JP2007153942A - Method for producing recycled polyester - Google Patents
Method for producing recycled polyester Download PDFInfo
- Publication number
- JP2007153942A JP2007153942A JP2005347310A JP2005347310A JP2007153942A JP 2007153942 A JP2007153942 A JP 2007153942A JP 2005347310 A JP2005347310 A JP 2005347310A JP 2005347310 A JP2005347310 A JP 2005347310A JP 2007153942 A JP2007153942 A JP 2007153942A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- glycol
- batch reactor
- pet
- depolymerization
- 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
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
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、リサイクルポリエステル、特に好ましくは、繊維やポリエステル製品の製造工程で発生するリサイクルポリエステル(以下、ポリエステル屑という。)を解重合する再生ポリエステルの製造方法に関する。 The present invention relates to a method for producing recycled polyester, particularly preferably recycled polyester for depolymerizing recycled polyester (hereinafter referred to as polyester waste) generated in the production process of fibers and polyester products.
従来、例えばポリエチレンテレフタレート（ＰＥＴ）は、まず、テレフタル酸（ＴＰＡ）とエチレングリコール（ＥＧ）がエステル化反応装置に送られてエステル化反応をさせた後、生成したポリエステル低重合体を続いて重縮合反応装置に送り、重縮合反応することにより製造される。かかるＰＥＴは、その優れた特性により繊維、フイルム、ボトル、プラスチック等として広く用いられている。これらの製造工程において発生する繊維状、フィルム状、樹脂状などのポリエステル屑の有効利用は、コストなどの点で工業的に極めて重要となっている。 Conventionally, for example, in polyethylene terephthalate (PET), first, terephthalic acid (TPA) and ethylene glycol (EG) are sent to an esterification reactor to cause esterification, and then the resulting polyester low polymer is subsequently polymerized. It is produced by sending it to a condensation reaction apparatus and carrying out a polycondensation reaction. Such PET is widely used as a fiber, film, bottle, plastic or the like because of its excellent characteristics. Effective utilization of polyester waste such as fibers, films, and resins generated in these manufacturing processes is extremely important industrially in terms of cost and the like.
ポリエステル屑の利用方法としては、例えば、ポリエステル屑を解重合するに際し、酸成分に対するグリコール成分の当量比が１．３〜２．０のビスヒドロキシエチルテレフタレートおよび／またはその低重合体を溶融状態で反応容器に存在させ、ＥＧとポリエステル屑を同時かつ連続的に添加し、かつ攪拌しながらエステル化反応装置を２１５〜２５０℃で酸成分に対するグリコール成分の当量比を１．３〜２．０に維持して解重合した後、反応物の一部を重合反応系に供給する方法（特許文献１参照）が開示されている。 As a method of using polyester waste, for example, when depolymerizing polyester waste, bishydroxyethyl terephthalate and / or a low polymer thereof in which the equivalent ratio of glycol component to acid component is 1.3 to 2.0 is melted. It is made to exist in a reaction vessel, EG and polyester waste are added simultaneously and continuously, and while stirring, the equivalent ratio of glycol component to acid component is adjusted to 1.3 to 2.0 at 215 to 250 ° C. A method of supplying a part of the reaction product to the polymerization reaction system after maintaining and depolymerizing is disclosed (see Patent Document 1).
しかしながら、ポリエステル屑中には水分が多少含有されているため解重合の進行に伴い、この水分が反応系に蓄積し、解重合反応を抑制するという問題があった。また、ポリエステル屑の解再重合を効率的に生産できる技術は、現在のところ未だ確立されていない。 However, since some moisture is contained in the polyester waste, the moisture accumulates in the reaction system as the depolymerization proceeds, and there is a problem that the depolymerization reaction is suppressed. In addition, a technology that can efficiently produce derepolymerization of polyester waste has not been established yet.
ＴＰＡとＥＧよりポリエステルを製造するポリエチレンテレフタレートの工業的製造においては、酸成分に対して、反応性を向上させるため、グリコール成分を過剰に用い、両末端にグリコールが縮合されたオリゴマーとした（エステル化反応）後に、これを高温減圧下のエステル交換による脱グリコール重縮合反応により、高分子量のポリエステルを得る方法が採用されている。 In the industrial production of polyethylene terephthalate, which produces polyester from TPA and EG, in order to improve the reactivity with respect to the acid component, an excessive glycol component was used and an oligomer in which glycol was condensed at both ends (ester) After the conversion reaction), a method of obtaining a high molecular weight polyester by deglycolization polycondensation reaction by transesterification under high temperature and reduced pressure is employed.
例えば、ＰＥＴ屑にメタノールを添加してジメチルテレフタレート(ＤＭＴ)とＥＧに分解する方法(特許文献２参照)などが提案されているがこれらの方法では比較的高品位の再生ＰＥＴが得られるものの、回収装置が複雑であるため経済的に好ましくないという問題点があった。 For example, methods of adding methanol to PET waste and decomposing it into dimethyl terephthalate (DMT) and EG have been proposed (see Patent Document 2), but these methods can provide relatively high-quality recycled PET, There is a problem that the recovery apparatus is complicated and economically undesirable.
ポリエステル屑をグリコールで解重合して、オリゴマーとした段階でフィルター濾過することにより、容易にポリエステル屑中の異物を除去する方法(特許文献３参照)が開示されているが、このような方法だけでは軟化点が高く色調の優れた高品質の再生ポリエステルは得られない問題があった。
本発明の目的は、ポリエステル屑の解重合における上記従来技術の問題点を解消し、解重合して得られたポリマーの品質、品位を向上させ、かつ、解重合反応時間を遅延することがなく、紡糸時における操業性が良好である再生ポリエステルの製造方法を提供することにある。 The object of the present invention is to eliminate the above-mentioned problems in the prior art in depolymerization of polyester waste, improve the quality and quality of the polymer obtained by depolymerization, and without delaying the depolymerization reaction time. Another object of the present invention is to provide a method for producing a regenerated polyester having good operability during spinning.
本発明者らは、前記課題を解決するために検討した結果、本発明に到達した。すなわち、本発明は以下の(１)、(２)、(３)、(４)、（５）を要旨とするものである。
（１）リサイクルポリエステルとグリコールおよびアルカリ化合物を第１の回分式反応装置に供給して解重合を行い、得られた低重合体を第２の回分式反応装置にて重縮合反応を行うことを特徴とする再生ポリエステルの製造方法。
（２）アルカリ化合物が水酸化テトラエチルアンモニウム、水酸化ナトリウム、又は水酸化カルシウムから選ばれたものであること。
（３）アルカリ化合物の添加量が、生成する再生ポリエステル１００重量部に対して０．０２〜０．１０重量部であること。
（４）グリコールが、エチレングリコールおよび／または１，４−ブタンジオールであること。
（５）リサイクルポリエステルが、繊維やポリエステル製品の製造工程で発生するリサイクルポリエステルであること。
The inventors of the present invention have arrived at the present invention as a result of studies to solve the above problems. That is, the gist of the present invention is the following (1), (2), (3), (4), (5).
(1) Supplying recycled polyester, glycol and alkali compound to the first batch reactor to perform depolymerization, and subjecting the resulting low polymer to a polycondensation reaction in the second batch reactor A method for producing a recycled polyester.
(2) The alkali compound is selected from tetraethylammonium hydroxide, sodium hydroxide, or calcium hydroxide.
(3) The addition amount of the alkali compound is 0.02 to 0.10 parts by weight with respect to 100 parts by weight of the regenerated polyester to be produced.
(4) The glycol is ethylene glycol and / or 1,4-butanediol.
(5) The recycled polyester is a recycled polyester generated in the manufacturing process of fibers and polyester products.
本発明によれば、ポリエステル屑を解重合する際にアルカリ化合物を添加することにより、軟化点も高く、色調も良好となり、ポリマー品質、品位を向上させ、かつ、解重合反応時間を遅延することなく、紡糸時における操業性良く、再生ポリエステルを製造することができる。また、本発明によれば、ポリエステル屑と、ＥＧ、１，４−ブタンジオール（ＢＧ）などのグリコールとを回分式反応装置を用いて解重合することにより、さらに再生ポリエステルの品質を安定化できる。 According to the present invention, by adding an alkali compound when depolymerizing polyester waste, the softening point is high, the color tone is good, the polymer quality and quality are improved, and the depolymerization reaction time is delayed. The recycled polyester can be produced with good operability during spinning. Further, according to the present invention, the quality of regenerated polyester can be further stabilized by depolymerizing polyester waste and glycols such as EG and 1,4-butanediol (BG) using a batch reactor. .
本発明においては、リサイクルポリエステルとグリコールおよびアルカリ化合物を第１の回分式反応装置に供給して解重合を行い、得られた低重合体を第２の回分式反応装置にて重縮合反応を行う。 In the present invention, the recycled polyester, glycol and alkali compound are supplied to the first batch reactor to perform depolymerization, and the resulting low polymer is subjected to a polycondensation reaction in the second batch reactor. .
本発明で使用するアルカリ化合物とは、エステル交換反応を促進するアルカリ化合物であれば如何なる物でも良く、例えばアルカリ金属の水酸化物を挙げることができる。具体的には水酸化ナトリウム、水酸化カルシウム、または水酸化テトラエチルアンモニウム等を用いることができる。 The alkali compound used in the present invention may be any compound as long as it promotes the transesterification reaction, and examples thereof include alkali metal hydroxides. Specifically, sodium hydroxide, calcium hydroxide, tetraethylammonium hydroxide, or the like can be used.
本発明において、アルカリ化合物の添加量は、生成する再生ポリエステル１００重量部に対して０．０２〜０．１０重量部であることが好ましい。 In this invention, it is preferable that the addition amount of an alkali compound is 0.02-0.10 weight part with respect to 100 weight part of reproduction | regeneration polyester to produce | generate.
本発明で使用するポリエステルは、エチレンテレフタレートを主成分とするポリエステルであり、具体的には例えば、テレフタル酸またはその低級アルキルエステルとＥＧとからなるポリエステルである。そのテレフタル酸成分の一部をイソフタル酸、ナフタレンジカルボン酸、ジフェノキシエタンジカルボン酸などの芳香族ジカルボン酸や、ドデカンジオン酸、アジピン酸、セバシン酸、アゼライン酸、デカンジカルボン酸などの脂肪族カルボン酸、さらにはシクロヘキサンジカルボン酸などの脂環族ジカルボン酸、ヒドロキシ安息香酸、グリコール酸、ヒドロキシエトキシ安息香酸などのヒドロキシカルボン酸などで置き換えてもよい。また、グリコール成分の一部をＢＧ、プロピレングリコール、ジエチレングリコール、ヘキサメチレングリコール、ｐ−キシレングリコール、１，４−シクロヘキサジメタノール、ビスフェノールなどの脂肪族、脂環族、芳香族のジオール化合物で置き換えてもよい。さらに熱可塑性を損なわない程度であれば、三官能以上の多官能性化合物を共重合したポリエステルでもよい。また、フタル酸、ジフェニルカルボン酸、コハク酸、アジピン酸、セバシン酸、Ｐ−ヒドロキシ安息香酸等の二官能性酸の１種または２種以上を置き換えたポリエステルであってもよい。また、顔料、耐熱材、蛍光増白剤などの添加物を含んでもよい。 The polyester used in the present invention is a polyester mainly composed of ethylene terephthalate, and specifically, for example, a polyester composed of terephthalic acid or a lower alkyl ester thereof and EG. Some of the terephthalic acid components are aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenoxyethanedicarboxylic acid, and aliphatic carboxylic acids such as dodecanedioic acid, adipic acid, sebacic acid, azelaic acid, and decanedicarboxylic acid. Furthermore, it may be replaced with an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, a hydroxycarboxylic acid such as hydroxybenzoic acid, glycolic acid, or hydroxyethoxybenzoic acid. Also, a part of the glycol component is replaced with aliphatic, alicyclic or aromatic diol compounds such as BG, propylene glycol, diethylene glycol, hexamethylene glycol, p-xylene glycol, 1,4-cyclohexadimethanol, bisphenol, etc. Also good. Further, a polyester obtained by copolymerizing a trifunctional or higher polyfunctional compound may be used as long as the thermoplasticity is not impaired. Moreover, the polyester which substituted the 1 type (s) or 2 or more types of bifunctional acids, such as a phthalic acid, diphenylcarboxylic acid, a succinic acid, adipic acid, sebacic acid, and P-hydroxybenzoic acid, may be sufficient. In addition, additives such as pigments, heat-resistant materials and fluorescent brighteners may be included.
本発明で使用するリサイクルポリエステルは、繊維やポリエステル製品の製造工程で発生するリサイクルポリエステルであることが好ましい。 The recycled polyester used in the present invention is preferably a recycled polyester generated in the production process of fibers and polyester products.
本発明において回分式反応装置に供給するグリコールは、通常、原料のリサイクルポリエステルを構成するグリコールと同種のグリコールを使用する。従って、ＥＧ、ＢＧ、プロピレングリコール、ジエチレングリコール、ヘキサメチレングリコール、ｐ−キシレングリコール、１，４−シクロヘキサジメタノール、ビスフェノールなどの脂肪族、脂環族、芳香族のジオール化合物が使用可能である。 In the present invention, the glycol supplied to the batch reactor is usually the same type of glycol as that constituting the recycled polyester as a raw material. Accordingly, aliphatic, alicyclic and aromatic diol compounds such as EG, BG, propylene glycol, diethylene glycol, hexamethylene glycol, p-xylene glycol, 1,4-cyclohexadimethanol, and bisphenol can be used.
本発明で使用する回分式反応装置は特に限定されない。解重合反応あるいは縮重合反応に各々適したものを使用すればよい。 The batch reactor used in the present invention is not particularly limited. Those suitable for the depolymerization reaction or the condensation polymerization reaction may be used.
以下、本発明方法を詳しく説明する。ポリエステルの製造では、一般的にあらかじめポリエステル低重合体が存在する回分式反応装置にポリエステル屑とＥＧを供給し、常圧で解重合させる。ポリエステル屑とＥＧを回分式反応装置に一定モル比、すなわち通常ポリエステル屑に対するＥＧのモル比は１．０〜２．０の範囲で供給する。第１の回分式反応装置中で行う解重合反応は、通常２３０〜２７０℃、常圧の条件にて反応させる。第１の回分式反応装置では、ほぼ解重合が完了し、生成したポリエステル低重合体が次工程の第２の回分式反応装置に送られる。第２の回分式反応装置では、２５０〜３００℃、０．０５〜３０ＫＰａの範囲で徐々に温度と、真空度を上げていくと、ポリエステルのポリマーが合成される。なお、ここではグリコール成分としてＥＧを用いたものについて説明しているが、本発明はグリコール成分がＥＧのみに限定されるものではない。また、回分式反応装置として、２槽構成のポリエステル重合方法を示したが、反応容器数はこれに限るものではない。 Hereinafter, the method of the present invention will be described in detail. In the production of polyester, generally, polyester waste and EG are supplied to a batch reactor in which a polyester low polymer is present in advance, and depolymerized at normal pressure. Polyester waste and EG are fed to the batch reactor in a fixed molar ratio, that is, the molar ratio of EG to normal polyester waste is in the range of 1.0 to 2.0. The depolymerization reaction performed in the first batch reactor is usually performed at 230 to 270 ° C. under normal pressure. In the first batch reactor, the depolymerization is almost completed, and the produced polyester low polymer is sent to the second batch reactor in the next step. In the second batch reactor, when the temperature and the degree of vacuum are gradually increased in the range of 250 to 300 ° C. and 0.05 to 30 KPa, a polyester polymer is synthesized. In addition, although the thing using EG as a glycol component is demonstrated here, this invention is not limited only to EG in a glycol component. Moreover, although the polyester polymerization method of 2 tank structure was shown as a batch type reaction apparatus, the number of reaction containers is not restricted to this.
以下、実施例にあげて本発明をさらに具体的に説明する。本実施例でいう「部」とは重量部を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. The “parts” in this example means parts by weight.
特性値の測定方法は次のとおりである。 The characteristic value is measured as follows.
（１）固有粘度
オルソクロロフェノール中、２５℃で測定した値である。
(1) Intrinsic viscosity This is a value measured in orthochlorophenol at 25 ° C.
（２）色調（ｂ値）
スガ試験機（株）製の“ＳＣ３Ｐカラーマシン”を使用して測定した。
(2) Color tone (b value)
Measurement was performed using “SC3P Color Machine” manufactured by Suga Test Instruments Co., Ltd.
（３）ジエチレングリコール含有率
試料１．０ｇに１級モノエタノールアミン２．５ｍｌを加え、全還流下２８０℃で４０ 分間加熱後、内部標準液を加える。さらに特級テレフタル酸４０ｇと１級エタノール５ｍｌを加え測定用試料を調製する。該測定用試料を島津製ガスクロマトグラフィー“ＧＣ−９Ａ”(使用カラム：島津Ｃ−Ｒ３Ａ)を用いて測定した。
(3) Diethylene glycol content rate Add 2.5 ml of primary monoethanolamine to 1.0 g of the sample, heat at 280 ° C for 40 minutes under total reflux, and then add the internal standard solution. Further, 40 g of special grade terephthalic acid and 5 ml of primary ethanol are added to prepare a sample for measurement. The sample for measurement was measured by using a gas chromatography “GC-9A” (column used: Shimadzu C-R3A) manufactured by Shimadzu.
（４）カルボキシル基含有量
ベンジルアルコールに得られたポリエステルを溶解し、０．０１Ｎ水酸化ナトリウム水 溶液で滴定することにより求めた。
(4) Carboxyl group content It calculated | required by melt | dissolving the polyester obtained in benzyl alcohol, and titrating with 0.01N sodium hydroxide aqueous solution.
実施例１
回分式反応装置１にＰＥＴ屑２５００部、ＥＧ８７０部、アルカリ化合物として水酸化テトラエチルアンモニウムを０．０１５７部を仕込み、原料仕込みと同時に昇温を開始して、常圧下に解重合反応を開始した。その後、解重合反応を開始して２時間５０分後（この時の缶温度：２４５℃）に解重合反応終了となった。
Example 1
The batch reactor 1 was charged with 2500 parts of PET waste, 870 parts of EG, and 0.0157 part of tetraethylammonium hydroxide as an alkali compound. The temperature was started at the same time as the raw materials were charged, and the depolymerization reaction was started under normal pressure. Thereafter, the depolymerization reaction was completed 2 hours and 50 minutes later (can temperature at this time: 245 ° C.).
この時の反応生成物であるＰＥＴ低重合体を回分式反応装置２に移液し、２９０℃、減圧下（１ｍｍＨｇ以下）で重縮合反応を行った。２時間４２分後に固有粘度０．６５６のＰＥＴポリマーを得た。ＤＥＧ量、ＣＯＯＨ量も低い値となっており、得られたＰＥＴの色調はｂ値が１３．７であった。得られた再生ＰＥＴの物性を表１に示す。軟化点、色調も問題なく再生ＰＥＴが得られることを確認した。 The PET low polymer, which is the reaction product at this time, was transferred to the batch reactor 2 and subjected to a polycondensation reaction at 290 ° C. under reduced pressure (1 mmHg or less). After 2 hours and 42 minutes, a PET polymer having an intrinsic viscosity of 0.656 was obtained. The amount of DEG and the amount of COOH were also low, and the color tone of the obtained PET had a b value of 13.7. Table 1 shows the physical properties of the obtained recycled PET. It was confirmed that regenerated PET could be obtained without any problems in softening point and color tone.
実施例２
アルカリ化合物として水酸化テトラエチルアンモニウムを０．０１１２部使用する以外は実施例１と同様にして解重合反応を行い、解重合反応を開始して２時間５１分後（この時の缶温度：２４５℃）に解重合反応終了となった。
Example 2
The depolymerization reaction was carried out in the same manner as in Example 1 except that 0.0112 parts of tetraethylammonium hydroxide was used as the alkali compound, and 2 hours and 51 minutes after starting the depolymerization reaction (can temperature at this time: 245 ° C. ) Completed the depolymerization reaction.
この時の反応生成物であるＰＥＴ低重合体を回分式反応装置２に移液し、２９０℃、減圧下（１ｍｍＨｇ以下）で重縮合反応を行った。２時間４３分後に固有粘度０．６６０のＰＥＴを得た。ＤＥＧ量、ＣＯＯＨ量も低い値となっており、得られたＰＥＴの色調はｂ値１３．２であった。得られた再生ＰＥＴの物性を表１に示す。軟化点、色調も問題なく再生ＰＥＴが得られることを確認した。 The PET low polymer, which is the reaction product at this time, was transferred to the batch reactor 2 and subjected to a polycondensation reaction at 290 ° C. under reduced pressure (1 mmHg or less). After 2 hours and 43 minutes, PET having an intrinsic viscosity of 0.660 was obtained. The amount of DEG and COOH were also low, and the color tone of the obtained PET had a b value of 13.2. Table 1 shows the physical properties of the obtained recycled PET. It was confirmed that regenerated PET could be obtained without any problems in softening point and color tone.
実施例３
アルカリ化合物として水酸化テトラエチルアンモニウムを０．００６８部使用する以外は実施例１と同様にして解重合反応を行い、、解重合反応を開始して２時間５０分後（この時の缶温度：２４５℃）に解重合反応終了となった。
Example 3
A depolymerization reaction was carried out in the same manner as in Example 1 except that 0.0068 parts of tetraethylammonium hydroxide was used as the alkali compound, and 2 hours and 50 minutes after the start of the depolymerization reaction (can temperature at this time: 245 (° C.), the depolymerization reaction was completed.
この時の反応生成物であるＰＥＴ低重合体を回分式反応装置２に移液し、２９０℃、減圧下（１ｍｍＨｇ以下）で重縮合反応を行った。２時間４０分後に固有粘度０．６５７のＰＥＴを得た。ＤＥＧ量、ＣＯＯＨ量も低い値となっており、得られたＰＥＴの色調はｂ値１３．４であった。得られた再生ＰＥＴの物性を表１に示す。軟化点、色調も問題なく再生ＰＥＴが得られることを確認した。 The PET low polymer, which is the reaction product at this time, was transferred to the batch reactor 2 and subjected to a polycondensation reaction at 290 ° C. under reduced pressure (1 mmHg or less). After 2 hours and 40 minutes, PET having an intrinsic viscosity of 0.657 was obtained. The amount of DEG and COOH were also low, and the color tone of the obtained PET had a b value of 13.4. Table 1 shows the physical properties of the obtained recycled PET. It was confirmed that regenerated PET could be obtained without any problems in softening point and color tone.
実施例４
アルカリ化合物を水酸化ナトリウムに変える以外は実施例３と同様にして解重合反応を行い、解重合反応を開始して２時間５５分後（この時の缶温度：２４５℃）に解重合反応終了となった。
Example 4
The depolymerization reaction was carried out in the same manner as in Example 3 except that the alkali compound was changed to sodium hydroxide, and the depolymerization reaction was completed 2 hours and 55 minutes after starting the depolymerization reaction (can temperature at this time: 245 ° C.). It became.
この時の反応生成物であるＰＥＴ低重合体を回分式反応装置２に移液し、２９０℃、減圧下（１ｍｍＨｇ以下）で重縮合反応を行った。２時間４２分後に固有粘度０．６５３のＰＥＴを得た。ＤＥＧ量、ＣＯＯＨ量も低い値となっており、得られたＰＥＴの色調はｂ値１４．０であった。得られた再生ＰＥＴの物性を表１に示す。軟化点、色調も問題なく再生ＰＥＴが得られることを確認した。 The PET low polymer, which is the reaction product at this time, was transferred to the batch reactor 2 and subjected to a polycondensation reaction at 290 ° C. under reduced pressure (1 mmHg or less). After 2 hours and 42 minutes, PET having an intrinsic viscosity of 0.653 was obtained. The amounts of DEG and COOH were also low, and the color tone of the obtained PET had a b value of 14.0. Table 1 shows the physical properties of the obtained recycled PET. It was confirmed that regenerated PET could be obtained without any problems in softening point and color tone.
実施例５
ＰＥＴをＰＢＴに変える以外は実施例３と同様にして解重合反応を行い、解重合反応を開始して２時間５４分後（この時の缶温度：２４５℃）に解重合反応終了となった。
Example 5
The depolymerization reaction was carried out in the same manner as in Example 3 except that PET was changed to PBT, and the depolymerization reaction was completed 2 hours and 54 minutes after starting the depolymerization reaction (can temperature at this time: 245 ° C.). .
この時の反応生成物であるＰＢＴ低重合体を回分式反応装置２に移液し、２９０℃、減圧下（１ｍｍＨｇ以下）で重縮合反応を行った。２時間４４分後に固有粘度０．６５８のＰＢＴを得た。ＤＥＧ量、ＣＯＯＨ量も低い値となっており、得られたＰＢＴの色調はｂ値１３．９であった。得られた再生ＰＢＴの物性を表１に示す。軟化点、色調も問題なく再生ＰＢＴが得られることを確認した。 The PBT low polymer which is the reaction product at this time was transferred to the batch reactor 2 and subjected to a polycondensation reaction at 290 ° C. under reduced pressure (1 mmHg or less). After 2 hours and 44 minutes, PBT having an intrinsic viscosity of 0.658 was obtained. The amount of DEG and COOH were also low, and the color tone of the obtained PBT had a b value of 13.9. Table 1 shows the physical properties of the obtained recycled PBT. It was confirmed that a regenerated PBT could be obtained without any problem in softening point and color tone.
比較例１
実施例１と同じ方法でＰＥＴ屑２５００部、ＢＧ８７０部を仕込み、原料仕込みと同時に昇温を開始して、常圧下に解重合反応を開始した。その後、解重合反応を開始して２時間５２分後（この時の缶温度：２４５℃）に解重合反応終了となった。
この時の反応生成物であるＰＥＴ低重合体を回分式反応装置２に移液し、２９０℃、減圧下（１ｍｍＨｇ以下）で重縮合反応を行った。２時間５１分後に固有粘度０．６５２のポリマーを得た。ＤＥＧ量、ＣＯＯＨ量も高い値となっており、得られた再生ＰＥＴの色調はｂ値１５．３であった。軟化点が低く、色調も好ましくない再生ＰＥＴしか得られなかった。
Comparative Example 1
In the same manner as in Example 1, 2500 parts of PET waste and 870 parts of BG were charged, and the temperature was increased simultaneously with the charging of the raw materials, and the depolymerization reaction was started under normal pressure. Thereafter, the depolymerization reaction was completed 2 hours and 52 minutes later (can temperature at this time: 245 ° C.).
The PET low polymer, which is the reaction product at this time, was transferred to the batch reactor 2 and subjected to a polycondensation reaction at 290 ° C. under reduced pressure (1 mmHg or less). After 2 hours and 51 minutes, a polymer with an intrinsic viscosity of 0.652 was obtained. The amount of DEG and COOH were also high, and the color tone of the obtained recycled PET had a b value of 15.3. Only regenerated PET having a low softening point and an unfavorable color tone was obtained.
アルカリ添加は、ポリエステル１００重量部に対するアルカリ化合物の添加量である。
ＥＧはエチレングリコール、ＢＧは１，４−ブタンジオールである。
ＥＡＨは水産課テトラエチルアンモニウム、ＮａＯＨは水酸化ナトリウムである。
Alkali addition is the amount of alkali compound added to 100 parts by weight of polyester.
EG is ethylene glycol and BG is 1,4-butanediol.
EAH is the fishery section tetraethylammonium, and NaOH is sodium hydroxide.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005347310A JP2007153942A (en) | 2005-11-30 | 2005-11-30 | Method for producing recycled polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005347310A JP2007153942A (en) | 2005-11-30 | 2005-11-30 | Method for producing recycled polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007153942A true JP2007153942A (en) | 2007-06-21 |
Family
ID=38238719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005347310A Pending JP2007153942A (en) | 2005-11-30 | 2005-11-30 | Method for producing recycled polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007153942A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173902A (en) * | 2007-12-25 | 2009-08-06 | Sumitomo Chemical Co Ltd | Method for decomposing aromatic ether compound |
| KR101124559B1 (en) | 2010-03-31 | 2012-03-16 | 웅진케미칼 주식회사 | Recycled polyester staple fiber using waste polyester and method thereof |
| KR101240341B1 (en) | 2011-05-31 | 2013-03-07 | 웅진케미칼 주식회사 | Recycled polyester filament having infrared ray and ultraviolet ray shielding effect and low melting property |
| KR101240340B1 (en) | 2010-04-23 | 2013-03-07 | 웅진케미칼 주식회사 | Fire retardancy recycled polyester filament for interior and method thereof |
| KR101303819B1 (en) * | 2011-05-31 | 2013-09-04 | 웅진케미칼 주식회사 | Recycled polyester filament having low melting property and antibacterial property |
| JP2014500781A (en) * | 2010-09-30 | 2014-01-16 | エクイポリマーズ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Mixing method and mixing device |
| JP2015515519A (en) * | 2012-03-30 | 2015-05-28 | サウディ ベーシック インダストリーズ コーポレイション | Biodegradable aliphatic-aromatic copolyester, process for its production, and article thereof |
| US9487625B2 (en) | 2012-03-01 | 2016-11-08 | Sabic Global Technologies B.V. | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
| US9487621B2 (en) | 2011-08-30 | 2016-11-08 | Sabic Global Technologies B.V. | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
| WO2020053051A1 (en) * | 2018-09-12 | 2020-03-19 | Rittec Umwelttechnik Gmbh | Method, device and use for reprocessing substantially polyalkylene terephthalate |
| JP2021120445A (en) * | 2019-03-29 | 2021-08-19 | ユニチカ株式会社 | Recycled polyester resin and method for producing recycled polyester resin |
| JP2022019537A (en) * | 2020-07-15 | 2022-01-27 | 南亞塑膠工業股▲分▼有限公司 | Polyester film for embossing and method for producing the same |
| JP2022063218A (en) * | 2020-10-09 | 2022-04-21 | ユニチカ株式会社 | Recycled polyester resin and method for producing recycled polyester resin |
-
2005
- 2005-11-30 JP JP2005347310A patent/JP2007153942A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173902A (en) * | 2007-12-25 | 2009-08-06 | Sumitomo Chemical Co Ltd | Method for decomposing aromatic ether compound |
| KR101124559B1 (en) | 2010-03-31 | 2012-03-16 | 웅진케미칼 주식회사 | Recycled polyester staple fiber using waste polyester and method thereof |
| KR101240340B1 (en) | 2010-04-23 | 2013-03-07 | 웅진케미칼 주식회사 | Fire retardancy recycled polyester filament for interior and method thereof |
| JP2014500781A (en) * | 2010-09-30 | 2014-01-16 | エクイポリマーズ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Mixing method and mixing device |
| KR101240341B1 (en) | 2011-05-31 | 2013-03-07 | 웅진케미칼 주식회사 | Recycled polyester filament having infrared ray and ultraviolet ray shielding effect and low melting property |
| KR101303819B1 (en) * | 2011-05-31 | 2013-09-04 | 웅진케미칼 주식회사 | Recycled polyester filament having low melting property and antibacterial property |
| US9487621B2 (en) | 2011-08-30 | 2016-11-08 | Sabic Global Technologies B.V. | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
| US9487625B2 (en) | 2012-03-01 | 2016-11-08 | Sabic Global Technologies B.V. | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
| JP2015515519A (en) * | 2012-03-30 | 2015-05-28 | サウディ ベーシック インダストリーズ コーポレイション | Biodegradable aliphatic-aromatic copolyester, process for its production, and article thereof |
| WO2020053051A1 (en) * | 2018-09-12 | 2020-03-19 | Rittec Umwelttechnik Gmbh | Method, device and use for reprocessing substantially polyalkylene terephthalate |
| JP2021120445A (en) * | 2019-03-29 | 2021-08-19 | ユニチカ株式会社 | Recycled polyester resin and method for producing recycled polyester resin |
| JP7072764B2 (en) | 2019-03-29 | 2022-05-23 | ユニチカ株式会社 | Manufacturing method of recycled polyester resin |
| JP2022019537A (en) * | 2020-07-15 | 2022-01-27 | 南亞塑膠工業股▲分▼有限公司 | Polyester film for embossing and method for producing the same |
| JP7200285B2 (en) | 2020-07-15 | 2023-01-06 | 南亞塑膠工業股▲分▼有限公司 | Polyester film for embossing and its manufacturing method |
| JP2022063218A (en) * | 2020-10-09 | 2022-04-21 | ユニチカ株式会社 | Recycled polyester resin and method for producing recycled polyester resin |
| JP7247433B2 (en) | 2020-10-09 | 2023-03-29 | ユニチカ株式会社 | Recycled polyester resin and method for producing recycled polyester resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2007153942A (en) | Method for producing recycled polyester | |
| TW583216B (en) | Polyester continuous production process | |
| JP2014001257A (en) | Method for producing biomass resource-derived polyester and biomass resource-derived polyester | |
| TWI487727B (en) | Method for producing polyester resin | |
| JP2010126660A (en) | Method for producing reclaimed polyester | |
| JPH09221540A (en) | Polyethylene terephthalate, hollow container, and oriented film | |
| KR101834666B1 (en) | Method of solid state polymerization for titianium based polyester | |
| JP2015140412A (en) | Method for manufacturing copolyester | |
| JP2006016548A (en) | Method for producing polyester | |
| JP2004217721A (en) | Polyester and its manufacturing method | |
| JP5062960B2 (en) | Copolyester | |
| JP2005248005A (en) | Method for manufacturing polyester | |
| JP5215074B2 (en) | Catalyst for producing polyester and production of polyester using the catalyst | |
| JP4781701B2 (en) | Method for producing polyethylene terephthalate and molded body | |
| JP2020528467A (en) | Methods for preparing polyesters with additives | |
| EP4141043A1 (en) | Valorisation of d-lactic acid stream in the production process of l-polylactic acid | |
| EP4141042A1 (en) | Valorisation of l-lactic acid stream in the production process of d-polylactic acid | |
| JP2001048968A (en) | Production of polybutylene terephtahlate | |
| TW581777B (en) | Process for producing a poly(ethylene aromatic dicarboxylate ester) resin, the resin, and fibers, films and bottle-formed products produced from the resin | |
| JP2007269896A (en) | Polyethylene terephthalate and method for producing the same | |
| JPH06234909A (en) | Polybutylene terephthalate resin composition and its production | |
| JP2001200042A (en) | Manufacturing method for polyester | |
| JP2017145274A (en) | Method of producing copolymerized polyester | |
| JPH11106364A (en) | Production of intermediate raw material for polyester | |
| TW202413479A (en) | Chemically recycled polyethylene terephthalate resin and its molded body, and method for producing chemically recycled polyethylene terephthalate resin |