CN109705633A - A kind of preparation method of acrylic fibers chemical fibre of titanium dioxide - Google Patents
A kind of preparation method of acrylic fibers chemical fibre of titanium dioxide Download PDFInfo
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Abstract
A kind of preparation method of acrylic fibers chemical fibre of titanium dioxide, it is characterised in that: anatase pigmentary titanium dioxide is first dispersed into water slurry, ground, diluted, being classified removal bulky grain；Then coating hydrous silica, hydrated alumina and hydrous zirconium oxide(HZO) are carried out to titanium dioxide granule surface；It is handled again with the silane coupling agent with unsaturated double-bond by the titanium dioxide granule surface of inorganic coating, makes the double bond that can carry out free radical polymerization by the titanium dioxide granule surface band of inorganic coating；Finally modified titanium dioxide is dispersed in acetonitrile solvent, causes the titanium dioxide granule surface of free radical polymerization after modification and coats one layer of polymeric, obtain acrylic fibers titanium dioxide for chemical fiber.
Description
Technical field
The present invention relates to a kind of preparation methods of acrylic fibers chemical fibre of titanium dioxide.
Background technique
Chemical fibre of titanium dioxide is incorporated into chemical fibre and staple fibre, plays the titanium dioxide of photoextinction, and chemical fibre of titanium dioxide makes
Fiber surface is non-reflective, fiber is opaque and improves dyeability, the feel etc. of fiber, is the essential addition of delustering fibre
Agent.
Application range: terylene, polyamide fibre, acrylic fibers and acetate fiber etc..
The characteristics of due to chemical fibre such as polyester fiber production application, determines that the various performances of chemical fibre titanium dioxide and technology are special
Property.Titanium dioxide applied to chemical fibre must be anatase titanium dioxide, with excellent whiteness, aqueous dispersion ability, extinction capability, few thick
Big particle, moderate partial size and more narrow size distribution, while must also be in polyester production process especially in polycondensation
Do not occur in the process or seldom occurs secondary aggregation phenomenon.
A kind of preparation method of acrylic fibers chemical fibre of titanium dioxide of the present invention, it is characterised in that: first by anatase pigmentary titanium dioxide
It is dispersed into water slurry, ground, diluted, being classified removal bulky grain；Then coating hydrous oxygen is carried out to titanium dioxide granule surface
SiClx, hydrated alumina and hydrous zirconium oxide(HZO)；Again with the silane coupling agent with unsaturated double-bond to titanium dioxide granule surface into
Row processing, makes titanium dioxide granule surface band that can carry out the double bond of free radical polymerization；It is molten that titanium dioxide is finally dispersed in acetonitrile
In agent, causes free radical polymerization on titanium dioxide granule surface and coat one layer of polymeric, obtain acrylic fibers titanium dioxide for chemical fiber.It is first
First, titanium dioxide for chemical fiber requires big particle very high, will appear as long as the particle for having a particle diameter to be greater than 5 microns disconnected
Silk, influences product quality, so having to be ground, being classified removal bulky grain and could use.Secondly in order to eliminate titanium dioxide
The light degradation effect on titanium surface, it is necessary to inorganic oxide cladding be carried out to titanium dioxide, otherwise fiber is in use for some time
The case where will appear dusting (except terylene chemical fibre, terylene titanium dioxide for chemical fiber is without cladding), secondly to titanium dioxide surface
Polymer overmold, the covering power that titanium dioxide surface polymer overmold can reduce reunion, play titanium dioxide to greatest extent,
The reunion that can prevent titanium dioxide makes it keep monodisperse status, enhances its covering power, improve the utilization of titanium dioxide
Rate.
In order to enable polymer covering layer preferably to be combined with titanium dioxide surface, the present invention is first with the silane with double bond
Coupling agent is modified titanium dioxide surface, modified mechanism are as follows: the mechanism four-step reaction of silane coupling agent, i.e. (1)
3 Si-X bases being connected with silicon are hydrolyzed into Si-OH；(2) between Si-OH dehydrating condensation at the oligosiloxane containing Si-OH；(3)
The OH on Si-OH and substrate titanium dioxide surface in oligomer forms hydrogen bond；(4) with dehydration in heat curing process
And covalent key connection is formed with substrate titanium dioxide.It is generally believed that the silicon of silane coupling agent and substrate titanium dioxide on interface
Only one bonding of surface, is left two Si-OH, perhaps with the Si-OH condensation in other silane or between free state.
Above-mentioned four-step reaction can be schematically as follows:
Titanium dioxide surface after silane coupler modified, the group that silane coupling agent contains unsaturated double-bond vinyl also stay in
Titanium dioxide surface, then carried out with ethyl acrylate and acrylonitrile with initiator free-radical polymerized, it finally obtained surface aggregate
The titanium dioxide of object cladding.It is copolymerized by two kinds of monomers of ethyl acrylate and acrylonitrile and to be obtained in titanium dioxide surface coating
Titanium dioxide has good dispersibility in acrylic fibers (i.e. polyacrylonitrile), in order to characterize the titanium dioxide after coating in acrylic fibers
Dispersibility, according to similar compatibility principle, we survey its dispersibility in 16% acetonitrile solution to characterize it in acrylic fibers
Dispersibility, the dispersibility in 16% acetonitrile solution is higher, and the dispersibility in acrylic fibers is also better.
Summary of the invention
A kind of preparation method of acrylic fibers chemical fibre of titanium dioxide, it is characterised in that: in parts by weight by anatase pigmentary titanium dioxide
200 parts of titanium are dispersed in 200 parts of deionized water, while 0.4~0.8 part of sodium polyacrylate disperant is added, and use high speed dispersion
Machine disperses slurry to be made in 30~60 minutes；Slurry grinder is ground twice, then slurry is transferred in stirred tank, toward slurry
Add 800 parts of deionized water to be diluted in material, the slurry after dilution is continuously introduced into horizontal screw unloading centrifugal classifying
It is classified, the big material of removal particle, it is stand-by that fine granular materials are sent into stirred tank；
Slurry is heated to 80 DEG C, 5~6 parts of non-hydrate sodium metasilicates are added into slurry under constant stirring, continues 30 points of stirring
Clock, is slowly added 12~15 parts of sulfuric acid of 10% into slurry, and the time was added at 2 hours in control；Under constant stirring into slurry
10~12 parts of sodium aluminates are added, continue stirring 30 minutes, 50~60 parts of sulfuric acid of 10% are slowly added into slurry, control is added
Time was at 2 hours；8~10 parts of zirconium oxychlorides are added into slurry under constant stirring, continue stirring 30 minutes, slowly to slurry
The time was added at 2 hours in 12~15 parts of sodium hydroxide of middle addition 10%, control；Continue stirring 10 minutes, slurry is sent into sheet frame
It is filtered in filter press, filter cake is washed with deionized to sulfate radical-free；
Filter cake is put into hollander tub, filter cake adds 500 parts of deionized water mashing, and sodium polyacrylate disperant is added into slurry
0.6~0.8 part, 0.3 part of silane coupling agent is weighed, adds 2 parts of dehydrated alcohol dilutions, the ethanol solution containing silane coupling agent is delayed
Slowly it is added drop-wise to TiO2In slurry；Then the pH value of 10% ammonium hydroxide adjusting slurry is added dropwise to 8-9, under agitation by TiO2Slurry
It is heated to 80 DEG C, and isothermal reaction 1 hour, obtains surface through silane coupler modified finely dispersed TiO2Slurry；By TiO2
Slurries filtration, drying, crushing obtain TiO2Powder will obtain TiO2Powder is dispersed in 1000 parts of acetonitriles, in high speed disperser
Carry out high speed dispersion；
Group is uniformly mixed with 0.8~2 part of ethyl acrylate and 2.0~3.5 parts of acrylonitrile by 0.1 part of initiator azodiisobutyronitrile
At mix monomer；
By the above-mentioned TiO dispersed with acetonitrile2Slurry is heated to 75 DEG C, toward TiO2It is different that 0.03 part of initiator azo two is added in slurry
The above-mentioned mix monomer mixed initiation reaction 5 minutes, is then slowly added into above-mentioned TiO by butyronitrile2Acetonitrile slurry
In, time control is added and maintains 80 DEG C at 2-5 hours, after addition isothermal reaction 1 hour, obtains the TiO being coated to surface2
Slurry；By TiO2Slurries filtration obtains TiO2Filter cake is dried in filter cake, and the material after drying is crushed with pulverizer, so
After be packaged to be acrylic fibers titanium dioxide for chemical fiber；
The silane coupling agent is vinyltriethoxysilane, vinyltrimethoxysilane, γ-(methacryloxypropyl
Base) propyl trimethoxy silicane is one such or two or more.
The test method of dispersibility of the acrylic fibers titanium dioxide for chemical fiber in 16% acetonitrile solution
(1) operating procedure
1, it weighs
Titanium pigment specimen 15g(standard is weighed to 0.1g) in 500ml conical flask, then measures 16% acetonitrile solution with graduated cylinder
285ml is added in bottle.
2, disperse
By the slurry in conical flask with magnetic stirrer 30 minutes.
3, the measurement of initial slurry concentration
The slurry 10ml after dispersion is drawn with pipette immediately, is put into the weighing bottle of constant weight simultaneously accurate weighing slurry weight
(W1), it is then put into 130-140 DEG C of baking ovens drying 4 hours or more, after solvent evaporating completely, puts into cold in normal temperature dryer
But, accurate weighing residue weight (W2)。
4, standing sedimentation
Remaining dispersion slurries are fitted into the graduated cylinder (250ml) of measurement dispersibility, make the high 200mm of liquid level, standing sedimentation 5 is small
When.
5, it samples
With aspirator by the dispersion liquid after standing, 170ml liquid is drawn since liquid level, is put into the conical flask of 500ml.It inhales
When taking slurries, it is careful not to vibration sedimentation pipe, and in the state that aspirator is permanently connected to liquid level, even air sucks together.
6, the measurement of dispersion liquid concentration after settling
After being shaken 30 minutes on the dispersed paste earthquake machine of absorption (or being stirred 30 minutes using mechanical agitator), immediately
It draws 10ml to be fitted into the weighing bottle of constant weight, accurate weighing slurry weight (W3), it is then put into 130-140 DEG C of baking ovens and does
Dry 4 hours or more, after making solvent evaporating completely, put cooling in normal temperature dryer, accurate weighing residue weight (W into4)。
(2) it calculates
Dispersibility is calculated according to following formula:
w1w4
Dispersed (%)=--- 100%
W2W3
W1: the weight of 10ml initial slurry before standing；
W2: W1Middle TiO2Weight；
W3: the weight of 10ml slurry after standing 5 hours；
W4: W3Middle TiO2Weight.
(3) Duplicate Samples are done simultaneously, Parallel errors are not greater than 5%.
Specific embodiment
Embodiment 1
Anatase pigmentary titanium dioxide 2000kg is dispersed in the deionized water of 2000kg, while 4kg polyacrylic acid is added
Sodium dispersing agent disperses slurry to be made in 30 minutes with high speed disperser；Slurry grinder is ground twice, then shifts slurry
Into stirred tank, into slurry plus the deionized water of 8000kg is diluted, and the slurry after dilution is continuously introduced into horizontal spiral
It is classified in discharging centrifugal classifying, the big material of removal particle, fine granular materials are sent into stirred tank.Slurry is heated to 80
DEG C, 50kg non-hydrate sodium metasilicate is added into slurry under constant stirring, continues stirring 30 minutes, is slowly added into slurry
The time was added at 2 hours in 10% sulfuric acid 120kg, control；100kg sodium aluminate is added into slurry under constant stirring, continues to stir
It mixes 30 minutes, 10% sulfuric acid 500kg is slowly added into slurry, the time was added at 2 hours in control；Under constant stirring to slurry
80kg zirconium oxychloride is added in material, continues stirring 30 minutes, 10% sodium hydroxide 120kg is slowly added into slurry, control adds
The angle of incidence was at 2 hours；Continue stirring 10 minutes, slurry is sent into plate and frame filter press and is filtered, filter cake is washed with deionized water
It washs to sulfate radical-free.
Filter cake is put into hollander tub, filter cake adds deionized water 5000kg to be beaten, and Sodium Polyacrylate point is added into slurry
Powder 6kg weighs 3kg vinyltriethoxysilane, and 20kg dehydrated alcohol is added to dilute, and the ethyl alcohol containing silane coupling agent is molten
Liquid is slowly dropped to TiO2In slurry；Then the pH value of 10% ammonium hydroxide adjusting slurry is added dropwise to 8, under agitation by TiO2Slurry
Material is heated to 80 DEG C, and isothermal reaction 1 hour, obtains surface through silane coupler modified finely dispersed TiO2Slurry；It will
TiO2It slurries filtration, 105 DEG C of dryings and then is crushed to obtain TiO2Powder will obtain TiO2Powder is dispersed in 10000kg acetonitrile
In, high speed dispersion is carried out in high speed disperser；By initiator azodiisobutyronitrile 1kg and ethyl acrylate 20kg and acrylonitrile
35kg is uniformly mixed composition mix monomer；By the above-mentioned TiO dispersed with acetonitrile2Slurry is heated to 75 DEG C, toward TiO2Slurry is added
The above-mentioned mix monomer mixed initiation reaction 5 minutes, is then slowly added by 0.3kg initiator azodiisobutyronitrile
The TiO stated2Acetonitrile slurry in, be added the time control at 2 hours, after addition maintain 80 DEG C isothermal reaction 1 hour, obtain
The TiO that surface is coated2Slurry；By TiO2Slurries filtration obtains TiO2Filter cake is dried in filter cake, and the material after drying is used
Pulverizer is crushed, and acrylic fibers titanium dioxide for chemical fiber is then packaged to be.
Embodiment 2
Anatase pigmentary titanium dioxide 2000kg is dispersed in the deionized water of 2000kg, while 4kg polyacrylic acid is added
Sodium dispersing agent disperses slurry to be made in 60 minutes with high speed disperser；Slurry grinder is ground twice, then shifts slurry
Into stirred tank, into slurry plus the deionized water of 8000kg is diluted, and the slurry after dilution is continuously introduced into horizontal spiral
It is classified in discharging centrifugal classifying, the big material of removal particle, fine granular materials are sent into stirred tank.Slurry is heated to 80
DEG C, 60kg non-hydrate sodium metasilicate is added into slurry under constant stirring, continues stirring 30 minutes, is slowly added into slurry
The time was added at 2 hours in 10% sulfuric acid 150kg, control；120kg sodium aluminate is added into slurry under constant stirring, continues to stir
It mixes 30 minutes, 10% sulfuric acid 600kg is slowly added into slurry, the time was added at 2 hours in control；Under constant stirring to slurry
100kg zirconium oxychloride is added in material, continues stirring 30 minutes, 10% sodium hydroxide 150kg, control are slowly added into slurry
The time is added at 2 hours；Continue stirring 10 minutes, slurry is sent into plate and frame filter press and is filtered, filter cake deionized water
It washs to sulfate radical-free.
Filter cake is put into hollander tub, filter cake adds deionized water 5000kg to be beaten, and Sodium Polyacrylate point is added into slurry
Powder 8kg weighs 3kg γ-(methacryloxy) propyl trimethoxy silicane, adds 20kg dehydrated alcohol to dilute, will contain
The ethanol solution of silane coupling agent is slowly dropped to TiO2In slurry；Then the ammonium hydroxide for being added dropwise 10% adjusts the pH value of slurry to 8,
Under agitation by TiO2Slurry is heated to 80 DEG C, and isothermal reaction 1 hour, obtains surface through silane coupler modified point
Dissipate uniform TiO2Slurry；By TiO2It slurries filtration, 105 DEG C of dryings and then is crushed to obtain TiO2Powder will obtain TiO2Powder
End is dispersed in 10000kg acetonitrile, and high speed dispersion is carried out in high speed disperser；By initiator azodiisobutyronitrile 1kg and third
Olefin(e) acid ethyl ester 8kg and acrylonitrile 20kg is uniformly mixed composition mix monomer；By the above-mentioned TiO dispersed with acetonitrile2Slurry heating
To 75 DEG C, toward TiO20.3kg initiator azodiisobutyronitrile is added in slurry, initiation reaction 5 minutes, then mixes above-mentioned
Mix monomer is slowly added into above-mentioned TiO2Acetonitrile slurry in, be added the time control at 4 hours, 80 are maintained after addition
DEG C isothermal reaction 1 hour, obtain the TiO being coated to surface2Slurry；By TiO2Slurries filtration obtains TiO2Filter cake carries out filter cake
Dry, the material after drying is crushed with pulverizer, is then packaged to be acrylic fibers titanium dioxide for chemical fiber.
Embodiment 3
Anatase pigmentary titanium dioxide 2000kg is dispersed in the deionized water of 2000kg, while 6kg polyacrylic acid is added
Sodium dispersing agent disperses slurry to be made in 45 minutes with high speed disperser；Slurry grinder is ground twice, then shifts slurry
Into stirred tank, into slurry plus the deionized water of 8000kg is diluted, and the slurry after dilution is continuously introduced into horizontal spiral
It is classified in discharging centrifugal classifying, the big material of removal particle, fine granular materials are sent into stirred tank.Slurry is heated to 80
DEG C, 55kg non-hydrate sodium metasilicate is added into slurry under constant stirring, continues stirring 30 minutes, is slowly added into slurry
The time was added at 2 hours in 10% sulfuric acid 135kg, control；110kg sodium aluminate is added into slurry under constant stirring, continues to stir
It mixes 30 minutes, 10% sulfuric acid 550kg is slowly added into slurry, the time was added at 2 hours in control；Under constant stirring to slurry
90kg zirconium oxychloride is added in material, continues stirring 30 minutes, 10% sodium hydroxide 135kg is slowly added into slurry, control adds
The angle of incidence was at 2 hours；Continue stirring 10 minutes, slurry is sent into plate and frame filter press and is filtered, filter cake is washed with deionized water
It washs to sulfate radical-free.
Filter cake is put into hollander tub, filter cake adds deionized water 5000kg to be beaten, and Sodium Polyacrylate point is added into slurry
Powder 7kg weighs 3kg vinyltrimethoxysilane, and 20kg dehydrated alcohol is added to dilute, and the ethyl alcohol containing silane coupling agent is molten
Liquid is slowly dropped to TiO2In slurry；Then the pH value of 10% ammonium hydroxide adjusting slurry is added dropwise to 9, under agitation by TiO2Slurry
Material is heated to 80 DEG C, and isothermal reaction 1 hour, obtains surface through silane coupler modified finely dispersed TiO2Slurry；It will
TiO2It slurries filtration, 105 DEG C of dryings and then is crushed to obtain TiO2Powder will obtain TiO2Powder is dispersed in 10000kg acetonitrile
In, high speed dispersion is carried out in high speed disperser；By initiator azodiisobutyronitrile 1kg and ethyl acrylate 15kg and acrylonitrile
30kg is uniformly mixed composition mix monomer；By the above-mentioned TiO dispersed with acetonitrile2Slurry is heated to 75 DEG C, toward TiO2Slurry is added
The above-mentioned mix monomer mixed initiation reaction 5 minutes, is then slowly added by 0.3kg initiator azodiisobutyronitrile
The TiO stated2Acetonitrile slurry in, be added the time control at 5 hours, after addition maintain 80 DEG C isothermal reaction 1 hour, obtain
The TiO that surface is coated2Slurry；By TiO2Slurries filtration obtains TiO2Filter cake is dried in filter cake, and the material after drying is used
Pulverizer is crushed, and acrylic fibers titanium dioxide for chemical fiber is then packaged to be.
Embodiment 4
Anatase pigmentary titanium dioxide 2000kg is dispersed in the deionized water of 2000kg, while 5kg polyacrylic acid is added
Sodium dispersing agent disperses slurry to be made in 40 minutes with high speed disperser；Slurry grinder is ground twice, then shifts slurry
Into stirred tank, into slurry plus the deionized water of 8000kg is diluted, and the slurry after dilution is continuously introduced into horizontal spiral
It is classified in discharging centrifugal classifying, the big material of removal particle, fine granular materials are sent into stirred tank.Slurry is heated to 80
DEG C, 53kg non-hydrate sodium metasilicate is added into slurry under constant stirring, continues stirring 30 minutes, is slowly added into slurry
The time was added at 2 hours in 10% sulfuric acid 130kg, control；110kg sodium aluminate is added into slurry under constant stirring, continues to stir
It mixes 30 minutes, 10% sulfuric acid 520kg is slowly added into slurry, the time was added at 2 hours in control；Under constant stirring to slurry
85kg zirconium oxychloride is added in material, continues stirring 30 minutes, 10% sodium hydroxide 130kg is slowly added into slurry, control adds
The angle of incidence was at 2 hours；Continue stirring 10 minutes, slurry is sent into plate and frame filter press and is filtered, filter cake is washed with deionized water
It washs to sulfate radical-free.
Filter cake is put into hollander tub, filter cake adds deionized water 5000kg to be beaten, and Sodium Polyacrylate point is added into slurry
Powder 6.5kg weighs 3kg vinyltriethoxysilane, adds 20kg dehydrated alcohol to dilute, by the ethyl alcohol containing silane coupling agent
Solution is slowly dropped to TiO2In slurry；Then the pH value of 10% ammonium hydroxide adjusting slurry is added dropwise to 9, under agitation by TiO2
Slurry is heated to 80 DEG C, and isothermal reaction 1 hour, obtains surface through silane coupler modified finely dispersed TiO2Slurry；
By TiO2It slurries filtration, 105 DEG C of dryings and then is crushed to obtain TiO2Powder will obtain TiO2Powder is dispersed in 10000kg second
In nitrile, high speed dispersion is carried out in high speed disperser；By initiator azodiisobutyronitrile 1kg and ethyl acrylate 12kg and propylene
Nitrile 28kg is uniformly mixed composition mix monomer；By the above-mentioned TiO dispersed with acetonitrile2Slurry is heated to 75 DEG C, toward TiO2Slurry adds
Enter 0.3kg initiator azodiisobutyronitrile, initiation reaction 5 minutes, is then slowly added into the above-mentioned mix monomer mixed
Above-mentioned TiO2Acetonitrile slurry in, be added the time control at 3 hours, after addition maintain 80 DEG C isothermal reaction 1 hour, obtain
The TiO being coated to surface2Slurry；By TiO2Slurries filtration obtains TiO2Filter cake is dried in filter cake, the material after drying
It is crushed with pulverizer, is then packaged to be acrylic fibers titanium dioxide for chemical fiber.
Embodiment 5
Anatase pigmentary titanium dioxide 2000kg is dispersed in the deionized water of 2000kg, while 7kg polyacrylic acid is added
Sodium dispersing agent disperses slurry to be made in 50 minutes with high speed disperser；Slurry grinder is ground twice, then shifts slurry
Into stirred tank, into slurry plus the deionized water of 8000kg is diluted, and the slurry after dilution is continuously introduced into horizontal spiral
It is classified in discharging centrifugal classifying, the big material of removal particle, fine granular materials are sent into stirred tank.Slurry is heated to 80
DEG C, 58kg non-hydrate sodium metasilicate is added into slurry under constant stirring, continues stirring 30 minutes, is slowly added into slurry
The time was added at 2 hours in 10% sulfuric acid 140kg, control；118kg sodium aluminate is added into slurry under constant stirring, continues to stir
It mixes 30 minutes, 10% sulfuric acid 580kg is slowly added into slurry, the time was added at 2 hours in control；Under constant stirring to slurry
95kg zirconium oxychloride is added in material, continues stirring 30 minutes, 10% sodium hydroxide 148kg is slowly added into slurry, control adds
The angle of incidence was at 2 hours；Continue stirring 10 minutes, slurry is sent into plate and frame filter press and is filtered, filter cake is washed with deionized water
It washs to sulfate radical-free.
Filter cake is put into hollander tub, filter cake adds deionized water 5000kg to be beaten, and Sodium Polyacrylate point is added into slurry
Powder 7.5kg weighs 3kg vinyltrimethoxysilane, adds 20kg dehydrated alcohol to dilute, by the ethyl alcohol containing silane coupling agent
Solution is slowly dropped to TiO2In slurry；Then the pH value of 10% ammonium hydroxide adjusting slurry is added dropwise to 8, under agitation by TiO2
Slurry is heated to 80 DEG C, and isothermal reaction 1 hour, obtains surface through silane coupler modified finely dispersed TiO2Slurry；
By TiO2It slurries filtration, 105 DEG C of dryings and then is crushed to obtain TiO2Powder will obtain TiO2Powder is dispersed in 10000kg second
In nitrile, high speed dispersion is carried out in high speed disperser；By initiator azodiisobutyronitrile 1kg and ethyl acrylate 16kg and propylene
Nitrile 31kg is uniformly mixed composition mix monomer；By the above-mentioned TiO dispersed with acetonitrile2Slurry is heated to 75 DEG C, toward TiO2Slurry adds
Enter 0.3kg initiator azodiisobutyronitrile, initiation reaction 5 minutes, is then slowly added into the above-mentioned mix monomer mixed
Above-mentioned TiO2Acetonitrile slurry in, be added the time control at 4.5 hours, after addition maintain 80 DEG C isothermal reaction 1 hour,
Obtain the TiO being coated to surface2Slurry；By TiO2Slurries filtration obtains TiO2Filter cake is dried in filter cake, the object after drying
Material is crushed with pulverizer, is then packaged to be acrylic fibers titanium dioxide for chemical fiber.
Embodiment 6
Anatase pigmentary titanium dioxide 2000kg is dispersed in the deionized water of 2000kg, while 4kg polyacrylic acid is added
Sodium dispersing agent disperses slurry to be made in 30 minutes with high speed disperser；Slurry grinder is ground twice, then shifts slurry
Into stirred tank, into slurry plus the deionized water of 8000kg is diluted, and the slurry after dilution is continuously introduced into horizontal spiral
It is classified in discharging centrifugal classifying, the big material of removal particle, fine granular materials are sent into stirred tank.Slurry is heated to 80
DEG C, 50kg non-hydrate sodium metasilicate is added into slurry under constant stirring, continues stirring 30 minutes, is slowly added into slurry
The time was added at 2 hours in 10% sulfuric acid 120kg, control；120kg sodium aluminate is added into slurry under constant stirring, continues to stir
It mixes 30 minutes, 10% sulfuric acid 600kg is slowly added into slurry, the time was added at 2 hours in control；Under constant stirring to slurry
92kg zirconium oxychloride is added in material, continues stirring 30 minutes, 10% sodium hydroxide 142kg is slowly added into slurry, control adds
The angle of incidence was at 2 hours；Continue stirring 10 minutes, slurry is sent into plate and frame filter press and is filtered, filter cake is washed with deionized water
It washs to sulfate radical-free.
Filter cake is put into hollander tub, filter cake adds deionized water 5000kg to be beaten, and Sodium Polyacrylate point is added into slurry
Powder 8kg weighs 3kg γ-(methacryloxy) propyl trimethoxy silicane, adds 20kg dehydrated alcohol to dilute, will contain
The ethanol solution of silane coupling agent is slowly dropped to TiO2In slurry；Then the ammonium hydroxide for being added dropwise 10% adjusts the pH value of slurry to 9,
Under agitation by TiO2Slurry is heated to 80 DEG C, and isothermal reaction 1 hour, obtains surface through silane coupler modified point
Dissipate uniform TiO2Slurry；By TiO2It slurries filtration, 105 DEG C of dryings and then is crushed to obtain TiO2Powder will obtain TiO2Powder
End is dispersed in 10000kg acetonitrile, and high speed dispersion is carried out in high speed disperser；By initiator azodiisobutyronitrile 1kg and third
Olefin(e) acid ethyl ester 10kg and acrylonitrile 25kg is uniformly mixed composition mix monomer；By the above-mentioned TiO dispersed with acetonitrile2Slurry heating
To 75 DEG C, toward TiO20.3kg initiator azodiisobutyronitrile is added in slurry, initiation reaction 5 minutes, then mixes above-mentioned
Mix monomer is slowly added into above-mentioned TiO2Acetonitrile slurry in, be added the time control at 3.5 hours, maintained after addition
80 DEG C isothermal reaction 1 hour, obtain the TiO being coated to surface2Slurry；By TiO2Slurries filtration obtains TiO2Filter cake, to filter cake into
Row drying, the material after drying are crushed with pulverizer, are then packaged to be acrylic fibers titanium dioxide for chemical fiber.
Embodiment 7
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Commercially available acrylic fibers TiO2 | |
| Dispersed % | 97.4 | 96.8 | 96.6 | 97.2 | 98.2 | 96.2 | 93.7 |
Claims (6)
1. a kind of preparation method of acrylic fibers chemical fibre of titanium dioxide, it is characterised in that: anatase pigmentary titanium dioxide is first dispersed into water
Slurry is ground, is diluted, being classified removal bulky grain；Then coating hydrous silica, hydration are carried out to titanium dioxide granule surface
Aluminium oxide and hydrous zirconium oxide(HZO)；Again with the silane coupling agent with unsaturated double-bond to the titanium dioxide granule table by inorganic coating
Face is handled, and the double bond that free radical polymerization can be carried out by the titanium dioxide granule surface band of inorganic coating is made；To finally it change
Property after titanium dioxide be dispersed in acetonitrile solvent, cause free radical polymerization after modification titanium dioxide granule surface cladding one
One polymer obtains acrylic fibers titanium dioxide for chemical fiber.
2. being ground according to the method described in claim 1, described be dispersed into water slurry for anatase pigmentary titanium dioxide
Mill, dilution, classification removal bulky grain, it is characterised in that: be in parts by weight dispersed in 200 parts of anatase pigmentary titanium dioxide
In 200 parts of deionized water, while 0.4~0.8 part of sodium polyacrylate disperant is added, disperses 30~60 points with high speed disperser
Slurry is made in clock；Slurry grinder is ground twice, then slurry is transferred in stirred tank, 800 parts are added into slurry
Deionized water is diluted, and the slurry after dilution is continuously introduced into horizontal screw unloading centrifugal classifying and is classified, removal
The big material of particle, it is stand-by that fine granular materials are sent into stirred tank.
3. according to the method described in claim 1, described carry out coating hydrous silica, hydration to titanium dioxide granule surface
Aluminium oxide and hydrous zirconium oxide(HZO), it is characterised in that: slurry is heated to 80 DEG C, is added 5~6 parts into slurry under constant stirring
Non-hydrate sodium metasilicate continues stirring 30 minutes, and 12~15 parts of sulfuric acid of 10% are slowly added into slurry, and the time is added 2 in control
Hour；10~12 parts of sodium aluminates are added into slurry under constant stirring, continues stirring 30 minutes, is slowly added into slurry
The time was added at 2 hours in 50~60 parts of 10% sulfuric acid, control；8~10 parts of oxychlorination are added into slurry under constant stirring
Zirconium continues stirring 30 minutes, and 12~15 parts of sodium hydroxide of 10% are slowly added into slurry, and the time was added at 2 hours in control；
Continue stirring 10 minutes, slurry is sent into plate and frame filter press and is filtered, filter cake is washed with deionized to sulfate radical-free.
4. according to the method described in claim 1, it is described with the silane coupling agent with unsaturated double-bond to pass through inorganic coating
Titanium dioxide granule surface handled, make that free radical polymerization can be carried out by the titanium dioxide granule surface band of inorganic coating
Double bond, it is characterised in that: filter cake is put into hollander tub, filter cake adds 500 parts of deionized water mashing, and poly- third is added into slurry
0.6~0.8 part of olefin(e) acid sodium dispersing agent weighs 0.3 part of silane coupling agent, adds 2 parts of dehydrated alcohol dilutions, will contain silane coupling agent
Ethanol solution be slowly dropped to TiO2In slurry；Then the pH value of 10% ammonium hydroxide adjusting slurry is added dropwise to 8-9, in stirring bar
By TiO under part2Slurry is heated to 80 DEG C, and isothermal reaction 1 hour, obtains surface through silane coupler modified finely dispersed
TiO2Slurry.
5. causing certainly according to the method described in claim 1, described be dispersed in modified titanium dioxide in acetonitrile solvent
Modified titanium dioxide granule surface cladding one layer of polymeric is aggregated in by base, it is characterised in that: by TiO2Slurries filtration is done
Dry, crushing obtains TiO2Powder will obtain TiO2Powder is dispersed in 1000 parts of acetonitriles, and high speed point is carried out in high speed disperser
It dissipates；
Group is uniformly mixed with 0.8~2 part of ethyl acrylate and 2.0~3.5 parts of acrylonitrile by 0.1 part of initiator azodiisobutyronitrile
At mix monomer；
By the above-mentioned TiO dispersed with acetonitrile2Slurry is heated to 75 DEG C, toward TiO2It is different that 0.03 part of initiator azo two is added in slurry
The above-mentioned mix monomer mixed initiation reaction 5 minutes, is then slowly added into above-mentioned TiO by butyronitrile2Acetonitrile slurry
In, time control is added and maintains 80 DEG C at 2-5 hours, after addition isothermal reaction 1 hour, obtains the TiO being coated to surface2
Slurry；By TiO2Slurries filtration obtains TiO2Filter cake is dried in filter cake, and the material after drying is crushed with pulverizer, so
After be packaged to be acrylic fibers titanium dioxide for chemical fiber.
6. according to the method described in claim 4, the silane coupling agent is vinyltriethoxysilane, vinyl front three
Oxysilane, γ-(methacryloxy) propyl trimethoxy silicane are one such or two or more.
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| CN110358329A (en) * | 2019-06-28 | 2019-10-22 | 东华大学 | A kind of low cost Fypro titanium dioxide delustering agent and its preparation and application |
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