JP3782907B2 - Process for producing bis-β-hydroxyethyl terephthalate and / or its low condensate - Google Patents
Process for producing bis-β-hydroxyethyl terephthalate and / or its low condensate Download PDFInfo
- Publication number
- JP3782907B2 JP3782907B2 JP22603399A JP22603399A JP3782907B2 JP 3782907 B2 JP3782907 B2 JP 3782907B2 JP 22603399 A JP22603399 A JP 22603399A JP 22603399 A JP22603399 A JP 22603399A JP 3782907 B2 JP3782907 B2 JP 3782907B2
- Authority
- JP
- Japan
- Prior art keywords
- bis
- hydroxyethyl terephthalate
- reaction
- low condensate
- ethylene glycol
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 91
- 229920000728 polyester Polymers 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 2
- -1 polyethylene terephthalate Polymers 0.000 description 21
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- 239000000835 fiber Substances 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 238000012691 depolymerization reaction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 229940119177 germanium dioxide Drugs 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
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QLIQIXIBZLTPGQ-UHFFFAOYSA-N 4-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=C(C(O)=O)C=C1 QLIQIXIBZLTPGQ-UHFFFAOYSA-N 0.000 description 1
- BCBHDSLDGBIFIX-UHFFFAOYSA-N 4-[(2-hydroxyethoxy)carbonyl]benzoic acid Chemical compound OCCOC(=O)C1=CC=C(C(O)=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 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
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 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
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、芳香族ポリエステルからビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物を製造する方法に関するものである。さらに詳しくは、結晶化度の高い回収芳香族ポリエステルからさえも効率的にビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物を製造することのできる方法に関するものである。
【０００２】
【従来の技術】
芳香族ポリエステルの特長のひとつは、繊維、フィルム、樹脂など広汎な各種成形品分野に適合するすぐれた性能を有することである。また、該ポリエステルの有する特長の他のひとつは、解重合により原料段階に回帰させることが比較的容易に行えることである。
【０００３】
芳香族ポリエステル、殊にポリエチレンテレフタレートを中心とするテレフタレート系ポリエステルは、上述の如く、各種成形品分野に広く用いられ、その製造方法としては、テレフタル酸とエチレングリコールとの直接エステル化によるか、テレフタル酸の低級アルキルエステル、殊にジメチルテレフタレートとエチレングリコールとのエステル交換反応を経由するかにより、ビス−β−ヒドロキシエチルテレフタレートを含む中間状態を経たのち、通常はそれをそのまま高温、高真空下に縮合重合を行わせる工程に供する方法が、現在、主として実用に供されている。さらに該芳香族ポリエステルは、解重合によりその原料段階に回帰させ、再度重合させてポリエステルとすることができ、省資源の見地からもすぐれた材料といえる。
【０００４】
テレフタレート系ポリエステルを解重合させるには、従来、基本的に該ポリエステルと過剰量のエチレングリコールを主たる構成成分とする反応系中において解重合反応を行わせるのが通常であった。かかる反応をスムースに遂行するには、該ポリエステルが解重合を受けやすい状態を作り出すことが重要なポイントになる。非晶性のポリエステルを原料とする場合などには、かかる反応は比較的進行しやすいが、、例えばポリエステルの形態が高結晶化度の繊維であるような場合などには、解重合反応が比較的進行しにくいことが多い。また、ポリエステルが樹脂成形品の一種であるボトルの形態を取る場合にも、結晶化の進行しているネック部分などは解重合が進みにくい傾向がある。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、芳香族ポリエステルからビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物を製造する方法を提供することにある。
本発明の他の目的は、高結晶化状態にある芳香族ポリエステル例えば芳香族ポリエステルからなる回収繊維、繊維層あるいは高結晶化度のネック部分を持つ回収ボトルでさえも効率的に分解できてビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物を製造する方法を提供することにある。
本発明のさらに他の目的および利点は、以下の説明から明らかになろう。
【０００６】
【課題を解決するための手段】
本発明によれば、本発明の上記目的および利点は、テレフタル酸を主たるジカルボン酸成分としエチレングリコールを主たるグリコール成分とする芳香族ポリエステルを、遊離のエチレングリコールを含まないビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物と加熱して該芳香族ポリエステルを予備分解し、次いで得られた予備分解物とエチレングリコールとを、該予備分解物１重量部当りエチレングリコールを３．０〜５．０重量部用いて、反応させて予備分解物のテレフタル酸成分をビス‐β‐ヒドロキシエチルテレフタレートおよび／またはその低縮合物に変換せしめることを特徴とする芳香族ポリエステルからビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物の製造法によって達成される。
【０００７】
従来、テレフタレート系ポリエステルの解重合反応を行わせるにあたって、該ポリエステルは、系内にペレット状、フレーク状、糸状、塊状など、種々の形態の１種以上で供給される。反応系において、これらの形態をとるポリエステルは徐々に微細化し、遂には、形態を留めなくなる。これに到るまでの時間は、供給されるポリエステルの形態や結晶化度、配向度、反応条件、例えば温度、撹拌の良し悪しや反応槽の形態などにより変動する。かかる反応条件などの設定は、予め最適化を検討することにより、できるだけ望ましい条件を設定できるが、系に供給されるテレフタレート系ポリエステルの形態や結晶状態は、入手するごとに変動することが多く、それによって反応の進行が大きく影響されるため、実際の操業に支障を来たすことが多かった。本発明者は、かかる点に着目し、解重合反応をスムースに進行させる方法につき検討を深めた結果、該テレフタレート系ポリエステルをビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物と加熱して該芳香族ポリエステルを予備分解し、次いで得られた予備分解物とエチレングリコールを反応させて予備分解物のテレフタル酸成分をビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物に分解せしめる方法が極めて有用であることを突き止め、本発明を完成するに到ったのである。
【０００８】
本発明において、芳香族ポリエステルとは、テレフタル酸を主たる酸成分とし、エチレングリコールを主たるグリコール成分とするものであり、他の成分の１種以上を少割合共重合したものも含まれる。その共重合成分の範囲は、例えば、全体として通常４０モル％以下、殊に３０モル％以下、さらには２０モル％以下である。共重合され得る成分の例としては、ジカルボン酸類としてイソフタル酸、ジフェニルジカルボン酸、ジフェニルスルフォンジカルボン酸、ジフェニルエーテルジカルボン酸、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、ナトリウムスルフォイソフタル酸の如き芳香族ジカルボン酸；セバチン酸、アジピン酸の如き脂肪族ジカルボン酸；ヘキサヒドロテレフタル酸の如き脂環族ジカルボン酸の如きものを挙げることができる。また、ジオール類としてトリメチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、シクロヘキサンジメタノール、ビス−β−ヒドロキシエチルビスフェノールＡ、ビス−β−ヒドロキシエトキシジフェニルスルフォン、ビス−β−ヒドロキシエトキシジフェニルエーテル、ジエチレングリコール、ポリエチレングリコールなどを挙げることができる。また、ヒドロキシカルボン酸類、例えば、ｐ−ヒドロキシエトキシ安息香酸の如きものも例として挙げることができる。さらに、３官能以上の多官能化合物および／または単官能化合物を併用することもポリエステルが線状を保つ範囲において可能である。３官能以上の多官能化合物の例としては、トリメシン酸、グリセリン、ペンタエリスリトールなど、また、単官能化合物の例としては、ジフェニルモノカルボン酸、ジフェニルエーテルモノカルボン酸、フェノキシポリエチレングリコールなどを挙げることができる。これら各種共重合成分はエステルの状態にするなど、機能的誘導体として用いることが可能であり、また、それらは１種または２種以上であり得る。
【０００９】
本発明では、まず芳香族ポリエステルをビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物と加熱して該芳香族ポリエステルを予備分解する。ここに言う低縮合物とは、具体的には、エチレンテレフタレートを繰り返し単位の主構成成分とする低重合度の、通常は混合物となっている化合物を言い、その平均的な重合度は、１以上〜１０程度、より好ましくは１以上〜６程度、さらに好ましくは１以上〜３程度のものである。加熱は、反応系におけるビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物が融解するような温度になるようにするのが好適である。具体的には、１５０〜２６５℃程度、より好ましくは２００〜２４５℃の温度である。予備分解における芳香族ポリエステルとビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物との量的な関係は、必要に応じて変動させ得るが、通常、芳香族ポリエステル１重量部当たり、ビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物を０.１〜４.５重量部、殊に０.７〜１.２重量部程度用いるのが好適である。予備分解の反応時間は、芳香族ポリエステルをビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物との量的な関係や、前述の如く供給されるポリエステルの形態や結晶化度、配向度、反応条件、例えば温度、攪拌の良し悪しや反応槽の形態などにより変動するのが通常であり、一概には言えないが、好ましくは、０.５〜５.０時間、特に好ましくは０.５〜１.５時間程度行うのが適当である。該予備分解反応は、常圧下で実施しても良いし、加圧下でも実施可能である。また、反応系からの留出物が反応の進行を阻害しない程度の減圧下での実施も可能である。該予備分解反応に用いられるビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物はフリーの状態のエチレングリコールを含まない。また、該予備分解反応は、芳香族ポリエステルとビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物を一挙に合一して反応させることも可能であり、また、一方および／または双方を２回以上に分割して系内に導入して反応させることも可能である。さらに、該予備分解反応に用いるビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物は、該予備分解反応に次いで実施される該予備分解物とエチレングリコールを反応させてビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物に得る反応の生成物をその少なくとも一部として用いることも可能であり、好ましい態様である。その場合にも、少割合のエチレングリコールが存在しても、上記の如く許容される。
【００１０】
予備分解に次いで該予備分解物とエチレングリコールを反応させて該予備分解物をビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物に分解せしめる反応、すなわち該予備分解物のテレフタル酸成分をビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物に変換せしめる反応が実施される。
【００１１】
この反応は、通常、１９０〜２６５℃、より好ましくは２００〜２２０℃の温度で実施される。また、その予備分解物１重量部当たり、エチレングリコール３ . ０〜５.０重量部の量比として実施するのが、良好な結果を得るうえで好ましい。また、反応は、一挙にそのような量比にして行うことも可能であり、一方および／または双方を２回以上に分割して行ってもよい。反応時間は、反応条件、例えば温度、攪拌の良し悪しや反応槽の形態などにより変動するし、また、上記の如く分割添加も可能であるので一概には言えないが、好ましくは、１.０〜８.０時間、より好ましくは１.５〜２.５時間である。該反応は、常圧下で実施してもよいし、加圧下でも実施可能である。また、反応系からの留出物が反応の進行を阻害しない程度の減圧下での実施も可能である。
【００１２】
また、この反応をスムースに行うにあたっては、適当な反応触媒の添加が推奨される。かかる反応触媒の例としては、公知のエステル交換反応触媒、例えば、ナトリウム、マグネシウムのメチラート、ホウ酸亜鉛、酢酸亜鉛に代表されるＺｎ、Ｃｄ、Ｍｎ、Ｃｏ、Ｃａ、Ｂａ等の脂肪酸塩、炭酸塩、金属Ｎａ、Ｍｇ、およびこれらの酸化物等を挙げることができ、これらの使用は１種または２種以上であってよい。そしてその添加量は、通常、原料のテレフタレート系ポリエステルに対して０.０５〜３.０重量％程度が好適である。
【００１３】
本発明の上記各反応は、反応釜の中に前述したような量関係の各原料を供給して反応させ、それを取り出すような、いわゆる回分反応方式で実施してもよいし、各原料の供給と取り出しを連続的に行うような、いわゆる連続反応方式を適用してもよく、また、これらを組み合わせて行ってもよい。
【００１４】
本発明者の検討結果によれば、本発明の方法によって得たビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物をその製造原料の少なくとも一部として用いて得たポリエステルは、繊維、フィルム、ボトルなどといった各種成形品として何ら問題なく使用可能である。さらに、各種ポリエステル成形物を解重合して実質的にビス−β−ヒドロキシエチルテレフタレートの段階に戻す場合にあって、それは前述の如くエチレングリコールを用いて解重合工程を実施することより、得られた解重合物はエチレングリコールを主溶媒とする溶液として得ることができる。その溶液をそのまま、あるいは適当な濃度に調製したり、必要に応じ、触媒除去などの処置をしたりし、また、カチオン、アニオンを除去する工程を適用したりして高品質化されたビス−β−ヒドロキシエチルテレフタレートを得ることができる。また、その場合、必要に応じその前、その間、その後の少なくともいずれかにおいて一回以上の脱色工程を経由することにより無色の高品質ビス−β−ヒドロキシエチルテレフタレートを得ることができやすい。
【００１５】
本発明の方法を適用して得たビス−β−ヒドロキシエチルテレフタレートは、その溶液状態のまま、もしくは適当な濃度に調製した溶液の状態として、あるいは再結晶工程を経たり、蒸留工程に供したりして高品質のポリエステルを再度製造するための原料の少なくとも一部として供することが可能である。そのような場合にあって、解重合せんとするポリエステル成形物が、商品形態となっていたりした場合のように他の材料と混在していたり、ごみのような異物と混在しているような状態にあっても、必要に応じ、選別、濾別、などの異物除去工程を適用することによって本発明を支障なく実施することができる。例えば、ポリエステルが繊維状の商品形態をとっていた場合、異種繊維と混在していたり、ポリエステル中に用いられている酸化チタンの如き無機物を含んでいたりする状態、ポリエステルがフィルム状の形態であった場合にポリエチレン、ポリアミドなど各種フィルム材料などと混在したり、ポリエステル中に用いられている各種滑剤などを含んでいたりする状態、ポリエステルがその他の各種成形品、例えばボトルの形態であった場合に、蓋部分やボトム部分に用いられたポリエチレンなどの各種材料とともに破砕されて混在するような状態や、ラベルなどに用いられた紙やプラスチックのような各種材料と混在しているような状態は、むしろ通常にある状態であるが、本発明者の検討結果によれば、液々分離や固液分離など、従来公知の手法を適用し、且つ本発明の方法と、必要に応じ前述したような各種手法を用いることにより、所期の目的を達することが可能となる。
【００１６】
本発明をさらに具体的な態様について説明するために、以下実施例を挙げる。本発明が、これらの例のみに限定されるものではない。
【００１７】
【実施例】
実施例１
使用済みペットボトルの粉砕フレーク７ｋｇと艶消し剤としてのチタンを含有しないポリエチレンテレフタレート短繊維３ｋｇとビス−β−ヒドロキシエチルテレフタレート１０ｋｇとを２４０リッターの撹拌機付オートクレーブに仕込み、２２０℃、常圧の条件下で１時間加熱・撹拌しペットボトルとポリエチレンテレフタレート短繊維を予備分解してポリエチレンテレフタレートのオリゴマーを得た。得られたオリゴマー２０ｋｇに対してエチレングリコール４０ｋｇと公知のエステル交換触媒であるナトリウムメチラート０.０７ｋｇを添加して２００℃、常圧の条件下で２時間加熱・撹拌してオリゴマーを解重合した。解重合して得られた溶液中にはポリエチレンテレフタレートの未分解物は目視されず、解重合溶液は透明であった。次いで、この解重合溶液に常温のエチレングリコール８５ｋｇを追加した後、さらに５５℃にまで降温してエチレングリコールを主たる溶媒としビス−β−ヒドロキシエチルテレフタレーを主たる溶質とする溶液を得た。この溶液を５５℃の温度で全量活性炭による脱色処理をし、さらにカチオン交換樹脂（オルガノ社製アンバーライト ＩＲ１２０−Ｂ）により脱カチオン、続いてアニオン交換樹脂（オルガノ社製アンバーライト ＩＲＡ−４００）により脱アニオンを行った。この脱カチオン・脱アニオンされた溶液を５００リッターの撹拌機付・真空発生装置付オートクレーブに仕込み、１３５℃、１０,６７０Ｐａ（８０ｍｍＨｇ）の条件で溶液中のエチレングリコール残重量が２０％になるまでエチレングリコールを留去した後、伝熱面積０.５ｍ2の真空薄膜蒸発機にて、１５０℃、２００Ｐａ（１.５ｍｍＨｇ）の条件でビス−β−ヒドロキシエチルテレフタレートの沸点より低い沸点の物質含有量が５.０重量％になるまで濃縮して粗ビス−β−ヒドロキシエチルテレフタレートを含む組成物を得た。さらにこの粗ビス−β−ヒドロキシエチルテレフタレートを含む組成物を伝熱面積０.５ｍ2の分子蒸留機にかけて、温度２００℃、２４Ｐａ（０.１８ｍｍＨｇ）の条件で７５分かけて分子蒸留し、精製ビス−β−ヒドロキシエチルテレフタレートを得た。得られた精製ビス−β−ヒドロキシエチルテレフタレートの品質分析値を表１に記す。
【００１８】
【表１】
表１中の光学密度とはビス−β−ヒドロキシエチルテレフタレートの品質評価法であり、着色物含量に比例する量である。１０％メタノール溶液の吸光度を波長３８０ｍμ、セル長１０ｍｍにて測定したものである。また、白度は測色色差計で測定し、ハンター法のＬ（明るさ）、ａ（赤色度）、ｂ（黄色度）値で示した。
【００２０】
次いで、得られた精製ビス−β−ヒドロキシエチルテレフタレートの常温粉末５００ｇを１,０００ｃｃの攪拌機付ガラス製重合器に入れ、窒素ガスで十分に置換し、窒素ガス雰囲気下で１３０℃まで加温してビス−β−ヒドロキシエチルテレフタレートを溶融した後、予め沸点状態のエチレングリコールに六法晶系の二酸化ゲルマニウムを完全溶解した二酸化ゲルマニウム０.２重量部の液２．７ｇを、重合触媒として窒素ガス雰囲気下で添加し攪拌しながら２０分かけてエチレングリコールの沸点（１９７℃）まで昇温し、さらに、常圧、１９７℃の条件で４５分間加熱、攪拌を行いポリエチレンテレフタレートのオリゴマーを得た。続けて、このオリゴマーを２８０℃、９０Ｐａ（０.７ｍｍＨｇ）の条件で２時間かけて重縮合してポリエチレンテレフタレートを得た。得られたポリエチレンテレフタレートの品質分析値を表２に記す。精製ビス−β−ヒドロキシエチルテレフタレートおよびポリエチレンテレフタレートのいずれも実用上極めて優れた品質レベルであった。
【００２１】
【表２】
表２中の極限粘度はオルソクロロフェノール中３０℃で測定した。また、白度は測色色差計で測定し、ハンター法のＬ（明るさ）、ａ（赤色度）、b（黄色度）値で示した。
【００２３】
比較例１
使用済みペットボトルの粉砕フレーク７ｋｇと艶消し剤としてのチタンを含有しないポリエチレンテレフタレート短繊維３ｋｇとエチレングリコール７２ｋｇとを２４０リッターの撹拌機付オートクレーブに仕込み、公知のエステル交換触媒であるナトリウムメチラート０.０７ｋｇを添加して２００℃、常圧の条件で３時間加熱・撹拌しペットボトルとポリエチレンテレフタレート短繊維を解重合した。解重合して得られた溶液中にはポリエチレンテレフタレートの未分解物が存在し、解重合溶液は白濁していた。この解重合溶液を５５℃にまで降温して５５℃の温度で全量活性炭による脱色処理、さらにカチオン交換樹脂（オルガノ社製アンバーライト ＩＲ１２０−Ｂ）により脱カチオン、続いてアニオン交換樹脂（オルガノ社製アンバーライト）により脱アニオンを行ったが、ポリエチレンテレフタレートの未分解物が瞬時にイオン交換樹脂に閉塞し、安定操作が不可能であった。
【００２４】
【発明の効果】
本発明によれば、高結晶化状態にある芳香族ポリエステル例えば芳香族ポリエステルからなる回収繊維、繊維層あるいは高結晶化度のネック部分を持つ回収ボトルでさえも効率的に分解できてビス−β−ヒドロキシエチルテレフタレートおよび／またはその低縮合物を製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing bis-β-hydroxyethyl terephthalate and / or a low condensate thereof from an aromatic polyester. More specifically, the present invention relates to a method capable of efficiently producing bis-β-hydroxyethyl terephthalate and / or a low condensate thereof even from a recovered aromatic polyester having a high degree of crystallinity.
[0002]
[Prior art]
One of the features of aromatic polyester is that it has excellent performance suitable for a wide variety of molded product fields such as fibers, films, and resins. Another feature of the polyester is that it can be relatively easily returned to the raw material stage by depolymerization.
[0003]
As described above, aromatic polyesters, particularly terephthalate-based polyesters mainly composed of polyethylene terephthalate, are widely used in the field of various molded products, and the production method thereof includes direct esterification of terephthalic acid and ethylene glycol, or terephthalate. After passing through an intermediate state containing bis-β-hydroxyethyl terephthalate depending on whether the lower alkyl ester of acid, especially dimethyl terephthalate and ethylene glycol, is passed through an ester exchange reaction, it is usually left under high temperature and high vacuum. At present, methods used for the step of performing condensation polymerization are mainly used in practice. Furthermore, the aromatic polyester can be returned to its raw material stage by depolymerization and polymerized again to be a polyester, which can be said to be an excellent material from the viewpoint of resource saving.
[0004]
In order to depolymerize a terephthalate-based polyester, conventionally, a depolymerization reaction is usually performed in a reaction system basically comprising the polyester and an excess amount of ethylene glycol as main components. In order to smoothly perform such a reaction, it is important to create a state in which the polyester is susceptible to depolymerization. When amorphous polyester is used as a raw material, the reaction is relatively easy to proceed. However, for example, when the form of the polyester is a fiber with high crystallinity, the depolymerization reaction is compared. Often difficult to progress. Also, when taking the form of a bottle in which polyester is a kind of resin molded product, depolymerization tends not to proceed easily at the neck portion where crystallization is progressing.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing bis-β-hydroxyethyl terephthalate and / or a low condensate thereof from an aromatic polyester.
Another object of the present invention is to efficiently decompose even a recovery fiber, a fiber layer made of aromatic polyester in a highly crystallized state, such as an aromatic polyester, or a recovery bottle having a neck portion with high crystallinity. It is to provide a method for producing -β-hydroxyethyl terephthalate and / or a low condensate thereof.
Still other objects and advantages of the present invention will become apparent from the following description.
[0006]
[Means for Solving the Problems]
According to the present invention, the above objects and advantages of the present invention are that bis-β-hydroxyethyl terephthalate containing no terephthalic acid as a main dicarboxylic acid component and ethylene glycol as a main glycol component is used. The aromatic polyester is predecomposed by heating with a low condensate thereof and / or its low condensate, and then the predecomposed product and ethylene glycol obtained are added in an amount of 3.0 to 5.5 ethylene glycol per part by weight of the predecomposed product. 0 part by weight is used to react to convert the terephthalic acid component of the predecomposition product into bis-β-hydroxyethyl terephthalate and / or a low condensate thereof from an aromatic polyester to bis-β-hydroxyethyl terephthalate And / or by a process for producing the low condensate thereof. .
[0007]
Conventionally, when performing a depolymerization reaction of a terephthalate-based polyester, the polyester is supplied into the system in one or more of various forms such as pellets, flakes, threads, and lumps. In the reaction system, polyesters taking these forms gradually become finer and eventually do not remain in form. The time required to reach this varies depending on the form of the polyester to be supplied, the degree of crystallinity, the degree of orientation, the reaction conditions, such as temperature, the quality of stirring, the form of the reaction tank, and the like. Such reaction conditions and the like can be set as desirable as possible by examining optimization in advance, but the form and crystal state of the terephthalate-based polyester supplied to the system often vary with each acquisition, As a result, the progress of the reaction was greatly affected, and the actual operation was often hindered. The present inventor paid attention to this point and, as a result of studying a method for smoothly proceeding the depolymerization reaction, heated the terephthalate-based polyester with bis-β-hydroxyethyl terephthalate and / or a low condensate thereof. A method in which the aromatic polyester is predecomposed and then the predecomposed product obtained is reacted with ethylene glycol to decompose the terephthalic acid component of the predecomposed product into bis-β-hydroxyethyl terephthalate and / or a low condensate thereof. As a result, the present invention has been completed.
[0008]
In the present invention, the aromatic polyester is one having terephthalic acid as the main acid component and ethylene glycol as the main glycol component, and includes those obtained by copolymerizing one or more of the other components in a small proportion. The range of the copolymerization component is, for example, generally 40 mol% or less, particularly 30 mol% or less, more preferably 20 mol% or less as a whole. Examples of components that can be copolymerized include aromatic dicarboxylic acids such as isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, naphthalenedicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium sulfoisophthalic acid as dicarboxylic acids. An aliphatic dicarboxylic acid such as sebacic acid and adipic acid; and an alicyclic dicarboxylic acid such as hexahydroterephthalic acid. Further, as diols, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexanedimethanol, bis-β-hydroxyethylbisphenol A, bis-β-hydroxyethoxydiphenyl sulfone, bis-β-hydroxyethoxydiphenyl ether, diethylene glycol, polyethylene A glycol etc. can be mentioned. Hydroxycarboxylic acids such as p-hydroxyethoxybenzoic acid can also be mentioned as examples. Furthermore, it is possible to use a polyfunctional compound having three or more functions and / or a monofunctional compound in a range where the polyester is kept linear. Examples of trifunctional or higher polyfunctional compounds include trimesic acid, glycerin, pentaerythritol and the like, and examples of monofunctional compounds include diphenyl monocarboxylic acid, diphenyl ether monocarboxylic acid, phenoxy polyethylene glycol and the like. . These various copolymer components can be used as functional derivatives such as in the form of an ester, and they can be used alone or in combination of two or more.
[0009]
In the present invention, first, the aromatic polyester is predecomposed by heating the aromatic polyester with bis-β-hydroxyethyl terephthalate and / or a low condensate thereof. Specifically, the low condensate herein refers to a compound having a low degree of polymerization and having a mixture of ethylene terephthalate as a main component of a repeating unit, and usually an average degree of polymerization of 1 From about 10 to about 10, more preferably from about 1 to about 6, and even more preferably from about 1 to 3. The heating is preferably performed at a temperature at which bis-β-hydroxyethyl terephthalate and / or a low condensate thereof in the reaction system melts. Specifically, the temperature is about 150 to 265 ° C, more preferably 200 to 245 ° C. The quantitative relationship between the aromatic polyester and bis-β-hydroxyethyl terephthalate and / or its low condensate in the predegradation can be varied as necessary, but usually, bis- It is preferable to use β-hydroxyethyl terephthalate and / or a low condensate thereof in an amount of about 0.1 to 4.5 parts by weight, particularly about 0.7 to 1.2 parts by weight. The reaction time of the predegradation is the quantitative relationship between the aromatic polyester and bis-β-hydroxyethyl terephthalate and / or its low condensate, the form, crystallinity and orientation of the polyester supplied as described above. Usually, it fluctuates depending on the reaction conditions, such as temperature, good / bad stirring, and the form of the reaction tank. Although it cannot be generally stated, it is preferably 0.5 to 5.0 hours, particularly preferably 0.5. It is appropriate to perform for about 1.5 hours. The preliminary decomposition reaction may be performed under normal pressure or under pressure. It is also possible to carry out the reaction under reduced pressure such that the distillate from the reaction system does not inhibit the progress of the reaction. The pre-decomposition reaction used in bis -β- hydroxyethyl terephthalate and / or its low condensation was not including ethylene glycol free. Also, the pre decomposition reaction, it is also possible to react taken together at once aromatic polyester and bis -β- hydroxyethyl terephthalate and / or its low condensate, also, on the other hand and / or both It is also possible to divide into two or more times and introduce into the system for reaction. Further, bis-β-hydroxyethyl terephthalate and / or a low condensate thereof used in the preliminary decomposition reaction is obtained by reacting the preliminary decomposition product carried out after the preliminary decomposition reaction with ethylene glycol to produce bis-β-hydroxyethyl. The product of the reaction obtained to terephthalate and / or its low condensate can also be used as at least a part thereof, which is a preferred embodiment. Even in that case, the presence of a small proportion of ethylene glycol is acceptable as described above.
[0010]
Next to the preliminary decomposition, the preliminary decomposed product is reacted with ethylene glycol to decompose the preliminary decomposed product into bis-β-hydroxyethyl terephthalate and / or a low condensate thereof, that is, the terephthalic acid component of the preliminary decomposed product is A reaction is carried out which converts -β-hydroxyethyl terephthalate and / or its low condensate.
[0011]
This reaction is usually carried out at a temperature of 190 to 265 ° C, more preferably 200 to 220 ° C. Also, the pre-decomposition product per part by weight, to carry out as the amount ratio of ethylene glycol from 3.0 to 5.0 parts by weight, preferable for obtaining good results. In addition, the reaction can be performed at such a quantitative ratio all at once, and one and / or both may be performed in two or more times. The reaction time varies depending on the reaction conditions such as temperature, stirring quality, reaction vessel form, etc. In addition, since it can be dividedly added as described above, it cannot be generally stated, but preferably 1.0. It is -8.0 hours, More preferably, it is 1.5-2.5 hours. The reaction may be performed under normal pressure or under pressure. It is also possible to carry out the reaction under reduced pressure such that the distillate from the reaction system does not inhibit the progress of the reaction.
[0012]
In addition, when performing this reaction smoothly, addition of an appropriate reaction catalyst is recommended. Examples of such reaction catalysts include known transesterification reaction catalysts such as sodium, magnesium methylates, zinc borates, fatty acid salts such as Zn, Cd, Mn, Co, Ca, Ba, and the like, carbonates A salt, metal Na, Mg, and these oxides etc. can be mentioned, These use may be 1 type, or 2 or more types. In general, the addition amount is preferably about 0.05 to 3.0% by weight with respect to the raw material terephthalate-based polyester.
[0013]
Each of the above reactions of the present invention may be carried out by a so-called batch reaction method in which the above-mentioned quantities of raw materials are fed into a reaction kettle and reacted, and then removed. A so-called continuous reaction system in which supply and removal are continuously performed may be applied, or a combination thereof may be performed.
[0014]
According to the results of the study by the present inventors, the polyester obtained using bis-β-hydroxyethyl terephthalate and / or a low condensate thereof obtained by the method of the present invention as at least a part of the production raw material is a fiber, film It can be used without any problem as various molded products such as bottles. Furthermore, when various polyester moldings are depolymerized and returned to the bis-β-hydroxyethyl terephthalate stage, it can be obtained by carrying out the depolymerization step using ethylene glycol as described above. The depolymerized product can be obtained as a solution containing ethylene glycol as the main solvent. The solution can be prepared as it is or as a suitable concentration, and if necessary, treatment such as catalyst removal is applied, and a process for removing cations and anions is applied to improve the quality of the bis- β-hydroxyethyl terephthalate can be obtained. Moreover, in that case, colorless high-quality bis-β-hydroxyethyl terephthalate can be easily obtained by going through one or more decoloring steps before, during and after that, if necessary.
[0015]
The bis-β-hydroxyethyl terephthalate obtained by applying the method of the present invention can be used in its solution state or in the state of a solution prepared to an appropriate concentration, or through a recrystallization step or a distillation step. Thus, it is possible to provide at least part of a raw material for producing high-quality polyester again. In such a case, the polyester molded product to be depolymerized is mixed with other materials, such as when it is in the form of a product, or mixed with foreign substances such as dust. Even if it is in a state, the present invention can be carried out without hindrance by applying a foreign matter removing process such as sorting, filtering, etc. as necessary. For example, if the polyester is in the form of a fibrous product, it is mixed with different types of fibers, or contains an inorganic material such as titanium oxide used in the polyester, or the polyester is in the form of a film. When mixed with various film materials such as polyethylene and polyamide, or when it contains various lubricants used in polyester, the polyester is in the form of other various molded products such as bottles. The state of being crushed and mixed with various materials such as polyethylene used for the lid part and the bottom part, and the state of being mixed with various materials such as paper and plastic used for labels, Rather, it is a normal state, but according to the results of the study by the present inventor, conventionally known methods such as liquid-liquid separation and solid-liquid separation Applying the method, and the method of the present invention, by using a variety of techniques such as those as required above, it is possible to achieve the intended purpose.
[0016]
The following examples are provided to further illustrate the present invention. The present invention is not limited to only these examples.
[0017]
【Example】
Example 1
7 kg of used PET bottle ground flakes, 3 kg of polyethylene terephthalate short fibers not containing titanium as matting agent, and 10 kg of bis-β-hydroxyethyl terephthalate were charged into a 240 liter autoclave equipped with a stirrer at 220 ° C. and normal pressure. Under the conditions, the mixture was heated and stirred for 1 hour to predecompose the PET bottle and the polyethylene terephthalate short fiber to obtain an oligomer of polyethylene terephthalate. To 20 kg of the obtained oligomer, 40 kg of ethylene glycol and 0.07 kg of sodium methylate which is a known transesterification catalyst were added, and the oligomer was depolymerized by heating and stirring at 200 ° C. under normal pressure for 2 hours. . The undecomposed product of polyethylene terephthalate was not visually observed in the solution obtained by depolymerization, and the depolymerization solution was transparent. Next, 85 kg of ordinary temperature ethylene glycol was added to the depolymerization solution, and the temperature was further lowered to 55 ° C. to obtain a solution containing ethylene glycol as a main solvent and bis-β-hydroxyethyl terephthalate as a main solute. This solution was decolorized with activated carbon at a temperature of 55 ° C., and further decationized with a cation exchange resin (Amberlite IR120-B made by Organo), followed by an anion exchange resin (Amberlite IRA-400 made by Organo). Deanion was performed. This decationized / deanionized solution is charged into a 500 liter autoclave with a stirrer / vacuum generator until the residual weight of ethylene glycol in the solution reaches 20% at 135 ° C. and 10,670 Pa (80 mmHg). After distilling off ethylene glycol, containing a substance with a boiling point lower than that of bis-β-hydroxyethyl terephthalate at 150 ° C. and 200 Pa (1.5 mmHg) in a vacuum thin film evaporator with a heat transfer area of 0.5 m 2 A composition containing crude bis-β-hydroxyethyl terephthalate was obtained by concentrating to an amount of 5.0% by weight. Further, the composition containing the crude bis-β-hydroxyethyl terephthalate was subjected to molecular distillation over 75 minutes under conditions of a temperature of 200 ° C. and 24 Pa (0.18 mmHg) through a molecular distillation machine having a heat transfer area of 0.5 m 2 for purification. Bis-β-hydroxyethyl terephthalate was obtained. Table 1 shows the quality analysis values of the obtained purified bis-β-hydroxyethyl terephthalate.
[0018]
[Table 1]
The optical density in Table 1 is a method for evaluating the quality of bis-β-hydroxyethyl terephthalate, and is an amount proportional to the color content. The absorbance of a 10% methanol solution was measured at a wavelength of 380 mμ and a cell length of 10 mm. The whiteness was measured with a colorimetric color difference meter and indicated by L (brightness), a (redness), and b (yellowness) values of the Hunter method.
[0020]
Next, 500 g of the obtained room temperature powder of purified bis-β-hydroxyethyl terephthalate was placed in a 1,000 cc glass polymerizer equipped with a stirrer, sufficiently replaced with nitrogen gas, and heated to 130 ° C. under a nitrogen gas atmosphere. After melting bis-β-hydroxyethyl terephthalate, 2.7 g of a solution of 0.2 parts by weight of germanium dioxide in which hexagonal germanium dioxide is completely dissolved in ethylene glycol in a boiling point in advance is used as a polymerization catalyst. The mixture was added in an atmosphere, stirred and heated to the boiling point of ethylene glycol (197 ° C.) over 20 minutes, and further heated and stirred at normal pressure and 197 ° C. for 45 minutes to obtain a polyethylene terephthalate oligomer. Subsequently, this oligomer was polycondensed under the conditions of 280 ° C. and 90 Pa (0.7 mmHg) over 2 hours to obtain polyethylene terephthalate. The quality analysis values of the obtained polyethylene terephthalate are shown in Table 2. Both purified bis-β-hydroxyethyl terephthalate and polyethylene terephthalate were practically excellent quality levels.
[0021]
[Table 2]
The intrinsic viscosity in Table 2 was measured in orthochlorophenol at 30 ° C. The whiteness was measured with a colorimetric color difference meter and indicated by L (brightness), a (redness), and b (yellowness) values of the Hunter method.
[0023]
Comparative Example 1
7 kg of used PET bottle ground flakes, 3 kg of polyethylene terephthalate short fibers not containing titanium as a matting agent, and 72 kg of ethylene glycol were charged into a 240 liter autoclave with a stirrer, and sodium methylate 0, a known transesterification catalyst, was added. 0.07 kg was added and heated and stirred at 200 ° C. under normal pressure for 3 hours to depolymerize the PET bottle and the polyethylene terephthalate short fiber. An undecomposed product of polyethylene terephthalate was present in the solution obtained by depolymerization, and the depolymerization solution was cloudy. The depolymerized solution was cooled down to 55 ° C. and decolorized with activated carbon at 55 ° C., and further decationized with a cation exchange resin (Amberlite IR120-B manufactured by Organo), followed by an anion exchange resin (manufactured by Organo). Deanion was performed by Amberlite), but the undecomposed product of polyethylene terephthalate was instantly blocked by the ion exchange resin, and stable operation was impossible.
[0024]
【The invention's effect】
According to the present invention, even an aromatic polyester in a highly crystallized state, such as a recovery fiber composed of an aromatic polyester, a fiber layer, or a recovery bottle having a neck portion with a high crystallinity can be efficiently decomposed and bis-β -Hydroxyethyl terephthalate and / or a low condensate thereof can be produced.
Claims (5)
Priority Applications (19)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22603399A JP3782907B2 (en) | 1999-08-10 | 1999-08-10 | Process for producing bis-β-hydroxyethyl terephthalate and / or its low condensate |
| DE69920025T DE69920025T2 (en) | 1999-08-04 | 1999-12-24 | PROCESS FOR THE PREPARATION OR PURIFICATION OF BIS- (BETA) -HYDROXYETHYLTEREPHTHALATE |
| CNA2004100013328A CN1511823A (en) | 1999-08-04 | 1999-12-24 | Bis-beta-hydroxyethyl terephthalate production process and purification process |
| US09/622,518 US6630601B1 (en) | 1999-08-04 | 1999-12-24 | Methods for the preparation or purification of bis-β-hydroxyethyl terephthalate |
| IDW20001563A ID26736A (en) | 1999-08-04 | 1999-12-24 | PRODUCTION PROCESS AND REFINED BIS-HYDROXYETHYL PURIFICATION PROCESS |
| CNA2004100013313A CN1511821A (en) | 1999-08-04 | 1999-12-24 | Bis-beta-hydroxyethyl terephthalate production process and purification process |
| EP99961372A EP1120394B1 (en) | 1999-08-04 | 1999-12-24 | Methods for the preparation or purification of bis-(beta)-hydroxyethyl terephthalate |
| KR1020007009039A KR100701842B1 (en) | 1999-08-04 | 1999-12-24 | Preparation and Purification Methods of Bis-β-hydroxyethyl terephthalate |
| KR1020067019510A KR100740059B1 (en) | 1999-08-04 | 1999-12-24 | Preparation and Purification Methods of Bis-β-hydroxyethyl terephthalate |
| CA002318761A CA2318761A1 (en) | 1999-08-04 | 1999-12-24 | Bis-beta-hydroxyethyl terephthalate production process and purification process |
| AT99961372T ATE275538T1 (en) | 1999-08-04 | 1999-12-24 | METHOD FOR PRODUCING OR PURIFYING BIS-(BETA)-HYDROXYETHYL TEREPHTHALATE |
| AU18005/00A AU764053B2 (en) | 1999-08-04 | 1999-12-24 | Methods for the preparation or purification of bis-beta-hydroxyethyl terephthalate |
| KR1020067019511A KR100740060B1 (en) | 1999-08-04 | 1999-12-24 | Preparation and Purification Methods of Bis-β-hydroxyethyl terephthalate |
| HK02101199.5A HK1040236A1 (en) | 1999-08-04 | 1999-12-24 | METHODS FOR THE PREPARATION OR PURIFICATION OF BIS- β -HYDROXYETHYL TEREPHTHALATE |
| CNB998114219A CN1195727C (en) | 1999-08-04 | 1999-12-24 | Method for producing and refining bis-β-hydroxyethyl terephthalate |
| PCT/JP1999/007284 WO2001010812A1 (en) | 1999-08-04 | 1999-12-24 | METHODS FOR THE PREPARATION OR PURIFICATION OF BIS-β-HYDROXYETHYL TEREPHTHALATE |
| ES99961372T ES2228142T3 (en) | 1999-08-04 | 1999-12-24 | PROCESS OF PRODUCTION OR PURIFICATION OF BIS- (BETA) -HYDROXIETIL TEREFTALATO. |
| TW089100024A TW506968B (en) | 1999-08-04 | 2000-01-03 | Bis-β-hydroxyethyl terephthalate production process and purification process |
| US10/623,002 US7193104B2 (en) | 1999-08-04 | 2003-07-18 | Bis-β-hydroxyethyl terephthalate production process and purification process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22603399A JP3782907B2 (en) | 1999-08-10 | 1999-08-10 | Process for producing bis-β-hydroxyethyl terephthalate and / or its low condensate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001048834A JP2001048834A (en) | 2001-02-20 |
| JP3782907B2 true JP3782907B2 (en) | 2006-06-07 |
Family
ID=16838731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22603399A Expired - Lifetime JP3782907B2 (en) | 1999-08-04 | 1999-08-10 | Process for producing bis-β-hydroxyethyl terephthalate and / or its low condensate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3782907B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264804C (en) | 2002-06-04 | 2006-07-19 | 株式会社爱维塑 | Refining method of bis(2-hydroxyethyl) terephthalate |
| KR101296226B1 (en) * | 2009-08-13 | 2013-08-13 | 웅진케미칼 주식회사 | Recycled polyester using waste polyester and method thereof |
-
1999
- 1999-08-10 JP JP22603399A patent/JP3782907B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001048834A (en) | 2001-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100740059B1 (en) | Preparation and Purification Methods of Bis-β-hydroxyethyl terephthalate | |
| US6472557B1 (en) | Process for recycling polyesters | |
| WO1999020684A1 (en) | Depolymerization process for recycling polyesters | |
| US7030264B1 (en) | Bis-β-hydroxyethyl terephthalate | |
| CA2355309C (en) | Method of polymerizing deionized bis-.beta.-hydroxyethyl terephthalate | |
| JPWO2001029110A1 (en) | Polymerization method for deionized bis-β-hydroxyethyl terephthalate | |
| JP2002121173A (en) | Crude bis-β-hydroxyethyl terephthalate purification method and purified bis-β-hydroxyethyl terephthalate | |
| JP2006016548A (en) | Method for producing polyester | |
| JP3782907B2 (en) | Process for producing bis-β-hydroxyethyl terephthalate and / or its low condensate | |
| JP3987724B2 (en) | Method for removing titanium oxide or bengara from ethylene glycol degradation products of polyester containing titanium oxide or bengara | |
| AU2575400A (en) | Novel sulforhamnosylacylglycerol derivatives and use thereof as medicaments | |
| JP3782906B2 (en) | Crude bis-β-hydroxyethyl terephthalate purification method | |
| JP3782905B2 (en) | Method for purifying crude bis-β-hydroxyethyl terephthalate and purified bis-β-hydroxyethyl terephthalate | |
| JPWO2001019775A1 (en) | Method for removing titanium oxide or red iron oxide from ethylene glycol decomposition products of polyester containing titanium oxide or red iron oxide | |
| JP2005105091A (en) | Polyalkylene terephthalate waste treatment body and treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051212 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060131 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060306 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060313 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3782907 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090317 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090317 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100317 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100317 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110317 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120317 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130317 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140317 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |