CN103172520A - Preparation method of 2,4,6-trichlorophenoxy formyl chloride - Google Patents

Abstract

The invention discloses a preparation method of an aromatic hydrocarbon derived compound, and in particular relates to a preparation method of 2,4,6-trichlorophenoxy formyl chloride. The preparation method comprises the following steps of: dissolving triphosgene in chlorobenzene to form liquid, wherein the mass concentration of triphosgene in chlorobenzene is 1-6%; then, adding trichlorophenol, a catalyst and the like into the liquid, and reacting for more than 4 hours under the condition of controlling the reaction temperature at 0-5 DEG C till no gases escape from the reaction liquid; and after standing for a half hour, removing ice-bath, then, continuously stirring for reaction for 2 hours at 25 DEG C, then, after stopping stirring and standing or a half hour, raising the temperature and reacting for 2 hours, and finally, after reacting for 2 hours in a normal pressure distilling apparatus, performing a distilling step and the like to obtain products. The method provided by the invention has the advantages that the antibacterial activity and the anti-fouling performance on the surface of the membrane are improved, and the comprehensive performance of the composite membrane is effectively improved.

Description

A kind of 2,4, the preparation method of 6-trichlorobenzene oxygen formyl chloride

Technical field

The present invention relates to a kind of preparation method of aromatic hydrocarbon derivative compound, specifically refer to a kind of 2,4, the preparation method of 6-trichlorobenzene oxygen formyl chloride.

Background technology

2,4,6-trichlorobenzene oxygen formyl chloride is mainly used in monomer polymerization and becomes in the macromolecular chain process, use as the macromolecular chain end-capping reagent, it contains-OCOCl oxygen acid chloride groups, and its activity is very high, with polynary amine and polyalcohols reaction the time, can form amino-formate bond.Add during cross-linked polymer during this monomer can be embedded in the cross linked chain framework of polymkeric substance with functional structure trichlorobenzene ring element in preparation, thereby can effectively improve the antibacterial and antifouling property on film surface.

Triphosgene claims again solid phosgene, compares with phosgene to have following advantage: toxicity is low, transportation, operational safety, and reactive behavior is high, and reaction conditions is gentle, so the present invention is take triphosgene as main acyl chlorinating agent, and under catalyst action, low temperature, synthesis under normal pressure prepare product.Trichlorophenol as raw material is important industrial chemicals, has certain anti-mold effect, main main raw material as dyestuff intermediate, sterilant, defoliating agent, preservation agent prochloraz also as the solvent of trevira, is widely used at organic synthesis, papermaking, dyeing.

Summary of the invention

The present invention is directed to deficiency of the prior art, proposed a kind ofly as acyl chlorinating agent, to have prepared the method for 2,4,6-trichlorobenzene oxygen formyl chloride take triphosgene (be called for short BTC) with 2,4,4-Trichlorophenol under catalyst action.

Reaction formula of the present invention is as follows:

In the present invention, specifically be achieved by following technical proposals:

A kind of 2,4, the preparation method of 6-trichlorobenzene oxygen formyl chloride, its feature comprises the following steps:

(1) triphosgene is dissolved in chlorobenzene, forms solution, wherein triphosgene is 1%～6% in the mass concentration of chlorobenzene;

(2) add Trichlorophenol again in above-mentioned solution, the mass concentration of Trichlorophenol in chlorobenzene is 0.05%～1.2%; And mixing solutions access device for recovering tail gas, add catalyst n under condition of ice bath, the N-N,N-DIMETHYLACETAMIDE, the mass concentration of catalyzer in solution is 0.02%～0.06%, then controlling temperature of reaction is that 0 ℃～5 ℃ lower reaction times of condition are more than 4 hours, until overflow without gas in reaction soln;

(3) remove ice bath after standing half an hour, then continued stirring reaction 2 hours under 25 ℃ of conditions;

(4) be positioned in well heater rising temperature to 100 ℃～130 ℃ reaction 2 hours after stopping again stirring standing half an hour;

(5) again device is converted to atmospheric distillation plant, rising temperature to 140 ℃ reaction 2 hours, reaction is standing cooling after finishing, pour out supernatant liquid, use extracted with diethyl ether, remove low-boiling point material and ether with the Rotary Evaporators underpressure distillation, be placed into vacuum drying oven vacuum-drying, get final product 2,4,6-trichlorobenzene oxygen formyl chloride.

The present invention prepared 2,4,6-trichlorobenzene oxygen formyl chloride contains-OCOCl oxygen acid chloride groups, its activity is very high, with the reaction of polynary amine and polyalcohols the time, can form amino-formate bond.Add during cross-linked polymer during this monomer can be embedded in the cross linked chain framework of polymkeric substance with functional structure trichlorobenzene ring element in preparation, thereby can effectively improve the antibacterial and antifouling property on film surface.In the present invention, the temperature condition in each step is controlled and the control in reaction times is crucial, can effectively control like this transformation efficiency of reaction product etc.Through the lower distillation of reducing pressure, get colourless transparent oil liquid in the present invention, being cooled to 2～4 ℃ of crystallizations becomes white blocks shape solid.Calculate productive rate according to product quality/theoretical yield, yield can reach 20%, in the dark-brown vial of packing into after taking-up, puts into Refrigerator store after sealing with wax.

Beneficial effect: through the present invention prepared 2,4,6-trichlorobenzene oxygen formyl chloride has the advantages such as the biocidal property that improves the film surface and resistance to crocking, effectively improves the over-all properties of composite membrane.

Description of drawings

Fig. 1: the IR collection of illustrative plates of 2,4,6-trichlorobenzene oxygen formyl chloride

Embodiment

The below illustrates enforcement of the present invention:

Embodiment 1

the 140g triphosgene is dissolved in the 2000mL chlorobenzene, then Trichlorophenol 10g is added in mentioned solution, the access device for recovering tail gas, drip catalyst n under ice bath, the reaction of N-N,N-DIMETHYLACETAMIDE 1mL stirring and refluxing, temperature is controlled at 0 ℃, reaction times be 4 hours to overflowing without gas, stop stirring after standing 0.5 hour and remove ice bath, 25 ℃ were continued stirring reaction 2 hours, stop stirring after standing 0.5 hour and be positioned in well heater, ℃ reaction of rising temperature to 120 is approximately after 2 hours, device is converted to atmospheric distillation plant, improve temperature to 140 ℃ reaction approximately after 2 hours, reaction ends standing cooling, pour out supernatant liquid, use extracted with diethyl ether, remove most of low-boiling point material and ether with the Rotary Evaporators underpressure distillation, be placed into vacuum drying oven vacuum-drying, under reduced pressure distillation, get colourless transparent oil liquid, be cooled to 2～4 ℃ of crystallizations and become white blocks shape solid.Calculate productive rate according to product quality/theoretical yield, yield is 20%, in the dark-brown vial of packing into after taking-up, puts into Refrigerator store after sealing with wax.Accompanying drawing 1 is seen figure for the infrared absorption spectrum of KBr sample actual measurement, infrared spectra as shown in the figure, 1787.28cm ^-1For-the OCOCl characteristic peak, prove that 2,4,6-trichlorobenzene oxygen formyl chloride is successfully prepared.

Embodiment 2～8

Changing the triphosgene consumption is 35g, 50g, 65g, 80g, 95g, 110g, 125g, and other operational conditions are all identical with embodiment 1, result such as following table:

Embodiment	Triphosgene consumption/g	The product outward appearance	Productive rate
				2	35	?	0
3	50	?	0
				4	65	Colourless transparent liquid	5%
5	80	Colourless transparent liquid	8%
				6	95	Colourless transparent liquid	11%
7	110	Colourless transparent liquid	16%
				8	125	Colourless transparent liquid	17%

Embodiment 9～11

Change Trichlorophenol 15,20g, 25g, other operational conditions are all identical with embodiment 1, result such as following table:

Embodiment	Trichlorophenol consumption/g	The product outward appearance	Productive rate
				9	15	Colourless transparent liquid	18%
10	20	Colourless transparent liquid	18%
				11	25	Colourless transparent liquid	14%

Embodiment 12～13

Change N,N-dimethylacetamide (DMAc) 0.6mL, 1.4mL, other operational conditions are all identical with embodiment 1, result such as following table:

Embodiment	DMAc consumption/mL	The product outward appearance	Productive rate
				12	0.6	Colourless transparent liquid	12%
13	1.4	Colourless transparent liquid	20%

Claims (1)

1. one kind 2,4, the preparation method of 6-trichlorobenzene oxygen formyl chloride, its feature comprises the following steps:

(1) triphosgene is dissolved in chlorobenzene, forms solution, wherein triphosgene is 1%～6% in the mass concentration of chlorobenzene;

(2) add Trichlorophenol again in above-mentioned solution, the mass concentration of Trichlorophenol in chlorobenzene is 0.05%～1.2%; And mixing solutions access device for recovering tail gas, add catalyst n under condition of ice bath, the N-N,N-DIMETHYLACETAMIDE, the mass concentration of catalyzer in solution is 0.02%～0.06%, then controlling temperature of reaction is that 0 ℃～5 ℃ lower reaction times of condition are more than 4 hours, until overflow without gas in reaction soln;

(3) remove ice bath after standing half an hour, then continued stirring reaction 2 hours under 25 ℃ of conditions;

(4) be positioned in well heater rising temperature to 100 ℃～130 ℃ reaction 2 hours after stopping again stirring standing half an hour;

(5) again device is converted to atmospheric distillation plant, rising temperature to 140 ℃ reaction 2 hours, reaction is standing cooling after finishing, pour out supernatant liquid, use extracted with diethyl ether, remove low-boiling point material and ether with the Rotary Evaporators underpressure distillation, be placed into vacuum drying oven vacuum-drying, get final product 2,4,6-trichlorobenzene oxygen formyl chloride.

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