CN104478710A - DPIP synthesis process - Google Patents
DPIP synthesis process Download PDFInfo
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- CN104478710A CN104478710A CN201410633053.7A CN201410633053A CN104478710A CN 104478710 A CN104478710 A CN 104478710A CN 201410633053 A CN201410633053 A CN 201410633053A CN 104478710 A CN104478710 A CN 104478710A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
Abstract
The invention discloses a diphenyl iso-phthalate (DPIP) synthesis process, and belongs to the field of organic synthesis. The synthesis process comprises that soluble caustic alkali is dissolved in water, phenol is added, stirring and dissolving are carried out, then an m-phthaloyl chloride solution dissolved in an organic solvent is dropwise added, and a synthesis reaction is generated; after the reaction is finished, diphenyl iso-phthalate, namely DPIP, can be obtained through extraction, distillation, crystallization, filtration and drying steps. The DPIP synthesis process is the green environment-friendly synthesis process, the reaction is mild, the conversion rate and yield are relatively high, and the reaction process is easy to operate.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to a kind of DPIP synthesis technique.
Background technology
DPIP full name is diphenylisophthalate, and white crystals is water insoluble.Diphenylisophthalate, can be used for organic synthesis, is one of monomer of PBT (polybenzothiozole) thermally stable polymer; The raw material of aromatic heterocycle superpolymer (as the heat resistant polymer such as polybenzimidazole, polybenzothiozole) can be made; Also can be used as the softening agent of nylon-based resin and the toughner of polyamide-based engineering plastics.
Since 2008, China is clearly classified as " crucial polymer monomer manufacturing technology " in the high performance polymer structured material of field of new the high-technology field of state key support.Along with the development of new material technology grows, the research that deepens continuously of novel high-performance synthon, the diphenylisophthalate as one of synthesis thermally stable polymer PBT monomer also receives much concern.
The main method of synthesis diphenylisophthalate has direct esterification, ester-interchange method and phase transfer catalysis process both at home and abroad at present.Direct esterification: adopt m-phthalic acid and phenol to be raw material, at catalyst A lCl
3with dewatering agent ZnCl
2condition under direct esterification.Because phenol itself is difficult to esterification, this reaction compares difficulty, and transformation efficiency is lower.Ester-interchange method: (1) take dimethyl isophthalate as raw material, with carboxylic acid phenyl ester under the catalysis of titanic acid ester, carries out transesterification reaction, obtains diphenylisophthalate.The method reaction process is longer and yield is low, complex operation, and workload is large.(2) make catalyzer with m-phthalic acid, diphenyl carbonate for raw material, tin protoxide, temperature, at 250 ~ 300 DEG C, is reacted 30 minutes to several hours.The method severe reaction conditions, energy consumption is large, and yield is low.Phase transfer catalysis process: with p-phthaloyl chloride (TPC), m-phthaloyl chloride (IPC), phenol, sodium hydroxide for raw material, by surface reaction synthesis terephthaldehyde's diphenyl phthalate (DPT) and diphenylisophthalate (DPI).The method cost is higher, and phase-transfer catalyst cannot recycle and reuse.
Summary of the invention
The object of the invention is to the shortcoming overcoming prior art, provide a kind of DPIP synthesis technique.
Object of the present invention is achieved through the following technical solutions: a kind of DPIP synthesis technique, and with m-phthaloyl chloride, phenol and solubility caustic alkali for raw material, water and organic solvent are solvent, synthesis diphenylisophthalate, i.e. DPIP.
Described a kind of DPIP synthesis technique is by soluble in water for solubility caustic alkali, adds phenol, stirring and dissolving, then drips the isophthaloyl chlorine solution being dissolved in organic solvent, and building-up reactions occurs.
Described m-phthaloyl chloride and phenol mole be 1:2.0 ~ 2.2, the mol ratio of phenol and solubility caustic alkali is 1:1.1 ~ 1.3; Described solubility caustic alkali is potassium hydroxide, i.e. KOH; Described organic solvent is methylene dichloride, i.e. DCM; Described m-phthaloyl chloride: the weight ratio of water is 1:2 ~ 3.
After described building-up reactions terminates, through extraction, distillation, crystallization, filtration and baking step, namely obtain diphenylisophthalate; Described m-phthaloyl chloride: the weight ratio of methylene dichloride is 1:5.5 ~ 8.5; In described extraction system, extraction agent is methylene dichloride, diphenylisophthalate: the weight ratio of methylene dichloride is 1:1.7 ~ 2.8; Described distillation system diphenylisophthalate: the weight ratio of water is 1:6 ~ 12.
A specific embodiment for DPIP synthesis technique, comprises the steps:
S1. the preparation of reaction soln: potassium hydroxide is dissolved in water, adds phenol, stirring and dissolving, obtain solution A; Added by m-phthaloyl chloride in solvent DCM, stirring and dissolving, obtains solution B;
S2. react: in the solution A that step S1 obtains, drip the B solution obtained in step S1, control temperature is at 0 ~ 30 DEG C, and time for adding is 2 ~ 3h; Drip and terminate, still keep this temperature, Keep agitation, reaction, until react completely;
S3. extract: separatory after reacting completely, aqueous phase DCM extraction 2 ~ 3 times, merges organic phase, washing organic phase 1 ~ 2 time, and wherein, middle layer bucket is collected and continued to employ;
S4. distillation, crystallization;
S5. filter;
S6. rewinding obtains white solid product.
Beneficial effect of the present invention: (1) does raw material with m-phthaloyl chloride, reaction temperature and, can react at normal temperature; (2) reaction process easily operates; (3) transformation efficiency and yield higher; (4) in the waste water discharged, organic content is few, and environmental pollution is little, more environmental protection; (5) do not need to add catalyzer, there is not catalyst recovery Utilizing question.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, and protection scope of the present invention is not limited to the following stated.
Embodiment 1: a kind of DPIP synthesis technique, its reaction principle is:
A kind of DPIP synthesis technique, specific experiment step is as follows:
S1. the preparation of reaction soln
S11. 212g potassium hydroxide is dissolved in 700g water, adds 324g phenol, stirring and dissolving, obtain solution A;
S12. add in 2000g DCM by 350g m-phthaloyl chloride, stirring and dissolving, obtains solution B;
S2. react
S21. drip B solution in step S12 in the solution A obtained to step S11, control temperature is at 0 DEG C, and time for adding is 3h;
S22. drip end, maintain the temperature at 0 DEG C, Keep agitation, reaction, until TLC1 detection reaction is complete, stop stirring reaction;
S3. extract
Separatory after reacting completely, aqueous phase DCM extracts 2 times, uses 500g at every turn, merges organic phase, and aqueous phase TLC2 detects with or without product, washes organic phase 1 time with 1000g, and wherein, middle layer bucket is collected and continued to employ;
S4. distillation, crystallization
By interior temperature control at 82 DEG C, distillation organic phase, add 3300g water when steaming 2000g DCM, slowly drip, time for adding is 2h, continues distillation until DCM all steams;
S5. filter
After solvent recuperation is complete, cools to 20 DEG C, stir 45 minutes; Filter, mother liquor TLC detects whether have product, with 700g water wash solid, obtains white solid product;
S6. rewinding obtains product
To obtain white solid product in step S5, carry out baking material, when surveying KF < 0.5%, rewinding obtains dry white solid.
Weighed by the white solid obtained, quality is 517.6g, and yield is 94.31%.
Embodiment 2: a kind of DPIP synthesis technique, its reaction principle is:
A kind of DPIP synthesis technique, specific experiment step is as follows:
S1. the preparation of reaction soln
S11. 275g potassium hydroxide is dissolved in 1050g water, adds 356g phenol, stirring and dissolving, obtain solution A;
S12. add in 2900g DCM by 350g m-phthaloyl chloride, stirring and dissolving, obtains solution B;
S2. react
S21. drip B solution in step S12 in the solution A obtained to step S11, control temperature is at 30 DEG C, and time for adding is 2h;
S22. drip end, maintain the temperature at 30 DEG C, Keep agitation, reaction, until TLC1 detection reaction is complete, stop stirring reaction;
S3. extract
Separatory after reacting completely, aqueous phase DCM extracts 3 times, uses 500g at every turn, merges organic phase, and aqueous phase TLC2 detects with or without product, washes organic phase 2 times with 1000g, and wherein, middle layer bucket is collected and continued to employ;
S4. distillation, crystallization
By interior temperature control at 84 DEG C, distillation organic phase, add 6600g water when steaming 2900g DCM, slowly drip, time for adding is 3h, continues distillation until DCM all steams;
S5. filter
After solvent recuperation is complete, cools to 23 DEG C, stir 50 minutes; Filter, mother liquor TLC detects whether have product, with 700g water wash solid, obtains white solid product;
S6. rewinding obtains product
To obtain white solid product in step S5, carry out baking material, when surveying KF < 0.5%, rewinding obtains dry white solid.
Weighed by the white solid obtained, quality is 521.9g, and yield is 95.09%.
Embodiment 3: a kind of DPIP synthesis technique, is characterized in that, its reaction principle is:
A kind of DPIP synthesis technique, specific experiment step is as follows:
S1. the preparation of reaction soln
S11. be dissolved in 800g water by 235g potassium hydroxide, add 335g phenol, stirring and dissolving obtains solution C;
S12. 350g m-phthaloyl chloride is added in 2300gDCM, stirring and dissolving, obtain solution D;
S2. react
S21. drip the solution D obtained in step S12 in the solution C obtained to step S11, control temperature is at 10 DEG C, and time for adding is 2.5h;
S22. drip end, maintain the temperature at 10 DEG C, Keep agitation, reaction, until TLC1 detection reaction completely after, stop stirring reaction;
S3. extract
Separatory after reacting completely, aqueous phase DCM extracts 2 times, uses 500g DCM at every turn, merges organic phase, and aqueous phase TLC2 detects with or without product, washes organic phase 1 time with 1000g, and wherein, middle layer bucket is collected and continued to employ;
S4. distillation, crystallization
By interior temperature control at 80 DEG C, distillation organic phase, add 4400g water when steaming 2300g DCM, slowly drip, time for adding is 2.5h, continues distillation until DCM all steams;
S5. filter
Solvent DCM reclaims completely, cools to 20 DEG C, stirs 1h; Filter, mother liquor TLC detects whether have product, with 700g water wash solid, obtains white solid product;
S6. rewinding obtains product
To obtain white solid product in step S5, carry out baking material, when surveying KF < 0.5%, rewinding obtains dry white solid.
Weighed by the white solid obtained, quality is 519.7g, and yield is 94.69%.
Embodiment 4: a kind of DPIP synthesis technique, is characterized in that, its reaction principle is:
A kind of DPIP synthesis technique, specific experiment step is as follows:
S1. the preparation of reaction soln
S11. be dissolved in 900g water by 260g potassium hydroxide, add 345g phenol, stirring and dissolving obtains solution C;
S12. 350g m-phthaloyl chloride is added in 2600gDCM, stirring and dissolving, obtain solution D;
S2. react
S21. drip the solution D obtained in step S12 in the solution C obtained to step S11, control temperature is at 20 DEG C, and time for adding is 2.5h;
S22. drip end, maintain the temperature at 20 DEG C, Keep agitation, reaction, until TLC1 detection reaction completely after, stop stirring reaction;
S3. extract
Separatory after reacting completely, aqueous phase DCM extracts 2 times, uses 500g DCM at every turn, merges organic phase, and aqueous phase TLC2 detects with or without product, washes organic phase 2 times with 1000g, and wherein, middle layer bucket is collected and continued to employ;
S4. distillation, crystallization
By interior temperature control at 88 DEG C, distillation organic phase, add 5000g water when steaming 2600g DCM, slowly drip, time for adding is 3h, continues distillation until DCM all steams;
S5. filter
Solvent DCM reclaims completely, cools to 23 DEG C, stirs 0.5h; Filter, mother liquor TLC detects whether have product, with 700g water wash solid, obtains white solid product;
S6. rewinding obtains product
To obtain white solid product in step S5, carry out baking material, when surveying KF < 0.5%, rewinding obtains dry white solid.
Weighed by the white solid obtained, quality is 522.3g, and yield is 95.16%.
Claims (10)
1. a DPIP synthesis technique, is characterized in that, with m-phthaloyl chloride, phenol and solubility caustic alkali for raw material, water and organic solvent are solvent, synthesis diphenylisophthalate, i.e. DPIP.
2. a kind of DPIP synthesis technique according to claim 1, it is characterized in that, described DPIP synthesis technique is by soluble in water for solubility caustic alkali, add phenol, stirring and dissolving, then drips the isophthaloyl chlorine solution being dissolved in organic solvent, and building-up reactions occurs.
3. a kind of DPIP synthesis technique according to claim 1 or 2, is characterized in that, described m-phthaloyl chloride and phenol mole be 1:2.0 ~ 2.2, the mol ratio of phenol and solubility caustic alkali is 1:1.1 ~ 1.3.
4. a kind of DPIP synthesis technique according to claim 1 or 2, is characterized in that, described solubility caustic alkali is potassium hydroxide, i.e. KOH.
5. a kind of DPIP synthesis technique according to claim 1 or 2, is characterized in that, described organic solvent is methylene dichloride, i.e. DCM.
6. a kind of DPIP synthesis technique according to claim 1 or 2, is characterized in that, described m-phthaloyl chloride: the weight ratio of water is 1:2 ~ 3.
7. a kind of DPIP synthesis technique according to claim 2, is characterized in that, after described building-up reactions terminates, through extraction, distillation, crystallization, filtration and baking step, namely obtain diphenylisophthalate.
8. a kind of DPIP synthesis technique according to claim 5, is characterized in that, described m-phthaloyl chloride: the weight ratio of methylene dichloride is 1:5.5 ~ 8.5.
9. a kind of DPIP synthesis technique according to claim 7, it is characterized in that, in described extraction system, extraction agent is methylene dichloride, diphenylisophthalate: the weight ratio of methylene dichloride is 1:1.7 ~ 2.8.
10. a kind of DPIP synthesis technique according to claim 7, is characterized in that, described distillation system diphenylisophthalate: the weight ratio of water is 1:6 ~ 12.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0044510A1 (en) * | 1980-07-18 | 1982-01-27 | General Electric Company | Process for the preparation of diaryl esters |
| US4393231A (en) * | 1978-09-19 | 1983-07-12 | Daikin Kogyo Co., Ltd. | Fluorine-containing phenyl benzoate compounds, and their production and use |
| CN102643199A (en) * | 2012-04-25 | 2012-08-22 | 中国石油化工股份有限公司 | Synthesis method of diphenyl isophthalate |
| CN102675112A (en) * | 2012-05-21 | 2012-09-19 | 山东凯盛新材料股份有限公司 | Synthetic method of diphenyl iso-phthalate |
-
2014
- 2014-11-11 CN CN201410633053.7A patent/CN104478710A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4393231A (en) * | 1978-09-19 | 1983-07-12 | Daikin Kogyo Co., Ltd. | Fluorine-containing phenyl benzoate compounds, and their production and use |
| EP0044510A1 (en) * | 1980-07-18 | 1982-01-27 | General Electric Company | Process for the preparation of diaryl esters |
| CN102643199A (en) * | 2012-04-25 | 2012-08-22 | 中国石油化工股份有限公司 | Synthesis method of diphenyl isophthalate |
| CN102675112A (en) * | 2012-05-21 | 2012-09-19 | 山东凯盛新材料股份有限公司 | Synthetic method of diphenyl iso-phthalate |
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