Polymerization inhibitor for polymerization of butadiene unsaturated olefin and preparation method thereof
By using materials such as 2,5-bis(2,4,6-tri-tert-butylanilin)-1,4-benzoquinone and other materials, the effect of benzoquinone-based polymer inhibitors on butadiene is solved. The best problem is that the polymerization of styrene and butadiene is effectively inhibited, and the polymerization resistance effect is significantly improved.
Patent Information
- Application Number
- CN202411464422.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-19
- Publication Date
- 2025-01-10
AI Technical Summary
Benzenequinone polymerization inhibitors have poor polymerization resistance on unsaturated olefins such as butadiene, and it is difficult to effectively inhibit their self-polymerization reaction.
2,5-bis(2,4,6-tri-tert-butylaniline)-1,4-benzoquinone is used as the main resisting polymerization agent, combined with the antioxidant 2,5-di-tert-butyl hydroquinone, Diethyl hydroxylamine and diethylene glycol butyl ether form a polymerization inhibitor containing a hindered amine structure through specific preparation methods and compounding processes, which are used to inhibit the polymerization of styrene and butadiene.
The polymerization resistance effect of styrene and butadiene is significantly improved, free radicals are captured through multiple tert-butyl hindered amine structures, which significantly inhibits the polymerization of unsaturated olefins and improves the purity and chemical quality of the compound.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polymerization inhibitors, in particular to a polymerization inhibitor for butadiene unsaturated olefin polymerization and a preparation method thereof. Background Art
[0002] Unsaturated olefins such as styrene and butadiene are important chemical raw materials and intermediates. They are widely used in polymer resins, plastics, rubbers, etc. However, unsaturated olefin compounds such as styrene and butadiene are highly active. When exposed to high temperatures or light during storage, they are prone to self-polymerization, which will affect the purity and chemical quality of the compounds. Usually, adding inhibitors to unsaturated olefins can effectively inhibit their self-polymerization.
[0003] Quinone-based polymerization inhibitors have the advantages of being diverse, cheap, readily available, and having high polymerization inhibition efficiency, and have good practical applications in the polymerization inhibition of unsaturated olefins. Hindered amine compounds have a strong effect of capturing free radicals and have broad application prospects in light stabilizers, polymerization inhibitors, etc. The present invention aims to prepare a novel quinone-based polymerization inhibitor containing a hindered amine structure, which is used to inhibit the polymerization of unsaturated olefins such as styrene and butadiene. Summary of the invention
[0004] The invention solves the following technical problems: the problem that benzoquinone polymerization inhibitors have poor inhibition effect on butadiene and the like.
[0005] The technical solution provided by the present invention is: a polymerization inhibitor for unsaturated olefin polymerization, comprising 10-30 parts by weight of a main polymerization inhibitor, 1-5 parts by weight of an antioxidant, 1-5 parts by weight of diethylhydroxylamine, 20-40 parts by weight of diethylene glycol butyl ether, 1-3 parts by weight of methanol, and 20-40 parts by weight of a solvent.
[0006] The main inhibitors are benzoquinone, p-benzoquinone, and 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone; The structural formula of 2-(N,N-diethylaminophenyl)amine-1,4-benzoquinone is formula (I): Formula (I).
[0007] Furthermore, the antioxidant is p-tert-butylcatechol or 2,5-di-tert-butylhydroquinone.
[0008] Furthermore, the solvent is any one or a combination of deionized water, acetonitrile or xylene.
[0009] Furthermore, the preparation method of 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone is as follows: N,N-dimethylformamide, 2,5-diiodo-1,4-benzoquinone, 2,4,6-tri-tert-butylaniline and a catalyst are added to a reaction bottle, water and ethyl acetate are added after the reaction, the mixture is allowed to stand for stratification after shaking, the aqueous phase is removed, anhydrous sodium sulfate is added to the ethyl acetate organic phase for drying, the mixture is filtered, the filtrate is distilled under reduced pressure, and the mixture is separated by silica gel column chromatography, a solution of petroleum ether and ethyl acetate is used as an eluent, and gradient elution is performed to obtain 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone.
[0010] Furthermore, the molar ratio of 2,5-diiodo-1,4-benzoquinone, 2,4,6-tri-tert-butylaniline, and catalyst is 1:(2-2.6):(6-8).
[0011] Furthermore, the catalyst is potassium fluoride or cesium fluoride.
[0012] Furthermore, the reaction temperature is 60-90°C, and the reaction time is 2-8h.
[0013] Furthermore, a method for preparing a polymerization inhibitor for unsaturated olefin polymerization is as follows: a solvent, methanol, a main polymerization inhibitor, an antioxidant, diethylhydroxylamine, and diethylene glycol butyl ether are added into a reaction bottle, and the mixture is stirred and mixed to obtain a polymerization inhibitor.
[0014] Technical effect: The present invention uses 2,5-diiodo-1,4-benzoquinone and 2,4,6-tri-tert-butylaniline as reactants and potassium fluoride or cesium fluoride as a catalyst to obtain a novel 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone containing a hindered amine structure through a substitution reaction.
[0015] The present invention uses benzoquinone, p-benzoquinone or 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone as the main component of the polymerization inhibitor, and compounding with antioxidant 2,5-di-tert-butylhydroquinone, diethylhydroxylamine, diethylene glycol butyl ether, methanol and solvent to obtain a new type of polymerization inhibitor for unsaturated olefin polymerization, which has a good inhibitory effect on unsaturated olefins such as styrene. Among them, 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone contains multiple tert-butyl hindered amine structures ( ), which has a strong ability to capture free radicals, is introduced into the structure of p-benzoquinone and can synergistically capture free radicals with p-benzoquinone, significantly inhibiting the polymerization of unsaturated olefins such as styrene and butadiene, showing an excellent inhibitory effect. DETAILED DESCRIPTION
[0016] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0017] Example 1 Add 2 g of solvent xylene, 0.1 g of methanol, 1 g of main polymerization inhibitor p-benzoquinone, 0.4 g of antioxidant 2,5-di-tert-butylhydroquinone, 0.1 g of diethylhydroxylamine, and 4 g of diethylene glycol butyl ether into a reaction bottle, stir and mix to obtain a polymerization inhibitor.
[0018] Example 2 Add 2 g of solvent ionized water, 0.3 g of methanol, 1 g of main inhibitor benzoquinone, 0.5 g of antioxidant 2,5-di-tert-butylhydroquinone, 0.5 g of diethylhydroxylamine, and 3 g of diethylene glycol butyl ether into a reaction bottle, stir and mix to obtain an inhibitor.
[0019] Example 3 Add 6mL N,N-dimethylformamide, 0.5mmol 2,5-diiodo-1,4-benzoquinone (CAS registration number is 203579-53-7), 1.2mmol 2,4,6-tri-tert-butylaniline (CAS registration number is 961-38-6), and 3mmol catalyst potassium fluoride to the reaction bottle, heat to 70°C, react for 6h, add water and ethyl acetate, shake and let stand for stratification, remove the aqueous phase, add anhydrous sodium sulfate to the ethyl acetate organic phase for drying, filter, distill the filtrate under reduced pressure, separate by silica gel column chromatography, use a solution of petroleum ether and ethyl acetate as the eluent, and gradient elute to obtain 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone. The reaction formula is: ; Add 2 g of solvent acetonitrile, 0.22 g of methanol, 1 g of main polymerization inhibitor 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone, 0.3 g of antioxidant p-tert-butylcatechol, 0.1 g of diethylhydroxylamine, and 2 g of diethylene glycol butyl ether into a reaction bottle, stir and mix to obtain a polymerization inhibitor.
[0020] Example 4 Add 4 mL of N,N-dimethylformamide, 0.5 mmol of 2,5-diiodo-1,4-benzoquinone, 1 mmol of 2,4,6-tri-tert-butylaniline, and 3 mmol of catalyst cesium fluoride to the reaction bottle, heat to 90°C, react for 2 h, add water and ethyl acetate, shake and let stand to separate, remove the aqueous phase, add anhydrous sodium sulfate to the ethyl acetate organic phase, dry, filter, distill the filtrate under reduced pressure, separate by silica gel column chromatography, use a solution of petroleum ether and ethyl acetate as eluent, and gradient elute to obtain 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone.
[0021] Add 2 g of solvent acetonitrile, 0.3 g of methanol, 2 g of main polymerization inhibitor 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone, 0.1 g of antioxidant p-tert-butylcatechol, 0.2 g of diethylhydroxylamine, and 2 g of diethylene glycol butyl ether into a reaction bottle, stir and mix to obtain a polymerization inhibitor.
[0022] Example 5 Add 6 mL of N,N-dimethylformamide, 0.5 mmol of 2,5-diiodo-1,4-benzoquinone, 1.3 mmol of 2,4,6-tri-tert-butylaniline, and 4 mmol of catalyst potassium fluoride to the reaction bottle, heat to 60°C, react for 8 h, add water and ethyl acetate, shake and let stand to separate, remove the aqueous phase, add anhydrous sodium sulfate to the ethyl acetate organic phase, dry, filter, distill the filtrate under reduced pressure, separate by silica gel column chromatography, use a solution of petroleum ether and ethyl acetate as eluent, and perform gradient elution to obtain 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone.
[0023] Add 4 g of solvent acetonitrile, 0.1 g of methanol, 3 g of main polymerization inhibitor 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone, 0.1 g of antioxidant p-tert-butylcatechol, 0.1 g of diethylhydroxylamine, and 4 g of diethylene glycol butyl ether into a reaction bottle, stir and mix to obtain a polymerization inhibitor.
[0024] Add styrene and inhibitor to the reaction bottle, control the amount of inhibitor to 50-300 ppm of styrene, heat to 80℃, react for 0.5 h, cool and add methanol to precipitate, filter and dry the precipitate, weigh and calculate the styrene conversion rate W, W=(m-m1)÷m×100%, m is the mass of styrene, m1 is the mass of precipitate. The lower the conversion rate, the better the inhibitory effect.
[0025] Table 1 Styrene conversion test
[0026] Add styrene and inhibitor to the reaction bottle, control the amount of inhibitor to 300 ppm of styrene, heat to 80°C, react for 0.5-2 h, cool and add methanol to precipitate, filter and dry the precipitate, weigh it, and calculate the styrene conversion rate W, W = (m-m1) ÷ m × 100%, m is the mass of styrene, m1 is the mass of the precipitate. The lower the conversion rate, the better the inhibitory effect.
[0027] Table 2 Styrene conversion at different reaction times
[0028] According to GB / T 17828-1999, the peroxide content of butadiene is determined as follows: butadiene, oxygen and polymerization inhibitor are introduced into the test device, the mass of oxygen is 800ppm of the mass of butadiene, and the mass of polymerization inhibitor is 100ppm of the mass of butadiene. At the same time, rusty iron nails are added to accelerate the generation of butadiene peroxide. After being placed at 25°C for 48 hours, the peroxide content in butadiene is determined. The lower the peroxide content, the better the polymerization inhibition effect.
[0029] Table 3 Determination of peroxide content in butadiene
[0030] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A polymerization inhibitor, characterized in that The polymerization inhibitor comprises 10-30 parts by weight of a main polymerization inhibitor, 1-5 parts by weight of an antioxidant, 1-5 parts by weight of diethylhydroxylamine, 20-40 parts by weight of diethylene glycol butyl ether, 1-3 parts by weight of methanol, and 20-40 parts by weight of a solvent; The main polymerization inhibitor is benzoquinone, p-benzoquinone or 2,5-di(2,4,6-tri-tert-butylanilino)-1,4-benzoquinone; The structural formula of the 2-(N,N-diethylaminophenyl)amine-1,4-benzoquinone is formula (I): Formula (I).
2. The polymerization inhibitor according to claim 1, characterized in that The antioxidant is p-tert-butylcatechol or 2,5-di-tert-butylhydroquinone.
3. The polymerization inhibitor according to claim 1, characterized in that The solvent is any one or a combination of deionized water, acetonitrile or xylene.
4. The polymerization inhibitor according to claim 1, characterized in that The preparation method of 2,5-di(2,4,6-tri-tert-butylaniline)-1,4-benzoquinone is as follows: N,N-dimethylformamide, 2,5-diiodo-1,4-benzoquinone, 2,4,6-tri-tert-butylaniline and a catalyst are added into a reaction bottle, water and ethyl acetate are added after the reaction, the mixture is allowed to stand for stratification after shaking, the aqueous phase is removed, anhydrous sodium sulfate is added to the ethyl acetate organic phase for drying, the mixture is filtered, the filtrate is distilled under reduced pressure, and the mixture is separated by silica gel column chromatography, a solution of petroleum ether and ethyl acetate is used as an eluent, and gradient elution is performed to obtain 2,5-di(2,4,6-tri-tert-butylaniline)-1,4-benzoquinone.
5. The polymerization inhibitor according to claim 3, characterized in that: The molar ratio of the 2,5-diiodo-1,4-benzoquinone, 2,4,6-tri-tert-butylaniline and the catalyst is 1:(2-2.6):(6-8).
6. The polymerization inhibitor according to claim 3, characterized in that: The catalyst is potassium fluoride or cesium fluoride.
7. The polymerization inhibitor according to claim 3, characterized in that: The reaction temperature is 60-90°C and the reaction time is 2-8h.
8. A method for preparing the polymerization inhibitor according to any one of claims 1 to 6, the preparation method comprising: adding a solvent, methanol, a primary polymerization inhibitor, an antioxidant, diethylhydroxylamine, and diethylene glycol butyl ether into a reaction bottle, stirring and mixing, and obtaining the polymerization inhibitor.
9. Use of the polymerization inhibitor obtained by the preparation method according to claim 8 in the polymerization inhibition of butadiene and styrene unsaturated olefins.