CN100500640C - Preparation method for separating product of diphenyl carbonate - Google Patents
Preparation method for separating product of diphenyl carbonate Download PDFInfo
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- CN100500640C CN100500640C CNB2005100191527A CN200510019152A CN100500640C CN 100500640 C CN100500640 C CN 100500640C CN B2005100191527 A CNB2005100191527 A CN B2005100191527A CN 200510019152 A CN200510019152 A CN 200510019152A CN 100500640 C CN100500640 C CN 100500640C
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- diphenyl carbonate
- solvent
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- phenol
- crystal
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- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007670 refining Methods 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 13
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 6
- LONDRPCAODOVLM-UHFFFAOYSA-N diphenyl carbonate;phenol Chemical compound OC1=CC=CC=C1.C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 LONDRPCAODOVLM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- -1 poly-aryl carbonates Chemical class 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 241001640117 Callaeum Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for separating and refining the diphenyl carbonate generated by non-homogeneous catalytic oxidizing-carbonylating method includes such steps as dissolving the mixture of diphenyl carbonate and phenol in solvent (methanol, ethanol, or n-butanol) while heating, cooling at 1 deg.C/5-10 min until initial crystallizing temp, adding crystal seeds of diphenyl carbonate, cooling to 0-10 deg.C, holding the temp, filter, vacuum drying at 35-40 deg.C, and recrystallizing.
Description
Technical field
The present invention relates to a kind of product of diphenyl carbonate, especially use the method for separating and preparing of heterogeneous catalytic oxidation carbonylation method diphenyl carbonate synthesis product and this separation method gained crystalline process for purification.
Background technology
Diphenyl carbonate (DPC) is a kind of important engineering plastics intermediate, is mainly used in polyester industrial, makes products such as poly-aryl carbonates, P-hydroxybenzoic acid polyester, monoisocyanates, vulcabond, also can be used for preparing plastic plasticizer.In addition, in Chemical Manufacture, also can be used as solvent and thermophore.DPC low toxicity, pollution-free is a kind of important environmental protective chemical industry product.
The synthetic method of diphenyl carbonate mainly contains phosgenation, ester-interchange method, heterogeneous oxidative carbonylation method.Wherein heterogeneous oxidative carbonylation method is directly with CO, O
2Reaching phenol is raw material, generates DPC and water under the effect of catalyzer, and no abraum salt, waste gas produce, and are a kind of synthesis techniques of green.Because the catalyzer that heterogeneous oxidative carbonylation method is adopted is a solid catalyst, its synthesis technique is simple, by product is few, product is easy to separate, and is the synthetic method of at present tool development prospect.
Carbon current diphenyl phthalate production method is mainly phosgenation or ester-interchange method on industry, and the method that supporting with it traditional separation and purification diphenyl carbonate adopts is mainly rectification method, also has the report of multistage Steppecd crystallization, solvent extration etc. in addition.Rectification method is that the reaction mixture that will contain diphenyl carbonate joins and carries out rectification under vacuum in the rectifying tower, and whole process keeps the temperature at the bottom of the tower to be higher than 150 ℃, and at cat head Fractional Collections cut, last last running is pure DPC.Though rectification method can access the DPC of suitable purity, rectifying needs higher vacuum, to the equipment requirements strictness, can produce a large amount of phenolic waste liquors, contaminate environment simultaneously.Multistage Steppecd crystallization joins thick DPC in the crystallizer that overcoat is housed, and after the precooling, makes the temperature of DPC remain on its Tc below 1-2 ℃.Small when crystal formation when occurring, with 0.01～1 ℃ of min
-1Speed, the temperature of crystallizer is cooled off from top to bottom.When reaching minimum Tc, open bottom valve, emit spissated uncrystallized liquid, this liquid can merge the continuation crystallization with thick DPC.Control certain speed then, the temperature of crystallizer is slowly risen, the crystal that contains impurity can melt, and collects the liquid of fusing, makes its circulation crystallization.Like this in the crystal after the multistep crystallization DPC content greater than 96.7%.This technology is simple, and the DPC loss is few, but time-consuming, and temperature controlling is required height, and the purity of DPC is not high yet.Solvent extration adds a kind of neutral polarity extracting agent (as dodecane) in mixture, DPC and phenol extraction in organic phase, are added the heat extraction extraction agent, separate DPC and phenol with the method for underpressure distillation again, but this method separation efficiency is not high, has the same shortcoming of rectification method simultaneously.
Diphenyl carbonate is the basic raw material of polycarbonate synthesis (PC).Along with the fast development of polycarbonate industry and the little disconnected reinforcement of social enviroment protection consciousness, the technology that phosgenation is produced diphenyl carbonate is eliminated at last, and adopt this friendly process diphenyl carbonate synthesis of catalyzed oxidation carbonylation method to become the research and development focus gradually, its synthesis technique reaches its maturity, but the research of supporting with it separating technology report is less.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method for separating product that is used for diphenyl carbonate at the deficiency of above-mentioned prior art existence, it has that technology is easy, energy consumption is low, the characteristics of pollution-free and constant product quality, and the separating product that is particularly suited for heterogeneous catalytic oxidation carbonylation method diphenyl carbonate synthesis is equipped with.
The present invention for the technical scheme of the separation preparation that problem adopted of the above-mentioned proposition of solution is: with methyl alcohol, ethanol or propyl carbinol as solvent, join in the reaction mixture that contains diphenyl carbonate-phenol, the dissolving of heating, make reaction mixture dissolving fully in solvent, speed cooling with 1 ℃/5-10 minute, when FCTA temprature, the diphenyl carbonate crystal seed that adds trace, continue to be cooled to 0～10 ℃, insulation, filter then, obtain the diphenyl carbonate coarse-grain 35～40 ℃ of following vacuum-dryings.
Press such scheme, described reaction mixture components and the content that contains diphenyl carbonate-phenol is by weight: diphenyl carbonate 20-30%, phenol 68-78%, Tetrabutyl amonium bromide 1-3%, phenylate trace.
Press such scheme, the time of insulation is more than 1 hour or 1 hour.
The further process for refining of the present invention is: the diphenyl carbonate coarse-grain with separation obtains, add solvent again, and described solvent is methyl alcohol, ethanol or propyl carbinol, and heating is dissolving fully, and crystallisation by cooling separates drying then, obtains refining crystal.
In the such scheme, the proportioning that the diphenyl carbonate coarse-grain adds solvent is by weight:
Diphenyl carbonate coarse-grain: solvent=1: 1 or 1: 2.
The yield of diphenyl carbonate can reach 55-80% in the above-mentioned method for separating and preparing, and the content of diphenyl carbonate can reach more than 90% in the coarse-grain; The content of refining back diphenyl carbonate can reach more than 99.5%.
Beneficial effect of the present invention is: 1, this separating technology is easy and simple to handle, energy consumption is low, pollution-free, can not etching apparatus.2, can directly serve as solvent after filtrate is reclaimed reuses.3, it is low to select for use alcohols to do recrystallisation solvent products obtained therefrom purity height, steady quality, cost.4, simultaneously separation method of the present invention is suitable for the product of diphenyl carbonate produced with ester-interchange method equally.
Embodiment
The present invention is described in further detail below in conjunction with the example example.
Embodiment 1
(its component and content are by weight: the dipheryl carbonate ester content is 30% to get the reaction mixture 20g that contains diphenyl carbonate, phenol content is 67.3%, and Tetrabutyl amonium bromide content is 2.1%, and phenylate content is 0.6%), add ethanol 20g, the dissolving of heating makes reaction mixture dissolving fully in solvent, again with 1 ℃/10 minutes speed cooling, when temperature is reduced to 12 ℃, add 0.1g diphenyl carbonate powder crystal (crystal seed), continue to be cooled to 4 ℃, be incubated 1 hour; Vacuum filtration obtains crystal then, and under 35～40 ℃, vacuum-drying gets diphenyl carbonate coarse-grain 4.732g to constant weight.
With the diphenyl carbonate coarse-grain 4.732g that above-mentioned separation obtains, the etoh solvent of weight such as adding, heating is dissolving fully, and crystallisation by cooling separates then, and 50 ℃ of vacuum-dryings are to constant weight, and obtaining the refining crystal weight of diphenyl carbonate is 4.700g.
It is mother liquid obtained to merge twice Crystallization Separation, fractionation by distillation gets etoh solvent 18.4g, phenol mixture 15.1g (wherein phenol content is 87.8% by weight, Tetrabutyl amonium bromide content is 2.8%, DPC content is 8.6%, phenylate and ethanol equal size be 0.8%).
The yield that separates the back diphenyl carbonate is 77.2%, and the content of diphenyl carbonate is 96.2% in the gained crystal; The content of diphenyl carbonate is 99.8% in the crystal of refining back.
Embodiment 2
(its component and content are by weight: the dipheryl carbonate ester content is 20% to get the reaction mixture 20g that contains diphenyl carbonate, phenol content is 77.7%, Tetrabutyl amonium bromide content is 1.8%, phenylate content is 0.5%), add ethanol 20g, the dissolving of heating, make reaction mixture dissolving fully in solvent, with the speed cooling of 1 ℃/10min, when temperature is reduced to 12 ℃, add 0.1g recrystallization diphenyl carbonate powder crystal, continue to be cooled to 2 ℃, insulation 1h; Vacuum filtration obtains crystal then, is dried to constant weight under 35～40 ℃, and the weighing crystal weight is 3.165g.
With the crystal 3 .165g that above-mentioned separation obtains, adding waits weight solvent ethanol, and heating is dissolving fully, and crystallisation by cooling separates, and 50 ℃ of freeze-day with constant temperature obtain crystal 3 .082g.
It is mother liquid obtained to merge twice Crystallization Separation, and fractionation by distillation gets etoh solvent 16.3g, phenol mixture 16.8g (wherein phenol content is 91.4%, Tetrabutyl amonium bromide content is 2.1%, DPC content is 5.8%, phenylate and ethanol equal size be 0.7%).
The yield that separates the back diphenyl carbonate is 76.6%, and the content of diphenyl carbonate is 96.8% in the gained crystal; The content of diphenyl carbonate is 99.8% in the crystal of refining back.
Embodiment 3
(its component and content are by weight: the dipheryl carbonate ester content is 40% to get the reaction mixture 20g that contains diphenyl carbonate, phenol quality percentage composition is 56.8%, Tetrabutyl amonium bromide quality percentage composition is 2.6%, phenylate quality percentage composition is 0.6%) 20g, add methyl alcohol 20g, with the speed cooling of 1 ℃/10min, when temperature is reduced to 12 ℃, add 0.1g diphenyl carbonate powder crystal, continue to be cooled to 4 ℃, insulation 1h; Vacuum filtration obtains crystal then, is dried to constant weight under 35～40 ℃, gets crystal 5 .292g.
With the crystal 5 .292g that above-mentioned separation obtains, adding waits weight solvent methyl alcohol, and heating is dissolving fully, and crystallisation by cooling separates, and 45 ℃ of freeze-day with constant temperature obtain crystal 5 .200g.
It is mother liquid obtained to merge twice Crystallization Separation, and fractionation by distillation gets etoh solvent 17.3g, phenol mixture 14.5g (wherein phenol content is 76.2%, Tetrabutyl amonium bromide content is 3.6%, DPC content is 19.3%, phenylate and ethanol equal size be 0.9%).
The yield that separates the back diphenyl carbonate is 64.9%, and the content of diphenyl carbonate is 96.1% in the gained crystal; The content of diphenyl carbonate is 99.7% in the crystal of refining back.
Embodiment 4
(its component and content are by weight: the dipheryl carbonate ester content is 30% to get the reaction mixture 20g that contains diphenyl carbonate, phenol content is 67.3%, Tetrabutyl amonium bromide content is 2.1%, phenylate content is 0.6%), add propyl carbinol 20g, heating is dissolving fully, with the speed cooling of 1 ℃/10min, when temperature is reduced to 12 ℃, add 0.1g diphenyl carbonate powder crystal, continue to be cooled to 4 ℃, insulation 1h; Vacuum filtration obtains crystal then, is dried to constant weight under 35～40 ℃, gets crystal 3 .682g.
With the crystal 3 .682g that above-mentioned separation obtains, adding waits the weight solvent propyl carbinol, and heating is dissolving fully, and crystallisation by cooling separates, and 45 ℃ of freeze-day with constant temperature obtain crystal 3 .546g.
It is mother liquid obtained to merge twice Crystallization Separation, fractionation by distillation gets solvent, n-butanol 16.5g, phenol mixture 17.9g (wherein phenol content is 75.2%, Tetrabutyl amonium bromide content is 2.3%, DPC content is 21.8%, phenylate and propyl carbinol equal size be 0.7%).
The yield that separates the back diphenyl carbonate is 59.7%, and the content of diphenyl carbonate is 94.0% in the gained crystal; The content of diphenyl carbonate is 99.5% in the crystal of refining back.
Claims (5)
1, a kind of preparation method for separating product of diphenyl carbonate, it is characterized in that with methyl alcohol, ethanol or propyl carbinol joining in the reaction mixture that contains diphenyl carbonate-phenol the dissolving of heating as solvent, make reaction mixture dissolving fully in solvent, speed cooling with 1 ℃/5-10 minute when FCTA temprature, adds the diphenyl carbonate crystal seed of trace, continue to be cooled to 0～10 ℃, insulation is filtered then, obtains the diphenyl carbonate coarse-grain 35～40 ℃ of following vacuum-dryings.
2, by the described preparation method for separating product of diphenyl carbonate of claim 1, it is characterized in that described reaction mixture components and the content that contains diphenyl carbonate-phenol is by weight: diphenyl carbonate 20-30%, phenol 68-78%, Tetrabutyl amonium bromide 1-3%, phenylate trace.
3, by claim 1 or 2 described preparation method for separating product of diphenyl carbonate, it is characterized in that the time that is incubated is more than 1 hour or 1 hour.
4, by claim 1 or 2 described preparation method for separating product of diphenyl carbonate, it is characterized in that further process for refining is: the diphenyl carbonate coarse-grain that separation is obtained, add solvent again, described solvent is methyl alcohol, ethanol or propyl carbinol, heating is dissolving fully, crystallisation by cooling separates drying then, obtains refining crystal.
5,, it is characterized in that the proportioning of diphenyl carbonate coarse-grain adding solvent is by weight: diphenyl carbonate coarse-grain: solvent=1: 1 or 1: 2 by the described preparation method for separating product of diphenyl carbonate of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100191527A CN100500640C (en) | 2005-07-25 | 2005-07-25 | Preparation method for separating product of diphenyl carbonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100191527A CN100500640C (en) | 2005-07-25 | 2005-07-25 | Preparation method for separating product of diphenyl carbonate |
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| Publication Number | Publication Date |
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| CN1727324A CN1727324A (en) | 2006-02-01 |
| CN100500640C true CN100500640C (en) | 2009-06-17 |
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| CNB2005100191527A Expired - Fee Related CN100500640C (en) | 2005-07-25 | 2005-07-25 | Preparation method for separating product of diphenyl carbonate |
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| CN109134255B (en) * | 2018-09-16 | 2021-08-24 | 辽宁科技学院 | Method for refining diphenyl carbonate |
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