CN108059825B - Extinction PA master batch and preparation method thereof - Google Patents

Extinction PA master batch and preparation method thereof Download PDF

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CN108059825B
CN108059825B CN201810029321.2A CN201810029321A CN108059825B CN 108059825 B CN108059825 B CN 108059825B CN 201810029321 A CN201810029321 A CN 201810029321A CN 108059825 B CN108059825 B CN 108059825B
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CN108059825A (en
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詹伟东
孙宾
许文菊
肖露露
翟丽鹏
孙小国
李晓明
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Zhejiang Dongtai New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • D—TEXTILES; PAPER
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The invention relates to an extinction PA master batch and a preparation method thereof, wherein the method comprises the following steps: the preparation method comprises the following steps of uniformly mixing PA slices and hollow porous microspheres coated with titanium dioxide nanoparticles, then carrying out melt extrusion granulation, and carrying out drying treatment to obtain the extinction PA master batch, wherein the hollow porous microspheres mainly comprise the titanium dioxide nanoparticles and cross-linked spheres which are connected with the titanium dioxide nanoparticles through covalent bonds and coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and have porous surfaces and cross-linked structures, and the cross-linked structures are formed by mutually cross-linking copolymer molecular chains containing styrene and bifunctional dimethacrylate monomer structural units. The prepared extinction PA master batch is uniformly dispersed with hollow porous microspheres, and the filtration pressure value of the PA resin with the titanium dioxide content of 5 wt% added with the extinction PA master batch is 0.60-2.86 bar/g. The method has simple and convenient process, and the prepared master batch has the advantages of good extinction effect, small pressure on a spinning assembly and wide application range.

Description

Extinction PA master batch and preparation method thereof
Technical Field
The invention belongs to the field of fiber preparation, and particularly relates to an extinction PA master batch and a preparation method thereof.
Background
Matte fibers are also called matte fibers and refer to chemical fibers with a matte surface. The method for preparing the extinction fiber is generally that the extinction agent is added into spinning solution or melt before spinning, and the extinction fiber prepared by spinning forming can scatter light rays to eliminate luster so as to reduce transparency and increase whiteness. In recent years, full-dull polyester fibers are more and more accepted by the weaving industry due to the unique appearance characteristics of the full-dull polyester fibers. Meanwhile, with the breakthrough of the preparation technology of the extinction fiber in China, the application field of the full-extinction fiber is continuously expanded, and the full-extinction fiber is widely applied to the vernonia and wool-like fabrics.
The titanium dioxide has outstanding tinting strength, covering power and extinction capability, is a white pigment with the best performance in the world at present, can be widely applied to the industrial fields of coatings, plastics, printing ink, paper making and the like, has larger demand and has excellent application prospect. The extinction PA master batch is mainly used for preparing the anti-full-extinction PA fiber through melt spinning, and the full-extinction fiber generally achieves the extinction effect through adding titanium dioxide. The method has the defects that the extinction substance is difficult to achieve good dispersion in the polyester resin, and the non-uniformly dispersed powder material can increase the spinning pressure during spinning, block a spinneret plate and influence the spinnability of the fiber. Meanwhile, because the compatibility of the titanium dioxide and the polymer is poor, when the titanium dioxide is used as an additive to prepare the extinction fiber, the extinction effect of the extinction fiber is poor under the condition of small addition amount.
The titanium dioxide can be coated with elements such as Al or Si in an inorganic manner to improve the dispersibility of the titanium dioxide to a certain extent. The high-voltage electrostatic spraying method is a method for preparing polymer particles from polymer solution or melt by using an electro-hydrodynamic technology. Compared with other methods for preparing the polymer particles, such as a precipitation method, a reversed-phase suspension crosslinking method, a spray drying method and the like, the electrostatic spraying method for preparing the microsphere material has the advantages of simple process, strong controllability, environmental protection and no need of using a large amount of emulsifying agents, the electrostatic spraying method is adopted to easily prepare the monodisperse particles, and the finally obtained particles can have various shapes, such as hollow and porous shapes and the like, for example, it has been reported in the literature (wariki. electrospinning method for preparing polystyrene functional material [ D ]. Jilin university, 2010.), that a polystyrene solution can be used to prepare porous hollow microspheres by electrostatic spray molding, and the prepared Polystyrene (PS) hollow microspheres have stable chemical properties at room temperature and good processability, however, since the glass transition temperature of Polystyrene (PS) is only 100 ℃, the three-dimensional structure is broken at a high temperature, and thus it cannot be applied to melt processing. This greatly affects the application of hollow microspheres of PS.
In addition, the titanium dioxide can also be subjected to surface modification, so that the problem that the titanium dioxide is easy to agglomerate and has poor dispersibility in an organic matrix is solved. The common surface modification method is coupling agent modification, but the coupling agent is only connected to the surface of the nano-particles in a chemical bond mode, so that the light-eliminating performance is not improved, and the silane coupling agent has small relative molecular mass, is easy to decompose at high temperature and is not beneficial to preparing high-performance fibers by melting.
Therefore, the research on the preparation method of the extinction master batch with good extinction effect and small pressure on the spinning assembly is very important.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides the extinction PA master batch with good extinction effect and small pressure on a spinning assembly and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
an extinction PA master batch, wherein hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the extinction PA master batch;
the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles;
the cross-linked sphere is hollow inside, porous in surface and provided with a cross-linked structure, and the cross-linked structure is formed by cross-linking copolymer molecular chains containing styrene and bifunctional dimethacrylate monomer structural units;
the titanium dioxide nano particles are connected with the cross-linked spheres through covalent bonds;
the filtering pressure value of the PA resin with the content of 5 wt% of titanium dioxide after the extinction PA master batch is added is 0.60-2.86 bar/g. Under the same condition, the filtration pressure value of the PA resin with the titanium dioxide content of 5 wt% added with the commercial titanium dioxide is 0.63-5.96 bar/g.
The testing of the filtering pressure is carried out according to the standard BS EN 13900-5:2005, the filtering performance of the master batch is detected by adopting an FCC-3 type filtering performance tester, a certain amount of extinction PA master batch and PA slices are mixed to obtain 1000g of mixture, the mass fraction of titanium dioxide in the mixture is 5%, and the calculation formula of the master batch filtering pressure value FPV is as follows:
FPV＝(pmax-ps)/mc；
in the formula, psFor the starting pressure values, in bar, pmaxThe maximum value of the test pressure is bar, and the content of the inorganic particles in the master batch is g. A1400-mesh filter screen is adopted in the experiment, the pressure of a machine head is controlled to be 6.5MPa, and the temperature of each area of a screw is respectively as follows: 220 deg.C, 265 deg.C.
As a preferred technical scheme:
the extinction PA master batch contains 20-80 wt% of titanium dioxide; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 0.6-1.2 wt%, and if unmodified titanium dioxide in the prior art is added, the content of titanium dioxide in the full extinction PA fiber needs to reach 1.5-2.0 wt%.
The extinction PA master batch has the advantages that the melting temperature of the hollow porous microspheres coated with the titanium dioxide nanoparticles is more than 530 ℃, and the thermal decomposition temperature is more than 380 ℃; the melt processing temperature of the extinction PA master batch is lower than that of the hollow porous microspheres, so that the hollow porous microspheres can keep a good three-dimensional structure without being damaged when the extinction PA master batch is prepared, and the full play of the efficacy of the hollow porous microspheres is facilitated;
the diameter of the cross-linked ball is 500-1500 nm, and the wall thickness of the cross-linked ball is 50-100 nm; the diameter of the titanium dioxide nano-particles is 300-400 nm; the number of the titanium dioxide nanoparticles in the crosslinking ball is 1-4.
When the number of the titanium dioxide nanoparticles in the cross-linked sphere is less than or equal to 2, the distribution density of pores on the surface of the cross-linked sphere is 1-60/1000 nm2The aperture of the small hole is 10-30 nm;
the amount of titanium dioxide nanoparticles inside the crosslinked spheres>2, the distribution density of the pores on the surface of the cross-linked ball is 1-20 pores/1000 nm2The aperture of the small hole is 10-80 nm.
The preparation method of the hollow porous microsphere coated with the titanium dioxide nanoparticles by using the extinction PA master batch comprises the following steps:
dissolving styrene, a bifunctional dimethacrylate organic monomer and a photoinitiator in a solvent to obtain an electric spraying solution, adding modified titanium dioxide with double bonds on the surface into the electric spraying solution, mechanically stirring at a rotating speed of 200-500 rpm for 1 hour to disperse uniformly, performing electrostatic spraying under the condition of visible light to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, and finally washing with methanol or ethanol and drying; the washing and drying function is to remove impurities on the surface of the microsphere in the electrostatic spraying process, such as redundant polymerized monomers, photoinitiators and the like; meanwhile, in the process, the modified titanium dioxide with double bonds on the surface can be uniformly dispersed in the solvent due to the organic functional groups on the surface, so that a uniform electrostatic spraying system can be prepared;
the bifunctional dimethacrylate organic monomer is Bis-GMA, EBPADMA, UDMA, TEGDMA and D3One or more of MA;
the specific structural formula of the bifunctional dimethacrylate organic monomer is as follows:
Figure BDA0001545988100000041
the photoinitiator is DMPOH (N, N-dimethylamino phenethyl alcohol) and/or CQ (1,7, 7-trimethyl bicyclo (2,2,1) -2,3 heptanedione); the wavelength of the visible light is 400-500 nm; the solvent is more than one of DMF, trichloromethane, dichloromethane and tetrahydrofuran;
the bifunctional dimethacrylate organic monomer in the electrospray solution accounts for 5-25 wt% of the total amount of the styrene and the bifunctional dimethacrylate organic monomer; the proportion of bifunctional organic dimethacrylate monomer in the total amount of styrene and bifunctional organic dimethacrylate monomer in the electric spraying solution is in direct proportion to the crosslinking degree of the crosslinking structure on the surface of the microsphere, the higher the crosslinking degree is, the larger the crosslinking mesh is, the faster the exchange speed is, but the strength of the crosslinking structure can be reduced to a certain extent, otherwise, the lower the crosslinking degree is, the smaller the crosslinking mesh is, the higher the crosslinking strength is, but the swellability to water is poor; the concentration of bifunctional dimethacrylate organic monomer in the electric spraying solution is too low, the crosslinking degree is low, the bifunctional dimethacrylate organic monomer cannot be applied to melt processing, and too high, the viscosity of a composite system is influenced, and microspheres cannot be formed;
the solvent accounts for 50-80 wt% of the total amount of the styrene and the bifunctional dimethacrylate organic monomer, and the photoinitiator accounts for 0.5-1.2 wt% of the total amount of the styrene and the bifunctional dimethacrylate organic monomer; the concentration of the photoinitiator in the electric spraying solution is too low, the initiation efficiency is too low, and the polymerization of the monomer cannot be initiated;
the adding amount of the modified titanium dioxide is 15-40% of the mass of the electronic injection solution;
the parameters of the electrostatic spraying are as follows: the output voltage of the high-voltage power supply is 10-15 kV, the distance between the spray nozzle and the coagulation bath pool is 7-13 cm, the temperature is 25-50 ℃, the propelling speed of the propelling pump is 1-4 mL/h, the diameter of the propeller is 5-15 mm, and the volume of the propeller is 3-10 mL.
The preparation method of the extinction PA master batch comprises the following steps:
(1) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid; the mass ratio of titanium dioxide, absolute ethyl alcohol and n-butyl titanate in the mixed dispersion liquid is 4-6: 150-250: 1;
(2) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4-5 h at the temperature of 60-70 ℃, and aging for 10-12 h at room temperature to obtain an aging liquid; the mass ratio of ethanol to water in the ethanol-water mixed solution is 2-5: 1, and the addition amount of the ethanol-water mixed solution is 20-30% of the volume of the mixed dispersion liquid;
(3) dripping a silane coupling agent into an ethanol water solution, stirring and hydrolyzing for 2-3 h at room temperature, adding into an aging solution subjected to ultrasonic dispersion for 30-60 min, and performing reflux reaction for 4-5 h at 60-70 ℃; the mass ratio of ethanol to water in the ethanol aqueous solution is 2-5: 1, the mass ratio of the silane coupling agent to the ethanol aqueous solution is 1: 8-12, the addition amount of the silane coupling agent is 5-10% of the mass of titanium dioxide in the aging liquid, and the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane;
(4) and (3) performing rotary evaporation drying at 50-70 ℃, and then performing vacuum drying at 70-80 ℃ for 12-16 h to obtain the modified titanium dioxide with the surface containing double bonds.
The preparation method of the extinction PA master batch comprises the following steps:
(1) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid; the mass ratio of titanium dioxide, absolute ethyl alcohol and n-butyl titanate in the mixed dispersion liquid is 4-6: 150-250: 1;
(2) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4-5 h at the temperature of 60-70 ℃, and aging for 10-12 h at room temperature to obtain an aging liquid; the mass ratio of ethanol to water in the ethanol-water mixed solution is 2-5: 1, and the addition amount of the ethanol-water mixed solution is 20-30% of the volume of the mixed dispersion liquid;
(3) dripping a silane coupling agent into an ethanol water solution, stirring and hydrolyzing for 2-3 h at room temperature, adding into an aging solution subjected to ultrasonic dispersion for 30-60 min, and performing reflux reaction for 4-5 h at 60-70 ℃; the mass ratio of ethanol to water in the ethanol aqueous solution is 2-5: 1, the mass ratio of the silane coupling agent to the ethanol aqueous solution is 1: 8-12, the addition amount of the silane coupling agent is 5-10% of the mass of titanium dioxide in the aging liquid, and the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane;
(4) and (3) performing rotary evaporation drying at 50-70 ℃, and then performing vacuum drying at 70-80 ℃ for 12-16 h to obtain the modified titanium dioxide with the surface containing double bonds.
The invention also provides a method for preparing the extinction PA master batch, which is characterized in that PA slices and hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly mixed, then are subjected to melt extrusion granulation, and are subjected to drying treatment to obtain the extinction PA master batch.
According to the method, 100 parts of PA slices and 80-150 parts of hollow porous microspheres coated with titanium dioxide nanoparticles are mixed according to parts by weight.
In the method, the step of uniformly mixing refers to mixing in a high-speed mixer for 30-40 min; the temperature of the melt extrusion is 240-280 ℃, and the pressure of the melt extrusion is 5-7 MPa; the temperature of the drying treatment is 60-80 ℃, and the time of the drying treatment is 30-40 min.
The invention mechanism is as follows:
the invention relates to an extinction PA master batch and a preparation method thereof, which firstly designs a method for preparing hollow porous microspheres coated with titanium dioxide nano particles by electrostatic spraying-photoinitiation polymerization crosslinking, in the process, firstly, a monofunctional styrene monomer, a bifunctional dimethacrylate organic monomer and a photoinitiator are dissolved in a solvent to prepare an electric spraying solution, then, modified titanium dioxide with double bonds on the surface is added and uniformly mixed, then, electrostatic spraying is carried out under a high pressure field to form liquid drops, visible light (according to the initiation wavelength law of the photoinitiator) is utilized to initiate the styrene monomer, the bifunctional dimethacrylate monomer and the double bonds on the surface of the modified titanium dioxide to carry out free radical polymerization, a copolymer containing structural units of the styrene and the bifunctional dimethacrylate monomer is formed on the surface of the titanium dioxide, and simultaneously, due to the bifunctional dimethacrylate monomer, molecular chains of a copolymer containing styrene and bifunctional dimethacrylate monomer structural units can be mutually crosslinked to form a body-shaped structure, hollow porous microspheres coated with titanium dioxide nanoparticles are formed in the forming process due to polymerization shrinkage, solvent volatilization and diffusion in a coagulating bath, so that the hollow porous microspheres coated with the titanium dioxide nanoparticles with the melting temperature of more than 530 ℃ and the thermal decomposition temperature of more than 380 ℃ are prepared, the molecular chains of the copolymer containing the styrene and bifunctional dimethacrylate monomer structural units are crosslinked to form a body-shaped structure, the melting temperature of the hollow porous microspheres is high, the three-dimensional structure can be kept in the subsequent processing process, and the functions of the hollow porous microspheres can be fully exerted, while the hollow microspheres prepared by electrostatic spraying in the prior art are generally prepared by dissolving the polymer in the solvent by electrostatic spraying, after the microspheres are obtained by the method, the polymer still keeps the original thermal property and is melted during melt processing, the appearance of the microsphere can not be kept, the polymer can not be used for melt processing, and then PA slices and hollow porous microspheres coated with titanium dioxide nano particles are uniformly mixed, melted, extruded, granulated and dried to prepare the extinction PA master batch.
In addition, the titanium dioxide has good extinction effect (scattering), the porous structure can effectively scatter incident light, and the utilization rate of the incident light is improved.
Has the advantages that:
(1) the extinction PA master batch has the advantages of good extinction effect, small pressure on a spinning assembly and wide application range.
(2) The extinction PA master batch uses modified titanium dioxide, and the surface of the modified titanium dioxide has organic functional groups, so that the modified titanium dioxide can be uniformly dispersed in a solvent, and the extinction PA master batch is favorable for subsequent reaction;
(3) the preparation method of the extinction PA master batch provided by the invention solves the problem of dispersibility of titanium dioxide, improves the extinction effect of the titanium dioxide and reduces the addition amount of the titanium dioxide in fibers in the subsequent processing process.
(4) The preparation method of the extinction PA master batch is simple and convenient in process, reasonable in preparation flow and extremely high in popularization value.
Drawings
Fig. 1 is a schematic structural view of hollow porous microspheres coated with titanium dioxide nanoparticles in the extinction PA master batch of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 4:150: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4 hours at 70 ℃, and aging for 11 hours at room temperature to obtain an aged solution, wherein the mass ratio of ethanol to water in the ethanol-water mixed solution is 2:1, and the adding amount of the ethanol-water mixed solution is 20% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 2h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 30min, and performing reflux reaction for 4h at 60 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 2:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:12, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 5 percent of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 60 ℃, and then vacuum drying at 70 ℃ for 13h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) dissolving styrene, Bis-GMA and DMPOH in DMF to obtain an electrospray solution, wherein the Bis-GMA accounts for 10 wt% of the total amount of the styrene and the Bis-GMA in the electrospray solution, the DMF accounts for 50 wt% of the total amount of the styrene and the Bis-GMA, and the DMPOH accounts for 0.5 wt% of the total amount of the styrene and the Bis-GMA;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 200rpm for 1h to ensure that the modified titanium dioxide is uniformly dispersed in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 400nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 15% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 10kV, the distance between a spray nozzle and a coagulation bath pool is 13cm, the temperature is 25 ℃, the propelling speed of a propelling pump is 4mL/h, the diameter of a propeller is 15mm, and the volume of the propeller is 3 mL;
(1.4) washing and drying the hollow porous microspheres coated with the titanium dioxide nanoparticles by using methanol after electrostatic spraying, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles have a structural schematic diagram shown in figure 1 and mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and porous on the surfaces, the cross-linked structures are formed by mutual cross-linking of copolymer molecular chains containing styrene and Bis-GMA structural units, the titanium dioxide nanoparticles are connected with the cross-linked spheres through covalent bonds, the diameter of each cross-linked sphere is 500nm, the wall thickness of each cross-linked sphere is 50nm, the diameter of each titanium dioxide nanoparticle is 310nm, the number of the titanium dioxide nanoparticles inside each cross-linked sphere is 1, and the distribution density of surface pores of each cross-linked sphere is 1-10/1000 nm2The aperture of the small hole is 25-30 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 561 ℃, and the thermal decomposition temperature is 410 ℃;
(2) mixing 100 parts of PA slices and 80 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 30min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 280 ℃, and the melt extrusion pressure is 5 MPa; the temperature of the drying treatment was 75 ℃ and the time of the drying treatment was 30 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 25 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 1.0 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 0.60 bar/g.
Example 2
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 5:200: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4h at 60 ℃, and aging for 10h at room temperature to obtain an aged solution, wherein the volume of ethanol and the added amount in the ethanol-water mixed solution is 30% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 3h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 40min, and performing reflux reaction for 4.5h at 65 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 3:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:11, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 6 percent of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 50 ℃, and then vacuum drying at 80 ℃ for 14h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) dissolving styrene, EBPADMA and CQ in trichloromethane to obtain an electrospray solution, wherein the EBPADMA accounts for 15 wt% of the total amount of the styrene and the EBPADMA in the electrospray solution, the trichloromethane accounts for 60 wt% of the total amount of the styrene and the EBPADMA in the electrospray solution, and the CQ accounts for 0.6 wt% of the total amount of the styrene EBPADMA in the electrospray solution;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 300rpm for 1h to uniformly disperse the modified titanium dioxide in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 420nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 20% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 11kV, the distance between a spray nozzle and a coagulation bath pool is 12cm, the temperature is 30 ℃, the propelling speed of a propelling pump is 3mL/h, the diameter of a propeller is 13mm, and the volume of the propeller is 4 mL;
(1.4) washing the hollow porous microspheres coated with the titanium dioxide nanoparticles with ethanol after electrostatic spraying is finished, and drying to obtain the hollow porous microspheres coated with the titanium dioxide nanoparticles, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and porous on the surfaces and have cross-linked structures, the cross-linked structures are formed by mutual cross-linking of copolymer molecular chains containing styrene and Bis-GMA structural units, the titanium dioxide nanoparticles are connected with the cross-linked spheres through covalent bonds, the diameter of each cross-linked sphere is 700nm, the wall thickness of each cross-linked sphere is 60nm, the diameter of each titanium dioxide nanoparticle is 330nm, the number of the titanium dioxide nanoparticles inside each cross-linked sphere is 1, and the distribution density of surface pores of each cross-linked sphere is2The aperture of the small hole is 10-18 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 532 ℃, and the thermal decomposition temperature is 415 ℃;
(2) mixing 100 parts of PA slices and 100 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 40min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 250 ℃, and the melt extrusion pressure is 5 MPa; the temperature of the drying treatment was 68 ℃ and the time of the drying treatment was 40 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 50 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 0.6 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 1.12 bar/g.
Example 3
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 6:250: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4.5h at 65 ℃, and aging for 11h at room temperature to obtain an aged solution, wherein the mass ratio of ethanol to water in the ethanol-water mixed solution is 3:1, and the adding amount of the ethanol-water mixed solution is 25% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 2.5h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 50min, and performing reflux reaction for 5h at 70 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 4:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:10, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 7 percent of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 70 ℃, and then vacuum drying at 75 ℃ for 12h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) dissolving styrene, UDMA and a mixture of DMPOH and CQ (mass ratio is 1:1) in dichloromethane to obtain an electrospraying solution, wherein in the electrospraying solution, the UDMA accounts for 5 wt% of the total amount of the styrene and the UDMA, the dichloromethane accounts for 70 wt% of the total amount of the styrene and the UDMA, and the mixture of DMPOH and CQ accounts for 0.7 wt% of the total amount of the styrene and the UDMA;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 400rpm for 1h to uniformly disperse the modified titanium dioxide in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 440nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 25% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 12kV, the distance between a spray nozzle and a coagulation bath pool is 11cm, the temperature is 35 ℃, the propelling speed of a propelling pump is 2mL/h, the diameter of a propeller is 11mm, and the volume of the propeller is 5 mL;
(1.4) washing the hollow porous microspheres coated with the titanium dioxide nanoparticles with methanol after electrostatic spraying is finished, and drying to obtain the hollow porous microspheres coated with the titanium dioxide nanoparticles, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and porous on the surfaces and have cross-linked structures, the cross-linked structures are formed by mutual cross-linking of copolymer molecular chains containing styrene and UDMA structural units, the titanium dioxide nanoparticles are connected with the cross-linked spheres through covalent bonds, the diameter of the cross-linked spheres is 900nm, the wall thickness of the cross-linked spheres is 70nm, the diameter of the titanium dioxide nanoparticles is 350nm, the number of the titanium dioxide nanoparticles inside the cross-linked spheres is 1, and the distribution density of surface pores of the cross-linked spheres2The aperture of the small hole is 20-24 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 535 ℃, and the thermal decomposition temperature is 390 ℃;
(2) mixing 100 parts of PA slices and 120 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 32min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 275 ℃, and the melt extrusion pressure is 7 MPa; the temperature of the drying treatment was 72 ℃ and the time of the drying treatment was 40 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 65 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 0.9 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 1.34 bar/g.
Example 4
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 4:180: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4h at 63 ℃, and aging for 12h at room temperature to obtain an aged solution, wherein the mass ratio of ethanol to water in the ethanol-water mixed solution is 4:1, and the addition amount of the ethanol-water mixed solution is 22% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 3h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 60min, and performing reflux reaction for 5h at 60 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 5:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:9, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 8 percent of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 50 ℃, and then vacuum drying at 70 ℃ for 15h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) dissolving styrene, TEGDMA and CQ in tetrahydrofuran to obtain an electrospray solution, wherein TEGDMA accounts for 20 wt% of the total amount of the styrene and the TEGDMA in the electrospray solution, the tetrahydrofuran accounts for 80 wt% of the total amount of the styrene and the TEGDMA, and the CQ accounts for 0.8 wt% of the total amount of the styrene and the TEGDMA in the electrospray solution;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 500rpm for 1h to uniformly disperse the modified titanium dioxide in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 450nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 30% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 13kV, the distance between a spray nozzle and a coagulation bath pool is 10cm, the temperature is 40 ℃, the propelling speed of a propelling pump is 1mL/h, the diameter of a propeller is 10mm, and the volume of the propeller is 6 mL;
(1.4) washing the hollow porous microspheres coated with the titanium dioxide nanoparticles by using ethanol after electrostatic spraying is finished, and drying to obtain the hollow porous microspheres coated with the titanium dioxide nanoparticles, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and porous on the surfaces and have cross-linked structures, the cross-linked structures are formed by mutual cross-linking of copolymer molecular chains containing styrene and TEGDMA structural units, the titanium dioxide nanoparticles are connected with the cross-linked spheres through covalent bonds, the diameter of each cross-linked sphere is 1000nm, the wall thickness of each cross-linked sphere is 80nm, the diameter of each titanium dioxide nanoparticle is 300nm, the number of the titanium dioxide nanoparticles inside each cross-linked sphere is 2, and the distribution density of surface pores of each cross-linked2The aperture of the small hole is 20-30 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 540 ℃, and the thermal decomposition temperature is 385 ℃;
(2) mixing 100 parts of PA slices and 150 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 34min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 240 ℃, and the melt extrusion pressure is 6 MPa; the temperature of the drying treatment was 60 ℃ and the time of the drying treatment was 32 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 80 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 1.2 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 1.68 bar/g.
Example 5
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 5:240: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 5h at 60 ℃, and aging for 12h at room temperature to obtain an aged solution, wherein the mass ratio of ethanol to water in the ethanol-water mixed solution is 2:1, and the adding amount of the ethanol-water mixed solution is 28% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 2.5h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 35min, and performing reflux reaction for 4h at 65 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 2:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:8, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 9 percent of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 65 ℃, and then vacuum drying at 80 ℃ for 12h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) mixing styrene and D3Dissolving MA and DMPOH in a mixture (mass ratio of 1:2) of DMF and chloroform to obtain an electrospray solution, and dissolving D in the electrospray solution3MA represents styrene and D325% by weight of the total amount of MA, the mixture of DMF and trichloromethane being based on styrene and D355 wt% of MA, DMPOH in styrene and D30.9 wt% of total MA;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 250rpm for 1h to uniformly disperse the modified titanium dioxide in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 460nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 35% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 14kV, the distance between a spray nozzle and a coagulation bath pool is 9cm, the temperature is 45 ℃, the propelling speed of a propelling pump is 2mL/h, the diameter of a propeller is 8mm, and the volume of the propeller is 6 mL;
(1.4) washing the hollow porous microspheres coated with the titanium dioxide nanoparticles with methanol after electrostatic spraying is finished, and drying to obtain the hollow porous microspheres coated with the titanium dioxide nanoparticles, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside, porous on the surfaces and have a cross-linked structure, and the cross-linked structure comprises styrene and D3The molecular chains of the copolymer of the MA structural unit are formed by mutual crosslinking, the titanium dioxide nanoparticles are connected with the crosslinking balls through covalent bonds, the diameter of each crosslinking ball is 1250nm, the wall thickness of each crosslinking ball is 90nm, the diameter of each titanium dioxide nanoparticle is 330nm, the number of the titanium dioxide nanoparticles in each crosslinking ball is 3, and the distribution density of small holes on the surface of each crosslinking ball is 1-8/1000 nm2The aperture of the small hole is 10-20 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 538 ℃, and the thermal decomposition temperature is 400 ℃;
(2) mixing 100 parts of PA slices and 90 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 30min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 255 ℃, and the melt extrusion pressure is 6 MPa; the temperature of the drying treatment was 70 ℃ and the time of the drying treatment was 35 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 60 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 0.7 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 1.92 bar/g.
Example 6
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 6:170: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4 hours at 62 ℃, and aging for 11 hours at room temperature to obtain an aged solution, wherein the mass ratio of ethanol to water in the ethanol-water mixed solution is 4:1, and the adding amount of the ethanol-water mixed solution is 24% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 2h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 45min, and performing reflux reaction for 4.5h at 70 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 3:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:12, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 10 percent of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 55 ℃, and then vacuum drying at 75 ℃ for 16h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) dissolving a mixture of Bis-GMA and EBPADMA (mass ratio of 2:1) and a mixture of styrene and DMPOH and CQ (mass ratio of 1:1) in a mixture of dichloromethane and tetrahydrofuran (mass ratio of 1:2) to obtain an electrospray solution, wherein the mixture of Bis-GMA and EBPADMA accounts for 20 wt% of the total amount of the mixture of styrene and Bis-GMA and EBPADMA, the mixture of dichloromethane and tetrahydrofuran accounts for 65 wt% of the total amount of the mixture of styrene and Bis-GMA and EBPADMA, and the mixture of DMPOH and CQ accounts for 1.0 wt% of the total amount of the mixture of styrene and Bis-GMA and EBPADMA;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 350rpm for 1h to uniformly disperse the modified titanium dioxide in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 480nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 40% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 15kV, the distance between a spray nozzle and a coagulation bath pool is 8cm, the temperature is 50 ℃, the propelling speed of a propelling pump is 3mL/h, the diameter of a propeller is 7mm, and the volume of the propeller is 7 mL;
(1.4) washing the hollow porous microspheres coated with the titanium dioxide nanoparticles with ethanol after electrostatic spraying is finished, and drying to obtain the hollow porous microspheres coated with the titanium dioxide nanoparticles, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and porous on the surfaces and have cross-linked structures, the cross-linked structures are formed by mutual cross-linking of copolymer molecular chains containing styrene and bifunctional dimethacrylate monomer structural units, the titanium dioxide nanoparticles are connected with the cross-linked spheres through covalent bonds, the diameter of the cross-linked spheres is 1300nm, the wall thickness of the cross-linked spheres is 100nm, the diameter of the titanium dioxide nanoparticles is 360nm, the number of the titanium dioxide nanoparticles inside the cross-linked spheres is 3, and the distribution density of surface pores of the cross-linked spheres is 10-152The aperture of the small hole is 30-40 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 545 ℃, and the thermal decomposition temperature is 410 ℃;
(2) mixing 100 parts of PA slices and 130 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 38min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 270 ℃, and the melt extrusion pressure is 7 MPa; the temperature of the drying treatment was 65 ℃ and the time of the drying treatment was 30 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 20 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 1.0 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 2.38 bar/g.
Example 7
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 4:230: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4.5h at 65 ℃, and aging for 10h at room temperature to obtain an aged solution, wherein the mass ratio of ethanol to water in the ethanol-water mixed solution is 2:1, and the adding amount of the ethanol-water mixed solution is 30% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 3h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 55min, and performing reflux reaction for 4.5h at 60 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 4:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:10, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 9 percent of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 50 ℃, and then vacuum drying at 80 ℃ for 16h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) reacting UDMA with D3Dissolving mixture of MA (mass ratio of 1:2) and styrene and DMPOH in mixture of DMF, chloroform and dichloromethane (mass ratio of 1:1:2) to obtain electrospray solution, and dissolving UDMA and D in the electrospray solution3Mixtures of MA with styrene and UDMA with D35% by weight of the total mixture of MA, the mixture of DMF, trichloromethane and methylene chloride being based on styrene and UDMA and D375 wt% of the total mixture of MA, DMPOH representing styrene and UDMA and D31.1 wt% of the total amount of the mixture of MA;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 450rpm for 1h to uniformly disperse the modified titanium dioxide in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 500nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 18% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 10kV, the distance between a spray nozzle and a coagulation bath pool is 7cm, the temperature is 25 ℃, the propelling speed of a propelling pump is 1mL/h, the diameter of a propeller is 6mm, and the volume of the propeller is 8 mL;
(1.4) washing the hollow porous microspheres coated with the titanium dioxide nanoparticles with methanol after electrostatic spraying is finished, and drying to obtain the hollow porous microspheres coated with the titanium dioxide nanoparticles, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and porous on the surfaces and have cross-linked structures, the cross-linked structures are formed by mutual cross-linking of copolymer molecular chains containing styrene and bifunctional dimethacrylate monomer structural units, the titanium dioxide nanoparticles are connected with the cross-linked spheres through covalent bonds, the diameter of each cross-linked sphere is 1500nm, the wall thickness of each cross-linked sphere is 50nm, the diameter of each titanium dioxide nanoparticle is 300nm, the number of the titanium dioxide nanoparticles inside each cross-linked sphere is 3, and the distribution density of surface pores of each cross-linked sphere is 14-202The aperture of the small hole is 60-65 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 545 ℃, and the thermal decomposition temperature is 392 ℃;
(2) mixing 100 parts of PA slices and 150 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 40min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 260 ℃, and the melt extrusion pressure is 5 MPa; the temperature of the drying treatment was 80 ℃ and the time of the drying treatment was 35 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 35 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 1.1 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 2.41 bar/g.
Example 8
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 6:150: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4 hours at 67 ℃, and aging for 12 hours at room temperature to obtain an aged solution, wherein the mass ratio of ethanol to water in the ethanol-water mixed solution is 5:1, and the adding amount of the ethanol-water mixed solution is 26% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 2.5h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 30min, and performing reflux reaction for 4.5h at 65 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 5:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:12, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 7 percent of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 70 ℃, and then vacuum drying at 70 ℃ for 14h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) dissolving Bis-GMA, a mixture of EBPADMA and UDMA (the mass ratio is 1:1:1), styrene and CQ in DMF to obtain an electrospray solution, wherein in the electrospray solution, the mixture of Bis-GMA, EBPADMA and UDMA accounts for 10 wt% of the total amount of the mixture of styrene, Bis-GMA, EBPADMA and UDMA, the DMF accounts for 80 wt% of the total amount of the mixture of styrene, Bis-GMA, EBPADMA and UDMA, and the CQ accounts for 1.2 wt% of the total amount of the mixture of styrene, Bis-GMA, EBPADMA and UDMA;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 500rpm for 1h to uniformly disperse the modified titanium dioxide in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 400nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 27% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 12kV, the distance between a spray nozzle and a coagulation bath pool is 13cm, the temperature is 35 ℃, the propelling speed of a propelling pump is 2mL/h, the diameter of a propeller is 5mm, and the volume of the propeller is 9 mL;
(1.4) washing the hollow porous microspheres coated with the titanium dioxide nanoparticles with methanol after electrostatic spraying is finished, and drying to obtain the hollow porous microspheres coated with the titanium dioxide nanoparticles, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and porous on the surfaces and have cross-linked structures, the cross-linked structures are formed by mutual cross-linking of copolymer molecular chains containing styrene and bifunctional dimethacrylate monomer structural units, the titanium dioxide nanoparticles are connected with the cross-linked spheres through covalent bonds, the diameter of each cross-linked sphere is 1500nm, the wall thickness of each cross-linked sphere is 50nm, the diameter of each titanium dioxide nanoparticle is 310nm, the number of the titanium dioxide nanoparticles inside each cross-linked sphere is 4, and the distribution density of surface pores of each cross-linked sphere is 1-52The aperture of the small hole is 70-80 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 550 ℃, and the thermal decomposition temperature is 418 ℃;
(2) mixing 100 parts of PA slices and 90 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 35min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 240 ℃, and the melt extrusion pressure is 7 MPa; the temperature of the drying treatment was 66 ℃ and the time of the drying treatment was 39 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 50 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 1.2 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 2.54 bar/g.
Example 9
A preparation method of extinction PA master batch comprises the following steps:
(1) preparing hollow porous microspheres coated with titanium dioxide nanoparticles;
(1.1) preparation of modified titanium dioxide:
a) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid, wherein the mass ratio of the titanium dioxide to the absolute ethyl alcohol to the n-butyl titanate in the mixed dispersion liquid is 4:220: 1;
b) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4 hours at 70 ℃, and aging for 10 hours at room temperature to obtain an aged solution, wherein the mass ratio of ethanol to water in the ethanol-water mixed solution is 3:1, and the adding amount of the ethanol-water mixed solution is 20% of the volume of the mixed dispersion liquid;
c) dropping gamma-methacryloxypropyl trimethoxysilane into an ethanol aqueous solution, stirring and hydrolyzing for 2h at room temperature, adding the mixture into an aging solution subjected to ultrasonic dispersion for 60min, and performing reflux reaction for 4.5h at 70 ℃, wherein the mass ratio of ethanol to water in the ethanol aqueous solution is 5:1, the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol aqueous solution is 1:9, and the addition amount of the gamma-methacryloxypropyl trimethoxysilane is 5% of the mass of titanium dioxide in the aging solution;
d) rotary evaporating and drying at 60 ℃, and then vacuum drying at 80 ℃ for 15h to obtain modified titanium dioxide with double bonds on the surface;
(1.2) mixing UDMA, TEGDMA and D3Dissolving mixture of MA (mass ratio of 1:2:2), styrene and mixture of DMPOH and CQ (mass ratio of 2:1) in chloroform to obtain electrospray solution containing UDMA, TEGDMA and D3Mixture of MA comprising styrene and UDMA, TEGDMA and D325 wt.% of the total mixture of MA, trichloromethane representing styrene and UDMA, TEGDMA and D350 wt% of the total amount of MA mixture, the mixture of DMPOH and CQ comprising styrene and UDMA, TEGDMA and D30.5 wt% of the total amount of the mixture of MA;
(1.3) adding modified titanium dioxide with double bonds on the surface into an electric spraying solution, mechanically stirring at the rotating speed of 200rpm for 1h to uniformly disperse the modified titanium dioxide in the electric spraying solution, and performing electrostatic spraying under the condition of visible light with the wavelength of 430nm to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, wherein the adding amount of the modified titanium dioxide is 39% of the mass of the electric spraying solution, and the parameters of the electrostatic spraying are as follows: the output voltage of a high-voltage power supply is 14kV, the distance between a spray nozzle and a coagulation bath pool is 10cm, the temperature is 45 ℃, the propelling speed of a propelling pump is 3mL/h, the diameter of a propeller is 15mm, and the volume of the propeller is 10 mL;
(1.4) washing the hollow porous microspheres coated with the titanium dioxide nanoparticles with ethanol after electrostatic spraying is finished, and drying to obtain the hollow porous microspheres coated with the titanium dioxide nanoparticles, wherein the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise the titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles, the cross-linked spheres are hollow inside and porous on the surfaces and have cross-linked structures, the cross-linked structures are formed by mutual cross-linking of copolymer molecular chains containing styrene and bifunctional dimethacrylate monomer structural units, the titanium dioxide nanoparticles are connected with the cross-linked spheres through covalent bonds, the diameter of each cross-linked sphere is 600nm, the wall thickness of each cross-linked sphere is 100nm, the diameter of each titanium dioxide nanoparticle is 340nm, the number of the titanium dioxide nanoparticles inside each cross-linked sphere is 1, and the distribution density of surface pores of each cross-linked sphere is 30-372The aperture of the small hole is 10-13 nm. The melting temperature of the hollow porous microspheres coated with the titanium dioxide nano particles is 546 ℃, and the thermal decomposition temperature is 398 ℃;
(2) mixing 100 parts of PA slices and 110 parts of hollow porous microspheres coated with titanium dioxide nanoparticles uniformly in a high-speed mixer for 36min, then performing melt extrusion granulation, and drying to obtain delustering PA master batches, wherein the melt extrusion temperature is 280 ℃, and the melt extrusion pressure is 6 MPa; the temperature of the drying treatment was 60 ℃ and the time of the drying treatment was 40 min.
Hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the finally prepared extinction PA master batch, wherein the content of titanium dioxide in the extinction PA master batch is 65 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 0.6 wt%. The filtration pressure value of the PA resin with the content of the titanium dioxide of 5 weight percent after the extinction PA master batch is added is 2.86 bar/g.

Claims (8)

1. An extinction PA master batch is characterized in that: hollow porous microspheres coated with titanium dioxide nanoparticles are uniformly dispersed in the extinction PA master batch;
the hollow porous microspheres coated with the titanium dioxide nanoparticles mainly comprise titanium dioxide nanoparticles and cross-linked spheres coated on the surfaces of the titanium dioxide nanoparticles;
the cross-linked sphere is hollow inside, porous in surface and provided with a cross-linked structure, and the cross-linked structure is formed by cross-linking copolymer molecular chains containing styrene and bifunctional dimethacrylate monomer structural units;
the titanium dioxide nano particles are connected with the cross-linked spheres through covalent bonds;
the preparation method of the hollow porous microsphere coated with the titanium dioxide nano particles comprises the following steps:
dissolving styrene, a bifunctional dimethacrylate organic monomer and a photoinitiator in a solvent to obtain an electric spraying solution, adding modified titanium dioxide with double bonds on the surface into the electric spraying solution, mechanically stirring at a rotating speed of 200-500 rpm for 1 hour to disperse uniformly, performing electrostatic spraying under the condition of visible light to prepare hollow porous microspheres coated with titanium dioxide nanoparticles, and finally washing with methanol or ethanol and drying;
the bifunctional dimethacrylate organic monomer is Bis-GMA, EBPADMA, UDMA, TEGDMA and D3One or more of MA; the photoinitiator is DMPOH and/or CQ; the wavelength of the visible light is 400-500 nm; the solvent is more than one of DMF, trichloromethane, dichloromethane and tetrahydrofuran;
in the electric spraying solution, the bifunctional dimethacrylate organic monomer accounts for 5-25 wt% of the total amount of the styrene and the bifunctional dimethacrylate organic monomer, the solvent accounts for 50-80 wt% of the total amount of the styrene and the bifunctional dimethacrylate organic monomer, and the photoinitiator accounts for 0.5-1.2 wt% of the total amount of the styrene and the bifunctional dimethacrylate organic monomer; the adding amount of the modified titanium dioxide is 15-40% of the mass of the electronic injection solution;
the parameters of the electrostatic spraying are as follows: the output voltage of the high-voltage power supply is 10-15 kV, the distance between the spray nozzle and the coagulation bath pool is 7-13 cm, the temperature is 25-50 ℃, the propelling speed of the propelling pump is 1-4 mL/h, the diameter of the propeller is 5-15 mm, and the volume of the propeller is 3-10 mL;
the filtering pressure value of the PA resin with the content of 5 wt% of titanium dioxide after the extinction PA master batch is added is 0.60-2.86 bar/g.
2. The extinction PA master batch according to claim 1, wherein the content of titanium dioxide in the extinction PA master batch is 20-80 wt%; when the fiber prepared from the extinction PA master batch achieves the full extinction effect, the content of titanium dioxide in the fiber is 0.6-1.2 wt%.
3. The extinction PA master batch according to claim 1, wherein the hollow porous microspheres coating the titanium dioxide nanoparticles have a melting temperature of >530 ℃ and a thermal decomposition temperature of >380 ℃;
the diameter of the cross-linked ball is 500-1500 nm, and the wall thickness of the cross-linked ball is 50-100 nm; the diameter of the titanium dioxide nano-particles is 300-400 nm; the number of the titanium dioxide nanoparticles in the crosslinking ball is 1-4.
4. The extinction PA master batch according to claim 3, wherein when the number of the titanium dioxide nanoparticles in the cross-linked sphere is less than or equal to 2, the distribution density of pores on the surface of the cross-linked sphere is 1-60 pores/1000 nm2The aperture of the small hole is 10-30 nm;
the amount of titanium dioxide nanoparticles inside the crosslinked spheres>2, the distribution density of the pores on the surface of the cross-linked ball is 1-20 pores/1000 nm2The aperture of the small hole is 10-80 nm.
5. The extinction PA masterbatch according to claim 1, wherein the modified titanium dioxide is prepared by the following steps:
(1) dispersing titanium dioxide in absolute ethyl alcohol, ultrasonically stirring, and then dropwise adding n-butyl titanate to obtain a mixed dispersion liquid; the mass ratio of titanium dioxide, absolute ethyl alcohol and n-butyl titanate in the mixed dispersion liquid is 4-6: 150-250: 1;
(2) dropwise adding an ethanol-water mixed solution into the mixed dispersion liquid, reacting for 4-5 h at the temperature of 60-70 ℃, and aging for 10-12 h at room temperature to obtain an aging liquid; the mass ratio of ethanol to water in the ethanol-water mixed solution is 2-5: 1, and the addition amount of the ethanol-water mixed solution is 20-30% of the volume of the mixed dispersion liquid;
(3) dripping a silane coupling agent into an ethanol water solution, stirring and hydrolyzing for 2-3 h at room temperature, adding into an aging solution subjected to ultrasonic dispersion for 30-60 min, and performing reflux reaction for 4-5 h at 60-70 ℃; the mass ratio of ethanol to water in the ethanol aqueous solution is 2-5: 1, the mass ratio of the silane coupling agent to the ethanol aqueous solution is 1: 8-12, the addition amount of the silane coupling agent is 5-10% of the mass of titanium dioxide in the aging liquid, and the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane;
(4) and (3) performing rotary evaporation drying at 50-70 ℃, and then performing vacuum drying at 70-80 ℃ for 12-16 h to obtain the modified titanium dioxide with the surface containing double bonds.
6. A process for preparing an extinction PA masterbatch according to any one of claims 1 to 5, characterized in that: and uniformly mixing the PA slices with hollow porous microspheres coated with titanium dioxide nanoparticles, then performing melt extrusion granulation, and drying to obtain the extinction PA master batch.
7. The method of claim 6, wherein the PA chip is 100 parts and the hollow porous microspheres coated with the titanium dioxide nanoparticles are 80-150 parts by weight when the mixing is performed.
8. The method according to claim 6, wherein the mixing uniformly is mixing in a high-speed mixer for 30-40 min; the temperature of the melt extrusion is 240-280 ℃, and the pressure of the melt extrusion is 5-7 MPa; the temperature of the drying treatment is 60-80 ℃, and the time of the drying treatment is 30-40 min.
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Citations (1)

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CN104250350A (en) * 2014-09-30 2014-12-31 复旦大学 Method for preparing porous polymer material with through-pore structure

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Publication number Priority date Publication date Assignee Title
CN104250350A (en) * 2014-09-30 2014-12-31 复旦大学 Method for preparing porous polymer material with through-pore structure

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