CN111471326A - Modification method of nylon uvioresistant nano titanium dioxide - Google Patents

Modification method of nylon uvioresistant nano titanium dioxide Download PDF

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Publication number
CN111471326A
CN111471326A CN202010390850.2A CN202010390850A CN111471326A CN 111471326 A CN111471326 A CN 111471326A CN 202010390850 A CN202010390850 A CN 202010390850A CN 111471326 A CN111471326 A CN 111471326A
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China
Prior art keywords
titanium dioxide
nano titanium
heating
speed mixer
stirring
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Application number
CN202010390850.2A
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Chinese (zh)
Inventor
王彦华
夏浙安
章圣苗
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East China University of Science and Technology
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East China University of Science and Technology
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Priority to CN202010390850.2A priority Critical patent/CN111471326A/en
Publication of CN111471326A publication Critical patent/CN111471326A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36Compounds of titanium
    • C09C1/3607Titanium dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36Compounds of titanium
    • C09C1/3607Titanium dioxide
    • C09C1/3676Treatment with macro-molecular organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10Treatment with macromolecular organic compounds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/106Radiation shielding agents, e.g. absorbing, reflecting agents
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

Abstract

A method for modifying nylon uvioresistant nano titanium dioxide is characterized by comprising the following steps: firstly, preparing a modifier, and then modifying: adding 100 parts of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.0-2.0 parts of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.

Description

Modification method of nylon uvioresistant nano titanium dioxide
Technical Field
The invention relates to a method for modifying nylon uvioresistant nano titanium dioxide.
Background
Titanium dioxide is an important inorganic product, has unique physical and chemical properties, namely strong light scattering power, high tinting strength, large covering power, good whiteness, strong decoloring power, high refractive index and high chemical inertness, is nontoxic and harmless to a human body, and simultaneously changes the surface electronic structure and the crystal structure along with the micronization of the particle size to generate the surface effect, the small particle size effect, the quantum effect and the macroscopic quantum tunnel effect which are not possessed by common-grade particles, thereby having excellent ultraviolet shielding effect, color effect, photochemical effect and the like.
The invention discloses a preparation method of a modified nano titanium dioxide/modified starch/chitosan composite membrane, which is characterized in that two membrane forming materials of acetylated distarch phosphate (ADSP) and Chitosan (CS) are blended to prepare the composite membrane, and nano TiO2 is modified by utilizing sodium laurate (S L) and an ultrasonic microwave synergistic technology, so that a new way is opened up for the application of ADSP, the economic benefit is increased, the modified nano titanium dioxide/modified starch/chitosan composite membrane can also be used as a novel low-cost green packaging material, new reference and theoretical basis are provided for the development of a biopolymer packaging material, meanwhile, the modification of nano TiO2 is realized, certain reference data can be provided for the modification research of the nano material, and the application value of the nano material is improved.
The invention discloses a method for modifying nano titanium dioxide and a method for preparing a coating by using the modified nano titanium dioxide, which are disclosed by the invention in Chinese patent CN 201710099948.0. The mixed solution of the nano titanium dioxide, the acid ester coupling agent, the absolute ethyl alcohol and the deionized water is stirred and dispersed by using magnetic stirring and ultrasonic dispersion titanium, so that the dispersibility of the nano titanium dioxide is increased; the nano titanium dioxide can be prevented from hardening or agglomerating by natural air drying, and the dispersibility of the nano titanium dioxide is further improved; further improving the performances of the nano titanium dioxide coating such as coating strength, weather resistance and the like.
The invention belongs to the field of nano titanium dioxide, and particularly relates to a preparation method of a modified nano titanium dioxide photocatalyst. A preparation method of a modified nanometer titanium dioxide photocatalyst comprises the steps of dissolving a titanium precursor of titanium dioxide and a precursor of a doping element in water, putting the solution into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, heating to 100-200 ℃ in a stirring process, preserving heat for 10 min-48 h, cooling to room temperature, washing the prepared product with water and an organic solvent for 2-5 times in sequence, and drying after washing to obtain the modified nanometer titanium dioxide photocatalyst. The invention obtains the doped modified nano titanium dioxide only through one-step reaction, and obviously improves the visible light response of the nano titanium dioxide.
The invention relates to a method for modifying nylon uvioresistant nano titanium dioxide, which is characterized by comprising the following steps of: firstly, preparing a modifier, wherein the preparation method of the modifier comprises the following steps: adding 10 parts by weight of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 part of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 parts of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.0-2.0 parts of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.
According to the invention, caprolactam oligomer with the polymerization degree of 30 is reacted with 1, 6-hexamethylene diisocyanate, the number of isocyanate groups of the 1, 6-hexamethylene diisocyanate is 2 times of the number of terminal amine groups of the caprolactam oligomer, the terminal amine groups of the caprolactam oligomer are completely replaced by the isocyanate groups after the reaction, the terminal of a chain of the caprolactam oligomer is completely isocyanate groups, the isocyanate groups can be reacted with hydroxyl groups on the surface of the nano titanium dioxide, the remaining caprolactam oligomer covers the surface of the nano titanium dioxide, the surface of the nano titanium dioxide is completely covered by the caprolactam oligomer, the modification of the surface of the nano titanium dioxide is realized, the modified surface of the nano titanium dioxide has very good compatibility with polyamide, and the nano titanium dioxide can be uniformly dispersed in polyamide resin.
Disclosure of Invention
A method for modifying nylon uvioresistant nano titanium dioxide is characterized by comprising the following steps: firstly, preparing a modifier, wherein the preparation method of the modifier comprises the following steps: adding 10 parts by weight of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 part of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 parts of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.0-2.0 parts of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.
Detailed Description
Example 1
Adding 10 kg of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 kg of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 kg of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.0 kg of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.
Example 2
Adding 10 kg of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 kg of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 kg of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 2.0 kg of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.
Example 3
Adding 10 kg of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 kg of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 kg of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.5 kg of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.
Example 4
Adding 10 kg of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 kg of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 kg of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.2 kg of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.
Example 5
Adding 10 kg of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 kg of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 kg of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.8 kg of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.
Example 6
Adding 10 kg of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 kg of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 kg of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.6 kg of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.

Claims (1)

1. A method for modifying nylon uvioresistant nano titanium dioxide is characterized by comprising the following steps: firstly, preparing a modifier, wherein the preparation method of the modifier comprises the following steps: adding 10 parts by weight of caprolactam oligomer with the polymerization degree of 30 into a reaction kettle, heating to 160 ℃, vacuumizing and dehydrating for 2 hours, adding 1.0 part of 1, 6-hexamethylene diisocyanate into the reaction kettle, and continuously reacting for 15 minutes to obtain a modifier for later use; adding 100 parts of commercially available uvioresistant nano titanium dioxide into a high-speed mixer with a heating device, starting a heating and stirring device of the high-speed mixer, adding 1.0-2.0 parts of the prepared modifier into the high-speed mixer when the temperature reaches 100 ℃, keeping the temperature at 100 ℃, stirring and mixing for 30 minutes, stopping heating and stirring, and naturally cooling to normal temperature to obtain the uvioresistant nano titanium dioxide with the modified surface.
CN202010390850.2A 2020-05-11 2020-05-11 Modification method of nylon uvioresistant nano titanium dioxide Withdrawn CN111471326A (en)

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Application Number Priority Date Filing Date Title
CN202010390850.2A CN111471326A (en) 2020-05-11 2020-05-11 Modification method of nylon uvioresistant nano titanium dioxide

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Application Number Priority Date Filing Date Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825480A (en) * 2020-08-13 2020-10-27 西藏大学 Ultraviolet-resistant super-hydrophobic anti-freezing material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825480A (en) * 2020-08-13 2020-10-27 西藏大学 Ultraviolet-resistant super-hydrophobic anti-freezing material and preparation method thereof

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Application publication date: 20200731