CN108277550A - A kind of delustring PET fiber and its slice electrospinning method for preparing - Google Patents

A kind of delustring PET fiber and its slice electrospinning method for preparing Download PDF

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CN108277550A
CN108277550A CN201810029328.4A CN201810029328A CN108277550A CN 108277550 A CN108277550 A CN 108277550A CN 201810029328 A CN201810029328 A CN 201810029328A CN 108277550 A CN108277550 A CN 108277550A
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titanium dioxide
nano particle
pet fiber
hollow porous
porous micro
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CN108277550B (en
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詹伟东
孙宾
肖露露
翟丽鹏
孙小国
陈珈
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Zhejiang Dongtai New Material Co Ltd
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Zhejiang Dongtai New Material Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a kind of delustring PET fiber and its slice electrospinning method for preparing, method to be：PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, the crosslinking ball for being coated on titania nanoparticles surface that wherein hollow porous micro sphere is mainly attached thereto by titania nanoparticles and by covalent bond forms, it is crosslinked ball inner hollow, porous surface and have cross-linked structure, cross-linked structure is formed by being cross-linked with each other between the copolymer molecule chain containing styrene and bifunctionality dimethylacrylate class monomeric building blocks, functional agglomerate and PET are sliced melt spinning after mixing again, delustring PET fiber is made.It is evenly dispersed in fiber obtained to have hollow porous micro sphere, and it is 0.6~2.0wt% that fiber, which reaches the content of titanium dioxide when totally disappeared light effect,.The method of the present invention simple process, fiber obtained have many advantages, such as that extinction effect is good, titanium dioxide additive amount is small and is uniformly dispersed.

Description

A kind of delustring PET fiber and its slice electrospinning method for preparing
Technical field
The invention belongs to fiber preparation fields, and in particular to a kind of delustring PET fiber and its slice electrospinning method for preparing.
Background technology
Delustering fibre is also known as delustering fibre, refers to the chemical fibre of mattness.The method for preparing delustering fibre is usual It is that delustering agent is added in spinning solution or melt before spinning, through spinning technique, delustering fibre obtained being capable of scattering light And gloss is eliminated to reduce transparency, increase whiteness.In recent years, full PET fiber is got over its unique external apparent characteristic Received to be more woven industry.Meanwhile with the breakthrough of domestic delustering fibre technology of preparing, it totally disappeared the application field of fiber optics not It is disconnected to expand, it especially spins in spring Asia and is widely used on wool-like fabric.
Tinting strength, tinting power, covering power and the extinction capability of titanium dioxide protrude, and are a kind of current best white of performance in the world Pigment can be widely applied to the industrial circles such as coating, plastics, ink and papermaking, and demand is larger, before having fabulous application Scape.Fiber optics be totally disappeared generally by the addition of titanium dioxide to reach extinction effect.It is delustring using the disadvantages of this method Substance is extremely difficult to good dispersion in polyester resin, and spinning pressure can be increased when spinning by disperseing irregular powder body material Power blocks spinneret, influences the spinnability of fiber.Simultaneously because the compatibility of titanium dioxide and polymer is poor, lead to dioxy When change titanium prepares delustering fibre as additive, in the case where additive amount is smaller, the extinction effect of delustering fibre is poor.
Titanium dioxide can carry out inorganic coating by elements such as Al or Si improves its dispersion performance to a certain extent.It is high It is a kind of side that polymer solution or melt are prepared into high molecular particle using electrohydrodynamics technology to press electrostatic spraying processes Method.The method such as precipitation method, inverse suspension crosslinking method, spray drying process etc. of high molecular particle, electrostatic are prepared relative to other Mist method prepares that micro-sphere material is simple for process, controllability is strong, environmentally protective and without using a large amount of emulsifiers, using electrostatic spraying processes It is easy obtained monodispersity particle and finally obtained particle can have different morphologies, such as is hollow porous, such as have document (method of electrostatic spinning preparation polystyrene functional material [D] Jilin University, 2010.) report, polystyrene solution can be by quiet Electron spray molding prepares Porous hollow microballoon, and polystyrene (PS) hollow microsphere obtained at normal temperatures stablize by chemical property, tool There is preferable machinability, but since the glass transition temperature of polystyrene (PS) only has 100 DEG C, under the high temperature conditions three Dimension structure can be destroyed, thus can not be applied to melt-processed.This largely affects the application of PS hollow microspheres.
In addition, titanium dioxide can also easily be reunited by carrying out surface modification to titanium dioxide to solve titanium dioxide In organic matrix the problem of bad dispersibility.It is coupling agent modified that common surface, which is modified gimmick, but coupling agent is only with chemistry The form of key is connected on nano grain surface, has no promotion to extinction performance itself, and the relative molecular mass of silane coupling agent is small, It easily decomposes at high temperature, is unfavorable for melt spinning and prepares high-performance fiber.
Therefore, study that a kind of extinction effect is good, titanium dioxide additive amount is small and the preparation side of finely dispersed delustering fibre Method has a very important role.
Invention content
The purpose of the invention is to overcome above-mentioned problems of the prior art, provide a kind of extinction effect it is good, Titanium dioxide additive amount is small and finely dispersed delustring PET fiber and its slice electrospinning method for preparing.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of delustring PET fiber, it is evenly dispersed in delustring PET fiber to have the hollow porous of cladding titanium dioxide nano particle Microballoon；
The hollow porous micro sphere of the cladding titanium dioxide nano particle mainly by titania nanoparticles and is coated on The crosslinking ball on titania nanoparticles surface forms；
The crosslinking ball inner hollow, porous surface and has cross-linked structure, and the cross-linked structure is by containing styrene and double It is cross-linked with each other to be formed between the copolymer molecule chain of degree of functionality dimethylacrylate class monomeric building blocks；
By being covalently keyed between the titania nanoparticles and crosslinking ball；
The content that the delustring PET fiber reaches titanium dioxide when totally disappeared light effect is 0.6~2.0wt%, commonly be totally disappeared The content of titanium dioxide is 2.2~2.5wt% in fiber optics, due to the enhancement effect of porous microsphere, titanium dioxide of the invention Content is 0.6~2.0wt%, you can reaches full-dull.
As preferred technical solution：
The fiber number of a kind of delustring PET fiber as described above, the delustring PET fiber is 3.2~4.0dtex, and fracture is strong Degree is 2.82~3.38cN/dtex, and elongation at break is 13.2~27.4%.
A kind of delustring PET fiber as described above, the hollow porous micro sphere of the cladding titanium dioxide nano particle melt Melt temperature>530 DEG C, heat decomposition temperature>380℃；The processing temperature of delustring PET fiber is less than the melting temperature of hollow porous micro sphere Degree, thus when preparation delustring PET fiber, hollow porous micro sphere can keep preferable three-dimensional structure not to be damaged, and be conducive to fill Its effect is waved in distribution；
The wall thickness of a diameter of 500~1500nm of the crosslinking ball, the crosslinking ball are 50~100nm；The titanium dioxide A diameter of 300~400nm of titanium nano particle；The quantity of the crosslinking ball inner silica titanium nano particle is 1~4.
A kind of delustring PET fiber as described above, when being crosslinked the quantity of ball inner silica titanium nano particle≤2, institute The distribution density for stating the surface aperture of crosslinking ball is 1~60/1000nm2, the aperture of aperture is 10~30nm；
When the quantity of crosslinking ball inner silica titanium nano particle>When 2, the distribution density of the surface aperture of the crosslinking ball For 1~20/1000nm2, the aperture of aperture is 10~80nm.
A kind of delustring PET fiber as described above, the system of the hollow porous micro sphere of the cladding titanium dioxide nano particle Preparation Method is：
The dissolving of styrene, bifunctionality dimethylacrylate class organic monomer and photoinitiator is obtained into electricity in a solvent Solution is sprayed, then the double bond containing modifying titanium dioxide in surface is added in EFI solution and is stirred with the rotating speed machinery of 200~500rpm It mixes 1h to be uniformly dispersed, electrostatic spray is carried out under visible light conditions, the hollow porous micro- of cladding titanium dioxide nano particle is made Ball is finally washed and is dried with methanol or ethyl alcohol；It washs and the effect dried is microsphere surface during removal electrostatic spray Impurity, such as extra polymerized monomer and photoinitiator etc.；In the process, the double bond containing modifying titanium dioxide in surface is due to table Face carries organo-functional group, in a solvent can be evenly dispersed, is conducive to prepare uniform electrostatic spray system；
The bifunctionality dimethylacrylate class organic monomer be Bis-GMA, EBPADMA, UDMA, TEGDMA and D3One or more of MA；
The concrete structure formula of the bifunctionality dimethylacrylate class organic monomer is as follows：
The photoinitiator be DMPOH (N, N- dimethylanunuphenylelhvl alcohol) and/or CQ (1,7,7- trimethyl bicyclics (2,2, 1) -2,3 heptadione)；The wavelength of the visible light is 400~500nm；The solvent be DMF, chloroform, dichloromethane and One or more of tetrahydrofuran；
Bifunctionality dimethylacrylate class organic monomer accounts for styrene and bifunctionality diformazan in the EFI solution 5~25wt% of base esters of acrylic acid organic monomer total amount；The organic list of bifunctionality dimethylacrylate class in EFI solution Body accounts for the friendship of the ratio and microsphere surface cross-linked structure of styrene and bifunctionality dimethylacrylate class organic monomer total amount Connection degree is directly proportional, and the degree of cross linking is higher, and crosslinking mesh is bigger, and exchange velocity is faster, but can reduce crosslinking knot to a certain extent The intensity of structure, conversely, the degree of cross linking is lower, crosslinking mesh is smaller, and cross-link intensity is higher, but poor to the swellability of water；EFI is molten It is low to cross low crosslinking degree for the concentration of bifunctionality dimethylacrylate class organic monomer in liquid, can not be applied to melt-processed, mistake Height influences the viscosity of compound system, can not form microballoon；
Solvent accounts for 50~80wt% of styrene and bifunctionality dimethylacrylate class organic monomer total amount, light-initiated Agent accounts for 0.5~1.2wt% of styrene and bifunctionality dimethylacrylate class organic monomer total amount；Light draws in EFI solution The too low efficiency of initiation of concentration of hair agent is too low can not to cause monomer polymerization；
The addition of the modifying titanium dioxide is the 15~40% of EFI solution quality；
The parameter of the electrostatic spray is：10~15kV of output voltage of high voltage power supply, atomizing nozzle with solidification bathing pool away from From 7~13cm, 25~50 DEG C of temperature promotes 1~4mL/h of fltting speed of pump, 5~15mm of diameter of propeller, propeller 3~10mL of volume.
A kind of delustring PET fiber as described above, the preparation process of the modifying titanium dioxide are as follows：
(1) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid；The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4~6 in the mixed dispersion liquid:150~250:1；
(2) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4~5h of reaction at 60~70 DEG C, room temperature ageing 10~ 12h obtains ageing liquid；The mass ratio of ethyl alcohol and water is 2~5 in the ethyl alcohol water mixed liquid:1, the ethyl alcohol water mixed liquid adds Enter 20~30% that amount is mixed dispersion liquid volume；
(3) silane coupling agent is instilled in ethanol water, 2~3h of hydrolysis is stirred at room temperature, is added to ultrasonic disperse In the ageing liquid of 30~60min, 4~5h of back flow reaction at 60~70 DEG C；The quality of ethyl alcohol and water in the ethanol water Than being 2~5:1, the mass ratio of the silane coupling agent and ethanol water is 1:8~12, the addition of the silane coupling agent It is 5~10% of titanium dioxide quality in ageing liquid, the silane coupling agent is γ-methacryloxypropyl trimethoxy Silane；
(4) it is dried in vacuo 12~16h at 70~80 DEG C after rotating evaporation drying at 50~70 DEG C, obtains surface containing double The modifying titanium dioxide of key.
The present invention also provides a kind of slice electrospinning method for preparing preparing delustring PET fiber as described above, and PET is sliced Functional agglomerate is prepared with the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle, then functional agglomerate and PET are cut Delustring PET fiber is made in melt spinning to piece after mixing.
As preferred technical solution：
Preparation method as described above, the hollow porous micro sphere of cladding titanium dioxide nano particle in the functional agglomerate Content is 44.4~60wt%, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle in the delustring PET fiber For 3.5~5.6wt%.
Preparation method as described above, described be uniformly mixed refers to 30~40min of mixing in super mixer；It is described molten The technological parameter for melting spinning is as follows：
Invention mechanism：
A kind of delustring PET fiber and its slice electrospinning method for preparing of the present invention, it is light-initiated poly- to devise electrostatic spray-first The method that crosslinking prepares the hollow porous micro sphere of cladding titanium dioxide nano particle is closed, in the process, first by single functionality It is molten that EFI is made in styrene monomer, bifunctionality dimethylacrylate class organic monomer and photoinitiator dissolving in a solvent Liquid adds the double bond containing modifying titanium dioxide in surface and is uniformly mixed, and electrostatic spray is then carried out under high-voltage field forms drop, Cause styrene monomer, the bifunctionality dimethyl propylene in drop using visible light (according to initiation wavelength law of photoinitiator) The double bond of olefin(e) acid esters monomer and modifying titanium dioxide surface carries out free radical polymerization, is formed in titanium dioxide surface and contains styrene With the copolymer of bifunctionality dimethylacrylate class monomeric building blocks, simultaneously because bifunctionality dimethylacrylate The bifunctionality of class monomer, the molecule of the copolymer containing styrene and bifunctionality dimethylacrylate class monomeric building blocks It can be cross-linked with each other to form three-dimensional-structure between chain, because of the volatilization of polymerization shrinkage and solvent and in coagulating bath in forming process Diffusion and form the hollow porous micro sphere of cladding titanium dioxide nano particle, to which melting temperature be made>530 DEG C, thermal decomposition Temperature>The hollow porous micro sphere of 380 DEG C of cladding titanium dioxide nano particle contains styrene and bifunctionality dimethacrylate The three-dimensional-structure being cross-linked to form between the strand of the copolymer of esters monomer structural unit so that its melting temperature is high, rear Three-dimensional structure can be kept during continuous melt-processed, gives full play to its function, and during the prior art is prepared using electrostatic spray Empty microballoon is generally by the way that by polymer dissolving, electrostatic spray obtains microballoon in a solvent, and after this method obtains microballoon, polymer is still It can keep its original thermal property and be melted in melt-processed and its microballoon pattern cannot be kept, be not used to melt-processed, so PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate afterwards, finally by work( Energy master batch is sliced melt spinning after mixing with PET and delustring PET fiber is made.
In addition, the titanium dioxide of the present invention itself possesses good extinction effect (scattering), porous structure can be effective Incident light is scattered, the utilization rate to incident light is improved, coated by titanium dioxide is the inside for being crosslinked ball in porous microsphere by the present invention, Light is incident on titanium dioxide surface after the scattering of titanium dioxide across porous structure, can be in titanium dioxide and microballoon inner wall Between be repeated as many times and scatter, finally only a small amount of light can penetrate microballoon and overflow, thus improve extinction effect.
Advantageous effect：
(1) a kind of delustring PET fiber of the invention has good extinction effect, good mechanical performance, titanium dioxide additive amount It is small and the advantages of be uniformly dispersed, have a wide range of application.
(2) the slice electrospinning method for preparing of a kind of delustring PET fiber of the invention, is asked in the dispersibility for solving titanium dioxide While topic, the extinction effect of titanium dioxide is improved, reduces the additive amount of titanium dioxide in the fibre.
(3) the slice electrospinning method for preparing of a kind of delustring PET fiber of the invention, simple process, preparation flow is reasonable, there is pole Good promotional value.
Description of the drawings
Fig. 1 is the hollow porous micro sphere of cladding titanium dioxide nano particle in the delustring PET fiber that the present invention is prepared Structural schematic diagram.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 wherein in mixed dispersion liquid:150:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 70 DEG C, room temperature ageing 11h is aged Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume 20%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature Solve 2h, be added in the ageing liquid of ultrasonic disperse 30min, the back flow reaction 4h at 60 DEG C, wherein in ethanol water ethyl alcohol with The mass ratio of water is 2:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:12, The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 5%；
D) it is dried in vacuo 13h at 70 DEG C after rotating evaporation drying at 60 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) styrene, Bis-GMA and DMPOH are dissolved in DMF and obtain EFI solution, Bis-GMA in EFI solution The 10wt% of styrene and Bis-GMA total amounts is accounted for, DMF accounts for the 50wt% of styrene and Bis-GMA total amounts, and DMPOH accounts for styrene With the 0.5wt% of Bis-GMA total amounts；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 200rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 400nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, the wherein addition of modifying titanium dioxide is EFI solution quality 15%, the parameter of electrostatic spray is：The output voltage 10kV of high voltage power supply, atomizing nozzle and solidification bathing pool distance 13cm, temperature 25 DEG C of degree, promotes the fltting speed 4mL/h of pump, the diameter 15mm of propeller, the volume 3mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with methanol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle, structural schematic diagram is as shown in Figure 1, mainly by nano titania Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool Crosslinking structure, cross-linked structure by being formed containing being cross-linked with each other between styrene and the copolymer molecule chain of Bis-GMA structural units, By being covalently keyed between titania nanoparticles and crosslinking ball, it is crosslinked a diameter of 500nm of ball, the wall thickness for being crosslinked ball is The quantity of 50nm, a diameter of 310nm of titania nanoparticles, crosslinking ball inner silica titanium nano particle are 1, crosslinking The distribution density of the surface aperture of ball is 1~10/1000nm2, the aperture of aperture is 25~30nm.Cladding titanium dioxide nano The melting temperature of the hollow porous micro sphere of particle is 561 DEG C, and heat decomposition temperature is 410 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 44.4wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 30min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 3.5wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 285 DEG C；Cross air blasting cooling wind temperature is 30 DEG C；Cross air blasting wind speed is 0.3m/s；Winding is spun Silk speed is 3700m/min；Draft ratio is 3.5.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and the delustring PET fiber being prepared, with good extinction effect, the content that commonly totally disappeared titanium dioxide in fiber optics is 2.2~2.5wt%, due to the enhancement effect of porous microsphere, content of titanium dioxide of the invention is 1.5wt%, you can reaches complete Delustring.Delustring PET fiber mechanical property is good, fiber number 3.2dtex, fracture strength 2.82cN/dtex, and elongation at break is 13.9%.
Embodiment 2
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 5 wherein in mixed dispersion liquid:200:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 60 DEG C, room temperature ageing 10h is aged Liquid, in ethyl alcohol water mixed liquid ethyl alcohol with addition is mixed dispersion liquid volume 30%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature 3h is solved, is added in the ageing liquid of ultrasonic disperse 40min, the back flow reaction 4.5h at 65 DEG C, wherein ethyl alcohol in ethanol water Mass ratio with water is 3:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1: The addition of 11, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 6%；
D) it is dried in vacuo 14h at 80 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) styrene, EBPADMA and CQ are dissolved in chloroform and obtain EFI solution, in EFI solution EBPADMA accounts for the 15wt% of styrene and EBPADMA total amounts, and chloroform accounts for the 60wt% of styrene and EBPADMA total amounts, CQ Account for the 0.6wt% of styrene EBPADMA total amounts；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 300rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 420nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, the wherein addition of modifying titanium dioxide is EFI solution quality 20%, the parameter of electrostatic spray is：The output voltage 11kV of high voltage power supply, atomizing nozzle and solidification bathing pool distance 12cm, temperature 30 DEG C of degree, promotes the fltting speed 3mL/h of pump, the diameter 13mm of propeller, the volume 4mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with ethyl alcohol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle obtained mainly by titania nanoparticles and is coated on two The crosslinking ball on Titanium dioxide nanoparticle surface forms, wherein crosslinking ball inner hollow, porous surface and has cross-linked structure, crosslinking Structure containing being cross-linked with each other between styrene and the copolymer molecule chain of Bis-GMA structural units by forming, nano titania By being covalently keyed between grain and crosslinking ball, it is crosslinked a diameter of 700nm of ball, the wall thickness for being crosslinked ball is 60nm, titanium dioxide The quantity of a diameter of 330nm of nano particle, crosslinking ball inner silica titanium nano particle are 1, are crosslinked the surface aperture of ball Distribution density be 15~25/1000nm2, the aperture of aperture is 10~18nm.Cladding titanium dioxide nano particle it is hollow The melting temperature of porous microsphere is 532 DEG C, and heat decomposition temperature is 415 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 50.5wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 30min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 4.2wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 270 DEG C；Cross air blasting cooling wind temperature is 29 DEG C；Cross air blasting wind speed is 0.4m/s；Winding is spun Silk speed is 4000m/min；Draft ratio is 4.0.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and there is the delustring PET fiber being prepared good extinction effect, PET fiber to reach titanium dioxide when totally disappeared light effect Content be 1.8wt%, delustring PET fiber mechanical property is good, fiber number 3.2dtex, fracture strength 2.85cN/dtex, disconnected It is 23.5% to split elongation.
Embodiment 3
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 wherein in mixed dispersion liquid:250:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4.5h is reacted at 65 DEG C, room temperature ageing 11h is aged Liquid, the mass ratio of ethyl alcohol and water is 3 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume 25%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature 2.5h is solved, is added in the ageing liquid of ultrasonic disperse 50min, the back flow reaction 5h at 70 DEG C, wherein ethyl alcohol in ethanol water Mass ratio with water is 4:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1: The addition of 10, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 7%；
D) it is dried in vacuo 12h at 75 DEG C after rotating evaporation drying at 70 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) by the mixture (mass ratio 1 of styrene, UDMA and DMPOH and CQ:1) it dissolves in methylene chloride Obtain EFI solution, UDMA accounts for the 5wt% of styrene and UDMA total amounts in EFI solution, and dichloromethane accounts for styrene and UDMA is total The mixture of 70wt%, DMPOH and the CQ of amount account for the 0.7wt% of styrene and UDMA total amounts；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 400rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 440nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, wherein the addition of the modifying titanium dioxide is EFI solution The parameter of the 25% of quality, electrostatic spray is：The output voltage 12kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool 11cm, 35 DEG C of temperature promote the fltting speed 2mL/h of pump, the diameter 11mm of propeller, the volume 5mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with methanol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle obtained mainly by titania nanoparticles and is coated on two The crosslinking ball on Titanium dioxide nanoparticle surface forms, wherein crosslinking ball inner hollow, porous surface and has cross-linked structure, crosslinking Structure by being formed containing being cross-linked with each other between styrene and the copolymer molecule chain of UDMA structural units, titania nanoparticles with By being covalently keyed between crosslinking ball, it is crosslinked a diameter of 900nm of ball, the wall thickness for being crosslinked ball is 70nm, nano titania The quantity of a diameter of 350nm of particle, crosslinking ball inner silica titanium nano particle are 1, are crosslinked point of the surface aperture of ball Cloth density is 52~60/1000nm2, the aperture of aperture is 20~24nm.Cladding titanium dioxide nano particle it is hollow porous The melting temperature of microballoon is 535 DEG C, and heat decomposition temperature is 390 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 60wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 40min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 4.9wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 275 DEG C；Cross air blasting cooling wind temperature is 28 DEG C；Cross air blasting wind speed is 0.5m/s；Winding is spun Silk speed is 4000m/min；Draft ratio is 3.3.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and there is the delustring PET fiber being prepared good extinction effect, PET fiber to reach titanium dioxide when totally disappeared light effect Content be 0.6wt%, delustring PET fiber mechanical property is good, fiber number 3.5dtex, fracture strength 3.20cN/dtex, disconnected It is 19.4% to split elongation.
Embodiment 4
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 wherein in mixed dispersion liquid:180:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 63 DEG C, room temperature ageing 12h is aged Liquid, the mass ratio of ethyl alcohol and water is 4 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume 22%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature Solve 3h, be added in the ageing liquid of ultrasonic disperse 60min, the back flow reaction 5h at 60 DEG C, wherein in ethanol water ethyl alcohol with The mass ratio of water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:9, The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 8%；
D) it is dried in vacuo 15h at 70 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) styrene, TEGDMA and CQ are dissolved in tetrahydrofuran and obtain EFI solution, TEGDMA in EFI solution The 20wt% of styrene and TEGDMA total amounts is accounted for, tetrahydrofuran accounts for the 80wt% of styrene and TEGDMA total amounts, and CQ accounts for styrene With the 0.8wt% of TEGDMA total amounts；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 500rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 450nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, wherein the addition of the modifying titanium dioxide is EFI solution The parameter of the 30% of quality, electrostatic spray is：The output voltage 13kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool 10cm, 40 DEG C of temperature promote the fltting speed 1mL/h of pump, the diameter 10mm of propeller, the volume 6mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with ethyl alcohol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle obtained mainly by titania nanoparticles and is coated on two The crosslinking ball on Titanium dioxide nanoparticle surface forms, wherein crosslinking ball inner hollow, porous surface and has cross-linked structure, crosslinking Structure containing being cross-linked with each other between styrene and the copolymer molecule chain of TEGDMA structural units by forming, titania nanoparticles By being covalently keyed between crosslinking ball, it is crosslinked a diameter of 1000nm of ball, the wall thickness for being crosslinked ball is 80nm, and titanium dioxide is received The quantity of a diameter of 300nm of rice grain, crosslinking ball inner silica titanium nano particle are 2, are crosslinked the surface aperture of ball Distribution density is 30~55/1000nm2, the aperture of aperture is 20~30nm.Cladding titanium dioxide nano particle it is hollow more The melting temperature of hole microballoon is 540 DEG C, and heat decomposition temperature is 385 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 56.4wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 40min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 3.5wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 280 DEG C；Cross air blasting cooling wind temperature is 28 DEG C；Cross air blasting wind speed is 0.5m/s；Winding is spun Silk speed is 3900m/min；Draft ratio is 3.7.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and there is the delustring PET fiber being prepared good extinction effect, PET fiber to reach titanium dioxide when totally disappeared light effect Content be 0.9wt%, delustring PET fiber mechanical property is good, fiber number 3.2dtex, fracture strength 2.95cN/dtex, disconnected It is 13.2% to split elongation.
Embodiment 5
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 5 wherein in mixed dispersion liquid:240:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 5h is reacted at 60 DEG C, room temperature ageing 12h is aged Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume 28%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature 2.5h is solved, is added in the ageing liquid of ultrasonic disperse 35min, the back flow reaction 4h at 65 DEG C, wherein ethyl alcohol in ethanol water Mass ratio with water is 2:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:8, The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 9%；
D) it is dried in vacuo 12h at 80 DEG C after rotating evaporation drying at 65 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) by styrene, D3MA and DMPOH is dissolved in the mixture (mass ratio 1 of DMF and chloroform:In 2) To EFI solution, D in EFI solution3MA accounts for styrene and D3The mixture of the 25wt% of MA total amounts, DMF and chloroform accounts for benzene Ethylene and D3The 55wt% of MA total amounts, DMPOH account for styrene and D3The 0.9wt% of MA total amounts；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 250rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 460nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, wherein the addition of the modifying titanium dioxide is EFI solution The parameter of the 35% of quality, electrostatic spray is：The output voltage 14kV of high voltage power supply, atomizing nozzle and solidification bathing pool distance 9cm, Temperature 45 C promotes the fltting speed 2mL/h of pump, the diameter 8mm of propeller, the volume 6mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with methanol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle obtained mainly by titania nanoparticles and is coated on two The crosslinking ball on Titanium dioxide nanoparticle surface forms, wherein crosslinking ball inner hollow, porous surface and has cross-linked structure, crosslinking Structure is by containing styrene and D3Be cross-linked with each other to be formed between the copolymer molecule chain of MA structural units, titania nanoparticles with By being covalently keyed between crosslinking ball, it is crosslinked a diameter of 1250nm of ball, the wall thickness for being crosslinked ball is 90nm, nano titania The quantity of a diameter of 330nm of particle, crosslinking ball inner silica titanium nano particle are 3, are crosslinked point of the surface aperture of ball Cloth density is 1~8/1000nm2, the aperture of aperture is 10~20nm.Cladding titanium dioxide nano particle it is hollow porous micro- The melting temperature of ball is 538 DEG C, and heat decomposition temperature is 400 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 48.8wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 40min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 5.5wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 295 DEG C；Cross air blasting cooling wind temperature is 30 DEG C；Cross air blasting wind speed is 0.3m/s；Winding is spun Silk speed is 3500m/min；Draft ratio is 3.0.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and there is the delustring PET fiber being prepared good extinction effect, PET fiber to reach titanium dioxide when totally disappeared light effect Content be 1.8wt%, delustring PET fiber mechanical property is good, fiber number 3.2dtex, fracture strength 3.09cN/dtex, disconnected It is 22.4% to split elongation.
Embodiment 6
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 wherein in mixed dispersion liquid:170:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 62 DEG C, room temperature ageing 11h is aged Liquid, the mass ratio of ethyl alcohol and water is 4 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume 24%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature 2h is solved, is added in the ageing liquid of ultrasonic disperse 45min, the back flow reaction 4.5h at 70 DEG C, wherein ethyl alcohol in ethanol water Mass ratio with water is 3:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1: The addition of 12, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 10%；
D) it is dried in vacuo 16h at 75 DEG C after rotating evaporation drying at 55 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) by the mixture (mass ratio 2 of Bis-GMA and EBPADMA:1), styrene and DMPOH's and CQ is mixed Close object (mass ratio 1:1) it is dissolved in mixture (the mass ratio 1 of dichloromethane and tetrahydrofuran:2) EFI solution is obtained in, The mixture of Bis-GMA and EBPADMA accounts for the amount of the mixture of styrene and Bis-GMA and EBPADMA in EFI solution The mixture of 20wt%, dichloromethane and tetrahydrofuran accounts for the amount of the mixture of styrene and Bis-GMA and EBPADMA The mixture of 65wt%, DMPOH and CQ account for the 1.0wt% of the amount of the mixture of styrene and Bis-GMA and EBPADMA；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 350rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 480nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, wherein the addition of the modifying titanium dioxide is EFI solution The parameter of the 40% of quality, electrostatic spray is：The output voltage 15kV of high voltage power supply, atomizing nozzle and solidification bathing pool distance 8cm, Temperature 50 C promotes the fltting speed 3mL/h of pump, the diameter 7mm of propeller, the volume 7mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with ethyl alcohol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle obtained mainly by titania nanoparticles and is coated on two The crosslinking ball on Titanium dioxide nanoparticle surface forms, wherein crosslinking ball inner hollow, porous surface and has cross-linked structure, crosslinking Structure between the copolymer molecule chain containing styrene and bifunctionality dimethylacrylate class monomeric building blocks by mutually handing over Connection is formed, and by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked a diameter of 1300nm of ball, is crosslinked ball Wall thickness be 100nm, a diameter of 360nm of titania nanoparticles, be crosslinked ball inner silica titanium nano particle quantity It it is 3, the distribution density for being crosslinked the surface aperture of ball is 10~15/1000nm2, the aperture of aperture is 30~40nm.Cladding The melting temperature of the hollow porous micro sphere of titania nanoparticles is 545 DEG C, and heat decomposition temperature is 410 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 46.2wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 35min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 5.0wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 295 DEG C；Cross air blasting cooling wind temperature is 29 DEG C；Cross air blasting wind speed is 0.4m/s；Winding is spun Silk speed is 3500m/min；Draft ratio is 3.0.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and there is the delustring PET fiber being prepared good extinction effect, PET fiber to reach titanium dioxide when totally disappeared light effect Content be 2.0wt%, delustring PET fiber mechanical property is good, fiber number 4.0dtex, fracture strength 3.38cN/dtex, disconnected It is 27.4% to split elongation.
Embodiment 7
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 wherein in mixed dispersion liquid:230:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4.5h is reacted at 65 DEG C, room temperature ageing 10h is aged Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume 30%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature 3h is solved, is added in the ageing liquid of ultrasonic disperse 55min, the back flow reaction 4.5h at 60 DEG C, wherein ethyl alcohol in ethanol water Mass ratio with water is 4:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1: The addition of 10, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 9%；
D) it is dried in vacuo 16h at 80 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) by UDMA and D3Mixture (the mass ratio 1 of MA:2), styrene and DMPOH are dissolved in DMF, trichlorine Mixture (the mass ratio 1 of methane and dichloromethane:1:2) EFI solution is obtained in, UDMA and D in EFI solution3MA's is mixed It closes object and accounts for styrene and UDMA and D3The mixture of the 5wt% of the amount of the mixture of MA, DMF, chloroform and dichloromethane account for Styrene and UDMA and D3The 75wt% of the amount of the mixture of MA, DMPOH account for styrene and UDMA and D3The amount of the mixture of MA 1.1wt%；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 450rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 500nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, wherein the addition of the modifying titanium dioxide is EFI solution The parameter of the 18% of quality, electrostatic spray is：The output voltage 10kV of high voltage power supply, atomizing nozzle and solidification bathing pool distance 7cm, 25 DEG C of temperature promotes the fltting speed 1mL/h of pump, the diameter 6mm of propeller, the volume 8mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with methanol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle obtained mainly by titania nanoparticles and is coated on two The crosslinking ball on Titanium dioxide nanoparticle surface forms, wherein crosslinking ball inner hollow, porous surface and has cross-linked structure, crosslinking Structure between the copolymer molecule chain containing styrene and bifunctionality dimethylacrylate class monomeric building blocks by mutually handing over Connection is formed, and by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked a diameter of 1500nm of ball, is crosslinked ball Wall thickness be 50nm, a diameter of 300nm of titania nanoparticles, crosslinking ball inner silica titanium nano particle quantity be 3, the distribution density for being crosslinked the surface aperture of ball is 14~20/1000nm2, the aperture of aperture is 60~65nm.Cladding two The melting temperature of the hollow porous micro sphere of Titanium dioxide nanoparticle is 545 DEG C, and heat decomposition temperature is 392 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 60wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 30min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 5.6wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 270 DEG C；Cross air blasting cooling wind temperature is 29 DEG C；Cross air blasting wind speed is 0.4m/s；Winding is spun Silk speed is 3800m/min；Draft ratio is 4.0.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and there is the delustring PET fiber being prepared good extinction effect, PET fiber to reach titanium dioxide when totally disappeared light effect Content be 0.6wt%, delustring PET fiber mechanical property is good, fiber number 4.0dtex, fracture strength 3.22cN/dtex, disconnected It is 14.6% to split elongation.
Embodiment 8
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 wherein in mixed dispersion liquid:150:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 67 DEG C, room temperature ageing 12h is aged Liquid, the mass ratio of ethyl alcohol and water is 5 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume 26%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature 2.5h is solved, is added in the ageing liquid of ultrasonic disperse 30min, the back flow reaction 4.5h at 65 DEG C, wherein second in ethanol water The mass ratio of alcohol and water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1: The addition of 12, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 7%；
D) it is dried in vacuo 14h at 70 DEG C after rotating evaporation drying at 70 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) by the mixture (mass ratio 1 of Bis-GMA, EBPADMA and UDMA:1:1), styrene and CQ dissolvings Obtain EFI solution in DMF, in EFI solution the mixture of Bis-GMA, EBPADMA and UDMA account for styrene and Bis-GMA, The 10wt% of the amount of the mixture of EBPADMA and UDMA, DMF account for styrene and the mixture of Bis-GMA, EBPADMA and UDMA The 80wt% of total amount, CQ account for the 1.2wt% of styrene and the amount of the mixture of Bis-GMA, EBPADMA and UDMA；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 500rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 400nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, wherein the addition of the modifying titanium dioxide is EFI solution The parameter of the 27% of quality, electrostatic spray is：The output voltage 12kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool 13cm, 35 DEG C of temperature promote the fltting speed 2mL/h of pump, the diameter 5mm of propeller, the volume 9mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with methanol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle obtained mainly by titania nanoparticles and is coated on two The crosslinking ball on Titanium dioxide nanoparticle surface forms, wherein crosslinking ball inner hollow, porous surface and has cross-linked structure, crosslinking Structure between the copolymer molecule chain containing styrene and bifunctionality dimethylacrylate class monomeric building blocks by mutually handing over Connection is formed, and by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked a diameter of 1500nm of ball, is crosslinked ball Wall thickness be 50nm, a diameter of 310nm of titania nanoparticles, crosslinking ball inner silica titanium nano particle quantity be 4, the distribution density for being crosslinked the surface aperture of ball is 1~5/1000nm2, the aperture of aperture is 70~80nm.Coat dioxy The melting temperature for changing the hollow porous micro sphere of titanium nano particle is 550 DEG C, and heat decomposition temperature is 418 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 54.1wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 40min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 4.0wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 295 DEG C；Cross air blasting cooling wind temperature is 30 DEG C；Cross air blasting wind speed is 0.5m/s；Winding is spun Silk speed is 3500m/min；Draft ratio is 3.5.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and there is the delustring PET fiber being prepared good extinction effect, PET fiber to reach titanium dioxide when totally disappeared light effect Content be 1.5wt%, delustring PET fiber mechanical property is good, fiber number 3.4dtex, fracture strength 2.91cN/dtex, disconnected It is 25.2% to split elongation.
Embodiment 9
A kind of delustring PET fiber slice mill preparation method, steps are as follows：
(1) hollow porous micro sphere of cladding titanium dioxide nano particle is prepared；
(1.1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 wherein in mixed dispersion liquid:220:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 70 DEG C, room temperature ageing 10h is aged Liquid, the mass ratio of ethyl alcohol and water is 3 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume 20%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature 2h is solved, is added in the ageing liquid of ultrasonic disperse 60min, the back flow reaction 4.5h at 70 DEG C, wherein ethyl alcohol in ethanol water Mass ratio with water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:9, The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 5%；
D) it is dried in vacuo 15h at 80 DEG C after rotating evaporation drying at 60 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
(1.2) by UDMA, TEGDMA and D3Mixture (the mass ratio 1 of MA:2:2), styrene and DMPOH and CQ Mixture (mass ratio 2:1) it is dissolved in chloroform and obtains EFI solution, UDMA, TEGDMA and D in EFI solution3MA's Mixture accounts for styrene and UDMA, TEGDMA and D3The 25wt% of the amount of the mixture of MA, chloroform account for styrene and UDMA, TEGDMA and D3The mixture of 50wt%, DMPOH and the CQ of the amount of the mixture of MA account for styrene and UDMA, TEGDMA and D3MA Amount of the mixture 0.5wt%；
(1.3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 200rpm 1h makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic spray is carried out in the case where wavelength is the visible light conditions of 430nm The hollow porous micro sphere of cladding titanium dioxide nano particle is made, wherein the addition of the modifying titanium dioxide is EFI solution The parameter of the 39% of quality, electrostatic spray is：The output voltage 14kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool 10cm, temperature 45 C promote the fltting speed 3mL/h of pump, the diameter 15mm of propeller, the volume 10mL of propeller；
(1.4) hollow porous micro sphere of cladding titanium dioxide nano particle is washed with ethyl alcohol and do after electrostatic spray Dry, the hollow porous micro sphere of cladding titanium dioxide nano particle obtained mainly by titania nanoparticles and is coated on two The crosslinking ball on Titanium dioxide nanoparticle surface forms, wherein crosslinking ball inner hollow, porous surface and has cross-linked structure, crosslinking Structure between the copolymer molecule chain containing styrene and bifunctionality dimethylacrylate class monomeric building blocks by mutually handing over Connection is formed, and by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked a diameter of 600nm of ball, is crosslinked ball Wall thickness be 100nm, a diameter of 340nm of titania nanoparticles, be crosslinked ball inner silica titanium nano particle quantity It it is 1, the distribution density for being crosslinked the surface aperture of ball is 30~37/1000nm2, the aperture of aperture is 10~13nm.Cladding The melting temperature of the hollow porous micro sphere of titania nanoparticles is 546 DEG C, and heat decomposition temperature is 398 DEG C；
(2) PET slices and the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle are prepared into functional agglomerate, The content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 55.7wt% in functional agglomerate；
(3) delustring PET is made in melt spinning after functional agglomerate being mixed 35min with PET slices in super mixer again Fiber, the content of the hollow porous micro sphere of cladding titanium dioxide nano particle is 5.6wt%, melt spinning in delustring PET fiber Technological parameter it is as follows：Spinning temperature is 290 DEG C；Cross air blasting cooling wind temperature is 30 DEG C；Cross air blasting wind speed is 0.3m/s；Winding is spun Silk speed is 4000m/min；Draft ratio is 4.0.
It is evenly dispersed in the delustring PET fiber being finally prepared to have the hollow porous micro- of cladding titanium dioxide nano particle Ball, and there is the delustring PET fiber being prepared good extinction effect, PET fiber to reach titanium dioxide when totally disappeared light effect Content be 1.2wt%, delustring PET fiber mechanical property is good, fiber number 4.0dtex, fracture strength 3.28cN/dtex, disconnected It is 16.2% to split elongation.

Claims (9)

1. a kind of delustring PET fiber, it is characterized in that：It is evenly dispersed in delustring PET fiber to have cladding titanium dioxide nano particle Hollow porous micro sphere；
The hollow porous micro sphere of the cladding titanium dioxide nano particle mainly by titania nanoparticles and is coated on dioxy Change the crosslinking ball composition on titanium nano particle surface；
The crosslinking ball inner hollow, porous surface and have cross-linked structure, the cross-linked structure is by containing styrene and difunctionality It is cross-linked with each other to be formed between the copolymer molecule chain of degree dimethylacrylate class monomeric building blocks；
By being covalently keyed between the titania nanoparticles and crosslinking ball；
The content that the delustring PET fiber reaches titanium dioxide when totally disappeared light effect is 0.6~2.0wt%.
2. a kind of delustring PET fiber according to claim 1, which is characterized in that the fiber number of the delustring PET fiber is 3.2~4.0dtex, fracture strength are 2.82~3.38cN/dtex, and elongation at break is 13.2~27.4%.
3. a kind of delustring PET fiber according to claim 1, which is characterized in that the cladding titanium dioxide nano particle Hollow porous micro sphere melting temperature>530 DEG C, heat decomposition temperature>380℃；
The wall thickness of a diameter of 500~1500nm of the crosslinking ball, the crosslinking ball are 50~100nm；The titanium dioxide is received A diameter of 300~400nm of rice grain；The quantity of the crosslinking ball inner silica titanium nano particle is 1~4.
4. a kind of delustring PET fiber according to claim 3, which is characterized in that when crosslinking ball inner silica titanium nanometer When the quantity of particle≤2, the distribution density of the surface aperture of the crosslinking ball is 1~60/1000nm2, the aperture of aperture is 10~30nm；
When the quantity of crosslinking ball inner silica titanium nano particle>When 2, the distribution density of the surface aperture of the crosslinking ball is 1 ~20/1000nm2, the aperture of aperture is 10~80nm.
5. according to a kind of delustring PET fiber of Claims 1 to 4 any one of them, which is characterized in that the cladding titanium dioxide The preparation method of the hollow porous micro sphere of nano particle is：
It is molten that the dissolving of styrene, bifunctionality dimethylacrylate class organic monomer and photoinitiator is obtained into EFI in a solvent Liquid, then the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation 1h in EFI solution with 200~500rpm It is uniformly dispersed, the hollow porous micro sphere that cladding titanium dioxide nano particle is made in electrostatic spray is carried out under visible light conditions, most It is washed and is dried with methanol or ethyl alcohol afterwards；
The bifunctionality dimethylacrylate class organic monomer is Bis-GMA, EBPADMA, UDMA, TEGDMA and D3In MA More than one；The photoinitiator is DMPOH and/or CQ；The wavelength of the visible light is 400~500nm；The solvent is One or more of DMF, chloroform, dichloromethane and tetrahydrofuran；
Bifunctionality dimethylacrylate class organic monomer accounts for styrene and bifunctionality dimethyl propylene in the EFI solution 5~25wt% of olefin(e) acid esters organic monomer total amount, solvent account for styrene and the organic list of bifunctionality dimethylacrylate class 50~80wt% of body total amount, photoinitiator account for styrene and bifunctionality dimethylacrylate class organic monomer total amount 0.5~1.2wt%；The addition of the modifying titanium dioxide is the 15~40% of EFI solution quality；
The parameter of the electrostatic spray is：10~15kV of output voltage of high voltage power supply, atomizing nozzle with solidification bathing pool at a distance from 7~ 13cm, 25~50 DEG C of temperature promote 1~4mL/h of fltting speed of pump, 5~15mm of diameter of propeller, the volume 3 of propeller ~10mL.
6. a kind of delustring PET fiber according to claim 5, which is characterized in that the preparation of the modifying titanium dioxide walks It is rapid as follows：
(1) titanium dioxide is dispersed in after being stirred by ultrasonic in absolute ethyl alcohol and tetrabutyl titanate is added dropwise obtains mixed dispersion liquid； The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4~6 in the mixed dispersion liquid:150~250:1；
(2) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4~5h is reacted at 60~70 DEG C, room temperature is aged 10~12h and obtains To ageing liquid；The mass ratio of ethyl alcohol and water is 2~5 in the ethyl alcohol water mixed liquid:1, the addition of the ethyl alcohol water mixed liquid It is the 20~30% of mixed dispersion liquid volume；
(3) by silane coupling agent instill ethanol water in, 2~3h of hydrolysis is stirred at room temperature, be added to ultrasonic disperse 30~ In the ageing liquid of 60min, 4~5h of back flow reaction at 60~70 DEG C；The mass ratio of ethyl alcohol and water is 2 in the ethanol water ~5:1, the mass ratio of the silane coupling agent and ethanol water is 1:8~12, the addition of the silane coupling agent is old Change 5~10% of titanium dioxide quality in liquid, the silane coupling agent is γ-methacryloxypropyl trimethoxy silicon Alkane；
(4) it is dried in vacuo 12~16h at 70~80 DEG C after rotating evaporation drying at 50~70 DEG C, it is double bond containing to obtain surface Modifying titanium dioxide.
7. such as a kind of slice electrospinning method for preparing of delustring PET fiber of claim 1~6 any one of them, it is characterized in that：It will PET is sliced prepares functional agglomerate with the hollow porous micro sphere melt blending of cladding titanium dioxide nano particle, then by functional agglomerate Delustring PET fiber is made in melt spinning after mixing with PET slices.
8. preparation method according to claim 7, which is characterized in that cladding titanium dioxide nano in the functional agglomerate The content of the hollow porous micro sphere of grain is 44.4~60wt%, cladding titanium dioxide nano particle in the delustring PET fiber The content of hollow porous micro sphere is 3.5~5.6wt%.
9. preparation method according to claim 7, which is characterized in that described be uniformly mixed refers to being mixed in super mixer Close 30~40min；The technological parameter of the melt spinning is as follows：
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