CN105131030A - Method for preparing phosphate ester from rubber seed oil with high acid value - Google Patents
Method for preparing phosphate ester from rubber seed oil with high acid value Download PDFInfo
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- CN105131030A CN105131030A CN201510562709.5A CN201510562709A CN105131030A CN 105131030 A CN105131030 A CN 105131030A CN 201510562709 A CN201510562709 A CN 201510562709A CN 105131030 A CN105131030 A CN 105131030A
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Abstract
The invention discloses a method for preparing phosphate ester from rubber seed oil with a high acid value, and especially relates to a preparation method for plant oil phosphate ester. The method is characterized in that rubber seed oil with high acid value and a phosphatizing agent are reacted to prepare rubber seed oil phosphate ester. The preparation method comprises three steps: firstly, rubber seed oil with an acid value being more than 1mgKOH/g and low mass molecule alcohol are subjected to an esterification deacidification reaction under action of acid catalysts, then dewatering processing is carried out, a little of water generated during the reaction process is removed, and esterified rubber seed oil is obtained; secondly, the esterified rubber seed oil obtained in the first step and low mass molecule alcohol are subjected to an alcoholization reaction under action of acid catalysts, liquid separation is carried out, unreacted alcohol in the upper layer is removed, unreacted alcohol is removed further through evaporation, and alcoholized rubber seed oil is obtained; thirdly, the alcoholized rubber seed oil obtained in the second step and the phosphatizing agent are reacted, and rubber seed oil phosphate ester is prepared.
Description
Technical field
The present invention relates to a kind of method that high acid value rubber seed oil prepares phosphoric acid ester, particularly the preparation method of a vegetable oil phosphoric acid ester.Belong to technical field of fine.
Technical background
The kind of phosphoric acid ester is a lot, and its preparation method overwhelming majority adopts phosphorous phosphorization agent such as the alcohol of petroleum base derivative and Vanadium Pentoxide in FLAKES, phosphorus trichloride etc. to react and obtains.Along with the exhaustion of fossil class resource and price go up increasingly, the production cost of this kind of alcohols is also more and more higher, in addition petroleum chemicals have greater environmental impacts, country is more and more stricter to environmental requirement, adopts the renewable resources of environment amenable self-sow to substitute petrochemical industry derivative development of raw materials product innovation imperative.
Rubber seed oil phosphoric acid ester is a kind of novel phosphate ester product, belongs to vegetables oil phosphoric acid ester.Due to the saturated and unsaturated fatty acid ester of the carbochain of rubber seed oil containing multiple different lengths itself, the product that it is made is rich in several functions but not simple function.Current vegetables oil phosphoric acid ester only has castor oil phosphate ester a kind of.In castor oil molecule structure, itself is containing hydroxyl, and acid number is lower, is less than 1mgKOH/g, can directly and phosphorization agent react and prepare castor oil phosphate ester, and, be all employing basic catalyst in its preparation method.And not hydroxyl in rubber seed oil molecular structure, preparation phosphoric acid ester can not be directly used in, first need will combine upper hydroxyl in its molecule through alcoholization process, could react with phosphorization agent and prepare rubber seed oil phosphoric acid ester.
Summary of the invention
A kind of high acid value rubber seed oil is the object of the present invention is to provide to prepare the method for phosphoric acid ester.
The method that the rubber seed oil of high acid value of the present invention prepares rubber seed oil phosphoric acid ester adopts high acid value rubber seed oil and phosphorization agent to react to prepare rubber seed oil phosphoric acid ester, and concrete preparation process is divided into following three steps:
1. rubber seed oil and low mass molecule alcohol are carried out esterification deacidification reaction under the effect of an acidic catalyst, then carry out processed, a small amount of water generated in removing reaction process, obtains esterification rubber seed oil;
2. the esterification rubber seed oil 1. obtained by step and low mass molecule alcohol carry out alcoholization reaction under an acidic catalyst effect, through separatory, and the unreacted alcohol in removing upper strata, then remove unreacted alcohol further through evaporation, obtain refining rubber seed oil;
3. the alcoholization rubber seed oil 2. obtained by step and phosphorization agent react, obtained rubber seed oil phosphoric acid ester.
Adopt one of raw material to be rubber seed oil, its acid number is greater than 1mgKOH/g.
One of raw material is adopted to be phosphorization agent; Phosphorization agent refers to the mixture of Vanadium Pentoxide in FLAKES, polyphosphoric acid, peroxophosphoric acid or their threes.
Described catalyzer is an acidic catalyst, and an acidic catalyst is one or more in the vitriol oil, Vanadium Pentoxide in FLAKES, polyphosphoric acid, peroxophosphoric acid, sulfonic acid or solid acid catalyst.
Described low mass molecule alcohol refers to the alcohol that methyl alcohol, ethanol, butanols, ethylene glycol, pentanediol or other molecular weight are less than 120.
Described catalyst levels is 0.2%-10%.
Described step reaction conditions is 1.: required alcohol/stock oil mol ratio is 2:1 ~ 10:1 (calculating based on acid number), temperature of reaction is close to the boiling point of selected low mass molecule alcohol, i.e. boiling point ± 10 DEG C of selected low mass molecule alcohol, the reaction times is 0.5 ~ 3 hour.
Described step reaction conditions is 2.: required alcohol/molar equivalent is the 2:1 ~ 30:1 alcohol consumption of 100% calculating (reaches according to the modification degree of depth based on), temperature of reaction is close to the boiling point of selected low mass molecule alcohol, i.e. boiling point ± 10 DEG C of selected low mass molecule alcohol, the reaction times is 2 ~ 8 hours.
Described step reaction conditions is 3.: alcoholized oil (by hydroxy radical content)/P mol ratio is 1:1 ~ 3:1, temperature of reaction 70-85 DEG C, and the reaction times is 0.5 ~ 4 hour.
The present invention utilizes renewable plant resources to substitute fossil class petroleum derivative to prepare a vegetable oil phosphoric acid ester, this rubber seed oil phosphate ester product contains the saturated and unsaturated fatty acid ester of more than 12 kinds different lengths carbochains due to itself, the product that it is made is rich in several functions but not simple function, and, vegetables oil itself has natural degradation, environmentally friendly, extremely meet Development of Green Industrialization direction.
Embodiment
By specific embodiment given below, the present invention can be well understood to further, but they not the restrictions to content of the present invention.
The present invention adopts rubber seed oil and phosphorization agent to react to prepare rubber seed oil phosphoric acid ester, preparation method is divided into three steps: the rubber seed oil and the low mass molecule alcohol that 1. acid number are greater than 1mgKOH/g carry out esterification deacidification reaction under an acidic catalyst effect, then processed is carried out, the a small amount of water generated in removing reaction process, obtains esterification rubber seed oil; 2. the esterification rubber seed oil 1. obtained by step and low mass molecule alcohol carry out alcoholization reaction under an acidic catalyst effect, through separatory, and the unreacted alcohol in removing upper strata, then remove unreacted alcohol further through evaporation, obtain refining rubber seed oil; 3. the alcoholization rubber seed oil 2. obtained by step and phosphorization agent react, obtained rubber seed oil phosphoric acid ester.
Embodiment 1: 5.2ml methyl alcohol being added 126.0 grams of acid numbers is in the rubber seed oil of 19.2mgKOH/g, at 60 DEG C, drip 0.6 gram of concentrated sulfuric acid catalyst, react 3 hours, then dewatering agent normal temperature dewatering is used, filter, the methyl alcohol of alcohol/molar equivalent 4:1 will be added in filtrate, at 60 DEG C, dropping 5ml methyl alcohol and 0.6 gram of vitriol oil are configured to mixed solution respectively, after dripping, dripping the methyl alcohol of alcohol/molar equivalent 4:1, react 6 hours, by gained reaction solution separating funnel separatory, be separated upper strata methyl alcohol, lower floor's feed liquid is evaporated at 65 DEG C, removing has neither part nor lot in the methyl alcohol of reaction, cool the temperature to less than 50 DEG C, add 2.4 grams of Vanadium Pentoxide in FLAKESs in batches, then 75-80 DEG C is warming up to, react 3 hours, obtain 126.6 grams of rubber seed oil phosphoric acid ester, its monoester content 36.2%.
Embodiment 2: take 100.6 grams of rubber seed oils that acid number is 21.2mgKOH/g, be heated to 95 DEG C, add 6.5ml butanols, be warming up to 115 DEG C, drip 0.8 gram of vitriol oil, react 1.5 hours, then less than 60 DEG C are cooled the temperature to, dewater with dewatering agent, filter, 86ml butanols will be added in filtrate, then the catalyst solution with 5ml butanols and 0.5 gram of vitriol oil configuration is dripped, 10-20 minute is reacted at 105-115 DEG C, and then drip 81ml butanols, react 6 hours, upper strata butanols is divided by gained feed liquid separating funnel, lower floor's feed liquid is evaporated at 110-117 DEG C, remove unreacted butanols.Feed temperature is down to 40-50 DEG C, adds the polyphosphoric acid of 6.0 gram 116% in batches, be then warming up to 75-80 DEG C, react 2.5 hours, obtain 108.8 grams of rubber seed oil phosphoric acid ester, its monoester content 68.4%.
Embodiment 3: taking 135.8 grams of acid numbers is the rubber seed oil of 19.2mgKOH/g, add 5.6ml methyl alcohol, be warming up to 60 DEG C, gradation adds 5.4 grams of solid acid catalysts, react 2.5 hours, gained feed liquid dewatering agent dewaters, and through centrifuging, removing solid acid catalyst and dewatering agent, 55ml methyl alcohol will be added in filtrate, at 60 DEG C, gradation adds 5.4 grams of solid acid catalysts, 50ml methyl alcohol is dripped in process, react 7.5 hours, by gained reaction solution separating funnel separatory, be separated upper strata methyl alcohol, lower floor's feed liquid is evaporated 1.5 hours at 65 DEG C, removing has neither part nor lot in the methyl alcohol of reaction, cool the temperature to less than 50 DEG C, add the mixed solution of 8.4 grams of Vanadium Pentoxide in FLAKESs and phosphoric acid several times, then 75-80 DEG C is warming up to, react 3 hours, obtain 138.2 grams of rubber seed oil phosphoric acid ester, its monoester content 42.2%.
Claims (9)
1. high acid value rubber seed oil prepares a method for phosphoric acid ester, it is characterized in that: adopt high acid value rubber seed oil and phosphorization agent to react and prepare rubber seed oil phosphoric acid ester, preparation process is divided into three steps:
1. rubber seed oil and low mass molecule alcohol are carried out esterification deacidification reaction under the effect of an acidic catalyst, then carry out processed, a small amount of water generated in removing reaction process, obtains esterification rubber seed oil;
2. the esterification rubber seed oil 1. obtained by step and low mass molecule alcohol carry out alcoholization reaction under an acidic catalyst effect, through separatory, and the unreacted alcohol in removing upper strata, then remove unreacted alcohol further through evaporation, obtain refining rubber seed oil;
3. the alcoholization rubber seed oil 2. obtained by step and phosphorization agent react, obtained rubber seed oil phosphoric acid ester.
2. method according to claim 1, it is characterized in that one of raw material adopted is rubber seed oil, its acid number is greater than 1mgKOH/g.
3. method according to claim 1, is characterized in that one of raw material adopted is phosphorization agent; Phosphorization agent refers to the mixture of Vanadium Pentoxide in FLAKES, polyphosphoric acid, peroxophosphoric acid or their threes.
4. method according to claim 1, is characterised in that described catalyzer is an acidic catalyst, and an acidic catalyst is one or more in the vitriol oil, Vanadium Pentoxide in FLAKES, polyphosphoric acid, peroxophosphoric acid, sulfonic acid or solid acid catalyst.
5. method according to claim 1, is characterized in that described low mass molecule alcohol refers to the alcohol that methyl alcohol, ethanol, butanols, ethylene glycol, pentanediol or other molecular weight are less than 120.
6. the method according to claim 1 or 4, is characterised in that described catalyst levels is 0.2%-10%.
7. according to claim 1, be characterised in that step reaction conditions is 1.: required alcohol/stock oil mol ratio is 2:1 ~ 10:1 (calculating based on acid number), temperature of reaction is close to the boiling point of selected low mass molecule alcohol, i.e. boiling point ± 10 DEG C of selected low mass molecule alcohol, the reaction times is 0.5 ~ 3 hour.
8. method according to claim 1, be characterised in that step reaction conditions is 2.: required alcohol/molar equivalent is the 2:1 ~ 30:1 alcohol consumption of 100% calculating (reaches according to the modification degree of depth based on), temperature of reaction is close to the boiling point of selected low mass molecule alcohol, i.e. boiling point ± 10 DEG C of selected low mass molecule alcohol, the reaction times is 2 ~ 8 hours.
9. method according to claim 1, is characterised in that step reaction conditions is 3.: alcoholized oil (by hydroxy radical content)/P mol ratio is 1:1 ~ 3:1, temperature of reaction 70-85 DEG C, and the reaction times is 0.5 ~ 4 hour.
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| CN201510562709.5A CN105131030A (en) | 2015-09-07 | 2015-09-07 | Method for preparing phosphate ester from rubber seed oil with high acid value |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115216362A (en) * | 2021-04-19 | 2022-10-21 | 苏州雪绒无疆食品科技有限公司 | Rubber seed oil and preparation method and application thereof |
Citations (4)
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|---|---|---|---|---|
| CN1226575A (en) * | 1998-02-20 | 1999-08-25 | 薛翠花 | Preparation of alkyl phosphate dipersant |
| CN102140380A (en) * | 2011-02-25 | 2011-08-03 | 常州大学 | Method for preparing nitrogenous phosphate extreme-pressure anti-wear additive by vegetable-oil solid alkali method |
| CN102140379A (en) * | 2011-02-25 | 2011-08-03 | 常州大学 | Method for preparing nitrogen phosphate-containing extreme pressure abrasion-resistant lubricating additive by using biodiesel |
| CN102775438A (en) * | 2012-08-03 | 2012-11-14 | 山东源根石油化工有限公司 | Triethanolamine phosphate ricinoleate compound, and total-synthesized water-based anti-wear hydraulic fluid containing same |
-
2015
- 2015-09-07 CN CN201510562709.5A patent/CN105131030A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226575A (en) * | 1998-02-20 | 1999-08-25 | 薛翠花 | Preparation of alkyl phosphate dipersant |
| CN102140380A (en) * | 2011-02-25 | 2011-08-03 | 常州大学 | Method for preparing nitrogenous phosphate extreme-pressure anti-wear additive by vegetable-oil solid alkali method |
| CN102140379A (en) * | 2011-02-25 | 2011-08-03 | 常州大学 | Method for preparing nitrogen phosphate-containing extreme pressure abrasion-resistant lubricating additive by using biodiesel |
| CN102775438A (en) * | 2012-08-03 | 2012-11-14 | 山东源根石油化工有限公司 | Triethanolamine phosphate ricinoleate compound, and total-synthesized water-based anti-wear hydraulic fluid containing same |
Non-Patent Citations (3)
| Title |
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| 兰云军等: "PVO系列磷酸化植物油加脂剂的研制", 《中国皮革》 * |
| 胡国辉: "《金属磷化工技术》", 31 December 2009 * |
| 范铁明等: "磷酸酯阻燃整理剂的合成与应用", 《毛纺科技》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115216362A (en) * | 2021-04-19 | 2022-10-21 | 苏州雪绒无疆食品科技有限公司 | Rubber seed oil and preparation method and application thereof |
| CN115216362B (en) * | 2021-04-19 | 2024-03-01 | 苏州雪绒无疆食品科技有限公司 | Rubber seed oil and preparation method and application thereof |
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Application publication date: 20151209 |