JPS5934171B2 - Production method of bisphenol A polyalkyl carbonate ester - Google Patents
Production method of bisphenol A polyalkyl carbonate esterInfo
- Publication number
- JPS5934171B2 JPS5934171B2 JP56023199A JP2319981A JPS5934171B2 JP S5934171 B2 JPS5934171 B2 JP S5934171B2 JP 56023199 A JP56023199 A JP 56023199A JP 2319981 A JP2319981 A JP 2319981A JP S5934171 B2 JPS5934171 B2 JP S5934171B2
- Authority
- JP
- Japan
- Prior art keywords
- bisphenol
- carbonate ester
- production method
- carbonate
- group
- 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
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、芳香族炭酸エステル、特に、一般式Ｒ−ＯΠ
ｏ□÷ΦｏＭｏ畑ＲＯＣＨ３０
（式中、Ｒはアルキル基であり、ｎは１以上の数である
）で表わされるビスフェノールＡポリアルキル炭酸エス
テルの製法に係わる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to aromatic carbonate esters, in particular compounds with the general formula R-OΠ
o□÷ΦoMohataROCH30 (wherein R is an alkyl group, and n is a number of 1 or more).
芳香族炭酸エステル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。Aromatic carbonate esters are produced by a complex process using the corresponding phenol as a raw material.It is known that phosgene (2) is produced by reaction with chloroform, but this process does not involve the risk of toxicity due to the raw materials used. It produces hydrochloric acid as a by-product.
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
。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。On the other hand, it is also known that phenol and alkyl carbonate can be reacted in the presence of a strong acid as a catalyst. 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℃・てビスフエ
ノールＡビスアセテートをジ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前記ビ
スフエノールＡポリアルキ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。The present inventors have demonstrated that the bisphenol A polyalkyl carbonate can be produced in high yield and with high selectivity by reacting bisphenol A bisacetate with a dialkyl carbonate at °C in the presence of an appropriate catalyst. It was discovered that the present invention can be obtained.
本発明で使用できる触媒は、ＴｉＸ４（Ｘはアルコキシ
ノレ基またはアリーロキシル基である）、ＡｌＸ′３お
よびＡｌＸ′４（Ｘ′はアルコキシル基である）の中か
ら選ばれ、代表的な触媒としてはＴｉ（０・イソＣ３Ｈ
７）４、Ｔｉ（０・φ）４、またはＡｌ（０・第２級Ｃ
３Ｈ７）３、Ａｌ（０・イソＣ３Ｈ７）４である。Catalysts that can be used in the present invention are selected from TiX4 (X is an alkoxynole group or aryloxyl group), AlX'3 and AlX'4 (X' is an alkoxyl group), and typical catalysts include Ti(0・isoC3H
7) 4, Ti(0・φ)4, or Al(0・secondary C
3H7)3, Al(0.isoC3H7)4.
次に、本発明方法の好適な具体例につ℃・て述べる。Next, a preferred specific example of the method of the present invention will be described.
以下の実施例は本発明をさらに詳細に説明するためのも
のであつて、本発明を限定するものではな（・ｏ実施例
１
分液用ヘツドを具備するたな段数２０段の蒸留カラムを
取何けた容積２５０ＣＣのフラスコを使用し、温度１４
０℃な（・し１５０℃にお（・て、ビスフエノールＡビ
スアセテート１５０７およびチタンテトライソブチレー
ト３ｅｃを前記反応器に導入し、つ（・でジエチル炭酸
エステル１３０ＣＣを徐々に加えた。The following examples are intended to explain the present invention in more detail, and are not intended to limit the present invention. Using a spare flask with a volume of 250 cc, the temperature was set to 14.
At 0° C. and 150° C., 1507 cc of bisphenol A bisacetate and 3 cc of titanium tetraisobutyrate were introduced into the reactor, and 130 cc of diethyl carbonate was gradually added at 150° C.
その間、反応系から連続して酢酸エチルが蒸留された。
１０時間後、ビスフエノールＡビヌアセテートのビスフ
エノールＡ−ビスエチル炭酸エステル（前記一般式にお
いてＲ−Ｃ２Ｈ５、料七ｎ−１に相当）への変化率は１
００％であつた。During this time, ethyl acetate was continuously distilled from the reaction system.
After 10 hours, the rate of change of bisphenol A binuacetate to bisphenol A-bisethyl carbonate (corresponding to R-C2H5, 7n-1 in the above general formula) was 1.
It was 00%.
実施例 ２温度１５０℃な（・し１７０℃にお℃・て、
ビスフエノールＡビスアセテート１５０７およびアルミ
ニウムテトライソプロピレート３７を前記実施例１の反
応器に導入し、つ（・でジメチル炭酸エステル１１０Ｃ
Ｃを徐々に添加した。Example 2 The temperature was 150°C (.) and then 170°C (°C).
Bisphenol A bisacetate 1507 and aluminum tetraisopropylate 37 were introduced into the reactor of Example 1, and dimethyl carbonate 110C
C was added gradually.
その間、酢酸メチルが連続して蒸留された。８時間後、
ビスフエノールＡビスメチル炭酸エステル（前記一般式
においてＲ＝ＣＨ３、ｎ−１に相当）への変化率は１０
０％であつた。Meanwhile, methyl acetate was continuously distilled. 8 hours later,
The rate of change to bisphenol A bismethyl carbonate (corresponds to R=CH3, n-1 in the above general formula) is 10
It was 0%.
実施例 ３
分液ヘツドを具備するたな段数３０段の蒸留カラムを取
付けた容積２５０ＣＣのフラスコに、ビスフエノールＡ
ビスアセテート１９０ｆおよびＴｉ（０−イソＣ３Ｈ７
）２２．５ｙを導入した。Example 3 Bisphenol A was added to a 250 cc flask equipped with a 30-shelf distillation column equipped with a separation head.
Bisacetate 190f and Ti (0-isoC3H7
)22.5y was introduced.
混合物を１５０な（・し１７０℃に加熱し、つ℃・でジ
メチル炭酸エステル１６０ＣＣを徐々に添加した。同時
に生成した酢酸メチル留去した。反応末期にお℃・て反
応系を減圧し、温度を２７０℃とした。反応の間に蒸留
されてくる炭酸ジメチルを冷却トラツプで回収した。４
時間後、平均分子量１７０００、一般的な芳香族ポリ炭
酸エステルと同じ構造を有するビスフエノールＡメチル
炭酸エステルの高分子化合物が得られた。The mixture was heated to 150 °C and 170 °C, and 160 CC of dimethyl carbonate was gradually added at 15 °C. At the same time, the produced methyl acetate was distilled off. At the end of the reaction, the reaction system was depressurized at 170 °C, and the temperature The temperature was 270° C. Dimethyl carbonate distilled during the reaction was collected in a cooling trap.
After a period of time, a polymer compound of bisphenol A methyl carbonate having an average molecular weight of 17,000 and the same structure as a general aromatic polycarbonate was obtained.
実施例 ４および５ 上記実施例３と同様に２つの反応を行なつた。Examples 4 and 5 Two reactions were conducted in the same manner as in Example 3 above.
Claims (1)
ーロキシル基である）、ＡｌＸ′＿３およびＡｌＸ′＿
４（式中、Ｘはアルコキシル基である）でなる群から選
ばれる触媒の存在下、ビスフェノールＡビスアセテート
を、一般式ＲＯ−Ｃ−ＯＲ （式中、Ｒはアルキル基である）で表わされるジアルキ
ル炭酸エステルと反応させることを特徴とする、一般式
▲数式、化学式、表等があります▼ （式中、Ｒは前記と同意義であり、ｎは１以上の数であ
る）で表わされるビスフェノールＡポリアルキル炭酸エ
ステルの製法。[Claims] 1 TiX_4 (wherein X is an alkoxyl group or an aryloxyl group), AlX'_3 and AlX'_
In the presence of a catalyst selected from the group consisting of Bisphenol represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R has the same meaning as above, and n is a number of 1 or more), which is characterized by reacting with a dialkyl carbonate ester. A Method for producing polyalkyl carbonate ester.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24392/74A IT1015377B (en) | 1974-06-25 | 1974-06-25 | PROCESS FOR THE PREPARATION OF AROMATIC CARBONATES |
| IT24392A/74 | 1974-06-25 | ||
| IT20191A/75 | 1975-02-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56123949A JPS56123949A (en) | 1981-09-29 |
| JPS5934171B2 true JPS5934171B2 (en) | 1984-08-21 |
Family
ID=11213360
Family Applications (2)
| 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 |
| JP56023198A Expired JPS5934170B2 (en) | 1974-06-25 | 1981-02-20 | Production method of diphenyl carbonate ester |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56023198A Expired JPS5934170B2 (en) | 1974-06-25 | 1981-02-20 | Production method of diphenyl carbonate ester |
Country Status (7)
| Country | Link |
|---|---|
| JP (2) | JPS5934171B2 (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 |
| WO2006006566A1 (en) | 2004-07-13 | 2006-01-19 | Asahi Kasei Chemicals Corporation | Industrial process for producing aromatic carbonate |
| JP4224511B2 (en) | 2004-07-13 | 2009-02-18 | 旭化成ケミカルズ株式会社 | Method for industrial production of aromatic carbonates |
| EP1767517A4 (en) | 2004-07-14 | 2008-08-20 | Asahi Kasei Chemicals Corp | Process for industrially producing an aromatic carbonate |
| BRPI0513225A (en) | 2004-07-14 | 2008-04-29 | Asahi Kasei Chemicals Corp | process for the production of an aromatic carbonate and, potassium carbonate, reactive distillation apparatus |
| CN101006045B (en) | 2004-08-25 | 2010-12-01 | 旭化成化学株式会社 | Process for producing high-purity diphenyl carbonate on commercial scale |
| CN101010285B (en) | 2004-09-03 | 2011-03-16 | 旭化成化学株式会社 | Process for producing high-purity diaryl carbonate on commercial scale |
| BRPI0514888B1 (en) | 2004-09-17 | 2015-06-09 | Asahi Kasei Chemicals Corp | Industrial process for the separation of an underproduced alcohol in a case of continuous mass production of an aromatic carbonate on an industrial scale |
| KR100898536B1 (en) | 2004-10-14 | 2009-05-20 | 아사히 가세이 케미칼즈 가부시키가이샤 | Process for production of high-purity diaryl carbonate |
| TWI321561B (en) | 2004-12-21 | 2010-03-11 | Asahi Kasei Chemicals Corp | Method for producing aromatic carbonate |
| US8138367B2 (en) | 2004-12-24 | 2012-03-20 | Asahi Kasei Chemicals Corporation | Process for production of 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 JP56023199A patent/JPS5934171B2/en not_active Expired
- 1981-02-20 JP JP56023198A patent/JPS5934170B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ZA753587B (en) | 1976-05-26 |
| JPS5934170B2 (en) | 1984-08-21 |
| IN143867B (en) | 1978-02-18 |
| JPS56123948A (en) | 1981-09-29 |
| JPS56123949A (en) | 1981-09-29 |
| HU171825B (en) | 1978-03-28 |
| BE830364A (en) | 1975-10-16 |
| IT1015377B (en) | 1977-05-10 |
| MW3575A1 (en) | 1976-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS5934171B2 (en) | Production method of bisphenol A polyalkyl carbonate ester | |
| US4410464A (en) | Diaryl carbonate process | |
| US4062884A (en) | Process for the preparation of dialkylcarbonates | |
| JPS5848537B2 (en) | Manufacturing method of diphenyl carbonate | |
| KR870000673B1 (en) | Process for the continuous production of n-methyl-carbamates | |
| JPH0753470A (en) | Production of dialkyl carbonate | |
| CA2692578A1 (en) | Method for producing ethylene glycol dimethacrylate | |
| JPS61172852A (en) | Production of diphenyl carbonate | |
| JP2554965B2 (en) | Method for purifying dialkyl carbonate | |
| CN1953957B (en) | Method for producing dialkyl dicarbonates | |
| US4533504A (en) | Process for the preparation of diaryl carbonates | |
| CA1326492C (en) | Method for the esterification of thiopropionates | |
| JPS5822108B2 (en) | Method for producing aromatic diurethane | |
| JP3963613B2 (en) | Method for producing hydroxyphenylcyclohexanone derivative | |
| CN113149953A (en) | Method for preparing 4, 5-dimethyl-1, 3-dioxol-2-one | |
| JPS6210053A (en) | Manufacture of omega-isocyanate alkylacrylate | |
| JPH08295646A (en) | Production of bis(hydroxyethoxyphenyl) compound | |
| JPH01165582A (en) | Production of glycerolcarbonate | |
| CN1304393A (en) | Method for producing alkyl chloride, alkenyl chloride and alkinyl chloride | |
| US5569780A (en) | Dialkyl 2-haloethyl malonates | |
| DE2528368C3 (en) | Process for the preparation of heterocyclic compounds | |
| US3238261A (en) | Piperitenone process | |
| JP6130516B2 (en) | Improved process for producing 1,4: 3,6-dianhydrohexitol di (alkyl carbonate) s | |
| JPH04283544A (en) | Preparation of carbonate | |
| JPS63192731A (en) | Manufacture of beta-allyl alcohol |