Non-hazardous chemical styrene green retarder and preparation method thereof

Abstract

The present application relates to the technical field of retarder, and provides a non-dangerous chemical styrene green retarder and a preparation method thereof, wherein the styrene green retarder comprises the following raw materials in parts by weight: quinone compound 40-60 parts, 2,6-di-tert-butyl phenol 20-30 parts, modified calcium lignosulfonate 1-3 parts, diethylene glycol butyl ether 4-7 parts, and solvent oil 50-70 parts; and further comprises a synergist 1-3 parts. The styrene green retarder provided by the present application has a high polymerization inhibition effect and does not contain nitrogen and meets the use requirements of non-dangerous chemicals.

Description

Technical Field

[0001] This invention relates to the field of retarders, and in particular to a green retarder for styrene, a non-hazardous chemical, and its preparation method. Background Technology

[0002] Styrene, as an important basic organic chemical raw material, is widely used in the synthesis of polymer materials, coatings, pesticides, pharmaceuticals, dyes, and other fields. In industrial production, styrene is mainly obtained by dehydrogenation of ethylbenzene followed by distillation purification. However, styrene monomers are chemically reactive and can undergo self-polymerization at room temperature, with the polymerization rate increasing at higher temperatures. This not only leads to blockages in pipelines, reboilers, and other equipment, causing plant shutdowns, but also reduces the yield and purity of styrene products, seriously affecting the economic benefits of production.

[0003] To prevent styrene monomers from polymerizing during storage and transportation, polymerization inhibitors or retarders are commonly used as key additives in industry. Currently, the retarders used in the market all use ethylbenzene to dissolve 2,4-dinitro-6-sec-butylphenol (DNBP) or solid quinones. However, 2,4-dinitro-6-sec-butylphenol is a highly toxic chemical that causes serious environmental pollution. Furthermore, ethylbenzene has extremely low flash point and is a highly flammable liquid. Products using ethylbenzene as a solvent are all hazardous chemicals. Therefore, such nitrogen-containing, low-flash point retarders have been gradually abandoned by the market.

[0004] Patent CN 110878209 A discloses an environmentally friendly polymerization inhibitor for styrene distillation systems and its application. This environmentally friendly polymerization inhibitor is a compound of component A, component B, component C, and an organic solvent. Component A is 4-benzylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, component B is 2,6-di-tert-butylphenol, component C is ethyl propargyl propionate, and the organic solvent is ethylbenzene or styrene. Although this polymerization inhibitor already meets the requirements of being nitrogen-free and not producing NO... X The requirements are met, and it has a good polymerization inhibition effect and effectively reduces tar viscosity. However, the polymerization inhibitor used in this application is still ethylbenzene or styrene, which still cannot meet the requirements for use as a high flash point, non-hazardous chemical.

[0005] Therefore, there is an urgent need in the market for a green styrene retarder that has a high efficiency in inhibiting polymerization and is nitrogen-free and meets the requirements for use as a non-hazardous chemical. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention discloses a green styrene retarder, a non-hazardous chemical, which uses quinone compounds and 2,6-di-tert-butylphenol as the main components. Modified calcium lignosulfonate and synergistic agents are added, along with diethylene glycol butyl ether and solvent oil, so that the green styrene retarder has a high-efficiency polymerization inhibition effect, is nitrogen-free, and meets the requirements for use as a non-hazardous chemical.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a non-hazardous chemical styrene green retarder, which, by weight, comprises the following raw materials: 40-60 parts of quinone compounds, 20-30 parts of 2,6-di-tert-butylphenol, 1-3 parts of modified calcium lignosulfonate, 4-7 parts of diethylene glycol butyl ether, and 50-70 parts of solvent oil.

[0008] In some embodiments of the present invention, the quinone compound is 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one.

[0009] In some embodiments of the present invention, the method for preparing the modified calcium lignin sulfonate includes the following steps: Calcium lignosulfonate was added to N,N-dimethylacetamide and stirred. Triethylamine was added under an inert atmosphere at 0-4℃, followed by trans-8-methyl-6-nonanoyl chloride and a polymerization inhibitor. The mixture was heated to 80-90℃ and stirred for 12-20 hours. The mixture was then filtered, washed, centrifuged, and dried to obtain modified calcium lignosulfonate.

[0010] In some embodiments of the present invention, the mass ratio of calcium lignosulfonate to trans-8-methyl-6-nonanoyl chloride is 1:(1-1.5).

[0011] Preferably, the mass ratio of calcium lignosulfonate to trans-8-methyl-6-nonanoyl chloride is 1:1.3.

[0012] Although the quinone compound 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one has a good retardation effect and meets the requirements of being a non-hazardous chemical and nitrogen-free, its solid powder form and the density difference between it and the solvent oil lead to poor dispersibility.

[0013] Calcium lignosulfonate is nitrogen-free and its flash point meets the requirements for non-hazardous chemicals. It can be added as a dispersant to retarder components to promote more uniform distribution of quinone compounds and effectively retard polymerization. However, calcium lignosulfonate is highly hydrophilic, and its polarity differs from that of other substances in the retarder, limiting its dispersing effect. The applicant selected trans-8-methyl-6-nonanoyl chloride as the esterifying agent to prepare modified calcium lignosulfonate through esterification. Trans-8-methyl-6-nonanoyl chloride introduces carbon-carbon double bonds, alkyl long chains, and branched structures into the modified calcium lignosulfonate structure, effectively improving its hydrophobicity and steric hindrance, thus enhancing its dispersibility of quinone substances and improving the polymerization inhibition effect of the styrene green retarder.

[0014] In some embodiments of the present invention, the synergist is further included in parts by weight by 1-3 parts.

[0015] In some embodiments of the present invention, the synergist is a mixture of triphenyl phosphite and pentaerythritol diisodecyl diphosphite.

[0016] In some embodiments of the present invention, the mass ratio of the triphenyl phosphite to the pentaerythritol diisodecyl diphosphite is 1:(0.5-1).

[0017] The applicant selected a mixture of triphenyl phosphite and pentaerythritol diisodecyl diphosphite as a synergist, which can decompose the hydroperoxides generated in the styrene system and chelate metal ions, thereby inhibiting the catalytic effect of metal ions on styrene polymerization. Furthermore, triphenyl phosphite and pentaerythritol diisodecyl diphosphite can also protect 2,6-di-tert-butylphenol and quinone compounds, thus synergistically reducing polymer formation. Even further, the applicant controls the ratio of triphenyl phosphite and pentaerythritol diisodecyl diphosphite to achieve a better balance between the rigid benzene ring π-stacking and the flexible long-chain hydrophobic association in the structure, thereby synergistically forming a more stable composite network structure, making the synergist's effect more stable and long-lasting. In addition, there are hydrogen bond and van der Waals interactions between the synergist and modified calcium lignin sulfonate, making the overall retarder more stable and improving the retarding effect.

[0018] In some embodiments of the present invention, the solvent oil is a heavy aromatic hydrocarbon.

[0019] Preferably, the heavy aromatic hydrocarbon is heavy aromatic hydrocarbon S-1800.

[0020] In another aspect, this invention provides a method for preparing a non-hazardous chemical styrene green retarder, comprising the following steps: S1. Add solvent oil to reaction vessel 1, heat and start the stirring device, first add 2,6-di-tert-butylphenol, then add quinone compounds, use ultrasound to assist stirring, and obtain a solution for later use. S2. Add 2,6-di-tert-butylphenol to reaction vessel 2, preheat, add modified calcium lignosulfonate, sonicate, and obtain a dispersion for later use. S3. Mix the solution from step S1 and the dispersion from step S2, add the synergist, stir, and filter to remove undissolved impurities to obtain the non-hazardous chemical styrene green retarder.

[0021] In some embodiments of the present invention, the heating temperature of step S1 is 72-80°C.

[0022] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention discloses a non-hazardous chemical styrene green retarder, which is mainly composed of quinone compounds and 2,6-di-tert-butylphenol. Modified calcium lignosulfonate and synergistic agents are designed to be added, along with diethylene glycol butyl ether and solvent oil. Through the synergistic effect between the components, the styrene green retarder has a high-efficiency polymerization inhibition effect and is nitrogen-free and meets the requirements for use as a non-hazardous chemical.

[0023] (2) In this invention, a modified calcium lignosulfonate was designed and synthesized. Trans-8-methyl-6-nonanoyl chloride was selected to modify the calcium lignosulfonate. Trans-8-methyl-6-nonanoyl chloride introduced carbon-carbon double bonds, alkyl long chains and branched structures into the modified calcium lignosulfonate structure, which effectively improved the hydrophobicity and steric hindrance of calcium lignosulfonate, so that its dispersibility could play a better role, thereby making the polymerization inhibition effect of styrene green retarder better.

[0024] (3) The present invention selects a mixture of triphenyl phosphite and pentaerythritol diisodecyl phosphite in a specific ratio as a synergistic synergist, thereby playing a synergistic role in reducing the amount of polymer generated. Furthermore, there is an interaction between the synergistic synergist and the modified calcium lignosulfonate through hydrogen bonds and van der Waals forces, which makes the overall retarder more stable and thus improves the retardation effect. Detailed Implementation

[0025] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0026] In the following examples and comparative examples, except for the modified calcium lignosulfonate, all other compound monomers and related reagents used were commercially available. Among them, the calcium lignosulfonate was purchased from Jinan Zhongcheng Chemical Co., Ltd.

[0027] Preparation Example 1 The method for synthesizing modified calcium lignosulfonate A includes the following steps: Add 10g of calcium lignosulfonate to 50g of N,N-dimethylacetamide and stir for 30min. Under a nitrogen atmosphere and at 0℃, add 2g of triethylamine, then add 13g of trans-8-methyl-6-nonanoyl chloride (added dropwise over 30min while stirring) and 0.01g of hydroquinone. Heat to 85℃ and stir for 16h. Filter and wash (wash successively with 0.1mol / L hydrochloric acid aqueous solution and deionized water until neutral and the nitrogen content is <0.1wt%). Centrifuge at 8000rpm for 15min and dry at 60℃ for 12h to obtain modified calcium lignosulfonate A.

[0028] Preparation Example 2 Modified calcium lignosulfonate B is implemented in the same way as modified calcium lignosulfonate A, except that the mass of trans-8-methyl-6-nonanoyl chloride is replaced with 8.5g.

[0029] Preparation Example 3 Modified calcium lignosulfonate C is implemented in the same way as modified calcium lignosulfonate A, except that the mass of trans-8-methyl-6-nonanoyl chloride is replaced with 16g.

[0030] Example 1 A non-hazardous chemical, a green styrene retarder, comprises the following raw materials by weight: 50 parts of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 25 parts of 2,6-di-tert-butylphenol, 2 parts of modified calcium lignosulfonate A, 2 parts of synergist, 6 parts of diethylene glycol butyl ether, and 60 parts of heavy aromatic hydrocarbon S-1800.

[0031] The synergistic agent is a mixture of triphenyl phosphite and pentaerythritol diisodecyl diphosphite in a mass ratio of 1:0.8.

[0032] The preparation method of the non-hazardous chemical styrene green retarder in this embodiment includes the following steps: S1. Add solvent oil to reaction vessel 1, heat to 75°C and start the stirring device. First add 2,6-di-tert-butylphenol, then add quinone compounds. Sonicate for 15 minutes and stir for 30 minutes to obtain a solution for later use. S2. Add 2,6-di-tert-butylphenol to reaction vessel 2, preheat to 60°C, add modified calcium lignosulfonate A, sonicate for 20 min, and obtain a dispersion for later use. S3. Mix the solution from step S1 and the dispersion from step S2, add the synergist, stir for 1 hour, filter to remove undissolved impurities, and obtain the non-hazardous chemical styrene green retarder.

[0033] Example 2 A non-hazardous chemical, a green styrene retarder, comprises the following raw materials by weight: 40 parts of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 20 parts of 2,6-di-tert-butylphenol, 1 part of modified calcium lignosulfonate A, 1 part of synergist, 4 parts of diethylene glycol butyl ether, and 50 parts of heavy aromatic hydrocarbon S-1800.

[0034] The synergistic agent is a mixture of triphenyl phosphite and pentaerythritol diisodecyl diphosphite in a mass ratio of 1:0.5.

[0035] The preparation method of the non-hazardous chemical styrene green retarder in this embodiment includes the following steps: S1. Add solvent oil to reaction vessel 1, heat to 72°C and start the stirring device. First add 2,6-di-tert-butylphenol, then add quinone compounds. Sonicate for 15 minutes and stir for 30 minutes to obtain a solution for later use. S2. Add 2,6-di-tert-butylphenol to reaction vessel 2, preheat to 60°C, add modified calcium lignosulfonate A, sonicate for 20 min, and obtain a dispersion for later use. S3. Mix the solution from step S1 and the dispersion from step S2, add the synergist, stir for 1 hour, filter to remove undissolved impurities, and obtain the non-hazardous chemical styrene green retarder.

[0036] Example 3 A non-hazardous chemical, a green styrene retarder, comprising the following raw materials by weight: 60 parts of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 30 parts of 2,6-di-tert-butylphenol, 3 parts of modified calcium lignosulfonate A, 3 parts of synergist, 7 parts of diethylene glycol butyl ether, and 70 parts of heavy aromatic hydrocarbon S-1800.

[0037] The synergistic agent is a mixture of triphenyl phosphite and pentaerythritol diisodecyl diphosphite in a mass ratio of 1:1.

[0038] The preparation method of the non-hazardous chemical styrene green retarder in this embodiment includes the following steps: S1. Add solvent oil to reaction vessel 1, heat to 80°C and start the stirring device. First add 2,6-di-tert-butylphenol, then add quinone compounds. Sonicate for 15 minutes and stir for 30 minutes to obtain a solution for later use. S2. Add 2,6-di-tert-butylphenol to reaction vessel 2, preheat to 60°C, add modified calcium lignosulfonate A, sonicate for 20 min, and obtain a dispersion for later use. S3. Mix the solution from step S1 and the dispersion from step S2, add the synergist, stir for 1 hour, filter to remove undissolved impurities, and obtain the non-hazardous chemical styrene green retarder.

[0039] Example 4 A non-hazardous chemical, a green styrene retarder, comprises the following raw materials by weight: 50 parts of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 25 parts of 2,6-di-tert-butylphenol, 2 parts of modified calcium lignosulfonate A, 6 parts of diethylene glycol butyl ether, and 60 parts of heavy aromatic hydrocarbon S-1800.

[0040] The preparation method of the non-hazardous chemical styrene green retarder in this embodiment includes the following steps: S1. Add solvent oil to reaction vessel 1, heat to 75°C and start the stirring device. First add 2,6-di-tert-butylphenol, then add quinone compounds. Sonicate for 15 minutes and stir for 30 minutes to obtain a solution for later use. S2. Add 2,6-di-tert-butylphenol to reaction vessel 2, preheat to 60°C, add modified calcium lignosulfonate A, sonicate for 20 min, and obtain a dispersion for later use. S3. Mix the solution from step S1 and the dispersion from step S2, stir for 1 hour, and filter to remove undissolved impurities to obtain the non-hazardous chemical styrene green retarder.

[0041] Example 5 This embodiment provides a non-hazardous chemical styrene green retarder and its preparation method. The specific implementation method is the same as that in Example 1, except that the synergistic synergist is a mixture of triphenyl phosphite and pentaerythritol diisodecyl diphosphite in a mass ratio of 1:0.3.

[0042] Example 6 This embodiment provides a non-hazardous chemical styrene green retarder and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that the synergistic synergist is a mixture of triphenyl phosphite and pentaerythritol diisodecyl diphosphite in a mass ratio of 1:1.2.

[0043] Example 7 This embodiment provides a non-hazardous chemical styrene green retarder and its preparation method. The specific implementation method is the same as in Example 1, except that an equal amount of triphenyl phosphite is used to replace the synergist.

[0044] Example 8 This embodiment provides a non-hazardous chemical styrene green retarder and its preparation method. The specific implementation method is the same as in Example 1, except that an equal amount of pentaerythritol diisodecyl diphosphite is used to replace the synergist.

[0045] Example 9 This embodiment provides a non-hazardous chemical styrene green retarder and its preparation method. The specific implementation method is the same as that in Embodiment 1, except that modified calcium lignosulfonate A is replaced by an equal amount of modified calcium lignosulfonate B.

[0046] Example 10 This embodiment provides a non-hazardous chemical styrene green retarder and its preparation method. The specific implementation method is the same as in Embodiment 1, except that modified calcium lignosulfonate A is replaced by modified calcium lignosulfonate C in an equal amount.

[0047] Comparative Example 1 This embodiment provides a non-hazardous chemical styrene green retarder and its preparation method. The specific implementation method is the same as in Embodiment 1, except that calcium lignosulfonate is used to replace modified calcium lignosulfonate A in an equal amount.

[0048] Performance testing The polymerization inhibition performance of the non-hazardous chemical styrene green retarder in Examples 1-10 and Comparative Example 1 was tested, and the test results are shown in Table 1.

[0049] Commercially available styrene was alkali washed and distilled to obtain pure styrene without any polymerization inhibitors. 500 ppm of the non-hazardous chemical styrene green polymerization retarder of Examples 1-10 and Comparative Example 1 was added to the pure styrene and reacted at 120°C for 30 min and 60 min respectively under nitrogen protection. Then, styrene polymer was precipitated with methanol or ethanol, filtered, dried, and weighed. The mass percentage of styrene polymer relative to the pure styrene was calculated as the polymer content. The amount of styrene green retarder added is expressed in parts per million (ppm); the polymer content is expressed as a percentage (%).

[0050] Table 1 As shown in Table 1, the polymer content in Examples 1-3 of this invention is relatively low. Furthermore, the increase in polymer content in Examples 1-3 is smaller than that in Examples 4-10 and Comparative Example 1 as the reaction time increases from 30 min to 60 min, indicating that the styrene green retarders in Examples 1-3 all exhibit good polymerization inhibition performance. Specifically, Example 4 (without synergist), Examples 5-8 (changing the ratio of the synergist triphenyl phosphite and pentaerythritol diisodecyl diphosphite, or using a single triphenyl phosphite / pentaerythritol diisodecyl diphosphite to replace the synergist), all resulted in a decrease in synergistic polymerization inhibition to varying degrees, leading to an increase in polymer content. Examples 9-10 (changing the modification ratio of trans-8-methyl-6-nonanoyl chloride to calcium lignin sulfonate during the synthesis of modified calcium lignin sulfonate), and Comparative Example 1 (equal substitution of modified calcium lignin sulfonate A with calcium lignin sulfonate), all showed worse polymerization inhibition performance of the styrene green retarders, with significantly increased polymer content.

[0051] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A non-hazardous chemical, a green styrene retarder, characterized in that, By weight, the styrene green retarder comprises the following raw materials: 40-60 parts of quinone compounds, 20-30 parts of 2,6-di-tert-butylphenol, 1-3 parts of modified calcium lignosulfonate, 4-7 parts of diethylene glycol butyl ether, 50-70 parts of solvent oil, and 1-3 parts of synergist. The quinone compound is 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one; The preparation method of the modified calcium lignin sulfonate includes the following steps: Calcium lignosulfonate was added to N,N-dimethylacetamide and stirred. Triethylamine was added under an inert atmosphere at 0-4℃, followed by trans-8-methyl-6-nonanoyl chloride and a polymerization inhibitor. The mixture was heated to 80-90℃ and stirred for 12-20 hours. The mixture was then filtered, washed, centrifuged, and dried to obtain modified calcium lignosulfonate. The mass ratio of calcium lignosulfonate to trans-8-methyl-6-nonanoyl chloride is 1:(1-1.5). The synergistic agent is a mixture of triphenyl phosphite and pentaerythritol diisodecyl diphosphite; The mass ratio of the triphenyl phosphite to pentaerythritol diisodecyl diphosphite is 1:(0.5-1).

2. The non-hazardous chemical styrene green retarder according to claim 1, characterized in that, The solvent oil is a heavy aromatic hydrocarbon.

3. A method for preparing a green styrene retarder, a non-hazardous chemical, according to any one of claims 1-2, characterized in that, Includes the following steps: S1. Add solvent oil to reaction vessel 1, heat and start the stirring device, first add 2,6-di-tert-butylphenol, then add quinone compounds, use ultrasound to assist stirring, and obtain a solution for later use. S2. Add 2,6-di-tert-butylphenol to reaction vessel 2, preheat, add modified calcium lignosulfonate, sonicate, and obtain a dispersion for later use. S3. Mix the solution from step S1 and the dispersion from step S2, add the synergist, stir, and filter to remove undissolved impurities to obtain the non-hazardous chemical styrene green retarder.

4. The method for preparing the non-hazardous chemical styrene green retarder according to claim 3, characterized in that, The heating temperature in step S1 is 72-80℃.

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