JPH07207059A - Recycling of waste aromatic polycarbonate resin - Google Patents
Recycling of waste aromatic polycarbonate resinInfo
- Publication number
- JPH07207059A JPH07207059A JP164694A JP164694A JPH07207059A JP H07207059 A JPH07207059 A JP H07207059A JP 164694 A JP164694 A JP 164694A JP 164694 A JP164694 A JP 164694A JP H07207059 A JPH07207059 A JP H07207059A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- aromatic polycarbonate
- aromatic
- compound
- waste
- 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.)
- Granted
Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 72
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 40
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 18
- -1 diaryl carbonate Chemical compound 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims description 28
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 13
- 239000007858 starting material Substances 0.000 abstract 1
- 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 description 17
- 150000002989 phenols Chemical class 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は廃芳香族ポリカーボネー
ト樹脂のリサイクル方法に関する。更に詳しくは、不用
の芳香族ポリカーボネート樹脂を分解して芳香族ポリカ
ーボネート樹脂の原料に転換して再利用する廃芳香族ポ
リカーボネート樹脂のリサイクル方法に関する。FIELD OF THE INVENTION The present invention relates to a method for recycling waste aromatic polycarbonate resin. More specifically, the present invention relates to a method for recycling a waste aromatic polycarbonate resin, in which unnecessary aromatic polycarbonate resin is decomposed, converted into a raw material of the aromatic polycarbonate resin, and reused.
【０００２】[0002]
【従来の技術】芳香族ポリカーボネート樹脂は、優れた
透明性、光学特性及び強靭な物性を有するのでレンズ、
コンパクトディスク、建築材料、自動車部品、OA機器の
シャーシー、カメラボディ等種々の用途に利用されてい
る極めて付加価値の高い材料であり、ますます需要が増
加しつつある。これらの製品はその利用が終了すると、
多くは廃棄物として焼却又は地中に埋める等の方法で処
分されている。これは重大な資源の無駄であるばかりで
なく、昨今増大する廃プラスチックの廃棄が地球環境問
題として社会問題化しており、規制の対象になりつつあ
る。一方、廃プラスチックを再成形して利用することが
行われている。しかしながら、廃プラスチックを再成形
すると分子量の低下、物性の低下、着色等の問題があ
り、大量に再利用することは困難である。また、再利用
するとしても、その使用後は廃棄されるため本質的なリ
サイクルになっていないのが現状である。2. Description of the Related Art Aromatic polycarbonate resins have excellent transparency, optical properties and tough physical properties,
It is an extremely high value-added material used for various applications such as compact discs, building materials, automobile parts, chassis for OA equipment, and camera bodies, and the demand for it is increasing more and more. When these products are no longer in use,
Most of the waste is incinerated as waste or buried in the ground. This is not only a significant waste of resources, but the increasing waste plastics disposal has become a social issue as a global environmental problem and is becoming a subject of regulation. On the other hand, waste plastics are being remolded and used. However, when waste plastic is remolded, there are problems such as a decrease in molecular weight, a decrease in physical properties, and coloring, and it is difficult to reuse a large amount of it. Moreover, even if it is reused, it is not essentially recycled because it is discarded after its use.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、廃芳香族ポ
リカーボネート樹脂を分解して得られる芳香族ジヒドロ
キシ化合物やジアリールカーボネート化合物を再び芳香
族ポリカーボネート樹脂の原料として利用する本質的な
リサイクル方法を提供することを目的とする。The present invention provides an essential recycling method in which an aromatic dihydroxy compound or a diaryl carbonate compound obtained by decomposing a waste aromatic polycarbonate resin is used again as a raw material for the aromatic polycarbonate resin. The purpose is to do.
【０００４】芳香族ポリカーボネート樹脂の原料として
使用する芳香族ジヒドロキシ化合物やジアリールカーボ
ネート化合物には高純度が要求される。ところが一旦使
用に供せられ、廃棄物となった芳香族ポリカーボネート
樹脂にはごみ、油脂等の汚れが付着しているだけでな
く、その表面には種々の加工が施されていたり、他の樹
脂との混合物であったり、着色剤や補強材が配合されて
いたりする場合が多い。従って廃芳香族ポリカーボネー
ト樹脂を、そのまま芳香族モノヒドロキシ化合物とエス
テル交換反応させて得られる反応液中には、有効成分の
他に種々の不純物が混入し、有効成分の分離精製が困難
なことが多く、場合によっては分解反応が進行し難かっ
たり、またせっかく得られた分解反応生成物の副反応や
分解反応等が併発して有効成分の品質の劣化や収率低下
を招く等の問題があった。Aromatic dihydroxy compounds and diaryl carbonate compounds used as raw materials for aromatic polycarbonate resins are required to have high purity. However, the aromatic polycarbonate resin that was once used and wasted as waste not only has dirt, fats and oils attached to it, but its surface has been subjected to various processing and other resins. In many cases, it is a mixture with and a colorant or a reinforcing material is blended. Therefore, in the reaction solution obtained by subjecting the waste aromatic polycarbonate resin to the transesterification reaction with the aromatic monohydroxy compound as it is, various impurities are mixed in addition to the active ingredient, and it is difficult to separate and purify the active ingredient. In many cases, there are problems that the decomposition reaction is difficult to proceed, and that side reactions or decomposition reactions of the decomposition reaction product obtained at the same time occur to cause deterioration of the quality and yield of the active ingredient. It was
【０００５】本発明者は、廃芳香族ポリカーボネート樹
脂を芳香族モノヒドロキシ化合物と共に加熱して芳香族
ジヒドロキシ化合物及びジアリールカーボネート化合物
にする方法を先に提案した。更に本発明者は、この方法
で得られた反応生成物から有効成分を、前記のような問
題を生じることなく工業的規模で経済的に回収する回収
法について鋭意研究し、本発明に到達した。The present inventor has previously proposed a method of heating a waste aromatic polycarbonate resin together with an aromatic monohydroxy compound into an aromatic dihydroxy compound and a diaryl carbonate compound. Furthermore, the present inventors have earnestly studied a recovery method for economically recovering the active ingredient from the reaction product obtained by this method on an industrial scale without causing the above problems, and arrived at the present invention. .
【０００６】[0006]
【課題を解決するための手段】本発明は、廃芳香族ポリ
カーボネート樹脂に芳香族モノヒドロキシ化合物をエス
テル交換反応させて芳香族ジヒドロキシ化合物及びジア
リールカーボネート化合物を回収するに際し、 (A）廃芳香族ポリカーボネート樹脂に芳香族モノヒドロ
キシ化合物をエステル交換反応させる第一工程 (B）第一工程で得られた反応生成物から芳香族モノヒド
ロキシ化合物を蒸留により留去する第二工程 (C）第二工程で残留した高沸点の混合物からジアリール
カーボネート化合物を蒸留して回収する第三工程 (D）第三工程で残留した更に高沸点の混合物から芳香族
ジヒドロキシ化合物を蒸留して回収する第四工程 よりなる廃芳香族ポリカーボネート樹脂のリサイクル方
法である。DISCLOSURE OF THE INVENTION According to the present invention, in recovering an aromatic dihydroxy compound and a diaryl carbonate compound by transesterifying a waste aromatic polycarbonate resin with an aromatic monohydroxy compound, (A) waste aromatic polycarbonate First step of transesterifying aromatic monohydroxy compound with resin (B) Second step of distilling aromatic monohydroxy compound from the reaction product obtained in first step by distillation (C) In second step The third step of distilling and recovering the diaryl carbonate compound from the residual high-boiling mixture (D) The waste consisting of the fourth step of distilling and recovering the aromatic dihydroxy compound from the higher-boiling mixture remaining in the third step It is a method of recycling an aromatic polycarbonate resin.
【０００７】本発明で対象とする廃芳香族ポリカーボネ
ート樹脂は、芳香族ジヒドロキシ化合物とカーボネート
前駆物質とを溶液法や溶融法で合成した芳香族ポリカー
ボネート樹脂であり、その合成中や成形中に発生した屑
ポリマーや不良品、その利用が終了したり不用になった
芳香族ポリカーボネート樹脂製品等である。芳香族ポリ
カーボネート樹脂の原料である芳香族ジヒドロキシ化合
物としては、通常２，２−ビス（４−ヒドロキシフェニ
ル）プロパン（以下ビスフェノールＡと略称する）が使
用されているが、本発明にあっては、かかるビスフェノ
ールＡの芳香族ポリカーボネート樹脂に限らず、他の芳
香族ジヒドロキシ化合物の芳香族ポリカーボネート樹脂
も対象とする。The waste aromatic polycarbonate resin targeted by the present invention is an aromatic polycarbonate resin synthesized by a solution method or a melting method of an aromatic dihydroxy compound and a carbonate precursor, and is generated during the synthesis or molding. They include scrap polymers, defective products, and aromatic polycarbonate resin products that have been used up or are no longer needed. As the aromatic dihydroxy compound which is a raw material of the aromatic polycarbonate resin, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) is usually used, but in the present invention, Not only the aromatic polycarbonate resin of bisphenol A, but also the aromatic polycarbonate resin of other aromatic dihydroxy compounds.
【０００８】かかる廃芳香族ポリカーボネート樹脂は必
要に応じて前処理を施し、又は施すことなく本発明の方
法に適用できるが、前処理するのが好ましい場合が多
い。前処理としては任意の方法が採用される。例えば廃
芳香族ポリカーボネート樹脂にごみ、油脂、その他の汚
染物質が付着している場合には充分洗浄するのが好まし
く、コンパクトディスクや光磁気ディスク等のディスク
類の場合は、その表面や裏面に加工されている加工層や
印刷層等を剥離除去してから適用するのが好ましく、廃
芳香族ポリカーボネート樹脂がアロイの場合は、予め芳
香族ポリカーボネート樹脂成分を分離してから適用する
のが好ましい。要は分解反応に不純物が混入することを
極力避けるのが好ましい。また、取扱上及び反応の点か
ら予め粉砕しておくのが好ましい。Such waste aromatic polycarbonate resin can be applied to the method of the present invention with or without pretreatment as necessary, but pretreatment is often preferable. Any method may be adopted as the pretreatment. For example, if the waste aromatic polycarbonate resin is contaminated with dust, oils, and other contaminants, it is preferable to thoroughly clean it, and in the case of disks such as compact disks and magneto-optical disks, the front and back surfaces should be processed. It is preferable to apply after removing the processed layer, the printing layer, etc., which have been removed, and when the waste aromatic polycarbonate resin is an alloy, it is preferable to apply the aromatic polycarbonate resin component after previously separating it. In short, it is preferable to avoid mixing impurities into the decomposition reaction as much as possible. Further, it is preferable to pulverize beforehand from the viewpoint of handling and reaction.
【０００９】芳香族モノヒドロキシ化合物としては各種
のフェノール類を用いることができる（以下芳香族モノ
ヒドロキシ化合物をフェノール類と略称する）が、フェ
ノールが特に好ましい。また、分解反応に水が存在する
と、得られるジアリールカーボネート化合物のカーボネ
ート基が加水分解するのでフェノール類の含水率を５重
量％以下、好ましくは１重量％以下、特に０．５重量％
以下にするのが好ましい。使用量は廃芳香族ポリカーボ
ネート樹脂に対して通常０．８〜１０００倍重量、好ま
しくは１〜１００倍重量であり、フェノール類は溶媒と
しての作用も果たすので５〜２０倍重量が特に好まし
い。As the aromatic monohydroxy compound, various phenols can be used (hereinafter, the aromatic monohydroxy compound is abbreviated as phenols), but phenol is particularly preferable. When water is present in the decomposition reaction, the carbonate group of the resulting diaryl carbonate compound is hydrolyzed, so that the water content of phenols is 5% by weight or less, preferably 1% by weight or less, and particularly 0.5% by weight.
The following is preferable. The amount used is usually 0.8 to 1000 times the weight of the waste aromatic polycarbonate resin, preferably 1 to 100 times the weight, and 5 to 20 times the weight is particularly preferable because the phenols also serve as a solvent.
【００１０】廃芳香族ポリカーボネート樹脂は先ず第一
工程の反応帯に供給される。供給される廃芳香族ポリカ
ーボネート樹脂は溶融状態であっても、固体でであって
もよく、またフェノール類と一緒に供給してもよい。第
一工程の反応帯におけるフェノール類と廃芳香族ポリカ
ーボネート樹脂とのエステル交換による分解反応は、生
成する芳香族ジヒドロキシ化合物やジアリールカーボネ
ート化合物が更に分解したり、副反応が起るような高温
度であってはならない。フェノール類としてフェノール
を使用するときはフェノールの融点〜２００℃、好まし
くは１００〜２００℃、特に好ましくは１５０〜１９０
℃である。この分解反応は、高温高圧下で行っても又は
エステル交換反応触媒を用いてもよいが、触媒は特に必
要なく、またマイルドな条件下で進めるのが副反応の発
生を防ぐ点で好ましく、通常大気圧下で充分である。な
お、この分解反応は回分式又は連続式のいずれで行って
もよい。The waste aromatic polycarbonate resin is first supplied to the reaction zone of the first step. The waste aromatic polycarbonate resin supplied may be in a molten state or a solid, and may be supplied together with the phenols. The decomposition reaction by transesterification of phenols and waste aromatic polycarbonate resin in the reaction zone of the first step is carried out at a high temperature such that the aromatic dihydroxy compound or diaryl carbonate compound produced is further decomposed or a side reaction occurs. It shouldn't be. When phenol is used as the phenols, the melting point of phenol to 200 ° C, preferably 100 to 200 ° C, particularly preferably 150 to 190.
℃. This decomposition reaction may be carried out under high temperature and high pressure or may use a transesterification catalyst, but a catalyst is not particularly required, and it is preferable to proceed under mild conditions from the viewpoint of preventing side reaction, At atmospheric pressure is sufficient. The decomposition reaction may be carried out batchwise or continuously.
【００１１】第一工程で得た分解反応物は必要に応じて
加熱又は冷却されて第二工程に送られる。分解反応物は
そのまま又は一旦フェノール類の一部又は大部分を留去
した後第二工程にかけられる。フェノール類の一部又は
大部分を留去する場合は、反応生成物中の芳香族ジヒド
ロキシ化合物とジアリールカーボネート化合物に対して
０．８〜５０倍重量、好ましくは１〜５０倍重量、特に
好ましくは１．５〜１０倍重量まで留去するのが、第二
工程のコスト低減及び品質保持の点から有利である。そ
の際の温度は１００〜２００℃、好ましくは１２０〜１
８０℃であり、圧力は４０Torr〜常圧、好ましくは１０
０〜７００Torrである。このフェノール類の留去は任意
の蒸発機で行われるが、滞留時間の短い例えば薄膜式の
ものが好ましい。The decomposition reaction product obtained in the first step is heated or cooled as required and sent to the second step. The decomposition reaction product is subjected to the second step as it is or after the phenol is partially or mostly distilled off. When a part or most of the phenols are distilled off, the aromatic dihydroxy compound and the diaryl carbonate compound in the reaction product are 0.8 to 50 times by weight, preferably 1 to 50 times by weight, and particularly preferably. It is advantageous to distill off to 1.5 to 10 times the weight in terms of cost reduction and quality maintenance of the second step. The temperature at that time is 100 to 200 ° C., preferably 120 to 1
80 ° C., pressure is 40 Torr to normal pressure, preferably 10
It is 0 to 700 Torr. The distillation of the phenols can be carried out by an arbitrary evaporator, but a thin film type having a short residence time is preferable.
【００１２】第二工程は、蒸留塔、その下部には蒸発
機、上部には凝縮装置及び還流装置を備えた蒸留装置よ
りなり、フェノール類を分離する。製造時に重合停止剤
を用いた廃芳香族ポリカーボネート樹脂の分解反応物に
は重合停止剤が存在するが、通常この第二工程において
重合停止剤もフェノール類と同時に分離される。この蒸
留装置としては任意の装置が使用されるが、コスト低減
及び品質劣化を防ぐには滞留量が少なく、滞留時間の短
いものが好ましい。例えば蒸留塔が充填塔方式の場合は
充填物が圧力損失の少ない接触効率の高いもの、蒸発機
は薄膜型のものが好ましい。第二工程の温度は１００〜
２００℃、好ましくは１４０〜２００℃であり、圧力は
１０Torr〜常圧、好ましくは２０〜５００Torrである。
フェノール類及び重合停止剤を留去して得られた液は蒸
留塔下部より取出され、第三工程に送られる。一方、第
二工程で分離されたフェノール類は、第一工程の反応帯
に循環され、分解反応に使用される。第二工程で分離さ
れたフェノール類中には重合停止剤や低沸点化合物が含
まれていることがあるので、これらを分離し、純度の高
いものにして循環使用するのが好ましい。この精製には
任意の方法が採用される。The second step consists of a distillation column, an evaporator in the lower part, and a distillation device in the upper part, which is equipped with a condenser and a reflux device, and separates phenols. A polymerization terminator is present in the decomposition reaction product of the waste aromatic polycarbonate resin using the polymerization terminator at the time of production, but the polymerization terminator is usually separated at the same time with the phenols in this second step. Although an arbitrary device is used as this distillation device, in order to reduce cost and prevent quality deterioration, a device having a small amount of stay and a short stay time is preferable. For example, when the distillation column is a packed column system, it is preferable that the packing material has a small contact loss and high contact efficiency and the evaporator is a thin film type. The temperature of the second step is 100-
The temperature is 200 ° C., preferably 140 to 200 ° C., and the pressure is 10 Torr to normal pressure, preferably 20 to 500 Torr.
The liquid obtained by distilling off the phenols and the polymerization terminator is taken out from the lower part of the distillation column and sent to the third step. On the other hand, the phenols separated in the second step are circulated in the reaction zone of the first step and used for the decomposition reaction. Since the phenols separated in the second step may contain a polymerization terminator and a low boiling point compound, it is preferable to separate them and make them of high purity for recycling. Any method is adopted for this purification.
【００１３】第三工程において有効成分の一つであるジ
アリールカーボネート化合物を分離回収する。第三工程
は、蒸留塔、その下部には蒸発機、上部には凝縮装置及
び還流装置を備えた蒸留装置よりなり、この蒸留装置と
しては任意の装置が使用されるが、コスト低減及び品質
劣化防止のため、滞留量が少なく、滞留時間の短いもの
が使用される。例えば蒸留塔が充填塔方式の場合は充填
物が圧力損失の少ない接触効率の高いもの、蒸発機は薄
膜型のものが好ましく、第二工程と同一型式の装置を用
いることができる。第三工程の温度は１２０〜２５０
℃、好ましくは１５０〜２２０℃であり、圧力は２〜５
００Torr、好ましくは５〜１００Torrである。分留留去
されたジアリールカーボネート化合物は、若干のフェノ
ール類が含むことがあるが、溶融状態のまま又は冷却し
て固体として回収される。更に必要に応じて任意の方法
により精製してもよい。ジアリールカーボネート化合物
を留去して得られた芳香族ジヒドロキシ化合物を主成分
とする液は蒸留塔下部より取出され、次の第四工程に送
られる。In the third step, a diaryl carbonate compound which is one of the active ingredients is separated and recovered. The third step consists of a distillation column, an evaporator in the lower part, and a distillation device equipped with a condenser and a reflux device in the upper part. Although any device is used as this distillation device, cost reduction and quality deterioration For prevention, a material having a small retention amount and a short retention time is used. For example, when the distillation column is a packed column system, it is preferable that the packing material has a small contact loss and high contact efficiency, and the evaporator is a thin film type, and the same apparatus type as the second step can be used. The temperature of the third step is 120 to 250
℃, preferably 150-220 ℃, the pressure is 2-5
00 Torr, preferably 5 to 100 Torr. The diaryl carbonate compound that has been distilled off by fractional distillation may contain some phenols, but it is recovered as a solid in the molten state or by cooling. Further, if desired, it may be purified by any method. A liquid containing an aromatic dihydroxy compound as a main component, which is obtained by distilling off the diaryl carbonate compound, is taken out from the lower part of the distillation column and sent to the next fourth step.
【００１４】第四工程においてもう一つの有効成分であ
る芳香族ジヒドロキシ化合物を高沸点成分より蒸留分離
する。第四工程は、蒸留塔、その下部には蒸発機、上部
には凝縮装置及び還流装置を備えた蒸留装置よりなり、
この蒸留装置としては任意の装置が使用されるが、コス
ト低減及び品質劣化防止のため、滞留量が少なく、滞留
時間の短いものが使用される。例えば蒸留塔が充填塔方
式の場合は充填物が圧力損失の少ない接触効率の高いも
の、蒸発機は薄膜型のものが好ましく、第二工程及び第
三工程と同一型式の装置を用いることができる。第四工
程の温度は１５０〜３００℃、好ましくは１８０〜２８
０℃であり、圧力は１〜２００Torr、好ましくは２〜１
００Torrである。芳香族ジヒドロキシ化合物は特に熱安
定性が充分でない場合が多いので、経済性も考慮して上
記範囲で実施する。第四工程において蒸留塔上部より取
出された芳香族ジヒドロキシ化合物は、そのまま又は冷
却して固体として回収される。In the fourth step, the aromatic dihydroxy compound which is another effective component is separated by distillation from the high boiling point component. The fourth step consists of a distillation column, an evaporator in the lower part thereof, and a distillation device equipped with a condenser and a reflux device in the upper part,
Although an arbitrary device is used as this distillation device, one having a small retention amount and a short retention time is used for cost reduction and quality deterioration prevention. For example, when the distillation column is a packed column system, it is preferable that the packing material has a small contact loss and high contact efficiency, and the evaporator is a thin film type, and an apparatus of the same type as the second step and the third step can be used. . The temperature of the fourth step is 150 to 300 ° C., preferably 180 to 28.
0 ° C., pressure is 1 to 200 Torr, preferably 2-1
It is 00 Torr. Since the aromatic dihydroxy compound often has insufficient heat stability in many cases, it is carried out in the above range in consideration of economical efficiency. The aromatic dihydroxy compound taken out from the upper part of the distillation column in the fourth step is recovered as a solid as it is or after cooling.
【００１５】本発明の方法は回分式又は連続式のいずれ
でも実施でき、また第二工程〜第四工程は、必要に応じ
て添加剤を加えて実施することもできる。The method of the present invention can be carried out in either a batch system or a continuous system, and the second to fourth steps can be carried out by adding additives as required.
【００１６】[0016]
【実施例】次に実施例を示すが、本発明はこれに何等制
限されるものではない。実施例中の部及び％は重量を基
準としたものである。EXAMPLES Examples will be shown below, but the present invention is not limited thereto. Parts and% in the examples are based on weight.
【００１７】［実施例１］粉砕したコンパクトディスク
１００部及び水１００部をオートクレーブに仕込み、１
２０℃で２時間保持した後、冷却して取出して流水で洗
浄し、剥離した加工層を除去し、乾燥して芳香族ポリカ
ーボネート樹脂９７．３部を回収した。 (A）得られた芳香族ポリカーボネート樹脂９５．４部
に、精製した回収フェノール（含水率０．０１％）６０
０部を加え、大気圧、攪拌下還流状態で１時間加熱し
た。得られた反応混合物を高速液体クロマト装置により
分析したところビスフェノールＡ８５．０部、ジフェニ
ールカーボネート７９．８部、フェノール５３１．０部
及び p−tert−ブチルフェノール１．８部が含まれてい
た。 (B）この反応混合物を、内径２０mm、高さ１m の充填塔
式蒸留塔（スルザーパッキング EX 使用）により蒸留塔
塔頂温度を１５０℃、圧力を３００Torrから次第に７０
Torrまで高真空にしてフェノール及び p−tert−ブチル
フェノールを蒸留分離した。 (C）留去が止まったら蒸留塔塔頂温度を２００℃に昇温
し、圧力を４０Torrに調整してジフェニールカーボネー
トを留去させた。 (D）次いで蒸留塔塔頂温度を２４５℃に昇温し、圧力を
１０Torrに調整してビスフェノールＡを留去させた。[Example 1] 100 parts of crushed compact disks and 100 parts of water were charged into an autoclave, and 1
After holding at 20 ° C. for 2 hours, it was cooled, taken out, washed with running water, the peeled processing layer was removed, and dried to recover 97.3 parts of an aromatic polycarbonate resin. (A) To the obtained aromatic polycarbonate resin 95.4 parts, purified recovered phenol (water content 0.01%) 60
0 part was added, and the mixture was heated at reflux under stirring at atmospheric pressure for 1 hour. When the obtained reaction mixture was analyzed by a high performance liquid chromatograph, it contained 85.0 parts of bisphenol A, 79.8 parts of diphenyl carbonate, 531.0 parts of phenol and 1.8 parts of p-tert-butylphenol. (B) This reaction mixture was subjected to a packed column type distillation column (using Sulzer Packing EX) having an inner diameter of 20 mm and a height of 1 m at a distillation column top temperature of 150 ° C. and a pressure gradually increasing from 70 Torr to 70
Phenol and p-tert-butylphenol were separated by distillation by applying a high vacuum to Torr. (C) When the distillation was stopped, the overhead temperature of the distillation column was raised to 200 ° C. and the pressure was adjusted to 40 Torr to distill off the diphenyl carbonate. (D) Next, the temperature at the top of the distillation column was raised to 245 ° C., the pressure was adjusted to 10 Torr, and bisphenol A was distilled off.
【００１８】蒸留分離したジフェニールカーボネートは
７９．０部、純度は９９．８％であり、ビスフェノール
Ａは８３．０部、純度は９９．５％であった。なお、缶
残として２．８部が残った。最初に留去した p−tert−
ブチルフェノールを含むフェノールは、上記と同じ蒸留
塔を用いて p−tert−ブチルフェノールを除いて回収
し、更にゼオライトで脱水して廃芳香族ポリカーボネー
ト樹脂のエステル交換反応に用いた。上記の蒸留分離し
たビスフェノールＡ１０部をメタノールとトルエンの混
合物（メタノール１：トルエン１）４０部に溶解し、冷
却し、結晶を濾別し、乾燥して９．５部のビスフェノー
ルＡを得た。純度は９９．８％であった。The diphenyl carbonate separated by distillation was 79.0 parts with a purity of 99.8%, and bisphenol A was 83.0 parts with a purity of 99.5%. 2.8 parts remained as a can residue. First distilled off p-tert-
Phenol containing butylphenol was recovered by removing the p-tert-butylphenol using the same distillation column as described above, further dehydrated with zeolite and used in the transesterification reaction of the waste aromatic polycarbonate resin. 10 parts of the above-distilled bisphenol A was dissolved in 40 parts of a mixture of methanol and toluene (methanol 1: toluene 1), cooled, the crystals were filtered off, and dried to obtain 9.5 parts of bisphenol A. The purity was 99.8%.
【００１９】このビスフェノールＡ６８．５部（０．３
モル）及び蒸留分離したジフェニールカーボネート６
６．４部（０．３１モル）にテトラメチルアンモニウム
ヒドロキシド０．００９１５部（０．０００１モル）を
加え、窒素ガスで置換した後２４０℃、３０Torrで溶融
重合反応させ、フェノールの留出が止まったところで窒
素ガスで大気圧に戻した。反応は２時間で終了した。得
られた反応物の極限粘度（塩化メチレン中２０℃でウベ
ローデ粘度計を用いて測定）は０．３８dl／g 、色相
（成形した芳香族ポリカーボネート樹脂を透過法で測定
した場合の黄色度）は１．１であり、良好な芳香族ポリ
カーボネート樹脂が得られた。This bisphenol A 68.5 parts (0.3
Mol) and diphenyl carbonate 6 separated by distillation
Tetramethylammonium hydroxide 0.00915 parts (0.0001 mol) was added to 6.4 parts (0.31 mol), and after substitution with nitrogen gas, a melt polymerization reaction was performed at 240 ° C. and 30 Torr, and phenol was distilled off. When it stopped, the pressure was returned to atmospheric pressure with nitrogen gas. The reaction was completed in 2 hours. The intrinsic viscosity of the obtained reaction product (measured in methylene chloride at 20 ° C. using an Ubbelohde viscometer) was 0.38 dl / g, and the hue (yellowness of the molded aromatic polycarbonate resin measured by the permeation method) was It was 1.1, and a good aromatic polycarbonate resin was obtained.
【００２０】[0020]
【発明の効果】本発明によれば工業的規模で高品質の芳
香族ジヒドロキシ化合物及びジアリールカーボネート化
合物が経済的に回収でき、必要に応じて溶融重合反応工
程にリサイクルすることができ、その奏する効果は格別
なものである。INDUSTRIAL APPLICABILITY According to the present invention, high-quality aromatic dihydroxy compounds and diaryl carbonate compounds can be economically recovered on an industrial scale, and can be recycled to the melt polymerization reaction step if necessary, and the effect to be achieved Is exceptional.
Claims (1)
モノヒドロキシ化合物をエステル交換反応させて、芳香
族ジヒドロキシ化合物及びジアリールカーボネート化合
物を回収するに際し、(A）廃芳香族ポリカーボネート樹
脂に芳香族モノヒドロキシ化合物をエステル交換反応さ
せる第一工程、(B）第一工程で得られた反応生成物から
芳香族モノヒドロキシ化合物を蒸留により留去する第二
工程、(C）第二工程で残留した高沸点の混合物からジア
リールカーボネート化合物を蒸留して回収する第三工
程、(D）第三工程で残留した更に高沸点の混合物から芳
香族ジヒドロキシ化合物を蒸留して回収する第四工程よ
りなることを特徴とする廃芳香族ポリカーボネート樹脂
のリサイクル方法。1. When recovering an aromatic dihydroxy compound and a diaryl carbonate compound by subjecting a waste aromatic polycarbonate resin to an ester exchange reaction with an aromatic monohydroxy compound, (A) a waste aromatic polycarbonate resin is added to the aromatic monohydroxy compound. In the first step of transesterification, (B) the second step of distilling off the aromatic monohydroxy compound from the reaction product obtained in the first step by distillation, and (C) the high boiling point residue remaining in the second step. It is characterized by comprising a third step of distilling and recovering the diaryl carbonate compound from the mixture, and (D) a fourth step of distilling and recovering the aromatic dihydroxy compound from the higher boiling point mixture remaining in the third step. Method for recycling waste aromatic polycarbonate resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP164694A JP3426318B2 (en) | 1994-01-12 | 1994-01-12 | Recycling method of waste aromatic polycarbonate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP164694A JP3426318B2 (en) | 1994-01-12 | 1994-01-12 | Recycling method of waste aromatic polycarbonate resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07207059A true JPH07207059A (en) | 1995-08-08 |
| JP3426318B2 JP3426318B2 (en) | 2003-07-14 |
Family
ID=11507289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP164694A Expired - Lifetime JP3426318B2 (en) | 1994-01-12 | 1994-01-12 | Recycling method of waste aromatic polycarbonate resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3426318B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006008598A (en) * | 2004-06-25 | 2006-01-12 | Teijin Chem Ltd | Method for obtaining metal salt aqueous solution of aromatic dihydroxy compound |
| JP2006502221A (en) * | 2002-10-08 | 2006-01-19 | ゼネラル・エレクトリック・カンパニイ | Fixed bed reactor with fluid distributor and fluid collector |
| JP2006022029A (en) * | 2004-07-07 | 2006-01-26 | Teijin Chem Ltd | Method for obtaining aromatic dihydroxy compound from waste aromatic polycarbonate |
| JP2006045129A (en) * | 2004-08-05 | 2006-02-16 | Teijin Chem Ltd | Method for obtaining aromatic dihydroxy compound from waste aromatic polycarbonate |
| JP2006052173A (en) * | 2004-08-12 | 2006-02-23 | Teijin Chem Ltd | Method for obtaining aromatic dihydroxy compound from waste aromatic polycarbonate |
| JP2006052174A (en) * | 2004-08-12 | 2006-02-23 | Teijin Chem Ltd | Method for obtaining aromatic dihydroxy compound from waste aromatic polycarbonate |
-
1994
- 1994-01-12 JP JP164694A patent/JP3426318B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006502221A (en) * | 2002-10-08 | 2006-01-19 | ゼネラル・エレクトリック・カンパニイ | Fixed bed reactor with fluid distributor and fluid collector |
| JP2006008598A (en) * | 2004-06-25 | 2006-01-12 | Teijin Chem Ltd | Method for obtaining metal salt aqueous solution of aromatic dihydroxy compound |
| JP4575046B2 (en) * | 2004-06-25 | 2010-11-04 | 帝人化成株式会社 | Method for obtaining an aqueous metal salt solution of an aromatic dihydroxy compound |
| JP2006022029A (en) * | 2004-07-07 | 2006-01-26 | Teijin Chem Ltd | Method for obtaining aromatic dihydroxy compound from waste aromatic polycarbonate |
| JP4575051B2 (en) * | 2004-07-07 | 2010-11-04 | 帝人化成株式会社 | Process for obtaining aromatic dihydroxy compounds from waste aromatic polycarbonates |
| JP2006045129A (en) * | 2004-08-05 | 2006-02-16 | Teijin Chem Ltd | Method for obtaining aromatic dihydroxy compound from waste aromatic polycarbonate |
| JP4575074B2 (en) * | 2004-08-05 | 2010-11-04 | 帝人化成株式会社 | Process for obtaining aromatic dihydroxy compounds from waste aromatic polycarbonates |
| JP2006052173A (en) * | 2004-08-12 | 2006-02-23 | Teijin Chem Ltd | Method for obtaining aromatic dihydroxy compound from waste aromatic polycarbonate |
| JP2006052174A (en) * | 2004-08-12 | 2006-02-23 | Teijin Chem Ltd | Method for obtaining aromatic dihydroxy compound from waste aromatic polycarbonate |
| JP4567397B2 (en) * | 2004-08-12 | 2010-10-20 | 帝人化成株式会社 | Process for obtaining aromatic dihydroxy compounds from waste aromatic polycarbonates |
| JP4575082B2 (en) * | 2004-08-12 | 2010-11-04 | 帝人化成株式会社 | Process for obtaining aromatic dihydroxy compounds from waste aromatic polycarbonates |
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| Publication number | Publication date |
|---|---|
| JP3426318B2 (en) | 2003-07-14 |
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