JPH02147628A - Preparation of polycarbonate compound - Google Patents
Preparation of polycarbonate compoundInfo
- Publication number
- JPH02147628A JPH02147628A JP29952488A JP29952488A JPH02147628A JP H02147628 A JPH02147628 A JP H02147628A JP 29952488 A JP29952488 A JP 29952488A JP 29952488 A JP29952488 A JP 29952488A JP H02147628 A JPH02147628 A JP H02147628A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- phenolic
- compd
- organic solvent
- phenolic compound
- 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.)
- Pending
Links
- 229920000515 polycarbonate Polymers 0.000 title description 5
- 239000004417 polycarbonate Substances 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002351 wastewater Substances 0.000 claims abstract description 24
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 150000002989 phenols Chemical class 0.000 claims description 42
- 239000003960 organic solvent Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- -1 carbonate compound Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 36
- 238000000034 method Methods 0.000 abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 6
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の利用分野］
本発明はカーボネート系化合物製造時の反応排水中の未
反応フェノール性化合物の塩を含むアルカリ水溶液から
フェノール性化合物を効率よく回収し、カーボネート化
合物の製造反応に再使用する方法に関するものである。Detailed Description of the Invention [Field of Application of the Invention] The present invention efficiently recovers phenolic compounds from an alkaline aqueous solution containing salts of unreacted phenolic compounds in reaction wastewater during the production of carbonate compounds, and It relates to a method of reusing it in a manufacturing reaction.
［従来技術及びその問題点］
カーボネート系化合物の製造法として、フェノール性化
合物のアルカリ水溶液とホスゲンとを有機溶媒の存在下
に反応させる所謂溶液法が広く採用されている。この方
法では相当量の反応排水が発生し、この反応排水中には
、原料として使用した二価のフェノール性化合物や末端
停止剤として使用した一価のフェノール性化合物の未反
応物が存在している。[Prior Art and its Problems] As a method for producing carbonate compounds, a so-called solution method in which an alkaline aqueous solution of a phenolic compound and phosgene are reacted in the presence of an organic solvent has been widely adopted. This method generates a considerable amount of reaction wastewater, and in this reaction wastewater there are unreacted substances of the divalent phenolic compound used as a raw material and the monovalent phenolic compound used as a terminal stopper. There is.
従来、カーボネート系化合物の反応排水中よりフェノー
ル性化合物を回収する方法としては、酸析して沈澱した
フェノール性化合物を？濾過分離して再利用する方法が
最も一般的に行われている。Conventionally, the method of recovering phenolic compounds from reaction wastewater of carbonate compounds is to recover the phenolic compounds precipitated by acid precipitation. The most commonly used method is to separate and reuse by filtration.
しかしながら、この方法で回収したフェノール性化合物
は不純物が多く、且つ固体状であるので再利用するには
精製、乾燥、秤量等面倒な工程を要する欠点がある。し
かも、この方法では酸析の際、フェノール性化合物は水
に対する溶解度弁までしか回収できず、水に対する溶解
度に達しない低濃度のフェノール性化合物を含んだ排水
からは回収できない。However, since the phenolic compound recovered by this method contains many impurities and is in solid form, it has the disadvantage that reusing it requires complicated steps such as purification, drying, and weighing. Moreover, in this method, during acid precipitation, phenolic compounds can only be recovered up to the solubility level in water, and cannot be recovered from wastewater containing low concentrations of phenolic compounds that do not reach solubility in water.
［発明の目的］
本発明の目的は、カーボネート系化合物の反応排水中の
未反応フェノール性化合物を効率よく回収し、カーボネ
ート系化合物の製造反応に再使用する方法を提供するこ
とにある。[Object of the Invention] An object of the present invention is to provide a method for efficiently recovering unreacted phenolic compounds in reaction wastewater of carbonate compounds and reusing them in reactions for producing carbonate compounds.
本発明者は、カーボネート系化合物の反応排水を酸性に
して遊離する未反応のフェノール性化合物を塩化メチレ
ンで抽出すれば、そのままカーボネート系化合物の製造
反応に使用しても、品質や収率に何形問題が生じないこ
とを見出した。本発明はこの知見に基いて更に鋭意検討
を重ねた結果、完成したものである。The present inventor has discovered that if the unreacted phenolic compound released by acidifying the reaction wastewater of carbonate compounds is extracted with methylene chloride, there will be no effect on quality or yield even if it is used as it is in the reaction for producing carbonate compounds. It was found that no shape problem occurred. The present invention was completed as a result of further intensive studies based on this knowledge.
［発明の構成］
本発明は、フェノール性化合物のアルカリ水溶液とホス
ゲンとを有機溶媒の存在下に反応せしめてカーボネート
系化合物を１Ｒ造する方法において、該反応から発生す
る未反応フェノール性化合物の塩を含む反応排水をｐＨ
５以下の酸性にすると共に、該反応排水に対して５容量
％以上の有機溶媒を接触せしめてフェノール性化合物を
抽出し、得られたフェノール性化合物を含有する有機溶
媒溶液をそのまま上記反応に再使用することを特徴とす
るカーボネート系化合物の製造方法である。[Structure of the Invention] The present invention provides a method for producing a carbonate compound in 1R by reacting an alkaline aqueous solution of a phenolic compound with phosgene in the presence of an organic solvent. The pH of the reaction wastewater containing
5 or less, the reaction wastewater is brought into contact with an organic solvent of 5% by volume or more to extract the phenolic compound, and the resulting organic solvent solution containing the phenolic compound is directly reused in the above reaction. This is a method for producing a carbonate-based compound.
本発明で言うフェノール性化合物としては２．２−ビス
（４−ヒドロキシフェニル）プロパン、１１−ヒス（４
−ビトロキシフェニル）エタン、ビス（４−ヒドロキシ
フェニル）メタン、１．１−ビス（４−ヒドロキシフェ
ニル）シクロヘキサン、更に末端停止剤としてｔ−ブチ
ルフェノール、７Ｉクチルフェノール、ノニルノエ、ノ
ール及びこれらの核ハロゲン置換体、更に２，４．６−
トリブロモフェノールのようなハロゲン化フェノー
ル等があげられる。The phenolic compounds referred to in the present invention include 2,2-bis(4-hydroxyphenyl)propane, 11-his(4-hydroxyphenyl)propane,
-bitroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and further terminal capping agents such as t-butylphenol, 7I-cutylphenol, nonylnoe, nor, and their nuclear halogens. Substituted product, further 2,4.6-
Examples include halogenated phenols such as tribromophenol.
本発明で用いる有機溶媒としては、例えば塩化メチレン
、１，２−ジクロロエタン、テトラクロロエタン、クロ
ロホルム等の塩素化脂肪族炭化水素。Examples of the organic solvent used in the present invention include chlorinated aliphatic hydrocarbons such as methylene chloride, 1,2-dichloroethane, tetrachloroethane, and chloroform.
クロロベンゼン２ジクロロベンゼン、クロロトルエン等
の塩素化芳香族炭化水素、アセトフェノン。Chlorobenzene 2 Dichlorobenzene, chlorinated aromatic hydrocarbons such as chlorotoluene, acetophenone.
シクロヘキサノン、アニソール等をあげることができる
。これらは単独又は混合物の形で用いることができる。Examples include cyclohexanone and anisole. These can be used alone or in a mixture.
これらのうち塩化メチレンが最も好ましい。Among these, methylene chloride is most preferred.
本発明にあっては、上記フェノール性化合物のアルカリ
、通常は苛性ソーダの水溶液とホスゲンを反応させてカ
ーボネート系化合物を製造する際に発生する未反応のフ
ェノール性化合物の塩（通常Ｎａ塩）を含む反応排水を
、ｐＨ５以下の酸性にして、フェノール性化合物を遊離
させる。ｐｔｌを５より高くしたのでは、フェノール性
化合物の遊離が不完全になり、フェノール性化合物の抽
出が充分になされ難い。ｐｔｌを５以下にするには鉱酸
、好ましくは塩酸又は硫酸が使用される。In the present invention, it contains an unreacted phenolic compound salt (usually Na salt) generated when a carbonate compound is produced by reacting an alkali of the phenolic compound, usually an aqueous solution of caustic soda, with phosgene. The reaction wastewater is made acidic to a pH of 5 or less to liberate the phenolic compound. If the ptl is higher than 5, the release of the phenolic compound will be incomplete and it will be difficult to extract the phenolic compound sufficiently. A mineral acid, preferably hydrochloric acid or sulfuric acid, is used to reduce the PTL to 5 or less.
遊離したフェノール性化合物の抽出は、前記の有機溶媒
と接触させ攪拌させることによって行われる。具体的に
は、反応排水に予め所定量の有機溶媒を添加してからｐ
Ｈを５以下に調整するか、又はｐＨを５以下に調整した
反応排水に所定ｍの有機溶媒を添加し、攪拌すればよい
。The liberated phenolic compound is extracted by bringing it into contact with the above-mentioned organic solvent and stirring. Specifically, a predetermined amount of organic solvent is added to the reaction wastewater in advance, and then p
A predetermined m amount of an organic solvent may be added to the reaction waste water whose H content is adjusted to 5 or less, or whose pH is adjusted to 5 or less, and the mixture is stirred.
攪拌には、任意の方法が採用されるが、特にホモジナイ
ｔアー、ミキサー、ホモミキサー等の高速攪拌機を使用
するのが好ましく、またオリフィスミキサー、スタティ
ックミキサー、コロイドミル。Any method can be used for stirring, but it is particularly preferable to use a high-speed stirrer such as a homogenizer, mixer, or homomixer, or an orifice mixer, static mixer, or colloid mill.
フロージェットミキサー、超音波乳化装置等も好ましい
。単純な攪拌機で行う場合は攪拌時間を５分以上、更に
は１０分以上にするのが好ましい。Flow jet mixers, ultrasonic emulsifiers, etc. are also preferred. When using a simple stirrer, the stirring time is preferably 5 minutes or more, more preferably 10 minutes or more.
有機溶媒の使用量は、反応排水量に対し５容量％以上に
する必要がおる。５容間％に達しない量ではフェノール
性化合物を充分に抽出し難い。有機溶媒量を多くするこ
とは差支えないが、極端に多くすることはコストの面か
ら不利であり、通常２０容ｗ％程度迄にするのが好まし
い。The amount of organic solvent used needs to be 5% by volume or more based on the amount of reaction waste water. If the amount is less than 5% by volume, it will be difficult to extract phenolic compounds sufficiently. Although it is acceptable to increase the amount of organic solvent, increasing the amount extremely is disadvantageous in terms of cost, and it is usually preferable to limit the amount to about 20% by volume (w%).
ここで使用する有機溶媒としては、前記したものが任意
に使用されるが、特に再利用する際のカーボネート系化
合物の製造に使用する有機溶媒と同一のものが好ましい
。また、フェノール性化合物を抽出した有機溶媒は抽出
効率が悪くなるまではそのまま循環して使用してもよい
。As the organic solvent used here, any of those mentioned above can be used, but it is particularly preferable to use the same organic solvent as the organic solvent used in the production of the carbonate compound for reuse. Further, the organic solvent from which the phenolic compound has been extracted may be recycled and used as is until the extraction efficiency deteriorates.
このようにして未反応フェノール性化合物を回収含有し
た有機溶媒をカーボネート系化合物の製造反応に再使用
するに際し、その分新規の仕込原料を補正することが好
ましいが、有機溶媒中のフェノール性化合物量が、新規
の仕込フェノール性化合物の１型組％以下であれば特に
補正しなくでも、反応収率ヤ品質のいずれにも何ら影響
はない。When the organic solvent containing unreacted phenolic compounds is recovered and reused in the reaction for producing carbonate compounds, it is preferable to correct the amount of new feed materials accordingly, but the amount of phenolic compounds in the organic solvent However, if the amount of the newly charged phenolic compound is 1% or less, there is no need to make any particular correction, and there will be no effect on either the reaction yield or quality.
また、この有機溶媒中に反応触媒が存在するときは、ホ
スゲンの添加後に添加するのが好ましい。Further, when a reaction catalyst is present in this organic solvent, it is preferably added after addition of phosgene.
［発明の効果］
本発明方法によれば、ポリカーボネートを製造する際に
発生する排水中から未反応フェノール性化合物を効率よ
く回収し、有効に再使用することができ、またフェノー
ル性化合物を有機溶媒で抽出した後の分離水にはフェノ
ール性化合物が徴用しか含まれていないので、充填塔で
の活性炭又はイオン交換樹脂による吸着によって、残留
したフェノール性化合物は殆んど完全に除去され、水質
汚濁防止に大きく寄与でき、更に充填塔の活性炭やイオ
ン交換樹脂への負荷も大幅に低減できる等格別の効果を
奏する。[Effects of the Invention] According to the method of the present invention, unreacted phenolic compounds can be efficiently recovered and effectively reused from wastewater generated during the production of polycarbonate, and the phenolic compounds can be converted into organic solvents. The separated water after extraction contains only phenolic compounds, so the remaining phenolic compounds are almost completely removed by adsorption with activated carbon or ion exchange resin in a packed column, resulting in no water pollution. It can greatly contribute to the prevention of this problem, and it also has the exceptional effect of significantly reducing the load on the activated carbon and ion exchange resin in the packed tower.
［実施例］
以下に実施例及び比較例をあげて本発明方法を説明する
が、本発明はこれらに限定されるものではない。なお、
水中のフェノール性化合物のｇｔ度は、アルカリ性にし
て紫外線吸収スペク１〜ルを測定する方法で求めた。[Example] The method of the present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition,
The gt degree of the phenolic compound in water was determined by making the water alkaline and measuring the ultraviolet absorption spectrum.
反応収率は水中のフェノール性化合物の濃度から未反応
フェノール類の間を算出し、下記式で求めた。The reaction yield was calculated from the concentration of phenolic compounds in water to that of unreacted phenols, and was determined by the following formula.
（仕込フェノ （未反応〕Ｊ
−ル類のω）−ノール類の吊）
実施例１〜３及び比較例１，２
（ａ）ポリカーボネートの合成
ホスゲン吹込管、温度計及び攪拌機を備えた２１三ツロ
フラスコに２，２−ビス（’３．５−ジブロモ４−ヒド
ロキシフェニル）１０パン（以下ＴＢΔと略す＞ １０
３．４（１（０゜１９モル）及び２，２−ビス（４−ヒ
ドロキシフェニル）プロパン（以下ＢＰ△と略す＞ ８
．７ｇ（０，０３８モル）を溶解した４、３７％ＮａＱ
Ｈ水溶液４３５ ｒｎ！と塩化メチレン６４０ｄを入
れ、攪拌下ホスゲン６３．４（Ｊ （０，６４モル）
及σ４８．５％ＮａＯＨ水溶液５５．３ｄｔ、２０〜２
７℃−（−ｐＨを１１．０〜１２．０に保らながら７０
分を要して加えてホスゲン化反応させた。次いで、触媒
としてトリエチルアミン０、４４ｍ （０，００３モル
）を加えて５分間攪拌した後２．４．６−１−リブロモ
フェノール（ＴＢＰと略す）７Ｂ、ＩにＪ （０，２
３モル）を溶解した７、６％Ｎａｐｌ−４水溶液３９１
ｄとトリエチルアミン１．１６ｒｎｆ！（０，００８モ
ル）を加えて３０〜３６℃で３時間攪拌して重合を終了
した。重合終了後静置して水層と塩化メチレン層に分離
した。塩化メチレン層は常法により、塩化メチレンを除
去し、水洗、乾燥してポリカーボネート体を得た。水層
の溶存フェノール類の濃度は２９４、Ｏｎｍ 、 ３０
９．９ｎｍ及び３１５．６ｒｌｌｌｌの吸光度を紫外線
吸収スペクトロメータ（日立’ｌ、 Ｕ−３２００形）
により測定し、夫々下記３式に代入して求めた。その結
果はＴ Ｂ Ａ １８Ｘ １０−３す／１ 、 Ｂ Ｐ
Ａ １５ｘ １０’ ｇ／Ｊ 、 Ｔ Ｂ Ｐ４０Ｘ
１０−３ ｇ／ｌで有り、反応収率は９９、９７％でめ
った。(Hanging of charged phenol (unreacted J-ru)-nols) Examples 1 to 3 and Comparative Examples 1 and 2 (a) Synthesis of polycarbonate 213 equipped with a phosgene blowing tube, a thermometer and a stirrer In a Tulo flask, add 10 pans of 2,2-bis('3,5-dibromo4-hydroxyphenyl) (hereinafter abbreviated as TBΔ> 10
3.4 (1 (0°19 mol) and 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as BP△)> 8
．． 7g (0,038 mol) of 4,37% NaQ dissolved in
H aqueous solution 435 rn! and 640 d of methylene chloride, and while stirring, add 63.4 (J (0.64 mol) of phosgene).
and σ48.5% NaOH aqueous solution 55.3dt, 20~2
7℃-(-70℃ while keeping the pH between 11.0 and 12.0)
It took a few minutes to add the phosgenation reaction. Next, 0.44m (0,003 mol) of triethylamine was added as a catalyst, and after stirring for 5 minutes, J (0,2
7.6% Napl-4 aqueous solution 391
d and triethylamine 1.16rnf! (0,008 mol) was added and stirred at 30 to 36°C for 3 hours to complete the polymerization. After the polymerization was completed, the mixture was allowed to stand and separated into an aqueous layer and a methylene chloride layer. The methylene chloride layer was removed by a conventional method, washed with water, and dried to obtain a polycarbonate body. The concentration of dissolved phenols in the aqueous layer is 294, Onm, 30
Measure the absorbance at 9.9 nm and 315.6 rllll using an ultraviolet absorption spectrometer (Hitachi'l, U-3200 type)
The values were determined by substituting them into the following three equations. The result is T B A 18X 10-3 S/1, B P
A 15x 10' g/J, T B P40X
The reaction yield was 99.97%.
Ａ２９４．Ｏｎｍ ＝２２．０２ｂＣＸ＋１１．４６ｂ
Ｃｙ＋ ７．５６ｂＣｚＡ３０９．９ｎｍ ＝６．２２
ｂＣｘ ＋１８．８５ｂＣｙ＋１３．０６ｂＣｚＡ３１
５．６ｎｍ ”” Ｌ３４ｔ）ＣＸ ＋１６．５２ｂＣ
Ｖ＋１３．８８ｂＣｚ（ｂ）反応排水より未反応モノマ
ーの回収還流冷却器及び攪拌橢を備えた２１三ツロフラ
スコに（ａ）と同様にして得た水層（反応排水）の全１
８７０ ｄを入れ、これに塩化メチレンを表１に示した
間加えて攪拌下３５．５％Ｈα水溶液にて表１に示した
ｐｔｌとし、１０分間攪拌した後静置して塩化メチレン
層と水層に分離した。水層の溶存モノマｇ度を（ａ）に
記載した方法と同様にして求め、結果を表１に示した。A294. Onm=22.02bCX+11.46b
Cy+ 7.56bCzA309.9nm =6.22
bCx +18.85bCy+13.06bCzA31
5.6nm "" L34t)CX +16.52bC
V+13.88bCz (b) Recovery of unreacted monomers from reaction wastewater Place all 1 of the aqueous layer (reaction wastewater) obtained in the same manner as in (a) in a 21 Mitsuro flask equipped with a reflux condenser and a stirring rack.
870 d, and add methylene chloride for the time period shown in Table 1. While stirring, prepare the PTL shown in Table 1 with a 35.5% Hα aqueous solution. After stirring for 10 minutes, let stand to separate the methylene chloride layer and the water. Separated into layers. The degree of dissolved monomer in the aqueous layer was determined in the same manner as described in (a), and the results are shown in Table 1.
（Ｃ）未反応上ツマー回収後の排水中のフェノール性化
合物岱
内径５ｃｍのガラスカラムにイオン交換樹脂（バイエル
製レバチット）ＩＰ−６２”） ６００ ｍを充填し、
これに（ｂ）で得た水層をそれぞれ流速０．２ Ｊ／ｍ
ｉｎで導入した。カラム通過後の反応排水をＮａ０ｔ−
１にてアルカリ性にし、（ａ）に記載した方法と同様に
してフェノール性化合物の濃度を求め、結果を表１に示
した。(C) Phenolic compounds in the waste water after collecting the unreacted upper zummer A glass column with an inner diameter of 5 cm was filled with 600 m of ion exchange resin (Levachit IP-62'') manufactured by Bayer,
Add the water layer obtained in (b) to this at a flow rate of 0.2 J/m.
It was introduced in. The reaction wastewater after passing through the column was treated with Na0t-
The mixture was made alkaline in Step 1, and the concentration of the phenolic compound was determined in the same manner as described in (a). The results are shown in Table 1.
（ｄ）回収モノマーの再使用
（ｂ）記載の方法で未反応フェノール性化合物を回収し
た塩化メチレン溶液全量を、（ａ）記載のポリカーボネ
ート製造反応において、ＴＢＰ投入直後に投入する以外
は（ａ）記載の条件と同様に反応させた。(d) Reuse of the recovered monomer (b) Except that the entire amount of the methylene chloride solution from which unreacted phenolic compounds were recovered by the method described in (b) is added to the polycarbonate production reaction described in (a) immediately after the TBP is added, (a) The reaction was carried out under the same conditions as described.
重合終了後水層と塩化メチレン層とを静置分離し、水層
の溶存モノマー濃度を（ａ）に記載した方法と同様にし
て算出し、反応収率を求めた。結果は表２に示した。After the polymerization was completed, the aqueous layer and the methylene chloride layer were separated by standing, and the dissolved monomer concentration in the aqueous layer was calculated in the same manner as described in (a) to determine the reaction yield. The results are shown in Table 2.
手続ネ１１１正書
］７成元年９月／ｒ日
（１）明細書の発明の名称を「カーボネート系化合物の
製ｊＢ方法」と訂正する。[Procedure No. 111] September 1997/r date (1) The name of the invention in the specification is corrected to "jB method for producing carbonate compounds."
以上that's all
Claims (1)
機溶媒の存在下に反応せしめてカーボネート系化合物を
製造する方法において、該反応から発生する未反応フェ
ノール性化合物の塩を含む反応排水をｐＨ５以下の酸性
にすると共に該反応排水に対して５容量％以上の有機溶
媒を接触せしめてフェノール性化合物を抽出し、得られ
たフェノール性化合物を含有する有機溶媒溶液をそのま
ま上記反応に再使用することを特徴とするカーボネート
系化合物の製造方法。In a method for producing a carbonate compound by reacting an alkaline aqueous solution of a phenolic compound with phosgene in the presence of an organic solvent, the reaction wastewater containing a salt of an unreacted phenolic compound generated from the reaction is made acidic to a pH of 5 or less. At the same time, the reaction waste water is brought into contact with 5% by volume or more of an organic solvent to extract the phenolic compound, and the obtained organic solvent solution containing the phenolic compound is reused as it is in the above reaction. A method for producing a carbonate compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29952488A JPH02147628A (en) | 1988-11-29 | 1988-11-29 | Preparation of polycarbonate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29952488A JPH02147628A (en) | 1988-11-29 | 1988-11-29 | Preparation of polycarbonate compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02147628A true JPH02147628A (en) | 1990-06-06 |
Family
ID=17873708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29952488A Pending JPH02147628A (en) | 1988-11-29 | 1988-11-29 | Preparation of polycarbonate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02147628A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02240136A (en) * | 1989-03-14 | 1990-09-25 | Idemitsu Petrochem Co Ltd | Production of branched polycarbonate |
| US6613868B2 (en) | 2001-04-12 | 2003-09-02 | Bayer Aktiengesellschaft | Process for producing polycarbonates |
| EP2096131A1 (en) | 2008-02-27 | 2009-09-02 | Bayer MaterialScience AG | Method for making polycarbonate |
| DE102009023940A1 (en) | 2009-06-04 | 2010-12-09 | Bayer Materialscience Ag | Process for the production of polycarbonate |
| WO2018029200A1 (en) | 2016-08-10 | 2018-02-15 | Covestro Deutschland Ag | Process for the electrochemical purification of chloride-containing process solutions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930726A (en) * | 1982-08-12 | 1984-02-18 | Nippon Sheet Glass Co Ltd | Manufacture of tempered glass plate masked with ceramic |
-
1988
- 1988-11-29 JP JP29952488A patent/JPH02147628A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930726A (en) * | 1982-08-12 | 1984-02-18 | Nippon Sheet Glass Co Ltd | Manufacture of tempered glass plate masked with ceramic |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02240136A (en) * | 1989-03-14 | 1990-09-25 | Idemitsu Petrochem Co Ltd | Production of branched polycarbonate |
| US6613868B2 (en) | 2001-04-12 | 2003-09-02 | Bayer Aktiengesellschaft | Process for producing polycarbonates |
| EP2096131A1 (en) | 2008-02-27 | 2009-09-02 | Bayer MaterialScience AG | Method for making polycarbonate |
| DE102008011473A1 (en) | 2008-02-27 | 2009-09-03 | Bayer Materialscience Ag | Process for the production of polycarbonate |
| US7858727B2 (en) | 2008-02-27 | 2010-12-28 | Bayer Materialscience Ag | Process for the preparation of polycarbonate |
| DE102009023940A1 (en) | 2009-06-04 | 2010-12-09 | Bayer Materialscience Ag | Process for the production of polycarbonate |
| EP2286898A1 (en) | 2009-06-04 | 2011-02-23 | Bayer MaterialScience AG | Method for making polycarbonate |
| US8106144B2 (en) | 2009-06-04 | 2012-01-31 | Bayer Materialscience Ag | Process for producing polycarbonate |
| WO2018029200A1 (en) | 2016-08-10 | 2018-02-15 | Covestro Deutschland Ag | Process for the electrochemical purification of chloride-containing process solutions |
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