CN102061203A - High-temperature diesel antioxidant and preparation method thereof - Google Patents
High-temperature diesel antioxidant and preparation method thereof Download PDFInfo
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- CN102061203A CN102061203A CN2009102303807A CN200910230380A CN102061203A CN 102061203 A CN102061203 A CN 102061203A CN 2009102303807 A CN2009102303807 A CN 2009102303807A CN 200910230380 A CN200910230380 A CN 200910230380A CN 102061203 A CN102061203 A CN 102061203A
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- diesel oil
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Abstract
The invention belongs to a diesel additive, and in particular relates to a phosphite compound high-temperature diesel antioxidant and a preparation method thereof. The preparation method of a trialkyl diphosphite diesel antioxidant comprises the following steps of: reacting pentaerythritol with phosphorus trichloride to generate dichloropentaerythritol diphosphite; and reacting the dichloropentaerythritol diphosphite with long-chain alkane alcohol to generate the trialkyl diphosphite diesel antioxidant. The antioxidant has the prominent effects of preventing oxidation, improving color and the like. The novel trialkyl phosphite compound has low toxicity and volatility and high compatibility with diesel, is environmental-friendly, and has a wide application prospect in the field of diesel additives.
Description
Technical field
The invention belongs to diesel-dope, relate in particular to high temperature diesel oil antioxidant of a kind of phosphite ester compound and preparation method thereof.
Background technology
In several big problem that present alive interface is faced, energy dilemma has become and has caused a human deep class problem of paying attention to.And diesel engine is owing to it has simple structure, moment of torsion is big, thermo-efficiency is high, the fuel availability advantages of higher, add the advantage of diesel engine aspect energy-conservation and CO2 discharging, be that all Thermal Motors that comprise petrol motor can't replace, therefore, advanced miniature high-speed diesel motor, its discharging has reached European III number standard, becomes " environmental-friendly engine ", has become the power set of American-European many zero-mileage cars at present.Cause the interior demand of world wide to increase day by day thus, the diesel fuel oil specification of quality is also being improved day by day diesel oil.
Well-known catalytic diesel oil in storage process because the polymerization of the unstable component of assorted elements such as unsaturated component that exists in the oil and nitrogenous, sulphur, DeR makes that the oil product color is sharply deepened, colloid increases fast and generates with sediment, oil quality descends, and has a strong impact on use properties.In order to prevent the diesel oil colloid sediment that oxidation generates in storage process, the colloid that in use is dissolved in the fuel deposits intake system because of carburretion and atomizing, influence the normal operation of engine, need to add the package stability that various oxidation inhibitor improve diesel oil.Using oxidation inhibitor at present mainly is various shielding phenol and aromatic amine compounds, as 2, and 6-di-t-butyl-4-cresols and N, N-two sec-butylbenzene diamines etc.The mechanism of action of these compounds is that more active hydrogen atom contained in its molecule can be supplied with the peroxide radical that generates in oxidising process, make its inactivation, thereby interruption oxidative chain reactions, oxidation induction period is prolonged, but influence easily after phenols and the amine oxidation diesel oil color and luster with and toxicity problem but be the problem that can not be ignored.
The phosphite ester kind antioxidant that grew up in the last few years is subjected to people's favor all the more with its particular performances.More complicated on the mechanism of action, it is generally acknowledged that phosphite ester compound mainly is as a kind of hydrogen peroxide decomposition agent, it can be with the hydroperoxide decomposition that generates in the diesel oil oxidation process, be meant the compound that transforms into non-activity, thereby stop or delay oxidising process, and itself is oxidized to phosphoric acid ester.
P(OR
1)
3+ROOH→ROH+(R
1O)
3P＝O
R·+O
2→ROO·
Phosphite ester compound can improve stability and the security in diesel oil processing, transportation and the storage process, and certain light stability is arranged.In addition, phosphite ester compound is as helping antioxidant and the common use of main anti-oxidant that good synergy is also arranged.U.S. Pat 3,951,912 (1975), Japanese Patent JP53,11944 and at periodical Plastic World, 1976,34 (9), 42 grades all have the record to this kind antioxidant.The phosphite ester kind antioxidant of having developed at present mainly comprises:
(1) Wytox 312
(2) phosphorous acid hexichol one monooctyl ester
Triphenylphosphate
But still there is shortcoming in above-mentioned phosphorous acid esters diesel oil antioxidant, such as be applied to toxic substance such as phenol in the building-up process, easily separate out, facile hydrolysis, have much room for improvement with the diesel oil intermiscibility, anti-oxidant efficient is not very high.
Summary of the invention
The present invention is for solving a kind of novel good trialkyl phosphite compounds of shortcoming synthetic such as above-mentioned phosphorous acid esters diesel oil antioxidant toxicity is big, poor with the diesel oil intermiscibility, efficient is low.This compounds has kept the advantage of above phosphorous acid and so on diesel oil antioxidant, and in molecule, introduced chain alkyl or alkoxy chain replaces phenyl, under the prerequisite that does not change its antioxidant property, improved the solubleness of this kind antioxidant in diesel oil, greatly reduce its toxicity and hydrolytic resistance, almost do not have residue after the burning.
The invention provides a kind of diesel oil antioxidant of novel diphosphite trialkyl ester class, its structure is:
Wherein the n value is preferably 10,12 in the molecular formula, and 14,16.Its corresponding raw material is respectively lauryl alcohol, tetradecyl alcohol, and hexadecanol, stearyl alcohol or substituted radical are polyoxyethylene glycol.
The preparation method of above-mentioned diphosphite trialkyl ester class diesel oil antioxidant is: generate the dichloro pentaerythritol bis-phosphite by tetramethylolmethane and phosphorus trichloride reaction earlier, and then generate diphosphite trialkyl ester class diesel oil antioxidant with the reaction of long chain alkane alcohol.
Concrete preparation process is as follows:
(1) in the four-hole boiling flask that thermometer, dropping funnel and reflux exchanger are housed, is metered into tetramethylolmethane, solvent, catalyzer respectively, it is 200 rev/mins that stirring velocity is set, drip phosphorus trichloride, the dropping time is 1-3 hour, controlled temperature 50-100 ℃, absorb the hydrogen chloride gas that generates with the tail gas absorption bottle, reaction does not generate to there being hydrogen chloride gas, promptly gets intermediate dichloro pentaerythritol bis-phosphite; Wherein the mol ratio of tetramethylolmethane and phosphorus trichloride was at 1: 2 to 1: 5, and catalyst consumption is at the 1%-5% of tetramethylolmethane amount, and described solvent quality is the 40%-200% of tetramethylolmethane; Described solvent is a benzene,toluene,xylene, and described catalyzer is a tetramethyl ammonium chloride;
(2) the dichloro pentaerythritol bis-phosphite that (1) is generated is transferred in the dropping funnel together with solvent, adding molar weight in four-hole boiling flask is 1.1 times long chain alkanol or the Macrogol 200 and the solvent of dichloro pentaerythritol bis-phosphite, the amount of solvent is the ml/mmol tetramethylolmethane, splash into dichloro pentaerythritol bis-phosphite solution under stirring, the dropping time of dichloro pentaerythritol bis-phosphite solution is 1 to 3 hour, 10 to 35 ℃ of controlled temperature;
(3) after reaction finished, wet distillation went out solvent, cooling, and suction filtration gets the white waxy solid product, and the described suction filtration time is 1 to 3 hour.
The mol ratio of tetramethylolmethane and phosphorus trichloride is preferably 1: 2.05 in the described step (1).
Catalyst consumption is preferably 3% in the tetramethylolmethane amount in described (1).
The preferred toluene of solvent in described (1), solvent quality is 50% of a tetramethylolmethane.
Temperature of reaction is preferably 75-85 ℃ in described (1).
Preferred 1 hour of the dropping time of phosphorus trichloride in described (1).
Preferred 2 hours of the dropping time of dichloro pentaerythritol bis-phosphite solution in described (2), preferred 30 ℃ of temperature of reaction.
Long chain alkane alcohol in described (2) is lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol.
The suction filtration time is preferably 2 hours in described (3).
Beneficial effect of the present invention is: because in the novel diphosphite trialkyl ester compound molecule that relates in the present invention, have radical scavenger tetramethylolmethane group and hydrogen peroxide decomposition agent phosphorous acid ester group, free radical scavenger and hydrogen peroxide decomposition agent are compounded in the molecule, therefore, this compound is a kind of minute subclass complex type antioxidant and thermo-stabilizer.It also can work in coordination with the generation effect in the Hinered phenols hindered amines, and good effect is arranged.Generally speaking, it is in anti-oxidation, and improving color and luster etc. has outstanding effect.This type of novel trialkyl phosphite compounds toxicity is little, does not produce pollution, and volatility is low, and is good with the consistency of diesel oil, will wide application prospect be arranged in field of fuel additives.In addition, the long-chain alkoxy base changed into polyoxyethylene glycol after, can also on certain amplitude, improve the anti-knocking property of diesel oil, improve its low-temperature fluidity.
Embodiment
Following embodiment is to further specifying of inventing, but the present invention is not limited only to this.
Embodiment 1
In the four-hole boiling flask that thermometer, dropping funnel and reflux exchanger are housed, add tetramethylolmethane, toluene, tetramethyl ammonium chloride respectively, wherein the toluene quality be tetramethylolmethane 100%, its quality of tetramethyl ammonium chloride is 2% of tetramethylolmethane amount, it is 200 rev/mins that stirring velocity is set, drip phosphorus trichloride, its molar weight is 4 times of tetramethylolmethane, the dropping time is that 0.5 hour controlled temperature is at 80 ℃, absorb the hydrogen chloride gas that generates with the tail gas absorption bottle, reaction does not generate to there being hydrogen chloride gas, promptly gets intermediate dichloro pentaerythritol bis-phosphite.The dichloro pentaerythritol bis-phosphite that generates is transferred in the dropping funnel together with solvent, in four-hole boiling flask, add lauryl alcohol, its be dichloro pentaerythritol bis-phosphite molar weight 2 times, splash into dichloro pentaerythritol bis-phosphite solution under stirring, the dropping time is 0.5 hour.Controlled temperature is at 30 ℃.After reaction finished, wet distillation went out solvent, cooling, and suction filtration gets the white waxy solid product, promptly two dodecyl pentaerythritol phosphites, the wherein said suction filtration time is 0.5 hour.Yield 84%.
Embodiment 2
In the four-hole boiling flask that thermometer, dropping funnel and reflux exchanger are housed, be metered into tetramethylolmethane, toluene, tetramethyl ammonium chloride respectively, wherein the toluene quality be tetramethylolmethane 100%, its quality of tetramethyl ammonium chloride is in 2% of tetramethylolmethane amount, it is 200 rev/mins that stirring velocity is set, its molar weight of dropping phosphorus trichloride is 4 times of tetramethylolmethane, the dropping time is 0.5 hour, controlled temperature is at 80 ℃, absorb the hydrogen chloride gas that generates with the tail gas absorption bottle, reaction does not generate to there being hydrogen chloride gas, promptly gets intermediate dichloro pentaerythritol bis-phosphite.The dichloro pentaerythritol bis-phosphite that generates is transferred in the dropping funnel together with solvent, in four-hole boiling flask, add tetradecyl alcohol its be dichloro pentaerythritol bis-phosphite molar weight 2 times, splash into dichloro pentaerythritol bis-phosphite solution under stirring, everybody is 0.5 hour the time, and controlled temperature is at 30 ℃.After reaction finished, wet distillation went out solvent, cooling, and suction filtration, the suction filtration time is 0.5 hour, gets the white waxy solid product, promptly two tetradecyl pentaerythritol phosphites, yield 86%.
Embodiment 3
In the four-hole boiling flask that thermometer, dropping funnel and reflux exchanger are housed, be metered into tetramethylolmethane, toluene, tetramethyl ammonium chloride respectively, its toluene quality be tetramethylolmethane 100%, its quality of tetramethyl ammonium chloride is in 2% of tetramethylolmethane amount, it is 200 rev/mins that stirring velocity is set, its molar weight of dropping phosphorus trichloride is 4 times of tetramethylolmethane, the dropping time is 0.5 hour, controlled temperature is at 80 ℃, absorb the hydrogen chloride gas that generates with the tail gas absorption bottle, reaction does not generate to there being hydrogen chloride gas, promptly gets intermediate dichloro pentaerythritol bis-phosphite.The dichloro pentaerythritol bis-phosphite that generates is transferred in the dropping funnel together with solvent, in four-hole boiling flask, add hexadecanol its be dichloro pentaerythritol bis-phosphite molar weight 2 times, splash into dichloro pentaerythritol bis-phosphite solution under stirring, the dropping time is 0.5 hour, and controlled temperature is at 30 ℃.After reaction finished, wet distillation went out solvent, cooling, suction filtration 0.5 hour, the white waxy solid product, i.e. double hexadecyl pentaerythritol phosphite, yield 82%.
Embodiment 4
In the four-hole boiling flask that thermometer, dropping funnel and reflux exchanger are housed, be metered into tetramethylolmethane, toluene, tetramethyl ammonium chloride respectively, the toluene quality be tetramethylolmethane 100%, its quality of tetramethyl ammonium chloride is in 2% of tetramethylolmethane amount, it is 200 rev/mins that stirring velocity is set, its molar weight of dropping phosphorus trichloride is 4 times of tetramethylolmethane, the dropping time is 0.5 hour, controlled temperature is at 80 ℃, absorb the hydrogen chloride gas that generates with the tail gas absorption bottle, reaction does not generate to there being hydrogen chloride gas, promptly gets intermediate dichloro pentaerythritol bis-phosphite.The dichloro pentaerythritol bis-phosphite that generates is transferred in the dropping funnel together with solvent, in four-hole boiling flask, add stearyl alcohol its be dichloro pentaerythritol bis-phosphite molar weight 2 times, splash into dichloro pentaerythritol bis-phosphite solution under stirring, the dropping time is 0.5 hour, and controlled temperature is at 30 ℃.After reaction finished, wet distillation went out solvent, cooling, and suction filtration gets the white waxy solid product, promptly two octadecyl pentaerythritol phosphites, yield 74%.
Above embodiment all is used to illustrate the preparation method of double long-chain alkyl pentaerythritol phosphite provided by the invention.
Measured above-mentioned four kinds of double long-chain alkyl pentaerythritol phosphites and diesel samples (0# of China Petrochemical Industry diesel oil) intermiscibility respectively.The results are shown in Table one.
The result shows that all the intermiscibility with diesel samples is good for these four kinds of double long-chain alkyl pentaerythritol phosphites, respectively than Wytox 312, and phosphorous acid hexichol one monooctyl ester, triphenyl phosphite has exceeded 15%, 20%, 21%.
Measured the antioxidant effect (addition be 0.5% of diesel quality, at 35 ℃ place 30 day) of above-mentioned four kinds of double long-chain alkyl pentaerythritol phosphites respectively to diesel samples.The results are shown in Table two.
The result shows that the adding of these four kinds of double long-chain alkyl pentaerythritol phosphites can make the antioxidant property of diesel samples increase substantially.Four kinds of products have reached the quality index of U.S. GE company respectively.The result shows, these four kinds of double long-chain alkyl pentaerythritol phosphites are all good with the oxidation-resistance of diesel samples, respectively than not adding oxidation inhibitor, Wytox 312, phosphorous acid hexichol one monooctyl ester, triphenyl phosphite has exceeded 35%, 12%, 13%, 17%.
Four kinds of double long-chain alkyl pentaerythritol phosphite samples have been carried out the water resisting property test, through 100 ℃ of boiling water tests, sample topography and and quality almost do not change, its flame retardant properties does not change basically yet, illustrates that the water resisting property of four kinds of double long-chain alkyl pentaerythritol phosphites of synthetic is good.
Poly ethyldiol modified pentaerythritol phosphite sample and diesel samples (0# of China Petrochemical Industry diesel oil) consistency has reached 45g/100ml for 25 ℃ in room temperature, and this solubility property that has shown itself and diesel oil is good.Addition be diesel quality 0.5% the time, place down 60 days acid numbers less than 0.05mg/L at 35 ℃.Through 100 ℃ of boiling water tests, sample topography and and almost not variation of quality.
Claims (10)
1. a high temperature diesel oil antioxidant is characterized in that this oxidation inhibitor is diphosphite trialkyl ester compound, and its structural formula is:
2. a kind of high temperature diesel oil antioxidant as claimed in claim 1 is characterized in that: described n value preferred 10,12,14,16.
3. the preparation method of a kind of high temperature diesel oil antioxidant as claimed in claim 1, it is characterized in that: generate the dichloro pentaerythritol bis-phosphite by tetramethylolmethane and phosphorus trichloride reaction earlier, and then generate diphosphite trialkyl ester class diesel oil antioxidant with the reaction of long chain alkane alcohol.
4. the preparation method of a kind of high temperature diesel oil antioxidant as claimed in claim 1 is characterized in that: concrete steps are:
(1) in the four-hole boiling flask that thermometer, dropping funnel and reflux exchanger are housed, is metered into tetramethylolmethane, solvent, catalyzer respectively, it is 200 rev/mins that stirring velocity is set, drip phosphorus trichloride, the dropping time is 1-3 hour, controlled temperature 50-100 ℃, absorb the hydrogen chloride gas that generates with the tail gas absorption bottle, reaction does not generate to there being hydrogen chloride gas, promptly gets intermediate dichloro pentaerythritol bis-phosphite; Wherein the mol ratio of tetramethylolmethane and phosphorus trichloride was at 1: 2 to 1: 5, and catalyst consumption is at the 1%-5% of tetramethylolmethane amount, and described solvent quality is the 40%-200% of tetramethylolmethane; Described solvent is a benzene,toluene,xylene, and described catalyzer is a tetramethyl ammonium chloride;
(2) the dichloro pentaerythritol bis-phosphite that (1) is generated is transferred in the dropping funnel together with solvent, adding molar weight in four-hole boiling flask is 1.1 times long chain alkane alcohol and solvent of dichloro pentaerythritol bis-phosphite, the amount of solvent is the ml/mmol tetramethylolmethane, splash into dichloro pentaerythritol bis-phosphite solution under stirring, the dropping time of dichloro pentaerythritol bis-phosphite solution is 1 to 3 hour, 10 to 35 ℃ of controlled temperature;
(3) after reaction finished, wet distillation went out solvent, cooling, and suction filtration gets the white waxy solid product, and the described suction filtration time is 1 to 3 hour.
5. the preparation method of a kind of high temperature diesel oil antioxidant as claimed in claim 4 is characterized in that: the mol ratio of tetramethylolmethane and phosphorus trichloride is preferably 1: 2.05 in the described step (1).
6. the preparation method of a kind of high temperature diesel oil antioxidant as claimed in claim 4 is characterized in that: catalyst consumption is preferably 3% in the tetramethylolmethane amount in described (1).
7. the preparation method of a kind of high temperature diesel oil antioxidant as claimed in claim 4 is characterized in that: temperature of reaction is preferably 75-85 ℃ in described (1).
8. the preparation method of a kind of high temperature diesel oil antioxidant as claimed in claim 4 is characterized in that: preferred 1 hour of the dropping time of phosphorus trichloride in described (1).
9. the preparation method of a kind of high temperature diesel oil antioxidant as claimed in claim 4 is characterized in that: preferred 2 hours of dropping time of dichloro pentaerythritol bis-phosphite solution in (2) wherein, preferred 30 ℃ of temperature of reaction.
10. the preparation method of a kind of high temperature diesel oil antioxidant as claimed in claim 4 is characterized in that: wherein the alcohol of the long chain alkane in (2) is lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047273A (en) * | 2017-12-26 | 2018-05-18 | 西尼尔（江西）化工科技有限公司 | The preparation method and application of liquid phosphite class compound |
| WO2023081347A1 (en) * | 2021-11-04 | 2023-05-11 | Dover Chemical Corporation | Phosphite antioxidants for fuels and related methods |
| WO2024146066A1 (en) * | 2023-01-05 | 2024-07-11 | 浙江万盛股份有限公司 | Synthesis method for high-efficiency phosphite ester-type antioxidant distearyl pentaerythritol diphosphite |
| CN120349675A (en) * | 2025-05-23 | 2025-07-22 | 广东彩格科技有限公司 | Printer ink and preparation method thereof |
-
2009
- 2009-11-16 CN CN2009102303807A patent/CN102061203A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047273A (en) * | 2017-12-26 | 2018-05-18 | 西尼尔（江西）化工科技有限公司 | The preparation method and application of liquid phosphite class compound |
| WO2023081347A1 (en) * | 2021-11-04 | 2023-05-11 | Dover Chemical Corporation | Phosphite antioxidants for fuels and related methods |
| WO2024146066A1 (en) * | 2023-01-05 | 2024-07-11 | 浙江万盛股份有限公司 | Synthesis method for high-efficiency phosphite ester-type antioxidant distearyl pentaerythritol diphosphite |
| CN120349675A (en) * | 2025-05-23 | 2025-07-22 | 广东彩格科技有限公司 | Printer ink and preparation method thereof |
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Application publication date: 20110518 |