Ash removal agent and application thereof, and gray removal method of polyolefin material
By using an ash removal agent prepared by mixing amino compounds, active carbonyl compounds and solvents, the problem of difficulty in reducing the ash content in low-ash polyolefin materials is solved, and efficient and rapid metal ash removal is achieved, which is suitable for the application of low-ash polyolefin materials.
Patent Information
- Application Number
- CN202510216703.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-26
- Publication Date
- 2025-05-30
AI Technical Summary
The prior art is difficult to effectively reduce the ash content of low ash polyolefin materials, especially when it encounters difficulty in directly producing polyolefin resins that meet the requirements.
The ash removal agent obtained by mixing an amino compound, an active carbonyl compound and a solvent and undergoing heating and reflux reaction is used. The deletion agent complexes with the metal ash by multiple active sites to achieve its efficient removal.
The ash removal agent can significantly improve the removal rate and rate of metal ash, and is easy to separate from the polyolefin material, and can reduce the ash content of the polyolefin material without affecting normal production stability.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of deashing treatment of polyolefin materials, and particularly relates to an ash removing agent, its application and a method for removing ash of polyolefin materials. Background Art
[0002] At present, low-ash polyolefin materials such as polyethylene (PE), polypropylene (PP) and ethylene-α olefin copolymers are widely used in industries such as medical devices, food, electrical appliances, and transportation due to their excellent mechanical strength and processing performance. Among low-ash polyolefin materials, polypropylene is favored because of its wide application range, large demand and high added value.
[0003] However, since the ash requirement of low-ash polyolefin materials is generally less than 50 ppm, it is difficult to directly produce polyolefin resins that meet the requirements. Therefore, the research and development of a new type of ash removing agent to reduce the ash of polyolefin materials is of great significance for expanding the application of low-ash polyolefin materials. Summary of the Invention
[0004] In view of this, the technical problem to be solved by the present invention is to provide an ash removing agent, its application and a method for removing ash of polyolefin materials. The ash removing agent can effectively remove metal ash in polyolefin materials, has a relatively fast ash removal rate, and the deashing agent is easy to separate from polypropylene materials.
[0005] To achieve the above object, the technical solution adopted by the present invention is as follows:
[0006] The present invention provides an ash removing agent, which is obtained by mixing an amino compound, an active carbonyl compound and a solvent and carrying out a heating reflux reaction;
[0007] The amino compound is selected from amino acids, amines, alkaloids, hydrazines, hydrazones or acylhydrazines;
[0008] The active carbonyl compound is selected from one or more of acetone, propanedione, acetylacetone, benzoylacetone, cyclopentanedione, dibenzoylmethane, trifluoroacetylacetone, salicylaldehyde, p-bromobenzaldehyde, ethyl acetoacetate, p-aminobenzoic acid; more preferably acetylacetone, benzoylacetone, salicylaldehyde, p-aminobenzoic acid, ethyl acetoacetate or trifluoroacetylacetone.
[0009] The temperature of the heating reflux reaction is 85°C - 110°C. In some specific embodiments of the present invention, it is 90°C or 95°C or 100°C or 105°C.
[0010] Preferably, the molar ratio of the amino compound to the active carbonyl compound is (0.1 - 10):1; more preferably (0.1 - 2):1. In some specific embodiments of the present invention, it is preferably 0.5:1 or 1:1.
[0011] Preferably, the amino acid is selected from one or more of glycine, alanine, lysine, phenylalanine, glutamic acid, and cysteine;
[0012] Preferably, the amine is selected from one or more of o-phenylenediamine, aniline, octylamine, triethylamine, triethanolamine, n-hexylamine, ethanolamine, and propanediamine; more preferably aniline, octylamine, n-hexylamine, propanediamine, or ethanolamine.
[0013] Preferably, the alkaloid is selected from one or more of amphetamine, trazodone, and opipramol;
[0014] Preferably, the hydrazone is selected from one or more of acetone hydrazone, 2,4-dinitrophenylhydrazone, acetaldehyde hydrazone, cyclohexanone hydrazone, and vanillin hydrazone.
[0015] Preferably, the hydrazide is selected from one or more of acetyl hydrazide, benzoyl hydrazide, isonicotinic hydrazide, succinyl hydrazide, oxalyl hydrazide, and p-nitrobenzoyl hydrazide.
[0016] More preferably, the amino compound is aniline and the active carbonyl compound is acetylacetone;
[0017] Or, the amino compound is octylamine and the active carbonyl compound is benzoylacetone;
[0018] Or, the amino compound is n-hexylamine and the active carbonyl compound is salicylaldehyde;
[0019] Or, the amino compound is propanediamine and the active carbonyl compound is p-aminobenzoic acid;
[0020] Or, the amino compound is ethanolamine and the active carbonyl compound is ethyl acetoacetate;
[0021] Or, the amino compound is n-hexylamine and the active carbonyl compound is trifluoroacetylacetone.
[0022] Preferably, the solvent is selected from one or more of absolute ethanol, n-hexane, ethyl acetate, methanol, N,N-dimethylformamide, and dimethyl sulfoxide; more preferably absolute ethanol, ethyl acetate, and methanol. In some specific embodiments of the present invention, absolute ethanol is preferred.
[0023] Preferably, after the heating reflux reaction is completed, the post-treatments of precipitation, filtration, washing, and drying are further included in sequence.
[0024] The present invention has no special limitation on the methods of the above precipitation, filtration, and drying, and any methods well-known to those skilled in the art can be used.
[0025] The present invention also provides the application of the above ash removing agent in the ash removal of polyolefin materials.
[0026] Preferably, after the ash removal of the polyolefin material, the ash content is 5 - 20 ppm.
[0027] The present invention also provides a method for removing ash from polyolefin materials, comprising the following steps:
[0028] (1) Mix the ash removing agent according to any one of claims 1 - 5 with a solvent to obtain an eluent;
[0029] (2) Wash the polyolefin material with the eluent to obtain the polyolefin material after ash removal;
[0030] Wherein, preferably, the concentration of the ash removing agent in the eluent is 0.1 - 50 g / L; more preferably 5 - 50 g / L. Further preferably 5 g / L or 10 g / L or 15 g / L or 30 g / L.
[0031] Preferably, the ratio of the eluent to the polyolefin material is 1 L:(1 - 1000) g; more preferably 1 L:(100 - 700) g. Further preferably 1 L:100 g or 1 L:200 g or 1 L:300 g or 1 L:400 g or 1 L:500 g or 1 L:600 g.
[0032] Preferably, the washing temperature is 80°C - 100°C; more preferably 80°C or 90°C or 100°C.
[0033] Preferably, after the washing in step (2), it further includes filtration and secondary washing;
[0034] Preferably, the solvent used for the secondary washing is selected from one or more of n - pentane, isopentane, n - hexane, petroleum ether, n - heptane, n - octane, n - decane.
[0035] Preferably, the temperature for the secondary washing is 10°C - 80°C; more preferably room temperature. The room temperature is preferably 10 - 30°C.
[0036] Compared with the prior art, the ash removing agent provided by the present invention is obtained by mixing an amino compound, an active carbonyl compound and a solvent and carrying out a heating reflux reaction; the amino compound is selected from amino acids, amines, alkaloids, hydrazines, hydrazones or acylhydrazines; the active carbonyl compound is selected from one or more of acetone, propanedione, acetylacetone, benzoylacetone, cyclopentanedione, dibenzoylmethane, trifluoroacetylacetone, salicylaldehyde, p-bromobenzaldehyde, ethyl acetoacetate; the temperature of the heating reflux reaction is 85°C - 110°C. The ash removing agent has multiple active sites and can fully complex with metal ash, thereby effectively removing the metal ash in the polyolefin material. And the ash removing agent has a high metal ion removal rate and a relatively fast removal rate, and has the advantages of a large adsorption capacity, being widely used without being limited by the basic ash content of the polyolefin material, and being easy to separate from the polyolefin material. In addition, the preparation of the ash removing agent is simple, not limited by the basic production process, and does not affect the stability and continuity of normal production. Detailed Description of the Invention
[0037] In order to further illustrate the present invention, the ash removing agent provided by the present invention, its application and the method for removing the gray scale of the polyolefin material will be described in detail below with reference to the embodiments.
[0038] Example 1
[0039] 1. Dissolve 9.2 mL of aniline in 20 mL of ethanol to obtain an aniline solution, dissolve 9.9 mL of acetylacetone in 20 mL of ethanol to obtain an acetylacetone solution, slowly drop the aniline solution into the acetylacetone solution, reflux at 95°C for 3 - 4 h, let stand overnight, filter, wash with ethanol, and dry in vacuum to obtain ash remover A.
[0040] 2. Take 2.5 g of ash remover A and dissolve it in 500 mL of ethanol to obtain an A eluent. Take 0.1 kg of polyolefin resin powder with an original ash content of 200 ppm in a washing kettle, add 0.5 L of the A eluent, and wash at 80°C for 1 h.
[0041] 3. Filter the polyolefin resin powder in 2 and discard the filtrate. Perform a secondary wash with n-hexane at a temperature of 20°C, rinse the filtered polyolefin powder, and dry in vacuum to obtain a low-ash polyolefin resin powder.
[0042] 4. Take 0.2 - 0.5 g of the powder in 3, perform microwave digestion and then detect it by ICP-MS, and characterize the ash of the polyolefin resin by the sum of elemental oxides.
[0043] Example 2
[0044] 1. Dissolve 16.4 mL of octylamine in 20 mL of methanol solution, dissolve 16.5 g of benzoylacetone in 100 mL of methanol solution, slowly drip the octylamine methanol solution into the benzoylacetone methanol solution, reflux at 100 °C for 2 - 4 h, let stand overnight, filter, wash with ethanol, and dry in vacuum to obtain deashing agent B.
[0045] 2. Take 15.0 g of deashing agent B and dissolve it in 1 L of methanol to obtain an elution solvent. Take 0.5 kg of polyolefin resin powder with an original ash content of 100 ppm in a washing kettle, add 1.5 L of elution solvent, and wash at 90 °C for 2 h.
[0046] 3. Filter the polyolefin resin powder in 2, discard the filtrate. Conduct a secondary wash with n - hexane at a temperature of 25 °C, rinse the filtered polyolefin powder, and dry in vacuum to obtain a low - ash polyolefin resin powder.
[0047] 4. Take 0.2 - 0.5 g of the powder in 3, after microwave digestion, detect by ICP - MS, and characterize the ash content of the polyolefin resin by the sum of elemental oxides.
[0048] Example 3
[0049] 1. Dissolve 12.6 mL of n - hexylamine in 20 mL of ethanol solution, dissolve 12.2 g of salicylaldehyde in 20 mL of ethanol solution, slowly drip the n - hexylamine solution into the salicylaldehyde solution, reflux at 100 °C for 6 - 8 h, let stand overnight, filter, wash with ethanol, and dry in vacuum to obtain deashing agent C.
[0050] 2. Take 100.0 g of deashing agent C and dissolve it in 3.3 L of absolute ethanol. Take 1.0 kg of polyolefin resin powder with an original ash content of 500 ppm in a washing kettle, add 3.3 L of elution solvent, and wash at 90 °C for 2 h.
[0051] 3. Filter the polyolefin resin powder in 2, discard the filtrate. Conduct a secondary wash with n - pentane at a temperature of 20 °C, rinse the filtered polyolefin powder, and dry in vacuum to obtain a low - ash polyolefin resin powder.
[0052] 4. Take 0.2 - 0.5 g of the powder in 3, after microwave digestion, detect by ICP - MS, and characterize the ash content of the polyolefin resin by the sum of elemental oxides.
[0053] Example 4
[0054] 1. Dissolve 4.5 mL of propylenediamine in 20 mL of ethanol solution, dissolve 13.7 g of p - aminobenzoic acid in 100 mL of ethanol, slowly drip the p - aminobenzoic acid solution into the propylenediamine solution, reflux at 95 °C for 5 - 6 h, let stand overnight, filter, wash with ethanol, and dry in vacuum to obtain deashing agent D.
[0055] 2. Dissolve 30.0 g of deashing agent D in 3 L of absolute ethanol to obtain a deashing agent solution. Take 1.0 kg of polyolefin resin powder with an original ash content of 150 ppm in a washing kettle, add 3 L of elution solvent, and wash at 100 °C for 1 h.
[0056] 3. Filter the polyolefin resin powder in 2, discard the filtrate. Wash it twice with isopentane at a temperature of 20 °C, rinse the filtered polyolefin powder, and dry it under vacuum to obtain a polyolefin resin powder with low ash content.
[0057] 4. Take 0.2 - 0.5 g of the powder in 3, perform microwave digestion and then detect it by ICP-MS, and characterize the ash content of the polyolefin resin by the sum of elemental oxides.
[0058] Example 5
[0059] 1. Dissolve 6.9 g of ethanolamine in 20 mL of ethanol, dissolve 13.0 g of ethyl acetoacetate in 20 mL of ethanol, slowly drop the ethanol solution of ethyl acetoacetate into the ethanol solution of ethanolamine, reflux at 90 °C for 3 - 4 h, let it stand overnight, filter, wash with ethanol, and dry under vacuum to obtain deashing agent E.
[0060] 2. Dissolve 10.0 g of deashing agent E in 3 L of absolute ethanol. Take 0.5 kg of polyolefin resin powder with an original ash content of 50 ppm in a washing kettle, add 3 L of elution solvent, and wash at 90 °C for 2 h.
[0061] 3. Filter the polyolefin resin powder in 2, discard the filtrate. Wash it twice with petroleum ether at a temperature of 20 °C, rinse the filtered polyolefin powder, and dry it under vacuum to obtain a polyolefin resin powder with low ash content.
[0062] 4. Take 0.2 - 0.5 g of the powder in 3, perform microwave digestion and then detect it by ICP-MS, and characterize the ash content of the polyolefin resin by the sum of elemental oxides.
[0063] Example 6
[0064] 1. Dissolve 12.6 mL of n-hexylamine in 50 mL of ethanol, dissolve 15.4 g of trifluoroacetylacetone in 50 mL of ethanol, slowly drop the ethanol solution of trifluoroacetylacetone into the ethanol solution of n-hexylamine, reflux at 100 °C for 8 - 10 h, let it stand overnight, filter, wash with ethanol, and dry under vacuum to obtain deashing agent F.
[0065] 2. Dissolve 100.0 g of deashing agent F in 3 L of absolute ethanol. Take 2.0 kg of polyolefin resin powder with an original ash content of 100 ppm in a washing kettle, add 3 L of elution solvent, and wash at 100 °C for 0.5 h.
[0066] 3. Filter the polyolefin resin powder in 2 and discard the filtrate. Perform secondary washing with n-heptane, rinse the filtered polyolefin powder at 20 °C for 3 - 5 times, and dry it under vacuum to obtain a polyolefin resin powder with low ash content.
[0067] 4. Take 0.2 - 0.5 g of the powder in 3, perform microwave digestion and then detect it by ICP-MS, and characterize the ash content of the polyolefin resin by the sum of elemental oxides.
[0068] Comparative Example 1
[0069] 1. The difference from Example 1 is that the deashing agent A was not synthesized by adding acetylacetone and aniline. Dissolve 2.7 g of aniline in 500 mL of ethanol to obtain the A-1 eluent. Take 0.1 kg of polyolefin resin powder with an original ash content of 200 ppm in a washing kettle, add 0.5 L of elution solvent, and wash at 80 °C for 1 h.
[0070] 2. Filter the polyolefin resin powder in 2 and discard the filtrate. Perform secondary washing with n-hexane, rinse the filtered polyolefin powder at 20 °C, and dry it under vacuum to obtain a polyolefin resin powder with low ash content.
[0071] 3. Take 0.2 - 0.5 g of the powder in 3, perform microwave digestion and then detect it by ICP-MS, and characterize the ash content of the polyolefin resin by the sum of elemental oxides.
[0072] Comparative Example 2
[0073] 1. The difference from Example 1 is that the deashing agent was not synthesized by adding aniline and acetylacetone. Dissolve 2.8 g of acetylacetone in 500 mL of ethanol to obtain the A-2 eluent. Take 0.1 kg of polyolefin resin powder with an original ash content of 200 ppm in a washing kettle, add 0.5 L of elution solvent, and wash at 80 °C for 1 h.
[0074] 2. Filter the polyolefin resin powder in 2 and discard the filtrate. Perform secondary washing with n-hexane, rinse the filtered polyolefin powder at 20 °C, and dry it under vacuum to obtain a polyolefin resin powder with low ash content.
[0075] 3. Take 0.2 - 0.5 g of the powder in 3, perform microwave digestion and then detect it by ICP-MS, and characterize the ash content of the polyolefin resin by the sum of elemental oxides.
[0076] Comparative Example 3
[0077] 1. The difference from Example 1 is that the deashing agent was not synthesized by aniline and acetylacetone, but directly added. Dissolve 2.8 g of acetylacetone and 2.7 g of aniline in 500 mL of ethanol to obtain the A-3 eluent. Take 0.1 kg of polyolefin resin powder with an original ash content of 200 ppm in a washing kettle, add 0.5 L of elution solvent, and wash at 80 °C for 1 h.
[0078] 2. Filter the polyolefin resin powder in 2 and discard the filtrate. Perform secondary washing with n-hexane at a temperature of 20 °C, rinse the filtered polyolefin powder, and dry it under vacuum to obtain a polyolefin resin powder with low ash content.
[0079] 3. Take 0.2 - 0.5 g of the powder in 3, perform microwave digestion and then detect it by ICP-MS, and characterize the ash content of the polyolefin resin by the sum of elemental oxides.
[0080] Estimate the ash content of the polypropylene sample using various elements. The specific results of the ash content of the products obtained in Examples 1 - 6 and Comparative Examples 1 - 3 are as follows:
[0081] Table 1 Ash content results of the products obtained in Examples 1 - 6 and Comparative Examples 1 - 3
[0082]
[0083]
[0084] The ash content test in Table 1 can refer to GB / T 38291-2019 Determination of lead content in plastic materials.
[0085] The results in Table 1 above show that the ash removal effect of the ash removal agent prepared in Examples 1 - 6 of the present invention is significantly better than that of Comparative Examples 1 - 3. This indicates that the ash removal agent obtained by mixing an amino compound, an active carbonyl compound and a solvent and performing a heating reflux reaction in the present invention has better performance than the ash removal effect of an eluent containing only an amino compound, or only an active carbonyl compound, or a mixture of an amino compound and an active carbonyl compound without reacting the two.
[0086] The description of the above examples is only used to help understand the method and its core idea of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims
1. An ash removal agent, characterized in that: It is obtained by mixing an amino compound, an active carbonyl compound and a solvent and heating and refluxing the mixture; The amino compound is selected from amino acids, amines, alkaloids, hydrazines, hydrazones or hydrazides; The active carbonyl compound is selected from one or more of acetone, propanedione, acetylacetone, benzoylacetone, cyclopentanedione, dibenzoylmethane, trifluoroacetylacetone, salicylaldehyde, p-bromobenzaldehyde, and ethyl acetoacetate; The temperature of the heating reflux reaction is 85°C-110°C.
2. The ash removal agent according to claim 1, characterized in that The molar ratio of the amino compound to the active carbonyl compound is (0.1-10):
1.
3. The ash removal agent according to claim 1, characterized in that The amino acid is selected from one or more of glycine, alanine, lysine, phenylalanine, glutamic acid, and cysteine; The amine is selected from one or more of o-phenylenediamine, aniline, octylamine, triethylamine, triethanolamine, n-hexylamine, ethanolamine, and propylenediamine; The alkaloid is selected from one or more of amphetamine, trazodone, and opipramol; The hydrazone is selected from one or more of acetone hydrazone, 2,4-dinitrophenylhydrazone, acetaldehyde hydrazone, cyclohexanone hydrazone, and vanillin hydrazone; The hydrazide is selected from one or more of acetohydrazide, benzohydrazide, isonicotinylhydrazide, succinylhydrazide, oxalohydrazide and p-nitrobenzoylhydrazide.
4. The ash removal agent according to claim 1, characterized in that The solvent is selected from one or more of anhydrous ethanol, n-hexane, ethyl acetate, methanol, N,N-dimethylamide, and dimethyl sulfoxide.
5. The ash removal agent according to claim 1, characterized in that After the heating reflux reaction is completed, the post-treatments include precipitation, filtration, washing and drying.
6. Use of the ash removing agent according to any one of claims 1 to 5 in the ash removal of polyolefin materials.
7. The use according to claim 6, characterized in that: The ash content of the polyolefin material after ash removal is 5-20 ppm.
8. A method for removing grayscale from polyolefin materials, characterized in that: The following steps are involved: (1) mixing the ash removal agent according to any one of claims 1 to 5 with a solvent to obtain an eluent; (2) washing the polyolefin material with an eluent to obtain a polyolefin material after grayscale removal; Wherein, the concentration of the ash removal agent in the eluent is 0.1-50 g / L; The ratio of eluent to polyolefin material is 1L:(1-1000)g; The washing temperature is 80℃-100℃.
9. The method for removing grayscale from polyolefin materials according to claim 8, characterized in that: The step (2) further comprises filtering and secondary washing after washing; The solvent used in the secondary washing is selected from one or more of n-pentane, isopentane, n-hexane, petroleum ether, n-heptane, n-octane and n-decane.
10. The method for removing grayscale from polyolefin materials according to claim 9, characterized in that: The temperature of the secondary washing is 10°C-80°C.