JPS5934170B2 - Production method of diphenyl carbonate ester - Google Patents
Production method of diphenyl carbonate esterInfo
- Publication number
- JPS5934170B2 JPS5934170B2 JP56023198A JP2319881A JPS5934170B2 JP S5934170 B2 JPS5934170 B2 JP S5934170B2 JP 56023198 A JP56023198 A JP 56023198A JP 2319881 A JP2319881 A JP 2319881A JP S5934170 B2 JPS5934170 B2 JP S5934170B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- diphenyl carbonate
- production method
- carbonate ester
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 diphenyl carbonate ester Chemical class 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000005910 alkyl carbonate group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229940049953 phenylacetate Drugs 0.000 description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCNSGSUGQPDYTK-UHFFFAOYSA-N ethyl phenyl carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1 YCNSGSUGQPDYTK-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
本発明は、一般式
、・−ｊ■・網
Ｒ（０〜５）Ｒ（ｏ〜５）
（式中Ｒはアルキル基、アルコキシル基、アリール基、
アリーロキシル基およびＮ０２基から選ばれる置換基で
ある）を有する芳香族炭酸エステル、特にジフェニル炭
酸エステルの製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula, -j■, network R(0-5)R(o-5) (wherein R is an alkyl group, an alkoxyl group, an aryl group,
The present invention relates to a method for producing an aromatic carbonate, in particular a diphenyl carbonate, having a substituent selected from an aryloxyl group and an N02 group.
前記化合物は相当するフェノールを原料として複雑な方
法に従つてホスゲンある（・はクロロホルムとの反応に
より生成されることは公知であるが、該方法では使用す
る原料の毒性による危険があり、副生成物として塩酸を
生成する。これに対して、触媒として強酸の存在下、フ
ェノールとアルキル炭酸エステルとを反応させうること
も公知である。It is known that phosgene is produced by a complex method using the corresponding phenol as a raw material by reaction with chloroform, but this method carries risks due to the toxicity of the raw materials used and does not produce by-products. It is also known that phenol can be reacted with an alkyl carbonate in the presence of a strong acid as a catalyst.
しかしながら、該方法は反応率が低く、副生成物として
多量のフェノールエーテルを生成する欠点がある。芳香
族炭酸エステルは芳香族ポリ炭酸エステルの製法ある（
・はイソシアネートの合成における中間体として使用さ
れるため、工業的に非常に重要である。However, this method has the disadvantage of a low reaction rate and the production of a large amount of phenol ether as a by-product. There is a method for producing aromatic polycarbonate ester (
- is of great industrial importance because it is used as an intermediate in the synthesis of isocyanates.
本発明者等は、適当な触媒の存在下にお（・て、相当の
フェノールあるいはアシルエステルをアルキル炭酸エス
テルある（・はアリール−アルキル炭酸エステルと反応
させることにより、高収率でしかも高選択率でジフェニ
ル炭酸エステルが得られることを見出し、本発明に至つ
たものである。The present inventors have demonstrated that by reacting a corresponding phenol or acyl ester with an alkyl carbonate (or aryl-alkyl carbonate) in the presence of an appropriate catalyst, a high yield and high selectivity can be obtained. The inventors have discovered that diphenyl carbonate can be obtained at a similar rate, leading to the present invention.
該反応は、液相において、溶媒を使用しまたは使用する
ことなく、温度２５な（ル３５０℃、好ましくは８０な
（・し２５０℃、圧力０．１ないし１００気圧、好まし
くは１な（・し２５気圧で行なわれる。フェノール化合
物と炭酸エステルとのモル比は１００：１な（・し１：
１００、好ましくは５：１な（・し１：１０である。有
効な触媒としては、ルイス酸ある（・はルイス酸を生成
しうる金属のまたは遷移金属の化合物、好ましくはＴｉ
Ｘ４またはＡｌＸ３（式中Ｘはアルコキシル基またはア
リーロキシル基である）で表わされる化合物が使用でき
る。本発明の方法は上記以外の芳香族誘導体、たとえば
相当するアルキル化合物を原料として芳香族チオ炭酸塩
ある℃・は芳香族炭酸イミドを製造する場合にも使用で
きる。The reaction is carried out in the liquid phase, with or without the use of a solvent, at a temperature of 25° C., preferably 80° C. and 250° C., and a pressure of 0.1 to 100 atm, preferably 100° C. The molar ratio of the phenol compound to the carbonate ester is 100:1 (.1:1).
100, preferably 5:1 (· and 1:10. Effective catalysts include Lewis acids, where * is a metal or transition metal compound capable of forming a Lewis acid, preferably Ti
Compounds represented by X4 or AlX3 (wherein X is an alkoxyl group or an aryloxyl group) can be used. The method of the present invention can also be used to produce aromatic derivatives other than those mentioned above, such as aromatic thiocarbonates and aromatic carbonic imides using the corresponding alkyl compounds as raw materials.
実施例 １
分液用ヘツドを具備するたな段数１０段の蒸留カラムを
取付けた容積２１のフラスコを使用し、温度１８０℃に
お℃・て、Ｔｉ（Ｏφ）４の存在下、ヘプタン中でフエ
ニルエチル炭酸エステルとフエノ一ルとを反応させた（
フエニルエチル炭酸エステル／フエノ一ル／Ｔｉ（Ｏφ
）のモル比−１／０．８／０．０４）。Example 1 Using a 21-volume flask equipped with a 10-shelf distillation column equipped with a liquid separation head, the reaction was carried out in heptane at a temperature of 180°C in the presence of Ti(Oφ)4. Phenylethyl carbonate and phenol were reacted (
Phenylethyl carbonate/phenol/Ti(Oφ
) molar ratio -1/0.8/0.04).
ノルマルーヘプタン−エチルアルコールの混合物を常時
蒸留しかつ蒸留された分を補充するためノルマル−ヘプ
タンを添加しながら反応を行なつた。反応４時間後では
、フエノ一ルの変化率は４２％であり、ジフエニル炭酸
エステルへの選択率は１００％であつた。The reaction was carried out while constantly distilling the n-heptane-ethyl alcohol mixture and adding n-heptane to make up for the distilled content. After 4 hours of reaction, the conversion rate of phenol was 42%, and the selectivity to diphenyl carbonate was 100%.
実施例 ２
分液用ヘツドを具備するたな段数２０段の蒸留カラムを
取付けた２５０ＣＣのフラスコを使用し、この中に、１
４５℃にお（・て、酢酸フエニル６８７、ジエチル炭酸
エステル６０７およびチタニウムフエネート２７を導入
した。Example 2 A 250CC flask equipped with a 20-shelf distillation column equipped with a separation head was used.
At 45° C., 687 phenyl acetate, 607 diethyl carbonate and 27 titanium phenate were introduced.
連続的に酢酸エチルを蒸留しながら４時間反応を行なつ
たところ、ジフエニル炭酸エステル（６８モル％）およ
びフエニルーエチル炭酸エステル（３０モル％）が得ら
れ、総選択率は９８％以上、酢酸フエニルの変化率は９
５％であつた。実施例 ３
前記と同じ反応器に、１４５℃で、酢酸フエニル７４７
、ジメチル炭酸エステル９０７および四メトキシチタン
１７を導入した。When the reaction was carried out for 4 hours while continuously distilling ethyl acetate, diphenyl carbonate (68 mol%) and phenyl-ethyl carbonate (30 mol%) were obtained, and the total selectivity was over 98%, indicating that the phenyl acetate The rate of change is 9
It was 5%. Example 3 In the same reactor as above, at 145°C, phenyl acetate 747
, dimethyl carbonate 907 and tetramethoxytitanium 17 were introduced.
酢酸メチルを連続的に蒸留しながら反応を４時間行なつ
たところ、ジフエニル炭酸エステル８０％（モル）およ
びフエノ一ルーメチル炭酸エステル１８％が得られた。
総選択率は９８％以上であり、酢酸メチルの選択率は９
７％であつた。実施例 ４
実施例２で使用したものと同じ反応器に、酢酸フエニル
６８７、フエニルメチル炭酸エステル８０ｙ１ノルマル
−ヘプタン２５ＣＣおよびアルミニウムエチレート１．
５７を温度１５０℃で導入した。When the reaction was carried out for 4 hours while continuously distilling methyl acetate, 80% (mol) of diphenyl carbonate and 18% of phenol-methyl carbonate were obtained.
The total selectivity is more than 98%, and the selectivity for methyl acetate is 9
It was 7%. Example 4 In the same reactor used in Example 2, 687 phenyl acetate, 80 y1 phenyl methyl carbonate, 25 cc normal heptane, and 1.
57 was introduced at a temperature of 150°C.
Claims (1)
シル基またはアリーロキシル基である）でなる群から選
ばれる触媒の存在下、フェノールまたはそのアシルエス
テルとアルキル炭酸エステルまたはアリール−アルキル
炭酸エステルとを反応させることを特徴とする、ジフェ
ニル炭酸エステルの製法。1 Reacting phenol or its acyl ester with an alkyl carbonate or an aryl-alkyl carbonate in the presence of a catalyst selected from the group consisting of TiX_4 or AlX_3 (wherein Characteristic manufacturing method of diphenyl carbonate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24392A/74 | 1974-06-25 | ||
| IT24392/74A IT1015377B (en) | 1974-06-25 | 1974-06-25 | PROCESS FOR THE PREPARATION OF AROMATIC CARBONATES |
| IT20191A/75 | 1975-02-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56123948A JPS56123948A (en) | 1981-09-29 |
| JPS5934170B2 true JPS5934170B2 (en) | 1984-08-21 |
Family
ID=11213360
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56023198A Expired JPS5934170B2 (en) | 1974-06-25 | 1981-02-20 | Production method of diphenyl carbonate ester |
| JP56023199A Expired JPS5934171B2 (en) | 1974-06-25 | 1981-02-20 | Production method of bisphenol A polyalkyl carbonate ester |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56023199A Expired JPS5934171B2 (en) | 1974-06-25 | 1981-02-20 | Production method of bisphenol A polyalkyl carbonate ester |
Country Status (7)
| Country | Link |
|---|---|
| JP (2) | JPS5934170B2 (en) |
| BE (1) | BE830364A (en) |
| HU (1) | HU171825B (en) |
| IN (1) | IN143867B (en) |
| IT (1) | IT1015377B (en) |
| MW (1) | MW3575A1 (en) |
| ZA (1) | ZA753587B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4452968A (en) * | 1981-11-30 | 1984-06-05 | General Electric Company | Synthesis of polycarbonate from dialkyl carbonate and bisphenol diester |
| JP2733035B2 (en) * | 1994-05-31 | 1998-03-30 | 株式会社日本触媒 | Method for producing carbonate ester |
| JP2733036B2 (en) * | 1994-07-05 | 1998-03-30 | 株式会社日本触媒 | Method for producing carbonate ester |
| JP2922848B2 (en) * | 1996-06-14 | 1999-07-26 | 株式会社日本触媒 | Method for producing aromatic carbonate |
| JP5014787B2 (en) | 2004-06-17 | 2012-08-29 | 旭化成ケミカルズ株式会社 | Method for producing aromatic carbonate |
| BRPI0513251A (en) | 2004-07-13 | 2008-05-13 | Asahi Kasei Chemicals Corp | process for the production of an aromatic carbonate, and aromatic carbonate |
| WO2006006566A1 (en) | 2004-07-13 | 2006-01-19 | Asahi Kasei Chemicals Corporation | Industrial process for producing aromatic carbonate |
| CN100543006C (en) | 2004-07-14 | 2009-09-23 | 旭化成化学株式会社 | Process for the industrial preparation of aromatic carbonates |
| CN100532348C (en) | 2004-07-14 | 2009-08-26 | 旭化成化学株式会社 | Process for industrial production of an aromatic carbonate |
| BRPI0514564B1 (en) | 2004-08-25 | 2015-06-09 | Asahi Kasei Chemicals Corp | Industrial process for producing high purity diphenyl carbonate and apparatus for producing high purity diphenyl carbonate |
| KR100880141B1 (en) | 2004-09-03 | 2009-01-23 | 아사히 가세이 케미칼즈 가부시키가이샤 | Industrial preparation method of high purity diaryl carbonate |
| CN100554241C (en) | 2004-09-17 | 2009-10-28 | 旭化成化学株式会社 | Industrial separation method of alcohol by-product |
| JP4292214B2 (en) | 2004-10-14 | 2009-07-08 | 旭化成ケミカルズ株式会社 | Method for producing high-purity diaryl carbonate |
| TWI321561B (en) | 2004-12-21 | 2010-03-11 | Asahi Kasei Chemicals Corp | Method for producing aromatic carbonate |
| JP4195717B2 (en) | 2004-12-24 | 2008-12-10 | 旭化成ケミカルズ株式会社 | Method for producing aromatic carbonate |
| JP5589266B2 (en) * | 2008-06-09 | 2014-09-17 | 宇部興産株式会社 | Method for producing poly (alkylene carbonate) compound |
-
1974
- 1974-06-25 IT IT24392/74A patent/IT1015377B/en active
-
1975
- 1975-06-03 ZA ZA00753587A patent/ZA753587B/en unknown
- 1975-06-07 MW MW35/75A patent/MW3575A1/en unknown
- 1975-06-16 IN IN1177/CAL/75A patent/IN143867B/en unknown
- 1975-06-18 BE BE157438A patent/BE830364A/en not_active IP Right Cessation
- 1975-06-24 HU HU75SA00002809A patent/HU171825B/en unknown
-
1981
- 1981-02-20 JP JP56023198A patent/JPS5934170B2/en not_active Expired
- 1981-02-20 JP JP56023199A patent/JPS5934171B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1015377B (en) | 1977-05-10 |
| BE830364A (en) | 1975-10-16 |
| JPS5934171B2 (en) | 1984-08-21 |
| HU171825B (en) | 1978-03-28 |
| MW3575A1 (en) | 1976-10-13 |
| IN143867B (en) | 1978-02-18 |
| JPS56123949A (en) | 1981-09-29 |
| JPS56123948A (en) | 1981-09-29 |
| ZA753587B (en) | 1976-05-26 |
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