CN106436311B - The processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS - Google Patents
The processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS Download PDFInfo
- Publication number
- CN106436311B CN106436311B CN201610850374.1A CN201610850374A CN106436311B CN 106436311 B CN106436311 B CN 106436311B CN 201610850374 A CN201610850374 A CN 201610850374A CN 106436311 B CN106436311 B CN 106436311B
- Authority
- CN
- China
- Prior art keywords
- uvioresistant
- fiber
- high performance
- performance fibers
- processing method
- 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.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/5135—Unsaturated compounds containing silicon atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/004—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated using dispersed dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/26—Polyamides; Polyurethanes using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS disclosed by the invention, this method be by the uvioresistant inorganic agent of following general structure by fiber weigh 1.5~5% be configured to bath raio be 15~50:1 treatment fluid stirs evenly and adjusts the pH to 5~7 of uvioresistant treatment fluid, and the high-temperature pressure dyeing processing step and condition after then AROMATIC HIGH PERFORMANCE FIBERS is put into uvioresistant treatment fluid routinely are handled：
Description
Technical field
The invention belongs to AROMATIC HIGH PERFORMANCE FIBERS and its preparing technical fields, and in particular to a kind of uvioresistant aromatic series is high
The processing method of performance fibers.
Background technology
The AROMATIC HIGH PERFORMANCE FIBERSs such as fully aromatic polyamide (aramid fiber) and polyparaphenylene 1,3,4- oxadiazoles (p-POD)
All there are the property such as excellent physical mechanical, thermal stability, electrical insulating property, solvent resistance, special electric conductivity and electroluminescent
Can, often by as high-temperature filter cloth, permeable membrane and insulating protection materials'use (Zhang Z, Ye G, Li W, Li T, Xu
J.Influence of sulfuric acid bath on morphological structure and mechanical
properties of poly(p-phenylene-1,3,4-oxadiazole)fibers[J].Journal of Applied
Polymer Science,2009,114(3):1485-1493；Schulz B,Bruma M,Brehmer L.Aromatic
Poly(1,3,4-Oxadiazoe)s as Advanced materials[J].Advanced Materials,1997,9(8):
601-613；The Xi'an correlation research [D] of the structure and aramid paper characteristic of Zhao's meeting virtue aramid fibers and Fanglun slurry cake：Shaanxi
University of Science and Technology, 2012；Kakida H,Chatani Y,Tadokoro H.Crystal structure of poly(m-
phenylene isophthalamide)[J].Journal of Polymer Science:Polymer Physics
Edition,1976,14(3):427-435).But the photostability of this fiber is poor, its strength after ultraviolet light
Lose larger (Johnson L D, Tincher W C, Bach H C.Photodegradative wavelength
dependence of thermally resistant organic polymers[J].Journal of Applied
Polymer Science,1969,13(9):1825-1832；Imai Y.Direct fiber formation and fiber
properties of aromatic polyoxadiazoles[J].Journal of Applied Polymer Science,
1970,14(1):225-239).In order to improve the light resistance of this fiber, the scientific worker of this field mainly carries through research
Go out four kinds of solutions：(1) TiO is used2Gel, carbon black, polyvinyl alcohol and sodium carboxymethylcellulose etc. carry out coating to fiber
Processing.Although this processing mode fiber strength retention rate increases, after washing three times its uvioresistant performance with not
Coated fiber quite (the light aging of the fragrant race's polyoxadiazole fibers of Dong Li nanmus virtues and the Chengdu stabilisation research [D]:Sichuan University,
2010；Poly- 1,3,4- oxadiazoles (POD) agings of Yang Xiao and the Chengdu Protective Research [D]：Sichuan University, 2011)；(2) in p-POD
The azo structure substance that there is selective absorbing to light is introduced when polymerization, to protect the heterocycle structure in macromolecular chain, but this
A little azo structure substances not only be easy to cause spinneret hole plug in spinning process, and the initial strength of fiber is declined
(Zhou W,Yang X,Jia E,Wang X,Xu J,Ye G.Ultraviolet resistance of azo-
containing poly(1,3,4-oxadiazole)fibres[J].Polymer Degradation and Stability,
2013,98(3):691-696)；(3) disperse dyes of the selection containing azo structure dye fiber, still, due to dyestuff
In azo group effect it is limited, the uvioresistant performance of fiber is only capable of improving about 30%, far from meet requirement (Ji Changqing,
Zhang Zaixing, Li Wentao, Xing Tieling, Chen Guoqiang disperse dyes print influence [J] of modified poly- fragrant oxadiazole fiber photostability
Dye, 2014,40 (9):1-4)；(4) using the method directly arranged, i.e., with (γ-the ammonia third of water solubility eight with uvioresistant function
Base) silsesquioxane be finishing agent fiber is surface-treated, this method is easy to operate, relatively low to equipment requirement, still, by
In this method using the water-soluble POSS with amino, after the methods of padding, baking processing fiber, POSS molecules are only
It in the form of absorption, can be anchored at by Van der Waals force at the position of fiber surface defect and the gap of fibril.Therefore, when to fibre
When dimension or fabric washing, eight (γ-aminopropyl) silsesquioxanes are easy to return in water phase, and washing fastness is poor, therefore one
As three times wash after its uvioresistant performance it is just suitable with untreatment fiber【Mao Y,Zhou W,Xu J.Ultraviolet
resistance modification of poly(p-phenylene-1,3,4-oxadiazole)and poly(p-
phenylene terephthalamide)fibers with polyhedral oligomeric silsesquioxane
[J].Journal of Applied Polymer Science,2015,132(41)】。
Invention content
The purpose of the present invention is being directed to defect existing for existent technique, it is fine to provide a kind of uvioresistant aromatic series high-performance
The processing method of dimension.
The present invention provides the processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS, and the processing step and condition of this method are such as
Under：
(1) it is 15~50 by weighing 1.5~5% to be configured to bath raio to fiber by uvioresistant inorganic agent:1 treatment fluid, stirring
PH to 5~7 that is uniform and adjusting uvioresistant treatment fluid also needs addition 4~8 when handling aramid fiber (i.e. PPTA and PMIA) fiber
Grams per liter Metadelphene is as non-toxic carrier；
(2) the high-temperature pressure dyeing processing step after AROMATIC HIGH PERFORMANCE FIBERS being put into uvioresistant treatment fluid routinely
It is handled with condition.
Uvioresistant inorganic agent used in the above processing method is to graft on shape in eight polysilsesquioxane by disperse dyes
At, general structure it is as follows：
In formula：R is-CH=CH2、-CH2CH=CH2With-CH2CH2CH=CH2At least one of, quantity be 7 to 0 or
R ' is-CH2-CH2-、-CH2CH2-CH2Or-CH2CH2CH2-CH2At least one of, quantity is 1 to 8, when the inorganic agent
When R quantity is 7 on middle eight polysilsesquioxane base, R ' quantity just be 1, R quantity when being 6, and R ' quantity is just 2 ... ..., and R quantity is
When 0, R ' quantity is just 8；Its infrared absorption spectrum is in 588cm-1, 1109cm-1And 782cm-1Place occurs respectively representing Si-O-
Si and Si-C stretching vibration peaks, in 3068,2962cm-1And 1460cm-1Place occurs respectively representing-CH2–CH2-、-CH2–CH2–
CH2Or-CH2–CH2–CH2–CH2Flexible and flexural vibrations peak；Its29There is generation in the places -109.63ppm in Si NMR spectras
The vibration peak of silicon atom in table POSS structures；It is appeared below in the uv-visible absorption spectroscopy medium wavelength 300nm of its solution
Absorption peak.
Above-described uvioresistant inorganic agent is prepared by following methods：
(1) eight polysilsesquioxane (POSS) and disperse dyes are ground into the powder that grain size is 0.5~1 μm respectively, pressed
0.6~3 part of eight polysilsesquioxane is uniformly mixed by parts by weight with 0.3~3.2 part of disperse dyes, under nitrogen atmosphere, together with
Stirring in 60~500 parts of organic solvents I is added together for 0.15~0.45 part of catalyst until fully dissolving, then temperature rising reflux is anti-
It answers 18~30 hours；
(2) mixed liquor is cooled to 5 DEG C to stir evenly hereinafter, being then added in 0.3~1.9 part of organic solvent II, is depressurized
Filtering, filtrate decompression distillation removal solvent obtain uvioresistant inorganic agent crude product；
(3) uvioresistant inorganic agent crude product is added in 130~790 parts of extractants, reflux extraction 18~30 hours, then into
Row is filtered under diminished pressure, and finally carrying out vacuum distillation to filtrate can be obtained refined uvioresistant inorganic agent,
The number of material used above is parts by weight.
Eight polysilsesquioxane used in above method (POSS) is specially eight vinyl silsesquioxanes, eight acrylic
At least one of silsesquioxane and eight cyclobutenyl silsesquioxanes, structural formula is as follows：
R is-CH=CH in formula2、-CH2CH=CH2With-CH2CH2CH=CH2At least one of.
Disperse dyes used in above method are disperse red 60 or Disperse Yellow 42.
Organic solvent I used in above method is at least one of carbon tetrachloride, carbon disulfide and benzene.
Catalyst used in above method is at least one in anhydrous ferric chloride, anhydrous magnesium chloride and anhydrous Aluminum chloride
Kind.
Organic solvent II used in above method is at least one of triethylamine, diethylamine and dichloromethane.
Extractant used in above method is at least one of chloroform, dichloromethane and toluene.
The conditioning agent that uvioresistant treatment fluid pH is used in the above processing method is the mixed liquor of glacial acetic acid/sodium acetate.
AROMATIC HIGH PERFORMANCE FIBERS described in the above processing method is fully aromatic polyamide【Aramid fiber, i.e. PPTA and
PMIA)】Or polyparaphenylene 1,3,4- oxadiazoles (p-POD).If processing is aramid fiber, 4~8 can also be added in treatment fluid
Grams per liter Metadelphene is as non-toxic carrier, to improve color yield.
High-temperature pressure dyeing processing step routinely and condition described in the above processing method are：
(1) fiber is put into the uvioresistant treatment fluid of preparation at room temperature, impregnate 10~30 minutes after, with 1~5 DEG C/
After minute is warming up to 120~150 DEG C, keeps the temperature 120~240 minutes and take out；
(2) fiber is put into the mixed solution being made of 1~5g/L sodium dithionites and 0.5~2.5g/L sodium carbonate
In, in bath raio：30:Under 1, in 60~90 DEG C of soap boilings 5~25 minutes, then fiber is respectively cleaned in hot and cold distilled water respectively
Twice, the last naturally dry in ventilated environment.
Compared with prior art, it mainly has the following advantages：
1. since the processing method provided by the present invention has abandoned the prior art using water-soluble eight (γ-aminopropyl) sesquialter silicon
Oxygen alkane directly handles the mode of fiber, and disperse dyes graft modification has been selected to be insoluble in the POSS with ethylene linkage of water as anti-
Ultraviolet inorganic agent, and fiber superficial is securely embedded in by means of dye molecule in uvioresistant inorganic agent by high temperature high pressure process method
Layer, achievees the purpose that be bonded on fiber, thus it is lasting to make the uvioresistant AROMATIC HIGH PERFORMANCE FIBERS of acquisition that can either play
Uvioresistant function, moreover it is possible to it is synchronous to realize being dyed accordingly to fiber, it kills two birds with one stone.
2. due to the eight poly- sesquialters for being grafted on cage modle in the uvioresistant inorganic agent that is used in the processing method provided by the present invention
Disperse dyes on siloxanes have higher affinity with AROMATIC HIGH PERFORMANCE FIBERS, can pass through conventional high temperature high pressure process
Technique is embedded in fiber superficial layer securely, thus not only solves the cage modle eight polysilsesquioxane with ethylene linkage because of no water solubility
The problem of cannot be directly used to the processing of fiber uvioresistant, and the protection of one layer of eight polysilsesquioxane can also be formed in fiber surface
Layer, can more effectively improve the strength retention of fiber after ultraviolet light.
3. due to the uvioresistant inorganic agent both color development system containing disperse dyes that the processing method provided by the present invention uses,
Also the cage modle uvioresistant structure containing POSS, thus can be synchronized by conventional high-temperature pressure dyeing technique and realize fiber dye
Color and the purpose for improving uvioresistant performance, can not only widen the application range of AROMATIC HIGH PERFORMANCE FIBERS, and can reduce the function
The cost of fiber.
4. due to the uvioresistant inorganic agent used in method provided by the invention only by the POSS containing alkenyl, disperse red 60 and
Disperse Yellow 42 dyestuff is made, the not only equal asepsis environment-protecting of raw material, to processing modified device without other particular/special requirements, and operating procedure
Simply, condition control is easy, thus is suitable for industrialized production.
Description of the drawings
Fig. 1 is disperse red 60 and is modified the uvioresistant processing of gained after the cage modle eight polysilsesquioxane containing alkenyl with it
The infrared absorption spectrum curve of agent.Two spectral lines are first as it can be seen that disperse red 60 is poly- in the modified cage modle eight containing alkenyl from figure
Overall shape change is little before and after silsesquioxane, does not cause after illustrating the modified cage modle eight polysilsesquioxane containing alkenyl
The precursor structure of the dyestuff and main chromophoric group significantly change, thus can speculate that the dominant hue of dyestuff does not change.
Secondly as it can be seen that in 588cm-1, 1109cm-1And 782cm-1Place has increased three newly compared with strong absworption peak, corresponds to Si-O-Si and Si-respectively
C stretching vibration peaks；In 3068,2962cm-1And 1460cm-1There are three moderate strength absorption peaks in place, respectively represents-CH2–
CH2-、-CH2–CH2–CH2Or-CH2–CH2–CH2–CH2Flexible and flexural vibrations peak, this illustrates that disperse red 60 molecule has been connected on
In the main functional group of cage modle eight polysilsesquioxane containing alkenyl.
The nucleus magnetic hydrogen spectrum of the uvioresistant inorganic agent of gained after Fig. 2 is present invention disperse red 60 modification POSS1H NMR figures.
It is shown in figure, the absorption peak at 2.08 and 1.25ppm corresponds to the alkyl hydrogen atom that dyestuff is connect with POSS；14.07 Hes
Hydrogen atom at 5.30ppm on the unimodal hydroxyl and amino corresponded to respectively on dye matrix；The multiple suction of 6.41~8.38ppm
Receive what peak was then generated by the hydrogen atom on aromatic ring.
The nuclear-magnetism of the uvioresistant inorganic agent of gained after Fig. 3 is present invention disperse red 60 modification POSS13C NMR figures.From figure
In as it can be seen that have at 15.68 and 29.06ppm by connection dyestuff and POSS alkyl carbon atoms generation absorption peak；139.14ppm
There is the absorption peak of carbon atom on the phenyl ring being connected with POSS at place；It is former all to belong to each carbon in anthraquinone ring for other absorption peaks in figure
Son, the specific situation that belongs to are shown in figure.
The nuclear-magnetism of the uvioresistant inorganic agent of gained after Fig. 4 is present invention disperse red 60 modification POSS29Si NMR spectras.From
As it can be seen that there is belonging to silicon atom (SiO in POSS structures in the places -109.63ppm in figure4) vibration peak.
In addition, be not specified in Fig. 1~31H NMR：5.88~6.13ppm of δ and13C NMR：76.70~77.33ppm points of δ
The alkenyl that reaction Biao Shi not be had neither part nor lot in POSS molecules remains hydrogen atom (the 3H CH=CH of base2) and carbon atom (2C CH=CH2)。
Fig. 5 be disperse red 60 solution and with its be modified POSS after the uvioresistant of gained handle agent solution (concentration be
0.02g/L) it is ultraviolet-can be by optical absorption spectra.It can be seen that relative to former disperse red 60 dyestuff, modified uvioresistant
Dye moiety is still in visible wavelength range in inorganic agent, and the position of absorption peak does not also change, but in ultraviolet light portion
Point, the absorption peak of uvioresistant inorganic agent is moved to small echo length direction.This phenomenon shows choosing of the anti ultraviolet agent to ultraviolet light
Selecting property influx and translocation, fiber obtains significant uvioresistant performance after can making processing.
Fig. 6 is using after the uvioresistant inorganic agent processing being grafted obtained by cage modle eight polysilsesquioxane by disperse red 60 dyestuff
The Cross-sectional optical microscope photo of p-POD fibre bundles.From photo as it can be seen that every fiber only has the outer circle of superficial layer one to take on a red color,
Show through the method for the present invention treated fiber, the dyestuff being grafted on uvioresistant inorganic agent is concentrated mainly on fiber superficial layer, greatly
The about thickness (RED sector in figure) of fiber radius 1/5, and the larger cage modle eight polysilsesquioxane of volume is just main concentrates
Outside, the protective layer that one layer of eight polysilsesquioxane is formed in fiber surface, thus can more effectively improve ultraviolet lighting
The strength retention for penetrating rear fiber achievees the purpose that protect fiber.
Specific implementation mode
Embodiment is given below so that the present invention to be specifically described, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, the people that is skilled in technique of this field
Member still falls within the protection of the present invention according to some nonessential modifications and adaptations that the content of aforementioned present invention makes the present invention
Range.
It is worth noting that fine with uvioresistant inorganic agent treated p-POD, PPTA and PMIA prepared by following embodiment
The strength of dimension and washing test are respectively according to (GB/T 3923.1-1997) and (GB/T 3921-2008) (10 times) progress
's；The K/S values of fiber measure in this way, i.e., first by test sample uniform winding on opaque plastic tab (2 × 2 ×
0.1cm), light transmission in order to prevent, for winding fiber respectively along respectively one layer of the winding of two vertical direction, the sample after winding is placed on computer
On color measurement and color match instrument (Spectra Flash SF 600, Datacolor, USA), using D6510 ° of standard viewing angles of light source are surveyed
Amount.
Embodiment 1
It is 0.3 part of the eight vinyl silsesquioxane of 0.5~1 μm of powder, eight acrylic sesquialters that grain size will be ground into respectively
0.8 part of 0.3 part of siloxanes and disperse red 60 dyestuff are uniformly mixed, under nitrogen atmosphere, together with 0.15 part of anhydrous Aluminum chloride
Stirring in 60 parts of carbon disulfide and 60 parts of carbon tetrachloride is added until fully dissolving, then heats to mixed solvent boiling point, keeps the temperature
Back flow reaction 24 hours；After stopping heating, mixed liquor is cooled to 0 DEG C with ice water, 0.4 part of triethylamine and 0.3 part is then added
It stirs evenly, is filtered under diminished pressure in diethylamine mixed liquor, remove insoluble catalyst, filtrate decompression distillation removal solvent obtains anti-purple
Outer inorganic agent crude product；Crude product is added in 250 parts of dichloromethane, reflux extraction 18 hours in Soxhlet extractor, then into
Row is filtered under diminished pressure, and removes undissolved former dyestuff, and finally carrying out vacuum distillation to filtrate can be obtained refined uvioresistant processing
Agent.Gained purified product yield is 73.9%.
Embodiment 2
It will be ground into 0.6 part of the eight acrylic silsesquioxane and disperse red 60 dyestuff that grain size is 0.5~1 μm of powder respectively
1.2 parts are uniformly mixed, and under nitrogen atmosphere, stirring in 60 parts of benzene are added together with 0.15 part of anhydrous ferric chloride until fully molten
Solution then heats to mixed solvent boiling point, heat preservation back flow reaction 30 hours；After stopping heating, mixed liquor is cooled to 2 with ice water
DEG C, it is then added in 1.9 parts of diethylamine and stirs evenly, be filtered under diminished pressure, remove insoluble catalyst, filtrate decompression distillation removal is molten
Agent obtains uvioresistant inorganic agent crude product；Crude product is added in 65 parts of dichloromethane and 65 parts of toluene, in Soxhlet extractor
Reflux extraction 30 hours, then be filtered under diminished pressure, undissolved former dyestuff is removed, being finally evaporated under reduced pressure to filtrate can obtain
To refined uvioresistant inorganic agent.Gained purified product yield is 75.4%.
Embodiment 3
It will be ground into 0.6 part of the eight cyclobutenyl silsesquioxane and Disperse Yellow 42 dyestuff that grain size is 0.5~1 μm of powder respectively
3.2 parts are uniformly mixed, and under nitrogen atmosphere, 300 are added together with 0.22 part of anhydrous ferric chloride and 0.23 part of anhydrous magnesium chloride
Stirring in part carbon disulfide and 200 parts of benzene then heats to mixed solvent boiling point until fully dissolving, and it is small to keep the temperature back flow reaction 18
When；After stopping heating, mixed liquor is cooled to 4 DEG C with ice water, 1.5 parts of diethylamine and 1.5 parts of dichloromethane mixing are then added
It stirs evenly, is filtered under diminished pressure in liquid, remove insoluble catalyst, it is thick that filtrate decompression distillation removal solvent obtains uvioresistant inorganic agent
Product；Crude product is added in 450 parts of dichloromethane and 340 parts of chloroforms, reflux extraction 24 hours in Soxhlet extractor,
It is filtered under diminished pressure again, removes undissolved former dyestuff, finally carrying out vacuum distillation to filtrate can be obtained refined uvioresistant
Inorganic agent.Gained purified product yield is 69.9%.
Embodiment 4
It is 1.5 parts of the eight vinyl silsesquioxane of 0.5~1 μm of powder, eight cyclobutenyl sesquialters that grain size will be ground into respectively
0.3 part of 1.5 parts of siloxanes and Disperse Yellow 42 dyestuff are uniformly mixed, under nitrogen atmosphere, together with 0.12 part of anhydrous magnesium chloride and
Stirring in 25 parts of benzene and 95 parts of carbon tetrachloride is added together for 0.03 part of anhydrous Aluminum chloride until fully dissolving, then heats to mixing
Solvent boiling point, heat preservation back flow reaction 20 hours；After stopping heating, mixed liquor is cooled to 1 DEG C with ice water, is then added 0.35 part
It stirs evenly, is filtered under diminished pressure in triethylamine and 0.35 portion of dichloromethane mixed liquor, remove insoluble catalyst, filtrate decompression distillation
Removal solvent obtains uvioresistant inorganic agent crude product；Crude product is added in 300 parts of chloroforms, is flowed back in Soxhlet extractor
Extraction 20 hours, then be filtered under diminished pressure, undissolved former dyestuff is removed, finally carrying out vacuum distillation to filtrate can be obtained essence
The uvioresistant inorganic agent of system.Gained purified product yield is 77.1%.
Embodiment 5
It will be ground into 1.2 parts of the eight vinyl silsesquioxane and disperse red 60 dyestuff that grain size is 0.5~1 μm of powder respectively
2 parts are uniformly mixed, and under nitrogen atmosphere, are added in 300 parts of carbon tetrachloride and are stirred until filling together with 0.3 part of anhydrous ferric chloride
Divide dissolving, then heats to mixed solvent boiling point, heat preservation back flow reaction 28 hours；After stopping heating, liquid cooling will be mixed with ice water
But it to 3 DEG C, is then added in 1.2 parts of triethylamines and stirs evenly, be filtered under diminished pressure, remove insoluble catalyst, filtrate decompression distillation
Removal solvent obtains uvioresistant inorganic agent crude product；Crude product is added in 500 parts of toluene, the reflux extraction in Soxhlet extractor
28 hours, then be filtered under diminished pressure, remove undissolved former dyestuff, finally to filtrate carry out vacuum distillation can be obtained it is refined
Uvioresistant inorganic agent.Gained purified product yield is 79.2%.
Embodiment 6
The uvioresistant inorganic agent that embodiment 1 is prepared is weighed 1.5% by fiber, it is 30 to be configured to bath raio:1 processing
Liquid, the pH value for stirring evenly and adjusting uvioresistant treatment fluid are 5, in the uvioresistant treatment fluid to handling PPTA and PMIA fibers also
5 grams per liter Metadelphenes are added as non-toxic carrier；Fiber is put at room temperature in the uvioresistant treatment fluid of preparation and impregnates 10 points
Zhong Hou is warming up to 120 DEG C with 1.5 DEG C/min, keeps the temperature 180 minutes and take out；Fiber is put by 3g/L sodium dithionites and
In the mixed solution of 1g/L sodium carbonate composition, in bath raio：30:Under 1, in 80 DEG C of soap boilings 10 minutes, then by fiber respectively it is cold,
It is respectively cleaned twice in hot distilled water, finally the naturally dry in ventilated environment.
The K/S values of p-POD, PPTA and PMIA fiber are respectively 8.61,7.21 and 7.83 after processing, directly through 72 hours
Ultraviolet light strength retention is respectively 89.0,71.8 and 76.7% (with fibrinogen strength for standard), is passed through after washing 10 times
72 hours ultraviolet light strength retentions are respectively 88.0,71.3 and 75.5%.
Embodiment 7
The uvioresistant inorganic agent that embodiment 2 is prepared is weighed 2.5% by fiber, it is 15 to be configured to bath raio:1 processing
Liquid, the pH value for stirring evenly and adjusting uvioresistant treatment fluid are 7, in the uvioresistant treatment fluid to handling PPTA and PMIA fibers also
4 grams per liter Metadelphenes are added as non-toxic carrier；Fiber is put at room temperature in the uvioresistant treatment fluid of preparation and impregnates 20 points
Zhong Hou is warming up to 150 DEG C with 1 DEG C/min, keeps the temperature 120 minutes and take out；Fiber is put by 1g/L sodium dithionites and
In the mixed solution of 2.5g/L sodium carbonate composition, in bath raio：30:Under 1, in 60 DEG C of soap boilings 25 minutes, then fiber is existed respectively
It is respectively cleaned twice in hot and cold distilled water, finally the naturally dry in ventilated environment.
The K/S values of p-POD, PPTA and PMIA fiber are respectively 9.53,8.22 and 8.40 after processing, directly through 72 hours
Ultraviolet light strength retention is respectively 90.2,72.8 and 79.7% (with fibrinogen strength for standard), is passed through after washing 10 times
72 hours ultraviolet light strength retentions are respectively 89.7,72.2 and 77.9%.
Embodiment 8
The uvioresistant inorganic agent that embodiment 3 is prepared is weighed 5% by fiber, it is 40 to be configured to bath raio:1 processing
Liquid, the pH value for stirring evenly and adjusting uvioresistant treatment fluid are 6.5, in the uvioresistant treatment fluid to handling PPTA and PMIA fibers
8 grams per liter Metadelphenes are also added into as non-toxic carrier；Fiber is put into the uvioresistant treatment fluid of preparation at room temperature and impregnates 15
After minute, 140 DEG C are warming up to 4 DEG C/min, 200 minutes is kept the temperature and takes out；Fiber is put by 5g/L sodium dithionites and
In the mixed solution of 0.5g/L sodium carbonate composition, in bath raio：30:Under 1, in 70 DEG C of soap boilings 20 minutes, then fiber is existed respectively
It is respectively cleaned twice in hot and cold distilled water, finally the naturally dry in ventilated environment.
The K/S values of p-POD, PPTA and PMIA fiber are respectively 10.23,8.46 and 8.54 after processing, directly small through 72
When ultraviolet light strength retention (with fibrinogen strength for standard) be respectively 85.9,70.5 and 73.1%, after washing 10 times
It is respectively 85.1,66.8 and 71.1% through 72 hours ultraviolet light strength retentions.
Embodiment 9
The uvioresistant inorganic agent that embodiment 4 is prepared is weighed 4% by fiber, it is 50 to be configured to bath raio:1 processing
Liquid, the pH value for stirring evenly and adjusting uvioresistant treatment fluid are 6, in the uvioresistant treatment fluid to handling PPTA and PMIA fibers also
6 grams per liter Metadelphenes are added as non-toxic carrier；Fiber is put at room temperature in the uvioresistant treatment fluid of preparation and impregnates 30 points
Zhong Hou is warming up to 130 DEG C with 5 DEG C/min, keeps the temperature 240 minutes and take out；Fiber is put by 4g/L sodium dithionites and 2g/L
In the mixed solution of sodium carbonate composition, in bath raio：30:Under 1, in 90 DEG C of soap boilings 5 minutes, then by fiber respectively in hot and cold steaming
It is respectively cleaned twice in distilled water, finally the naturally dry in ventilated environment.
The K/S values of p-POD, PPTA and PMIA fiber are respectively 10.35,8.52 and 8.46 after processing, directly small through 72
When ultraviolet light strength retention (with fibrinogen strength for standard) be respectively 84.8,71.4 and 73.8%, after washing 10 times
It is respectively 83.5,70.1 and 71.9% through 72 hours ultraviolet light strength retentions.
Embodiment 10
The uvioresistant inorganic agent that embodiment 5 is prepared is weighed 3% by fiber, it is 40 to be configured to bath raio:1 processing
Liquid, the pH value for stirring evenly and adjusting uvioresistant treatment fluid are 5.5, in the uvioresistant treatment fluid to handling PPTA and PMIA fibers
6 grams per liter Metadelphenes are also added into as non-toxic carrier；Fiber is put into the uvioresistant treatment fluid of preparation at room temperature and impregnates 30
After minute, 150 DEG C are warming up to 1 DEG C/min, 150 minutes is kept the temperature and takes out；Fiber is put by 2g/L sodium dithionites and
In the mixed solution of 1g/L sodium carbonate composition, in bath raio：30:Under 1, in 70 DEG C of soap boilings 15 minutes, then by fiber respectively it is cold,
It is respectively cleaned twice in hot distilled water, finally the naturally dry in ventilated environment.
The K/S values of p-POD, PPTA and PMIA fiber are respectively 9.48,8.20 and 8.61 after processing, directly through 72 hours
Ultraviolet light strength retention is respectively 90.0,72.2 and 78.9% (with fibrinogen strength for standard), is passed through after washing 10 times
72 hours ultraviolet light strength retentions are respectively 89.7,72.0 and 77.3%.
Comparative example 1
By p-POD, PPTA and PMIA fiber handled without uvioresistant inorganic agent of the present invention through 72 hours ultraviolet lights
Strength retention is respectively 30.8%, 32.8% and 26.7% afterwards.
Dyeing processing is carried out respectively to p-POD, PPTA and PMIA fiber, dyeing is：Commodity disperse red 60 is pressed
2.5% is weighed to fiber, it is 15 to be configured to bath raio:1 dye liquor, the pH value for stirring evenly and adjusting dye liquor are 7, PPTA and PMIA fine
It ties up in the dye liquor of dyeing and is also added into 4 grams per liter Metadelphenes as non-toxic carrier；Fiber is put into the dye liquor of preparation at room temperature
It impregnates after twenty minutes, is warming up to 150 DEG C with 1 DEG C/min, keeps the temperature 120 minutes and take out；Fiber is put by 1g/L hydrosulfurous acids
In the mixed solution of sodium and 2.5g/L sodium carbonate composition, in bath raio：30:Under 1, in 60 DEG C of soap boilings 25 minutes, then by fiber point
It is not cleaned respectively twice in hot and cold distilled water, finally the naturally dry in ventilated environment.
K/S values with fiber after disperse red 60 dyeing were respectively 9.71,8.41 and 8.63, through 72 hours ultraviolet lightings
It is respectively 31.6%, 32.3% and 31.7% to penetrate strength retention, is retained through 72 hours ultraviolet light strengths after washing 10 times
Rate is respectively 31.5%, 31.5% and 30.2%.
Comparative example 2
By p-POD, PPTA and PMIA fiber handled without uvioresistant inorganic agent of the present invention through 72 hours ultraviolet lights
Strength retention is respectively 30.8%, 32.8% and 26.7% afterwards.
Dyeing processing is carried out respectively to p-POD, PPTA and PMIA fiber, dyeing is：It will be by commodity Disperse Yellow 42
4% is weighed by fiber, it is 50 to be configured to bath raio:1 dye liquor, the pH value for stirring evenly and adjusting dye liquor are 6, PPTA and PMIA fine
It ties up in the dye liquor of dyeing and is also added into 6 grams per liter Metadelphenes as non-toxic carrier；Fiber is put into the dye liquor of preparation at room temperature
After impregnating 30 minutes, 130 DEG C are warming up to 5 DEG C/min, 240 minutes is kept the temperature and takes out；Fiber is put by 4g/L hydrosulfurous acids
In the mixed solution of sodium and 2g/L sodium carbonate composition, in bath raio：30:Under 1, in 90 DEG C of soap boilings 5 minutes, then fiber is existed respectively
It is respectively cleaned twice in hot and cold distilled water, finally the naturally dry in ventilated environment.
It is respectively 11.26,9.45 and 9.33 with the K/S values of the fiber after Disperse Yellow 42 dyeing, directly through 72 hours
Ultraviolet light strength retention is respectively 31.6%, 32.3% and 29.7%, through 72 hours ultraviolet lights after washing 10 times
Strength retention is respectively 31.5%, 31.5% and 29.6%.
Claims (8)
1. a kind of processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS, the processing step and condition of this method are as follows：
(1) it is 15~50 by weighing 1.5~5% to be configured to bath raio to fiber by uvioresistant inorganic agent:1 treatment fluid, stirs evenly
And the pH to 5~7 of uvioresistant treatment fluid is adjusted, when handling aramid fiber, also need 4~8 grams per liter Metadelphene of addition as nontoxic
Carrier；
(2) high-temperature pressure dyeing processing step and item after AROMATIC HIGH PERFORMANCE FIBERS being put into uvioresistant treatment fluid routinely
Part is handled,
Uvioresistant inorganic agent used in it is to be grafted on to be formed in eight polysilsesquioxane by disperse dyes, and general structure is such as
Under：
In formula：R is-CH=CH2、-CH2CH=CH2With-CH2CH2CH=CH2At least one of, quantity is 7 to 0 or R '
For-CH2-CH2-、-CH2CH2-CH2Or-CH2CH2CH2-CH2At least one of；Its infrared absorption spectrum is in 588cm-1,
1109cm-1And 782cm-1Place occurs respectively representing Si-O-Si and Si-C stretching vibration peaks, in 3068,2962cm-1With
1460cm-1Place occurs respectively representing-CH2–CH2-、-CH2–CH2–CH2Or-CH2–CH2–CH2–CH2Flexible and bending vibration
Peak；Its29Occur in the places -109.63ppm representing the vibration peak of silicon atom in POSS structures in Si NMR spectras；In its solution
Uv-visible absorption spectroscopy medium wavelength 300nm has appeared below absorption peak.
2. the processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS according to claim 1, the anti-purple described in this method
Outer inorganic agent is prepared by following methods：
(1) eight polysilsesquioxane and disperse dyes are ground into the powder that grain size is 0.5~1 μm respectively, by weight by 0.6
~3 parts of eight polysilsesquioxanes are uniformly mixed with 0.3~3.2 part of disperse dyes, under nitrogen atmosphere, together with 0.15~0.45 part
Stirring in 60~500 parts of organic solvents I is added together for catalyst until fully dissolving, then temperature rising reflux reaction 18~30 is small
When；
(2) mixed liquor is cooled to 5 DEG C to stir evenly hereinafter, being then added in 0.3~1.9 part of organic solvent II, is filtered under diminished pressure,
Filtrate decompression distillation removal solvent obtains uvioresistant inorganic agent crude product；
(3) uvioresistant inorganic agent crude product is added in 130~790 parts of extractants, reflux extraction 18~30 hours, then is subtracted
Press filtration finally carries out vacuum distillation to filtrate and can be obtained refined uvioresistant inorganic agent,
The number of material used above is parts by weight.
3. the processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS according to claim 1 or 2, eight used in this method
Polysilsesquioxane is specially in eight vinyl silsesquioxanes, eight acrylic silsesquioxanes and eight cyclobutenyl silsesquioxanes
At least one, structural formula is as follows：
R is-CH=CH in formula2、-CH2CH=CH2With-CH2CH2CH=CH2At least one of.
4. the processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS according to claim 1 or 2, used in this method point
It is disperse red 60 or Disperse Yellow 42 to dissipate dyestuff.
5. the processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS according to claim 3, disperse used in this method
Dyestuff is disperse red 60 or Disperse Yellow 42.
6. the processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS according to claim 1 or 2, have used in this method
Solvent I is at least one of carbon tetrachloride, carbon disulfide and benzene；Catalyst used is anhydrous ferric chloride, anhydrous chlorination
At least one of magnesium and anhydrous Aluminum chloride；Organic solvent II used be triethylamine, diethylamine and dichloromethane at least
It is a kind of；Extractant used is at least one of chloroform, dichloromethane and toluene.
It is organic used in this method 7. the processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS according to claim 3
Solvent I is at least one of carbon tetrachloride, carbon disulfide and benzene；Catalyst used is anhydrous ferric chloride, anhydrous magnesium chloride
At least one of with anhydrous Aluminum chloride；Organic solvent II used is at least one in triethylamine, diethylamine and dichloromethane
Kind；Extractant used is at least one of chloroform, dichloromethane and toluene.
It is organic used in this method 8. the processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS according to claim 4
Solvent I is at least one of carbon tetrachloride, carbon disulfide and benzene；Catalyst used is anhydrous ferric chloride, anhydrous magnesium chloride
At least one of with anhydrous Aluminum chloride；Organic solvent II used is at least one in triethylamine, diethylamine and dichloromethane
Kind；Extractant used is at least one of chloroform, dichloromethane and toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610850374.1A CN106436311B (en) | 2016-09-26 | 2016-09-26 | The processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610850374.1A CN106436311B (en) | 2016-09-26 | 2016-09-26 | The processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106436311A CN106436311A (en) | 2017-02-22 |
| CN106436311B true CN106436311B (en) | 2018-08-14 |
Family
ID=58169555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610850374.1A Active CN106436311B (en) | 2016-09-26 | 2016-09-26 | The processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106436311B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109130402B (en) * | 2018-08-06 | 2020-12-29 | 濮阳玉润新材料有限公司 | Preparation method of high-performance fiber composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184697B (en) * | 2013-04-26 | 2014-10-22 | 四川大学 | One-bath dyeing and anti-mosquito finishing method of aramid fiber disperse dye |
| CN105951477A (en) * | 2016-05-31 | 2016-09-21 | 新昌县卓远纺织有限公司 | Method for dyeing chemical-fiber textile cloth |
-
2016
- 2016-09-26 CN CN201610850374.1A patent/CN106436311B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106436311A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI547619B (en) | Meta-type master aromatic polyamide fiber | |
| CN106521967B (en) | One kind is based on POSS grafting uvioresistant AROMATIC HIGH PERFORMANCE FIBERSs and its method of modifying | |
| CN106436311B (en) | The processing method of uvioresistant AROMATIC HIGH PERFORMANCE FIBERS | |
| WO2010120020A1 (en) | Aromatic polyamide molecular miscible blend solution and non-crystalline polymer, preparation method thereof, aromatic polyamide blend fiber obtained therefrom and method for dyeing fiber | |
| KR100762851B1 (en) | Process of dyeing meta-liked aramid using cation dye | |
| KR100762952B1 (en) | Para type aramid fiber and method for dyeing of the same | |
| CN103603217A (en) | Color fixing agent and preparation method thereof | |
| CN106432321B (en) | A kind of uvioresistant inorganic agent and preparation method thereof modified based on disperse dyes | |
| CN104530406A (en) | Fluorine-containing anti-fouling fire-resisting polyester and preparation method thereof | |
| EP0668942B2 (en) | Fibers and films of improved flame resistance | |
| CN109456065A (en) | Preparation method of SiC ceramic fiber | |
| KR20060130031A (en) | Thermally stable anthrapyridone compositions | |
| CN106496557A (en) | A kind of preparation method of high transparency high temperature resistant fluorinated polyimide resin | |
| CN110592711A (en) | Composite luminescent fiber and preparation method and application thereof | |
| JP4266678B2 (en) | Process for producing readily dyeable meta-type wholly aromatic polyamide fiber | |
| CN107337662B (en) | Water-soluble bi-fluorenyl quinoid thiophene derivative, preparation method and dyeing application thereof | |
| JPH01287167A (en) | Production of high polymer composite material | |
| JP2004525203A (en) | Anthraquinone dyes, their production and use | |
| KR101217151B1 (en) | Dyeing method of meta aramid staple fiber | |
| CN110499650A (en) | A kind of fireproof wear-resisting fabric | |
| US3600401A (en) | Deketo-benzo-dipyrole polymers | |
| WO2009040318A2 (en) | Dyes for polymer coloration, their preparation and their use | |
| CN107164979B (en) | A kind of polyimide support colouring method | |
| Gaffer et al. | New azo disperse dyes containing cyclohexanone ring for dyeing polyester and nylon fabrics | |
| CN115260785A (en) | Disperse dye containing bis (trisiloxy) anthraquinone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |