CN110922640B - Modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC (polyvinyl chloride) and application thereof - Google Patents
Modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC (polyvinyl chloride) and application thereof Download PDFInfo
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Abstract
The invention discloses a modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC (polyvinyl chloride) and application thereof, wherein the modified titanium dioxide and rare earth composite stabilizer is formed by compounding a folic acid modified nano titanium dioxide complex serving as a co-stabilizer and a photodegradation catalyst, organic tin serving as a heat stabilizer and rare earth lanthanum cerium metal soap serving as an auxiliary stabilizer; the components are as follows by mass: 1.0-5.0 parts of folic acid modified nano titanium dioxide complex, 0.1-0.5 part of organic tin and 1.0-10 parts of rare earth lanthanum cerium metal soap. According to the invention, the natural auxiliary agents, namely the vitamin folic acid modified nano titanium dioxide complex, the rare earth lanthanum cerium metal soap and the organic tin heat stabilizer generate strong synergistic effect, the thermal stability of PVC is obviously improved, and the PVC is non-toxic and has good environmental compatibility.
Description
Technical Field
The invention belongs to the field of polymer material processing aids, and particularly relates to a modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC (polyvinyl chloride) and application thereof.
Background
Polyvinyl chloride (PVC) engineering plastics are unstable at high temperature, and lead salt (which tends to be eliminated due to high toxicity), calcium zinc, organic tin, rare earth, hydrotalcite and organic heat stabilizer are generally required to be added in order to obtain higher heat resistance; along with the increase of environmental protection, the heat stabilizer develops towards the direction of no toxicity, high efficiency and degradability, in recent years, the usage amount of the organic tin heat stabilizer in the processing of PVC products is increased year by year, and the organic tin heat stabilizer replaces a lead salt stabilizer, but the organic tin is expensive, has peculiar smell and has an unsatisfied heat stabilization effect; in addition, the preparation of the composite stabilizer such as the interaction, dissolution and mixing of liquid-solid and solid-solid molecules such as PVC resin, plasticizer, stabilizer, auxiliary agent and the like has great influence on the thermal, physical and chemical properties and mechanical properties of PVC products, and is far from being solved; therefore, the reduction of the use amount and the use cost of the organic tin and the search of the synergistic interaction and the environmental degradability become urgent matters; in addition to this, the use of ultrasound-assisted heating and mixing techniques to enhance the interaction between PVC, plasticizers, stabilizers, adjuvants and material molecules is also one of the most important means. Because of the high ultrasonic frequency and the large energy, the medium can generate obvious thermal effect when absorbed, and can promote certain chemical reactions to occur or accelerate. For example, during cavitation effect of ultrasonic wave, air bubbles can generate high temperature up to 5000K and pressure more than 200MPa, which becomes an energy source for chemical synthesis of ultrasonic wave, and nano particles can be synthesized on the surfaces of some particles by using the energy. The application of the ultrasonic chemistry in material processing has attracted extensive attention at present, and the published literature is CN102786747A discloses a PVC reinforced plasticized nano material, CN104387699A discloses a medical PVC paste material and a preparation method thereof, and CN106565872A discloses a preparation method of CPVC resin by an aqueous phase suspension method. The electrostatic attraction between the folic acid modified titanium dioxide nano-particles and the rare earth lanthanum cerium compound and the stabilizing effect thereof on PVC are not reported in documents, and the composite stabilizer has the functions of low price, easy obtaining, safety, no toxicity, environmental friendliness, light stabilization and light degradation.
Disclosure of Invention
The invention provides a modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC and application thereof, aiming at solving the problems of high price of organic tin and poor heat resistance when used alone, and aims to improve the heat stability of a PVC film.
The invention relates to a modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC, which is prepared by compounding a folic acid modified nano titanium dioxide complex serving as an auxiliary stabilizer and a photodegradation catalyst, organic tin serving as a heat stabilizer and rare earth lanthanum cerium metal soap serving as an auxiliary stabilizer. The components are composed of the following components in parts by mass (hereinafter referred to as parts for short):
1.0-5.0 parts of folic acid modified nano titanium dioxide complex, 0.1-0.5 part of organic tin and 1.0-10 parts of rare earth lanthanum cerium metal soap.
More preferably: 1.0-3.0 parts of folic acid modified nano titanium dioxide complex, 0.5 parts of organic tin and 1.0-5.0 parts of rare earth lanthanum cerium metal soap.
The rare earth lanthanum cerium metal soap is lanthanum stearate or cerium stearate.
The organotin includes methyltin mercaptide, octyltin mercaptide, butyltin mercaptide, dioctyltin laurate, and the like.
The folic acid modified nano titanium dioxide complex is obtained by modifying nano titanium dioxide by using folic acid as a modifier and adopting an ultrasonic radiation process.
Wherein the addition amount of the nano titanium dioxide is 100 parts, the addition amount of the modifier folic acid is 1-15 parts, and the preferred addition amount is 5 parts.
The modification process comprises the following steps:
firstly, nano TiO is added2Adding the particles into deionized water, and ultrasonically stirring and uniformly dispersing to obtain a 5% titanium dioxide suspension; then adding folic acid into deionized water, and carrying out ultrasonic dissolution at 80 ℃ to obtain 0.5wt% folic acid solution; adding the folic acid solution into the titanium dioxide suspension, and carrying out ultrasonic radiation treatment at 80 ℃ for 1.0h to obtain the folic acid modified nano titanium dioxide complex.
The principle of the ultrasonic disperser adopted by the invention is to convert electric energy into sound energy through the ultrasonic transducer, the energy is changed into dense small bubbles through a liquid medium, and the small bubbles are quickly broken to generate a plurality of tiny energies, thereby playing a role in crushing reaction materials.
Folic Acid (FA), also known as antianemic vitamin, has the molecular formula (C)19H19N7O6) Consisting of pteridine, p-aminobenzoic acid and glutamic acid; is a biologically safe natural synthetic macromolecule with hydroxyl (OH) and amine (NH)2) A carboxyl group (COOH), an amide group (CONH), and the like. Therefore, various interactions such as hydrogen bonds, electrostatic attraction and van der waals force can occur between the PVC substrate and the folic acid modified nano titanium dioxide complex, the generation of chlorine free radicals can be prevented when the PVC substrate and the folic acid modified nano titanium dioxide complex are heated, and the folic acid modified nano titanium dioxide complex is also a photocatalyst.
The folic acid modified nano titanium dioxide complex provided by the invention takes natural organic matter-folic acid as a nano particle surface modifier, and changes the surface characteristics of nano particles by changing surface charges and aggregation behaviors, so as to obtain a novel PVC heat stabilizer which has an excellent heat stabilization effect and is potentially photodegradable in the environment.
The application of the modified titanium dioxide and rare earth composite stabilizer is to add the modified titanium dioxide and rare earth composite stabilizer into a PVC material so as to improve the thermal stability of PVC. The folic acid modified nano titanium dioxide complex is used as a co-stabilizer and a photodegradation catalyst, organic tin is used as a heat stabilizer, rare earth lanthanum cerium metal soap is used as an auxiliary stabilizer, and the folic acid modified nano titanium dioxide complex has obvious synergistic effect on the organic tin and the rare earth lanthanum cerium metal soap, and can effectively improve the heat resistance of PVC.
Wherein the mass ratio of each component is as follows: 100 parts of PVC resin, 50 parts of dioctyl terephthalate DOTP, 1.0-5.0 parts of folic acid modified nano titanium dioxide complex, 1.0-10 parts of rare earth lanthanum cerium metal soap and 0.1-0.5 part of organic tin.
The preferable mixture ratio is as follows: 100 parts of PVC resin, 50 parts of DOTP, 1.0-3.0 parts of folic acid modified nano titanium dioxide complex, 1.0-5.0 parts of rare earth lanthanum cerium metal soap and 0.5 part of organic tin.
The invention selects organic materials as the surface modifier of the nano particles, namely natural organic matters of organic compounds-folic acid, and changes the surface characteristics of the nano particles by changing the surface charge and the aggregation behavior; the auxiliary stabilizer of the metal soaps of the rare earth lanthanum and cerium is safe and nontoxic, but has poor stability when used alone. The natural auxiliary agents, namely the vitamin folic acid modified nano titanium dioxide complex, the rare earth lanthanum cerium metal soap and the organic tin heat stabilizer generate strong synergistic effect, the thermal stability of the PVC is obviously improved, and the PVC is non-toxic and has good environmental compatibility.
According to the invention, folic acid is used for carrying out surface modification on titanium dioxide nano particles, and an ultrasonic radiation process is adopted as a green and environment-friendly preparation method, so that PVC nano composite films coated with folic acid modified titanium dioxide nano particles with different addition amounts are prepared; and the release rates of hydrogen chloride of different composite membranes are measured by adopting a 195 ℃ conductivity method.
The method for evaluating the thermal stability of PVC is conductivity or hydrogen chloride release rate, and the test device refers to ENIS 0182-3: 2000 standard; introducing high-purity nitrogen into PVC powder, heating to 195 ℃, keeping the temperature, and observing the change of the conductivity or the concentration of the hydrogen chloride along with the time of the hydrogen chloride absorbed and released by deionized water. PVC can be rapidly decomposed at the temperature of 180-195 ℃ to release hydrogen chloride gas, and a platinum electrode in a conductivity meter can rapidly sense the conductivity change of hydrogen protons and chloride ions in deionized water. The composite stabilizer is added to inhibit the decomposition of the composite stabilizer, and the quality of the effect of the composite heat stabilizer can be judged by measuring the induction period and the stabilization time through a conductivity curve.
Compared with the prior art, the invention has the beneficial effects that:
1. the modifier folic acid adopted by the invention belongs to all natural substances, is environment-compatible and is easy to degrade;
2. the folic acid modified nano titanium dioxide complex is used as a potential photodecomposition promoter, and can promote the photodegradation of polyvinyl chloride in the environment when the service life of the polyvinyl chloride is terminated;
3. the folic acid modified nano titanium dioxide complex can promote the generation of electrostatic attraction and chemical bond force between tin, lanthanum, cerium and titanium metal oxides and polyvinyl chloride molecules;
4. the folic acid modified nano titanium dioxide complex has obvious synergistic stabilization effect on methyl tin mercaptide and rare earth lanthanum cerium metal soap, can reduce the using amount of the methyl tin mercaptide, has better effect than that of singly using a methyl tin mercaptide stabilizer, and effectively improves the heat resistance of PVC;
5. the folic acid modified nano titanium dioxide complex, the methyl tin mercaptide and the rare earth lanthanum cerium metal soap belong to nontoxic environment-friendly substances, completely meet the development requirements for environmental protection at home and abroad, and have potential application prospects.
6. The ultrasonic radiation is used for processing the heat stabilizer, and has the advantages of environmental friendliness, high efficiency, energy conservation and no pollution.
Drawings
FIG. 1 is a graph of hydrogen chloride release conductivity versus time for PVC films prepared by ultrasonic and non-ultrasonic methods; oil bath temperature is 195 ℃, high-purity nitrogen is used as purge gas, heating time/min is shown on abscissa, and electric conductivity/mu Scm is shown on ordinate-1Wherein curve S0 is without any adjuvant added; curve S1 with the addition of only 1.0 part of methyltin mercaptide; curve C-10 is mechanical stirring; curve C-20 is ultrasonic oscillation; both methods are 1 part of folic acid modified nano titanium dioxide complex, 0.5 part of methyl tin mercaptide and 5 parts of cerium stearate; 100 parts of PVC and 50 parts of DOTP were added to each of samples S0, S1, C-10 and C-20.
FIG. 2 is a graph of HCl release conductivity versus time for PVC films prepared by ultrasonic and non-ultrasonic processes; oil bath temperature is 195 ℃, high-purity nitrogen is used as purge gas, heating time/min is shown on abscissa, and electric conductivity/mu Scm is shown on ordinate-1Wherein curve S0 is without any adjuvant added; curve S1 with the addition of only 1.0 part of methyltin mercaptide; the curve L-10 is mechanical stirring, the curve L-20 is ultrasonic oscillation, and 1 part of folic acid modified nano titanium dioxide complex, 0.5 part of methyl tin mercaptide and 5 parts of lanthanum stearate are added; 100 parts of PVC and 50 parts of DOTP were added to each of samples S0, S1, L-10 and L-20.
Detailed Description
According to the invention, nano titanium dioxide and folic acid complex are used as an auxiliary stabilizer and a photodegradation catalyst, the usage amount is that every 100 parts by mass (referred to as parts for short, the same below) of PVC is added with 1-15 parts of folic acid, and 85-99 parts of modified nano titanium dioxide, wherein 1.0 part of 100 parts of PVC added complex is preferred; the folic acid modified nanometer titanium dioxide has folic acid content of 5 percent.
Rare earth lanthanum and cerium metal soap are used as co-stabilizers, and the using amount is 1-10 parts per 100 parts of PVC, preferably 5 parts.
Taking 100 parts of PVC resin model S-65 and 50 parts of DOTP, and specifically:
1 part of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of lanthanum or cerium stearate;
3 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of lanthanum or cerium stearate;
5 parts of folic acid modified nano titanium dioxide complex; 0.5 part of methyl tin mercaptide and 5 parts of lanthanum or cerium stearate;
the control sample is:
s1 methyl tin mercaptide 1 part;
s0 blank.
Example 1:
4.75 g of TiO are taken2Dispersing the nano particles into 90.25ml of deionized water to prepare 5 percent TiO2Heating the aqueous solution to 80 ℃, ultrasonically shaking for 30min, then dissolving 0.25 g of folic acid in 49.75ml of deionized water, and ultrasonically dissolving for 30min to obtain a uniform solution. And adding a folic acid solution into the titanium dioxide suspension, performing ultrasonic treatment at 80 ℃ for 1h to facilitate grafting to the surfaces of the nano particles, stirring and refluxing for 3h in a water bath at 95 ℃, washing, filtering, drying for 2h at 80 ℃, drying in vacuum, and grinding to obtain folic acid modified titanium dioxide complex powder.
Comparative example 1:
4.75 g of TiO are taken2Dispersing the nano particles in 90.25ml of deionized water, mechanically stirring for 30min, dissolving 0.25 g of folic acid in 49.75ml of deionized water to prepare 0.5% folic acid aqueous solution, dissolving for 30min, and stirring to obtain uniform solution. And adding the folic acid solution into the titanium dioxide suspension, mechanically stirring for 1h at 80 ℃ to facilitate grafting to the surfaces of the nano particles, stirring and refluxing for 3h in a water bath at 95 ℃, washing, filtering, drying for 2h at 80 ℃, vacuum drying, and grinding to obtain folic acid modified titanium dioxide complex powder.
Example 2:
100 parts of PVC, 50 parts of DOTP, 1 part of folic acid modified nano titanium dioxide complex (folic acid content is 5 percent) prepared in example 1, 5 parts of cerium metal soap and 0.5 part of methyl tin mercaptide; mixing and dissolving all components except PVC, ultrasonically shaking at 80 ℃ for 30min, pouring the mixed solution after ultrasonic treatment into PVC resin, and uniformly stirring to obtain a premix; and (3) banburying the obtained premix in a small internal mixer at the melt temperature of 175 ℃ for 2-3min, increasing after the shearing force is reduced, and tabletting at 100 ℃ by using a flat vulcanizing machine to the thickness (1mm) after the shearing force is finished to obtain the PVC film containing the complex and the cerium-tin composite stabilizer.
Comparative example 2:
100 parts of PVC, 50 parts of DOTP, 1 part of folic acid modified nano titanium dioxide complex (folic acid content is 5 percent) prepared in comparative example 1, 5 parts of cerium metal soap and 0.5 part of methyl tin mercaptide; firstly, mixing and dissolving all components except PVC, mechanically stirring for 30min at 80 ℃, then pouring the mixed solution after mechanical stirring treatment into PVC resin, and uniformly stirring to obtain a premix; and (3) banburying the obtained premix in a small internal mixer at the melt temperature of 175 ℃ for 2-3min, increasing after the shearing force is reduced, and tabletting at 100 ℃ by using a flat vulcanizing machine to the thickness (1mm) after the shearing force is finished to obtain the PVC film containing the complex and the cerium-tin composite stabilizer.
Example 3:
the same procedures as in example 2 were repeated except for using 1 part (folic acid content: 5%) of the folic acid-modified nano titanium dioxide complex prepared in example 1 and 5 parts of lanthanum metal soap to obtain a PVC film containing the complex and a lanthanum-tin composite stabilizer (I).
Comparative example 3:
the folic acid modified nano titanium dioxide complex 1 part (FA is 5 wt%), lanthanum metal soap 5 parts, and the balance of the folic acid modified nano titanium dioxide complex prepared in the comparative example 1 and the comparative example 2 are adopted to obtain the PVC film containing the complex and the lanthanum-tin composite stabilizer.
Comparative example 4:
mixing and dissolving PVC (100 parts) and DOTP (50 parts), and stirring for 30min to obtain a uniform premix; and (3) placing the obtained premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 5:
taking methyl tin mercaptide (1 part), mixing and dissolving, and obtaining the single-component organic tin PVC film in the same way as the comparative example 4.
TABLE 1 conductivity of PVC films releasing hydrogen chloride upon ultrasonic and non-ultrasonic heating
(Note: TiO2-FA (5%) -Folic acid modified nano-titanium dioxide complex (Folic acid 5%); LaSt 3-lanthanum stearate; CeSt 3-cerium stearate; OT-methyl tin mercaptide; all samples contained 100 parts of PVC-50 parts, and the other components were charged as shown in Table 1. oil bath temperature 195 deg.C, hydrogen chloride purge gas released by thermal degradation of the samples was high purity nitrogen; PVC films were prepared by ultrasonic irradiation; comparative examples 2, 3, 4 and 5 were all mechanically stirred)
The evaluation method of the PVC thermal stability comprises the following steps: the conductivity of the aqueous hydrogen chloride solution released was determined, with reference to ENIS 0182-3: 2000 standard; introducing high-purity nitrogen into a PVC powder heating test tube, using silicone oil as an oil bath, heating at 195 ℃, and observing the change curve of the conductivity of the deionized water absorbing and releasing hydrogen chloride along with time. The PVC sample can be decomposed to release hydrogen chloride gas at the temperature of 180-195 ℃, and a platinum electrode in the conductivity meter can quickly sense the conductivity change of hydrogen protons and chloride ions in deionized water. The composite stabilizer is added to inhibit the decomposition of the heat stabilizer, and the quality of the effect of the heat stabilizer can be judged by measuring the induction period and the stabilization time through a conductivity curve.
As can be seen from Table 1 and FIG. 1, S0 was not heat resistant at 195 deg.C, S1 was substantially stable until 28min, and the amount of hydrogen chloride released increased dramatically over 28min, indicating that the sample began to decompose; and the PVC added with the three-component compound is mechanically stirred with the PVC sample of C-10 and ultrasonically vibrated with C-20, so that the conductivity of the released hydrogen chloride is relatively slow, which shows that the release of the hydrogen chloride is inhibited. The longest induction period of C-20 is 55min, the best stability is, C-10 times; the thermal stability time is that the samples are C-20> C-10> S1> S0 from large to small. Therefore, the thermal stability of 1 part of folic acid modified titanium dioxide complex (5 percent of folic acid) synthesized by ultrasonic wave assistance, 5 parts of cerium stearate and 0.5 part of OT to the PVC film C-20 is obviously superior to that of the PVC film C-10 with mechanical stirring and the same formula.
As can be seen from Table 1 and FIG. 2, the PVC samples with the three-component compound added, mechanically stirred L-10 and ultrasonically vibrated L-20 released hydrogen chloride slowly, indicating that the release of hydrogen chloride is inhibited. The longest L-10 induction period is 40min, the best stability is, and the L-10 induction period is L-20 times; the thermal stability time is as follows from big to small: l-10> L-20> S1> S0. Therefore, the initial stability of the folic acid modified titanium dioxide complex (folic acid 5%) synthesized by ultrasonic wave assisted with 5 parts of lanthanum stearate and 0.5 part of OT to the PVC film L-20 is not as good as that of the PVC film L-10 with mechanical stirring and the same formula, but is still better than that of the 1 part of single-component OT film S1.
Claims (4)
1. The application of the modified titanium dioxide and rare earth composite stabilizer is characterized in that:
adding the modified titanium dioxide and the rare earth composite stabilizer into a PVC material to improve the thermal stability of PVC;
the mass ratio of each component is as follows: 100 parts of PVC resin, 50 parts of dioctyl terephthalate DOTP, 1.0-5.0 parts of folic acid modified nano titanium dioxide complex, 1.0-10 parts of rare earth lanthanum cerium metal soap and 0.1-0.5 part of organic tin;
the rare earth lanthanum cerium metal soap is lanthanum stearate or cerium stearate;
the organic tin comprises methyl tin mercaptide, octyl tin mercaptide, butyl tin mercaptide or dioctyl tin laurate;
the folic acid modified nano titanium dioxide complex is obtained by modifying nano titanium dioxide by using folic acid as a modifier and adopting an ultrasonic radiation process.
2. Use according to claim 1, characterized in that:
the modification process comprises the following steps:
firstly, nano TiO is added2Adding the particles into deionized water, and ultrasonically stirring and uniformly dispersing to obtain a 5% titanium dioxide suspension; then will beAdding folic acid into deionized water, and ultrasonically dissolving at 80 ℃ to obtain 0.5wt% folic acid solution; adding the folic acid solution into the titanium dioxide suspension, and carrying out ultrasonic radiation treatment at 80 ℃ for 1.0h to obtain the folic acid modified nano titanium dioxide complex.
3. Use according to claim 2, characterized in that:
the addition amount of the nano titanium dioxide is 100 parts, and the addition amount of the modifier folic acid is 1-15 parts.
4. Use according to claim 1, characterized in that:
the mass ratio of each component is as follows: 100 parts of PVC resin, 50 parts of DOTP, 1.0-3.0 parts of folic acid modified nano titanium dioxide complex, 1.0-5.0 parts of rare earth lanthanum cerium metal soap and 0.5 part of organic tin.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480353A (en) * | 2013-10-01 | 2014-01-01 | 大连理工大学 | Method for synthesis of carbon quantum dot solution by hydrothermal process to prepare composite nano-photocatalyst |
| CN103908978A (en) * | 2014-01-27 | 2014-07-09 | 山西医科大学 | Folic acid-nano-TiO2 composite photocatalyst and its preparation method and use |
| CN104031429A (en) * | 2014-05-12 | 2014-09-10 | 谷屿 | Surface-modified nanometer titanium dioxide with anti-ageing effect and preparation method thereof |
| CN105728052A (en) * | 2016-01-27 | 2016-07-06 | 西安工程大学 | Method for preparing high-photo catalytic active nanometer titania by using waste wool |
| DE102015016400A1 (en) * | 2015-12-18 | 2017-06-22 | Julius-Maximilians-Universität Würzburg | Process for the preparation of salts with Perfluoralkyltricyanoboratanionen or Tetracyanoboratanionen |
| CN109810290A (en) * | 2018-12-14 | 2019-05-28 | 安徽理工大学 | A kind of composite thermal stabilizer and its application containing organotin, cerium and titanium |
-
2019
- 2019-12-16 CN CN201911291025.0A patent/CN110922640B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480353A (en) * | 2013-10-01 | 2014-01-01 | 大连理工大学 | Method for synthesis of carbon quantum dot solution by hydrothermal process to prepare composite nano-photocatalyst |
| CN103908978A (en) * | 2014-01-27 | 2014-07-09 | 山西医科大学 | Folic acid-nano-TiO2 composite photocatalyst and its preparation method and use |
| CN104031429A (en) * | 2014-05-12 | 2014-09-10 | 谷屿 | Surface-modified nanometer titanium dioxide with anti-ageing effect and preparation method thereof |
| DE102015016400A1 (en) * | 2015-12-18 | 2017-06-22 | Julius-Maximilians-Universität Würzburg | Process for the preparation of salts with Perfluoralkyltricyanoboratanionen or Tetracyanoboratanionen |
| CN105728052A (en) * | 2016-01-27 | 2016-07-06 | 西安工程大学 | Method for preparing high-photo catalytic active nanometer titania by using waste wool |
| CN109810290A (en) * | 2018-12-14 | 2019-05-28 | 安徽理工大学 | A kind of composite thermal stabilizer and its application containing organotin, cerium and titanium |
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