CN110564002A - Surface modification method of special antimony trioxide for flame-retardant master batch - Google Patents
Surface modification method of special antimony trioxide for flame-retardant master batch Download PDFInfo
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Abstract
The invention discloses a surface modification method of special antimony trioxide for flame-retardant master batches, which belongs to the field of preparation of active antimony trioxide, and the method comprises the steps of preparing a solution by using absolute ethyl alcohol as a solvent and white graphite powder, chromium oxide powder, hexadecyl trimethyl ammonium chloride, ethylene dioleamide and palm alcohol as solutes, putting the antimony trioxide powder into a high-efficiency ball mill for 5-8min, adding the solution, carrying out ball milling, filtering, drying in a vacuum drying oven, and crushing and grading again to obtain the modified antimony trioxide. As can be seen from the data of examples 1-3 and comparative example 5, the oxygen index of the samples is increased by at least 28.6% and the smoke density rating is decreased by at least 25%. The flame retardant synergy of the modified antimony trioxide is improved, so that the using amount of the antimony trioxide in the flame retardant field can be reduced, and resources are saved.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of preparation of active antimony trioxide, and particularly relates to a surface modification method of special antimony trioxide for flame-retardant master batches.
[ background of the invention ]
With the improvement of science and technology and the improvement of the living standard of people, the high polymer materials are particularly synthesized into high polymers: such as plastics, rubber, etc., are becoming more and more important in people's lives, and their applications are showing a tendency to increase year by year. However, most organic polymer materials have flammability characteristics of different degrees in air, and flame retardant modification of the organic polymer materials for application in various industries such as military, aerospace, transportation, electric power, civil use and the like is a new problem. At present, the ideal method for modifying the flame retardance of plastics is to add products such as flame retardants or flame-retardant master batches to improve the fireproof performance of the plastics.
the flame-retardant master batch is a granular product prepared by carrying out organic combination, modification treatment and synergistic effect on a plurality of flame-retardant components on the basis of a flame retardant and carrying out mixing, extrusion and granulation by a double-screw or three-screw extruder. Different from a flame retardant, the flame-retardant master batch has the advantages of easiness in adding into resin, cleanness, sanitation, high flame-retardant efficiency, small addition amount, small influence on the mechanical property of the resin, difficulty in generating adverse phenomena such as layering, patterns and precipitation after adding, labor and material cost saving, time saving and the like. Generally speaking, the dispersibility, the fluidity, the compatibility with resin, the thermal stability and the weather resistance of the flame-retardant master batch in resin are greatly superior to those of common flame retardants, and in addition, the flame-retardant efficiency and the efficiency of the flame-retardant master batch with a proper formula are also far superior to those of the common flame retardants. Therefore, the flame-retardant master batch becomes one of the best choices for realizing the fireproof requirements of the flame-retardant plastic products at present.
Antimony trioxide is a functional material with wide application, is used as a flame-retardant synergist, has very large dosage and is mainly used for plastic products and textiles. Antimony trioxide is the same as other inorganic powder, has high surface energy, is easy to agglomerate, has poor hydrophilic and oleophobic property on the surface of the powder, has poor affinity with lipophilic polymer molecules, and is difficult to disperse uniformly in the polymer, thereby influencing the physical and mechanical properties of the material, and has large dosage when being used alone and poor flame retardant synergy. Therefore, the antimony trioxide is subjected to surface organic modification to improve the surface hydrophobicity and improve the dispersion, wetting and compatibility of the antimony trioxide in the high polymer material, and the antimony trioxide has important significance. The Chinese patent document 'a method for preparing high-content antimony oxide master batch (patent number: ZL 201210014564.1)' discloses a method for preparing high-content antimony oxide master batch, wherein a surface treatment mode of antimony oxide is mentioned, and the method specifically comprises the following steps: mixing unmodified antimony oxide powder with an ethanol solution containing phosphate, dispersing at high speed by a dispersion machine, transferring into a reactor with a stirring and refluxing device for surface modification, filtering and drying to obtain modified antimony oxide powder. The method can improve the compatibility of antimony oxide and high molecular polymers to a certain extent, but because most of phosphate ester is liquid, the flame retardant effect and flame retardant durability are influenced by small molecular weight, high volatility and low heat resistance, and dripping substances are generated during combustion, the treatment cost is increased, and the industrial application is difficult.
[ summary of the invention ]
The invention provides a surface modification method of special antimony trioxide for flame-retardant master batches, which aims to solve the problems that the antimony trioxide is high in surface energy, easy to agglomerate, poor in affinity of hydrophilic and oleophobic polymer molecules on the powder surface, difficult to disperse uniformly in a polymer, poor in flame-retardant synergy of modified antimony trioxide in the prior art and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
A surface modification method of antimony trioxide special for flame-retardant master batches comprises the following steps:
S1, weighing white graphite powder, chromium oxide powder, antimony trioxide, hexadecyl trimethyl ammonium chloride, ethylene dioleyl amide, palmityl alcohol and absolute ethyl alcohol according to the weight part ratio of the raw materials;
S2, mixing white graphite powder, chromium oxide powder, hexadecyl trimethyl ammonium chloride, ethylene dioleamide and absolute ethyl alcohol, performing ultrasonic dispersion, and stirring at constant temperature to obtain a mixed material A;
and S3, putting the dried antimony trioxide into a high-efficiency ball mill, adding the mixed material A for modification, filtering after the reaction is finished, putting the mixture into a vacuum drying oven for drying, and crushing and grading again to obtain the modified antimony trioxide.
The technical principle of the invention is as follows: the white graphite powder can fill and level up the rough surface of the antimony trioxide powder to form a smooth surface, so that the resistance and the electrostatic force are reduced; chromium trioxide powder as an inhibitor for inhibiting the expansion of the refractory; when the dodecyl trimethyl ammonium chloride is adsorbed on the surface of the antimony trioxide powder, the hydrophilic group faces outwards, the steric hindrance barrier effect can be better stretched in an aqueous medium, the reaggregation of antimony trioxide powder particles is prevented, the dispersion stability of the antimony trioxide is increased, and the antimony trioxide is uniformly dispersed in a polymer; the ethylene dioleoyl amide and the dodecyl trimethyl ammonium chloride contain flame retardant elements, and can cooperate with antimony trioxide powder to perform flame retardant synergy by means of compounding and the like; the palm alcohol has lubricity and dispersibility, so that the frictional resistance among molecules can be reduced, the fluidity of the raw material is enhanced, and the modification time is shortened; the ethylene dioleyl amide has smoothness and can promote fusion of various flame-retardant components in cooperation with the palmityl alcohol; the palm alcohol can be cooperated with hexadecyl trimethyl ammonium chloride to improve the defect of poor thermal stability of the ethylene dioleamide, so that the flame retardant synergy of the sample is improved.
Preferably, in the surface modification method of the special antimony trioxide for the flame-retardant master batch, in the step S1, the raw materials comprise, by weight: chromium oxide powder: antimony trioxide: hexadecyltrimethylammonium chloride: ethylene dioleamide: palm alcohol: anhydrous ethanol 2-8: 1-5: 45-60: 1-4: 2-6: 1-5: 90-100.
More preferably, in the surface modification method of the special antimony trioxide for flame-retardant master batches, in the step S1, the raw materials are white graphite powder in parts by weight: chromium oxide powder: antimony trioxide: hexadecyltrimethylammonium chloride: ethylene dioleamide: palm alcohol: anhydrous ethanol ═ 4: 3: 50: 3: 6: 1: 95.
Preferably, in the surface modification method of the special antimony trioxide for the flame-retardant master batch, in the step S2, the ultrasonic frequency is 55-65HZ, and the ultrasonic dispersion time is 25-35 min.
preferably, in the surface modification method of the special antimony trioxide for the flame-retardant master batch, the stirring temperature in the step S2 is 40-50 ℃, and the stirring time is 20-30 min.
Preferably, in the surface modification method of the special antimony trioxide for the flame-retardant master batch, the drying temperature of the antimony trioxide in the step S3 is 45-55 ℃, and the drying time is 2-4 h.
Preferably, in the surface modification method of the antimony trioxide special for the flame-retardant master batch, in step S3, the dried antimony trioxide is put into a high-efficiency ball mill for 5-8min, and then the mixed material A is added.
preferably, in the surface modification method of the antimony trioxide special for the flame-retardant master batch, the rotating speed of the efficient ball mill in the step S3 is 600-800rpm/min, and the ball milling time is 5-8 h.
Preferably, in the surface modification method of the special antimony trioxide for the flame-retardant master batch, the drying temperature in the step S3 is 110-120 ℃, and the time is 6-8 h.
Preferably, in the surface modification method of the antimony trioxide special for the flame-retardant master batch, the particle size of the modified antimony trioxide in the step S3 is 0.2-0.7 μm.
the invention has the following beneficial effects:
(1) As can be seen from the data of examples 1-3, example 1 is the most preferred example; compared with the comparative example 1, the oxygen index of the sample is improved by 55.7% and the smoke density grade is reduced by 32.9% after the white graphite powder, the chromium oxide powder, the hexadecyl trimethyl ammonium chloride, the ethylene dioleamide and the palm alcohol are added into the raw materials; as can be seen from the data of examples 1-3 and comparative example 5, the oxygen index of the sample is improved by at least 28.6%, the smoke density grade is reduced by at least 25%, and the modified antimony trioxide of the invention has better flame retardant synergistic performance compared with the sample of comparative example 5 (prior art), which shows that the invention has remarkable progress compared with the prior art.
(2) As can be seen from the data of example 1 and comparative examples 1-4, cetyltrimethylammonium chloride, ethylenedioleylamide and palmityl alcohol have a synergistic effect in the modified antimony trioxide, and the synergistic effect at least improves the flame retardant synergy of the sample. This is because:
when the dodecyl trimethyl ammonium chloride is adsorbed on the surface of the antimony trioxide powder, the hydrophilic group faces outwards, the steric hindrance barrier effect can be better stretched in an aqueous medium, the reaggregation of antimony trioxide powder particles is prevented, the dispersion stability of the antimony trioxide is increased, and the antimony trioxide is uniformly dispersed in a polymer; the ethylene dioleoyl amide and the dodecyl trimethyl ammonium chloride contain flame retardant elements, and can cooperate with antimony trioxide powder to perform flame retardant synergy by means of compounding and the like; the palm alcohol has lubricity and dispersibility, so that the frictional resistance among molecules can be reduced, the fluidity of the raw material is enhanced, and the modification time is shortened; the ethylene dioleyl amide has smoothness and can promote fusion of various flame-retardant components in cooperation with the palmityl alcohol; the palm alcohol can be cooperated with hexadecyl trimethyl ammonium chloride to improve the defect of poor thermal stability of the ethylene dioleamide, so that the flame retardant synergy of the sample is improved.
(3) The flame retardant effect of the modified antimony trioxide is improved, so that the using amount of the antimony trioxide can be reduced, and energy is saved.
[ description of the drawings ]
FIG. 1 is a process flow diagram for antimony trioxide modification according to the present invention
[ detailed description ] embodiments
Example 1
As shown in fig. 1, a surface modification method of antimony trioxide special for flame-retardant master batch comprises the following steps:
S1, weighing 4 parts of white graphite powder, 3 parts of chromium oxide powder, 50 parts of antimony trioxide, 3 parts of hexadecyl trimethyl ammonium chloride, 6 parts of ethylene dioleamide, 1 part of palm alcohol and 95 parts of absolute ethyl alcohol according to the weight part ratio of the raw materials;
s2, mixing white graphite powder, chromium oxide powder, hexadecyl trimethyl ammonium chloride, ethylene dioleyl amide, palmityl alcohol and absolute ethyl alcohol, performing ultrasonic dispersion at an ultrasonic frequency of 55HZ for 35min, and stirring at 40 ℃ for 25min to obtain a mixed material A;
S3, putting the antimony trioxide which is dried for 2 hours at the temperature of 50 ℃ into a high-efficiency ball mill with the rotating speed of 750rpm/min for ball milling for 5 minutes, adding the mixed material A for ball milling for 7 hours, filtering after the reaction is finished, placing the mixture in a vacuum drying oven for drying for 6 hours at the temperature of 120 ℃, and crushing and grading again to obtain the modified antimony trioxide with the particle size of 0.2 mu m.
Example 2
As shown in fig. 1, a surface modification method of antimony trioxide special for flame-retardant master batch comprises the following steps:
s1, weighing 2 parts of white graphite powder, 5 parts of chromium oxide powder, 55 parts of antimony trioxide, 4 parts of hexadecyl trimethyl ammonium chloride, 4 parts of ethylene dioleamide, 1.5 parts of palm alcohol and 98 parts of absolute ethyl alcohol according to the weight part ratio of the raw materials;
S2, mixing white graphite powder, chromium oxide powder, hexadecyl trimethyl ammonium chloride, ethylene dioleyl amide, palmityl alcohol and absolute ethyl alcohol, performing ultrasonic dispersion at an ultrasonic frequency of 60HZ for 30min, and stirring at 45 ℃ for 20min to obtain a mixed material A;
S3, putting the antimony trioxide which is dried for 2 hours at 55 ℃ into a high-efficiency ball mill with the rotating speed of 600rpm/min for ball milling for 8 minutes, adding the mixed material A for ball milling for 8 hours, filtering after the reaction is finished, placing the mixture in a vacuum drying oven for drying for 6 hours at the temperature of 115 ℃, and crushing and grading again to obtain the modified antimony trioxide with the particle size of 0.5 mu m.
Example 3
As shown in fig. 1, a surface modification method of antimony trioxide special for flame-retardant master batch comprises the following steps:
S1, weighing 4 parts of white graphite powder, 4 parts of chromium oxide powder, 60 parts of antimony trioxide, 3.5 parts of hexadecyl trimethyl ammonium chloride, 5 parts of ethylene dioleamide, 2 parts of palm alcohol and 90 parts of absolute ethyl alcohol according to the weight part ratio of the raw materials;
S2, mixing white graphite powder, chromium oxide powder, hexadecyl trimethyl ammonium chloride, ethylene dioleyl amide, palmityl alcohol and absolute ethyl alcohol, performing ultrasonic dispersion at an ultrasonic frequency of 65HZ for 25min, and stirring at 50 ℃ for 30min to obtain a mixed material A;
s3, putting antimony trioxide which is dried for 3 hours at 45 ℃ into a high-efficiency ball mill with the rotating speed of 800rpm/min for ball milling for 6 minutes, adding a mixed material A for ball milling for 6 hours, filtering after the reaction is finished, placing the mixture in a vacuum drying oven for drying for 8 hours at 110 ℃, and crushing and grading again to obtain the modified antimony trioxide with the particle size of 0.7 mu m.
comparative example 1
the preparation process is basically the same as that of example 1, except that the raw materials of the surface modification method for preparing the special antimony trioxide for flame-retardant master batch lack hexadecyl trimethyl ammonium chloride, ethylene dioleyl amide and palm alcohol.
Comparative example 2
The preparation process is basically the same as that of example 1, except that the raw materials of the surface modification method for preparing the special antimony trioxide for flame-retardant master batch lack hexadecyl trimethyl ammonium chloride.
Comparative example 3
the preparation process is basically the same as that of the example 1, except that the raw materials of the surface modification method for preparing the antimony trioxide special for the flame-retardant master batch lack ethylene dioleamide.
Comparative example 4
The preparation process is basically the same as that of the example 1, except that the raw materials of the surface modification method for preparing the special antimony trioxide for flame-retardant master batches lack the palm alcohol.
Comparative example 5
The modified antimony trioxide is prepared by the method of example 1-9 of Chinese patent document 'a method for preparing high-content antimony oxide master batch (patent number: ZL 201210014564.1').
The samples of examples 1-3 and comparative examples 1-5 are blended with a certain mass part of resin and a brominated flame retardant to prepare flame retardant samples, and the oxygen index, smoke density grade and vertical burning performance of each example and comparative example are tested, wherein the oxygen index is tested according to GB/T2406-1993 and the test results are shown in Table 1; the combustion performance is tested according to ANLIUM L-94-1985; the smoke density grade is tested according to GB/T8823-2008.
Table 1: results of sample testing
| Experimental groups | Oxygen index/% | Smoke density rating | Vertical combustion performance |
| Example 1 | 33 | 70 | V-0 |
| Example 2 | 31.5 | 72 | V-0 |
| example 3 | 32.6 | 71 | V-0 |
| Comparative example 1 | 21.2 | 93 | V-1 |
| Comparative example 2 | 29.7 | 75 | V-1 |
| Comparative example 3 | 29.4 | 76 | V-1 |
| Comparative example 4 | 30.0 | 79 | V-1 |
| comparative example 5 | 21.8-24.5 | 90-93 | V-1 |
From the above table, it can be seen that: (1) as can be seen from the data of examples 1-3, example 1 is the most preferred example; compared with the comparative example 1, the oxygen index of the sample is improved by 55.7% and the smoke density grade is reduced by 32.9% after the white graphite powder, the chromium oxide powder, the hexadecyl trimethyl ammonium chloride, the ethylene dioleamide and the palm alcohol are added into the raw materials; as can be seen from the data of examples 1-3 and comparative example 5, the oxygen index of the sample is improved by at least 28.6%, the smoke density grade is reduced by at least 25%, and the modified antimony trioxide of the invention has better flame retardant synergy compared with the sample of comparative example 5 (prior art), which shows that the invention has significant progress compared with the prior art.
(2) From the data of example 1 and comparative examples 1-4, it can be seen that cetyltrimethylammonium chloride, ethylenedioleylamide, and palmitol act synergistically in the modified antimony trioxide to synergistically enhance the flame retardant synergy of the sample because:
when the dodecyl trimethyl ammonium chloride is adsorbed on the surface of the antimony trioxide powder, the hydrophilic group faces outwards, the steric hindrance barrier effect can be better stretched in an aqueous medium, the reaggregation of antimony trioxide powder particles is prevented, the dispersion stability of the antimony trioxide is increased, and the antimony trioxide is uniformly dispersed in a polymer; the ethylene dioleoyl amide and the dodecyl trimethyl ammonium chloride contain flame retardant elements, and can cooperate with antimony trioxide powder to perform flame retardant synergy by means of compounding and the like; the palm alcohol has lubricity and dispersibility, so that the frictional resistance among molecules can be reduced, the fluidity of the raw material is enhanced, and the modification time is shortened; the ethylene dioleyl amide has smoothness and can promote fusion of various flame-retardant components in cooperation with the palmityl alcohol; the palm alcohol can be cooperated with hexadecyl trimethyl ammonium chloride to improve the defect of poor thermal stability of the ethylene dioleamide, so that the flame retardant synergy of the sample is improved.
(3) the flame retardant synergy of the modified antimony trioxide is improved, so that the using amount of the antimony trioxide in the flame retardant field can be reduced, and resources are saved.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (10)
1. A surface modification method of antimony trioxide special for flame-retardant master batches is characterized by comprising the following steps:
S1, weighing white graphite powder, chromium oxide powder, antimony trioxide, hexadecyl trimethyl ammonium chloride, ethylene dioleyl amide, palmityl alcohol and absolute ethyl alcohol according to the weight part ratio of the raw materials;
S2, mixing white graphite powder, chromium oxide powder, hexadecyl trimethyl ammonium chloride, ethylene dioleyl amide, palmityl alcohol and absolute ethyl alcohol, performing ultrasonic dispersion, and stirring at constant temperature to obtain a mixed material A;
And S3, putting the dried antimony trioxide into a high-efficiency ball mill, adding the mixed material A for modification, filtering after the reaction is finished, putting the mixture into a vacuum drying oven for drying, and crushing and grading again to obtain the modified antimony trioxide.
2. The surface modification method of special antimony trioxide for flame-retardant masterbatch according to claim 1, characterized in that the raw materials in the step S1 are white graphite powder in parts by weight: chromium oxide powder: antimony trioxide: hexadecyltrimethylammonium chloride: ethylene dioleamide: palm alcohol: anhydrous ethanol 2-8: 1-5: 45-60: 1-4: 2-6: 1-5: 90-100.
3. The surface modification method of antimony trioxide special for flame-retardant masterbatch according to claim 2, characterized in that the mass ratio of the raw materials in step S1 is white graphite powder: chromium oxide powder: antimony trioxide: hexadecyltrimethylammonium chloride: ethylene dioleamide: palm alcohol: anhydrous ethanol ═ 4: 3: 50: 3: 6: 1: 95.
4. The surface modification method of antimony trioxide special for flame-retardant masterbatch according to claim 1, characterized in that in step S2, the ultrasonic frequency is 55-65HZ, and the ultrasonic dispersion time is 25-35 min.
5. the surface modification method of antimony trioxide special for flame-retardant masterbatch according to claim 1, characterized in that the stirring temperature in step S2 is 40-50 ℃, and the stirring time is 20-30 min.
6. The surface modification method of antimony trioxide special for flame-retardant masterbatch according to claim 1, wherein the drying temperature of antimony trioxide in step S3 is 45-55 ℃, and the drying time is 2-4 h.
7. The surface modification method of antimony trioxide special for flame-retardant masterbatch according to claim 1, characterized in that in step S3, the dried antimony trioxide is put into a high-efficiency ball mill for 5-8min, and then the mixture a is added.
8. The surface modification method of antimony trioxide special for flame-retardant masterbatch according to claim 1, characterized in that the rotation speed of the high-efficiency ball mill in step S3 is 600-800rpm/min, and the ball milling time is 5-8 h.
9. The surface modification method of antimony trioxide special for flame-retardant masterbatch according to claim 1, characterized in that the drying temperature in step S3 is 110-120 ℃, and the time is 6-8 h.
10. The surface modification method of antimony trioxide special for flame-retardant masterbatch according to claim 1, wherein the particle size of the modified antimony trioxide in step S3 is 0.2-0.7 μm.
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