CN101555035B - Preparation and application of local surface-modified nanometre zinc oxide by sol-gel method - Google Patents
Preparation and application of local surface-modified nanometre zinc oxide by sol-gel method Download PDFInfo
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- CN101555035B CN101555035B CN2009100515401A CN200910051540A CN101555035B CN 101555035 B CN101555035 B CN 101555035B CN 2009100515401 A CN2009100515401 A CN 2009100515401A CN 200910051540 A CN200910051540 A CN 200910051540A CN 101555035 B CN101555035 B CN 101555035B
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Abstract
The invention discloses preparation and application of local surface-modified nanometre zinc oxide by sol-gel method. The preparation method comprises the steps as follows: (1) dispersant is firstly heated and melted; zinc salt and surface modifier are then added and mixed to obtain sol; the sol is cooled off to obtain gel; (2) the gel obtained in step (1) is calcined at 400 DEG C-800 DEG C for 3-9 hours, thereby obtaining surface-modified nanometre zinc oxide powder. The invention uses surface modifier to carry out local surface modification to nanometre zinc oxide during the generating process, that is to say, surface modification is carried out to nanometre zinc oxide before the nanometre zinc oxide is agglomerated, so as to eliminate agglomeration caused by high surface energy while ensuring high activity of nanometre granules. The method of the invention has simple process and the prepared nanometre zinc oxide has high purity and is free of agglomeration. The local surface-modified nanometre zinc oxide can be used in natural rubber and has obvious nanometre effect and excellent vulcanizate physical properties, thereby has wide application prospect.
Description
Technical field
The present invention relates to adopt sol-gel method in-situ-surface modifying nano-ZnO preparation and the application in natural rubber.
Background technology
The research of modern sol-gel technique starts from the middle of the 19th century, utilizes colloidal sol and preparing gel single component compound.1846, french chemist J.J.Ebelmen found SiCl
4Mix back hydrolysis and formed gel in wet air with ethanol, but do not arouse attention.After the thirties in 20th century, scientists has systematically been studied this process, and proof such as W.Gefcken can make sull with the hydrolysis and the gelationization of metal alkoxide; Early stage up to latter stage in the sixties and the seventies, because electronics, mechanics of communication, energy technology and other high-tech technical fields are more and more higher to the requirement of novel material, sol-gel technique begins to enter the developmental stage of advancing by leaps and bounds.
The process of sol-gel method is: with liquid chemical reagent (or powdered reagent is dissolved in solvent) or colloidal sol is reactant, and uniform mixing and reacting in liquid phase generates stable and do not have sedimentary sol system.Changing gel into after placing certain hour, through processed, is goods at colloidal sol or gel state compacted under, again a little less than traditional sintering temperature.Sol-gel method has that reaction is easily carried out and temperature is low, can prepare high-purity or ultrapure oxide compound, prepare the doping type oxide compound easily, easily prepare characteristics such as various films, fiber or deposition material.
China's publication number: 1587061A, patent name: the sol-gel low-temperature preparation technology of nano zine oxide, this patent disclosure a kind of method for preparing nano zine oxide with sol-gel method low temperature, at first prepare precursor, carry out drying again, high-temperature heat treatment, thus nanometer Zinc oxide powder obtained, but this method does not solve the agglomeration traits that how alleviates or solve nano zine oxide from the angle of surface modification.Therefore, there is the unconspicuous defective of nano effect in the product that is obtained.
Summary of the invention
The objective of the invention is to disclose a kind of zinc oxide and method for making and application of adopting the sol-gel method in-situ-surface modifying, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
(1) earlier with the dispersion agent heating and melting, adds zinc salt and surface-modifying agent then, mixed 1～3 hour, acquire colloidal sol, be cooled to 10～30 ℃, obtain gel;
Described dispersion agent is more than one in oleic acid, stearic acid, oxalic acid or the citric acid;
Described zinc salt is more than one in zinc acetate, zinc sulfate, zinc nitrate or the zinc oxalate;
Described surface-modifying agent is more than one in sim alkylphenol Soxylat A 25-7, sorbitol anhydride oleate, bromohexadecane yl pyridines, polyoxyethylene glycol (PEG-2000) or the sodium lauryl sulfate;
(2) with the gel of step (1) 400 ℃～800 ℃ temperature lower calcination 3～9 hours, promptly get the nanometer Zinc oxide powder of in-situ-surface modifying;
The nanometer Zinc oxide powder of the in-situ-surface modifying that the present invention obtains can be used as the vulcanization leveller of rubber, is used to prepare the alkadiene rubber of sulfur vulcanization: tire, adhesive tape, rubber overshoes or technical rubber goods;
The component and the mass parts of described vulcanized rubber are as follows:
100 parts of natural rubbers
2 parts of the nano zine oxides of in-situ-surface modifying
1.5 parts of stearic acid
1.5 parts of captaxs
1 part of vulkacit D
1 part of antioxidant H
3 parts in lime carbonate
2 parts in machine oil.
The chemical name of described captax is the 2-benzothiazolyl mercaptan, and the chemical name of described vulkacit D is a vulkacit D, and the chemical name of antioxidant H is N, and N '-diphenyl-para-phenylene diamine, described machine oil are No. 4 rubber oil, as " sea " board machine oil of Shanghai refinery.
The nano zine oxide of in-situ-surface modifying is joined in the natural rubber, vulcanize by GB/T16584-1996 then, and make dumbbell-shaped specimen, carry out the test of physicals by GB/T 528-1998, GB/T531-1999, the result shows, the vulcanizating glue physical performance excellence can be used for preparing the alkadiene rubber of sulfur vulcanization: tire, adhesive tape, rubber overshoes or technical rubber goods.
The present invention uses surface-modifying agent in the process that generates nano zine oxide it to be carried out in-situ-surface modifying, promptly before nano zine oxide is reunited, it is carried out surface modification, guaranteeing highly active its agglomeration that brings owing to high surface energy of having eliminated simultaneously of nano particle like this.
Method of the present invention, technology is simple, the nano zine oxide purity height that makes, no agglomeration.Be applied in the natural rubber, nano effect is remarkable, and the physicals excellence of cross-linked rubber has a extensive future.
Embodiment
Among the embodiment, the component and the mass parts of described vulcanized rubber are as follows:
100 parts of natural rubbers, 2 parts of the nano zine oxides of in-situ-surface modifying, 1.5 parts of stearic acid, 1.5 parts of captaxs, 1 part of vulkacit D, 1 part of antioxidant H, 3 parts in lime carbonate, 2 parts in machine oil.
Comparative Examples 1
(1) take by weighing the hard ester acid of 120 grams and add in the three-necked flask, then three-necked flask is put into the oil bath pan of heating unit, when oil bath pan temperature limit rose to 80 ℃, the hard ester acid of fused was stirred on the limit;
(2) in three-necked flask, add zinc nitrate 25.10 grams, continue stirring and obtain colloidal sol after 2 hours;
(3) colloidal sol is poured out, naturally cooled to 25 ℃ and form gel;
(4) gel was calcined 5 hours in 600 ℃ retort furnace, promptly got nanometer Zinc oxide powder.
(5) this is not had the nano zine oxide of surface modification join in the natural rubber, the natural rubber after the sulfuration is made dumb bell sample, carries out the test of physicals by GB/T 528-1998, GB/T 531-1999, records tensile strength and elongation at break sees Table 1.
Embodiment 1
(1) take by weighing the hard ester acid of 120 grams and add in the three-necked flask, then three-necked flask is put into the oil bath pan of heating unit, when oil bath pan temperature limit rose to 75 ℃, the hard ester acid of fused was stirred on the limit;
(2) in three-necked flask, add zinc sulfate 40.43 grams, add bromohexadecane yl pyridines 2.70 grams subsequently, continue stirring and obtain colloidal sol after 1 hour;
(3) colloidal sol is poured out, naturally cooled to 20 ℃ and form gel;
(4) gel was calcined 3 hours in 800 ℃ retort furnace, promptly got nanometer Zinc oxide powder.
(5) nano zine oxide behind the in-situ-surface modifying is joined in the natural rubber, the natural rubber after the sulfuration is made dumb bell sample, presses GB/T 528-1998, and GB/T 531-1999 carries out the test of physicals, records tensile strength and elongation at break sees Table 1.
Embodiment 2
(1) take by weighing the hard ester acid of 120 grams and add in the three-necked flask, then three-necked flask is put into the oil bath pan of heating unit, when oil bath pan temperature limit rose to 90 ℃, the hard ester acid of fused was stirred on the limit;
(2) in three-necked flask, add zinc acetate 11.57 grams, add sim alkylphenol Soxylat A 25-7 1.70 grams subsequently, continue stirring and obtain colloidal sol after 2.5 hours;
(3) colloidal sol is poured out, naturally cooled to 10 ℃ and form gel;
(4) gel was calcined 6 hours in 500 ℃ retort furnace, promptly got nanometer Zinc oxide powder.
(5) nano zine oxide behind the in-situ-surface modifying is joined in the natural rubber, the natural rubber after the sulfuration is made dumb bell sample, carries out the test of physicals by GB/T 528-1998, GB/T 531-1999, records tensile strength and elongation at break sees Table 1.
Embodiment 3
(1) take by weighing the hard ester acid of 120 grams and add in the three-necked flask, then three-necked flask is put into the oil bath pan of heating unit, when oil bath pan temperature limit rose to 85 ℃, the hard ester acid of fused was stirred on the limit;
(2) in three-necked flask, add zinc acetate 15.43 grams, add sim alkylphenol Soxylat A 25-7 3.03 grams subsequently, continue stirring and obtain colloidal sol after 3 hours;
(3) colloidal sol is poured out, naturally cooled to 15 ℃ and form gel;
(4) gel was calcined 8 hours in 450 ℃ retort furnace, promptly got nanometer Zinc oxide powder.
(5) nano zine oxide behind the in-situ-surface modifying is joined in the natural rubber, the natural rubber after the sulfuration is made dumb bell sample, carries out the test of physicals by GB/T 528-1998, GB/T 531-1999, records tensile strength and elongation at break sees Table 1.
Embodiment 4
(1) take by weighing the hard ester acid of 120 grams and add in the three-necked flask, then three-necked flask is put into the oil bath pan of heating unit, when oil bath pan temperature limit rose to 80 ℃, the hard ester acid of fused was stirred on the limit;
(2) in three-necked flask, add zinc nitrate 25.10 grams, add sorbitan monooleate 3.61 grams subsequently, continue stirring and obtain colloidal sol after 2 hours;
(3) colloidal sol is poured out, naturally cooled to 25 ℃ and form gel;
(4) gel was calcined 5 hours in 600 ℃ retort furnace, promptly got nanometer Zinc oxide powder.
(5) nano zine oxide behind the in-situ-surface modifying is joined in the natural rubber, the natural rubber after the sulfuration is made dumb bell sample, carries out the test of physicals by GB/T 528-1998, GB/T 531-1999, records tensile strength and elongation at break sees Table 1.
Embodiment 5
(1) take by weighing the hard ester acid of 120 grams and add in the three-necked flask, then three-necked flask is put into the oil bath pan of heating unit, when oil bath pan temperature limit rose to 100 ℃, the hard ester acid of fused was stirred on the limit;
(2) in three-necked flask, add zinc sulfate 30.32 grams, add bromohexadecane yl pyridines 2.38 grams subsequently, continue stirring and obtain colloidal sol after 2.5 hours;
(3) colloidal sol is poured out, naturally cooled to 30 ℃ and form gel;
(4) gel was calcined 9 hours in 400 ℃ retort furnace, promptly got nanometer Zinc oxide powder.
(5) nano zine oxide behind the in-situ-surface modifying is joined in the natural rubber, the natural rubber after the sulfuration is made dumb bell sample, carries out the test of physicals by GB/T 528-1998, GB/T 531-1999, records tensile strength and elongation at break sees Table 1.
Table 1
Compare with Comparative Examples, product of the present invention, tensile strength and elongation at break obviously improve.
Claims (1)
1. adopt sol-gel method in-situ-surface modifying nano-ZnO preparation, it is characterized in that, comprise the steps:
(1) earlier with the dispersion agent heating and melting, adds zinc salt and surface-modifying agent then, mixed 1～3 hour, obtain colloidal sol, be cooled to 10～30 ℃, obtain gel;
Described dispersion agent is more than one in oleic acid, stearic acid, oxalic acid or the citric acid;
Described zinc salt is more than one in zinc acetate, zinc sulfate, zinc nitrate or the zinc oxalate;
Described surface-modifying agent is more than one in sim alkylphenol Soxylat A 25-7, sorbitol anhydride oleate, bromohexadecane yl pyridines, polyoxyethylene glycol or the sodium lauryl sulphate;
(2) with the gel of step (1) 400 ℃～800 ℃ temperature lower calcination 3～9 hours, promptly get the nanometer Zinc oxide powder of surface modification.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102050967A (en) * | 2010-11-11 | 2011-05-11 | 上海工程技术大学 | Method for improving thermo-oxidative aging resistant performance of conventional sulfur vulcanizing system of natural rubber |
| CN102251285B (en) * | 2011-07-18 | 2013-06-05 | 北京工业大学 | Soakage controllable zinc oxide single crystal surface modification method |
| CN104071826B (en) * | 2013-03-31 | 2015-07-15 | 黄冈师范学院 | Preparation method of modified nanometer ZnO powder |
| CN103817759A (en) * | 2014-02-24 | 2014-05-28 | 浙江农林大学 | In-situ controllable growth method for synthesis of nanometer ZnO on surface of bamboo wood |
| CN104072819A (en) * | 2014-06-27 | 2014-10-01 | 江西耐普矿机新材料股份有限公司 | Highly wear-resistant and tear-resistant rubber formula for vibrating screen |
| CN104842421A (en) * | 2015-05-15 | 2015-08-19 | 浙江农林大学 | Method for preparing super-amphiphobic nano-film on bamboo surface in bionic way |
| CN105419626A (en) * | 2015-10-28 | 2016-03-23 | 天长市润达金属防锈助剂有限公司 | Macromolecule aluminum alloy anti-corrosion Czochralski collosol and preparation method thereof |
| CN105355565B (en) * | 2015-11-20 | 2018-02-13 | 中国科学院电工研究所 | A kind of method that electron beam annealing prepares zinc-oxide film |
| CN109233002A (en) * | 2018-07-26 | 2019-01-18 | 安徽锦华氧化锌有限公司 | A kind of preparation method for the rubber material that mechanical property is good |
| CN115321488B (en) * | 2022-06-30 | 2023-10-27 | 苏州大学 | Method for preparing self-dispersion nano metal oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1587061A (en) * | 2004-08-26 | 2005-03-02 | 复旦大学 | Process for preparing sol-gel of nano zinc oxide by low temperature |
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| CN1587061A (en) * | 2004-08-26 | 2005-03-02 | 复旦大学 | Process for preparing sol-gel of nano zinc oxide by low temperature |
Non-Patent Citations (1)
| Title |
|---|
| Jin Joo et al.Synthesis of ZnO nanocrystals with cone, hexagonal cone, and rod shapes via non-hydrolytic ester elimination sol-gel reactions.《Advanced Materials》.2005,第17卷1873-1877. * |
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