JP2012012523A - Treatment method of polyester, and polyester composition and molding containing polyester obtained by the treatment method - Google Patents
Treatment method of polyester, and polyester composition and molding containing polyester obtained by the treatment method Download PDFInfo
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- JP2012012523A JP2012012523A JP2010151288A JP2010151288A JP2012012523A JP 2012012523 A JP2012012523 A JP 2012012523A JP 2010151288 A JP2010151288 A JP 2010151288A JP 2010151288 A JP2010151288 A JP 2010151288A JP 2012012523 A JP2012012523 A JP 2012012523A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 156
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000000465 moulding Methods 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 27
- 239000013638 trimer Substances 0.000 claims abstract description 27
- 238000003672 processing method Methods 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005809 transesterification 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、抽出溶媒として水を用いて、ポリエステル中における低分子量物（特に、環状三量体）の含有量を低減するポリエステルの処理方法、ならびに、その処理方法で得られたポリエステルを含有するポリエステル組成物および成形体に関するものである。 The present invention includes a polyester processing method for reducing the content of low molecular weight substances (particularly, cyclic trimers) in polyester using water as an extraction solvent, and the polyester obtained by the processing method. The present invention relates to a polyester composition and a molded body.
ポリエステルは、通常、ジカルボン酸成分とグリコール成分とから重縮合反応により製造されるポリマーである。しかしながら、従来公知のポリエステルには、モノマーやオリゴマー（例えば、環状三量体）などの低分子量物が数質量％程度含まれている。このような低分子量物は、ポリエステルの加熱加工時に外部に析出して金型や工程を汚染する。また、ポリエステルをフィルムなどに加工して用いる場合には、加熱加工により表面に析出した低分子量物が欠陥となり、得られたポリエステルフィルムの品質を低下させる。 Polyester is usually a polymer produced from a dicarboxylic acid component and a glycol component by a polycondensation reaction. However, conventionally known polyesters contain about several mass% of low molecular weight substances such as monomers and oligomers (for example, cyclic trimers). Such low molecular weight substances are deposited on the outside during heat processing of the polyester and contaminate the mold and the process. Moreover, when processing and using polyester for a film etc., the low molecular weight thing deposited on the surface by heat processing becomes a defect, and the quality of the obtained polyester film is reduced.
従来、ポリエステルから低分子量物を抽出する方法として、例えば、特許文献１，２では、各種の有機溶媒を用いて、ポリエステルフィルムから低分子量物を抽出する方法が実施されている。また、特許文献３〜５では、超臨界状態の二酸化炭素を用いて、ポリエステル樹脂または成形体から低分子量物を抽出する方法が実施されている。 Conventionally, as a method for extracting a low molecular weight product from polyester, for example, in Patent Documents 1 and 2, a method of extracting a low molecular weight product from a polyester film using various organic solvents has been implemented. Moreover, in patent documents 3-5, the method of extracting a low molecular weight thing from a polyester resin or a molded object is implemented using the carbon dioxide of a supercritical state.
最近、環境に配慮する意識の向上により、環境負荷の少ないプロセス技術への要望が高まっている。しかし、特許文献１，２の処理方法を工業的規模のポリエステル生産に利用するには、大量の有機溶媒を用いるので、環境問題のみならず、有害物質の取り扱いも困難であり、事実上実施することができない。さらに、特許文献３〜５の処理方法では、低分子量物の抽出に一定の効果は認められるものの、処理により大量の二酸化炭素を排出するので、環境への悪影響がある。また、抽出効率を向上するためにジオキサンなどの有機溶媒を抽出助剤として用いることがあるので、工業的規模のポリエステル生産に利用するにあたっては、環境リスクが非常に高い。 Recently, the demand for process technology with less environmental impact is increasing due to the improvement of environmental awareness. However, in order to use the treatment methods of Patent Documents 1 and 2 for industrial-scale polyester production, since a large amount of organic solvent is used, not only environmental problems but also the handling of harmful substances is difficult, which is practically performed. I can't. Furthermore, in the processing methods of Patent Documents 3 to 5, although a certain effect is recognized in the extraction of low molecular weight substances, a large amount of carbon dioxide is discharged by the processing, which has an adverse effect on the environment. In addition, an organic solvent such as dioxane is sometimes used as an extraction aid in order to improve the extraction efficiency. Therefore, when it is used for industrial scale polyester production, the environmental risk is very high.
上述した状況の下、本発明が解決すべき課題は、環境性能に優れ、工業的規模のポリエステル生産に利用可能なポリエステルの処理方法、ならびに、その処理方法で得られたポリエステルを含有するポリエステル組成物および成形体を提供することにある。 Under the circumstances described above, the problem to be solved by the present invention is a method for treating polyester that is excellent in environmental performance and can be used for production of polyester on an industrial scale, and a polyester composition containing the polyester obtained by the treatment method. It is to provide a product and a molded body.
本発明者らは、種々検討の結果、抽出溶媒として超臨界または亜臨界状態の水を用いれば、ポリエステルから低分子量物（特に、環状三量体）を効率的に抽出できることを見出して、本発明を完成した。 As a result of various studies, the present inventors have found that if supercritical or subcritical water is used as an extraction solvent, low molecular weight substances (particularly, cyclic trimers) can be efficiently extracted from polyester. Completed the invention.
すなわち、本発明は、ポリエステルに超臨界または亜臨界状態の水を接触させて、ポリエステル中における環状三量体の含有量を処理前に比べて０．０１質量％以上低減することを特徴とするポリエステルの処理方法を提供する。 That is, the present invention is characterized in that the polyester is brought into contact with water in a supercritical or subcritical state to reduce the content of the cyclic trimer in the polyester by 0.01% by mass or more compared to before treatment. A method for treating polyester is provided.
この処理方法においては、下記式：
ポリエステルの重量平均分子量の低下率 ＝ ［（処理前のポリエステルの重量平均分子量−処理後のポリエステルの重量平均分子量）／処理前のポリエステルの重量平均分子量］×１００
により求めたポリエステルの重量平均分子量の低下率が好ましくは５０％以下である。
In this treatment method, the following formula:
Rate of decrease in weight average molecular weight of polyester = [(weight average molecular weight of polyester before treatment−weight average molecular weight of polyester after treatment) / weight average molecular weight of polyester before treatment] × 100
The reduction rate of the weight average molecular weight of the polyester determined by the above is preferably 50% or less.
また、本発明は、上記のようなポリエステルの処理方法で得られたポリエステルを含有することを特徴とするポリエステル組成物および成形体を提供する。 The present invention also provides a polyester composition and a molded article containing the polyester obtained by the polyester processing method as described above.
本発明によれば、抽出溶媒として水を用いているので、環境性能に優れ、工業的規模のポリエステル生産に利用可能なポリエステルの処理方法を提供することができる。この処理方法で得られたポリエステルは、低分子量物（特に、環状三量体）の含有量が低減されているので、工業的に好適に利用することができ、例えば、ポリエステル組成物および成形体に用いられる。 According to the present invention, since water is used as the extraction solvent, it is possible to provide a method for treating polyester that is excellent in environmental performance and can be used for industrial scale polyester production. The polyester obtained by this treatment method can be suitably used industrially because the content of low molecular weight substances (particularly, cyclic trimers) is reduced. For example, polyester compositions and molded articles Used for.
≪ポリエステルの処理方法≫
本発明によるポリエステルの処理方法（以下「本発明の処理方法」ということがある）は、ポリエステルに超臨界または亜臨界状態の水を接触させて、ポリエステル中における環状三量体の含有量を処理前に比べて０．０１質量％以上低減することを特徴とする。
≪Polyester treatment method≫
The polyester processing method according to the present invention (hereinafter sometimes referred to as “the processing method of the present invention”) is to treat the content of cyclic trimer in the polyester by bringing the polyester into contact with water in a supercritical or subcritical state. It is characterized by being reduced by 0.01% by mass or more compared to before.
＜ポリエステル＞
本発明の処理方法において、ポリエステルとは、ジカルボン酸成分とジオール成分との重縮合により得られる主鎖にエステル結合を有する高分子化合物である。代表的なジカルボン酸成分としては、例えば、テレフタル酸、イソフタル酸、フタル酸、ナフタレンジカルボン酸、それらの誘導体などが挙げられる。代表的なジオール成分としては、例えば、エチレングリコール、１，３−プロパンジオール、ブチレングリコール、ポリエチレングリコール、ジエチレングリコール、ネオペンチルグリコール、それらの誘導体などが挙げられる。
<Polyester>
In the treatment method of the present invention, the polyester is a polymer compound having an ester bond in the main chain obtained by polycondensation of a dicarboxylic acid component and a diol component. Examples of typical dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and derivatives thereof. Representative diol components include, for example, ethylene glycol, 1,3-propanediol, butylene glycol, polyethylene glycol, diethylene glycol, neopentyl glycol, and derivatives thereof.
本発明の処理方法に好適なポリエステルは、ジカルボン酸成分として芳香族ジカルボン酸を用いて得られるポリエステルであり、その具体例としては、例えば、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン−２，６−ナフタレートなどが挙げられる。これらのポリエステルのうち、ポリエチレンテレフタレートが特に好適である。 The polyester suitable for the treatment method of the present invention is a polyester obtained by using an aromatic dicarboxylic acid as a dicarboxylic acid component, and specific examples thereof include, for example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene- Examples include 2,6-naphthalate. Of these polyesters, polyethylene terephthalate is particularly suitable.
ポリエチレンテレフタレート（以下「ＰＥＴ」ということがある）を製造する方法としては、例えば、テレフタル酸とエチレングリコールとを直接エステル化させる方法（必要に応じて、他のジカルボン酸成分、他のジオール成分を併用してもよい）；テレフタル酸ジメチルエステルとエチレングリコールとをエステル交換させる方法（必要に応じて、他のジカルボン酸メチルエステル、他のジオール成分を併用してもよい）；などが挙げられるが、特に限定されるものではなく、任意の製造方法を用いることができる。 As a method for producing polyethylene terephthalate (hereinafter sometimes referred to as “PET”), for example, a method in which terephthalic acid and ethylene glycol are directly esterified (if necessary, other dicarboxylic acid components and other diol components are added). A method of transesterifying terephthalic acid dimethyl ester and ethylene glycol (if necessary, other dicarboxylic acid methyl ester and other diol components may be used in combination); However, it is not particularly limited, and any manufacturing method can be used.
ポリエステルを製造する際には、従来公知の触媒、例えば、マグネシウム化合物、カルシウム化合物、チタン化合物、マンガン化合物、コバルト化合物、アルミニウム化合物、ゲルマニウム化合物、リン化合物、アンチモン化合物などを用いることができ、特に限定されるものではない。 In producing the polyester, conventionally known catalysts such as magnesium compounds, calcium compounds, titanium compounds, manganese compounds, cobalt compounds, aluminum compounds, germanium compounds, phosphorus compounds, antimony compounds and the like can be used. Is not to be done.
本発明の処理方法において、処理されるポリエステルは、粗製または精製状態の樹脂、組成物、成形体、再生品（リサイクル品）など、いかなる形態であってもよい。また、処理されるポリエステルは、例えば、安定剤、顔料、染料、核剤、充填剤、紫外線吸収剤、酸化防止剤、抗菌剤、帯電防止剤、滑剤、離型剤などの添加剤を含有していてもよい。 In the treatment method of the present invention, the polyester to be treated may be in any form such as a resin in a crude or purified state, a composition, a molded product, and a recycled product (recycled product). In addition, the polyester to be treated contains additives such as stabilizers, pigments, dyes, nucleating agents, fillers, UV absorbers, antioxidants, antibacterial agents, antistatic agents, lubricants, and release agents. It may be.
＜ポリエステルの処理＞
本発明の処理方法において、抽出溶媒としては、超臨界または亜臨界状態の水が用いられる。この処理方法に用いられる水は、特に限定されるものではなく、例えば、蒸留水、脱イオン水などを用いることができる。
<Polyester treatment>
In the treatment method of the present invention, supercritical or subcritical water is used as the extraction solvent. The water used in this treatment method is not particularly limited, and for example, distilled water, deionized water, or the like can be used.
通常、水は、温度および圧力に応じて、固体−液体−気体の３つの状態をとる。水は、１気圧（約０．１ＭＰａ）の大気圧下では、約１００℃で気体（水蒸気）になるが、約２２ＭＰａの圧力をかけると、約３７４℃まで液体状態を保持する。本発明では、温度が１００℃以上、３７４℃以下、圧力が０．１ＭＰａ以上、２２ＭＰａ以下の領域であり、かつ、物質状態図における気液平衡の共存線以上の領域にある液体状態の水を亜臨界状態の水と定義する。この領域では、水分子の凝集力と拡散力とが拮抗状態にある。そして、水分子の凝集力と拡散力とがほぼ等しくなる点（温度が約３７４℃、圧力が約２２ＭＰａ）を臨界点という。本発明では、臨界点以上の温度および圧力の領域にある水を超臨界状態の水と定義する。この領域では、水は気体でも液体でもない特殊な性質を発現する。 Usually, water takes three states, solid-liquid-gas, depending on temperature and pressure. Water becomes a gas (water vapor) at about 100 ° C. under an atmospheric pressure of 1 atm (about 0.1 MPa), but maintains a liquid state up to about 374 ° C. when a pressure of about 22 MPa is applied. In the present invention, water in a liquid state in a region where the temperature is 100 ° C. or more and 374 ° C. or less, the pressure is 0.1 MPa or more and 22 MPa or less, and in the region above the coexistence line of gas-liquid equilibrium in the substance state diagram. Defined as subcritical water. In this region, the cohesion force and diffusion force of water molecules are in an antagonistic state. And the point (temperature is about 374 degreeC and a pressure is about 22 MPa) in which the cohesion force and diffusion force of a water molecule become substantially equal is called a critical point. In the present invention, water in a temperature and pressure region above the critical point is defined as supercritical water. In this region, water develops special properties that are neither gas nor liquid.
ポリエステルに含まれる低分子量物のうちオリゴマーは、通常状態の水に難溶である。ところが、超臨界または亜臨界状態の水は、オリゴマー（特に、環状三量体）を効率よく溶解する。この作用機構については、よく分からないが、超臨界または亜臨界状態では、水の極性が変化しているのではないかと推察している。 Of the low molecular weight substances contained in polyester, oligomers are hardly soluble in normal water. However, supercritical or subcritical water efficiently dissolves oligomers (particularly, cyclic trimers). The mechanism of action is not well understood, but it is presumed that the polarity of water is changing in the supercritical or subcritical state.
本発明の処理方法は、ポリエステルに超臨界または亜臨界状態の水を接触させることにより、ポリエステルに含まれる低分子量物（特に、環状三量体）を効率よく除去することができる。この処理方法では、水が超臨界または亜臨界状態であることが重要であり、そのような状態の水を調製する方法は、特に限定されるものではない。以下、本発明の処理方法における具体的な処理条件について説明する。 The treatment method of the present invention can efficiently remove low molecular weight substances (particularly, cyclic trimers) contained in the polyester by bringing the polyester into contact with water in a supercritical or subcritical state. In this treatment method, it is important that the water is in a supercritical or subcritical state, and the method for preparing water in such a state is not particularly limited. Hereinafter, specific processing conditions in the processing method of the present invention will be described.
本発明の処理方法において、水の温度は、好ましくは１００℃以上、より好ましくは１２５℃以上、さらに好ましくは１５０℃以上である。また、水の圧力は、飽和水蒸気圧以上であれば、特に限定されるものではないが、好ましくは０．１ＭＰａ以上、より好ましくは１ＭＰａ以上、さらに好ましくは３ＭＰａ以上である。このような高圧高温の水を用いることにより、ポリエステルから低分子量物（特に、環状三量体）を効率よく抽出して除去することができる。 In the treatment method of the present invention, the temperature of water is preferably 100 ° C. or higher, more preferably 125 ° C. or higher, and further preferably 150 ° C. or higher. The water pressure is not particularly limited as long as it is equal to or higher than the saturated water vapor pressure, but is preferably 0.1 MPa or higher, more preferably 1 MPa or higher, and further preferably 3 MPa or higher. By using such high-pressure and high-temperature water, low molecular weight substances (particularly, cyclic trimers) can be efficiently extracted and removed from the polyester.
本発明の処理方法では、抽出溶媒として水を用いているので、ポリエステルが加水分解を起こして、その分子量が低下することがある。そのため、水の温度は、好ましくは４００℃以下、より好ましくは３５０℃以下、さらに好ましくは３００℃以下である。また、水の圧力は、好ましくは３０ＭＰａ以下、より好ましくは２５ＭＰａ以下、さらに好ましくは２０ＭＰａ以下である。ポリエステルの分子量低下を抑制し、かつ、低分子量物（特に、環状三量体）を効率よく抽出して除去するという、相反する２つの機能を併せ持つという点では、臨界点近傍の亜臨界状態の水を用いることが好ましい。 In the treatment method of the present invention, since water is used as the extraction solvent, the polyester may be hydrolyzed and its molecular weight may be reduced. Therefore, the temperature of water is preferably 400 ° C. or lower, more preferably 350 ° C. or lower, and further preferably 300 ° C. or lower. Moreover, the pressure of water becomes like this. Preferably it is 30 MPa or less, More preferably, it is 25 MPa or less, More preferably, it is 20 MPa or less. In terms of having both two contradictory functions of suppressing the molecular weight reduction of polyester and efficiently extracting and removing low molecular weight substances (especially cyclic trimers), it is a subcritical state near the critical point. It is preferable to use water.
本発明の処理方法における処理時間としては、特に限定されるものではないが、好ましくは３分間以上、より好ましくは５分間以上である。また、処理時間が長くなると、ポリエステルの加水分解が進行しやすくなるので、処理時間は、好ましくは３００分間以下、より好ましくは２００分間以下、さらに好ましくは１００分間以下である。 Although it does not specifically limit as processing time in the processing method of this invention, Preferably it is 3 minutes or more, More preferably, it is 5 minutes or more. Moreover, since the hydrolysis of the polyester tends to proceed as the treatment time becomes longer, the treatment time is preferably 300 minutes or less, more preferably 200 minutes or less, and even more preferably 100 minutes or less.
ポリエステルに超臨界または亜臨界状態の水を接触させることにより、ポリエステルに含まれる低分子量物（特に、環状三量体）を効率よく抽出して除去することができる。そのため、ポリエステル中における環状三量体の含有量を処理前に比べて０．０１質量％以上、より好ましくは０．０２質量％以上、さらに好ましくは０．０４質量％以上低減することができる。このような環状三量体の低減量は、上記のような処理条件により達成することができる。 By bringing the polyester into contact with water in a supercritical or subcritical state, low molecular weight substances (particularly, cyclic trimers) contained in the polyester can be efficiently extracted and removed. Therefore, the content of the cyclic trimer in the polyester can be reduced by 0.01% by mass or more, more preferably by 0.02% by mass or more, and further preferably by 0.04% by mass or more, compared with that before the treatment. Such a reduction amount of the cyclic trimer can be achieved by the processing conditions as described above.
本発明の処理方法では、温度条件などを制御することにより、ポリエステルの加水分解を制御することが好ましい。具体的には、下記式：
ポリエステルの重量平均分子量の低下率 ＝ ［（処理前のポリエステルの重量平均分子量−処理後のポリエステルの重量平均分子量）／処理前のポリエステルの重量平均分子量］×１００
により求めたポリエステルの重量平均分子量の低下率が好ましくは５０％以下、より好ましくは３０％以下、さらに好ましくは１０％以下となるように、ポリエステルの加水分解を制御する。
In the treatment method of the present invention, it is preferable to control the hydrolysis of the polyester by controlling temperature conditions and the like. Specifically, the following formula:
Rate of decrease in weight average molecular weight of polyester = [(weight average molecular weight of polyester before treatment−weight average molecular weight of polyester after treatment) / weight average molecular weight of polyester before treatment] × 100
The hydrolysis of the polyester is controlled so that the decrease rate of the weight average molecular weight of the polyester obtained by the above is preferably 50% or less, more preferably 30% or less, and even more preferably 10% or less.
ポリエステルと水との接触方法としては、環状三量体の含有量を低減できる限り、特に限定されるものではないが、例えば、ポリエステルと超臨界または亜臨界状態の水とを密閉した容器内で攪拌または振動するか、あるいは、ポリエステルに超臨界または亜臨界状態の水を流通させることなどが可能である。 The method for contacting the polyester with water is not particularly limited as long as the content of the cyclic trimer can be reduced. For example, in a container in which the polyester and water in a supercritical or subcritical state are sealed. It is possible to stir or vibrate, or to circulate supercritical or subcritical water through the polyester.
≪ポリエステル組成物および成形体≫
本発明の処理方法で得られたポリエステルは、例えば、ポリエステル組成物および成形体に用いられる。本発明のポリエステル組成物および成形体は、本発明の処理方法で得られたポリエステルを含有すること以外は、従来公知のポリエステル組成物および成形体と同様である。それゆえ、ポリエステル以外の成分などは、従来公知のポリエステル組成物および成形体と同様に構成すればよい。すなわち、本発明のポリエステル組成物および成形体は、従来公知のポリエステル組成物および成形体のポリエステルを本発明の処理方法で得られたポリエステルで構成することにより得られる。
≪Polyester composition and molded article≫
The polyester obtained by the treatment method of the present invention is used for, for example, a polyester composition and a molded body. The polyester composition and molded body of the present invention are the same as the conventionally known polyester composition and molded body except that the polyester obtained by the treatment method of the present invention is contained. Therefore, components other than polyester may be configured in the same manner as conventionally known polyester compositions and molded bodies. That is, the polyester composition and molded article of the present invention can be obtained by constituting a polyester of a conventionally known polyester composition and molded article with the polyester obtained by the treatment method of the present invention.
例えば、本発明のポリエステル組成物または成形体には、本発明の処理方法で得られたポリエステルを単独で用いても２種以上を併用してもよい。また、本発明のポリエステル組成物または成形体には、本発明の処理方法で得られたポリエステルと、本発明の処理方法で得られたポリエステル以外のポリエステルとを併用してもよい。さらに、本発明のポリエステル組成物または成形体には、その最終用途に応じて、例えば、安定剤、顔料、染料、核剤、充填剤、紫外線吸収剤、酸化防止剤、抗菌剤、帯電防止剤、滑剤、離型剤などの添加剤を配合していてもよい。 For example, in the polyester composition or molded product of the present invention, the polyester obtained by the treatment method of the present invention may be used alone or in combination of two or more. Moreover, you may use together polyester obtained by the processing method of this invention, and polyester other than polyester obtained by the processing method of this invention in the polyester composition or molded object of this invention. Furthermore, the polyester composition or molded article of the present invention may contain, for example, a stabilizer, a pigment, a dye, a nucleating agent, a filler, an ultraviolet absorber, an antioxidant, an antibacterial agent, and an antistatic agent, depending on the end use. In addition, additives such as a lubricant and a release agent may be blended.
なお、ポリエステル成形体とは、ポリエステルまたはその組成物を様々な方法で成形したものであり、例えば、ポリエステルペレット、ストランド状のポリエステル、ポリエステル繊維（例えば、ステープルやフィラメント）、ポリエステルフィルム、ポリエステルシート、ポリエステルの中空成形体（例えば、ボトル）などが挙げられる。具体例としては、例えば、衣料用繊維；カーテン、カーペット、布団綿などに代表されるインテリア・寝装用繊維；タイヤコード、ロープなどに代表される産業資材用繊維；織物、編物、短繊維不織布、長繊維不織布などの各種布用繊維；包装用フィルム、工業用フィルム、光学用フィルム、磁気テープ用フィルム、写真用フィルム、缶ラミネート用フィルム、コンテンサ用フィルム、熱収縮フィルム、ガスバリアフィルム、白色フィルム、易カットフィルムなどの各種フィルム；Ａ−ＰＥＴ、Ｃ−ＰＥＴなどの各種シート；非耐熱延伸ボトル、耐熱延伸ボトル、ダイレクトブローボトル、ガスバリアボトル、耐圧ボトル、耐熱圧ボトルなどの中空成形体；ガラス繊維強化ポリエステル、ポリエステルエラストマーなどに代表されるエンジニアリングプラスチックの各種成形体；などが挙げられる。また、ポリエステル成形体は、ポリエステルと他の素材とを複合または結合させたものであってもよい。 The polyester molded body is obtained by molding polyester or a composition thereof by various methods. For example, polyester pellets, strand-like polyester, polyester fiber (for example, staple or filament), polyester film, polyester sheet, Examples include polyester hollow molded bodies (for example, bottles). Specific examples include, for example, clothing fibers; interior / bedding fibers such as curtains, carpets, and futon cotton; fibers for industrial materials such as tire cords and ropes; woven fabrics, knitted fabrics, short fiber nonwoven fabrics, Various fabric fibers such as long-fiber nonwoven fabric; packaging film, industrial film, optical film, magnetic tape film, photographic film, can laminate film, contentor film, heat shrink film, gas barrier film, white film, Various films such as easy-cut films; various sheets such as A-PET and C-PET; non-heat-resistant stretch bottles, heat-resistant stretch bottles, direct blow bottles, gas barrier bottles, pressure-resistant bottles, heat-resistant pressure bottles and other hollow molded articles; glass fibers Engineers such as reinforced polyester and polyester elastomer Various molded body ring plastic; and the like. The polyester molded body may be a composite or combination of polyester and another material.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記の実施例により制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and appropriate modifications are made within a range that can meet the purpose described above and below. Any of these can be carried out and are included in the technical scope of the present invention.
≪ポリエステルの評価方法≫
下記の方法により、ポリエステルの重量平均分子量およびその低下率、固有粘度、ポリエステル中における環状三量体の低減量を評価した。
≪Evaluation method of polyester≫
By the following method, the weight average molecular weight of the polyester, its reduction rate, intrinsic viscosity, and the amount of reduction of the cyclic trimer in the polyester were evaluated.
＜重量平均分子量およびその低下率＞
処理前後の細かく粉砕したポリエステル４ｍｇをヘキサフルオロイソプロパノール（ＨＦＩＰ）／クロロホルム（容量比２／３）の混合溶媒０．４ｍＬに溶解させた後、クロロホルム７．６ｍＬで希釈して、試料溶液とした。高速ＧＰＣ装置（東ソー株式会社製、ＨＬＣ−８３２０ＧＰＣ）を用いて、温度４０℃、検出器：ＵＶ２５４ｎｍの条件下で、スチレンを基準物質として、ＧＰＣ測定を行って、重量平均分子量を求めた。
<Weight average molecular weight and rate of decrease thereof>
4 mg of the finely pulverized polyester before and after the treatment was dissolved in 0.4 mL of a mixed solvent of hexafluoroisopropanol (HFIP) / chloroform (volume ratio 2/3), and then diluted with 7.6 mL of chloroform to obtain a sample solution. Using a high-speed GPC device (manufactured by Tosoh Corporation, HLC-8320GPC), GPC measurement was performed using styrene as a reference substance under the conditions of a temperature of 40 ° C. and a detector: UV254 nm, and the weight average molecular weight was determined.
なお、重量平均分子量の低下率は、下記式：
ポリエステルの重量平均分子量の低下率 ＝ ［（処理前のポリエステルの重量平均分子量−処理後のポリエステルの重量平均分子量）／処理前のポリエステルの重量平均分子量］×１００
により求めた。
In addition, the decreasing rate of a weight average molecular weight is the following formula:
Rate of decrease in weight average molecular weight of polyester = [(weight average molecular weight of polyester before treatment−weight average molecular weight of polyester after treatment) / weight average molecular weight of polyester before treatment] × 100
Determined by
＜固有粘度＞
固有粘度は、ＪＩＳ Ｋ ７３６７−５に準拠し、溶媒としてフェノール（６０質量％）と１，１，２，２−テトラクロロエタン（４０質量％）との混合溶媒を用いて、３０℃で測定した。単位はｄＬ／ｇである。
<Intrinsic viscosity>
The intrinsic viscosity was measured at 30 ° C. using a mixed solvent of phenol (60% by mass) and 1,1,2,2-tetrachloroethane (40% by mass) as a solvent in accordance with JIS K 7367-5. . The unit is dL / g.
＜環状三量体の低減量＞
処理前後の細かく粉砕したポリエステル０．１ｇをヘキサフルオロイソプロパノールール（ＨＦＩＰ）／クロロホルム（容量比２／３）の混合溶媒３ｍＬに溶解させた。得られた溶液にクロロホルム２０ｍＬを加えて、均一に混合した。得られた混合液にメタノール１０ｍＬを加えて、ポリエステルを再沈殿させた。次いで、この混合液を濾過して、沈殿物を採取した。得られた沈殿物をクロロホルム／メタノール（容量比２／１）の混合溶媒３０ｍＬで洗浄し、さらに濾過した。得られた濾液をロータリーエバポレーターで濃縮乾固した。濃縮乾固物にジメチルホルムアミド１０ｍＬを加えて、測定溶液とした。この測定溶液に含まれる環状三量体を、高速液体クロマトグラフィー（横河電気株式会社製、ＬＣ１００型）を用いて定量した。
<Reduced amount of cyclic trimer>
0.1 g of the finely pulverized polyester before and after the treatment was dissolved in 3 mL of a mixed solvent of hexafluoroisopropanol (HFIP) / chloroform (volume ratio 2/3). To the resulting solution was added 20 mL of chloroform and mixed uniformly. 10 mL of methanol was added to the resulting mixture to reprecipitate the polyester. Subsequently, this liquid mixture was filtered and the deposit was extract | collected. The resulting precipitate was washed with 30 mL of a mixed solvent of chloroform / methanol (volume ratio 2/1) and further filtered. The obtained filtrate was concentrated to dryness on a rotary evaporator. 10 mL of dimethylformamide was added to the concentrated dried product to obtain a measurement solution. The cyclic trimer contained in this measurement solution was quantified using high performance liquid chromatography (Yokogawa Electric Co., Ltd., LC100 type).
処理前のポリエステル中における環状三量体の含有量（単位は質量％）から処理後のポリエステル中における環状三量体の含有量（単位は質量％）を減算して、環状三量体の低減量（単位は質量％）を求めた。 Reduce the cyclic trimer content by subtracting the cyclic trimer content (unit: mass%) in the treated polyester from the cyclic trimer content (unit: mass%) in the polyester before treatment. The amount (unit: mass%) was determined.
≪ポリエステルの調製≫
ジメチルテレフタレート１，０００質量部、エチレングリコール７００質量部、酢酸亜鉛・２水和物０．３質量部をエステル交換反応缶に仕込み、温度１２０〜２１０℃でエステル交換を行い、生成するメタノールを留去した。エステル交換が終了した時点で、リン酸０．１３質量部および三酸化アンチモン０．３質量部を加え、系内を徐々に減圧にし、７５分間で１ｍｍＨｇ以下とした。同時に、徐々に昇温して、温度２８０℃とした。同条件で７０分間重縮合反応を行い、溶融ポリマーを吐出ノズルより水中に押し出し、カッターにより切断して、直径約３ｍｍ、長さ約５ｍｍの円柱チップ状の粗製ポリエステルを得た。得られた粗製ポリエステルの固有粘度は０．６１ｄＬ／ｇ、重量平均分子量は４８，０００、環状三量体の含有量は１．０５質量％であった。
≪Preparation of polyester≫
1,000 parts by mass of dimethyl terephthalate, 700 parts by mass of ethylene glycol, and 0.3 parts by mass of zinc acetate dihydrate were charged into a transesterification reactor, and transesterification was performed at a temperature of 120 to 210 ° C. Left. When the transesterification was completed, 0.13 parts by mass of phosphoric acid and 0.3 parts by mass of antimony trioxide were added, and the pressure in the system was gradually reduced to 1 mmHg or less in 75 minutes. At the same time, the temperature was gradually raised to a temperature of 280 ° C. A polycondensation reaction was carried out for 70 minutes under the same conditions, and the molten polymer was extruded into water from a discharge nozzle and cut with a cutter to obtain a cylindrical chip-like crude polyester having a diameter of about 3 mm and a length of about 5 mm. The obtained crude polyester had an intrinsic viscosity of 0.61 dL / g, a weight average molecular weight of 48,000, and a cyclic trimer content of 1.05% by mass.
次いで、固相重合を行った。得られたポリエステルの固有粘度は１．０２ｄＬ／ｇ、重量平均分子量は１００，０００、環状三量体の含有量は０．３３質量％であった。得られたポリエステルの評価結果を、比較例１として、表１に示す。 Next, solid phase polymerization was performed. The obtained polyester had an intrinsic viscosity of 1.02 dL / g, a weight average molecular weight of 100,000, and a cyclic trimer content of 0.33% by mass. The evaluation results of the obtained polyester are shown in Table 1 as Comparative Example 1.
≪ポリエステルの処理≫
＜実施例１＞
反応セルにポリエステルを入れ、ポンプから抽出溶媒である蒸留水を供給し、セル内とステンレスチューブ内とを抽出溶媒で充填した。セル内部の圧力が５ＭＰａになるように排圧弁を調整し、抽出溶媒を４ｍＬ／ｍｉｎの流量で流し続けた。その後、反応セル内部の温度を１９０℃まで上昇させ、１０分間処理を行った。処理終了後、抽出溶媒の供給を停止させ、降温し、排圧弁を開いて圧力を大気圧に戻し、ポリエステルを取り出した。得られたポリエステルの評価結果を表１に示す。
≪Polyester treatment≫
<Example 1>
Polyester was put into the reaction cell, distilled water as an extraction solvent was supplied from a pump, and the inside of the cell and the stainless tube were filled with the extraction solvent. The exhaust valve was adjusted so that the pressure inside the cell was 5 MPa, and the extraction solvent was kept flowing at a flow rate of 4 mL / min. Thereafter, the temperature inside the reaction cell was increased to 190 ° C., and the treatment was performed for 10 minutes. After completion of the treatment, the supply of the extraction solvent was stopped, the temperature was lowered, the pressure relief valve was opened to return the pressure to atmospheric pressure, and the polyester was taken out. The evaluation results of the obtained polyester are shown in Table 1.
＜実施例２＞
処理圧力を１５ＭＰａ、抽出溶媒の流量を２ｍＬ／ｍｉｎ、処理時間を２０分間に変更したこと以外は、実施例１と同様にして、ポリエステルを処理した。得られたポリエステルの評価結果を表１に示す。
<Example 2>
The polyester was treated in the same manner as in Example 1 except that the treatment pressure was changed to 15 MPa, the flow rate of the extraction solvent was changed to 2 mL / min, and the treatment time was changed to 20 minutes. The evaluation results of the obtained polyester are shown in Table 1.
＜実施例３＞
抽出溶媒の流量を２ｍＬ／ｍｉｎ、処理時間を２０分間に変更したこと以外は、実施例１と同様にして、ポリエステルを処理した。得られたポリエステルの評価結果を表１に示す。
<Example 3>
The polyester was treated in the same manner as in Example 1 except that the flow rate of the extraction solvent was changed to 2 mL / min and the treatment time was changed to 20 minutes. The evaluation results of the obtained polyester are shown in Table 1.
＜実施例４＞
抽出溶媒の流量を２ｍＬ／ｍｉｎ、処理時間を４０分間に変更したこと以外は、実施例１と同様にして、ポリエステルを処理した。得られたポリエステルの評価結果を表１に示す。
<Example 4>
The polyester was treated in the same manner as in Example 1 except that the flow rate of the extraction solvent was changed to 2 mL / min and the treatment time was changed to 40 minutes. The evaluation results of the obtained polyester are shown in Table 1.
＜実施例５＞
処理温度を１７５℃、抽出溶媒の流量を２ｍＬ／ｍｉｎ、処理時間を７０分間に変更したこと以外は、実施例１と同様にして、ポリエステルを処理した。得られたポリエステルの評価結果を表１に示す。
<Example 5>
The polyester was treated in the same manner as in Example 1 except that the treatment temperature was changed to 175 ° C., the flow rate of the extraction solvent was changed to 2 mL / min, and the treatment time was changed to 70 minutes. The evaluation results of the obtained polyester are shown in Table 1.
＜実施例６＞
処理温度を１５０℃、抽出溶媒の流量を２ｍＬ／ｍｉｎに変更したこと以外は、実施例１と同様にして、ポリエステルを処理した。得られたポリエステルの評価結果を表１に示す。
<Example 6>
The polyester was treated in the same manner as in Example 1 except that the treatment temperature was changed to 150 ° C. and the flow rate of the extraction solvent was changed to 2 mL / min. The evaluation results of the obtained polyester are shown in Table 1.
表１から明らかなように、いずれの実施例においても、ポリエステルに所定の温度および圧力の水を接触させることにより、環状三量体の低減量が０．０１質量％以上となる、すなわちポリエステル中における環状三量体の含有量が処理前に比べて０．０１質量％以上低減する。また、この処理によるポリエステルの重量平均分子量の低下率は、５０％以下である。かくして、本発明の処理方法は、ポリエステルの分子量低下を抑制し、かつ、低分子量物（特に、環状三量体）を効率よく抽出して除去するという、相反する２つの機能を併せ持つことがわかる。 As is clear from Table 1, in any of the examples, when the polyester is brought into contact with water at a predetermined temperature and pressure, the amount of reduction of the cyclic trimer is 0.01% by mass or more. The content of the cyclic trimer in is reduced by 0.01% by mass or more compared with that before the treatment. Moreover, the reduction rate of the weight average molecular weight of polyester by this process is 50% or less. Thus, it can be seen that the treatment method of the present invention has two contradictory functions of suppressing the decrease in the molecular weight of the polyester and efficiently extracting and removing low molecular weight substances (particularly, cyclic trimers). .
本発明は、抽出溶媒として水を用いているので、環境性能に優れた従来にないクリーンなポリエステルの処理技術として、また、工業的規模のポリエステル生産に利用可能な低コストのポリエステルの処理技術として、ポリエステルに関連する産業分野で多大の貢献をなすものである。 Since water is used as an extraction solvent, the present invention is an unprecedented clean polyester processing technology with excellent environmental performance, and a low-cost polyester processing technology that can be used for industrial scale polyester production. It makes a great contribution in the industrial field related to polyester.
Claims (4)
ポリエステルの重量平均分子量の低下率 ＝ ［（処理前のポリエステルの重量平均分子量−処理後のポリエステルの重量平均分子量）／処理前のポリエステルの重量平均分子量］×１００
により求めたポリエステルの重量平均分子量の低下率が５０％以下である請求項１に記載の処理方法。 Following formula:
Rate of decrease in weight average molecular weight of polyester = [(weight average molecular weight of polyester before treatment−weight average molecular weight of polyester after treatment) / weight average molecular weight of polyester before treatment] × 100
The processing method according to claim 1, wherein the reduction rate of the weight average molecular weight of the polyester obtained by the above is 50% or less.
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| JP2014156517A (en) * | 2013-02-14 | 2014-08-28 | Kumamoto Univ | Polyester production method and polyester compact production method |
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| JPH03217422A (en) * | 1990-01-23 | 1991-09-25 | Toray Ind Inc | Treatment of polyester |
| JPH0531000A (en) * | 1990-09-08 | 1993-02-09 | Kobe Steel Ltd | Selective hydrolysis and/or thermal decomposition of natural or synthetic polymer |
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