CN104744232A - Method for preparing isophthaloyl dichloride - Google Patents
Method for preparing isophthaloyl dichloride Download PDFInfo
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- CN104744232A CN104744232A CN201510118684.XA CN201510118684A CN104744232A CN 104744232 A CN104744232 A CN 104744232A CN 201510118684 A CN201510118684 A CN 201510118684A CN 104744232 A CN104744232 A CN 104744232A
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- phthaloyl chloride
- isophthaloyl dichloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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Abstract
The invention discloses a method for preparing isophthaloyl dichloride. The method comprises the steps of performing reaction on isophthalic acid serving as a raw material, N-phenyl-N-methylbenzamide or 4-dimethylamino-pyridine serving as a catalyst, dichloroethane or methylbenzene, chlorobenzene and xylene serving as a reacting solvent, phosgene COCl2 serving as a chlorinating agent; driving hydrogen chloride gas generated in reaction and chlorinating agent gas which is not completely reacted with nitrogen gas; rectifying at reduced pressure to obtain 99.95% by mass of high-quality isophthaloyl dichloride. According to the preparation method, the N-phenyl-N-methylbenzamide or 4-dimethylamino-pyridine is adopted as the catalyst, the intermediate formed with phosgene is stable and cannot be remained in the solution, the color of isophthaloyl dichloride is not influenced, the main problem that the product isophthaloyl dichloride is discolored because catalyst residues is easily distilled with the product at the same time during product rectification by the prior art; and the method has the advantages of simple process, easily available raw materials, low cost, convenience in operation, high product quality and stable quality, and can be used for completely meeting the product requirement of downstream products.
Description
Technical field
The present invention relates to a kind of preparation method of m-phthaloyl chloride.
Background technology
M-phthaloyl chloride can be used for the intermediate of aramid fiber, polyacrylic ester, fire resistant resin, insulating material, medicine, agricultural chemicals etc., the main monomer being used as synthesis aramid fiber 1313 (Nomax), polymeric amide, polyester, polyarylester, polyaramide, liquid crystal polymer etc., can be used as the properties-correcting agent of superpolymer simultaneously.
At present, the common method preparing m-phthaloyl chloride has phosgenation, sulfur oxychloride method, phosphorus trichloride method, phosphorus pentachloride method, ester chlorination process, p-xylene oxidation method, but current used method, because selected discoloring agent exists deposition, remains, so that the purity of the m-phthaloyl chloride of impact preparation, product content is low, impurity is many, and color is unstable.Such as to containing adding discoloring agent gac, DMF hydrochloride in the solution of m-phthaloyl chloride, gac is as discoloring agent complex process, operating environment is poor, filter leakiness carbon, affect decolorizing effect, N, dinethylformamide hydrochloride is large as discoloring agent usage quantity, make to there is trace catalyst resistates in the solution of m-phthaloyl chloride, relict catalyst is sticky mass, suspends in the solution, cause m-phthaloyl chloride product quality poor, easy variable color.And preparation manipulation is loaded down with trivial details, complex process, waste residue amount large, recycling difficulty, cost is high.
Summary of the invention
The preparation method of m-phthaloyl chloride provided by the invention is with N-phen yl-N-meth benzamide or DMAP for catalyzer, with ethylene dichloride or toluene, chlorobenzene, dimethylbenzene for reaction solvent, with phosgene COC1
2for chlorizating agent, react with m-phthalic acid raw material, then drive hydrogen chloride gas and the unreacted chlorizating agent gas completely of reaction generation with nitrogen, the high-quality m-phthaloyl chloride that obtained mass percentage is greater than 99.95% after rectification under vacuum.
The molar ratio of m-phthalic acid of the present invention and catalyzer is 1 ︰ 0.005-0.02; The molar ratio of m-phthalic acid and chlorizating agent is 1 ︰ 2.0-2.5; The mass ratio of m-phthalic acid and reaction solvent is 1 ︰ 1.5-2.6.The described reaction times is 3-7 hour, and temperature of reaction is 70-120 DEG C; Rectifying vacuum tightness is 10-50kpa, tower top temperature 40-90 DEG C, still liquid temp 120-150 DEG C.
Concrete operation step is as follows:
reinforced: under room temperature, to add inert solvent in the reactor, then add raw material, catalyzer, stir;
reaction: be progressively warming up to 70-120 DEG C, add chlorination reaction 3-7 hour, obtain reaction solution;
off gas treatment: pass into nitrogen in reaction solution, remains in chlorizating agent gas in reaction solution and hydrogen chloride gas to drive out of;
be separated: isolating the reaction solution containing m-phthaloyl chloride and the raffinate containing catalyzer by being separated, obtaining the reaction solution after separation;
rectifying: by the reaction solution after filtration Separation and Recovery solvent and other light constituent material under 20-50kpa vacuum tightness and 40-90 DEG C of tower top temperature; The high-quality m-phthaloyl chloride that content is greater than 99.95% is obtained again under 10-30kpa vacuum tightness and 120-150 DEG C of still liquid temp.
The present invention is owing to adopting N-phen yl-N-meth benzamide or DMAP to be catalyzer, the intermediate formed with phosgene is stablized, can not remain in the solution, the color of m-phthaloyl chloride is not affected, solve prior art relict catalyst very easily to steam with product when product rectifying simultaneously, make the main bugbear of product m-phthaloyl chloride variable color, and technique is simple, raw material is easy to get, cost is low, easy to operate, and product quality is high, steady quality, meets the production requirement of derived product completely.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
At room temperature, first 300 kilograms of ethylene dichloride, 160 kilograms of m-phthalic acids and 2 kilograms of DMAPs are joined in blender loader, start stirring and carry out mixing raw material liquid, with mateiral pump by compound feedstock transportation to the 1000 L reactor that mixes, close mateiral pump and material inlet valve; Open the whipping appts of reactor, compound stock liquid is heated to 50 DEG C, opens-5 DEG C of freezing water-cooled condensers in reactor top, open tail gas valve, then open phosgene valve, regulate gaseous state COC1
2flow is 35L/h, and feed temperature rises to 75 DEG C gradually, and remains to reaction end, reaction times is 4 hours, in reaction process, and the raw material in reaction solution is fewer and feweri, the color of solution gradually becomes faint yellow, when question response liquid does not have solid particulate and floss substantially, closes COC1
2feed valve, opens nitrogen valve, in reaction solution, pass into nitrogen, and to drive the gas such as phosgene and HCl remained in reaction solution out of, the catalyzer being positioned at reactor bottom is the mixture of faint yellow solid block mutually; Close nitrogen valve, obtain the solution containing m-phthaloyl chloride by phase separation.
The solution obtained by phase separation containing m-phthaloyl chloride is dropped in rectifying tower, rectifying tower is built with glass filler, overhead condenser is directly connected to vacuum pump, tower internal pressure keeps in certain scope, the tail gas that vacuum pump is discharged directly removes tail gas absorbing system, the light constituent materials such as solvent are isolated under the tower top temperature of the distillation pressure of 50kpa and 40 DEG C, the m-phthaloyl chloride of high-quality is obtained again under the still liquid temp of the rectifying pressure of 10kpa and 140 DEG C, through liquid-phase chromatographic analysis, the content of the m-phthaloyl chloride in product is greater than 99.95%.
Embodiment 2
At room temperature, first 300 kilograms of toluene, 160 kilograms of m-phthalic acids and 2 kilograms of N-phen yl-N-meth benzamide are joined in blender loader, start stirring and carry out mixing raw material liquid, with mateiral pump by compound feedstock transportation to the 1000 L reactor that mixes, close mateiral pump and material inlet valve; Open the whipping appts of reactor, compound stock liquid is heated to 50 DEG C, opens-5 DEG C of freezing water-cooled vent condensers in reactor top, open tail gas valve, then open phosgene valve, regulate gaseous state COC1
2flow is 35L/h, and feed temperature rises to 100 DEG C gradually, and remains to reaction end, reaction times is 4 hours, in reaction process, and the raw material in reaction solution is fewer and feweri, the color of solution gradually becomes faint yellow, when question response liquid does not have solid particulate and floss substantially, closes COC1
2feed valve, opens nitrogen valve, in reaction solution, pass into nitrogen, and to drive the gas such as phosgene and HCl remained in reaction solution out of, the catalyzer being positioned at reactor bottom is the mixture of faint yellow solid block mutually; Close nitrogen valve, obtain the solution containing m-phthaloyl chloride by phase separation.
The solution obtained by phase separation containing m-phthaloyl chloride is dropped in rectifying tower, rectifying tower is built with glass filler, overhead condenser is directly connected to vacuum pump, tower internal pressure keeps in certain scope, the tail gas that vacuum pump is discharged directly removes tail gas absorbing system, the light constituent materials such as solvent are isolated under the tower top temperature of the distillation pressure of 50kpa and 40 DEG C, the m-phthaloyl chloride of high-quality is obtained again under the still liquid temp of the rectifying pressure of 10kpa and 140 DEG C, through liquid-phase chromatographic analysis, the content of the m-phthaloyl chloride in product is greater than 99.95%.
Embodiment 3
At room temperature, first 300 kilograms of chlorobenzenes, 160 kilograms of m-phthalic acids and 2 kilograms of N-phen yl-N-meth benzamide are joined in blender loader, start stirring and carry out mixing raw material liquid, with mateiral pump by compound feedstock transportation to the 1000 L reactor that mixes, close mateiral pump and material inlet valve; Open the whipping appts of reactor, compound stock liquid is heated to 50 DEG C, opens-5 DEG C of freezing water-cooled vent condensers in reactor top, open tail gas valve, then open phosgene valve, regulate gaseous state COC1
2flow is 35L/h, and feed temperature rises to 100 DEG C gradually, and remains to reaction end, reaction times is 5 hours, in reaction process, and the raw material in reaction solution is fewer and feweri, the color of solution gradually becomes faint yellow, when question response liquid does not have solid particulate and floss substantially, closes COC1
2feed valve, opens nitrogen valve, in reaction solution, pass into nitrogen, and to drive the gas such as phosgene and HCl remained in reaction solution out of, the catalyzer being positioned at reactor bottom is the mixture of faint yellow solid block mutually; Close nitrogen valve, obtain the solution containing m-phthaloyl chloride by phase separation.
The solution obtained by phase separation containing m-phthaloyl chloride is dropped in rectifying tower, rectifying tower is built with glass filler, overhead condenser is directly connected to vacuum pump, tower internal pressure keeps in certain scope, the tail gas that vacuum pump is discharged directly removes tail gas absorbing system, the light constituent materials such as solvent are isolated under the tower top temperature of the distillation pressure of 50kpa and 40 DEG C, the m-phthaloyl chloride of high-quality is obtained again under the still liquid temp of the rectifying pressure of 10kpa and 140 DEG C, through liquid-phase chromatographic analysis, the content of the m-phthaloyl chloride in product is greater than 99.95%.
Embodiment 4
At room temperature, first 300 kilograms of dimethylbenzene, 160 kilograms of m-phthalic acids and 2 kilograms of N-phen yl-N-meth benzamide are joined in blender loader, start stirring and carry out mixing raw material liquid, with mateiral pump by compound feedstock transportation to the 1000 L reactor that mixes, close mateiral pump and material inlet valve; Open the whipping appts of reactor, compound stock liquid is heated to 50 DEG C, opens-5 DEG C of freezing water-cooled vent condensers in reactor top, open tail gas valve, then open phosgene valve, regulate gaseous state COC1
2flow is 35L/h, and feed temperature rises to 100 DEG C gradually, and remains to reaction end, reaction times is 5 hours, in reaction process, and the raw material in reaction solution is fewer and feweri, the color of solution gradually becomes faint yellow, when question response liquid does not have solid particulate and floss substantially, closes COC1
2feed valve, opens nitrogen valve, in reaction solution, pass into nitrogen, and to drive the gas such as phosgene and HCl remained in reaction solution out of, the catalyzer being positioned at reactor bottom is the mixture of faint yellow solid block mutually; Close nitrogen valve, obtain the solution containing m-phthaloyl chloride by phase separation.
The solution obtained by phase separation containing m-phthaloyl chloride is dropped in rectifying tower, rectifying tower is built with glass filler, overhead condenser is directly connected to vacuum pump, tower internal pressure keeps in certain scope, the tail gas that vacuum pump is discharged directly removes tail gas absorbing system, the light constituent materials such as solvent are isolated under the tower top temperature of the distillation pressure of 50kpa and 40 DEG C, the m-phthaloyl chloride of high-quality is obtained again under the still liquid temp of the rectifying pressure of 10kpa and 140 DEG C, through liquid-phase chromatographic analysis, the content of the m-phthaloyl chloride in product is greater than 99.95%.
Claims (2)
1. a preparation method for m-phthaloyl chloride, is characterized in that with N-phen yl-N-meth benzamide or DMAP for catalyzer, with ethylene dichloride or toluene, chlorobenzene, dimethylbenzene for reaction solvent, with phosgene COC1
2for chlorizating agent, react with m-phthalic acid raw material, then drive hydrogen chloride gas and the unreacted chlorizating agent gas completely of reaction generation with nitrogen, the high-quality m-phthaloyl chloride that obtained mass percentage is greater than 99.95% after rectification under vacuum.
2. the preparation method of m-phthaloyl chloride according to claim 1, it is characterized in that the molar ratio of m-phthalic acid and catalyzer is 1 ︰ 0.005-0.02, the molar ratio of m-phthalic acid and chlorizating agent is 1 ︰ 2.0-2.5, the mass ratio of m-phthalic acid and reaction solvent is 1 ︰ 1.5-2.6, reaction times is 3-7 hour, and temperature of reaction is 70-120 DEG C, and rectifying vacuum tightness is 10-50kpa, tower top temperature 40-90 DEG C, still liquid temp 120-150 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510118684.XA CN104744232A (en) | 2015-03-18 | 2015-03-18 | Method for preparing isophthaloyl dichloride |
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| CN201510118684.XA CN104744232A (en) | 2015-03-18 | 2015-03-18 | Method for preparing isophthaloyl dichloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601502A (en) * | 2016-03-08 | 2016-05-25 | 天津市敬业精细化工有限公司 | Method for preparing acyl chloride by catalyzing phosgene and acid |
| CN109621656A (en) * | 2018-12-29 | 2019-04-16 | 安徽广信农化股份有限公司 | A kind of tail gas treatment process synthesizing NSC 87419 |
Citations (4)
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|---|---|---|---|---|
| CN102093209A (en) * | 2009-12-14 | 2011-06-15 | 烟台氨纶股份有限公司 | Method for preparing aromatic dimethyl chloride |
| CN102344362A (en) * | 2011-09-30 | 2012-02-08 | 圣欧（苏州）安全防护材料有限公司 | Preparation method of high-purity isophthaloyl dichloride |
| CN102701960A (en) * | 2012-05-22 | 2012-10-03 | 天津大学 | Method and device for refining crude products of m-phthaloyl chloride |
| CN104086404A (en) * | 2014-06-30 | 2014-10-08 | 海利贵溪化工农药有限公司 | Preparation method of high-quality m-phthaloyl chloride |
-
2015
- 2015-03-18 CN CN201510118684.XA patent/CN104744232A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093209A (en) * | 2009-12-14 | 2011-06-15 | 烟台氨纶股份有限公司 | Method for preparing aromatic dimethyl chloride |
| CN102344362A (en) * | 2011-09-30 | 2012-02-08 | 圣欧（苏州）安全防护材料有限公司 | Preparation method of high-purity isophthaloyl dichloride |
| CN102701960A (en) * | 2012-05-22 | 2012-10-03 | 天津大学 | Method and device for refining crude products of m-phthaloyl chloride |
| CN104086404A (en) * | 2014-06-30 | 2014-10-08 | 海利贵溪化工农药有限公司 | Preparation method of high-quality m-phthaloyl chloride |
Non-Patent Citations (1)
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| 盛丽萍等: "光气法合成间苯二甲酰氯的工艺研究", 《企业技术开发》, vol. 24, no. 9, 30 September 2005 (2005-09-30) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601502A (en) * | 2016-03-08 | 2016-05-25 | 天津市敬业精细化工有限公司 | Method for preparing acyl chloride by catalyzing phosgene and acid |
| CN109621656A (en) * | 2018-12-29 | 2019-04-16 | 安徽广信农化股份有限公司 | A kind of tail gas treatment process synthesizing NSC 87419 |
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Application publication date: 20150701 |