CN1069892C

CN1069892C - Process for synthesizing isopropyl salicylate

Info

Publication number: CN1069892C
Application number: CN98108649A
Authority: CN
Inventors: 廖世军; 梅慈云; 张保安; 林性雄
Original assignee: South China University of Technology SCUT
Current assignee: South China University of Technology SCUT
Priority date: 1998-05-22
Filing date: 1998-05-22
Publication date: 2001-08-22
Anticipated expiration: 2018-05-22
Also published as: CN1202480A

Abstract

The present invention relates to a technology method for synthesizing isopropyl salicylate. The present invention uses salicylic acid and propene as a raw material and uses liquid acid, such as sulphuric acid, etc., solid acid, such as superstrong acid, cation exchange resin, etc., and phospho-tungstic acid as a catalyst to carry out a reaction for 10 to 40 hours at 80 to 120 DEG C and 0.5 to 1.5 Ma, the raw material and the catalyst are cooled to room temperature, the unreacted salicylic acid is filtered and recovered to be neutralized by CaO or calcium carbonate, and the isopropyl salicylate of a finished product is obtained by filtration and deslagging. The method has the advantages of advanced technology, nearly no side reaction, little raw material consumption, high conversion rates, energy saving, low cost, good product quality and conspicuous economic benefit, and the reaction is completed in one step.

Description

A kind of method of Synthesis of Isopropyl Salicylate

The present invention is a kind of method of salicylate isopropyl acid ester, belongs to the technology of preparing of chemical industry solvent, agricultural chemicals.

Isopropyl salicylate is a kind of important pesticide intermediate, is the higher effective and lower toxic pesticide with good action of contace poison by its isocarbophos, isofenphos_methyl that makes that set out.In addition, isopropyl salicylate can be used as spices, solvent etc.At present, the industrial synthetic processing method that goes up isopropyl salicylate is: with Whitfield's ointment and Virahol is raw material, and direct esterification makes isopropyl salicylate under the katalysis of catalyzer, and catalyst system therefor mainly contains the vitriol oil, thionyl chloride and polynary mixing acid.Because the shipwreck that generates in reaction process is in telling and having a side reaction, therefore, problems such as low, poor product quality of big (consumption of isopropyl ester often is 2 to 3 times of theoretical consumption), aftertreatment trouble of ubiquity long reaction time, raw material consumption, yield and etching apparatus.If adopt the thionyl chloride catalyzer also to have problems such as exhaust gas emission and catalyzer price height, cause production cost height, poor product quality, isopropyl salicylate content is generally about 95%.

Purpose of the present invention be exactly for overcome and solve long reaction time that the technology of existing industrial Synthesis of Isopropyl Salicylate exists, have side reaction, raw material consumption is big, subsequent disposal trouble, yield are low, poor product quality, etching apparatus and high shortcoming and the problem of production cost, research is created a kind of reaction process and is once finished, and almost do not have side reaction, raw material consumption is few, yield is high, quality product is high, energy-saving and cost-reducing, production cost is lower, the processing method of the Synthesis of Isopropyl Salicylate of remarkable in economical benefits.

The present invention realizes by following method and technology scheme: the inventive method is a raw material with Whitfield's ointment and propylene, and the consumption rate of Whitfield's ointment and propylene is about 1: 1.05 (mol ratio), is 50%～98% fluid sulphuric acid H with concentration range ₂SO ₄, mixture of sulfuric phosphoric acid and super acids SO ₄ ^2-/ ZrO ₂, SO ₄ ^2-/ ZrO ₂-SiO ₂Solid acids such as acidic cation-exchange resin and phospho-wolframic acid are catalyzer, and can use the solvent that comprises isopropyl acetate, cyclohexane, benzene etc., under 80～120 ℃, 0.5～1.5Mpa pressure, react, catalyst consumption is 1.0%～15% (wt), reaction times is 10～40 hours, leach catalyzer while hot after reaction is finished to solid acid catalyst, after being cooled to room temperature, the unreacted Whitfield's ointment of filtered and recycled (the general rate of recovery is more than 80%), filtrate is used excessive oxidation calcium CaO or lime carbonate CaCO ₃Neutralisation of sulphuric acid and most of residual Whitfield's ointment also absorb moisture, filter, discard filter residue, and filtrate is the finished product isopropyl salicylate, and content is generally greater than 98%; Its concrete technological operation step is: (1) adds Whitfield's ointment in stainless steel cauldron, adds the liquid or solid acid catalyst of above-mentioned amount ranges and concentration range again; (2) lead to air in the propylene replacement reaction kettle into somewhat to dozens of minutes, close outlet again; (3) leading to into propylene, to make pressure to the reactor be certain pressure of above-mentioned pressure range, be warming up to certain temperature in the said temperature scope after, after certain reaction times through reacting above-mentioned reaction time range, be cooled to room temperature; (4) emit unnecessary propylene, take out the product weighing, the product that takes out certainweight adds in a certain amount of ethanol, with the titration of 0.1MKOH solution, calculates transformation efficiency; (5) cooled product is to room temperature, the unreacted Whitfield's ointment of filtered and recycled, and filtrate is with excessive calcium oxide CaO or lime carbonate CaCO ₃Neutralisation of sulphuric acid and residual Whitfield's ointment also absorb moisture, and filtration can obtain the finished product isopropyl salicylate, the calculating productive rate of weighing at last.

The present invention compared with prior art has following advantage and beneficial effect: (1) good product quality, and product is of light color, isopropyl salicylate content height; (2) raw material consumption is low, and feed stock conversion can reach 99%, and remarkable in economical benefits is at current price calculated, and the ton cost of technology synthetic isopropyl salicylate of the present invention only is about 75% of a prior art processes; (3) energy-saving and cost-reducing, owing to there is not the separation problem of water, needn't cold repeatedly doubtful heating, so energy consumption can reduce significantly, the while can reduce the discharging of waste water significantly; (4) technology advanced person, this technology does not almost have side reaction, and selectivity of product can reach more than 96%, and reaction process is once finished in sealing autoclave.There are not in the prior art processes decomposition, volatilization and Virahol and problems such as separating of water such as Virahol.And the advanced in addition subsequent treatment process of the present invention, but the most unreacted Whitfield's ointment of efficient recovery is reused.

The contriver is through years of researches, design, test, and creatively summary comprehensively goes out Synthesis of Isopropyl Salicylate technology of the present invention, and many successful implementation examples are arranged, and now lists wherein following 8

Embodiment:

Embodiment 1:

At 0.1dm ³It is 98% the vitriol oil as the Whitfield's ointment of raw material and 2.0ml as catalyst concentration that stainless steel cauldron adds 25g, and air was closed outlet after 3～5 minutes in the logical propylene displacement still; Lead to into that propylene to pressure is 1.0Mpa, be warming up to 110 ℃ after, reacted 20 hours; After being cooled to room temperature, put unnecessary propylene, take out the product weighing, get the 0.5g product and add in the 10ml ethanol,, calculate transformation efficiency with the titration of 0.1MKOH solution.Cooled product is to room temperature, the Whitfield's ointment that filtered and recycled does not react; Filtrate adds 5gCaO (or 6gCaCO ₃) neutralisation of sulphuric acid, residual Whitfield's ointment and absorb moisture, filtration can obtain the finished product isopropyl salicylate; Last weighing calculates productive rate, and it is 1 listed that its transformation efficiency, productive rate all see Table.

Embodiment 2:

Remove with concentration be 98% sulfuric acid to change concentration into be 70% sulfuric acid, and consumption is changed into outside the 3ml, other is all identical with embodiment 1.

Embodiment 3:

Except that the sulfuric acid that with 2ml concentration is 98% changes 3ml concentration into is that other is all with embodiment 1 50% the sulfuric acid.

Embodiment 4:

Remove H ₂SO ₄Sulfuric acid catalyst changes 3.0ml mixture of sulfuric phosphoric acid H into ₂SO ₄-H ₃PO ₄, temperature of reaction changes into outside 100 ℃, and other is all with embodiment 1.

Embodiment 5:

Replace sulfuric acid catalyst with the acid big aperture cation exchange resin catalyst of 3.0gHD-72, temperature of reaction changes 120 ℃ into, and the reaction times changes 30 hours into, after reaction is finished, filter out catalyzer after, directly weighing, alkalimetric titration calculate transformation efficiency.Other is all with embodiment 1.

Embodiment 6:

Remove and change the acid macroporous cation exchange resin catalyst of HD-72 into super acids SO ₄ ^2-/ ZrO ₂Catalyzer, and consumption changed into outside the 2.0g, other is all with embodiment 5.

Embodiment 7: remove SO ₄ ^2-/ ZrO ₂Catalyzer changes SO into ₄ ^2-/ ZrO ₂-SiO ₂Outside the catalyzer, other is all with embodiment 6 and embodiment 5.

Embodiment 8:

Remove super acids SO ₄ ^2-/ ZrO ₂Catalyzer changes into outside the phospho-wolframic acid, and other is all with embodiment 6 and embodiment 5.

Table 1

Embodiment	Catalyzer		Temperature of reaction (℃)	Reaction pressure Mpa	Time (hr)	Transformation efficiency (ml%)	Productive rate (ml%)
	Catalyzer							Title	Consumption
	1	98％H ₂SO ₄						Title	Consumption	2.0ml	110	1.0	20	95	86
2	1	98％H ₂SO ₄	70％H ₂SO ₄	3.0ml	110	1.0	20	99	90	2.0ml	110	1.0	20	95	86
2	3	50％H ₂SO ₄	70％H ₂SO ₄	3.0ml	110	1.0	20	99	90	3.0ml	110	1.0	20	75	67
4	3	50％H ₂SO ₄	H ₂SO ₄- H ₃PO ₄	3.0ml	100	1.0	20	98	90	3.0ml	110	1.0	20	75	67
4	4	HD-72	H ₂SO ₄- H ₃PO ₄	3.0ml	100	1.0	20	98	90	3.0g	120	1.0	30	89	80
5	4	HD-72	SZ	2.0g	120	1.0	30	60	55	3.0g	120	1.0	30	89	80
5	6	SZS	SZ	2.0g	120	1.0	30	60	55	2.0g	120	1.0	30	89	81
7	6	SZS	Phospho-wolframic acid	2.0g	110	0.9	30	56	50	2.0g	120	1.0	30	89	81

In the table: HD-72 is SO for acid big aperture Zeo-karb: SZ ₄ ^2-/ ZrO ₂SZS is SO ₄ ^2-/ ZrO ₂-SiO ₂" productive rate " is the actual output of final product and the ratio of theoretical yield (press Whitfield's ointment 100% and transform, and selectivity also is 100% calculating).

Claims

1, a kind of processing method of Synthesis of Isopropyl Salicylate is characterized in that: with Whitfield's ointment and propylene is raw material, and the consumption rate of Whitfield's ointment and propylene is 1: 1.05 mol ratio, is 50%～98% fluid sulphuric acid H with concentration range ₂SO ₄, mixture of sulfuric phosphoric acid, super acids SO ₄ ^2-/ ZrO ₂, SO ₄ ^2-/ ZrO ₂-SiO ₂Acidic cation-exchange resin solid acid or phospho-wolframic acid are catalyzer, and can use the solvent that comprises isopropyl acetate, hexanaphthene or benzene, and under 80～120 ℃, 0.5～1.5Mpa pressure, to react, catalyst consumption is benchmark with the Whitfield's ointment, its consumption is 1.0%～15% weight, reaction times is 10～40 hours, leaches catalyzer while hot after solid acid catalyst reaction is finished, be cooled to room temperature after, the unreacted Whitfield's ointment of filtered and recycled, filtrate is used excessive oxidation calcium CaO or lime carbonate CaCO ₃Neutralisation of sulphuric acid and most of residual Whitfield's ointment also absorb moisture, filtration, discard filter residue, and filtrate is the finished product isopropyl salicylate; Its concrete technological operation step is: (1) adds Whitfield's ointment in stainless steel cauldron, adds the liquid or solid acid catalyst of above-mentioned amount ranges and concentration range again; (2) lead to air in the propylene replacement reaction kettle into somewhat to dozens of minutes, close outlet again; (3) leading to into propylene, to make pressure to the reactor be above-mentioned pressure range, be warming up to the said temperature scope after, after the time through reacting above-mentioned reaction time range, be cooled to room temperature; (4) emit unnecessary propylene, take out the product weighing, take out the certainweight product and add in a certain amount of ethanol,, calculate transformation efficiency with the titration of 0.1MKOH solution; (5) cooled product is to room temperature, the unreacted Whitfield's ointment of filtered and recycled, and filtrate is with excessive calcium oxide CaO or lime carbonate CaCO ₃Neutralisation of sulphuric acid and residual Whitfield's ointment also absorb moisture, and filtration can obtain the finished product isopropyl salicylate, and last weighing calculates productive rate.