JP6957449B2 - 触媒担体用ビニルピリジン樹脂、その製造方法およびメタノールのカルボニル化反応用触媒 - Google Patents
触媒担体用ビニルピリジン樹脂、その製造方法およびメタノールのカルボニル化反応用触媒 Download PDFInfo
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- JP6957449B2 JP6957449B2 JP2018505840A JP2018505840A JP6957449B2 JP 6957449 B2 JP6957449 B2 JP 6957449B2 JP 2018505840 A JP2018505840 A JP 2018505840A JP 2018505840 A JP2018505840 A JP 2018505840A JP 6957449 B2 JP6957449 B2 JP 6957449B2
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- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- YXTWPSHEGIZWEU-UHFFFAOYSA-N propoxy propyl carbonate Chemical compound CCCOOC(=O)OCCC YXTWPSHEGIZWEU-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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Description
D=4V/A
架橋度(モル%)=A/B×100
A:ビニルピリジン樹脂の合成に用いた架橋剤(ビニル基等の反応性部位を2個以上有する化合物)のモル数
B:ビニルピリジン樹脂の合成に用いたモノマーの合計モル数
SP絶対差=|触媒担体用ビニルピリジン樹脂のSP値−細孔形成剤のSP値|
細孔形成剤のSP値=(第1有機溶媒のSP値×(第1有機溶媒の体積/細孔形成剤の体積))+(第2有機溶媒のSP値×(第2有機溶媒の体積/細孔形成剤の体積))+(第3有機溶媒のSP値×(第3有機溶媒の体積/細孔形成剤の体積))
[実施例1]
10質量%のNaCl(比重調整剤)、0.3質量%のNaNO2(消ラジカル剤)、0.064質量%のゼラチン(分散安定剤)及び0.009質量%のドデシルベンゼンスルホン酸ナトリウム(界面活性剤)をイオン交換水に溶解させて、625gの水性媒体を調製した。
ジビニルベンゼン(架橋剤)、細孔形成剤種及び比率、重合温度、重合開始剤添加量を表1に示すようにした以外は実施例1と同様にして、触媒担体用4−ビニルピリジン樹脂を得た。表1に、架橋度、および、触媒担体用ビニルピリジン樹脂のSP値と細孔形成剤のSP値との差の絶対値(SP絶対差)も記載する。比較例1の触媒担体用ビニルピリジン樹脂が、特許文献7に記載のビニルピリジン樹脂に相当する。各実施例2〜14および比較例1〜7で得られた触媒担体用4−ビニルピリジン樹脂は、それぞれ球状であった。
得られた触媒担体用4−ビニルピリジン樹脂の物性を以下の方法により測定した。
(1)比表面積、全細孔容積、10nm以上の細孔径を有する細孔が全細孔に占める容積の割合、平均細孔径の測定
得られた触媒担体用4−ビニルピリジン樹脂の比表面積、全細孔容積、10nm以上の細孔径を有する細孔が全細孔に占める容積の割合、平均細孔径を、上記の方法で、ユアサアイオニクス(株)製、AUTOSORB−1を用いて測定した。比表面積に関して、ビニルピリジン樹脂全体の比表面積(Total)、および、2.0nm以下の細孔径を有する細孔のみの比表面積(≦2nm)を求め、さらに、全体の比表面積に対する該2.0nm以下の細孔径を有する細孔のみの比表面積の割合(比率(%))を求めた。結果を表2に記載する。
CHNコーダーにより、樹脂に含まれる炭素、水素、窒素量を分析し、その値から、窒素含有量(N含有量)、炭素原子と窒素原子とのモル比(C/N比)を求めた。結果を表1に示す。
得られた触媒担体用4−ビニルピリジン樹脂を17g(dry)分取し、ヨウ化メチル17質量%メタノール溶液を100g加え、18時間振とうを行い、ピリジン基の4級化を行った。
(i)触媒化
得られた触媒担体用4−ビニルピリジン樹脂8.5g(dry基準)と反応液79.7g(メタノール31.3質量%、ヨウ化メチル21.6質量%、酢酸47.1質量%)及び所定量の酢酸ロジウムを200mlジルコニウム製オートクレーブに仕込み、反応温度180℃、CO圧力5.0MPaGで1時間反応させ、触媒化した。反応終了後の液をICP発光分光法で分析した結果、反応液へのロジウムの残存率は0.2モル%以下(担持率99.8モル%以上)であった。
(ii)反応試験
得られた触媒担体用4−ビニルピリジン樹脂を前記方法で触媒化し、ヨウ化メチル8.0質量%、水5.5質量%、酢酸86.5質量%の溶液100mlと共に200mlジルコニウム製オートクレーブに仕込み、オートクレーブ内の空気を窒素で置換した後、攪拌しながら220℃に加熱した。その後、オートクレーブ内で撹拌しながら220℃の状態を維持し、24時間後に液を採取して窒素濃度を測定し、離脱したピリジン基量を求めた。また、得られた触媒担体用4−ビニルピリジン樹脂中の窒素濃度を別途測定し、上記24時間後に液を採取して求めた離脱ピリジン基との比(離脱ピリジン基量(モル)/得られた触媒担体用4−ビニルピリジン樹脂中の窒素量(モル))を求め、該比を分解時間(24時間)で除することで1時間当たりの熱分解速度を求めた。
2 フラッシャー
4 ライトエンド蒸留塔
5 デカンタ
Claims (6)
- ビニルピリジンとジビニルベンゼンの共重合体であって、ピリジン基に由来する窒素含有量が3.00質量%以上8.00質量%以下、架橋度が35モル%以上70モル%以下、炭素原子と窒素原子とのモル比C/Nが12.00以上36.00以下、全細孔容積が0.20cc/g以上0.45cc/g以下、比表面積が70.0m2/g以上280m2/g以下、平均細孔径が5.0nm以上25.0nm以下、且つ10nm以上の細孔径を有する細孔が全細孔に占める容積の割合が4.0%以上90.0%以下であることを特徴とする、メタノールのカルボニル化反応用触媒の触媒担体用ビニルピリジン樹脂。
- ビニルピリジン、架橋剤、細孔形成剤及び重合開始剤を含む油性媒体と水性媒体とを混合して懸濁重合することによる、メタノールのカルボニル化反応用触媒の触媒担体用ビニルピリジン樹脂の製造方法であって、
前記重合開始剤は、主重合開始剤と主重合開始剤よりも半減期温度が低い補助重合開始剤とを含み、前記補助重合開始剤がモノマー全量に対して0.25質量%以下であり、
前記細孔形成剤は2種類以上の有機溶媒を含み、該細孔形成剤はベンゼン環を有する有機溶媒を含み、前記触媒担体用ビニルピリジン樹脂のSP値と前記細孔形成剤のSP値との差の絶対値が、1.80以上2.80以下であり、前記架橋剤は不純物モノマーの含有量がモノマー全量に対して3.0モル%以下であることを特徴とする触媒担体用ビニルピリジン樹脂の製造方法。 - 前記主重合開始剤が前記モノマー全量に対して1.50質量%以下であることを特徴とする請求項2に記載する触媒担体用ビニルピリジン樹脂の製造方法。
- 前記補助重合開始剤は、半減期温度が前記懸濁重合の温度よりも低く、
前記主重合開始剤は、半減期温度が前記懸濁重合の温度よりも高いことを特徴とする請求項2または3に記載する触媒担体用ビニルピリジン樹脂の製造方法。 - 請求項1に記載する触媒担体用ビニルピリジン樹脂に、ロジウムを担持してなることを特徴とするメタノールのカルボニル化反応用触媒。
- 酢酸86.5質量%、ヨウ化メチル8.0質量%、水5.5質量%の混合液中における、220℃、窒素雰囲気の条件での熱分解速度が、1時間当たり0.25モル%以下であることを特徴とする請求項5に記載するメタノールのカルボニル化反応用触媒。
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