CN108192299A - A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof - Google Patents

A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof Download PDF

Info

Publication number
CN108192299A
CN108192299A CN201810029324.6A CN201810029324A CN108192299A CN 108192299 A CN108192299 A CN 108192299A CN 201810029324 A CN201810029324 A CN 201810029324A CN 108192299 A CN108192299 A CN 108192299A
Authority
CN
China
Prior art keywords
organic
delustring
master batch
titanium dioxide
pet master
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810029324.6A
Other languages
Chinese (zh)
Inventor
詹伟东
孙宾
许文菊
肖露露
翟丽鹏
孙小国
敖翔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Dongtai New Material Co Ltd
Original Assignee
Zhejiang Dongtai New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Dongtai New Material Co Ltd filed Critical Zhejiang Dongtai New Material Co Ltd
Priority to CN201810029324.6A priority Critical patent/CN108192299A/en
Publication of CN108192299A publication Critical patent/CN108192299A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • C08J2435/00—Characterised by the use of homopolymers or 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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2435/06—Copolymers with vinyl aromatic monomers
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

The present invention relates to a kind of delustring uvioresistant high-performance PET master batch and preparation method thereof, preparation methods：By PET slices, melting extrusion is granulated and is dried obtained delustring uvioresistant high-performance PET master batch after mixing with nucleocapsid organic/inorganic composite hollow porous microsphere.It is uniformly dispersed in final product obtained by the nucleocapsid organic/inorganic composite hollow porous microsphere being mainly made of crosslinking ball, titania nanoparticles and organic uv absorbers；It is crosslinked ball inner hollow, porous surface and with by the structure that is formed of being cross-linked with each other between the copolymer molecule chain containing styrene and bifunctionality dimethylacrylate class monomeric building blocks；Titania nanoparticles are coated in crosslinking ball and between crosslinking ball by being covalently keyed；Organic uv absorbers are entrained in cross-linked structure and/or are attached on crosslinking ball inner wall.The product of the present invention, delustring and ultraviolet shielded effect are good, using wide；The method of the present invention, simple process, flow are reasonable.

Description

A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of delustring uvioresistant high-performance PET master batch and its preparation Method.
Background technology
Master batch, alias masterbatch are a kind of plastic processing additives.During plastics forming, for operational side Just, required various auxiliary agents, filler and a small amount of vector resin are first subjected to mixed milling, measured by equipment such as extruders, Particulate material, referred to as master batch made from the process such as mixing, melting, extrusion, pelletizing.Master batch by vector resin, various fillers and Various auxiliary agent compositions.The limit of auxiliary agent or the content of filler several times higher than requirement in practical plastic products are extremely in master batch More than ten times.In molding process, it is necessary to the amount added in is needed according in the content and actual product in relation to component in master batch, The proportioning of master batch and matrix resin is adjusted, master batch can be generally divided into filler parent granule and functional master batch.
In recent years, people have found the harm of ultraviolet radiation more and more.The excessive exposure of ultraviolet light can lead to skin Skin cancer.Ultraviolet light can not only make the macromolecular chain in plastics, synthetic resin and rubber degrade, and lead to the aging of material, moreover it is possible to make The weatherability of paint is deteriorated, and leads to the easy dusting of paint, easy to crack or even come off, in addition, the flavescence of paper, becoming fragile Deng related with ultraviolet light.Therefore also increasingly cause the concern of people for the research of ultraviolet shielding material.
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, and pass through the members such as Al or Si Element, which carries out inorganic coating, can effectively solve the disadvantage that its bad dispersibility in polymer matrix, there is fabulous application prospect. However the compatibility of titanium dioxide and polymer is poor, when causing the titanium dioxide to prepare delustering fibre as additive, is adding Measure it is smaller in the case of, the extinction effect of delustering fibre is poor, at the same in fiber add titanium dioxide can also deposit delustering fibre It is being difficult to the shortcomings that thinner.In addition, when preparing ultraviolet shielded material using titanium dioxide, because absorbing wavelength is by the chemical combination The band gap of object determines, thus its to the shield effectiveness of ultraviolet light that long wave ultraviolet (UV-A) i.e. wavelength is 320~400nm compared with Difference, the protective capacities of centering long wave ultraviolet are also limited.
In addition, traditional ultraviolet absorber mostly by physical absorption, cohere, the means such as cross-linking agents or doping are fixed It, in use inevitably can be there are base material binding strength difference and the problems such as be easy to run off, with prolonging for usage time into base material Long, the uvioresistant ability of material can also be gradually decreased and finally be disappeared, in addition, the simple combination of organic uv absorbers and base material Poor compatibility between the two can not only be made, the performance of base material can also be had an impact.
High-voltage electrostatic spraying method is that polymer solution or melt are prepared into high score by a kind of utilization electrohydrodynamics technology The method of sub- particle.The method such as precipitation method, inverse suspension crosslinking method, the spray drying process of high molecular particle are prepared relative to other It prepares that micro-sphere material is simple for process, controllability is strong, environmentally protective and without using a large amount of emulsifiers Deng, electrostatic spraying processes, uses The particle that electrostatic spraying processes are easily made monodispersity particle and finally obtain can have different morphologies, such as hollow porous, example Such as have document (war is that universe method of electrostatic spinning prepares polystyrene functional material [D] Jilin University, 2010.) report, polyphenyl Vinyl solution can prepare Porous hollow microballoon by electrostatic spray molding, and polystyrene (PS) hollow microsphere obtained is in room temperature Lower chemical property is stablized, and has preferable machinability, but since the glass transition temperature of polystyrene (PS) only has 100 DEG C, three-dimensional structure can be destroyed under the high temperature conditions, thus can not be applied to melt-processed.This largely affects PS The application of hollow microsphere.
As can titanium dioxide and organic uv absorbers are added in master batch, master batch performance is improved, then master batch is added in In polyester forming process, the performance of moulding material is greatly promoted.
Therefore, the delustring that a kind of extinction effect is good, uvioresistant performance is good, melting temperature is high and thermal degradation temperature is high is studied to resist Ultraviolet high-performance PET master batch and preparation method thereof has a very important significance.
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, Delustring uvioresistant high-performance PET master batch that uvioresistant performance is good, melting temperature is high and thermal degradation temperature is high and preparation method thereof.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of delustring uvioresistant high-performance PET master batch, uniformly dispersing in delustring uvioresistant high-performance PET master batch has nucleocapsid knot Structure organic/inorganic composite hollow porous microsphere；
The nucleocapsid organic/inorganic composite hollow porous microsphere mainly by crosslinking ball, titania nanoparticles and Organic uv absorbers form；
The crosslinking ball inner hollow, porous surface and with cross-linked structure, 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；
The titania nanoparticles are coated in crosslinking ball, and by being covalently keyed between crosslinking ball；
The organic uv absorbers are entrained in cross-linked structure and/or are attached on crosslinking ball inner wall；
The filter pressure for the PET resin that the content of titanium dioxide is 5wt% after addition delustring uvioresistant high-performance PET master batch It is worth for 0.51~2.31bar/g.Under the same terms, the content for adding titanium dioxide after commercially available titanium dioxide is the delustring of 5wt% The filtration pressure force value of PET resin is 0.59~4.89bar/g.
The test establishing criteria BS EN 13900-5 of filter pressure:2005, it is examined using FCC-3 type strainabilities tester Master batch strainability is surveyed, a certain amount of delustring PET master batch and PET is taken to be sliced and be mixed to get 1000g mixtures, dioxy in mixture The mass fraction for changing titanium is 5%, and the calculation formula of master batch filtration pressure force value FPV is as follows：
FPV=(pmax-ps)/mc；
In formula, psFor initiation pressure value, unit bar, pmaxFor test pressure maximum value, unit bar is inorganic in master batch The content of particle, unit g.Experiment controls head pressure 6.5MPa, each area's temperature of screw rod is respectively using 1400 mesh filter screens： 180℃、290℃、290℃、290℃、290℃、290℃。
As preferred technical solution：
A kind of delustring uvioresistant high-performance PET master batch as described above, two in the delustring uvioresistant high-performance PET master batch The content of titanium oxide is 20~80wt%, and the content of organic uv absorbers is 22.3~39.4wt%；
The fiber prepared by delustring uvioresistant high-performance PET master batch reaches when totally disappeared light effect, titanium dioxide in fiber Content is 0.6~2.0wt%, add the content of titanium dioxide in the full-dull PET fiber of unmodified titanium dioxide for 2.5~ 3.0wt%；
By the film of 20~100 μ m-thicks prepared by delustring uvioresistant high-performance PET master batch to purple of the wavelength for 290~400nm The absorptivity of outside line is 99.0~99.9%, the absorption of ultraviolet light after 240h is radiated under wavelength is the ultraviolet light of 290~400nm The reduced rate of rate is less than 10%, and the content of titanium dioxide is 0.61~1.36wt% in film, and the content of organic uv absorbers is 0.61~1.5wt%.
A kind of delustring uvioresistant high-performance PET master batch as described above, the nucleocapsid organic/inorganic composite hollow are more The melting temperature of hole microballoon>500 DEG C, heat decomposition temperature>350 DEG C, the generally base material processing temperature compound with titanium dioxide is all small In 280 DEG C, thus during machining composite material, nucleocapsid organic/inorganic composite hollow porous microsphere of the invention can be kept Preferable three-dimensional structure is not damaged；Be conducive to give full play to the load factor of its effect organic uv absorbers for 3.6~ 11.2wt%；
A diameter of 500~1500nm of the crosslinking ball, the wall thickness of the crosslinking ball is 60~100nm；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；When crosslinking ball inner silica titanium nanometer During 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 10~20nm；When the quantity of crosslinking ball inner silica titanium nano particle>When 2, the distribution of the surface aperture of the crosslinking ball is close It spends for 1~20/1000nm2, the aperture of aperture is 10~40nm.
A kind of delustring uvioresistant high-performance PET master batch as described above, the nucleocapsid organic/inorganic composite hollow are more The preparation method of hole microballoon is：
Styrene, bifunctionality dimethylacrylate class organic monomer, photoinitiator and organic uv absorbers are molten Solution obtains EFI solution in a solvent, then the double bond containing modifying titanium dioxide in surface is added in EFI solution and is uniformly dispersed, Electrostatic spray is carried out under visible light conditions, nucleocapsid organic/inorganic composite hollow porous microsphere is made, finally washed with methanol It washs and dries；The effect for washing and drying nucleocapsid organic/inorganic composite hollow porous microsphere is removal electrostatic spray process The impurity of middle microsphere surface, such as extra polymerized monomer and photoinitiator etc..The double bond containing modified dioxy in surface in the present invention Change titanium since surface is with organo-functional group, can uniformly disperse in a solvent, be conducive to prepare uniform electrostatic spray system.
The bifunctionality dimethylacrylate class organic monomer for 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 is DMPOH and/or CQ；The organic uv absorbers for salicylic acid, benzophenone or Benzotriazole；The wavelength of the visible ray is 400~500nm；The solvent is DMF, chloroform, dichloromethane and tetrahydrochysene One or more of furans；30~the 50min of rotating speed mechanical agitation referred to 200~500rpm that is uniformly dispersed；
In the EFI solution, bifunctionality dimethylacrylate class organic monomer accounts for styrene and bifunctionality diformazan 5~28wt% 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；
Photoinitiator accounts for styrene and 0.6~1.8wt% of bifunctionality dimethylacrylate class organic monomer total amount； The too low efficiency of initiation of the concentration of photoinitiator is too low in EFI solution can not cause monomer polymerization；
Organic uv absorbers account for styrene and bifunctionality dimethylacrylate class organic monomer total amount 10~ 25wt%；Organic uv absorbers adding too much can influence the molding of microballoon, and microballoon is caused to crush, and reduce and incident light is dissipated Ability is penetrated, additive amount is too low, it is impossible to reach ideal ultraviolet shielded effect；
Solvent accounts for styrene and 56~83wt% of bifunctionality dimethylacrylate class organic monomer total amount；It is described to change Property titanium dioxide addition be EFI solution quality 18~42%；
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, 20~40 DEG C of temperature promotes 1~4mL/h of fltting speed, the 5~15mm of diameter of propeller of pump, propeller 3~10mL of volume.
A kind of delustring uvioresistant high-performance PET master batch as described above, the salicylic acid are sour or right for phenylo salicylic acid Tert-butyl salicylic acid vinegar, the benzophenone be ESCALOL 567 or 2,2 '-dihydroxy -4,4 '-diformazan Oxygroup benzophenone, the benzotriazole for 2- (2 '-hydroxyl -2 '-tert-butyl-phenyl) benzotriazole or 2- (2 '-hydroxyl - 2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole.
Organic uv absorbers absorption mechanism：
Salicylic acid：There are intramolecular hydrogen bond, wavelength models very low in the energy for starting to absorb, and absorbing for this kind of substance When enclosing extremely narrow and be less than 340nm, but being irradiated through ultraviolet light, intramolecular rearrangement occurs, it is stronger to be converted into ultraviolet absorption ability Benzophenone structural, so as to which absorption be made gradually to enhance, until absorption maximum；
Benzophenone：Carbonyl in molecule, into holy intramolecular hydrogen bond, forms a chelate ring, when molecule is by purple with hydroxyl Outside line absorbs energy, molecule thermal vibration aggravation when irradiating, intramolecular hydrogen bond destroys, and ultraviolet luminous energy is converted to by chelate ring open loop Discharged for thermal energy, in addition, in molecule carbonyl can also the energy of absorbed ultraviolet light excited, generate isomerism, generation alkene Alcohol of formula structure, so as to consume part energy；
Benzotriazole：Similar with benzophenone, cis-trans isomerization makes the energy of light change into thermal energy and releases；It can Other substances for meeting above-mentioned acceptance condition also can be as the organic uv absorbers of the present invention.
A kind of delustring uvioresistant high-performance PET master batch 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) 12~16h is dried in vacuo at 70~80 DEG C after evaporation drying is rotated at 50~70 DEG C, obtains surface containing double The modifying titanium dioxide of key.
A kind of method of delustring uvioresistant high-performance PET master batch as described above is prepared the present invention also provides a kind of, by PET Melting extrusion is granulated and is dried obtained disappear slice after mixing with nucleocapsid organic/inorganic composite hollow porous microsphere Light uvioresistant high-performance PET master batch.
As preferred technical solution：
Method as described above, when mixing, are additionally added dispersant and antioxidant, count in parts by weight, each component contains Amount is as follows：
Method as described above, the dispersant are one or more of polyethylene wax, calcium stearate and zinc stearate；It is described Antioxidant is 2,4- bis--(n-octylthiomethylene) -6- methylphenols or 2,4- bis- (dodecylthiomethyl) -6- methylbenzenes Phenol.
Method as described above, the mixing refer to mix 30~40min in super mixer；The temperature of the melting extrusion It is 220~250 DEG C to spend, and the pressure of the melting extrusion is 4~6MPa；The temperature of the drying process is 60~80 DEG C, described The time of drying process is 30~40min.
Invention mechanism：
The present invention is more by electrostatic spray-obtained nucleocapsid organic/inorganic composite hollow of light initiation polymerization crosslinking first Hole microballoon, then nucleocapsid organic/inorganic composite hollow porous microsphere and PET are sliced melting extrusion after mixing and are granulated To delustring uvioresistant high-performance PET master batch.
The prior art prepares hollow microsphere commonly used in fields such as medicament slow releases using electrostatic spray, generally by that will polymerize Electrostatic spray obtains microballoon in a solvent for object dissolving, after this method obtains microballoon, polymer can still keep its original thermal property and It is melted in melt-processed and its microballoon pattern cannot be kept, be not used to melt-processed.
The preparation process of the nucleocapsid organic/inorganic composite hollow porous microsphere of the present invention：First single functionality Styrene monomer, the bifunctionality dimethylacrylate class organic monomer of bifunctionality, photoinitiator and organic ultraviolet absorb EFI solution is made in agent dissolving in a solvent, then adds in the double bond containing modifying titanium dioxide in surface and is uniformly mixed, then in height Lower progress electrostatic spray of having a meeting, an audience, etc. well under one's control forms drop, is caused in drop using visible ray (according to initiation wavelength law of photoinitiator) The double bond of styrene monomer, bifunctionality dimethylacrylate class monomer and modifying titanium dioxide surface carries out radical polymerization It closes, forms the copolymer of styrene and bifunctionality dimethylacrylate class monomeric building blocks in titanium dioxide surface, together When due to the bifunctionality of dimethylacrylate class monomer, containing styrene and bifunctionality dimethylacrylate class monomer knot It can be cross-linked with each other to form three-dimensional-structure between the strand of the copolymer of structure unit, because of polymerization shrinkage and molten in forming process The volatilization of agent and the diffusion in coagulating bath and form nucleocapsid organic/inorganic composite hollow porous microsphere, while be molded Organic uv absorbers can be entrained in cross-linked structure or be attached on the inner and outer wall of hollow porous micro sphere in the process, The organic uv absorbers of attachment on the outer wall are removed in last handling process, finally obtained melting temperature and thermal degradation temperature High nucleocapsid organic/inorganic composite hollow porous microsphere, three-dimensional structure can be kept in subsequent melt process, is filled Its function is waved in distribution, has expanded the application range of hollow microsphere structure in actual use.
The porous structure of hollow microsphere can effectively scatter incident light, improve the utilization rate to incident light, light is micro- Scattering (and being scattered repeatedly to be multiple), increases the distance that light is contacted in organic uv absorbers, therefore organic in spherical structure The efficiency of ultraviolet absorber is obviously improved, and being added to ultraviolet shielded effect after matrix will also get a promotion, simultaneously as this hair Bright middle organic uv absorbers are in crosslinked micro-sphere structure, after being added in matrix, can keep its UV absorption for a long time Ability, and the influence to substrate performance is smaller.
In addition, titanium dioxide possesses the ultraviolet shielded effect of good extinction effect (scattering) and good middle long wave in itself (scattering+absorption), the strong anti-uv-ray of nano-titanium dioxide is since it is with high refractivity and high photolytic activity, anti-purple Outside line ability and its mechanism are related with its grain size：When grain size is larger, the barrier to ultraviolet light be based on reflecting, scatter, and It is effective to medium wave area and long-wavelength region ultraviolet light.Porous structure can effectively scatter incident light, improve the utilization to incident light Rate.By coated by titanium dioxide inside porous microsphere, light is incident on titanium dioxide surface across porous structure to be passed through the present invention After the scattering of titanium dioxide, it can be repeated as many times and scatter between titanium dioxide and microballoon inner wall, finally only a small amount of light can It is overflowed through microballoon, thus improves extinction effect and ultraviolet shielded effect.
Nucleocapsid organic/inorganic composite hollow porous microsphere and PET slice melting extrusion be granulated made from PET master batch after The extinction effect that has held nucleocapsid organic/inorganic composite hollow porous microsphere is good, uvioresistant performance is good, melting temperature and heat drop Solve the high characteristic of temperature.
Advantageous effect：
(1) a kind of delustring uvioresistant high-performance PET master batch of the invention, with uvioresistant performance is good, usage time is long, molten The advantages that melting temperature and high thermal degradation temperature, and it is small on the performance influence of base material in itself in subsequent applications, have a wide range of application；
(2) a kind of delustring uvioresistant high-performance PET master batch of the invention, extinction effect is good, compatible good, the centering long wave of dispersion Ultraviolet shielding effect is good, melting temperature and thermal degradation temperature are high, meets the requirement of general fiber process, has a wide range of application；
(3) preparation method of a kind of delustring uvioresistant high-performance PET master batch of the invention, simple process, preparation flow close Reason has fabulous promotional value.
Description of the drawings
Fig. 1 is the nucleocapsid schematic diagram of the nucleocapsid organic/inorganic composite hollow porous microsphere in the present invention.
Specific embodiment
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 preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) styrene, Bis-GMA, DMPOH and phenylo salicylic acid acid are dissolved in DMF and obtain EFI solution, wherein electricity It sprays in solution, Bis-GMA accounts for styrene and the 5wt% of Bis-GMA total amounts, and DMPOH accounts for styrene and Bis-GMA total amounts 1.0wt%, phenylo salicylic acid acid account for styrene and the 10wt% of Bis-GMA total amounts, and DMF accounts for styrene and Bis-GMA total amounts 80wt%；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 in liquid, wherein 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) 13h is dried in vacuo at 70 DEG C after rotating evaporation drying at 60 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 250rpm 30min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 460nm Nucleocapsid organic/inorganic composite hollow porous microsphere is made in mist, and the wherein addition of modifying titanium dioxide is EFI solution matter The 35% of amount, the parameter of electrostatic spray are：The output voltage 14kV of high voltage power supply, the distance 9cm of atomizing nozzle and solidification bathing pool, temperature 20 DEG C of degree promotes the fltting speed 1mL/h, the diameter 5mm of propeller, the volume 5mL of propeller of pump；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices with nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1) with 100:80 Melting extrusion is granulated and is dried obtained delustring uvioresistant high-performance PET master batch mass ratio after mixing, wherein mixing is Finger mixes 30min in super mixer；The temperature of melting extrusion is 220 DEG C, and the pressure of melting extrusion is 4MPa；It is dried Temperature for 60 DEG C, the time of drying process is 40min.
Structure diagram such as Fig. 1 institutes of nucleocapsid organic/inorganic composite hollow porous microsphere obtained by step (1) Show, be mainly made of crosslinking ball, titania nanoparticles and phenylo salicylic acid acid, be crosslinked ball inner hollow, porous surface and With cross-linked structure, cross-linked structure is by containing the shape that is cross-linked with each other between styrene and the copolymer molecule chain of Bis-GMA structural units Into titania nanoparticles are coated in crosslinking ball, and by being covalently keyed between crosslinking ball, phenylo salicylic acid acid is mixed It is miscellaneous in cross-linked structure.It is crosslinked a diameter of 800nm, wall thickness 100nm of ball；A diameter of 300nm of titania nanoparticles； The quantity of ball inner silica titanium nano particle is crosslinked as 1, be crosslinked ball surface aperture distribution density for 1/ 1000nm2, the aperture of aperture is 20nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 510 DEG C, Heat decomposition temperature is 380 DEG C, and the load factor of phenylo salicylic acid acid is 3.6wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；In delustring uvioresistant high-performance PET master batch the content of titanium dioxide be 20wt%, the content of phenylo salicylic acid acid For 23.6wt%；The fiber prepared by delustring uvioresistant high-performance PET master batch reaches when totally disappeared light effect, titanium dioxide in fiber Content be 1.3wt%；The PET resin that the content of titanium dioxide is 5wt% after addition delustring uvioresistant high-performance PET master batch Filtration pressure force value is 0.51bar/g；The film of 20 μ m-thicks prepared by delustring uvioresistant high-performance PET master batch is 290nm's to wavelength The absorptivity of ultraviolet light is 99.0%, the reduction of the absorptivity of ultraviolet light after 240h is radiated under wavelength is the ultraviolet light of 400nm Rate is 9.9%, and the content of titanium dioxide is 0.62wt% in film, and the content of phenylo salicylic acid acid is 0.61wt%.
Embodiment 2
A kind of preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) it by styrene, EBPADMA, CQ and tert-butyl salicylic acid vinegar is dissolved in chloroform obtains EFI solution, EBPADMA accounts for styrene and the 15wt% of EBPADMA total amounts in EFI solution, and chloroform accounts for styrene and EBPADMA total amounts 56wt%, CQ accounts for the 0.6wt% of styrene EBPADMA total amounts, styrene EBPADMA total amounts accounted for tert-butyl salicylic acid vinegar 15wt%；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 5 in liquid, wherein 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 silane is be aged titanium dioxide quality in liquid 6%；
D) 14h is dried in vacuo at 80 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 300rpm 35min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic 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 in mist, and the wherein addition of modifying titanium dioxide is EFI solution matter The 18% of amount, the parameter of electrostatic spray are：The output voltage 11kV of high voltage power supply, the distance 12cm of atomizing nozzle and solidification bathing pool, 30 DEG C of temperature promotes the fltting speed 3mL/h of pump, the diameter 13mm of propeller, the volume 4mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices with nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1) with 100:150 Mass ratio melting extrusion is granulated and is dried obtained delustring uvioresistant high-performance PET master batch after mixing, wherein mixing Refer to mix 40min in super mixer；The temperature of melting extrusion is 250 DEG C, and the pressure of melting extrusion is 6MPa；At dry The temperature of reason is 80 DEG C, and the time of drying process is 30min.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide as made from step (1) Nano particle and tert-butyl salicylic acid vinegar is formed, be crosslinked ball inner hollow, porous surface and with cross-linked structure, cross-linked structure By being formed containing being cross-linked with each other between styrene and the copolymer molecule chain of EBPADMA structural units, titania nanoparticles packet It overlays in crosslinking ball, and by being covalently keyed between crosslinking ball, receiving agent to tert-butyl salicylic acid vinegar is entrained in cross-linked structure Neutralization is attached on crosslinking ball inner wall.It is crosslinked a diameter of 1500nm, wall thickness 80nm of ball；The diameter of titania nanoparticles For 350nm；The quantity of ball inner silica titanium nano particle is crosslinked as 2, be crosslinked ball surface aperture distribution density for 30/ 1000nm2, the aperture of aperture is 10nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 520 DEG C, Heat decomposition temperature is 400 DEG C, and the load factor to tert-butyl salicylic acid vinegar is 4.9wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；The content of titanium dioxide is 80wt% in delustring uvioresistant high-performance PET master batch, to tert-butyl salicylic acid vinegar Content is 38.5wt%；The fiber prepared by delustring uvioresistant high-performance PET master batch reaches when totally disappeared light effect, dioxy in fiber The content for changing titanium is 0.6wt%；The PET trees that the content of titanium dioxide is 5wt% after addition delustring uvioresistant high-performance PET master batch The filtration pressure force value of fat is 0.57bar/g；The film of 60 μ m-thicks prepared by delustring uvioresistant high-performance PET master batch is to wavelength The absorptivity of the ultraviolet light of 345nm is 99.5%, the absorptivity of ultraviolet light after 240h is radiated under wavelength is the ultraviolet light of 345nm Reduced rate for 9%, the content of titanium dioxide is 1.2wt% in film, and the content to tert-butyl salicylic acid vinegar is 1.5wt%.
Embodiment 3
A kind of preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by styrene, the mixture (mass ratio 1 of UDMA, DMPOH and CQ:And 2- hydroxyl -4- methoxyl group hexichol 1) Ketone dissolving obtains EFI solution in methylene chloride, and UDMA accounts for styrene and the 5wt% of UDMA total amounts, dichloro in EFI solution Methane accounts for styrene and the mixture of 70wt%, DMPOH and the CQ of UDMA total amounts account for styrene and the 1.8wt% of UDMA total amounts, ESCALOL 567 accounts for styrene and the 20wt% of UDMA total amounts；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 in liquid, wherein 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 silane is be aged titanium dioxide quality in liquid 7%；
D) 12h is dried in vacuo at 75 DEG C after rotating evaporation drying at 70 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 400rpm 40min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic 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 in mist, wherein the addition of the modifying titanium dioxide is molten for EFI The 25% of liquid quality, the parameter of electrostatic spray are：The output voltage 12kV of high voltage power supply, the distance of atomizing nozzle and solidification bathing pool 11cm, 35 DEG C of temperature promote the fltting speed 2mL/h, the diameter 11mm of propeller, the volume 5mL of propeller of pump；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices with nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1) with 100:115 Mass ratio melting extrusion is granulated and is dried obtained delustring uvioresistant high-performance PET master batch after mixing, wherein mixing Refer to mix 35min in super mixer；The temperature of melting extrusion is 235 DEG C, and the pressure of melting extrusion is 5MPa；At dry The temperature of reason is 70 DEG C, and the time of drying process is 35min.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide as made from step (1) Nano particle and ESCALOL 567 composition, are crosslinked ball inner hollow, porous surface and with cross-linked structure, Cross-linked structure by being formed containing being cross-linked with each other between styrene and the copolymer molecule chain of UDMA monomeric building blocks, receive by titanium dioxide Rice grain is coated in crosslinking ball, and by being covalently keyed between crosslinking ball, ESCALOL 567 attachment On crosslinking ball inner wall.It is crosslinked a diameter of 900nm, wall thickness 60nm of ball；A diameter of 340nm of titania nanoparticles； Be crosslinked ball inner silica titanium nano particle quantity be 3 when, be crosslinked ball surface aperture distribution density for 20/ 1000nm2, the aperture of aperture is 10nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 580 DEG C, Heat decomposition temperature is 370 DEG C, and the load factor of ESCALOL 567 is 10.5wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；In delustring uvioresistant high-performance PET master batch the content of titanium dioxide be 50wt%, 2- hydroxyl -4- methoxyl groups two The content of Benzophenone is 31.6wt%；The fiber prepared by delustring uvioresistant high-performance PET master batch reaches when totally disappeared light effect, fine The content of titanium dioxide is 2.0wt% in dimension；The content of titanium dioxide is after addition delustring uvioresistant high-performance PET master batch The filtration pressure force value of the PET resin of 5wt% is 0.67bar/g；The film of 60 μ m-thicks prepared by delustring uvioresistant high-performance PET master batch The absorptivity for the ultraviolet light for being 400nm to wavelength is 99.9%, the ultraviolet light after radiation 240h in the case where wavelength is the ultraviolet light of 400nm Absorptivity reduced rate for 9.5%, the content of titanium dioxide is 0.94wt% in film, ESCALOL 567 Content be 0.72wt%.
Embodiment 4
A kind of preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) styrene, TEGDMA, CQ and 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone are dissolved in tetrahydrochysene furan EFI solution is obtained in muttering, TEGDMA accounts for styrene and the 20wt% of TEGDMA total amounts in EFI solution, and tetrahydrofuran accounts for benzene second The 56wt% of alkene and TEGDMA total amounts, CQ account for styrene and the 0.8wt% of TEGDMA total amounts, and 2,2 '-dihydroxy -4,4 '-diformazan Oxygroup benzophenone accounts for styrene and the 25wt% of TEGDMA total amounts；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 in liquid, wherein 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) 15h is dried in vacuo at 70 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 500rpm 45min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic 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 in mist, wherein the addition of the modifying titanium dioxide is molten for EFI The 30% of liquid quality, the parameter of electrostatic spray are：The output voltage 13kV of high voltage power supply, the distance of atomizing nozzle and solidification bathing pool 10cm, 40 DEG C of temperature promote the fltting speed 1mL/h, the diameter 10mm of propeller, the volume 6mL of propeller of pump；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices with nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1) with 100:90 Melting extrusion is granulated and is dried obtained delustring uvioresistant high-performance PET master batch mass ratio after mixing, wherein mixing is Finger mixes 36min in super mixer；The temperature of melting extrusion is 240 DEG C, and the pressure of melting extrusion is 4.5MPa；At dry The temperature of reason is 65 DEG C, and the time of drying process is 36min.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide as made from step (1) Nano particle and 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone composition are crosslinked ball inner hollow, porous surface and have Cross-linked structure, cross-linked structure containing being cross-linked with each other between styrene and the copolymer molecule chain of TEGDMA structural units by forming, and two Titanium dioxide nanoparticle is coated in crosslinking ball, and by being covalently keyed between crosslinking ball, and 2,2 '-dihydroxy -4,4 '-two Methoxy benzophenone is entrained in cross-linked structure.It is crosslinked a diameter of 700nm, wall thickness 100nm of ball；Nano titania A diameter of 300nm of grain；The quantity for being crosslinked ball inner silica titanium nano particle is 4, and the distribution for being crosslinked the surface aperture of ball is close It spends for 10/1000nm2, the aperture of aperture is 40nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere It is 550 DEG C, heat decomposition temperature is 390 DEG C, 2,2 '-dihydroxy -4, the load factor of 4 '-dimethoxy-benzophenone is 8.9wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；In delustring uvioresistant high-performance PET master batch the content of titanium dioxide be 40wt%, 2,2 '-dihydroxy -4,4 ' - The content of dimethoxy-benzophenone is 31.3wt%；The fiber prepared by delustring uvioresistant high-performance PET master batch, which reaches, totally disappeared During light effect, the content of titanium dioxide is 1.0wt% in fiber；Titanium dioxide after addition delustring uvioresistant high-performance PET master batch Content be 5wt% the filtration pressure force value of PET resin be 0.64bar/g；The 40 of delustring uvioresistant high-performance PET master batch preparation The absorptivity for the ultraviolet light that the film of μ m-thick is 320nm to wavelength is 99.4%, and 240h is radiated in the case where wavelength is the ultraviolet light of 320nm The reduced rate of the absorptivity of ultraviolet light is 8.9% afterwards, and the content of titanium dioxide is 0.71wt% in film, 2,2 '-dihydroxy -4, The content of 4 '-dimethoxy-benzophenone is 0.61wt%.
Embodiment 5
A kind of preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
And mixture (the mass ratio 1 of chloroform:2) EFI solution is obtained in, D in EFI solution3MA accounts for styrene And D3The mixture of the 25wt% of MA total amounts, DMF and chloroform accounts for styrene and D3The 75wt% of MA total amounts, DMPOH account for benzene second Alkene and D3The 1.8wt% of MA total amounts, 2- (2 '-hydroxyl -2 '-tert-butyl-phenyl) benzotriazole accounts for styrene and D3MA total amounts 18wt%；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 5 in liquid, wherein 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) 12h is dried in vacuo at 80 DEG C after rotating evaporation drying at 65 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 250rpm 50min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic 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 in mist, and the wherein addition of modifying titanium dioxide is EFI solution matter The 35% of amount, the parameter of electrostatic spray are：The output voltage 14kV of high voltage power supply, the distance 7cm of atomizing nozzle and solidification bathing pool, temperature 25 DEG C of degree promotes the fltting speed 2mL/h, the diameter 8mm of propeller, the volume 3mL of propeller of pump；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices and nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1), dispersant and Antioxidant is with 100:100:2:Melting extrusion is granulated and is dried obtained delustring uvioresistant height 1 mass ratio after mixing Performance PET master batch, wherein mixing refers to mix 40min in super mixer；The temperature of melting extrusion is 220 DEG C, and melting is squeezed The pressure gone out is 5.5MPa；The temperature of drying process is 75 DEG C, and the time of drying process is 32min, and dispersant is polyethylene wax, Antioxidant is 2,4- bis--(n-octylthiomethylene) -6- methylphenols.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide as made from step (1) Nano particle and 2- (2 '-hydroxyl -2 '-tert-butyl-phenyl) benzotriazole composition, are crosslinked ball inner hollow, porous surface and have Cross-linked structure, cross-linked structure is by containing styrene and D3It is cross-linked with each other to be formed between the copolymer molecule chain of MA structural units, dioxy Change titanium nano particle to be coated in crosslinking ball, and by being covalently keyed between crosslinking ball, 2- (2 '-hydroxyls -2 '-tertiary butyl Phenyl) benzotriazole be entrained in cross-linked structure neutralization be attached to crosslinking ball inner wall on.A diameter of 1200nm of ball is crosslinked, wall thickness is 60nm；A diameter of 400nm of titania nanoparticles；The quantity for being crosslinked ball inner silica titanium nano particle is 2, is crosslinked ball Surface aperture distribution density be 40/1000nm2, the aperture of aperture is 17nm.Nucleocapsid organic/inorganic composite hollow The melting temperature of porous microsphere is 540 DEG C, and heat decomposition temperature is 400 DEG C, 2- (2 '-hydroxyl -2 '-tert-butyl-phenyl) benzotriazole Load factor be 11.2wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；In delustring uvioresistant high-performance PET master batch the content of titanium dioxide be 25wt%, 2- (2 '-hydroxyls -2 '-tertiary fourth Base phenyl) benzotriazole content be 22.3wt%；The fiber prepared by delustring uvioresistant high-performance PET master batch reaches full-dull During effect, the content of titanium dioxide is 0.8wt% in fiber；Titanium dioxide after addition delustring uvioresistant high-performance PET master batch The filtration pressure force value for the PET resin that content is 5wt% is 0.69bar/g；100 μ prepared by delustring uvioresistant high-performance PET master batch The absorptivity of ultraviolet light that the film of m thickness is 400nm to wavelength is 99.9%, and 240h is radiated in the case where wavelength is the ultraviolet light of 290nm The reduced rate of the absorptivity of ultraviolet light is 9.2% afterwards, and the content of titanium dioxide is 0.61wt% in film, 2- (2 '-hydroxyls -2 '-uncle Butyl phenyl) benzotriazole content be 0.74wt%.
Embodiment 6
A kind of preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by the mixture (mass ratio 2 of Bis-GMA and EBPADMA:1), (mass ratio is the mixture of DMPOH and CQ 1:1), styrene and 2- (2 '-hydroxyl -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole are dissolved in dichloromethane With the mixture (mass ratio 1 of tetrahydrofuran:2) EFI solution is obtained in, Bis-GMA's and EBPADMA is mixed in EFI solution Close the mixture of the 28wt% that object accounts for the amount of the mixture of styrene and Bis-GMA and EBPADMA, dichloromethane and tetrahydrofuran Account for 83wt%, DMPOH and the CQ of the amount of the mixture of styrene and Bis-GMA and EBPADMA mixture account for styrene and The 1.3wt% of the amount of the mixture of Bis-GMA and EBPADMA, 2- (2 '-hydroxyl -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- Chlorine) benzotriazole account for styrene and Bis-GMA and EBPADMA amount of the mixture 13wt%；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 in liquid, wherein 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 silane is be aged titanium dioxide quality in liquid 10%；
D) 16h is dried in vacuo at 75 DEG C after rotating evaporation drying at 55 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 350rpm 30min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic 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 in mist, wherein the addition of the modifying titanium dioxide is molten for EFI The 42% of liquid quality, the parameter of electrostatic spray are：The output voltage 15kV of high voltage power supply, the distance of atomizing nozzle and solidification bathing pool 8cm, 30 DEG C of temperature promote the fltting speed 3mL/h, the diameter 7mm of propeller, the volume 7mL of propeller of pump；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices and nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1), dispersant and Antioxidant is with 100:150:6:Melting extrusion is granulated and is dried obtained delustring uvioresistant height 3 mass ratio after mixing Performance PET master batch, wherein mixing refers to mix 35min in super mixer；The temperature of melting extrusion is 240 DEG C, and melting is squeezed The pressure gone out is 4.8MPa；The temperature of drying process is 72 DEG C, and the time of drying process is 38min, and dispersant is calcium stearate, Antioxidant is 2,4- bis- (dodecylthiomethyl) -6- methylphenols.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide as made from the above method Titanium nano particle and 2- (2 '-hydroxyl -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole composition, are crosslinked in ball inside Sky, porous surface and with cross-linked structure, cross-linked structure is by the mixture structure list containing styrene and Bis-GMA and EBPADMA Member copolymer molecule chain between be cross-linked with each other to be formed, titania nanoparticles be coated on crosslinking ball in, and with crosslinking ball it Between by being covalently keyed 2- (2 '-hydroxyl -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole be attached to crosslinking ball On inner wall.It is crosslinked a diameter of 500nm, wall thickness 70nm of ball；A diameter of 370nm of titania nanoparticles；It is crosslinked in ball When the quantity of portion's titania nanoparticles is 2, the distribution density for being crosslinked the surface aperture of ball is 60/1000nm2, aperture Aperture is 18nm；The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 600 DEG C, heat decomposition temperature 385 DEG C, the load factor of 2- (2 '-hydroxyl -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole is 3.6wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；In delustring uvioresistant high-performance PET master batch the content of titanium dioxide be 80wt%, 2- (2 '-hydroxyls -2 '-tertiary fourth Base benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole content be 30.6wt%；It is prepared by delustring uvioresistant high-performance PET master batch Fiber reach when totally disappeared light effect, the content of titanium dioxide is 1.5wt% in fiber；Add delustring uvioresistant high performance PE T The filtration pressure force value for the PET resin that the content of titanium dioxide is 5wt% after master batch is 0.69bar/g；Delustring uvioresistant high-performance The absorptivity of ultraviolet light that the film of 70 μ m-thicks prepared by PET master batch is 300nm to wavelength is 99.8%, is 300nm's in wavelength The reduced rate of the absorptivity of ultraviolet light is 9% after radiation 240h under ultraviolet light, and the content of titanium dioxide is 0.68wt%, 2- in film The content of (2 '-hydroxyl -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole is 0.63wt%.
Embodiment 7
A kind of preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by UDMA and D3Mixture (the mass ratio 1 of MA:2), styrene, DMPOH and the dissolving of phenylo salicylic acid acid In the mixture (mass ratio 1 of DMF, chloroform and dichloromethane:1:2) EFI solution is obtained in, UDMA in EFI solution With D3The mixture of MA accounts for styrene and UDMA and D3The 5wt% of the amount of the mixture of MA, DMF, chloroform and dichloromethane Mixture accounts for styrene and UDMA and D3The 75wt% of the amount of the mixture of MA, DMPOH account for styrene and UDMA and D3The mixing of MA The 1.1wt% of object total amount, phenylo salicylic acid acid account for styrene and UDMA and D3The 10wt% of the amount of the mixture of MA；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 in liquid, wherein 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 silane is be aged titanium dioxide quality in liquid 9%；
D) 16h is dried in vacuo at 80 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 450rpm 50min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic 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 in mist, wherein the addition of the modifying titanium dioxide is molten for EFI The 18% of liquid quality, the parameter of electrostatic spray are：The output voltage 10kV of high voltage power supply, the distance of atomizing nozzle and solidification bathing pool 7cm, 25 DEG C of temperature promote the fltting speed 1mL/h, the diameter 6mm of propeller, the volume 8mL of propeller of pump；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices and nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1), dispersant and Antioxidant is with 100:140:4:Melting extrusion is granulated and is dried obtained delustring uvioresistant height 2 mass ratio after mixing Performance PET master batch, wherein mixing refers to mix 36min in super mixer；The temperature of melting extrusion is 235 DEG C, and melting is squeezed The pressure gone out is 5.5MPa；The temperature of drying process is 70 DEG C, and the time of drying process is 36min, and dispersant is zinc stearate, Antioxidant is 2,4- bis--(n-octylthiomethylene) -6- methylphenols.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide as made from step (1) Nano particle and phenylo salicylic acid acid composition, are crosslinked ball inner hollow, porous surface and with cross-linked structure, and cross-linked structure is by containing Styrene and UDMA and D3It is cross-linked with each other to be formed between the copolymer molecule chain of the mixture structural unit of MA, nano titania For particles coat in crosslinking ball, and by being covalently keyed between crosslinking ball, phenylo salicylic acid acid is attached to crosslinking ball inner wall On.It is crosslinked a diameter of 1400nm, wall thickness 90nm of ball；A diameter of 300nm of titania nanoparticles；It is crosslinked two inside ball When the quantity of Titanium dioxide nanoparticle is 1, the distribution density for being crosslinked the surface aperture of ball is 50/1000nm2, the aperture of aperture For 20nm；The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 590 DEG C, and heat decomposition temperature is 390 DEG C, The load factor of phenylo salicylic acid acid is 11.2wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；In delustring uvioresistant high-performance PET master batch the content of titanium dioxide be 60wt%, the content of phenylo salicylic acid acid For 33.4wt%；The fiber prepared by delustring uvioresistant high-performance PET master batch reaches when totally disappeared light effect, titanium dioxide in fiber Content be 1.8wt%；The PET resin that the content of titanium dioxide is 5wt% after addition delustring uvioresistant high-performance PET master batch Filtration pressure force value is 1.28bar/g；The film of 80 μ m-thicks prepared by delustring uvioresistant high-performance PET master batch is 400nm's to wavelength The absorptivity of ultraviolet light is 99.2%, the reduction of the absorptivity of ultraviolet light after 240h is radiated under wavelength is the ultraviolet light of 400nm Rate is 9.8%, and the content of titanium dioxide is 0.95wt% in film, and the content of phenylo salicylic acid acid is 0.74wt%.
Embodiment 8
A kind of preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by the mixture (mass ratio 1 of Bis-GMA, EBPADMA and UDMA:1:1), styrene, CQ and to tertiary fourth Base bigcatkin willow vinegar, which is dissolved in DMF, obtains EFI solution, and the mixture of Bis-GMA, EBPADMA and UDMA account for benzene in EFI solution The 10wt% of ethylene and the amount of the mixture of Bis-GMA, EBPADMA and UDMA, DMF account for styrene and Bis-GMA, EBPADMA With the 80wt% of the amount of the mixture of UDMA, styrene and Bis-GMA, EBPADMA and UDMA are accounted for tert-butyl salicylic acid vinegar The 12wt% of amount of the mixture, CQ account for the 1.2wt% of styrene and the amount of the mixture of Bis-GMA, EBPADMA and UDMA；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 in liquid, wherein 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 silane is be aged titanium dioxide quality in liquid 7%；
D) 14h is dried in vacuo at 70 DEG C after rotating evaporation drying at 70 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 500rpm 45min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic 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 in mist, wherein the addition of the modifying titanium dioxide is molten for EFI The 27% of liquid quality, the parameter of electrostatic spray are：The output voltage 12kV of high voltage power supply, the distance of atomizing nozzle and solidification bathing pool 13cm, 35 DEG C of temperature promote the fltting speed 2mL/h, the diameter 15mm of propeller, the volume 9mL of propeller of pump；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices and nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1), dispersant and Antioxidant is with 100:80~150:2:Melting extrusion is granulated and is dried the anti-purple of obtained delustring 3 mass ratio after mixing Outer high-performance PET master batch, wherein mixing refers to mix 30min in super mixer；The temperature of melting extrusion is 220 DEG C, is melted The pressure for melting extrusion is 4MPa；The temperature of drying process is 80 DEG C, and the time of drying process is 40min, and dispersant is polyethylene The mixture of wax and calcium stearate (mass ratio 1:1), antioxidant 2,4- bis--(n-octylthiomethylene) -6- methylbenzenes Phenol.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide as made from step (1) Nano particle and tert-butyl salicylic acid vinegar is formed, be crosslinked ball inner hollow, porous surface and with cross-linked structure, cross-linked structure By the shape that is cross-linked with each other between the copolymer molecule chain containing styrene and the mixture structural unit of Bis-GMA, EBPADMA and UDMA Into titania nanoparticles are coated in crosslinking ball, and by being covalently keyed between crosslinking ball, to tert-butyl salicylic acid Vinegar is entrained in cross-linked structure neutralization and is attached on crosslinking ball inner wall.It is crosslinked a diameter of 500nm, wall thickness 100nm of ball；Titanium dioxide A diameter of 400nm of titanium nano particle；The quantity for being crosslinked ball inner silica titanium nano particle is 3, is crosslinked the surface aperture of ball Distribution density be 15/1000nm2, the aperture of aperture is 30nm.Nucleocapsid organic/inorganic composite hollow porous microsphere Melting temperature is 620 DEG C, and heat decomposition temperature is 420 DEG C, and the load factor to tert-butyl salicylic acid vinegar is 5.8wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；The content of titanium dioxide is 40wt% in delustring uvioresistant high-performance PET master batch, to tert-butyl salicylic acid vinegar Content is 39.4wt%；The fiber prepared by delustring uvioresistant high-performance PET master batch reaches when totally disappeared light effect, dioxy in fiber The content for changing titanium is 1.6wt%；The PET trees that the content of titanium dioxide is 5wt% after addition delustring uvioresistant high-performance PET master batch The filtration pressure force value of fat is 1.92bar/g；The film of 70 μ m-thicks prepared by delustring uvioresistant high-performance PET master batch is to wavelength The absorptivity of the ultraviolet light of 350nm is 99.6%, the absorptivity of ultraviolet light after 240h is radiated under wavelength is the ultraviolet light of 350nm Reduced rate for 9.6%, the content of titanium dioxide is 1.36wt% in film, and the content to tert-butyl salicylic acid vinegar is 1.27wt%.
Embodiment 9
A kind of preparation method of delustring uvioresistant high-performance PET master batch：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by UDMA, TEGDMA and D3Mixture (the mass ratio 1 of MA:2:2), the mixture (mass ratio of DMPOH and CQ It is 2:1), styrene and phenylo salicylic acid acid, which are dissolved in chloroform, obtains EFI solution, UDMA in EFI solution, TEGDMA and D3The mixture of MA accounts for styrene and UDMA, TEGDMA and D3The 28wt% of the amount of the mixture of MA, chloroform account for Styrene and UDMA, TEGDMA and D3The mixture of 56wt%, DMPOH and the CQ of the amount of the mixture of MA account for styrene and UDMA, TEGDMA and D3The 0.6wt% of the amount of the mixture of MA, phenylo salicylic acid acid account for styrene and UDMA, TEGDMA and D3MA Amount of the mixture 25wt%；
2) 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 The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 in liquid, wherein 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) 15h is dried in vacuo at 80 DEG C after rotating evaporation drying at 60 DEG C, obtains the double bond containing modified dioxy in surface Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation of 200rpm 30min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic 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 in mist, wherein the addition of the modifying titanium dioxide is molten for EFI The 39% of liquid quality, the parameter of electrostatic spray are：The output voltage 14kV of high voltage power supply, the distance of atomizing nozzle and solidification bathing pool 10cm, 40 DEG C of temperature promote the fltting speed 4mL/h, the diameter 15mm of propeller, the volume 10mL of propeller of pump；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) master batch is prepared：
By PET slices and nucleocapsid organic/inorganic composite hollow porous microsphere obtained in step (1), dispersant and Antioxidant is with 100:140:6:Melting extrusion is granulated and is dried obtained delustring uvioresistant height 1 mass ratio after mixing Performance PET master batch, wherein mixing refers to mix 38min in super mixer；The temperature of melting extrusion is 238 DEG C, and melting is squeezed The pressure gone out is 4.8MPa；The temperature of drying process is 68 DEG C, and the time of drying process is 38min, and dispersant is calcium stearate With the mixture (mass ratio 1 of zinc stearate:2), antioxidant 2,4- bis--(n-octylthiomethylene) -6- methylphenols.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide as made from step (1) Nano particle and phenylo salicylic acid acid composition, are crosslinked ball inner hollow, porous surface and with cross-linked structure, and cross-linked structure is by containing Styrene and UDMA, TEGDMA and D3It is cross-linked with each other to be formed between the copolymer molecule chain of the mixture structural unit of MA, dioxy Change titanium nano particle to be coated in crosslinking ball, and by being covalently keyed between crosslinking ball, phenylo salicylic acid acid doping is being handed over It is coupled in structure.It is crosslinked a diameter of 1500nm, wall thickness 70nm of ball；A diameter of 310nm of titania nanoparticles；It is crosslinked ball The quantity of inner silica titanium nano particle is 4, and the distribution density for being crosslinked the surface aperture of ball is 1/1000nm2, aperture Aperture is 10nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 520 DEG C, heat decomposition temperature 440 DEG C, the load factor of phenylo salicylic acid acid is 11.4wt%.
Uniformly dispersed in final obtained delustring uvioresistant high-performance PET master batch have nucleocapsid organic/inorganic it is compound in Empty porous microsphere；In delustring uvioresistant high-performance PET master batch the content of titanium dioxide be 38wt%, the content of phenylo salicylic acid acid For 25.7wt%；The fiber prepared by delustring uvioresistant high-performance PET master batch reaches when totally disappeared light effect, titanium dioxide in fiber Content be 0.8wt%；The PET resin that the content of titanium dioxide is 5wt% after addition delustring uvioresistant high-performance PET master batch Filtration pressure force value is 2.31bar/g；The film of 38 μ m-thicks prepared by delustring uvioresistant high-performance PET master batch is 338nm's to wavelength The absorptivity of ultraviolet light is 99.8%, the reduction of the absorptivity of ultraviolet light after 240h is radiated under wavelength is the ultraviolet light of 338nm Rate is 8.8%, and the content of titanium dioxide is 1.31wt% in film, and the content of phenylo salicylic acid acid is 0.95wt%.

Claims (10)

1. a kind of delustring uvioresistant high-performance PET master batch, it is characterized in that：It is uniformly dispersed in delustring uvioresistant high-performance PET master batch There is nucleocapsid organic/inorganic composite hollow porous microsphere；
The nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titania nanoparticles and organic Ultraviolet absorber forms；
The crosslinking ball inner hollow, porous surface and with 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；
The titania nanoparticles are coated in crosslinking ball, and by being covalently keyed between crosslinking ball；
The organic uv absorbers are entrained in cross-linked structure and/or are attached on crosslinking ball inner wall；
Addition delustring uvioresistant high-performance PET master batch after titanium dioxide content be 5wt% the filtration pressure force value of PET resin be 0.51~2.31bar/g.
A kind of 2. delustring uvioresistant high-performance PET master batch according to claim 1, which is characterized in that the anti-purple of delustring The content of titanium dioxide is 20~80wt% in outer high-performance PET master batch, the contents of organic uv absorbers for 22.3~ 39.4wt%；
The fiber prepared by delustring uvioresistant high-performance PET master batch reaches when totally disappeared light effect, the content of titanium dioxide in fiber For 0.6~2.0wt%；
By the film of 20~100 μ m-thicks prepared by delustring uvioresistant high-performance PET master batch to ultraviolet light of the wavelength for 290~400nm Absorptivity for 99.0~99.9%, in the case where wavelength is the ultraviolet light of 290~400nm after radiation 240h ultraviolet light absorptivity Reduced rate is less than 10%, and the content of titanium dioxide is 0.61~1.36wt% in film, and the content of organic uv absorbers is 0.61 ~1.5wt%.
A kind of 3. delustring uvioresistant high-performance PET master batch according to claim 1, which is characterized in that the nucleocapsid The melting temperature of organic/inorganic composite hollow porous microsphere>500 DEG C, heat decomposition temperature>350 DEG C, organic uv absorbers are born Load rate is 3.6~11.2wt%；
A diameter of 500~1500nm of the crosslinking ball, the wall thickness of the crosslinking ball is 60~100nm；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；When crosslinking ball inner silica titanium nano particle Quantity≤2 when, the distribution density of the surface aperture of the crosslinking ball is 1~60/1000nm2, the aperture of aperture for 10~ 20nm；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 10~40nm.
4. according to a kind of delustring uvioresistant high-performance PET master batch of claims 1 to 3 any one of them, which is characterized in that described The preparation method of nucleocapsid organic/inorganic composite hollow porous microsphere is：
Styrene, bifunctionality dimethylacrylate class organic monomer, photoinitiator and organic uv absorbers are dissolved in EFI solution is obtained in solvent, then the double bond containing modifying titanium dioxide in surface is added in EFI solution and is uniformly dispersed, can Nucleocapsid organic/inorganic composite hollow porous microsphere is made in progress electrostatic spray under the conditions of seeing light, is finally washed simultaneously with methanol It is dry；
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 organic uv absorbers are salicylic acid, benzophenone Or benzotriazole；The wavelength of the visible ray is 400~500nm；The solvent is DMF, chloroform, dichloromethane and four One or more of hydrogen furans；30~the 50min of rotating speed mechanical agitation referred to 200~500rpm that is uniformly dispersed；
In the EFI solution, bifunctionality dimethylacrylate class organic monomer accounts for styrene and bifunctionality dimethyl propylene 5~28wt% of olefin(e) acid esters organic monomer total amount；Photoinitiator, which accounts for styrene and bifunctionality dimethylacrylate class, to be had 0.6~1.8wt% of machine monomer total amount；Organic uv absorbers account for styrene and bifunctionality dimethylacrylate class is organic 10~25wt% of monomer total amount；Solvent account for styrene and bifunctionality dimethylacrylate class organic monomer total amount 56~ 83wt%；The addition of the modifying titanium dioxide is the 18~42% of EFI solution quality；
The parameter of the electrostatic spray is：The distance 7 of 10~15kV of output voltage of high voltage power supply, atomizing nozzle and solidification bathing pool~ 13cm, 20~40 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.
A kind of 5. delustring uvioresistant high-performance PET master batch according to claim 4, which is characterized in that the salicylic acid For phenylo salicylic acid acid or to tert-butyl salicylic acid vinegar, the benzophenone is ESCALOL 567 or 2, 2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, the benzotriazole are 2- (2 '-hydroxyl -2 '-tert-butyl-phenyl) benzo Triazole or 2- (2 '-hydroxyl -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole.
A kind of 6. delustring uvioresistant high-performance PET master batch according to claim 4, which is characterized in that the modified dioxy The preparation process for changing titanium is 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 20~30% for 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) 12~16h is dried in vacuo at 70~80 DEG C after evaporation drying is rotated at 50~70 DEG C, it is double bond containing to obtain surface Modifying titanium dioxide.
7. it prepares such as a kind of method of delustring uvioresistant high-performance PET master batch of claim 1~6 any one of them, feature It is：By PET slices, melting extrusion is granulated and dries place after mixing with nucleocapsid organic/inorganic composite hollow porous microsphere Delustring uvioresistant high-performance PET master batch is made in reason.
8. method according to claim 7, which is characterized in that dispersant and antioxidant are additionally added during the mixing, by weight Number meter is measured, the content of each component is as follows：
9. method according to claim 8, which is characterized in that the dispersant is polyethylene wax, calcium stearate and stearic acid One or more of zinc；The antioxidant is 2,4- bis--(n-octylthiomethylene) -6- methylphenols or 2,4- bis- (12 Alkyl thiomethyl) -6- methylphenols.
10. method according to claim 7, which is characterized in that the mixing refer in super mixer mixing 30~ 40min；The temperature of the melting extrusion is 220~250 DEG C, and the pressure of the melting extrusion is 4~6MPa；The drying process Temperature for 60~80 DEG C, the time of the drying process is 30~40min.
CN201810029324.6A 2018-01-12 2018-01-12 A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof Pending CN108192299A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810029324.6A CN108192299A (en) 2018-01-12 2018-01-12 A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810029324.6A CN108192299A (en) 2018-01-12 2018-01-12 A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108192299A true CN108192299A (en) 2018-06-22

Family

ID=62588784

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810029324.6A Pending CN108192299A (en) 2018-01-12 2018-01-12 A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108192299A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112353699A (en) * 2020-12-11 2021-02-12 长沙蓝姿生物科技有限公司 Sunscreen skin care product and preparation method thereof
CN112457691A (en) * 2020-11-26 2021-03-09 海宁澜钛新材料有限公司 Low-photocatalytic-activity delustering agent and preparation method and application thereof
CN112760784A (en) * 2020-12-28 2021-05-07 绍兴天普纺织有限公司 Preparation process of nylon-polyester blended fabric with cool feeling
CN113004609A (en) * 2021-02-08 2021-06-22 江南大学 "ZnO @ SiO2UV-9 powder modified PP packaging film and preparation method thereof
CN114591554A (en) * 2022-03-11 2022-06-07 界首市锦丰塑业有限公司 Extinction master batch for plastics and preparation method thereof
WO2022227012A1 (en) * 2021-04-29 2022-11-03 苏州三鑫时代新材料股份有限公司 Preparation process for light diffusion plate containing nitrogen sphere or carbon dioxide gas sphere

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2070030B (en) * 1980-02-04 1983-09-21 Konishiroku Photo Ind Toner for electrophotography and method of preparing the ssame
CN101437883A (en) * 2006-05-05 2009-05-20 荷兰颜料股份有限公司 Titanium dioxide based colour concentrate for polyester materials
US20090192240A1 (en) * 2008-01-29 2009-07-30 Coltene Whaledent Ag Dental composite material
CN102492269A (en) * 2011-12-06 2012-06-13 宁波长阳科技有限公司 Weather-resistant white master batch, weather-resistant polyester material and preparation methods of weather-resistant white master batch and weather-resistant polyester material
CN102617989A (en) * 2012-03-21 2012-08-01 太仓振辉化纤有限公司 Formula of full-dull master batch and preparation method thereof
CN102641220A (en) * 2012-04-10 2012-08-22 同济大学 Method for preparing high-efficiency ultraviolet-resistant titanium-dioxide nano granules
CN102643519A (en) * 2012-05-04 2012-08-22 绍兴文理学院 Preparation method of nanometer ultraviolet resistant master batches for superfine polyester fibers
CN103937173A (en) * 2014-04-09 2014-07-23 佛山佛塑科技集团股份有限公司 Polyester titanium dioxide masterbatch for label film and preparation method of masterbatch
CN104250350A (en) * 2014-09-30 2014-12-31 复旦大学 Method for preparing porous polymer material with through-pore structure

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2070030B (en) * 1980-02-04 1983-09-21 Konishiroku Photo Ind Toner for electrophotography and method of preparing the ssame
CN101437883A (en) * 2006-05-05 2009-05-20 荷兰颜料股份有限公司 Titanium dioxide based colour concentrate for polyester materials
US20090192240A1 (en) * 2008-01-29 2009-07-30 Coltene Whaledent Ag Dental composite material
CN102492269A (en) * 2011-12-06 2012-06-13 宁波长阳科技有限公司 Weather-resistant white master batch, weather-resistant polyester material and preparation methods of weather-resistant white master batch and weather-resistant polyester material
CN102617989A (en) * 2012-03-21 2012-08-01 太仓振辉化纤有限公司 Formula of full-dull master batch and preparation method thereof
CN102641220A (en) * 2012-04-10 2012-08-22 同济大学 Method for preparing high-efficiency ultraviolet-resistant titanium-dioxide nano granules
CN102643519A (en) * 2012-05-04 2012-08-22 绍兴文理学院 Preparation method of nanometer ultraviolet resistant master batches for superfine polyester fibers
CN103937173A (en) * 2014-04-09 2014-07-23 佛山佛塑科技集团股份有限公司 Polyester titanium dioxide masterbatch for label film and preparation method of masterbatch
CN104250350A (en) * 2014-09-30 2014-12-31 复旦大学 Method for preparing porous polymer material with through-pore structure

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DAYANE CARVALHO RAMOS SALLES DE OLIVEIRA 等: "Effect of different photoinitiators and reducing agents on cure efficiency and color stability of resin-based composites using different LED wavelengths", 《JOURNAL OF DENTISTRY》 *
YU, SHUOHAN，等: "Preparation of Ag-Modified (B,P)-Codoped TiO2 Hollow Spheres with Enhanced Photocatalytic Activity", 《EUROPEAN JOURNAL OF INORGANIC CHEMISTRY》 *
冯亚青，等: "《助剂化学及工艺学》", 30 June 1997, 化学工业出版社 *
沙力争，等: "《造纸技术实用教程》", 31 August 2017, 中国轻工业出版社 *
陈红余，等: "《基础化学实验》", 30 June 2010, 山东教育出版社 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112457691A (en) * 2020-11-26 2021-03-09 海宁澜钛新材料有限公司 Low-photocatalytic-activity delustering agent and preparation method and application thereof
CN112353699A (en) * 2020-12-11 2021-02-12 长沙蓝姿生物科技有限公司 Sunscreen skin care product and preparation method thereof
CN112760784A (en) * 2020-12-28 2021-05-07 绍兴天普纺织有限公司 Preparation process of nylon-polyester blended fabric with cool feeling
CN113004609A (en) * 2021-02-08 2021-06-22 江南大学 "ZnO @ SiO2UV-9 powder modified PP packaging film and preparation method thereof
CN113004609B (en) * 2021-02-08 2022-04-15 江南大学 "ZnO @ SiO2UV-9 powder modified PP packaging film and preparation method thereof
WO2022227012A1 (en) * 2021-04-29 2022-11-03 苏州三鑫时代新材料股份有限公司 Preparation process for light diffusion plate containing nitrogen sphere or carbon dioxide gas sphere
CN114591554A (en) * 2022-03-11 2022-06-07 界首市锦丰塑业有限公司 Extinction master batch for plastics and preparation method thereof

Similar Documents

Publication Publication Date Title
CN108192299A (en) A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof
CN108144558B (en) Hollow porous microsphere coated with titanium dioxide nanoparticles and preparation method thereof
CN106674852B (en) A kind of anti-blue light eyeglass and its resin raw material
CN101555340B (en) Highly-transparent ultraviolet-resistant energy-saving film and preparation method thereof
CN110172258A (en) A kind of composite polyolefine material and preparation method thereof containing coffee grounds
CN105672023A (en) Cellulose fiber assembly and production method for same, fibrillated cellulose fiber and production method for same, and cellulose fiber complex
CN108246216A (en) A kind of nucleocapsid organic/inorganic composite hollow porous microsphere and preparation method thereof
CN106590310A (en) Uvioresistant paint with self-repairing function and preparation method and application thereof
CN107418159A (en) BOPET ultraviolet screeners master batch and its manufacture method
CN108060468B (en) Melt direct spinning preparation method of extinction PET (polyethylene terephthalate) fibers
CN111718565A (en) Terahertz functional mother particle and application thereof
CN105061784A (en) Polyethylene wax coated stable potassium ferrate and preparation method thereof
CN108129895B (en) Preparation method of nano cerium oxide/silicon dioxide ultraviolet shielding agent
CN108148364A (en) A kind of delustring uvioresistant high-performance PET film and preparation method thereof
CN106118270B (en) A kind of electric pole reflectorised paint
CN108277550B (en) A kind of delustring PET fiber and its slice electrospinning method for preparing
CN109251457B (en) Self-cleaning solar cell panel film with lotus leaf bionic structure and preparation method thereof
CN108003823A (en) A kind of preparation method that may extend away cured UV-LED cationic curings adhesive
CN109651789A (en) A kind of transparent polyester material and preparation method thereof with light absorption and solvent resistant cracking
CN108164631B (en) Styrene-bifunctionality monomer copolymer hollow porous micro sphere and preparation method
CN110105510B (en) Porous core-shell SiO2Per PS microsphere light diffusant, preparation and application
CN108484998A (en) Coprecipitated glue of a kind of wet method mixing and preparation method thereof
CN102604453A (en) Special nanometer composite seal paint for woodware and preparing method thereof
CN110531447A (en) A kind of anti-dazzle protective film and preparation method thereof
CN108456947A (en) A kind of uvioresistant PET fiber and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180622

WD01 Invention patent application deemed withdrawn after publication