CN102381981B - Method for synthesizing antioxidant for gasoline - Google Patents
Method for synthesizing antioxidant for gasoline Download PDFInfo
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- CN102381981B CN102381981B CN2011102674185A CN201110267418A CN102381981B CN 102381981 B CN102381981 B CN 102381981B CN 2011102674185 A CN2011102674185 A CN 2011102674185A CN 201110267418 A CN201110267418 A CN 201110267418A CN 102381981 B CN102381981 B CN 102381981B
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Abstract
The invention discloses a method for preparing an antioxidant for gasoline, wherein p-phenylenediamine and 2-bromobutane serve as raw materials; in an aprotic solvent system, a supported solid base catalyst serves as an acid binding agent and N, N' di-sec-butyl p-phenylenediamine is synthesized with high selectivity; and the purity of a product can be further increased after a crude product is extracted by utilizing n-hexane. According to the invention, the supported solid base catalyst adopting Al2O3 as a supporter serves as the acid binding agent and alkali waste liquid is not produced; the supporter can be conveniently recycled; the aprotic solvent is adopted; the dissolubility of the raw materials in the solvent is good; and therefore, the usage amount of the solvent can be decreased, the reaction temperature is decreased, the reaction time is shortened and the reaction selectivity is increased. The method has the advantages of mild reaction condition, simpleness and convenience for operation, cleaness in production process, higher product yield and more than 95% of product purity.
Description
Technical field
The present invention relates to a kind of synthetic method of antioxidant for gasoline, definite a kind of N, N '-di-sec-butyl-p-phenyl enediamine's the synthetic method of saying.
Background technology
N, N '-di-sec-butyl-p-phenyl enediamine (DBPD) is the widely used gasoline oxidation inhibitor of a class, DBPD can extend induction period of gasoline effectively, reduce gasoline and generate carbon distribution in combustion processes, prevent from stopping up sparking plug and pipeline road, DBPD can be with gasoline with arbitrarily than miscible, compare outstanding advantage is arranged with conventional solid oxidation inhibitor, it adds convenient, antioxidant property is strong, add micro-DBPD can play extraordinary antioxidant effect, the general antiozonidate of DBPD or rubber and plastics, can prevent that organic compound from going bad because of oxidation in addition.
The method that at present DBPD can produce in batches is mainly reductive amination method (US3384663), and reduction amination can improve the selectivity of product, but still inevitably can produce the by product that aromatic ring, ketone are reduced; Hydrogenation catalyst generally mostly is transition metal or its mixture in addition, increases production cost, and temperature of reaction, pressure are all higher, the production process complicated operation, and cost is higher.
Directly the synthetic Ursol D of N-alkylation also has relevant report, ([Zhang Xiaoyun, Liu Yali, Xia Hongdao, refining of petroleum and chemical industry, 35(5), 2004,32-34.) but feed stock conversion is not high, poor selectivity, aftertreatment technology complexity, and use alkali lye to increase burden as acid binding agent to follow-up sewage disposal, can not meet environmental requirement.The domestic main dependence import of this product at present, and expensive, for this reason, DBPD has potential huge economic benefit.
Summary of the invention
The object of the present invention is to provide that a kind of reaction conditions is simple, selectivity good, yield is high, environmental protection and easy-operating preparation N, N '-di-sec-butyl-p-phenyl enediamine's method.
Realize that technical solution of the present invention is: under nitrogen protection; select non-protonic solvent; take Ursol D and 2-n-butyl bromide directly carries out the N-alkylated reaction as raw material; with load-type solid as in acid binding agent and the by product HBr generated, at suitable temperature, through the suitable reaction times; preparation N; N '-di-sec-butyl-p-phenyl enediamine, with obtaining the product N that purity is higher, N '-di-sec-butyl-p-phenyl enediamine after the n-hexane extraction crude product.
In described method, the preparation method of load-type solid is: metal-salt is through deionized water dissolving, add carrier impregnation 1-2 days, underpressure distillation water outlet in 50-60 ℃, normal pressure 100-140 ℃ of dry 4-6h, in 400-500 ℃ of calcining 8-12h, can make load-type solid in the immigration muffle furnace.
The preferred KF of described metal-salt, KCl, KNO
3, the preferred Al of described carrier
2O
3, the preferred 25-40w% of the charge capacity of metal-salt.
The mass ratio of described load-type solid and Ursol D consumption is (3-5) preferably: 1.
The preferred 1-Methyl-2-Pyrrolidone of described non-protonic solvent, dimethyl sulfoxide (DMSO), the preferred 20:1 of the mol ratio of aprotic solvent and Ursol D.
In described method, the mol ratio of 2-n-butyl bromide and Ursol D is (1-4) preferably: 1, and preferably 50～80 ℃ of temperature of reaction, preferred 8-10h of reaction times.
Compared with prior art, its remarkable advantage is in the present invention:
The method and traditional N-hydrocarbylation method have significant advantage: (1) present method adopts Al
2O
3As acid binding agent, can not produce alkali wasteliquid, and carrier can conveniently be recycled for the load-type solid of carrier.(2) present method adopts non-protonic solvent, and the solvability of raw material in solvent is good, can reduce the usage quantity of solvent; And can reduce temperature of reaction, Reaction time shorten, raising reaction preference in this reaction system.(3) adopting Ursol D and 2-n-butyl bromide is raw material, and operation is simple, and mild condition is convenient to suitability for industrialized production.(4) to adopt normal hexane be extraction agent to present method aftertreatment technology, and the solvability difference of major-minor product in extraction agent is obvious, can improve the purity of target product, and solution is divided into obviously, solved the use ether for the unconspicuous deficiency of extraction agent layering.
The accompanying drawing explanation
Fig. 1 is N prepared by synthetic method of the present invention, N '-di-sec-butyl-p-phenyl enediamine's mass spectrum (a is the one-level mass spectrum, and b is second order ms figure).
Fig. 2 is N prepared by synthetic method of the present invention, N '-di-sec-butyl-p-phenyl enediamine's gas chromatogram.
Embodiment
Following examples illustrate application of the present invention, but do not represent restriction processing condition of the present invention.
In the present invention, the preparation method of load-type solid is method commonly known in the art.
N of the present invention, N '-di-sec-butyl-p-phenyl enediamine's synthetic method comprises the following steps:
1. prepare load-type solid: metal-salt is dissolved in deionized water, adds Al
2O
3Carrier, dipping 24-48h, underpressure distillation water outlet in the time of 50-60 ℃, normal pressure 100-140 ℃ of dry 4-6h, in 400-500 ℃ of calcining 8-12h, can make load-type solid in the immigration muffle furnace; The charge capacity of metal-salt is 25-40w%;
2. add non-protonic solvent, Ursol D and above-mentioned load-type solid in reaction vessel, the rising temperature, in 50～80 ℃, under agitation slowly drips the 2-n-butyl bromide, continues reaction 8-10h;
3. after reaction finishes, stop heating, filtering reacting liquid, recycle Al
2O
3, the solvent in Distillation recovery filtrate, obtain N, N '-di-sec-butyl-p-phenyl enediamine's crude product;
4. with n-hexane extraction above-mentioned crude product 2-3 time, merging normal hexane layer, use deionized water wash, then uses anhydrous sodium sulfate drying normal hexane layer, obtains N, N '-di-sec-butyl-p-phenyl enediamine after distilling out normal hexane.
At first example 1. prepares the KF/Al that charge capacity is 40w%
2O
3: 20gKF is dissolved in the 100ml deionized water, adds 30gAl
2O
3Carrier, dipping 24h, underpressure distillation water outlet in the time of 60 ℃, 100 ℃ of dry 4h of normal pressure, in 400 ℃ of calcining 8h, can make KF/Al in the immigration muffle furnace
2O
3.Then add successively Ursol D 1.08g (10mmol), 1-Methyl-2-Pyrrolidone 20mL(200mmol in the 100mL there-necked flask), add the KF/Al that charge capacity is 40w%
2O
33.24g(mass ratio, Ursol D: KF/Al
2O
3=1:3); Be warming up to 80 ℃, under agitation slowly drip 2-n-butyl bromide 4.8mL (40mmol), dropwise in 2h, after reaction 8h, stop heating; Filtering reacting liquid, recycle Al
2O
3, the solvent 1-Methyl-2-Pyrrolidone in Distillation recovery filtrate, obtain N, N '-di-sec-butyl-p-phenyl enediamine's crude product; Use n-hexane extraction N, N '-di-sec-butyl-p-phenyl enediamine's crude product 2-3 time, merge the normal hexane layer, uses deionized water wash, and with anhydrous sodium sulfate drying normal hexane layer, obtains N, N '-di-sec-butyl-p-phenyl enediamine 2.11g after distilling out normal hexane.It is 95.1% that gas chromatographic purity detects, yield 95.5%.
At first example 2. prepares the KF/Al that charge capacity is 40w%
2O
3: 20gKF is dissolved in the 100ml deionized water, adds 30gAl
2O
3Carrier, dipping 48h, underpressure distillation water outlet in the time of 50 ℃, 140 ℃ of dry 6h of normal pressure, in 500 ℃ of calcining 12h, can make KF/Al in the immigration muffle furnace
2O
3.React the synthesis step experiment condition with embodiment 1,2-n-butyl bromide add-on 3.6mL(30mmol) replace 4.8mL (40mmol), obtain N, N '-di-sec-butyl-p-phenyl enediamine 2.03g, purity is 96.0%, yield 91.9%.
At first example 3. prepares the KF/Al that charge capacity is 40w%
2O
3: 20gKF is dissolved in the 100ml deionized water, adds 30gAl
2O
3Carrier, dipping 36h, underpressure distillation water outlet in the time of 55 ℃, 120 ℃ of dry 5h of normal pressure, in 450 ℃ of calcining 10h, can make KF/Al in the immigration muffle furnace
2O
3.React the synthesis step experiment condition with embodiment 1,2-n-butyl bromide add-on 1.2mL(10mmol) replace 4.8mL (40mmol), obtain N, N '-di-sec-butyl-p-phenyl enediamine 0.89g, purity is 96.0%, yield is 40.3%.
Example 4. repeats the method for embodiment 1, and in synthesis step, temperature of reaction replaces 80 ℃ with 65 ℃, and the reaction times replaces 8h with 9h, and other condition is constant, obtains N after reaction, N '-di-sec-butyl-p-phenyl enediamine 2.01g, and purity is 96.1%, yield is 90.9%.
Example 5. repeats the method for embodiment 1, and in synthesis step, temperature of reaction replaces 80 ℃ with 50 ℃, and the reaction times replaces 8h with 10h, and other condition is constant, obtains N after reaction, N '-di-sec-butyl-p-phenyl enediamine 1.95g, and purity is 96.0%, yield is 88.2%.
At first example 6. prepares the KF/Al that charge capacity is 30w%
2O
3: 12.9gKF is dissolved in the 100ml deionized water, adds 30gAl
2O
3Carrier, dipping 24h, underpressure distillation water outlet in the time of 60 ℃, 100 ℃ of dry 4h of normal pressure, in 400 ℃ of calcining 8h, can make KF/Al in the immigration muffle furnace
2O
3.Reaction synthesis step experiment condition is with embodiment 1, but the KF/Al that is 30w% by charge capacity
2O
34.32g(mass ratio, Ursol D: KF/Al
2O
3=1:4) replace the KF/Al that charge capacity is 40w%
2O
33.24g(mass ratio, Ursol D: KF/Al
2O
3=1:3), all the other experiment conditions are constant, obtain N after reaction, N '-di-sec-butyl-p-phenyl enediamine 2.03g, and purity is 95.4%, yield 91.8%.
At first example 7. prepares the KF/Al that charge capacity is 25w%
2O
3: 10gKF is dissolved in the 100ml deionized water, adds 30gAl
2O
3Carrier, dipping 24h, underpressure distillation water outlet in the time of 60 ℃, 100 ℃ of dry 4h of normal pressure, in 400 ℃ of calcining 8h, can make KF/Al in the immigration muffle furnace
2O
3.Reaction synthesis step experiment condition is with embodiment 1, but the KF/Al that is 25w% by charge capacity
2O
35.4g(mass ratio, Ursol D: KF/Al
2O
3=1:5) replace the KF/Al that charge capacity is 40w%
2O
33.24g(mass ratio, Ursol D: KF/Al
2O
3=1:3), all the other experiment conditions are constant, obtain N after reaction, N '-di-sec-butyl-p-phenyl enediamine 2.08g, and purity is 95.0%, yield 94.1%.
Example 8. repeats the method for embodiment 1, and in synthesis step, solvent replaces 1-Methyl-2-Pyrrolidone with dimethyl formamide, and other condition is constant, obtains N after reaction, N '-di-sec-butyl-p-phenyl enediamine 1.92g.It is 95.1% that gas chromatographic purity detects, yield 86.0%.
Example 9. repeats the method for embodiment 1, supported solid KCl/Al in synthesis step
2O
3Replace KF/Al
2O
3, other condition is constant, obtains N after reaction, N '-di-sec-butyl-p-phenyl enediamine 0.93g.It is 95.2% that gas chromatographic purity detects, yield 42.0%.
Example 10. repeats the method for embodiment 1, supported solid KNO in synthesis step
3/ Al
2O
3Replace KF/Al
2O
3, other condition is constant, obtains N after reaction, N '-di-sec-butyl-p-phenyl enediamine 0.43g.It is 95.0% that gas chromatographic purity detects, yield 19.4%.
Claims (4)
1. the synthetic method of an antioxidant for gasoline is characterized in that carrying out according to the following steps:
Step 1, add non-protonic solvent 1-methyl-2 pyrrolidone or dimethyl formamide, Ursol D and load-type solid in reaction vessel, wherein said load-type solid is made by following steps: by metal-salt KF, KCl or KNO
3Be dissolved in deionized water, add carrier A l
2O
3, the charge capacity of metal-salt is 25-40w%, dipping 24-48h, and underpressure distillation in 50-60 ℃, normal pressure 100-140 ℃ of dry 4-6h, move in muffle furnace and make load-type solid after 400-500 ℃ of calcining 8-12h;
After step 2, agitation and dropping 2-n-butyl bromide, reacted;
Step 3, filtering reacting liquid, the solvent in Distillation recovery filtrate, obtain N, N '-di-sec-butyl-p-phenyl enediamine's crude product;
Step 4, extract above-mentioned crude product and then after distillation extraction liquid, obtain N, N '-di-sec-butyl-p-phenyl enediamine.
2. the synthetic method of a kind of antioxidant for gasoline according to claim 1, the mol ratio that it is characterized in that the non-protonic solvent described in step 1 and Ursol D is 20:1, and the mass ratio of described load-type solid and Ursol D consumption is (3-5): 1.
3. the synthetic method of a kind of antioxidant for gasoline according to claim 1, the mol ratio that it is characterized in that the 2-n-butyl bromide described in step 2 and Ursol D is (1-4): 1, temperature of reaction is 50-80 ℃, the reaction times is 8-12h.
4. the synthetic method of a kind of antioxidant for gasoline according to claim 1, is characterized in that in step 4, extraction agent used is normal hexane.
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| CN2011102674185A CN102381981B (en) | 2011-09-09 | 2011-09-09 | Method for synthesizing antioxidant for gasoline |
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| CN114349645A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Method for purifying p-phenylenediamine and application thereof |
| CN112876840A (en) * | 2021-02-28 | 2021-06-01 | 刘水臣 | PA (polyamide) environment-friendly plastic with high impact strength and preparation method thereof |
| CN114671777B (en) * | 2022-03-18 | 2023-09-19 | 天津利安隆新材料股份有限公司 | Preparation method of amide antioxidant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4372811A (en) * | 1980-05-07 | 1983-02-08 | Mo Och Domsjo Aktiebolag | Alkaline oxygen delignification and bleaching of cellulose pulp in the presence of aromatic diamines |
| CN1370768A (en) * | 2001-12-16 | 2002-09-25 | 辽宁天合精细化工股份有限公司 | Synthesis of N,N'-di-sec-alkyl p-phenylenediamine |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123148A (en) * | 1981-01-26 | 1982-07-31 | Sumitomo Chem Co Ltd | Production of secondary amine by reductive alkylation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4372811A (en) * | 1980-05-07 | 1983-02-08 | Mo Och Domsjo Aktiebolag | Alkaline oxygen delignification and bleaching of cellulose pulp in the presence of aromatic diamines |
| CN1370768A (en) * | 2001-12-16 | 2002-09-25 | 辽宁天合精细化工股份有限公司 | Synthesis of N,N'-di-sec-alkyl p-phenylenediamine |
Non-Patent Citations (5)
| Title |
|---|
| JP昭57-123148A 1982.07.31 |
| KF/Al2O3催化1,2,3-苯并三唑N-烷基化;张洪奎 等;《厦门大学学报》;19990131;第38卷(第1期);第77-78页实验部分2) KF/Al2O3的制备、第78页实验部分3)1,2,3-苯并三唑烷基化的一般方法 * |
| 乙醇溶剂法合成N,N′-二仲丁基对苯二胺的研究;刘公召 等;《化学世界》;20091231(第8期);第489页1.4合成步骤、2.2摩尔比对产物收率的影响第2段 * |
| 刘公召等.乙醇溶剂法合成N N′-二仲丁基对苯二胺的研究.《化学世界》.2009 |
| 张洪奎 等.KF/Al2O3催化1,2,3-苯并三唑N-烷基化.《厦门大学学报》.1999,第38卷(第1期),第77-78页实验部分2) KF/Al2O3的制备、第78页实验部分3)1,2,3-苯并三唑烷基化的一般方法. |
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