CN102504537B - Anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and preparation method thereof - Google Patents
Anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and preparation method thereof Download PDFInfo
- Publication number
- CN102504537B CN102504537B CN 201110363941 CN201110363941A CN102504537B CN 102504537 B CN102504537 B CN 102504537B CN 201110363941 CN201110363941 CN 201110363941 CN 201110363941 A CN201110363941 A CN 201110363941A CN 102504537 B CN102504537 B CN 102504537B
- Authority
- CN
- China
- Prior art keywords
- polysulfonamides
- titanium dioxide
- solvent
- spinning solution
- preparation
- 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
Landscapes
- Artificial Filaments (AREA)
Abstract
The invention provides an anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and a preparation method thereof. A solution blending method is adopted, polysulfone amide is adopted as a matrix, titanium dioxide is added to prepare the polysulfone amide/titanium dioxide nano-composite material with a mass fraction of 0-7%, and the polysulfone amide/titanium dioxide nano-composite material is prepared into composite fiber or a composite thin film. According to the present invention, an ultrasonic blending technology is adopted, such that a small amount of the titanium dioxide can be uniformly dispersed in the polysulfone amide matrix in the nanometer scale; the titanium dioxide is adopted as the nanoparticles with excellent anti-ultraviolet performance, when the titanium dioxide content is 7%, the ultraviolet transmittances of the composite material at a wavelength of 280-315 nm and a wavelength of 315-400 nm respectively reach 0.046% and 0.013%, such that the prepared polysulfone amide/titanium dioxide nano-composite material has excellent anti-ultraviolet performance; the method of the present invention has advantages of simple process, strong operability and low cost.
Description
Technical field
The present invention relates to field of nanocomposite materials, be specifically related to a kind of uvioresistant polysulfonamides/titanic oxide nano compound material and preparation method thereof.
Background technology
Polysulfonamides fibre is as a kind of novel textile materials, have good thermotolerance, thermostability and flame retardant properties etc., be applied to protection and other civil areas that fire-retardant requirement is arranged under aerospace field and the high-temperature work environment, in national defense and military and modern industry important purposes arranged.Yet conventional polysulfonamides fibre exist anti-ultraviolet property relatively poor, problem such as photoxidation phenomenon takes place under the irradiation of UV-light easily, have a strong impact on the application in its following process and other the functional industrial field.Therefore, how to improve the anti-ultraviolet property of polysulfonamides fibre and to optimize its over-all properties be one of important subject of current high temperature material exploitation.
At present, the domestic research that concentrates on thermal characteristics for the research emphasis of polysulfonamides fibre mostly, the research that its performance is improved also mainly concentrates on the dyeability that improves the polysulfonamides fabric and to the optimization of its technology, lessly see the relevant report that adopts the nano modification technology to prepare polysulfonamides and the matrix material of nano particle, and do not see the research that the employing nanotechnology prepares polysulfonamides/titanic oxide nano compound material as yet.
Summary of the invention
One of purpose of the present invention is to provide a kind of uvioresistant polysulfonamides/titanic oxide nano compound material.
One of purpose of the present invention is to provide the preparation method of this nano composite material.
For achieving the above object, the present invention adopts following technical scheme:
A kind of uvioresistant polysulfonamides/titanic oxide nano compound material, this nano composite material is matrix with the polysulfonamides, the Nano titanium dioxide particles dispersed is in the polysulfonamides matrix, wherein to account for the massfraction of described matrix material be 1～7% to the Nano titanium dioxide particle, and the mass ratio of polysulfonamides and titanium dioxide can be adjusted according to the requirement of anti-ultraviolet property.
Described Nano titanium dioxide particle grain size is 30～50nm, the content of titanium dioxide of rutile-type 〉=99%.
The preparation method's of above-described polysulfonamides/titanic oxide nano compound material concrete steps are:
1) with the Nano titanium dioxide particles dispersed in dimethylacetamide solvent, adopt ultrasonic blending technology that the Nano titanium dioxide uniform particles is disperseed then, ultra-sonic dispersion 60～120min, make the solvent dispersions of Nano titanium dioxide particle, wherein the mass ratio of titanium dioxide and N,N-DIMETHYLACETAMIDE is 1: 10～30;
2) solvent dispersions that step 1) is made joins in the polysulfonamides stoste, carries out mechanical stirring ultrasonic blend then earlier, forms polysulfonamides/titanic oxide nano compound material spinning solution;
3) with step 2) polysulfonamides/titanic oxide nano compound material spinning solution of making carries out spinning or film processed, makes uvioresistant polysulfonamides/titanic oxide nano compound material.
Step 2) churned mechanically speed is 10000～28000r/min, and the time is 30～60min.
Step 2) time of ultrasonic blend is 30～60min, and frequency is 30～40KHz.
Step 2) in when nano particle and polysulfonamides blend, the upper layer of co-mixing system contacts with air, under churned mechanically reactive force, sneak into the part air easily and form bubble, these bubbles easily along with the nano composite material spinning solution is together taken out of and remained in the fiber through orifice, reduce the mechanical property of fiber in follow-up spinning process.Therefore can suitably shorten churned mechanically time to 5～20min, reduce the probability that bubble produces, and the time to 90 of the ultrasonic blend of proper extension～120min to remove the bubble that exists in the spinning solution, reduces bubble to the influence of fibrous mechanical property.
The concrete steps of spinning described in the step 3) are as follows:
A is at nitrogen atmosphere, 0.5 under～2.0 normal atmosphere, matrix material spinning solution thread is extruded in orifice and enters with the pure water is in the tank of precipitation bath, solvent in the matrix material spinning solution thread spreads to precipitation bath, precipitation bath is permeated to matrix material spinning solution thread, thereby make matrix material spinning solution thread reach threshold concentration, in precipitation bath, separate out the formation nascent fibre;
B washes the gained nascent fibre and unwinding, to remove residual solvent in the nascent fibre, then nascent fibre is carried out nervous heat setting type, further remove residual solvent in the nascent fibre simultaneously, obtain polysulfonamides/titanium dioxide conjugated fibre, wherein heat setting temperature is 100～120 ℃, and the time is 60～120min.
The concrete steps of film processed described in the step 3) are as follows:
A puts into matrix material spinning solution standing and defoaming on the substrate of glue evenning table then, makes the matrix material spinning solution form the uniform film of thickness at substrate;
B removes solvent and the oven dry in the film, makes polysulfonamides/titania coextruded film.
The method of removing the solvent in the film among the step b is: will on have substrate static placement 30～60min in air of film to make solvent evaporates in the film, then it is immersed in that 30～60min extracts solvent in the water.
With substrate in air during static placement, mix impurity such as dust easily, will influence the performance characterization of laminated film to a certain extent, for example the test of scanning electron microscope, infrared spectra and X-ray diffraction etc., therefore, the film for preparing directly can be immersed in and extract solvent in the water; Time to 100～120min that this moment, but proper extension soaked.
Since conventional polysulfonamides exist anti-ultraviolet property relatively poor, problem such as photoxidation phenomenon takes place under the irradiation of UV-light easily, have a strong impact on the following process of polysulfonamides and the application of other functional industrial field.Titanium dioxide is a kind of good conductor oxidate, ultraviolet ray possessed excellent absorption and scattering function, therefore can be by solution blending and wet-spinning technology, be functional polyalkylene sulfonamide/nano titania conjugated fibre that matrix adds the titanium dioxide preparation with the polysulfonamides, will significantly improve the anti-ultraviolet property of nano composite material.
When the particle diameter of titanium dioxide drop to the de broglie wavelength of Bohr radius or conduction electron quite or more hour, the nanoparticle subnumber of unit volume or quality will increase, thereby many scatter points and absorption point have been increased, stop or intercept and capture ultraviolet probability and increase, therefore under irradiation of sunlight, ultraviolet energy major part is by nano particle scattering or absorption, therefore is not enough to allow the high-polymer molecular splitting of chain, thereby improved the anti-ultraviolet property of polysulfonamides matrix material.
The present invention utilizes ultrasonic blending technology, and a spot of titanium dioxide can be dispersed in the polysulfonamides matrix with nanoscale; Titanium dioxide makes the uvioresistant polysulfonamides/titanic oxide nano compound material of preparation have good anti-ultraviolet property as a kind of nano particle of anti-ultraviolet property excellence.The advantage of the inventive method is that technology is simple and convenient, and is workable and with low cost.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Raw material is prepared: main raw material is that (density is 0.9366g/cm to dimethylacetamide solvent
3); Polysulfonamides stoste, solid content are 12%; Described Nano titanium dioxide particle grain size is 30～50nm, the content of titanium dioxide of rutile-type 〉=99%.
Embodiment 1: preparation polysulfonamides/nano titania conjugated fibre
Concrete steps are as follows:
1) preparation of titanium dioxide solvent dispersions:
The titanium dioxide that takes by weighing 0.12g is dispersed in the dimethylacetamide solvent of 3mL; The ultrasonic blend processing of above-mentioned solvent dispersions being carried out 60min evenly spreads in the dimethylacetamide solvent titanium dioxide, forms the titanium dioxide solvent dispersions with good dispersion;
2) take by weighing 100g polysulfonamides spinning solution, above-mentioned titanium dioxide solvent dispersions is added in the Erlenmeyer flask, the shearing mechanism that carries out 30min with the speed of 10000r/min stirs, under the ultrasonic frequency of 30～40KHz, carry out the ultrasonic blend of 90min then, thereby preparation obtains polysulfonamides/titanic oxide nano compound material spinning solution;
3) adopt the small-sized wet-spinning device of single hole to carry out wet-spinning, concrete steps are as follows:
1. adjust spinning condition: the output pressure of control nitrogen is at 0.5～2.0 normal atmosphere; Receiving range is 1.2～2m; Spray silk speed is 60～100m/min; Winding speed is 30～70m/min;
2. under nitrogen pressure, matrix material spinning solution thread extrudes in orifice and enters with the pure water is in the tank of precipitation bath, solvent in the matrix material spinning solution thread spreads to precipitation bath, precipitation bath is permeated to thread, thereby make matrix material spinning solution thread reach threshold concentration, in precipitation bath, separate out the formation nascent fibre;
3. under the driving of stepper-motor, nascent fibre is wound up on the spool, and adjust the velocity of rotation of stepper-motor this moment, can do further drawing-off to nascent fibre;
4. the fiber behind the coiling full packages is in time washed and unwinding repeatedly;
5. nascent fibre is put into the electric heating convection oven and carried out nervous heat setting type, heat setting temperature is 100 ℃, and the time is 120min, obtains massfraction at last and be polysulfonamides/nano titania conjugated fibre of 1%.
Set-up procedure 1) to make the titanium dioxide massfraction be polysulfonamides/nano titania conjugated fibre of 3%, 5% and 7% to the quality of titanium dioxide and N,N-DIMETHYLACETAMIDE in.
Embodiment 2: preparation polysulfonamides/titania coextruded film
Adopt the desk-top digital display glue evenning table of SJT-B type to prepare the polysulfonamides nano compound film, concrete steps are as follows:
1) film forming condition of instrument is set: the low-speed running 5s of 2000RPM and the 20s that runs up of 4000RPM;
2) it is an amount of to get the nano composite material spinning solution that embodiment 1 makes, put into after the standing and defoaming on the substrate of glue evenning table, and be earlier that the low-speed running 5s of 2000RPM spreads spinning solution out with the rotations per minute;
3) after the time of setting, the 20s that runs up that is transformed into rotations per minute automatically and is 4000RPM makes spinning solution form the uniform film of thickness at substrate;
4) substrate static placement 30min in air is made after the solvent evaporates and it to be immersed in 60min extracts solvent in the water;
5) film is placed under 100 ℃ of temperature of electric heating convection oven and handle 120min, obtain massfraction after the oven dry and be respectively polysulfonamides/titania coextruded film of 1%.
Set-up procedure 1) to make the titanium dioxide massfraction be polysulfonamides/titania coextruded film of 3%, 5% and 7% to the quality of titanium dioxide and N,N-DIMETHYLACETAMIDE in.
Performance index:
Adopt Labsphere UV-1000F type textiles uvioresistant tester that the resulting matrix material of the present invention is carried out the test of anti-ultraviolet property, test result is as shown in table 1.
Table 1 as seen, the adding of titanium dioxide makes matrix material than pure PSA significant decline be arranged to ultraviolet transmitance in 280～400nm wavelength band, and data presentation is along with the increase of nano-particle content in the table, and matrix material strengthens gradually to ultraviolet shield effectiveness.In the UVA wavelength band, along with the content of nano particle rises to 7% by 1% gradually, the ultraviolet ray transmissivity of each matrix material has descended 44.2% than pure PSA successively, 61.9%, 64.0% and 95.0%, wherein, when the content of titanium dioxide is 7%, matrix material reaches maximum to the fall of ultraviolet ray transmissivity, anti-ultraviolet property to improve effect best, at this moment, 7% polysulfonamides nano composite material only is 0.013% at the ultraviolet ray transmissivity of UVB, illustrate that the polysulfonamides nano composite material can absorb or scatters ultraviolet effectively, titanium dioxide adds the anti-ultraviolet property that has significantly improved matrix material.
The relation of the content of table 1 titanium dioxide and uvioresistant effect
Wherein: the UVA wavelength band is 315～400nm;
The UVB wavelength band is 280～315nm.
Above-described embodiment is interpreted as only being used for explanation the present invention and is not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
Claims (6)
1. the preparation method of a polysulfonamides/titanic oxide nano compound material, described nano composite material is matrix with the polysulfonamides, the Nano titanium dioxide particles dispersed is in the polysulfonamides matrix, wherein the massfraction of Nano titanium dioxide particle in described matrix material is 1～7%, it is characterized in that, comprise following concrete steps:
1) with the Nano titanium dioxide particles dispersed in dimethylacetamide solvent, adopt ultrasonic blending technology that the Nano titanium dioxide uniform particles is disperseed then, ultra-sonic dispersion 60～120min, make the solvent dispersions of Nano titanium dioxide particle, wherein the mass ratio of Nano titanium dioxide particle and N,N-DIMETHYLACETAMIDE is 1:10～30;
2) solvent dispersions that step 1) is made joins in the polysulfonamides spinning solution, carry out earlier mechanical stirring then the ultrasonic blend shearing mechanism that carries out 30～60min with the speed of 10000～28000r/min stir, under the ultrasonic frequency of 30～40KHz, carry out the ultrasonic blend of 60～120min then, form polysulfonamides/titanic oxide nano compound material spinning solution;
3) with step 2) polysulfonamides/titanic oxide nano compound material spinning solution of making carries out spinning or film processed, makes uvioresistant polysulfonamides/titanic oxide nano compound material.
2. the preparation method of polysulfonamides/titanic oxide nano compound material according to claim 1 is characterized in that, the concrete steps of spinning described in the step 3) are as follows:
A is at nitrogen atmosphere, 0.5 under～2.0 normal atmosphere, matrix material spinning solution thread is extruded in orifice and enters with the pure water is in the tank of precipitation bath, solvent in the matrix material spinning solution thread spreads to precipitation bath, precipitation bath is permeated to matrix material spinning solution thread, thereby make matrix material spinning solution thread reach threshold concentration, in precipitation bath, separate out the formation nascent fibre;
B washes the gained nascent fibre and unwinding, then nascent fibre is carried out nervous heat setting type, obtains polysulfonamides/titanium dioxide conjugated fibre, and wherein heat setting temperature is 100～120 ℃, and the time is 60～120min.
3. the preparation method of polysulfonamides/titanic oxide nano compound material according to claim 2 is characterized in that, the processing condition of step a spinning are: receiving range is 1.2～2m; Spray silk speed is 60～100m/min; Winding speed is 30～70m/min.
4. the preparation method of polysulfonamides/titanic oxide nano compound material according to claim 1 is characterized in that, the concrete steps of film processed described in the step 3) are as follows:
A puts into matrix material spinning solution standing and defoaming on the substrate of glue evenning table then, makes the matrix material spinning solution form the uniform film of thickness at substrate;
B removes solvent and the oven dry in the film, makes polysulfonamides/titania coextruded film.
5. the preparation method of polysulfonamides/titanic oxide nano compound material according to claim 4, it is characterized in that, the method of removing solvent among the step b is: will on have substrate static placement 30～60min in air of film to make solvent evaporates in the film, then it is immersed in that 30～60min extracts solvent in the water.
6. the preparation method of polysulfonamides/titanic oxide nano compound material according to claim 4, it is characterized in that, the method of removing solvent among the step b is: the film for preparing directly is immersed in extracts solvent in the water, the time of immersion is 100～120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110363941 CN102504537B (en) | 2011-11-16 | 2011-11-16 | Anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110363941 CN102504537B (en) | 2011-11-16 | 2011-11-16 | Anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504537A CN102504537A (en) | 2012-06-20 |
| CN102504537B true CN102504537B (en) | 2013-10-09 |
Family
ID=46216675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110363941 Expired - Fee Related CN102504537B (en) | 2011-11-16 | 2011-11-16 | Anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504537B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184581A (en) * | 2013-03-21 | 2013-07-03 | 上海工程技术大学 | Method for preparing polysulfonamide/nanometer TiO2 composition fiber by electrostatic spinning method |
| CN106087396B (en) * | 2016-06-07 | 2018-11-23 | 上海工程技术大学 | A kind of graphene/polysulfonamides compound fabric and preparation method thereof |
| CN106087243B (en) * | 2016-06-12 | 2018-07-27 | 中材装备集团有限公司 | A kind of filter felt and preparation method thereof of polyimides and polysulfonamides blending |
| CN107164825A (en) * | 2017-06-22 | 2017-09-15 | 上海工程技术大学 | A kind of 1,8 eucalyptol health care polysulfonamides fibres and preparation method thereof |
-
2011
- 2011-11-16 CN CN 201110363941 patent/CN102504537B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 陈卓明等.功能性聚砜酰胺纳米复合材料的研究现状与分析.《产业用纺织品》.2011,(第06期),1-8. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504537A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Functional modification of breathable polyacrylonitrile/polyurethane/TiO2 nanofibrous membranes with robust ultraviolet resistant and waterproof performance | |
| CN110528314B (en) | Composite sheet containing melt-blown polyphenylene sulfide superfine fibers and preparation method and application thereof | |
| CN102504537B (en) | Anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and preparation method thereof | |
| CN110258021B (en) | High-waterproof high-air-permeability nanofiber membrane and preparation method thereof | |
| JP5838868B2 (en) | Cellulose nanofiber film | |
| CN103451851B (en) | A kind of preparation method of pliable and tough high-strength zirconia nano fibrous membrane | |
| Chen et al. | Length-controlled cellulose nanofibrils produced using enzyme pretreatment and grinding | |
| CN102931370A (en) | Organic/inorganic composite nanofiber membrane of lithium ion power battery and preparation method of organic/inorganic composite nanofiber membrane | |
| Abdelmoez et al. | Electrospun PDA‐CA nanofibers toward hydrophobic coatings | |
| CN103173892A (en) | Preparation method of nano bamboo fiber composite material | |
| CN102766358B (en) | Surface treatment method for flatting agent for chinlon chemical fiber | |
| CN107611320A (en) | Lithium battery applies cloth diaphragm water paste, lithium battery applies cloth diaphragm and their preparation method | |
| CN102504536B (en) | Carbon nano tube/titanium dioxide/polysulfonamide nano ternary composite material and preparation method thereof | |
| CN103130968A (en) | Low-surface-free-energy TiO2 nano composite particles and preparation method thereof | |
| Zheng et al. | Surface functionalization of PEO nanofibers using a TiO2 suspension as sheath fluid in a modified coaxial electrospinning process | |
| CN109505026A (en) | Moisture absorption sweat-releasing terylene fiber and preparation method thereof | |
| CN110343293A (en) | A kind of cellulose nano-fibrous/dopamine redox graphene enhancing starch film and preparation method thereof | |
| CN102418164B (en) | Antistatic polysulfonamide/carbon nano-tube composite material and preparation method thereof | |
| CN103059323B (en) | Preparation method of high-transparency ultraviolet-rejection ceramic-like nano composite film material | |
| CN114763627A (en) | Electrostatic spinning cellulose nanofiber and preparation method thereof | |
| JP2019099687A (en) | Resin composition and manufacturing method of resin composition | |
| CN104097358A (en) | Nano-fiber composite material with anti-ultraviolet function and making method thereof | |
| CN106995601A (en) | A kind of biodegradable polymers composite and preparation method thereof | |
| JP7143628B2 (en) | Resin molding and its manufacturing method | |
| Gao et al. | Application of cerium phosphate in preparing anti-ultraviolet PET fibers with masterbatch method |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131009 Termination date: 20201116 |