CN103923119A - Preparation method and applications of alkyl phosphite - Google Patents
Preparation method and applications of alkyl phosphite Download PDFInfo
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- CN103923119A CN103923119A CN201410173627.7A CN201410173627A CN103923119A CN 103923119 A CN103923119 A CN 103923119A CN 201410173627 A CN201410173627 A CN 201410173627A CN 103923119 A CN103923119 A CN 103923119A
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- alcohol
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- acid ester
- phosphorous acid
- phosphorus trichloride
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Abstract
The invention relates to a preparation method of alkyl phosphite. The prepared alkyl phosphite can be used for a non-sulfide ore floatation collecting agent. The preparation method comprises the following steps: firstly adding fatty alcohol and water into a reaction kettle, slowly dropwise adding phosphorus trichloride at room temperature and continuously stirring, and reacting at 30DEG C-90DEG C after the dropwise addition of phosphorus trichloride is completed, wherein the fatty alcohol is linear-chain fatty acid alcohol of C6-C18, benzene ring fatty alcohol or different carbon chains of mixed alcohol; adding caustic alkali at 30DEG C-90DEG C and continuously stirring, and reacting for 0.5-1.5 hours at 30DEG C-60DEG C after stopping adding of the caustic alkali, thus obtaining the alkyl phosphate. The method for preparing alkyl phosphite is simple in production technology, low in the cost of raw materials, convenient for industrial production, and aiming at different types of ores, different alkyl phosphite can be prepared by changing raw materials fatty alcohol.
Description
Technical field
The present invention relates to a kind of preparation method of mineral floating medicament alkyl phosphorous acid ester, and the purposes of the alkyl phosphorous acid ester that makes of the method.
Background technology
Mineral Resources in China is abundant, but great majority belong to the mineral products of low-grade refractory choosing, and along with continuous exploitation utilization, Mineral resources present poor, thin, assorted feature gradually, and this has caused great difficulty to the exploitation of China's mineral products.Finding the efficient flotation reagent of exploitation is the key that solves this difficult problem, and in numerous medicaments, alkylphosphonic acid carboxylic acid research because its special structure is widely used in flotation field, is the important flotation collector of a class.The alkyl phosphonic acid that contains suitable carbon chain lengths is the effective flotation collector in the ore deposits such as wolframite, cassiterite ore deposit, Rock Phosphate (72Min BPL) and rare-earth mineral, but the synthesis technique complexity of alkylphosphonic acid carboxylic acid, and productive rate is lower, makes reagent cost higher.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide a kind of new, production technique is simple, raw material sources are extensive, be convenient to the preparation method of industrial alkyl phosphorous acid ester.
Another object of the present invention is that alkyl phosphorous acid ester that aforementioned preparation method the makes purposes in non-sulfide ore flotation collector is also provided.
The object of the invention is to realize by following technical proposals.The present invention is a kind of preparation method of alkyl phosphorous acid ester, is characterized in, its step is as follows:
(1) in reactor, add fatty alcohol and water, the ratio of both amount of substances is, alcohol: water=1:1.5～3.0, under room temperature, slowly drip phosphorus trichloride solution and constantly stir, the ratio of the amount of substance adding is, alcohol: phosphorus trichloride=1:1～1.5, after dripping, phosphorus trichloride reacts 2 ~ 6 hours at 30 DEG C～90 DEG C; Described fatty alcohol is C
6~ C
18the alcohol mixture of straight chain fatty acid alcohol, phenyl ring fatty alcohol or different carbon chain;
(2) at 30 DEG C～90 DEG C, add caustic alkali and constantly stir, adding the ratio of amount of substance to be, alcohol: alkali=1:3.5 ~ 5.0, after adding, caustic alkali reacts 0.5～1.5 hour at 30 DEG C～60 DEG C, to obtain final product.
In the preparation method of a kind of alkyl phosphorous acid ester of the present invention: the ratio of the amount of substance of reaction raw materials is preferably, fatty alcohol: phosphorus trichloride: water: caustic alkali=1:1 ~ 1.1:2 ~ 2.3:4 ~ 4.3.
In the preparation method of a kind of alkyl phosphorous acid ester of the present invention: described caustic alkali, preferably from sodium hydroxide or potassium hydroxide, is Powdered or particulate state or sheet.
In the preparation method's of a kind of alkyl phosphorous acid ester of the present invention step (1), phosphorus trichloride drips and preferably at 40 DEG C～70 DEG C, reacts 3 ~ 5 hours afterwards.
In the preparation method's of a kind of alkyl phosphorous acid ester of the present invention step (1), phosphorus trichloride drips and further preferably at 50 DEG C～60 DEG C, reacts 3 ~ 5 hours afterwards.
In the preparation method's of a kind of alkyl phosphorous acid ester of the present invention step (2), preferably at 40 DEG C～70 DEG C, add caustic alkali and constantly stir; After adding, caustic alkali reacts 0.5～1.0 hour at 30 DEG C～60 DEG C.
In the preparation method of a kind of alkyl phosphorous acid ester of the present invention: the charge temperature of phosphorus trichloride is preferably lower than 30 DEG C.
In the preparation method of a kind of alkyl phosphorous acid ester of the present invention: described fatty alcohol is selected from hexanol, octanol, decyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, phenylcarbinol, phenylethyl alcohol, C
8~ C
12alcohol mixture or C
12~ C
14alcohol mixture.
The alkyl phosphorous acid ester that preparation method of the present invention makes possesses the purposes of making collecting agent in non-sulfide ore flotation.
Alkyl phosphorous acid ester is the isomers of alkylphosphonic acid carboxylic acid, and functional group is similar, and according to the viewpoint of the principle of isomerism of flotation reagent, alkyl phosphorous acid ester is also the effective collector of multi mineral.The correlation test of flotation shows that alkyl phosphorous acid ester is the effective collector of mineral really.Research decyl phosphorous acid ester to the flotation test in cassiterite ore deposit in, by decyl phosphorous acid ester, compared with vinylbenzene phosphoric acid, decyl phosphorous acid ester is better than styryl phosphonic acid to the collecting ability of cassiterite, its dosing is less than vinylbenzene phosphoric acid.In cassiterite and quartzy mixing in the flotation test of ore deposit, the flotation effect of decyl phosphorous acid ester is better than benzyl arsenic acid.Therefore, alkyl phosphorous acid ester is also the effective collector of mineral.
In the inventive method, alkyl phosphorous acid ester preparation method's raw material sources are extensive, and technique is simple, be convenient to produce, its production cost is well below alkylphosphines acids collecting agent, and this can effectively reduce the comprehensive cost of ore dressing, for the exploitation of low-grade mineral resource in China provide the foundation.
Compared with prior art, the present invention prepares the method for alkyl phosphorous acid ester, and its production technique is simple, and raw materials cost is low, is convenient to suitability for industrialized production, for dissimilar ore, can pass through feed change fatty alcohol, can prepare different alkyl phosphorous acid esters.
Embodiment
Below specific embodiment of the invention method is further described, but interest field of the present invention is not subject to the restriction of these embodiment.In embodiment, unless otherwise specified all umbers and percentage ratio all refer to quality.
Embodiment 1, a kind of preparation method of alkyl phosphorous acid ester, its step is as follows:
(1) in reactor, add fatty alcohol and water, the ratio of both amount of substances is, alcohol: water=1:1.5, under room temperature, slowly drip phosphorus trichloride solution and constantly stir, the ratio of the amount of substance adding is that alcohol: phosphorus trichloride=1:1 reacts 2 ~ 6 hours after phosphorus trichloride drips at 30 DEG C; Described fatty alcohol is C
6~ C
18the alcohol mixture of straight chain fatty acid alcohol, phenyl ring fatty alcohol or different carbon chain;
(2) at 30 DEG C, add caustic alkali and constantly stir, adding the ratio of amount of substance to be, alcohol: alkali=1:3.5 reacts 0.5～1.5 hour after caustic alkali adds at 30 DEG C, to obtain final product.
Embodiment 2, a kind of preparation method of alkyl phosphorous acid ester, its step is as follows:
(1) in reactor, add fatty alcohol and water, the ratio of both amount of substances is, alcohol: water=1:3.0, under room temperature, slowly drip phosphorus trichloride solution and constantly stir, the ratio of the amount of substance adding is, alcohol: phosphorus trichloride=1:1.5 reacts 2 ~ 6 hours after phosphorus trichloride drips at 90 DEG C; Described fatty alcohol is C
6~ C
18the alcohol mixture of straight chain fatty acid alcohol, phenyl ring fatty alcohol or different carbon chain;
(2) at 90 DEG C, add caustic alkali and constantly stir, adding the ratio of amount of substance to be, alcohol: alkali=1:5.0 reacts 0.5～1.5 hour after caustic alkali adds at 60 DEG C, to obtain final product.
Embodiment 3, a kind of preparation method of alkyl phosphorous acid ester, its step is as follows:
(1) in reactor, add fatty alcohol and water, the ratio of both amount of substances is, alcohol: water=1:2.0, under room temperature, slowly drip phosphorus trichloride solution and constantly stir, the ratio of the amount of substance adding is that alcohol: phosphorus trichloride=1:1.2 reacts 2 ~ 6 hours after phosphorus trichloride drips at 40 DEG C; Described fatty alcohol is C
6~ C
18the alcohol mixture of straight chain fatty acid alcohol, phenyl ring fatty alcohol or different carbon chain;
(2) at 40 DEG C, add caustic alkali and constantly stir, adding the ratio of amount of substance to be, alcohol: alkali=1:3.8 reacts 0.5～1.5 hour after caustic alkali adds at 35 DEG C, to obtain final product.
Embodiment 4, a kind of preparation method of alkyl phosphorous acid ester, its step is as follows:
(1) in reactor, add fatty alcohol and water, the ratio of both amount of substances is, alcohol: water=1:2.5, under room temperature, slowly drip phosphorus trichloride solution and constantly stir, the ratio of the amount of substance adding is that alcohol: phosphorus trichloride=1:1.3 reacts 2 ~ 6 hours after phosphorus trichloride drips at 70 DEG C; Described fatty alcohol is C
6~ C
18the alcohol mixture of straight chain fatty acid alcohol, phenyl ring fatty alcohol or different carbon chain;
(2) at 70 DEG C, add caustic alkali and constantly stir, adding the ratio of amount of substance to be, alcohol: alkali=1:4.5 reacts 0.5～1.5 hour after caustic alkali adds at 40 DEG C, to obtain final product.
Embodiment 5, a kind of preparation method of alkyl phosphorous acid ester, its step is as follows:
(1) in reactor, add fatty alcohol and water, the ratio of both amount of substances is, alcohol: water=1:2, under room temperature, slowly drip phosphorus trichloride solution and constantly stir, the ratio of the amount of substance adding is that alcohol: phosphorus trichloride=1:1 reacts 3 ~ 5 hours after phosphorus trichloride drips at 50 DEG C; Described fatty alcohol is C
6~ C
18the alcohol mixture of straight chain fatty acid alcohol, phenyl ring fatty alcohol or different carbon chain;
(2) at 50 DEG C, add caustic alkali and constantly stir, adding the ratio of amount of substance to be, alcohol: alkali=1:4 reacts 0.5～1.5 hour after caustic alkali adds at 45 DEG C, to obtain final product.
Embodiment 6, a kind of preparation method of alkyl phosphorous acid ester, its step is as follows:
(1) in reactor, add fatty alcohol and water, the ratio of both amount of substances is, alcohol: water=1:2.3, under room temperature, slowly drip phosphorus trichloride solution and constantly stir, the ratio of the amount of substance adding is, alcohol: phosphorus trichloride=1:1.1 reacts 3 ~ 5 hours after phosphorus trichloride drips at 60 DEG C; Described fatty alcohol is C
6~ C
18the alcohol mixture of straight chain fatty acid alcohol, phenyl ring fatty alcohol or different carbon chain;
(2) at 60 DEG C, add caustic alkali and constantly stir, adding the ratio of amount of substance to be, alcohol: alkali=1:4.3 reacts 0.5～1.5 hour after caustic alkali adds at 50 DEG C, to obtain final product.
Embodiment 7, in the preparation method of the alkyl phosphorous acid ester of embodiment 1-6 described in any one: described caustic alkali is selected from sodium hydroxide or potassium hydroxide, is Powdered or particulate state or sheet.
Embodiment 8, in the preparation method of the alkyl phosphorous acid ester of embodiment 1-7 described in any one: the charge temperature of phosphorus trichloride is lower than 30 DEG C.
Embodiment 9, in the preparation method of the alkyl phosphorous acid ester of embodiment 1-8 described in any one: described fatty alcohol is selected from hexanol, octanol, decyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, phenylcarbinol, phenylethyl alcohol, C
8~ C
12alcohol mixture or C
12~ C
14alcohol mixture.
Described in above-described embodiment the alkyl phosphorous acid ester that makes of preparation method can be for non-sulfide ore flotation collector.While doing the use of non-sulfide ore flotation collector, can directly use the product making, and can not need to refine.
Embodiment 10, the preparation method of alkyl phosphorous acid ester tests one: the preparation of dodecyl phosphorous acid ester
The water of the lauryl alcohol of 186 parts and 41.4 parts is joined in reactor, fully stir; In 30 minutes, add 150 parts of phosphorus trichlorides, control temperature of reaction system and be no more than 30 DEG C, add after phosphorus trichloride, temperature is risen to 60 DEG C, stirring reaction 4 hours; Add the sodium hydroxide of 172 parts at 40 DEG C, to continue stirring reaction 0.5 hour, to obtain final product.Reaction finishes rear to whole system fast cooling, and system temperature is down to 5 DEG C of left and right, and compression is filtered, and in product, the purity of dodecyl phosphorous acid ester is 76.2% by analysis, and product yield is 85.3%.
Embodiment 11, the preparation method of alkyl phosphorous acid ester tests two: the preparation of styroyl phosphorous acid ester
The water of the phenylethyl alcohol of 122 parts and 37.8 parts is joined in reactor, fully stir; In 30 minutes, add 150 parts of phosphorus trichlorides, control temperature of reaction system and be no more than 30 DEG C, add after phosphorus trichloride, temperature is risen to 70 DEG C, stirring reaction 3 hours; Add the sodium hydroxide of 166 parts at 40 DEG C, to continue stirring reaction 0.5 hour, to obtain final product.Reaction finishes rear to whole system fast cooling, and system temperature is down to 5 DEG C of left and right, and compression is filtered, and in product, the purity of phenylethyl alcohol phosphorous acid ester is 79.3% by analysis, and product yield is 83.6%.
Embodiment 12, the preparation method of alkyl phosphorous acid ester tests three: the preparation of decyl phosphorous acid ester
It is 158 parts of nonylcarbinols that 186 parts of lauryl alcohols in embodiment 10 are used instead, and other conditions are constant, and in the product obtaining, the purity of decyl phosphorous acid ester is 75.6%, and the product yield of decyl phosphorous acid ester is 86.5%.
Embodiment 13, the preparation method of alkyl phosphorous acid ester tests four: the preparation of phenmethyl phosphorous acid ester
It is the phenylcarbinol of 108 parts that 122 parts of phenylethyl alcohols in embodiment 11 are used instead, and other conditions are constant, and in the product obtaining, the purity of phenmethyl phosphorous acid ester is 78.7%, and the product yield of phenmethyl phosphorous acid ester is 83.9%.
Embodiment 14, the preparation method of alkyl phosphorous acid ester tests five: C
12~ C
14mix the preparation of phosphorous acid ester
By the C of 200 parts
12~ C
14the water of alcohol mixture and 41.4 parts joins in reactor, fully stirs; In 30 minutes, add 150 parts of phosphorus trichlorides, control temperature of reaction system and be no more than 30 DEG C, add after phosphorus trichloride, temperature is risen to 60 DEG C, stirring reaction 5 hours; Add the sodium hydroxide of 172 parts at 40 DEG C, to continue stirring reaction 1 hour, to obtain final product.Reaction finishes rear to whole system fast cooling, and system temperature is down to 5 DEG C of left and right, and compression is filtered, and in product, the purity of base phosphorous acid ester is 76.8% by analysis, and product yield is 85.1%.
Claims (9)
1. a preparation method for alkyl phosphorous acid ester, is characterized in that, its step is as follows:
(1) in reactor, add fatty alcohol and water, the ratio of both amount of substances is, alcohol: water=1:1.5～3.0, under room temperature, slowly drip phosphorus trichloride solution and constantly stir, the ratio of the amount of substance adding is, alcohol: phosphorus trichloride=1:1～1.5, after dripping, phosphorus trichloride reacts 2 ~ 6 hours at 30 DEG C～90 DEG C; Described fatty alcohol is C
6~ C
18the alcohol mixture of straight chain fatty acid alcohol, phenyl ring fatty alcohol or different carbon chain;
(2) at 30 DEG C～90 DEG C, add caustic alkali and constantly stir, adding the ratio of amount of substance to be, alcohol: alkali=1:3.5 ~ 5.0, after adding, caustic alkali reacts 0.5～1.5 hour at 30 DEG C～60 DEG C, to obtain final product.
2. the preparation method of a kind of alkyl phosphorous acid ester according to claim 1, is characterized in that: the ratio of the amount of substance of reaction raw materials is, fatty alcohol: phosphorus trichloride: water: caustic alkali=1:1 ~ 1.1:2 ~ 2.3:4 ~ 4.3.
3. the preparation method of a kind of alkyl phosphorous acid ester according to claim 1, is characterized in that: described caustic alkali is selected from sodium hydroxide or potassium hydroxide, is Powdered or particulate state or sheet.
4. the preparation method of a kind of alkyl phosphorous acid ester according to claim 1, is characterized in that: in step (1), after phosphorus trichloride drips, at 40 DEG C～70 DEG C, react 3 ~ 5 hours.
5. the preparation method of a kind of alkyl phosphorous acid ester according to claim 1, is characterized in that: in step (1), after phosphorus trichloride drips, at 50 DEG C～60 DEG C, react 3 ~ 5 hours.
6. the preparation method of a kind of alkyl phosphorous acid ester according to claim 1, is characterized in that: in step (2), add caustic alkali and constantly stir at 40 DEG C～70 DEG C; After adding, caustic alkali reacts 0.5～1.0 hour at 30 DEG C～60 DEG C.
7. the preparation method of a kind of alkyl phosphorous acid ester according to claim 1, is characterized in that, the charge temperature of phosphorus trichloride is lower than 30 DEG C.
8. according to the preparation method of the alkyl phosphorous acid ester described in any one in claim 1-7, it is characterized in that: described fatty alcohol is selected from hexanol, octanol, decyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, phenylcarbinol, phenylethyl alcohol, C
8~ C
12alcohol mixture or C
12~ C
14alcohol mixture.
9. the purposes of the alkyl phosphorous acid ester that in claim 1-8, the preparation method described in any one makes in non-sulfide ore flotation collector.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107637A (en) * | 2015-09-30 | 2015-12-02 | 广西大学 | Method for preparing collecting agent for recycling sulphide ores from tailings |
| CN105149107A (en) * | 2015-07-13 | 2015-12-16 | 中南大学 | Application of phosphoric acid ester compound to flotation of calcium-containing minerals |
| CN105170338A (en) * | 2015-08-28 | 2015-12-23 | 张好勇 | Non-sulfide mineral flotation collector, preparation method thereof and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105149107A (en) * | 2015-07-13 | 2015-12-16 | 中南大学 | Application of phosphoric acid ester compound to flotation of calcium-containing minerals |
| CN105170338A (en) * | 2015-08-28 | 2015-12-23 | 张好勇 | Non-sulfide mineral flotation collector, preparation method thereof and application thereof |
| CN105107637A (en) * | 2015-09-30 | 2015-12-02 | 广西大学 | Method for preparing collecting agent for recycling sulphide ores from tailings |
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