JP2007099910A - Gas flow reactor and method for producing high molecular weight polyketone using the reactor - Google Patents
Gas flow reactor and method for producing high molecular weight polyketone using the reactor Download PDFInfo
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- JP2007099910A JP2007099910A JP2005292105A JP2005292105A JP2007099910A JP 2007099910 A JP2007099910 A JP 2007099910A JP 2005292105 A JP2005292105 A JP 2005292105A JP 2005292105 A JP2005292105 A JP 2005292105A JP 2007099910 A JP2007099910 A JP 2007099910A
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- Prior art keywords
- gas
- polyketone
- molecular weight
- reaction tank
- high molecular
- Prior art date
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- 229920001470 polyketone Polymers 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 21
- 150000002941 palladium compounds Chemical class 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 230000037048 polymerization activity Effects 0.000 abstract description 28
- 239000007789 gas Substances 0.000 description 103
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 57
- 238000006116 polymerization reaction Methods 0.000 description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 16
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 14
- 229910052763 palladium Inorganic materials 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- -1 (2-methoxyphenyl) phosphino Chemical group 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000001294 propane Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- SXXPTCXIFIOPQF-UHFFFAOYSA-N 3-bis(2-methoxyphenyl)phosphanylpropyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CCCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC SXXPTCXIFIOPQF-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052696 pnictogen Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000003586 protic polar solvent Substances 0.000 description 4
- 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 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 238000012685 gas phase polymerization Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZDJMEIUMFOTGDV-UHFFFAOYSA-N [2-[bis(2-methoxyphenyl)phosphanylmethyl]phenyl]methyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CC1=CC=CC=C1CP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC ZDJMEIUMFOTGDV-UHFFFAOYSA-N 0.000 description 2
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
【課題】一酸化炭素と少なくとも１つのエチレン性不飽和化合物を原料として、より安価な触媒系で、高いポリケトン重合活性を達成しつつ、優れた機械的、熱的特性を発現する固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンを製造し得るガス流通型反応器の提供。
【解決手段】下部に原料ガスを気泡として供給するための１つ以上の原料ガス供給口を有することを特徴とする反応槽（Ａ）、該反応槽（Ａ）より抜き出される余剰ガスから未反応原料ガスと溶媒とを分離する気液分離器（Ｂ）、該反応槽（Ａ）で生成した反応生成物を含むスラリーを抜き出して反応生成物を濾過・分離する濾過装置（Ｃ）、該気液分離器（Ｂ）で分離された未反応原料ガスを反応槽（Ａ）に循環させるための循環用配管及び循環ポンプを備えてなるガス流通型反応器。
【選択図】図１1. Intrinsic viscosity which exhibits excellent mechanical and thermal properties while achieving high polyketone polymerization activity in a cheaper catalyst system using carbon monoxide and at least one ethylenically unsaturated compound as raw materials Providing a gas flow reactor capable of producing a high molecular weight polyketone of 5 dl / g or more.
A reaction tank (A) having one or more source gas supply ports for supplying a source gas as bubbles in a lower part, and an excess gas extracted from the reaction tank (A) A gas-liquid separator (B) for separating the reaction raw material gas and the solvent, a filtration device (C) for extracting the slurry containing the reaction product produced in the reaction tank (A), and filtering and separating the reaction product, A gas flow reactor comprising a circulation pipe and a circulation pump for circulating the unreacted source gas separated by the gas-liquid separator (B) to the reaction tank (A).
[Selection] Figure 1
Description
本発明は、ポリケトンを重合する際に使用するガス流通型反応器と該反応器による高分子量ポリケトンの製造法に関する。更に詳しくは、一酸化炭素及び少なくとも１つのエチレン性不飽和化合物を含む原料ガスを任意の溶剤を充填した反応槽下部より気泡として供給し、より安価な触媒系で、高いポリケトン重合活性を達成しつつ、優れた機械的、熱的特性を発現する高分子量ポリケトンを製造し得るガス流通型反応器と該反応器を用いる高分子量ポリケトンの製造法に関するものである。 The present invention relates to a gas flow reactor used when polymerizing a polyketone and a method for producing a high molecular weight polyketone using the reactor. More specifically, a raw material gas containing carbon monoxide and at least one ethylenically unsaturated compound is supplied as bubbles from the lower part of the reaction tank filled with an arbitrary solvent, and high polyketone polymerization activity is achieved with a cheaper catalyst system. The present invention also relates to a gas flow reactor capable of producing a high molecular weight polyketone that exhibits excellent mechanical and thermal properties and a method for producing a high molecular weight polyketone using the reactor.
下記化学式（１）で表される（i）一酸化炭素由来のユニットと（ii）少なくとも１つのエチレン性不飽和化合物由来のユニットとからなる繰り返し単位が実質的に交互に連結した構造のポリケトンは、機械的性質及び熱的性質に優れ、耐摩耗性、耐薬品性、ガスバリア性も高く、さまざまな用途に有用な材料である事が知られている。 A polyketone having a structure in which a repeating unit consisting of (i) a unit derived from carbon monoxide and (ii) a unit derived from at least one ethylenically unsaturated compound represented by the following chemical formula (1) is substantially alternately connected. It is known to be a material useful for various applications because of its excellent mechanical and thermal properties, high wear resistance, chemical resistance and gas barrier properties.
特に、固有粘度が２．５ｄｌ／ｇ以上を有する高分子量ポリケトンは、より高い機械的特性、及び熱的特性を発現し、エンジニアリングプラスチック材や繊維素材としてより好適である。例えば、その耐磨耗性の高さから自動車のギア等の部品、耐薬品性及びガスバリア性の高さから軽量樹脂製ガソリンタンク等への利用が期待できる。また、繊維に応用する場合、高倍率の延伸が可能であり、その延伸方向に高度に配向した高強度・高弾性率を有する繊維が得られ、ベルト、ホースやタイヤコード等のゴム補強材や、コンクリート補強材等、建築材料や産業資材用途に有用である。 In particular, a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more expresses higher mechanical properties and thermal properties, and is more suitable as an engineering plastic material or a fiber material. For example, it can be expected to be used for parts such as automobile gears because of its high wear resistance, and for lightweight resin gasoline tanks because of its high chemical resistance and gas barrier properties. In addition, when applied to fibers, it is possible to stretch at a high magnification, and fibers having high strength and high elastic modulus highly oriented in the stretching direction can be obtained, and rubber reinforcing materials such as belts, hoses and tire cords, It is useful for building materials and industrial materials such as concrete reinforcement.
上記、機械的、熱的特性を有するポリケトンの重合方法は、その技術に関する多数の報告がなされている。多くの場合、その重合は、一酸化炭素と少なくとも１つのエチレン性不飽和化合物とを含む系において、メタノール等のアルコール溶媒中、パラジウム化合物と１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパンなどのリン系二座配位子と酸の陰イオンとからなる触媒系を用いて行うことを特徴としている。 The above-mentioned polymerization method of polyketone having mechanical and thermal properties has been reported in many respects. In many cases, the polymerization is carried out in a system comprising carbon monoxide and at least one ethylenically unsaturated compound in an alcohol solvent such as methanol and 1,3-bis {di (2-methoxyphenyl) phosphino. } It is characterized by using a catalyst system comprising a phosphorus bidentate ligand such as propane and an anion of an acid.
例えば、バッチ式反応器を用いて一酸化炭素とエチレンとからなる原料ガスの一定圧力下（４〜８ＭＰa）、メタノール等のアルコール溶媒中、パラジウム化合物と１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパンなどのリン系二座配位子と酸（例えば、硫酸など）の陰イオンとからなる触媒系で重合を行う製造方法では、重合活性が１．１〜１０．２ｋｇ／ｇ−Ｐｄ・ｈｒと触媒当りのポリケトンの収量は高いが、得られるポリマーの分子量が低く、この技術では固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンを得ることができない（例えば、特許文献１、特許文献２参照）。 For example, a palladium compound and 1,3-bis {di (2-methoxy) in an alcohol solvent such as methanol under a constant pressure (4 to 8 MPa) of a raw material gas composed of carbon monoxide and ethylene using a batch reactor. In the production method in which polymerization is carried out in a catalyst system comprising a phosphorus bidentate ligand such as phenyl) phosphino} propane and an anion of an acid (for example, sulfuric acid), the polymerization activity is 1.1 to 10.2 kg / g. Although the yield of polyketone per catalyst and Pd · hr is high, the resulting polymer has a low molecular weight, and this technology cannot provide a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more (for example, Patent Document 1, Patent Document 2).
更に、同様のバッチ式反応器を用いて９０℃、８ＭＰａ以上という高温高圧条件でポリケトンの重合を行う製造方法が開示されている（例えば、特許文献３参照）。この方法によると、単位パラジウムあたりの重合活性は３０ｋｇ／ｇ−Ｐｄ・ｈｒに達する。しかしながら、固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンは得られていない。 Furthermore, a production method is disclosed in which a polyketone is polymerized under high temperature and high pressure conditions of 90 ° C. and 8 MPa or more using a similar batch reactor (see, for example, Patent Document 3). According to this method, the polymerization activity per unit palladium reaches 30 kg / g-Pd · hr. However, no high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more has been obtained.
一方、バッチ式反応器を用いてパラジウム化合物とリン系二座配位子及び、より酸性度の高い酸（例えば、トリフルオロ酢酸など）からなる触媒で重合を行う製造方法を用いると、単位パラジウムあたりの重合活性は６．８ｋｇ／ｇ−Ｐｄ・ｈｒ以上にまで向上するが、固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンは得られていない（例えば、特許文献４参照）。 On the other hand, when a production method in which polymerization is carried out using a catalyst comprising a palladium compound, a phosphorus bidentate ligand and a higher acidity acid (for example, trifluoroacetic acid) using a batch reactor, unit palladium The permeation polymerization activity is improved to 6.8 kg / g-Pd · hr or more, but no high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more has been obtained (for example, see Patent Document 4).
また、溶媒を必要としない気相重合技術を用いた製造方法も開示されている。例えば、パラジウム及び１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパンからなる有機金属錯体に、コバルトカルボレート等の硼素化合物を加えた触媒による気相重合技術（例えば、特許文献５参照）、パラジウム及び１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパンからなる有機金属錯体に、過塩素酸金属塩を加えた触媒による気相重合技術（例えば、特許文献６参照）などがあり、触媒当りのポリケトンの収量はかなり高くなる。しかしながら、得られるポリケトンの分子量は５時間を超える長時間の重合を行って、ようやく固有粘度２〜３ｄｌ／ｇのポリケトンが得られるに過ぎず、加える金属塩は高価であり、効率及びその経済性に問題点を有する。
ここに挙げた製造方法で用いられているリン系二座配位子、１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパンは、合成が煩雑である上、非常に高価であり工業的プロセスでの使用には経済上の問題点を残している。
A production method using a gas phase polymerization technique that does not require a solvent is also disclosed. For example, a gas phase polymerization technique using a catalyst in which a boron compound such as cobalt carbolate is added to an organometallic complex composed of palladium and 1,3-bis {di (2-methoxyphenyl) phosphino} propane (see, for example, Patent Document 5) ), A gas phase polymerization technique using a catalyst obtained by adding a perchloric acid metal salt to an organometallic complex composed of palladium and 1,3-bis {di (2-methoxyphenyl) phosphino} propane, etc. (see, for example, Patent Document 6) And the yield of polyketone per catalyst is quite high. However, the resulting polyketone has a molecular weight exceeding 5 hours, and only a polyketone having an intrinsic viscosity of 2 to 3 dl / g is finally obtained. The added metal salt is expensive, and the efficiency and economical efficiency Have problems.
The phosphorus-based bidentate ligand 1,3-bis {di (2-methoxyphenyl) phosphino} propane used in the production method described here is complicated and very expensive and industrial. Economic problems remain in the use of the process.
一方、高い固有粘度を有する高分子量ポリケトンの製造方法も開示されている。例えば、パラジウム化合物、１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパン及び酸の陰イオンとからなる触媒を用い、重合温度が７０℃という低い温度で重合する方法（例えば、特許文献１参照）、またパラジウム化合物、１，３−ビス（ジフェニルホスフィノ）プロパン及びボロン系弗化物の陰イオンとからなる触媒を用い、ｔｅｒｔ−ブタノール溶媒中で重合する方法（例えば、特許文献７参照）などである。しかし、いずれも高分子量化のために長時間の重合が必要であり、触媒活性が低く、生成するポリケトン中のパラジウム残渣が多い（単位パラジウム当りのポリケトン生成量が低い為）という問題点を有する。 On the other hand, a method for producing a high molecular weight polyketone having a high intrinsic viscosity is also disclosed. For example, a polymerization method using a catalyst comprising a palladium compound, 1,3-bis {di (2-methoxyphenyl) phosphino} propane and an anion of an acid at a polymerization temperature as low as 70 ° C. (for example, patent document) 1), and a polymerization method in a tert-butanol solvent using a catalyst comprising a palladium compound, 1,3-bis (diphenylphosphino) propane and anion of boron fluoride (see, for example, Patent Document 7) ) Etc. However, both of them have problems in that long-time polymerization is required for increasing the molecular weight, the catalytic activity is low, and there are many palladium residues in the resulting polyketone (because the amount of polyketone produced per unit palladium is low). .
更に、パラジウム化合物と、第１５族元素の原子を含む二座配位子と、ｐＫａが４以下の酸の陰イオンからなる触媒を用いて、イソプロパノール溶媒中に一酸化炭素と少なくとも１つのエチレン性不飽和化合物を共重合させ、２．５ｄｌ／ｇ以上の固有粘度を有する高分子量ポリケトンを製造する方法が開示されている（例えば、特許文献８参照）。しかし、この方法では触媒活性が十分ではないうえ、用いる触媒が高価であるという問題点を有する。
従って、一酸化炭素と少なくとも１つのエチレン性不飽和化合物を原料として、より安価な触媒系を用いて、高いポリケトン重合活性を達成しつつ、その固有粘度が２．５ｄｌ／ｇ以上を発現する高分子量ポリケトンを製造し得るポリケトンの製造方法の開発が望まれている。
Furthermore, using a catalyst comprising a palladium compound, a bidentate ligand containing an atom of a Group 15 element, and an anion of an acid having a pKa of 4 or less, carbon monoxide and at least one ethylenic acid in an isopropanol solvent A method for producing a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more by copolymerizing an unsaturated compound is disclosed (for example, see Patent Document 8). However, this method has problems that the catalytic activity is not sufficient and the catalyst used is expensive.
Therefore, using carbon monoxide and at least one ethylenically unsaturated compound as raw materials, using a cheaper catalyst system, while achieving high polyketone polymerization activity, the intrinsic viscosity is 2.5 dl / g or higher. Development of a method for producing a polyketone capable of producing a molecular weight polyketone is desired.
本発明の目的は、より安価な触媒系で、高いポリケトン重合活性を達成しつつ、優れた機械的、熱的特性を発現する固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンを製造し得るガス流通型反応器、及び該ガス流通型反応器を用いるポリケトンの製造方法を提供する事である。 An object of the present invention is to provide a gas capable of producing a high-molecular-weight polyketone having an intrinsic viscosity of 2.5 dl / g or more that exhibits excellent mechanical and thermal properties while achieving high polyketone polymerization activity with a cheaper catalyst system. It is to provide a flow type reactor and a method for producing a polyketone using the gas flow type reactor.
本発明者らは、前記課題を解決する為に鋭意検討を重ねた結果、下部に原料ガスを気泡として供給するための１つ以上の原料ガス供給口を有することを特徴とする反応槽（Ａ）と、気液分離器（Ｂ）、濾過装置（Ｃ）、循環用配管、及び循環ポンプからなる新規な構成のガス流通型反応器を用いて、一酸化炭素と少なくとも１つのエチレン性不飽和化合物を含む原料ガスを任意の溶剤を充填した反応槽（Ａ）下部より気泡として供給し、重合反応を行うことにより、より安価な触媒系で、高い重合活性を達成しつつ、固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンを製造し得るという驚くべき事実を見出し、本発明をなすに至った。 As a result of intensive studies to solve the above problems, the present inventors have one or more source gas supply ports for supplying source gas as bubbles in the lower part (A ), A gas-liquid separator (B), a filtration device (C), a circulation pipe, and a gas flow reactor having a novel configuration, and carbon monoxide and at least one ethylenic unsaturation Intrinsic viscosity is achieved while supplying a raw material gas containing a compound as bubbles from the lower part of the reaction tank (A) filled with an arbitrary solvent and carrying out a polymerization reaction, while achieving high polymerization activity with a cheaper catalyst system. The surprising fact that high molecular weight polyketone of 5 dl / g or more can be produced has been found, and the present invention has been made.
すなわち本発明は、新規なガス流通型反応器並びに該ガス流通型反応器及びパラジウム化合物と、第１５族の原子を有する二座配位子と、ｐＫａが４以下の酸の陰イオンとからなるより安価な触媒系を用いた固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンの製造法に関するものであり、その具体的な構成は以下に記載するとおりである。 That is, the present invention comprises a novel gas flow reactor, the gas flow reactor and a palladium compound, a bidentate ligand having a group 15 atom, and an anion of an acid having a pKa of 4 or less. The present invention relates to a method for producing a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more using a cheaper catalyst system, and its specific configuration is as described below.
（１）下部に原料ガスを気泡として供給するための１つ以上の原料ガス供給口を有することを特徴とする反応槽（Ａ）、該反応槽（Ａ）より抜き出される余剰ガスから未反応原料ガスと溶媒とを分離する気液分離器（Ｂ）、該反応槽（Ａ）で生成した反応生成物を含むスラリーを抜き出して反応生成物を濾過・分離する濾過装置（Ｃ）、該気液分離器（Ｂ）で分離された未反応原料ガスを反応槽（Ａ）に循環させるための循環用配管及び循環ポンプを備えてなるガス流通型反応器。
（２）前記反応槽（Ａ）下部の原料ガス供給口が、微細孔構造を有する供給口で構成されていることを特徴とする（１）に記載のガス流通型反応器。
（３）（１）または（２）に記載のガス流通型反応器を用いて、パラジウム化合物、第１５族の原子を有する二座配位子、及び酸の陰イオンからなる触媒系の存在下に、溶剤を充填した反応槽（Ａ）中に一酸化炭素と少なくとも１つのエチレン性不飽和化合物を含む原料ガスを連続的に気泡として供給することにより、下記化学式（１）で示される、（i）一酸化炭素由来のユニットと（ii）少なくとも１つのエチレン性不飽和化合物由来のユニットとが実質的に交互に配置されるポリケトンを重合することを特徴とする高分子量ポリケトンの製造方法。
(1) A reaction tank (A) characterized by having one or more source gas supply ports for supplying source gas as bubbles in the lower part, unreacted from surplus gas extracted from the reaction tank (A) A gas-liquid separator (B) for separating the source gas and the solvent, a filtration device (C) for extracting the slurry containing the reaction product produced in the reaction tank (A), and filtering and separating the reaction product, A gas flow reactor comprising a circulation pipe and a circulation pump for circulating the unreacted source gas separated by the liquid separator (B) to the reaction tank (A).
(2) The gas flow reactor according to (1), wherein the raw material gas supply port at the lower part of the reaction tank (A) is constituted by a supply port having a fine pore structure.
(3) Using the gas flow reactor according to (1) or (2), in the presence of a catalyst system comprising a palladium compound, a bidentate ligand having a group 15 atom, and an acid anion In addition, a raw material gas containing carbon monoxide and at least one ethylenically unsaturated compound is continuously supplied as bubbles in a reaction tank (A) filled with a solvent, and is represented by the following chemical formula (1). A method for producing a high molecular weight polyketone, comprising polymerizing a polyketone in which i) units derived from carbon monoxide and (ii) units derived from at least one ethylenically unsaturated compound are substantially alternately arranged.
（４）（３）に記載の高分子量ポリケトンの製造方法によって得られる固有粘度が２．５〜３０ｄｌ／ｇである高分子量ポリケトン。 (4) A high molecular weight polyketone having an intrinsic viscosity of 2.5 to 30 dl / g obtained by the method for producing a high molecular weight polyketone according to (3).
本発明のガス流通型反応器は、パラジウム化合物と、第１５族の原子を有する二座配位子と、ｐＫａが４以下の酸の陰イオンとからなるより安価な触媒系で、高いポリケトン重合活性を達成するとともに、固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンを製造する事を可能とする。 The gas flow reactor of the present invention is a more inexpensive catalyst system comprising a palladium compound, a bidentate ligand having a Group 15 atom, and an anion of an acid having a pKa of 4 or less, and high polyketone polymerization. While achieving the activity, it is possible to produce a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more.
本発明のポリケトンの重合に用いる新規なガス流通型反応器、及びそのガス流通型反応器を用いるポリケトンの製造方法を以下でより詳細に説明する。
図１に本発明のガス流通型反応器（以下、単に「反応器」ともいう）の装置の構成例を示す。
本発明の新規な反応器は、下部に原料ガスを気泡として供給するための１つ以上の原料ガス供給口を有することを特徴とする反応槽（Ａ）、該反応槽（Ａ）より抜き出される余剰ガスから未反応原料ガスと溶媒とを分離する気液分離器（Ｂ）、該反応槽（Ａ）で生成した反応生成物を含むスラリーを抜き出して反応生成物を濾過・分離する濾過装置（Ｃ）、該気液分離器（Ｂ）で分離された未反応原料ガスを反応槽（Ａ）に循環させるための循環用配管及び循環ポンプを備えてなり、一酸化炭素と少なくとも１つのエチレン性不飽和化合物を含む原料ガスが、パラジウム化合物、第１５族の原子を有する二座配位子、酸の陰イオンからなる触媒系を含む溶剤で充填された反応槽中に下部より気泡として（連続的に）供給される事が特徴である。
The novel gas flow reactor used for the polymerization of the polyketone of the present invention and the method for producing the polyketone using the gas flow reactor will be described in more detail below.
FIG. 1 shows a configuration example of an apparatus of a gas flow type reactor (hereinafter also simply referred to as “reactor”) of the present invention.
The novel reactor of the present invention has one or more source gas supply ports for supplying source gas as bubbles in the lower part, and is extracted from the reaction tank (A) and the reaction tank (A). Gas-liquid separator (B) for separating the unreacted raw material gas and the solvent from the surplus gas, and a filtration device for extracting the slurry containing the reaction product generated in the reaction tank (A) and filtering and separating the reaction product (C) comprising a circulation pipe and a circulation pump for circulating the unreacted raw material gas separated by the gas-liquid separator (B) to the reaction tank (A), and comprising carbon monoxide and at least one ethylene The raw material gas containing the organic unsaturated compound is bubbled from the bottom into a reaction tank filled with a palladium compound, a bidentate ligand having a group 15 atom, and a catalyst system comprising an acid anion ( It is characterized by being supplied continuously)
ポリケトン重合では、原料である一酸化炭素と少なくとも1つのエチレン性不飽和化合物とを気相状態で系に供給するが、実際には、反応器内の（与えられた温度、圧力条件下で）溶媒に溶解し得る溶解度分が重合反応に関与して生成物であるポリケトンを与える。従って、原料ガスの溶媒への速やかな溶解が、溶媒中に存在する触媒への原料供給律速を回避することにつながる。結果、得られるポリケトンの高分子量化、及び収率の向上（高い重合活性、即ち単位パラジウム当りポリケトン収量の増加を意味する）を期待できる。 In polyketone polymerization, the raw materials, carbon monoxide and at least one ethylenically unsaturated compound, are supplied to the system in the gas phase, but are actually in the reactor (under the given temperature and pressure conditions). The solubility that can be dissolved in the solvent is involved in the polymerization reaction to give the product polyketone. Therefore, the rapid dissolution of the raw material gas in the solvent leads to avoiding the rate of supply of the raw material to the catalyst present in the solvent. As a result, high molecular weight of the resulting polyketone and improvement in yield (high polymerization activity, meaning increase in polyketone yield per unit palladium) can be expected.
従来、バッチ式反応器では、附帯する攪拌装置を用い溶媒を高速攪拌することによって原料ガスの溶媒への溶解を促進させる手法が用いられていたが、溶媒へのガス溶解を支配する気−液界面積に限界があり、結果として満足し得るポリケトンの高分子量化、高い重合活性を発現するに至っていない。加えて、生成するポリケトンの攪拌器及び反応槽壁への付着・堆積などの問題があった。 Conventionally, in batch reactors, a method of promoting dissolution of a raw material gas in a solvent by stirring the solvent at high speed using an attached stirring device has been used, but the gas-liquid governing gas dissolution in the solvent is used. There is a limit to the interfacial area, and as a result, a high molecular weight polyketone and a high polymerization activity have not been achieved. In addition, there were problems such as adhesion and deposition of the generated polyketone on the stirrer and reaction vessel wall.
一方、本発明のガス流通型反応器では、上記原料ガスを溶媒を充填した反応槽内部に反応槽下部から気泡として供給する。この気泡サイズは、ガス供給口の孔径、孔数、及びガス流量（圧力）により制御される。気泡サイズを細かくするほど、バッチ式反応器と異なり溶媒へのガス溶解を支配する気−液界面積を増加させることが可能であり、結果として高い重合活性と得られるポリケトンの高分子量化を達成し得る。 On the other hand, in the gas flow reactor of the present invention, the raw material gas is supplied as bubbles from the bottom of the reaction tank into the reaction tank filled with the solvent. The bubble size is controlled by the hole diameter of the gas supply port, the number of holes, and the gas flow rate (pressure). The finer the bubble size, the higher the gas-liquid interfacial area governing gas dissolution in the solvent, unlike the batch reactor, resulting in higher polymerization activity and higher molecular weight of the resulting polyketone. Can do.
また、ガス流通型反応器は、従来のバッチ式反応器、連続式反応器と比較して、反応器に何ら攪拌装置を持たない点で決定的に異なる。すなわち、本発明のガス流通型反応器では、反応槽下部より気泡として供給される原料ガスのガス線速により生じる乱流で反応溶媒を攪拌、流動させることが可能であり、攪拌装置を必要としない極めて簡便な反応器であるといえる。このことは、反応槽内部に攪拌器等の突起物が存在しないために、不要なポリマーの付着・堆積をも減じることが可能である。 Further, the gas flow type reactor is decisively different from the conventional batch type reactor and continuous type reactor in that the reactor does not have any stirring device. That is, in the gas flow type reactor of the present invention, it is possible to stir and flow the reaction solvent by the turbulent flow generated by the gas linear velocity of the raw material gas supplied as bubbles from the lower part of the reaction tank, and a stirring device is required. It can be said that this is a very simple reactor. This is because there are no protrusions such as a stirrer in the reaction vessel, and therefore, unnecessary polymer adhesion / deposition can be reduced.
また、本発明のガス流通型反応器は回分式ガス流通型反応器としてだけではなく、パラジウム化合物、第１５族の原子を有する二座配位子、及び酸の陰イオンかなる触媒系、及び溶媒を反応槽中に連続的に追添するとともに、生成したポリケトンを連続的にスラリー抜き出し、濾過処理することにより連続式ガス流通型反応器としても使用することが可能である。 The gas flow reactor of the present invention is not only a batch gas flow reactor, but also a catalyst system comprising a palladium compound, a bidentate ligand having a group 15 atom, and an acid anion, and The solvent can be continuously added to the reaction tank, and the produced polyketone can be continuously extracted from the slurry and filtered to be used as a continuous gas flow reactor.
本発明のガス流通型反応器は、パラジウム化合物と、第１５族の原子を有する二座配位子と、ｐＫａが４以下の酸の陰イオンからなるより安価な触媒系で、従来のバッチ式反応器による重合と比較して、高いポリケトン重合活性を達成する事で生成するポリケトン中へのパラジウム残渣が低下するとともに、生成するポリケトンの反応器への付着を低減し、且つ固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンを製造する事を可能とする。
以下、本発明を（１）回分式ガス流通型反応器、（２）本発明で用いる重合方法、（３）本発明で製造される高分子量ポリケトン、の順に詳細に説明する。
The gas flow reactor of the present invention is a more inexpensive catalyst system comprising a palladium compound, a bidentate ligand having a group 15 atom, and an anion of an acid having a pKa of 4 or less, and is a conventional batch type. Compared with the polymerization by the reactor, the palladium residue in the polyketone produced by achieving high polyketone polymerization activity is reduced, the adhesion of the produced polyketone to the reactor is reduced, and the intrinsic viscosity is 2.5 dl. / G or higher molecular weight polyketone can be produced.
Hereinafter, the present invention will be described in detail in the order of (1) a batch type gas flow reactor, (2) a polymerization method used in the present invention, and (3) a high molecular weight polyketone produced in the present invention.
（１） ガス流通型反応器
一酸化炭素と少なくとも１つのエチレン性不飽和化合物を含む原料ガスをプロトン性溶剤、及び／又は非プロトン性溶剤を充填した反応槽（Ａ）下部より連続的、または間歇的に供給する。その時の原料ガス流量は常に一定であってもよいし、又は任意に変化させても構わない。この時、反応槽下部より継続的に供給される原料ガスのうち重合反応で消費されない余剰ガスは、溶媒を飛散・減少させないために気液分離機（Ｂ）を介して反応槽気相部より分離・継続的に抜出すことにより反応槽内圧力を一定に保持する。反応槽より分離・抜出された原料ガスは、適正ガス組成・圧力に調整・リサイクルした後、循環用配管を通り、再び反応槽下部より供給することができる。生成したポリケトンは、反応槽下部よりスラリーとして抜き出し、濾過装置（Ｃ）で濾過・分離される。
また、重合開始前に反応槽内を原料ガスでポリケトンの重合所定圧力まで昇圧後、重合を開始、重合により消費された原料ガス量のみを反応槽下部より供給、補充する半バッチ式での重合も可能である。ここでの継続的とは、ポリケトンの重合開始から、重合停止時までの重合反応間における連続的、または間歇的な原料ガス供給を意味する。
(1) Gas flow type reactor A raw material gas containing carbon monoxide and at least one ethylenically unsaturated compound is continuously added from the bottom of the reaction tank (A) filled with a protic solvent and / or an aprotic solvent, or Supply intermittently. The raw material gas flow rate at that time may be always constant or may be arbitrarily changed. At this time, surplus gas which is not consumed in the polymerization reaction among the raw material gas continuously supplied from the lower part of the reaction tank is removed from the gas phase part of the reaction tank via the gas-liquid separator (B) in order not to scatter and reduce the solvent. The pressure in the reaction vessel is kept constant by separating and continuously withdrawing. The raw material gas separated / extracted from the reaction tank can be adjusted / recycled to an appropriate gas composition / pressure, and then can be supplied again from the lower part of the reaction tank through the circulation pipe. The produced polyketone is extracted as a slurry from the lower part of the reaction tank, and is filtered and separated by the filtration device (C).
In addition, the pressure inside the reaction vessel is increased to the predetermined pressure of polyketone with the raw material gas before the polymerization is started, the polymerization is started, and only the amount of the raw material gas consumed by the polymerization is supplied and replenished from the lower part of the reaction vessel. Is also possible. The term “continuous” as used herein means continuous or intermittent supply of raw material gas during the polymerization reaction from the start of polymerization of the polyketone to the end of the polymerization.
本発明の反応器において、一酸化炭素と少なくとも１つのエチレン性不飽和化合物とを含む原料ガスを任意の溶剤を充填した反応槽下部より反応槽内へ気泡として供給する必要があるが、その時の原料ガスを供給する供給口形式に特に制限はない。例えば、通常の配管などによる大口径の供給口からの原料ガス供給であったり、複数の供給口となる細孔を有する多孔板を介した原料ガス供給などを選択することが可能である。特に、複数の供給口を用いる場合、その供給口の数には特に制限はなく、重合温度や重合圧力などの条件、触媒量、重合させる分子量などの範囲等によっても異なる。通常、ポリケトンを重合活性２０ｋｇ／ｇ−Ｐｄ・ｈｒ以上で製造するには１〜１０箇所の原料ガス供給口を配することが好ましい。より好ましくは、その供給口を多孔板などの複数の細孔を持つものにするである。 In the reactor of the present invention, it is necessary to supply a raw material gas containing carbon monoxide and at least one ethylenically unsaturated compound as bubbles from the lower part of the reaction tank filled with an arbitrary solvent into the reaction tank. There is no particular limitation on the supply port type for supplying the source gas. For example, it is possible to select a source gas supply from a large-diameter supply port such as a normal pipe or a source gas supply via a perforated plate having pores serving as a plurality of supply ports. In particular, when a plurality of supply ports are used, the number of supply ports is not particularly limited, and varies depending on conditions such as polymerization temperature and polymerization pressure, a catalyst amount, a range of molecular weight to be polymerized, and the like. Usually, in order to produce a polyketone with a polymerization activity of 20 kg / g-Pd · hr or more, it is preferable to provide 1 to 10 raw material gas supply ports. More preferably, the supply port has a plurality of pores such as a perforated plate.
この多孔板の孔形は、通常、円状、長円状、三角形状、スリット状、多角形状、星型状などの任意な形状から選ばれる。孔径は、通常、０．１μｍ〜３ｃｍ程度であり、より好ましくは０．１μｍ〜０．１ｃｍであり、更に好ましくは０．１μｍ〜０．０１ｃｍである。孔と孔の間隔は任意の距離で構わず、原料ガス供給口の位置は反応器内へ充填された重合溶媒の液深の半分以下にある事が好ましいが、より好ましくは反応槽下部、特に好ましくは反応槽底面にある事である。更に、好ましくは底面全体に均一に細孔が分散している事である。多孔板の材質は通常、ステンレススチール製、カーボンスチール製、ハステロイ製、チタン製、セラミック製、その他の合金製等の様々な材質から選択することが可能である。
図２に本発明のガス流通型反応器における反応槽（Ａ）の一例の模式図を示す。
図２に示した反応槽においては原料ガス供給口を微細孔構造を有する多孔質焼結板（焼結フィルター）から構成し、原料ガスを微細な気泡として反応槽中の溶媒と接触させている。
The hole shape of the perforated plate is usually selected from arbitrary shapes such as a circular shape, an oval shape, a triangular shape, a slit shape, a polygonal shape, and a star shape. The pore diameter is usually about 0.1 μm to 3 cm, more preferably 0.1 μm to 0.1 cm, and still more preferably 0.1 μm to 0.01 cm. The distance between the holes may be an arbitrary distance, and the position of the raw material gas supply port is preferably not more than half the depth of the polymerization solvent charged in the reactor, more preferably at the bottom of the reaction tank, particularly Preferably, it is at the bottom of the reaction vessel. Furthermore, it is preferable that the pores are uniformly dispersed over the entire bottom surface. The material of the perforated plate can usually be selected from various materials such as stainless steel, carbon steel, hastelloy, titanium, ceramic, and other alloys.
FIG. 2 shows a schematic diagram of an example of the reaction tank (A) in the gas flow reactor of the present invention.
In the reaction tank shown in FIG. 2, the raw material gas supply port is composed of a porous sintered plate (sintered filter) having a fine pore structure, and the raw material gas is brought into contact with the solvent in the reaction tank as fine bubbles. .
原料ガスとして供給する一酸化炭素と少なくとも１つのエチレン性不飽和化合物とを含むガスの流量は、反応槽供給口の供給口の数、孔径、及び反応圧力などの重合条件によってその好適な値が異なるため、一概にその範囲を定めることはできないが、単位溶媒量（１Ｌ）当り１ＮＬ／ｈr〜３０００ＮＬ／ｈｒ程度供給することが好ましい。
本発明のガス流通型反応器を用いると、従来のバッチ式反応器を用いる場合より重合活性が高く、且つ高分子量のポリマーが得られることを確認した。また、不要なポリマーの付着・堆積がないことも確認した。
The flow rate of the gas containing carbon monoxide and at least one ethylenically unsaturated compound supplied as the raw material gas has a suitable value depending on the polymerization conditions such as the number of supply ports of the reaction tank supply port, the hole diameter, and the reaction pressure. However, the range cannot be generally defined, but it is preferable to supply about 1 NL / hr to 3000 NL / hr per unit solvent amount (1 L).
When the gas flow reactor of the present invention was used, it was confirmed that a polymer having a higher polymerization activity and a higher molecular weight was obtained than when a conventional batch reactor was used. It was also confirmed that there was no unnecessary polymer adhesion / deposition.
（２）本発明で用いる重合方法
本発明では、一酸化炭素と少なくとも１つのエチレン性不飽和化合物を含む原料ガスを本発明のガス流通型反応器の反応槽下部より気泡として添加し、固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンを製造することができる。
エチレン性不飽和化合物の具体例としては、エチレン；プロピレン、１−ブテン、１−ヘキセン、１−オクテン、１−デセン等の炭素数３〜２０のα−オレフィン；イソブテン等のビニリデン化合物；スチレン、α−メチルスチレン等のアルケニル芳香族化合物；シクロペンテン、シクロヘキセン、ノルボルネン、５−メチルノルボルネン、テトラシクロドデセン、トリシクロデセン、ペンタシクロペンタデセン、ペンタシクロヘキサデセン等の環状オレフィン；塩化ビニル等のハロゲン化ビニル；エチルアクリレート、メチルメタクリレート等のアクリル酸エステル等を挙げることができる。これらのエチレン性不飽和化合物は１種単独又は２種以上組み合わせて用いることができる。これらエチレン性不飽和化合物の中で、エチレン及び／又は炭素数３〜２０のα−オレフィンの使用が得られる高分子量ポリケトンの機械的、熱的特性に優れる点で好ましい。
(2) Polymerization method used in the present invention In the present invention, a raw material gas containing carbon monoxide and at least one ethylenically unsaturated compound is added as bubbles from the lower part of the reaction tank of the gas flow reactor of the present invention, and intrinsic viscosity is obtained. A high molecular weight polyketone of 2.5 dl / g or more can be produced.
Specific examples of the ethylenically unsaturated compound include: ethylene; α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-hexene, 1-octene and 1-decene; vinylidene compound such as isobutene; styrene, Alkenyl aromatic compounds such as α-methylstyrene; Cyclic olefins such as cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, tetracyclododecene, tricyclodecene, pentacyclopentadecene, pentacyclohexadecene; halogenation such as vinyl chloride Examples of vinyl include acrylic acid esters such as ethyl acrylate and methyl methacrylate. These ethylenically unsaturated compounds can be used singly or in combination of two or more. Among these ethylenically unsaturated compounds, ethylene and / or α-olefins having 3 to 20 carbon atoms are preferred because they are excellent in mechanical and thermal properties of high molecular weight polyketones.
反応に際して、一酸化炭素と少なくとも１つのエチレン性不飽和化合物とを含む原料ガスのガス流通型反応器へのガス供給方法には特に制限はなく、予め、両者を混合してから一つの供給ラインを用いて添加してもよく、また、それぞれ別の供給ラインを用いて添加してもよい。
また、一酸化炭素と少なくとも1つのエチレン性不飽和化合物を含む原料ガスの、本発明のガス流通型反応器内への供給割合に特に制限はないが、好ましくは［エチレン性不飽和化合物／一酸化炭素］のモル比が０．１〜１０の範囲にある。さらに好ましくは０．２〜５の範囲にある。
In the reaction, there is no particular limitation on the gas supply method of the raw material gas containing carbon monoxide and at least one ethylenically unsaturated compound to the gas flow reactor, and both are mixed in advance before one supply line. Or may be added using separate supply lines.
Also, there is no particular limitation on the supply ratio of the raw material gas containing carbon monoxide and at least one ethylenically unsaturated compound into the gas flow reactor of the present invention, but preferably [ethylenically unsaturated compound / one The molar ratio of carbon oxide] is in the range of 0.1-10. More preferably, it exists in the range of 0.2-5.
重合反応を行うに当たって、溶剤としてプロトン性溶剤、及び／又は非プロトン性溶剤を用いることができる。プロトン性の溶剤としては、水、炭素数１〜１０のヒドロキシル基含有化合物等が挙げられ、具体的には、メタノール、エタノール、１‐プロパノール、２‐プロパノール、ブタノール、ヘキサフルオロイソプロパノール、ベンジルアルコール；エチレングリコール等のアルコール類；ｍ−クレゾール等のフェノール類を挙げることができる。 In carrying out the polymerization reaction, a protic solvent and / or an aprotic solvent can be used as the solvent. Examples of the protic solvent include water, a hydroxyl group-containing compound having 1 to 10 carbon atoms, specifically, methanol, ethanol, 1-propanol, 2-propanol, butanol, hexafluoroisopropanol, benzyl alcohol; Examples include alcohols such as ethylene glycol; and phenols such as m-cresol.
また、非プロトン性溶剤としては、炭素数３〜２０の炭化水素；アセトン、メチルエチルケトン等のケトン類；ジエチルエーテル、テトラヒドロフラン、ジグライム等のエーテル類；アセトニトリル等のニトリル類；酢酸、酢酸メチル、酢酸エチル等のエステル類；クロロホルム、塩化メチレン、１，１、２，２−テトラクロロエタン等のハロゲン化炭化水素；トルエン、ＤＭＦ、ＤＭＳＯ、γ−ブチロラクトン、Ｎ−メチルピロリドン等を挙げることができる。 Examples of aprotic solvents include hydrocarbons having 3 to 20 carbon atoms; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, tetrahydrofuran and diglyme; nitriles such as acetonitrile; acetic acid, methyl acetate and ethyl acetate. Esters such as: halogenated hydrocarbons such as chloroform, methylene chloride, 1,1,2,2-tetrachloroethane; toluene, DMF, DMSO, γ-butyrolactone, N-methylpyrrolidone, and the like.
反応活性の点からは、プロトン性溶剤の使用が好ましく、水、メタノール、エタノール、２‐プロパノールが好適である。一方、得られるポリケトンの分子量が高くできるという点からは、非プロトン性溶剤が好ましく、ヘキサン、アセトン、メチルエチルケトンが好適である。これらの溶剤の中から選ばれた２種以上の溶剤を同時に用いてもよい。 From the viewpoint of reaction activity, use of a protic solvent is preferable, and water, methanol, ethanol, and 2-propanol are preferable. On the other hand, from the viewpoint that the molecular weight of the resulting polyketone can be increased, an aprotic solvent is preferred, and hexane, acetone, and methyl ethyl ketone are preferred. Two or more solvents selected from these solvents may be used simultaneously.
本発明では、ポリケトン重合に際し、有機金属錯体からなる触媒系を用いて重合反応を行うことが好適である。
ポリケトンの重合に用いる触媒系としては、周期律表（無機化学命名法（１９９３）東京化学同人）の第１０族元素であるパラジウムを含む化合物、及び第１５族元素の原子を有する二座配位子、並びにｐＫａが４以下の酸の陰イオンとから調製される金属錯体からなる触媒系である。
In the present invention, it is preferable to perform a polymerization reaction using a catalyst system composed of an organometallic complex in the polyketone polymerization.
The catalyst system used for the polymerization of the polyketone includes a compound containing palladium which is a group 10 element of the periodic table (inorganic chemical nomenclature (1993) Tokyo Kagaku Dojin), and a bidentate coordination having atoms of a group 15 element. And a catalyst system comprising a metal complex prepared from an anion of an acid having a pKa of 4 or less.
パラジウム化合物として、パラジウムのカルボン酸塩、リン酸塩、カルバミン酸塩、スルホン酸塩等を挙げることができ、その具体例としては、酢酸パラジウム、トリフルオロ酢酸パラジウム、パラジウムアセチルアセトネート、塩化パラジウム、ビス（Ｎ，Ｎ−ジエチルカーバメート）ビス（ジエチルアミノ）パラジウム、硫酸パラジウム等を挙げることができる。これらは単独又は数種類を混合して用いることもできる。
第１５族元素の原子を有する二座配位子における配位子とは、化学大辞典７縮刷版第１６刷（１９７４）共立出版ｐ．４で定義されているように、錯体中で中心原子に直接結合している原子を含む原子団のことをいい、結合している原子が二つのものを二座配位子という。
Examples of the palladium compound include palladium carboxylates, phosphates, carbamates, sulfonates, etc. Specific examples thereof include palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, palladium chloride, Bis (N, N-diethylcarbamate) bis (diethylamino) palladium, palladium sulfate and the like can be mentioned. These can be used alone or in combination.
The ligand in the bidentate ligand having an atom of a Group 15 element refers to the Chemical Dictionary, 7th edition, 16th edition (1974) Kyoritsu Shuppan. As defined in 4, it refers to an atomic group containing an atom directly bonded to a central atom in a complex, and two bonded atoms are called a bidentate ligand.
本発明における配位子として、第１５族の原子を有する配位子が好ましく、その例として、ピリジン等の窒素の一座配位子；トリフェニルホスフィン、トリナフチルホスフィン等のリン一座配位子；トリフェニルアルシン等の砒素一座配位子；トリフェニルアンチモニイ等のアンチモン一座配位子；２，２’−ビピリジル、４，４’−ジメチル−２，２’−ビピリジル、２，２’−ビ−４−ピコリン、２，２’−ビキノリン等の窒素二座配位子；１，２−ビス（ジフェニルホスフィノ）エタン、１，３−ビス（ジフェニルホスフィノ）プロパン、１，４−ビス（ジフェニルホスフィノ）ブタン、１，３−ビス｛ジ（２−メチル）ホスフィノ｝プロパン、１，３−ビス｛ジ（２−イソプロピル）ホスフィノ｝プロパン、１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパン、１，３−ビス｛ジ（２−メトキシ−４−スルホン酸ナトリウム−フェニル）ホスフィノ｝プロパン、１，２−ビス（ジフェニルホスフィノ）シクロヘキサン、１，２−ビス（ジフェニルホスフィノ）ベンゼン、１，２−ビス｛（ジフェニルホスフィノ）メチル｝ベンゼン、１，２−ビス［｛ジ（２−メトキシフェニル）ホスフィノ｝メチル］ベンゼン、１，２−ビス［｛ジ（２−メトキシ−４−スルホン酸ナトリウム−フェニル）ホスフィノ｝メチル］ベンゼン、１，１’−ビス（ジフェニルホスフィノ）フェロセン、２−ヒドロキシ−１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパン、２，２−ジメチル−１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパン等のリン二座配位子等を挙げることができる。 As the ligand in the present invention, a ligand having a Group 15 atom is preferable. Examples thereof include a monodentate ligand of nitrogen such as pyridine; a phosphorus monodentate ligand such as triphenylphosphine and trinaphthylphosphine; Arsenic monodentate ligands such as triphenylarsine; antimony monodentate ligands such as triphenylantimony; 2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl, 2,2′-bi Nitrogen bidentate ligands such as -4-picoline and 2,2′-biquinoline; 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis ( Diphenylphosphino) butane, 1,3-bis {di (2-methyl) phosphino} propane, 1,3-bis {di (2-isopropyl) phosphino} propane, 1,3-bis {di (2- Toxiphenyl) phosphino} propane, 1,3-bis {di (sodium 2-methoxy-4-sulfonate-phenyl) phosphino} propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenyl) Phosphino) benzene, 1,2-bis {(diphenylphosphino) methyl} benzene, 1,2-bis [{di (2-methoxyphenyl) phosphino} methyl] benzene, 1,2-bis [{di (2 Sodium methoxy-4-sulfonate-phenyl) phosphino} methyl] benzene, 1,1′-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis {di (2-methoxyphenyl) phosphino} propane 2,2-dimethyl-1,3-bis {di (2-methoxyphenyl) phosphino} propane, etc. Mention may be made of the emissions bidentate ligand, and the like.
これらの中で、より好ましい配位子はリン二座配位子であり、１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパン、及び１，２−ビス［｛ジ（２−メトキシフェニル）ホスフィノ｝メチル］ベンゼン、２−ヒドロキシ−１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパン、及び２，２−ジメチル−１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパン、１，３−ビス｛ジ（２−メトキシ−４−スルホン酸ナトリウム−フェニル）ホスフィノ｝プロパン、及び１，２−ビス［｛ジ（２−メトキシ−４−スルホン酸ナトリウム−フェニル）ホスフィノ｝メチル］ベンゼン、１，３−ビス（ジフェニルホスフィノ）プロパン及び１，４−ビス（ジフェニルホスフィノ）ブタンを挙げることができる。なかでも１，３−ビス（ジフェニルホスフィノ）プロパンが、その合成の簡便さと、それを含む触媒系を用いて重合した際の、ポリケトンの収量、分子量、及び物性のバランスに優れることから最も好ましい。 Among these, more preferred ligands are phosphorus bidentate ligands, such as 1,3-bis {di (2-methoxyphenyl) phosphino} propane and 1,2-bis [{di (2-methoxy Phenyl) phosphino} methyl] benzene, 2-hydroxy-1,3-bis {di (2-methoxyphenyl) phosphino} propane, and 2,2-dimethyl-1,3-bis {di (2-methoxyphenyl) phosphino } Propane, 1,3-bis {di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino} propane, and 1,2-bis [{di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] } Methyl] benzene, 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane. Of these, 1,3-bis (diphenylphosphino) propane is most preferred because of its excellent balance between the ease of synthesis and the yield, molecular weight, and physical properties of polyketone when polymerized using a catalyst system containing the same. .
ｐＫａが４以下の酸の陰イオンの例として、トリフルオロ酢酸、メタンスルホン酸、トリフルオロメタンスルホン酸、ｐ−トルエンスルホン酸等のｐＫａが４以下の有機酸の陰イオン；過塩素酸、硫酸、硝酸、リン酸、ヘテロポリ酸、テトロフルオロ硼酸、ヘキサフルオロリン酸、フルオロ硅酸等のｐＫａが４以下の無機酸の陰イオン；トリスペンタフルオロフェニルボラン、トリスフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ−ジメチルアニリウムテトラキス（ペンタフルオロフェニル）ボレート等の硼素化合物の陰イオンを挙げることができ、単独もしくは複数種を混合しても使用できる。
これらの中で、好ましい酸の陰イオンはポリケトンの収量と分子量の両方において、硫酸、メタンスルホン酸、トリフルオロメタンスルホン酸である。ここで、ｐＫａとは、酸の解離定数をＫａとしたときのｐＫａ＝−ｌｏｇ１０Ｋａで定義される数値で、値が小さいほど酸として強い。
Examples of an anion of an acid having a pKa of 4 or less include anions of organic acids having a pKa of 4 or less, such as trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; perchloric acid, sulfuric acid, Anions of inorganic acids such as nitric acid, phosphoric acid, heteropolyacid, tetrofluoroboric acid, hexafluorophosphoric acid, fluorosuccinic acid and the like whose pKa is 4 or less; trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate Anions of boron compounds such as N, N-dimethylanilium tetrakis (pentafluorophenyl) borate can be used, and these can be used alone or in combination.
Of these, the preferred acid anions are sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid in both polyketone yield and molecular weight. Here, pKa is a numerical value defined by pKa = −log 10 Ka where the acid dissociation constant is Ka, and the smaller the value, the stronger the acid.
触媒として用いるパラジウム化合物の使用量は、選ばれるエチレン性不飽和化合物の種類や他の重合条件によってその好適な値が異なるため、一概にその範囲を定めることはできないが、好ましくは、反応帯域の容量１リットル当り０．０１〜１００００マイクロモル、より好ましくは、０．１〜１０００マイクロモルである。ここで、反応帯域の容量とは、反応器の液相の容量をいう。
配位子の使用量は限定されないが、パラジウム化合物１モル当たり、好ましくは、０．１〜１０モル、より好ましくは、１〜３モルである。
ｐＫａが４以下の酸の陰イオンの使用量は、パラジウム１モル当たり、好ましくは０．０１〜１００００モル、より好ましくは０．１〜１０００モルである。
The amount of the palladium compound used as a catalyst varies depending on the type of ethylenically unsaturated compound selected and other polymerization conditions, and therefore the range cannot generally be determined. It is 0.01 to 10000 micromoles per liter of volume, more preferably 0.1 to 1000 micromoles. Here, the capacity of the reaction zone refers to the capacity of the liquid phase of the reactor.
Although the usage-amount of a ligand is not limited, Preferably it is 0.1-10 mol per mol of palladium compounds, More preferably, it is 1-3 mol.
The amount of the anion of the acid having a pKa of 4 or less is preferably 0.01 to 10000 mol, more preferably 0.1 to 1000 mol, per mol of palladium.
本発明の触媒系は、特定量の液状媒体（水を含む）の中で、パラジウム化合物と、第１５族元素の原子を有する二座配位子と、ｐＫａが４以下の酸の陰イオンとを接触させることにより形成される。接触させる方法としては、任意の方法を採用し得る。例えば、前記の３成分を、適当な溶媒中に、予め混合した溶液として用いてもよいし、重合系へ３成分を、各々、別々に供給して、重合系内で接触させてから用いてもよい。
また、パラジウム化合物と、第１５族元素の原子を有する二座配位子とを予め反応させて得られる錯体と、ｐＫａが４以下の酸の陰イオンとを接触させて用いてもよい。
The catalyst system of the present invention comprises a palladium compound, a bidentate ligand having an atom of a Group 15 element, an anion of an acid having a pKa of 4 or less in a specific amount of a liquid medium (including water). It is formed by contacting. Arbitrary methods can be adopted as the contact method. For example, the above three components may be used as a premixed solution in an appropriate solvent, or each of the three components may be separately supplied to the polymerization system and contacted in the polymerization system. Also good.
Alternatively, a complex obtained by reacting a palladium compound with a bidentate ligand having an atom of a Group 15 element in advance and an anion of an acid having a pKa of 4 or less may be used.
さらに、前記３成分からなる触媒系にベンゾキノン、ナフトキノン等の酸化剤を添加して用いてもよい。これらキノン類の添加量は、遷移金属化合物１モル当たり、好ましくは１〜１０００モル、より好ましくは１０〜２００モルである。キノン類の添加は、触媒組成物に添加してから反応容器に添加する方法、および重合溶剤に添加する方法のいずれであってもよく、必要に応じて、反応中に反応容器内に連続的に添加してもよい。 Further, an oxidizing agent such as benzoquinone or naphthoquinone may be added to the catalyst system composed of the three components. The addition amount of these quinones is preferably 1 to 1000 mol, more preferably 10 to 200 mol, per 1 mol of the transition metal compound. Addition of quinones may be either a method of adding to the catalyst composition and then adding to the reaction vessel, or a method of adding to the polymerization solvent, and if necessary, continuously in the reaction vessel during the reaction. You may add to.
反応温度としては、５０℃〜２００℃が好ましく、７０℃〜１５０℃がより好ましく、８０℃〜１２０℃が最も好ましい。また、反応圧力としては、０．１ＭＰa〜３００ＭＰaが好ましく、１〜１００ＭＰaがより好ましく、２〜３０ＭＰaであることが最も好ましい。反応時間は１〜２４時間が好ましく、より好ましくは１．５〜１０時間、最も好ましくは〜６時間である。反応時間が１時間未満では、残触媒量が多くなり、特別な触媒除去工程が必要となる。 As reaction temperature, 50 to 200 degreeC is preferable, 70 to 150 degreeC is more preferable, and 80 to 120 degreeC is the most preferable. The reaction pressure is preferably 0.1 MPa to 300 MPa, more preferably 1 to 100 MPa, and most preferably 2 to 30 MPa. The reaction time is preferably 1 to 24 hours, more preferably 1.5 to 10 hours, and most preferably ˜6 hours. When the reaction time is less than 1 hour, the amount of the remaining catalyst increases, and a special catalyst removal step is required.
以上に述べた条件下、本発明のガス流通型反応器でポリケトンを重合すると、従来製造技術で得られるポリケトンに対し同等以上の物性を有する高分子量ポリケトンを、より安価な触媒系で、高いポリケトン重合活性を達成し、かつ生成するポリケトン中へのパラジウム残渣が低く、その固有粘度が２．５ｄｌ／ｇ以上の高分子量ポリケトンを製造する事が可能となった。 When the polyketone is polymerized in the gas flow reactor of the present invention under the conditions described above, a high molecular weight polyketone having a physical property equivalent to or higher than that of the polyketone obtained by the conventional production technology can be obtained with a cheaper catalyst system and a high polyketone. It has become possible to produce a high molecular weight polyketone that achieves polymerization activity and has a low palladium residue in the polyketone to be produced and has an intrinsic viscosity of 2.5 dl / g or more.
また、本発明のガス流通型反応器は、完全なバッチ式での反応器としても用いる事が出来るが、連続的に反応ガスを供給する事から、生成した高分子量ポリケトンをスラリーとして連続的又は間歇的に抜出しつつ、重合溶媒、触媒を適宜追添する事で、連続式ガス流通型反応器としてポリケトンの重合に供する事も出来る。 The gas flow reactor of the present invention can also be used as a complete batch reactor. However, since the reaction gas is continuously supplied, the produced high molecular weight polyketone is continuously or as a slurry. By adding a polymerization solvent and a catalyst as needed while intermittently withdrawing, it can be used for polymerization of polyketone as a continuous gas flow reactor.
（３）本発明で製造される高分子量ポリケトン
本発明のガス流通型反応器で重合して得られる高分子量ポリケトンについて、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ及びＩＲを用いて解析した結果、得られる高分子量ポリケトンは、エチレン由来の繰り返し単位と一酸化炭素由来の繰り返し単位とが実質的に交互に配列したポリケトンであることが確かめられた。また、固有粘度を測定したところ、固有粘度が２．５ｄｌ／ｇ以上の高分子量ポリケトンが得られていることを確認した。
また、本発明により得られるポリケトンは重合活性が高く、重合に用いるパラジウム触媒の使用量を抑える事が可能となる為、パラジウム残渣の少ないポリケトンを得る事が出来る。パラジウム残渣は熱劣化等の一因となる為、１０ｐｐｍ以下である事が好ましく、５ｐｐｍ以下がより好ましく、パラジウム残渣が無い事が最も好ましい。
更には、本発明により得られるポリケトンのポリマー形状は、バッチ式反応法で得られるポリマーよりも表面の凹凸が大きく表面積が大きなポリマーであること、さらに、嵩密度も低く、溶剤になじみ易いポリマーであることを確認した。
(3) High molecular weight polyketone produced by the present invention As a result of analysis using a 1 H-NMR, 13 C-NMR and IR, the high molecular weight polyketone obtained by polymerization in the gas flow reactor of the present invention was obtained. It was confirmed that the obtained high molecular weight polyketone was a polyketone in which repeating units derived from ethylene and repeating units derived from carbon monoxide were substantially alternately arranged. Further, when the intrinsic viscosity was measured, it was confirmed that a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more was obtained.
Moreover, since the polyketone obtained by the present invention has high polymerization activity and the amount of palladium catalyst used for the polymerization can be suppressed, a polyketone with little palladium residue can be obtained. Since the palladium residue contributes to thermal degradation and the like, it is preferably 10 ppm or less, more preferably 5 ppm or less, and most preferably no palladium residue.
Furthermore, the polymer shape of the polyketone obtained according to the present invention is a polymer having a large surface area and a large surface area than the polymer obtained by the batch reaction method, and is a polymer having a low bulk density and easily adapting to a solvent. I confirmed that there was.
本発明のガス流通型反応器で重合することにより得られる固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンは、繊維素材としてその紡糸に供すると、延伸倍率を高くすることができるため、より高強度、高弾性率のポリケトン繊維が得られベルト、ホースやタイヤコード等のゴム補強材や、コンクリート補強材等、建築材料や産業資材用途に有用である。また、エンジニアリングプラスチック材として、例えば、その耐磨耗性の高さから、自動車のギア等の部品、耐薬品性及びガスバリア性の高さから軽量樹脂製ガソリンタンク等への利用が期待できる。 Since the high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more obtained by polymerization in the gas flow reactor of the present invention can be used for spinning as a fiber material, the draw ratio can be increased. A polyketone fiber having a high strength and a high elastic modulus can be obtained, and is useful for building materials and industrial materials such as rubber reinforcing materials such as belts, hoses and tire cords, and concrete reinforcing materials. In addition, as an engineering plastic material, for example, it can be expected to be used for parts such as automobile gears, chemical tanks and gas barrier properties because of its high wear resistance, and for lightweight resin gasoline tanks.
以下、本発明の好ましい態様について実施例に基づいて説明する。
実施例に用いた有機溶媒は、有機合成用に脱水されたものを重合前に乾燥窒素気流下で硫酸マグネシウムにより更に脱水させて得られる完全乾燥溶媒である。水は金属等の不純物を含まない蒸留水を用いた。硫酸としては、試薬特級９６質量％硫酸を用いた。この硫酸は、４質量％の水分を含んでおり、それを考慮して、実施例の硫酸使用量及び水含量になるよう調製し重合を行った。
Hereinafter, preferred embodiments of the present invention will be described based on examples.
The organic solvent used in the examples is a completely dry solvent obtained by further dehydrating what was dehydrated for organic synthesis with magnesium sulfate under a stream of dry nitrogen before polymerization. Distilled water containing no impurities such as metals was used as water. As sulfuric acid, reagent special grade 96 mass% sulfuric acid was used. This sulfuric acid contained 4% by mass of water, and in consideration thereof, the sulfuric acid was prepared so as to have the amount of sulfuric acid used and the water content in the examples, and polymerization was performed.
本発明に用いられる各測定値の測定方法は次の通りである。
（１）固有粘度
固有粘度［η］は次の定義式に基づいて求められる値である。
The measuring method of each measured value used in the present invention is as follows.
(1) Intrinsic viscosity Intrinsic viscosity [η] is a value determined based on the following defining formula.
式中、ｔ及びＴはそれぞれ純度９８％以上のヘキサフルオロイソプロパノール及びヘキサフルオロイソプロパノールに溶解したポリケトンの希釈溶液の２５℃での粘度管の流過時間、Ｃは上記溶液１００ｍｌ中のグラム単位による溶質質量値である。
（２）触媒活性
触媒活性とは、単位パラジウムグラム量、単位時間あたりの高分子量ポリケトンの収量を表すものであり、下記の式によって定義される。
In the formula, t and T are hexafluoroisopropanol having a purity of 98% or more and a polyketone diluted solution dissolved in hexafluoroisopropanol at 25 ° C., and C is a solute in grams in 100 ml of the above solution. Mass value.
(2) Catalytic activity The catalytic activity represents the yield of high molecular weight polyketone per unit gram of palladium and unit time, and is defined by the following formula.
［実施例１］
酢酸パラジウム２０マイクロモル、１，３−ビス（ジフェニルホスフィノ）プロパン２４マイクロモル、硫酸１００マイクロモル、及びベンゾキノン１００マイクロモルを、イソプロパノール８Ｌに溶解し、この溶液を窒素置換したステンレス製（容積１２Ｌ）の本発明のガス流通型反応器に投入した。
反応器を密閉後、窒素ガスを反応器底部よりブローし内容物を流動させながら加温した。内温が９５℃に達した時点で、一酸化炭素とエチレンの等モル混合気体を反応器底部に接続された内径１インチ配管より、反応器内圧が８．０ＭＰａになるまで加え重合を開始した。原料ガスをフィードし続け、反応器内圧と内温を保ちながら重合を継続した。４時間後、原料ガスのフィード、及び加熱を止めた。室温まで、冷却後、反応器内の気体をパージ、窒素置換した。反応器を開放し、反応溶液を回収した。反応溶液を濾過し、イソプロパノールで数回洗浄後、減圧乾燥し、高分子量ポリケトンを得た。
１３Ｃ−ＮＭＲ及びＩＲの測定結果から、この高分子量ポリケトンは、一酸化炭素由来の繰り返し単位とエチレン由来の繰り返し単位が実質的に交互に配列したポリケトンであることが確かめられた。
重合活性は２２．９ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は４．８ｄｌ／ｇ、Ｐｄ残渣は５ｐｐｍであった。
[Example 1]
20 μmol of palladium acetate, 24 μmol of 1,3-bis (diphenylphosphino) propane, 100 μmol of sulfuric acid, and 100 μmol of benzoquinone were dissolved in 8 L of isopropanol, and the solution was made of stainless steel (volume 12 L). ) In the gas flow reactor of the present invention.
After sealing the reactor, nitrogen gas was blown from the bottom of the reactor to heat the contents while flowing. When the internal temperature reached 95 ° C., polymerization was started by adding an equimolar mixture of carbon monoxide and ethylene from a 1-inch inner diameter pipe connected to the bottom of the reactor until the internal pressure of the reactor reached 8.0 MPa. . The raw material gas was continuously fed and polymerization was continued while maintaining the reactor internal pressure and temperature. After 4 hours, the feed of the source gas and the heating were stopped. After cooling to room temperature, the gas in the reactor was purged and purged with nitrogen. The reactor was opened and the reaction solution was collected. The reaction solution was filtered, washed several times with isopropanol, and then dried under reduced pressure to obtain a high molecular weight polyketone.
From the measurement results of 13 C-NMR and IR, it was confirmed that the high molecular weight polyketone was a polyketone in which repeating units derived from carbon monoxide and repeating units derived from ethylene were substantially alternately arranged.
The polymerization activity was 22.9 kg / g-Pd · hr, [η] was 4.8 dl / g, and the Pd residue was 5 ppm.
［実施例２］
実施例１における原料ガス供給口に孔径３００μｍを有した焼結板を敷設したことを除いて、実施例１と同様に操作したところ、重合活性は２４．３ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は５．２ｄｌ／ｇ、Ｐｄ残渣は５ｐｐｍの高分子量ポリケトンを得た。
[Example 2]
When the same operation as in Example 1 was performed except that a sintered plate having a pore diameter of 300 μm was laid at the raw material gas supply port in Example 1, the polymerization activity was 24.3 kg / g-Pd · hr, [η ] Was 5.2 dl / g, and the Pd residue was 5 ppm to obtain a high molecular weight polyketone.
［実施例３］
実施例１における原料ガス供給口に孔径５０μｍを有した焼結板に変更した事を除いて、実施例１と同様に操作したところ、重合活性は２５．７ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は５．２ｄｌ／ｇ、Ｐｄ残渣は４ｐｐｍの高分子量ポリケトンを得た。
[Example 3]
When the same operation as in Example 1 was performed except that the raw material gas supply port in Example 1 was changed to a sintered plate having a hole diameter of 50 μm, the polymerization activity was 25.7 kg / g-Pd · hr, [η ] Was 5.2 dl / g, and the Pd residue was 4 ppm to obtain a high molecular weight polyketone.
［実施例４］
実施例１における原料ガス供給口に孔径５μｍを有した焼結板に変更した事を除いて、実施例１と同様に操作したところ、重合活性は２６．３ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は５．３ｄｌ／ｇ、Ｐｄ残渣は５ｐｐｍの高分子量ポリケトンを得た。
[Example 4]
When the same operation as in Example 1 was performed except that the raw material gas supply port in Example 1 was changed to a sintered plate having a pore diameter of 5 μm, the polymerization activity was 26.3 kg / g-Pd · hr, [η ] Was 5.3 dl / g, and Pd residue was 5 ppm to obtain a high molecular weight polyketone.
［実施例５］
実施例１における原料ガス供給口に孔径０．１μｍを有した焼結板に変更した事を除いて、実施例１と同様に操作したところ、重合活性は２５．５ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は５．２ｄｌ／ｇ、Ｐｄ残渣は５ｐｐｍの高分子量ポリケトンを得た。
[Example 5]
When the same operation as in Example 1 was performed except that the raw material gas supply port in Example 1 was changed to a sintered plate having a pore diameter of 0.1 μm, the polymerization activity was 25.5 kg / g-Pd · hr, [Η] was 5.2 dl / g, and the Pd residue was 5 ppm.
［実施例６］
実施例１における反応圧力を１２．０ＭＰａに、また、温度を１００℃にそれぞれ変更したことを除いて、実施例１と同様に操作したところ、重合活性は４７．８ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は６．８ｄｌ／ｇ、Ｐｄ残渣は２ｐｐｍの高分子量ポリケトンを得た。
[Example 6]
When the same operation as in Example 1 was performed except that the reaction pressure in Example 1 was changed to 12.0 MPa and the temperature was changed to 100 ° C., the polymerization activity was 47.8 kg / g-Pd · hr, [Η] was 6.8 dl / g, and Pd residue was 2 ppm to obtain a high molecular weight polyketone.
［比較例１］
酢酸パラジウム１．２５マイクロモル、１，３−ビス（ジフェニルホスフィノ）プロパン１．５マイクロモル、硫酸６．２５マイクロモル、及びベンゾキノン６．２５マイクロモルを、イソプロパノール５０ｍｌに溶解し、この溶液を窒素置換したステンレス製１００ｍｌ容積のオートクレーブに投入した。オートクレーブを密閉後、内容物を攪拌しながら加温し、内温が９５℃に達した時点で一酸化炭素とエチレンの等モル混合気体をオートクレーブ内圧が８．０ＭＰａになるまで加えた。内温と内圧を保ちながら４時間攪拌を続けた。冷却後、オートクレーブ内気体をパージし、内容物を取り出した。反応溶液を濾過し、イソプロパノールで数回洗浄後、減圧乾燥し、高分子量ポリケトンを得た。
重合活性は１８．１ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は２．６ｄｌ／ｇ、Ｐｄ残渣は１１ｐｐｍであった。
[Comparative Example 1]
Palladium acetate 1.25 μmol, 1,3-bis (diphenylphosphino) propane 1.5 μmol, sulfuric acid 6.25 μmol, and benzoquinone 6.25 μmol were dissolved in 50 ml of isopropanol. The sample was put into a 100 ml autoclave made of stainless steel purged with nitrogen. After sealing the autoclave, the contents were heated with stirring, and when the internal temperature reached 95 ° C., an equimolar mixed gas of carbon monoxide and ethylene was added until the internal pressure of the autoclave reached 8.0 MPa. Stirring was continued for 4 hours while maintaining the internal temperature and pressure. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed several times with isopropanol, and then dried under reduced pressure to obtain a high molecular weight polyketone.
The polymerization activity was 18.1 kg / g-Pd · hr, [η] was 2.6 dl / g, and the Pd residue was 11 ppm.
［比較例２］
比較例１における反応圧力を１２．０ＭＰａに変更した事を除いて、比較例１と同様に操作したところ、重合活性は３０．６ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は３．９ｄｌ／ｇ、Ｐｄ残渣は７ｐｐｍの高分子量ポリケトンを得た。
[Comparative Example 2]
When operated in the same manner as in Comparative Example 1 except that the reaction pressure in Comparative Example 1 was changed to 12.0 MPa, the polymerization activity was 30.6 kg / g-Pd · hr, and [η] was 3.9 dl / g. The Pd residue obtained 7 ppm high molecular weight polyketone.
［比較例３］
比較例１における反応溶媒をターシャリーブタノールに変更した事を除いて、比較例１と同様に操作したところ、重合活性は７．２ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は５．４ｄｌ／ｇ、Ｐｄ残渣は２８ｐｐｍの高分子量ポリケトンを得た。
[Comparative Example 3]
When the same operation as in Comparative Example 1 was performed except that the reaction solvent in Comparative Example 1 was changed to tertiary butanol, the polymerization activity was 7.2 kg / g-Pd · hr, and [η] was 5.4 dl / g. , Pd residue obtained 28 ppm high molecular weight polyketone.
［比較例４］
比較例１における１，３−ビス（ジフェニルホスフィノ）プロパンの変わりに１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパンに変更した事を除いて、比較例１と同様に操作したところ、重合活性は２７．５ｋｇ／ｇ−Ｐｄ・ｈｒ、［η］は３．１ｄｌ／ｇ、Ｐｄ残渣は８ｐｐｍの高分子量ポリケトンを得た。
以上の結果を表１にまとめた。
[Comparative Example 4]
The same operation as in Comparative Example 1 was performed except that 1,3-bis {di (2-methoxyphenyl) phosphino} propane was used instead of 1,3-bis (diphenylphosphino) propane in Comparative Example 1. However, a high molecular weight polyketone having a polymerization activity of 27.5 kg / g-Pd · hr, [η] of 3.1 dl / g, and Pd residue of 8 ppm was obtained.
The above results are summarized in Table 1.
本発明のガス流通型反応器によるポリケトン重合では、その重合活性が従来のバッチ式反応器によるポリケトン重合よりも四割程度高くなることが分かる。（例えば、比較例１：１８ｋｇ／ｇ−Ｐｄ・ｈｒ⇒実施例４：２６ｋｇ／ｇ−Ｐｄ・ｈｒ）。結果として、触媒使用量を少量に抑えることが可能となる為、得られる高分子量ポリケトン中に熱劣化等の一因となる触媒残渣を極少まで減じることができる。
本発明を好ましい実施態様に関連して説明してきたが、当業者が容易に理解されるように本発明の原理及び範囲を逸脱することなく改変及び変更を実施し得ることを理解すべきである。従って、前記改変は本発明の範囲内で実施され得る。
It can be seen that the polymerization activity of the polyketone polymerization by the gas flow reactor of the present invention is about 40% higher than the polyketone polymerization by the conventional batch reactor. (For example, Comparative Example 1: 18 kg / g-Pd · hr⇒Example 4: 26 kg / g-Pd · hr). As a result, since the amount of catalyst used can be suppressed to a small amount, catalyst residues that contribute to thermal degradation and the like can be reduced to a minimum in the high molecular weight polyketone obtained.
Although the invention has been described with reference to preferred embodiments, it is to be understood that modifications and changes can be made without departing from the principles and scope of the invention as will be readily appreciated by those skilled in the art. . Accordingly, such modifications can be implemented within the scope of the present invention.
本発明のガス流通型反応器は、一酸化炭素と少なくとも１つのエチレン性不飽和化合物を含む原料ガスを用いて、パラジウム化合物と、第１５族元素の原子を含む二座配位子と、ｐＫａが４以下の酸の陰イオンからなるより安価な触媒系で、高いポリケトン重合活性を達成するとともに、固有粘度２．５ｄｌ／ｇ以上の高分子量ポリケトンを製造する事を可能とする。また、得られる高分子量ポリケトンは、繊維素材やエンジニアリングプラスチック材として用いるのに好適である。 The gas flow reactor of the present invention uses a raw material gas containing carbon monoxide and at least one ethylenically unsaturated compound, a palladium compound, a bidentate ligand containing an atom of a Group 15 element, pKa Is a cheaper catalyst system comprising an anion of 4 or less acid, and achieves high polyketone polymerization activity and makes it possible to produce a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more. The obtained high molecular weight polyketone is suitable for use as a fiber material or an engineering plastic material.
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