JP2006290996A - Method for producing pet having good hue by using raw material washed with water - Google Patents
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- JP2006290996A JP2006290996A JP2005112066A JP2005112066A JP2006290996A JP 2006290996 A JP2006290996 A JP 2006290996A JP 2005112066 A JP2005112066 A JP 2005112066A JP 2005112066 A JP2005112066 A JP 2005112066A JP 2006290996 A JP2006290996 A JP 2006290996A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 title abstract description 11
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 36
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 35
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000003456 ion exchange resin Substances 0.000 abstract description 9
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract 2
- 238000000034 method Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- CLVDXAJCTVOTRB-UHFFFAOYSA-N CCCCOP(O)(O)=O.P Chemical class CCCCOP(O)(O)=O.P CLVDXAJCTVOTRB-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
Description
予め水で洗浄しておいたビス−（２−ヒドロキシエチル）テレフタレートを原料として、円滑に重合反応を進行させて得ることを特徴とする色相良好なポリエチレンテレフタレートの製法に関する。 The present invention relates to a method for producing a polyethylene terephthalate having good hue, characterized in that it is obtained by using a bis- (2-hydroxyethyl) terephthalate that has been washed with water in advance as a raw material to smoothly advance the polymerization reaction.
ポリエステル、特にポリエチレンテレフタレート（以下ＰＥＴと略称する。）は、その優れた機械的性質、化学的性質から、繊維、フィルム、工業用樹脂、ボトル、カップ、トレイ等に成形されて広く用いられている。 Polyester, especially polyethylene terephthalate (hereinafter abbreviated as PET), is widely used by being molded into fibers, films, industrial resins, bottles, cups, trays, etc. because of its excellent mechanical and chemical properties. .
近年、環境意識の高まりにともない廃棄物から資源を回収し省資源及び、焼却・埋立てされる廃棄物量の削減が図られている。ＰＥＴに関しても数多くのリサイクル方法及びリサイクル製品が考案されており、そのうちのひとつにＰＥＴ屑をアルカリ触媒の存在下にエチレングリコ−ルと反応させ解重合して得たビス−（２−ヒドロキシエチル）テレフタレート（以下ＢＨＥＴと略称する。）を、その中のイオン成分をイオン交換樹脂を使用して吸着除去することにより精製し、その後重合を行い良好な色相のポリエチレンテレフタレートを得るという手法がある（例えば文献１参照。）。 In recent years, with increasing environmental awareness, resources have been recovered from waste to save resources and to reduce the amount of waste incinerated and landfilled. A number of recycling methods and products have been devised for PET, one of which is bis- (2-hydroxyethyl) obtained by depolymerizing PET waste by reaction with ethylene glycol in the presence of an alkali catalyst. There is a technique in which terephthalate (hereinafter abbreviated as BHET) is purified by adsorbing and removing ionic components therein using an ion exchange resin, followed by polymerization to obtain polyethylene terephthalate having a good hue (for example, Reference 1).
しかしながら、イオン交換樹脂は使用していくと飽和状態になり吸着能力が低下するので、イオン交換樹脂を交換もしくは再生処理をする必要があり運転操作が煩瑣で経済的に不利である。また、イオン交換樹脂は高価であるため、再生処理して使用するのが好ましいが、その再生処理には強酸や強アルカリなどを用いる必要があり、再生処理により発生する廃液の処理にもコストが掛かる。またイオン交換樹脂は水の精製に使用される場合でさえ、懸濁物質や鉄分、油分、コロイド状有機物質と接触させると著しく樹脂の性能が劣化することが知られており、特にＢＨＥＴのような有機化合物そのものの精製処理に使用すると性能劣化がより早く進み交換頻度が高くなることは自明である（例えば非特許文献１参照。） However, since the ion exchange resin becomes saturated with use and the adsorption capacity decreases, it is necessary to exchange or regenerate the ion exchange resin, which is cumbersome and economically disadvantageous. In addition, since the ion exchange resin is expensive, it is preferable to use it after regenerating it. However, it is necessary to use strong acid or strong alkali for the regenerating process, and the waste liquid generated by the regenerating process is also costly. It takes. In addition, even when ion exchange resins are used for purification of water, it is known that the performance of the resin will be significantly deteriorated when contacted with suspended solids, iron, oil or colloidal organic substances, especially BHET. It is self-evident that when used for the purification process of a simple organic compound itself, the performance deterioration is accelerated and the replacement frequency is increased (for example, see Non-Patent Document 1).
さらに、ＢＨＥＴを重合して飲料充填用ボトル向けのポリエチレンテレフタレートを生産する場合、これに５質量ｐｐｂ程度の僅かな量でも異種のポリマーが混じると、得られたポリエチレンテレフタレートの物性、特に成形品の結晶性などに大きな差異が生じる恐れがあり、この点からもポリエチレンテレフタレートの原料を異種の樹脂と接触／処理する工程はできるだけ避けた方が好ましい（例えば特許文献２参照。）。 Furthermore, when polymerizing BHET to produce polyethylene terephthalate for bottles for beverage filling, if even a small amount of about 5 mass ppb is mixed with dissimilar polymers, the physical properties of the obtained polyethylene terephthalate, especially the molded product There is a possibility that a large difference in crystallinity may occur. From this point, it is preferable to avoid the step of contacting / treating the raw material of polyethylene terephthalate with a different resin as much as possible (see, for example, Patent Document 2).
テレフタル酸などの他のポリエステルモノマーとして知られている化合物を添加することなく、ビス−（２−ヒドロキシエチル）テレフタレートだけを原料として、円滑に重合反応を進行させて色相良好なポリエチレンテレフタレートを提供することにある。 Without adding a compound known as another polyester monomer such as terephthalic acid, a polymerization reaction is smoothly advanced using only bis- (2-hydroxyethyl) terephthalate as a raw material to provide polyethylene terephthalate having a good hue. There is.
本発明者らは、上記従来技術に鑑み鋭意検討を重ねた結果、本発明を完成するに至った。即ち、本発明の目的は、予め水で洗浄したビス−（２−ヒドロキシエチル）テレフタレートを重合反応させるポリエチレンテレフタレートの製造方法によって達成することができる。 As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention. That is, the object of the present invention can be achieved by a method for producing polyethylene terephthalate in which bis- (2-hydroxyethyl) terephthalate previously washed with water is subjected to a polymerization reaction.
本発明の方法により、ビス−（２−ヒドロキシエチル）テレフタレートを原料としたポリエチレンテレフタレートのみを原料とし、煩瑣で経済的に不利なイオン交換樹脂によるビス−（２−ヒドロキシエチル）テレフタレートの精製操作無しでも、円滑に重合反応を進行させ良好な色相のポリエチレンテレフタレートを得ることができる。 By the method of the present invention, there is no purification operation of bis- (2-hydroxyethyl) terephthalate with an ion exchange resin which is a cumbersome and economically disadvantageous, using only polyethylene terephthalate from bis- (2-hydroxyethyl) terephthalate as a raw material. However, it is possible to smoothly progress the polymerization reaction and obtain polyethylene terephthalate having a good hue.
本発明においてはビス−（２−ヒドロキシエチル）テレフタレート（ＢＨＥＴ）を用いる必要がある。ＢＨＥＴの製造方法については特に限定されず、例えばテレフタル酸とエチレンオキシドを反応させたものでも、テレフタル酸とエチレングリコール（以下ＥＧと略称する。）とから直接エステル化反応により生成したものでも、ジメチルテレフタレート（以下ＤＭＴと略称する。）とＥＧとからエステル交換反応により生成したものでも、あるいは新品のＰＥＴ製品を製造する段階で発生する屑ＰＥＴや飲料ボトル等の使用済の回収ＰＥＴをＥＧで解重合することにより生成したものでもよい。省資源化等の観点からは、少なくとも一部は、回収ＰＥＴをＥＧで解重合することによって生成した解重合生成物から得られたものを用いることが好ましい。 In the present invention, it is necessary to use bis- (2-hydroxyethyl) terephthalate (BHET). The method for producing BHET is not particularly limited. For example, dimethyl terephthalate may be obtained by reacting terephthalic acid and ethylene oxide, or by direct esterification from terephthalic acid and ethylene glycol (hereinafter abbreviated as EG). (Hereinafter abbreviated as DMT) and EG, which are produced by transesterification reaction, or used recovered PET such as waste PET and beverage bottles generated at the stage of manufacturing new PET products are depolymerized with EG It may be generated by doing so. From the viewpoint of resource saving and the like, it is preferable to use at least a part obtained from a depolymerized product generated by depolymerizing recovered PET with EG.
上記回収ＰＥＴをＥＧで解重合することによって生成した解重合生成物（粗製ＢＨＥＴ）は、少なくとも蒸留精製を行う精製工程を経ることにより、精製ＢＨＥＴにしてから、予備反応工程及び重合工程で用いることが好ましい。 The depolymerized product (crude BHET) produced by depolymerizing the recovered PET with EG is used in the preliminary reaction step and the polymerization step after being purified BHET through at least a purification step for distillation purification. Is preferred.
蒸留操作によりＢＨＥＴを精製する蒸留工程では、粗製ＢＨＥＴに含まれるＥＧを除去する方法は特に限定されない。しかし、ＢＨＥＴの化学的な性質上、出来る限り低温でかつ出来る限り短時間で蒸留しなければ、蒸留釜に滞留中や蒸発中に望まぬ重合が進むおそれがある。そこで、この蒸留工程では、より短時間でかつより低温でＥＧを除去すべく、分子蒸留器を用いることが好ましい。 In the distillation step of purifying BHET by distillation, the method for removing EG contained in crude BHET is not particularly limited. However, due to the chemical nature of BHET, if the distillation is not performed at the lowest possible temperature and in the shortest possible time, undesired polymerization may proceed during residence or evaporation in the still. Therefore, in this distillation step, it is preferable to use a molecular distiller in order to remove EG in a shorter time and at a lower temperature.
精製工程を経て得られた精製ＢＨＥＴの精製度を示す因子の一例としてはＢＨＥＴの色調を挙げることができ、例えば色差計で測定した値でＡＳＴＭ−Ｄ１４８２−５７Ｔによる表示法での色相ｂ値が３以下であることが好ましく、１．０以下であることがより好ましい。この色相ｂ値が３を超えるＢＨＥＴからＰＥＴを製造すると、ＰＥＴの色相ｂ値が５を大きく超えることとなり、実質的に実用に耐えられなくなる。続いてこのようにして得られたＢＨＥＴを以下に示すような重合工程によりポリエチレンテレフタレートを製造する。 An example of a factor indicating the degree of purification of purified BHET obtained through the purification process is the color tone of BHET. For example, the hue b value in the display method according to ASTM-D1482-57T is a value measured with a color difference meter. It is preferably 3 or less, and more preferably 1.0 or less. When PET is produced from BHET having a hue b value exceeding 3, the hue b value of PET greatly exceeds 5, and the practical use cannot be practically achieved. Subsequently, polyethylene terephthalate is produced from the thus obtained BHET by a polymerization process as shown below.
この重合工程は、例えば、以下のように実施することができる。まず、窒素雰囲気下に重合容器内に所定量のＢＨＥＴと重合触媒及び／又は安定剤を入れ、望ましくは撹拌下に１３０〜２００℃に昇温させてＢＨＥＴを溶融状態にしてから、撹拌下に上記反応液を一気に又は徐々に添加して混合する。そして、常圧下に徐々に反応系の温度を２３０〜２４５℃程度まで上げ、副生するＥＧや水を含む低沸成分を蒸留除去し、その蒸発が止まることを確認する。その後、さらに昇温を続けて２６０〜２９０℃程度の重合反応温度に保ちながら反応系を徐々に減圧し、最終的には内圧を１０〜８０Ｐａ程度まで下げる。系内の反応物の溶融粘度は徐々に増加し、所定の粘度（例えば、撹拌に消費される電力によって確認することができる。）となった時点で重合反応を終了する。 This polymerization step can be performed, for example, as follows. First, a predetermined amount of BHET and a polymerization catalyst and / or a stabilizer are put in a polymerization vessel under a nitrogen atmosphere, and the temperature is preferably raised to 130 to 200 ° C. with stirring, and then the BHET is melted and then stirred. The reaction solution is added at once or gradually and mixed. And the temperature of a reaction system is gradually raised to about 230-245 degreeC under a normal pressure, the low boiling component containing EG and water byproduced is distilled off, and it confirms that the evaporation stops. Thereafter, the temperature is further increased and the reaction system is gradually depressurized while maintaining the polymerization reaction temperature of about 260 to 290 ° C., and finally the internal pressure is lowered to about 10 to 80 Pa. The melt viscosity of the reactant in the system gradually increases, and the polymerization reaction is terminated when the viscosity reaches a predetermined viscosity (for example, it can be confirmed by electric power consumed for stirring).
なお重合触媒としてはゲルマニウム、アンチモン、チタン、アルミニウムなどの化合物が好ましく使用される。添加量は全ジカルボン酸成分の質量（本発明の場合には重合容器に投入したＢＨＥＴの質量）に対する触媒金属元素の質量割合として２〜８００ｐｐｍ、好ましくは４〜４００ｐｐｍである。２ｐｐｍより少ないと反応速度が遅く、８００ｐｐｍを超えると重合後の分解反応を促進させることがあり、好ましくない。 As the polymerization catalyst, compounds such as germanium, antimony, titanium, and aluminum are preferably used. The addition amount is 2 to 800 ppm, preferably 4 to 400 ppm as the mass ratio of the catalytic metal element to the mass of all dicarboxylic acid components (in the present invention, the mass of BHET charged into the polymerization vessel). If it is less than 2 ppm, the reaction rate is slow, and if it exceeds 800 ppm, the decomposition reaction after polymerization may be accelerated, which is not preferable.
安定剤としてはトリメチルホスフェート、トリエチルホスフェート、トリフェニルホスフェート、トリエチルホスホノアセテート等のリン酸エステル、トリフェニルホスファイト、トリスドデシルホスファイト等の亜リン酸エステル、メチルアシッドホスフェート、ジブチルホスフェート、モノブチルホスフェート、リン酸、亜リン酸、次亜リン酸、ポリリン酸等のリン化合物が好ましい。安定剤の添加量は、得られると予想される全ポリエステル質量に対する安定剤中のリン元素の質量割合として通常１０〜１０００ｐｐｍ、好ましくは２０〜５００ｐｐｍである。１０ｐｐｍより少ないと安定剤としての効果が表れず、１０００ｐｐｍより多いとむしろ加熱分解・酸化分解を促進させることがあり好ましくない。 As stabilizers, phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, phosphites such as triphenyl phosphite, trisdodecyl phosphite, methyl acid phosphate, dibutyl phosphate, monobutyl phosphate Phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid and polyphosphoric acid are preferred. The addition amount of the stabilizer is usually 10 to 1000 ppm, preferably 20 to 500 ppm as a mass ratio of phosphorus element in the stabilizer to the total polyester mass expected to be obtained. If it is less than 10 ppm, the effect as a stabilizer does not appear, and if it exceeds 1000 ppm, the thermal decomposition / oxidative decomposition may be promoted rather.
このようにして得られたポリエチレンテレフタレートはペレット化されたのち、必要に応じて固相重合工程で更に重縮合を進めてもよく、その固相重合方法に関しては従来公知のいずれの方法を採用してもよい。さらにこれらのポリエチレンテレフタレートを製造する際に必要に応じて他の添加剤、例えば、着色剤、抗酸化剤、紫外線吸収剤、帯電防止剤、難燃剤などを使用してもよい。 After the polyethylene terephthalate obtained in this way is pelletized, it may be further subjected to polycondensation in a solid phase polymerization step as necessary. Any known method can be used for the solid phase polymerization method. May be. Furthermore, when manufacturing these polyethylene terephthalates, you may use another additive, for example, a coloring agent, an antioxidant, a ultraviolet absorber, an antistatic agent, a flame retardant, etc. as needed.
一方本発明においては、ＢＨＥＴを予め水で洗浄しておく必要がある。洗浄方法は回分式でも連続式でも良い。洗浄する水の温度は１℃以上〜１００℃以下つまり冷水でも温水でも沸騰水でも良く、ＢＨＥＴに対する水の量はハンドリング性と経済性の点から質量で３倍〜１０倍程度が好ましい。洗浄時間は洗浄効率、操作性と経済性の面から１０分〜２時間程度が好ましい。ポリマー黄色化の原因物質の除去や重合工程での熱負荷低減のため、洗浄後に脱水する必要がある。脱水方法は回分式でも連続式でも良く、遠心分離やろ過でも良い。脱水後、更に加熱及び／又は減圧操作により乾燥させても、乾燥無しでそのまま重合反応に使用しても良い。なお通常の遠心分離やろ過操作で含水率５質量％程度は容易に到達可能であり、本特許においても、洗浄／脱水処理後の含水率５．３質量％のＢＨＥＴを原料にして良好な品質のポリエチレンテレフタレートが得られている。 On the other hand, in the present invention, it is necessary to wash BHET with water in advance. The cleaning method may be batch or continuous. The temperature of the water to be washed may be 1 ° C. or more and 100 ° C. or less, that is, cold water, warm water or boiling water, and the amount of water relative to BHET is preferably about 3 to 10 times in terms of mass from the viewpoint of handling properties and economy. The washing time is preferably about 10 minutes to 2 hours from the viewpoint of washing efficiency, operability and economy. It is necessary to dehydrate after washing in order to remove the cause of polymer yellowing and reduce the heat load in the polymerization process. The dehydration method may be batch or continuous, and may be centrifugal separation or filtration. After dehydration, it may be further dried by heating and / or decompression, or it may be used in the polymerization reaction as it is without drying. It should be noted that a water content of about 5% by mass can be easily reached by ordinary centrifugation or filtration operation. In this patent, good quality is obtained using BHET having a water content of 5.3% by mass after washing / dehydration as a raw material. Of polyethylene terephthalate.
以下、実施例により本発明を更に具体的に説明するが、本発明はこれにより何等限定を受けるものでは無い。なお、実施例中の各値は以下の方法により求めた。
１）極限粘度（ＩＶ）：
ポリエチレンテレフタレート０．６ｇをｏ−クロロフェノール５０ｃｃ中に加熱溶解した後、一旦冷却させ、ウベローデ式粘度計を用いて３５℃の温度条件で測定したその溶液の溶液粘度から算出した。
２）色相（Ｃｏｌ）：
反応器からポリエチレンテレフタレートを溶融状態でサンプリングして金属板で挟み込んで水冷して円盤状のポリマーサンプルを得る。これを１４０℃×６０分乾燥機中で熱処理し、結晶化させた後、カラーマシン社製ＣＭ−７５００型カラーマシンで測定した。固相後サンプルについては、熱処理工程を省き同様に測定した。Ｃｏｌ−ｂ値により黄色味を評価した。
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive any limitation by this. In addition, each value in an Example was calculated | required with the following method.
1) Intrinsic viscosity (IV):
After 0.6 g of polyethylene terephthalate was dissolved by heating in 50 cc of o-chlorophenol, the solution was once cooled and calculated from the solution viscosity of the solution measured at 35 ° C. using an Ubbelohde viscometer.
2) Hue (Col):
Polyethylene terephthalate is sampled from the reactor in a molten state, sandwiched between metal plates, and cooled with water to obtain a disk-shaped polymer sample. This was heat-treated in a dryer at 140 ° C. for 60 minutes for crystallization, and then measured with a CM-7500 type color machine manufactured by Color Machine Co., Ltd. The sample after the solid phase was measured in the same manner without the heat treatment step. Yellowness was evaluated by the Col-b value.
［実施例１］
丸善ケミカル株式会社製のビス−（２−ヒドロキシエチル）テレフタレート（ＢＨＥＴ）３００質量部をイオン交換水９００質量部と混合し９０℃で２時間攪拌した後、回分式ろ過装置で水と分離し、含水率５．３質量％のＢＨＥＴを得た。この熱水洗浄した丸善ケミカル株式会社製のビス−（２−ヒドロキシエチル）テレフタレート（ＢＨＥＴ）２６７質量部、重合触媒として二酸化ゲルマニウムをＢＨＥＴに対するゲルマニウム元素のモル比が２０×１０−５になるような量、安定剤としてトリメチルホスフェートをＢＨＥＴに対するリン元素のモル比が２０×１０−５になるような量を窒素雰囲気常圧下の反応器内に投入した。
[Example 1]
After mixing 300 parts by mass of bis- (2-hydroxyethyl) terephthalate (BHET) manufactured by Maruzen Chemical Co., Ltd. with 900 parts by mass of ion-exchanged water and stirring at 90 ° C. for 2 hours, it was separated from water with a batch filter, BHET having a water content of 5.3% by mass was obtained. 267 parts by mass of bis- (2-hydroxyethyl) terephthalate (BHET) manufactured by Maruzen Chemical Co., Ltd. washed with hot water, germanium dioxide as a polymerization catalyst, and the molar ratio of germanium element to BHET is 20 × 10 −5 The amount of trimethyl phosphate as a stabilizer and an amount such that the molar ratio of phosphorus element to BHET was 20 × 10 −5 was charged into the reactor under nitrogen atmosphere and normal pressure.
次に反応器内の温度を２８５℃とし常圧で２０分間、４ｋＰａで２０分間、０．４ｋＰａで１００分の条件でそれぞれ段階的に減圧し、反応で発生するエチレングリコールなどを系外に溜去しながら重縮合反応を行った。溜出部へのオリゴマー閉塞などは発生しなかった。生成したポリエチレンテレフタレートの品質を表１に示す。 Next, the temperature in the reactor is set to 285 ° C., and the pressure is reduced stepwise under normal pressure for 20 minutes, 4 kPa for 20 minutes, and 0.4 kPa for 100 minutes, respectively, and ethylene glycol generated in the reaction is accumulated outside the system. The polycondensation reaction was carried out while leaving. No oligomer blockage or the like in the distilling portion occurred. Table 1 shows the quality of the produced polyethylene terephthalate.
［実施例２］
実施例１において、水によるＢＨＥＴの洗浄の条件を９０℃の熱水で４時間の代わりに１８℃の水で１０分とし、含水率４．９質量％のＢＨＥＴを得た以外は同様の操作を行った。生成したポリエチレンテレフタレートの品質を表１に示す。
[Example 2]
In Example 1, the procedure for washing BHET with water was changed to 90 ° C. hot water for 4 hours, but 18 ° C. water for 10 minutes, and BHET having a water content of 4.9% by mass was obtained. Went. The quality of the produced polyethylene terephthalate is shown in Table 1.
［比較例１］
実施例１において、ＢＨＥＴを水洗処理せずそのまま原料として使用した以外は同様の操作を行った。生成したポリエチレンテレフタレートの品質を表１に示す。実施例１、２と比較してポリマーのＣｏｌ−ｂ値が高く（黄色味が強い）、同一重合時間での到達ＩＶも低い(重合速度が遅い)ことが分かる。
[Comparative Example 1]
In Example 1, the same operation was performed except that BHET was used as a raw material without being washed with water. The quality of the produced polyethylene terephthalate is shown in Table 1. Compared to Examples 1 and 2, it can be seen that the Col-b value of the polymer is high (strong yellowishness), and the IV reached at the same polymerization time is low (polymerization rate is slow).
本発明の方法により、ビス−（２−ヒドロキシエチル）テレフタレートを原料としてポリエチレンテレフタレートを製造する場合に、ビス−（２−ヒドロキシエチル）テレフタレートを経済的に不利なイオン交換樹脂による精製処理無しでも、良好な色相のポリエチレンテレフタレートを得ることができ、その工業的意義は大きい。 When polyethylene terephthalate is produced using bis- (2-hydroxyethyl) terephthalate as a raw material by the method of the present invention, bis- (2-hydroxyethyl) terephthalate can be purified without an economically disadvantageous ion exchange resin. A polyethylene terephthalate having a good hue can be obtained, and its industrial significance is great.
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| KR20220055192A (en) * | 2020-10-26 | 2022-05-03 | 에스케이케미칼 주식회사 | Method for preparation of polyester copolymer comprising recycled monomers |
| KR20220064077A (en) * | 2020-11-11 | 2022-05-18 | 에스케이케미칼 주식회사 | Polyester copolymer comprising recycled monomers |
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| KR20220055192A (en) * | 2020-10-26 | 2022-05-03 | 에스케이케미칼 주식회사 | Method for preparation of polyester copolymer comprising recycled monomers |
| KR102583652B1 (en) | 2020-10-26 | 2023-09-26 | 에스케이케미칼 주식회사 | Method for preparation of polyester copolymer comprising recycled monomers |
| KR20220064077A (en) * | 2020-11-11 | 2022-05-18 | 에스케이케미칼 주식회사 | Polyester copolymer comprising recycled monomers |
| KR102583653B1 (en) | 2020-11-11 | 2023-09-26 | 에스케이케미칼 주식회사 | Polyester copolymer comprising recycled monomers |
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