A (en) | Preparation method of nano micro cellulose fiber non-woven fabric | |
| CN110387588A (en) | A method of preparing the micro nanometer fiber film of core-shell structure using Janus syringe needle electrostatic spinning arranged side by side | |
| CN1837435B (en) | Composite nano-grade silk fiber product and method for preparing the same | |
| CN106498508B (en) | A kind of preparation method of polylactic acid electrostatic spinning solution | |
| CN105200559A (en) | Phase-change blend fiber | |
| Al-BiRuNi | Electrospun nylon-6 nanofibers and their characteristics | |
| CN102899734A (en) | Silk fibroin hollow fiber and preparation method thereof | |
| CN103143060B (en) | Preparation method of three-dimensional porous membrane with ordered hierarchical nano-structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070314 Termination date: 20100702 |