CN112940348A - Transparent powder calcium-zinc composite heat stabilizer for PVC and preparation method thereof - Google Patents
Transparent powder calcium-zinc composite heat stabilizer for PVC and preparation method thereof Download PDFInfo
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Abstract
The invention provides a transparent powder calcium-zinc composite heat stabilizer for PVC and a preparation method thereof, wherein the transparent powder calcium-zinc composite heat stabilizer comprises the following raw materials in parts by weight: 30-35 parts of a calcium-zinc composite main heat stabilizer, 25-30 parts of an auxiliary heat stabilizer, 10-20 parts of hydrotalcite, 5-10 parts of silicon dioxide, 5 parts of an antioxidant and 5 parts of an ultraviolet absorber, wherein the calcium-zinc composite main heat stabilizer is formed by compounding zinc epoxy oleate and calcium epoxy oleate, the auxiliary heat stabilizer is formed by adopting magnesium acetylacetonate, the hydrotalcite is formed by adopting modified ternary hydrotalcite, and the silicon dioxide is formed by adopting fumed silica. According to the invention, the calcium-zinc composite main heat stabilizer, the magnesium acetylacetonate auxiliary heat stabilizer, the sex ternary hydrotalcite and the gas-phase silica are used as fillers and combined according to the proportion, so that the coloring characteristic is effectively inhibited according to the high-efficiency property, and the transparency of the heat stabilizer is effectively improved.
Description
Technical Field
The invention relates to the technical field of production of calcium-zinc composite heat stabilizers, and particularly relates to a transparent powdery calcium-zinc composite heat stabilizer for PVC and a preparation method thereof.
Background
The PVC transparent heat stabilizer commonly used in the market at present comprises organic tin, a liquid calcium zinc (barium zinc) heat stabilizer, a powder calcium zinc heat stabilizer and the like, wherein the organic tin stabilizer is expensive and has a controversial toxicity problem, the liquid stabilizer is reasonable in price and excellent in performance, but different manufacturers have different standards and different solvents which have different influences on product performance, usually have negative influences on plasticization problems and have toxicity problems and precipitation problems, and the powder heat stabilizer is convenient to package, transport, add and the like and also has great advantages in performance.
However, zinc stearate is used as a heat stabilizer powder raw material commonly used in PVC, and is a main component in a calcium-zinc heat stabilizer, namely calcium soap is used as a complex, so that zinc burning can be obviously reduced. Although the calcium soap has great influence on the coloring performance of the product, the calcium soap has unique relieving effect on zinc burning, so that the calcium soap becomes an effective substance for inhibiting the zinc burning, and particularly, the calcium hydroxide and other powder have obvious effect on improving the Congo red time of the calcium zinc stabilizer. However, since the coloring property is high, even a trace amount of the coloring agent cannot be applied to a transparent product, and the transparency is low.
Therefore, it is necessary to invent a transparent powdery calcium-zinc composite heat stabilizer for PVC and a preparation method thereof to solve the problems
Disclosure of Invention
The invention aims to provide a transparent powdery calcium-zinc composite heat stabilizer for PVC and a preparation method thereof, and aims to solve the technical problems.
In order to solve the technical problems, the invention adopts the following technical scheme:
a transparent powder calcium-zinc composite heat stabilizer for PVC comprises the following raw materials in parts by weight: 30-35 parts of a calcium-zinc composite main heat stabilizer, 25-30 parts of an auxiliary heat stabilizer, 10-20 parts of hydrotalcite, 5-10 parts of silicon dioxide, 5 parts of an antioxidant and 5 parts of an ultraviolet absorber, wherein the calcium-zinc composite main heat stabilizer is formed by compounding zinc epoxy oleate and calcium epoxy oleate, the auxiliary heat stabilizer is formed by magnesium acetylacetonate, the hydrotalcite is formed by modified ternary hydrotalcite, the silicon dioxide is formed by gas-phase silicon dioxide, the total raw material range ratio of the transparent powder calcium-zinc composite heat stabilizer is 3-3.5:2.5-3:1-2:0.5-1:0.5:0.5, the mass ratio of zinc epoxy oleate to calcium epoxy oleate in the calcium-zinc composite main heat stabilizer is 5:3, and the mass ratio of calcium, magnesium and aluminum in the modified ternary hydrotalcite is 7:1: 2.
The preparation method of the transparent powder calcium-zinc composite heat stabilizer for PVC based on the PVC comprises the following steps:
s1 preparation of epoxy oleic acid: adding oleic acid and formic acid in a certain mass ratio into a reaction container, placing the mixture into a constant-temperature water bath kettle, stirring and heating the mixture, slowly dropwise adding a mixed solution of hydrogen peroxide and phosphoric acid, reacting at a constant temperature for a period of time, transferring a reaction product into a pear-shaped separating funnel, standing and layering the reaction product, and taking an upper-layer oily product to prepare epoxy oleic acid;
s2 preparation of calcium epoxy oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature required by the reaction, slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a pre-dissolved calcium chloride solution into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying a product to obtain white solid powder, and preparing to obtain epoxy calcium oleate;
s3 preparation of epoxy zinc oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature required by the reaction, slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a zinc chloride solution dissolved in advance into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying a product to obtain white solid powder, and preparing to obtain epoxy zinc oleate;
s4 preparation of auxiliary heat stabilizer: adding a certain amount of magnesium hydroxide into a reaction container filled with an ethanol solvent, refluxing for 30min to uniformly disperse the magnesium hydroxide, then dropwise adding acetylacetone into the mixture in a certain amount through a constant-pressure funnel, refluxing for reaction for 3h, and performing suction filtration and drying after the mixture is cooled to room temperature to prepare an auxiliary heat stabilizer;
s5 preparation of modified ternary hydrotalcite: sequentially adding calcium hydroxide, magnesium hydroxide and aluminum hydroxide into a reaction container according to a set proportion, adding water, heating to 80 ℃, stirring and mixing for 0.5h, adding sodium carbonate, stirring and reacting for 1h, adding a surface modifier, continuously stirring and reacting for 1h, transferring a reaction mixture into a crystallization kettle, placing the reaction mixture into a forced air drying oven, heating to 10 ℃, crystallizing for 17h, cooling, filtering, drying and grinding a solid to obtain modified Ca-Mg-Al hydrotalcite, and crushing the modified Ca-Mg-Al hydrotalcite into powder of 0.2 mu m;
s6, preparing a transparent powdery calcium-zinc composite heat stabilizer, sequentially adding the calcium-zinc composite main heat stabilizer, the auxiliary heat stabilizer, the hydrotalcite, the silicon dioxide, the antioxidant and the ultraviolet absorber into a high-speed mixer according to the proportion, mixing at a high speed for 10min, heating the mixed raw materials into a plasticizing machine, plasticizing at 170 ℃, adding into a crusher, and crushing to obtain the transparent powdery calcium-zinc composite heat stabilizer.
Preferably, the charging ratio of the oleic acid, the formic acid, the hydrogen peroxide and the phosphoric acid in the step S1 is 20:4:18:0.1, the reaction temperature is 58 ℃, and the reaction time is 5 h.
Preferably, the reaction temperature in the steps S2 and S3 is 90 ℃.
Preferably, the dropping speed of the acetylacetone in the step S4 is 1-2 d/S.
Preferably, the surface modifier of the ternary hydrotalcite in step S5 is one of sodium stearate, zinc stearate, epoxidized soybean oil, or glyceryl monostearate.
The invention has the beneficial effects that:
(1) according to the invention, zinc epoxy oleate and calcium epoxy oleate are compounded as a main heat stabilizer, so that the heat stability and the anti-coloring property in the early stage are increased, the transparency of the heat stabilizer is ensured, magnesium acetylacetonate is used as an auxiliary heat stabilizer, so that the heat stabilizer has good effects on the coloring property in the early stage and the long-term stability, and the modified ternary hydrotalcite and fumed silica are used as fillers, so that the coloring property is effectively inhibited according to the high efficiency of the modified ternary hydrotalcite and the fumed silica, and the transparency of the heat stabilizer is efficiently increased.
Detailed Description
The present invention will be further described with reference to specific embodiments for the purpose of facilitating an understanding of technical means, characteristics of creation, objectives and functions realized by the present invention, but the following embodiments are only preferred embodiments of the present invention, and are not intended to be exhaustive. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention. The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The first embodiment is as follows:
the invention provides a transparent powdery calcium-zinc composite heat stabilizer for PVC, which comprises the following raw materials in parts by weight: 35 parts of a calcium-zinc composite main heat stabilizer, 25 parts of an auxiliary heat stabilizer, 20 parts of hydrotalcite, 10 parts of silicon dioxide, 5 parts of an antioxidant and 5 parts of an ultraviolet absorber, wherein the calcium-zinc composite main heat stabilizer is formed by compounding zinc epoxy oleate and calcium epoxy oleate, the auxiliary heat stabilizer is formed by adopting magnesium acetylacetonate, the hydrotalcite is formed by adopting modified ternary hydrotalcite, the silicon dioxide is formed by adopting fumed silica, the total raw material range ratio of the transparent powder calcium-zinc composite heat stabilizer is 3.5:2.5:2:1:0.5:0.5, the mass ratio of the zinc epoxy oleate to the calcium epoxy oleate in the calcium-zinc composite main heat stabilizer is 5:3, and the mass ratio of calcium, magnesium and aluminum in the modified ternary hydrotalcite is 7:1: 2.
The preparation method of the transparent powder calcium-zinc composite heat stabilizer for PVC based on the PVC comprises the following steps:
s1 preparation of epoxy oleic acid: adding oleic acid and formic acid in a certain mass ratio into a reaction container, placing the mixture into a constant-temperature water bath kettle, stirring and heating the mixture, slowly dropwise adding a mixed solution of hydrogen peroxide and phosphoric acid, reacting at a constant temperature for a period of time, wherein the feeding ratio of the oleic acid to the formic acid to the hydrogen peroxide to the phosphoric acid is 20:4:18:0.1, the reaction temperature is 58 ℃, the reaction time is 5 hours, transferring a reaction product into a pear-shaped separating funnel, standing and layering the mixture, and taking an upper oily product to prepare epoxy oleic acid;
s2 preparation of calcium epoxy oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature of 90 ℃ required by the reaction, slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a pre-dissolved calcium chloride solution into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying a product to obtain white solid powder, and preparing to obtain epoxy calcium oleate;
s3 preparation of epoxy zinc oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature of 90 ℃ required by the reaction, then slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a zinc chloride solution dissolved in advance into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying the product to obtain white solid powder, and preparing to obtain epoxy zinc oleate;
s4 preparation of auxiliary heat stabilizer: adding a certain amount of magnesium hydroxide into a reaction container containing an ethanol solvent, refluxing for 30min to uniformly disperse the magnesium hydroxide, then dripping acetylacetone into the reaction container at a certain speed of 1-2d/s through a constant-pressure funnel, refluxing for reaction for 3h, cooling to room temperature, performing suction filtration and drying to prepare an auxiliary heat stabilizer;
s5 preparation of modified ternary hydrotalcite: sequentially adding calcium hydroxide, magnesium hydroxide and aluminum hydroxide into a reaction container according to a set proportion, adding water, heating to 80 ℃, stirring and mixing for 0.5h, adding sodium carbonate, stirring and reacting for 1h, adding one surface modifier of sodium stearate, zinc stearate, epoxidized soybean oil or glyceryl monostearate, continuously stirring and reacting for 1h, transferring the reaction mixture into a crystallization kettle, placing the reaction mixture into a forced air drying box, heating to 10 ℃ for crystallization for 17h, cooling, filtering, drying and grinding solids to prepare modified Ca-Mg-Al hydrotalcite, and crushing the modified Ca-Mg-Al hydrotalcite into powder of 0.2 mu m;
s6, preparing a transparent powdery calcium-zinc composite heat stabilizer, sequentially adding the calcium-zinc composite main heat stabilizer, the auxiliary heat stabilizer, the hydrotalcite, the silicon dioxide, the antioxidant and the ultraviolet absorber into a high-speed mixer according to the proportion, mixing at a high speed for 10min, heating the mixed raw materials into a plasticizing machine, plasticizing at 170 ℃, adding into a crusher, and crushing to obtain the transparent powdery calcium-zinc composite heat stabilizer.
Example two:
the invention provides a transparent powdery calcium-zinc composite heat stabilizer for PVC, which comprises the following raw materials in parts by weight: 30 parts of a calcium-zinc composite main heat stabilizer, 30 parts of an auxiliary heat stabilizer, 20 parts of hydrotalcite, 10 parts of silicon dioxide, 5 parts of an antioxidant and 5 parts of an ultraviolet absorber, wherein the calcium-zinc composite main heat stabilizer is formed by compounding zinc epoxy oleate and calcium epoxy oleate, the auxiliary heat stabilizer is formed by adopting magnesium acetylacetonate, the hydrotalcite is formed by adopting modified ternary hydrotalcite, the silicon dioxide is formed by adopting fumed silica, the total raw material range ratio of the transparent powder calcium-zinc composite heat stabilizer is 3:3:2:1:0.5:0.5, the mass ratio of the zinc epoxy oleate to the calcium epoxy oleate in the calcium-zinc composite main heat stabilizer is 5:3, and the mass ratio of calcium, magnesium and aluminum in the modified ternary hydrotalcite is 7:1: 2.
The preparation method of the transparent powder calcium-zinc composite heat stabilizer for PVC based on the PVC comprises the following steps:
s1 preparation of epoxy oleic acid: adding oleic acid and formic acid in a certain mass ratio into a reaction container, placing the mixture into a constant-temperature water bath kettle, stirring and heating the mixture, slowly dropwise adding a mixed solution of hydrogen peroxide and phosphoric acid, reacting at a constant temperature for a period of time, wherein the feeding ratio of the oleic acid to the formic acid to the hydrogen peroxide to the phosphoric acid is 20:4:18:0.1, the reaction temperature is 58 ℃, the reaction time is 5 hours, transferring a reaction product into a pear-shaped separating funnel, standing and layering the mixture, and taking an upper oily product to prepare epoxy oleic acid;
s2 preparation of calcium epoxy oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature of 90 ℃ required by the reaction, slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a pre-dissolved calcium chloride solution into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying a product to obtain white solid powder, and preparing to obtain epoxy calcium oleate;
s3 preparation of epoxy zinc oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature of 90 ℃ required by the reaction, then slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a zinc chloride solution dissolved in advance into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying the product to obtain white solid powder, and preparing to obtain epoxy zinc oleate;
s4 preparation of auxiliary heat stabilizer: adding a certain amount of magnesium hydroxide into a reaction container containing an ethanol solvent, refluxing for 30min to uniformly disperse the magnesium hydroxide, then dripping acetylacetone into the reaction container at a certain speed of 1-2d/s through a constant-pressure funnel, refluxing for reaction for 3h, cooling to room temperature, performing suction filtration and drying to prepare an auxiliary heat stabilizer;
s5 preparation of modified ternary hydrotalcite: sequentially adding calcium hydroxide, magnesium hydroxide and aluminum hydroxide into a reaction container according to a set proportion, adding water, heating to 80 ℃, stirring and mixing for 0.5h, adding sodium carbonate, stirring and reacting for 1h, adding one surface modifier of sodium stearate, zinc stearate, epoxidized soybean oil or glyceryl monostearate, continuously stirring and reacting for 1h, transferring the reaction mixture into a crystallization kettle, placing the reaction mixture into a forced air drying box, heating to 10 ℃ for crystallization for 17h, cooling, filtering, drying and grinding solids to prepare modified Ca-Mg-Al hydrotalcite, and crushing the modified Ca-Mg-Al hydrotalcite into powder of 0.2 mu m;
s6, preparing a transparent powdery calcium-zinc composite heat stabilizer, sequentially adding the calcium-zinc composite main heat stabilizer, the auxiliary heat stabilizer, the hydrotalcite, the silicon dioxide, the antioxidant and the ultraviolet absorber into a high-speed mixer according to the proportion, mixing at a high speed for 10min, heating the mixed raw materials into a plasticizing machine, plasticizing at 170 ℃, adding into a crusher, and crushing to obtain the transparent powdery calcium-zinc composite heat stabilizer.
Example three:
the invention provides a transparent powdery calcium-zinc composite heat stabilizer for PVC, which comprises the following raw materials in parts by weight: 35 parts of a calcium-zinc composite main heat stabilizer, 30 parts of an auxiliary heat stabilizer, 15 parts of hydrotalcite, 10 parts of silicon dioxide, 5 parts of an antioxidant and 5 parts of an ultraviolet absorber, wherein the calcium-zinc composite main heat stabilizer is formed by compounding zinc epoxy oleate and calcium epoxy oleate, the auxiliary heat stabilizer is formed by adopting magnesium acetylacetonate, the hydrotalcite is formed by adopting modified ternary hydrotalcite, the silicon dioxide is formed by adopting fumed silica, the total raw material range ratio of the transparent powder calcium-zinc composite heat stabilizer is 3.5:3:1.5:1:0.5:0.5, the mass ratio of the zinc epoxy oleate to the calcium epoxy oleate in the calcium-zinc composite main heat stabilizer is 5:3, and the mass ratio of calcium, magnesium and aluminum in the modified ternary hydrotalcite is 7:1: 2.
The preparation method of the transparent powder calcium-zinc composite heat stabilizer for PVC based on the PVC comprises the following steps:
s1 preparation of epoxy oleic acid: adding oleic acid and formic acid in a certain mass ratio into a reaction container, placing the mixture into a constant-temperature water bath kettle, stirring and heating the mixture, slowly dropwise adding a mixed solution of hydrogen peroxide and phosphoric acid, reacting at a constant temperature for a period of time, wherein the feeding ratio of the oleic acid to the formic acid to the hydrogen peroxide to the phosphoric acid is 20:4:18:0.1, the reaction temperature is 58 ℃, the reaction time is 5 hours, transferring a reaction product into a pear-shaped separating funnel, standing and layering the mixture, and taking an upper oily product to prepare epoxy oleic acid;
s2 preparation of calcium epoxy oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature of 90 ℃ required by the reaction, slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a pre-dissolved calcium chloride solution into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying a product to obtain white solid powder, and preparing to obtain epoxy calcium oleate;
s3 preparation of epoxy zinc oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature of 90 ℃ required by the reaction, then slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a zinc chloride solution dissolved in advance into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying the product to obtain white solid powder, and preparing to obtain epoxy zinc oleate;
s4 preparation of auxiliary heat stabilizer: adding a certain amount of magnesium hydroxide into a reaction container containing an ethanol solvent, refluxing for 30min to uniformly disperse the magnesium hydroxide, then dripping acetylacetone into the reaction container at a certain speed of 1-2d/s through a constant-pressure funnel, refluxing for reaction for 3h, cooling to room temperature, performing suction filtration and drying to prepare an auxiliary heat stabilizer;
s5 preparation of modified ternary hydrotalcite: sequentially adding calcium hydroxide, magnesium hydroxide and aluminum hydroxide into a reaction container according to a set proportion, adding water, heating to 80 ℃, stirring and mixing for 0.5h, adding sodium carbonate, stirring and reacting for 1h, adding one surface modifier of sodium stearate, zinc stearate, epoxidized soybean oil or glyceryl monostearate, continuously stirring and reacting for 1h, transferring the reaction mixture into a crystallization kettle, placing the reaction mixture into a forced air drying box, heating to 10 ℃ for crystallization for 17h, cooling, filtering, drying and grinding solids to prepare modified Ca-Mg-Al hydrotalcite, and crushing the modified Ca-Mg-Al hydrotalcite into powder of 0.2 mu m;
s6, preparing a transparent powdery calcium-zinc composite heat stabilizer, sequentially adding the calcium-zinc composite main heat stabilizer, the auxiliary heat stabilizer, the hydrotalcite, the silicon dioxide, the antioxidant and the ultraviolet absorber into a high-speed mixer according to the proportion, mixing at a high speed for 10min, heating the mixed raw materials into a plasticizing machine, plasticizing at 170 ℃, adding into a crusher, and crushing to obtain the transparent powdery calcium-zinc composite heat stabilizer.
The calcium-zinc composite main heat stabilizer, the magnesium acetylacetonate auxiliary heat stabilizer, the sex ternary hydrotalcite and the gas-phase silica are used as fillers to be combined according to the proportion, the product obtained according to the embodiments 1 to 3 is used as a sample to detect the heat stability and the light transmittance and Congo red test, and the data are shown in the following table:
| thermal stability time/min | Transmittance (a) | Congo red 200 ℃/min | |
| Example one | 48 | 95 | 35 |
| Example two | 45 | 93 | 29 |
| EXAMPLE III | 47 | 92 | 34 |
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A transparent powdery calcium-zinc composite heat stabilizer for PVC is characterized in that: the transparent powdery calcium-zinc composite heat stabilizer comprises the following raw materials in parts by weight: 30-35 parts of a calcium-zinc composite main heat stabilizer, 25-30 parts of an auxiliary heat stabilizer, 10-20 parts of hydrotalcite, 5-10 parts of silicon dioxide, 5 parts of an antioxidant and 5 parts of an ultraviolet absorber, wherein the calcium-zinc composite main heat stabilizer is formed by compounding zinc epoxy oleate and calcium epoxy oleate, the auxiliary heat stabilizer is formed by magnesium acetylacetonate, the hydrotalcite is formed by modified ternary hydrotalcite, the silicon dioxide is formed by gas-phase silicon dioxide, the total raw material range ratio of the transparent powder calcium-zinc composite heat stabilizer is 3-3.5:2.5-3:1-2:0.5-1:0.5:0.5, the mass ratio of zinc epoxy oleate to calcium epoxy oleate in the calcium-zinc composite main heat stabilizer is 5:3, and the mass ratio of calcium, magnesium and aluminum in the modified ternary hydrotalcite is 7:1: 2.
2. The preparation method of the transparent powdery calcium-zinc composite heat stabilizer for PVC according to claim 1, characterized by comprising the following steps: the method comprises the following steps:
s1 preparation of epoxy oleic acid: adding oleic acid and formic acid in a certain mass ratio into a reaction container, placing the mixture into a constant-temperature water bath kettle, stirring and heating the mixture, slowly dropwise adding a mixed solution of hydrogen peroxide and phosphoric acid, reacting at a constant temperature for a period of time, transferring a reaction product into a pear-shaped separating funnel, standing and layering the reaction product, and taking an upper-layer oily product to prepare epoxy oleic acid;
s2 preparation of calcium epoxy oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature required by the reaction, slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a pre-dissolved calcium chloride solution into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying a product to obtain white solid powder, and preparing to obtain epoxy calcium oleate;
s3 preparation of epoxy zinc oleate: dissolving a certain mass of sodium hydroxide in a reactor filled with deionized water, heating to the temperature required by the reaction, slowly adding epoxy oleic acid, adjusting the pH value to obtain epoxy sodium oleate, slowly adding a zinc chloride solution dissolved in advance into the epoxy sodium oleate solution, adjusting the pH value to obtain epoxy calcium oleate, filtering, washing and drying a product to obtain white solid powder, and preparing to obtain epoxy zinc oleate;
s4 preparation of auxiliary heat stabilizer: adding a certain amount of magnesium hydroxide into a reaction container filled with an ethanol solvent, refluxing for 30min to uniformly disperse the magnesium hydroxide, then dropwise adding acetylacetone into the mixture in a certain amount through a constant-pressure funnel, refluxing for reaction for 3h, and performing suction filtration and drying after the mixture is cooled to room temperature to prepare an auxiliary heat stabilizer;
s5 preparation of modified ternary hydrotalcite: sequentially adding calcium hydroxide, magnesium hydroxide and aluminum hydroxide into a reaction container according to a set proportion, adding water, heating to 80 ℃, stirring and mixing for 0.5h, adding sodium carbonate, stirring and reacting for 1h, adding a surface modifier, continuously stirring and reacting for 1h, transferring a reaction mixture into a crystallization kettle, placing the reaction mixture into a forced air drying oven, heating to 100 ℃ for crystallization for 17h, cooling, filtering, drying and grinding a solid to prepare modified Ca-Mg-Al hydrotalcite, and crushing the modified Ca-Mg-Al hydrotalcite into powder of 0.2 mu m;
s6, preparing a transparent powdery calcium-zinc composite heat stabilizer, sequentially adding the calcium-zinc composite main heat stabilizer, the auxiliary heat stabilizer, the hydrotalcite, the silicon dioxide, the antioxidant and the ultraviolet absorber into a high-speed mixer according to the proportion, mixing at a high speed for 10min, heating the mixed raw materials into a plasticizing machine, plasticizing at 170 ℃, adding into a crusher, and crushing to obtain the transparent powdery calcium-zinc composite heat stabilizer.
3. The preparation method of the transparent powdery calcium-zinc composite heat stabilizer for PVC according to claim 2, characterized by comprising the following steps: in the step S1, the feeding ratio of the oleic acid to the formic acid to the hydrogen peroxide to the phosphoric acid is 20:4:18:0.1, the reaction temperature is 58 ℃, and the reaction time is 5 hours.
4. The preparation method of the transparent powdery calcium-zinc composite heat stabilizer for PVC according to claim 2, characterized by comprising the following steps: the reaction temperature in the steps S2 and S3 was 90 ℃.
5. The preparation method of the transparent powdery calcium-zinc composite heat stabilizer for PVC according to claim 2, characterized by comprising the following steps: the dropping speed of the acetylacetone in the step S4 is 1-2 d/S.
6. The preparation method of the transparent powdery calcium-zinc composite heat stabilizer for PVC according to claim 2, characterized by comprising the following steps: the surface modifier of the ternary hydrotalcite in the step S5 is one of sodium stearate, zinc stearate, epoxidized soybean oil or glyceryl monostearate.
Priority Applications (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113816842A (en) * | 2021-10-11 | 2021-12-21 | 山东键兴新材料科技有限公司 | Calcium acetylacetonate, preparation method and application thereof |
| CN114181477A (en) * | 2021-12-22 | 2022-03-15 | 成都绮萝科技有限公司 | Safe and environment-friendly PVC stabilizer and preparation method thereof |
| CN114805927A (en) * | 2022-04-11 | 2022-07-29 | 安徽华文塑胶科技有限公司 | Liquid calcium-zinc composite stabilizer and processing method thereof |
| CN115260596A (en) * | 2022-09-29 | 2022-11-01 | 圣地亚科技(江苏)有限公司 | Moistureproof environment-friendly calcium-zinc stabilizer and preparation method thereof |
| CN117801525A (en) * | 2023-12-30 | 2024-04-02 | 东莞市振中塑胶有限公司 | High-performance composite heat stabilizer and preparation method thereof |
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| CN113816842A (en) * | 2021-10-11 | 2021-12-21 | 山东键兴新材料科技有限公司 | Calcium acetylacetonate, preparation method and application thereof |
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| CN117801525B (en) * | 2023-12-30 | 2024-06-04 | 东莞市振中塑胶有限公司 | High-performance composite heat stabilizer and preparation method thereof |
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