JPWO2017170585A1 - 金属担持型触媒および水素化共役ジエン系重合体の製造方法 - Google Patents
金属担持型触媒および水素化共役ジエン系重合体の製造方法 Download PDFInfo
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- JPWO2017170585A1 JPWO2017170585A1 JP2018508094A JP2018508094A JPWO2017170585A1 JP WO2017170585 A1 JPWO2017170585 A1 JP WO2017170585A1 JP 2018508094 A JP2018508094 A JP 2018508094A JP 2018508094 A JP2018508094 A JP 2018508094A JP WO2017170585 A1 JPWO2017170585 A1 JP WO2017170585A1
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- Prior art keywords
- metal
- supported catalyst
- conjugated diene
- weight
- catalyst
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- BHZSLLSDZFAPFH-UHFFFAOYSA-L palladium(2+);difluoride Chemical compound F[Pd]F BHZSLLSDZFAPFH-UHFFFAOYSA-L 0.000 description 1
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- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- OZVHAYAOFBRGQV-UHFFFAOYSA-K pentanoate;rhodium(3+) Chemical compound [Rh+3].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O OZVHAYAOFBRGQV-UHFFFAOYSA-K 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- QRRFFHBDASQYFJ-UHFFFAOYSA-K rhodium(3+);triformate Chemical compound [Rh+3].[O-]C=O.[O-]C=O.[O-]C=O QRRFFHBDASQYFJ-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
Description
本発明は、このような実状に鑑みてなされたものであり、高い水素添加率を実現可能な金属担持型触媒を提供することを目的とする。
本発明の金属担持型触媒において、前記ポリビニルピロリドン水溶液中に含まれるポリビニルピロリドンのポリスチレン換算での重量平均分子量が8,000〜12,000であることが好ましい。
本発明の金属担持型触媒は、体積基準で求めた粒子径分布における50%累積径が、0μm超、100μm以下であることが好ましい。
本発明の金属担持型触媒は、個数基準で求めた粒子径分布における50%累積径が、0μm超、2μm以下であることが好ましい。
本発明の金属担持型触媒は、金属および/または金属化合物を担体に担持させてなるものであり、
2.3重量%のポリビニルピロリドン水溶液中において、水素雰囲気下、温度50℃、36rpmの条件で1時間振とうさせた際における、金属担持型触媒中に含まれる金属および/または金属化合物の減少率が20重量%以上であるものである。
PVP分散時金属減少率(重量%)=100−(「PVP水溶液中で振とうさせた後の金属担持型触媒中に含まれる金属および/または金属化合物の重量(g)」÷「PVP水溶液中で振とうさせる前の金属担持型触媒中に含まれる金属および/または金属化合物の重量(g)」)×100 ・・・(1)
本発明の水素化共役ジエン系重合体の製造方法は、溶媒中、上述した本発明の金属担持型触媒の存在下で、共役ジエン系重合体を水素化する工程を備えるものである。
100mlのステンレス製加圧容器に、Pd/SiO2触媒0.15gおよびポリビニルピロリドン(PVP)水溶液(PVP:Ashland製、PVP−K15、ポリスチレン換算での重量平均分子量10,000)(PVPの含有量:2.3重量%)20gを入れた。次いで、このステンレス製加圧容器内の気体を、H2に置換した後、1MPa(ゲージ圧)まで昇圧させた。次いで、このステンレス製加圧容器を、温度50℃の恒温槽内に設置された回転具に固定し、回転数:36rpmで1時間振とうさせた。
そして、PVP溶液中で振とうさせる前、および振とうさせた後のPd/SiO2触媒について、Pd/SiO2触媒を秤取し、硝酸、ふっ化水素酸および硫酸で加熱分解したのち、定容とした。この溶液について、原子吸光装置(商品名「SPS−5000」、セイコーインスツルメンツ社製)を用いて、原子吸光測定を行うことで、Pdの含有量(g)を求め、下記式にしたがって、PVP分散時金属減少率を算出した。
PVP分散時金属減少率(重量%)=100−(PVP溶液中で振とうさせた後のPd/SiO2触媒中のPdの含有量(g)÷PVP溶液中で振とうさせる前のPd/SiO2触媒中のPdの含有量(g))×100
水素添加率は、水素添加前のアクリロニトリル−ブタジエン共重合体のヨウ素価、および水素添加後のアクリロニトリル−ブタジエン共重合体のヨウ素価を測定し、これらの割合から求めた。なお、ヨウ素価は、JIS K 6235に準じて測定した。
パラジウム化合物としての塩化パラジウム5質量部を、溶媒として塩酸水85質量部に溶解させ、平均粒子径が1000μmであるシリカ10質量部を含浸した。次いで、溶媒を揮発させた後、焼成することで、パラジウムがシリカに担持されてなる未粉砕Pd/SiO2触媒を得た。得られた未粉砕Pd/SiO2触媒は、個数基準で求めた粒子径分布における50%累積径が1000μm、体積基準で求めた粒子径分布における50%累積径が1000μmであった。また、得られた未粉砕Pd/SiO2触媒について、上述した方法にしたがって、PVP分散時金属減少率を測定したところ、18重量%であった。
上記にて得られた未粉砕Pd/SiO2触媒のうち一部を取り出し、粉砕装置として小型超高速粉砕機(商品名「ワンダーブレンダ― WB−1」、大阪ケミカル社製)を使用して、粉砕することで、粉砕Pd/SiO2触媒を得た。得られた粉砕Pd/SiO2触媒は、個数基準で求めた粒子径分布における50%累積径が0.4μm、体積基準で求めた粒子径分布における50%累積径が25μmであった。また、得られた粉砕Pd/SiO2触媒について、上述した方法にしたがって、PVP分散時金属減少率を測定したところ、35重量%であった。
反応器に、オレイン酸カリウム2部、イオン交換水180部、アクリロニトリル37部、およびt−ドデシルメルカプタン0.5部を、この順に仕込んだ。次いで、反応器内部を窒素で置換した後、ブタジエン63部を添加し、反応器を10℃に冷却して、クメンハイドロパーオキサイド0.01部、および硫酸第一鉄0.01部を添加した。次いで、反応器を10℃に保ったまま内容物を16時間攪拌した。その後、反応器内へ10重量%のハイドロキノン水溶液を添加して重合反応を停止させた後、重合反応液から未反応の単量体を除去することで、アクリロニトリル−ブタジエン共重合体のラテックスを得た。重合転化率は90%であった。
製造例2で得られた粉砕Pd/SiO2触媒の使用量を、アクリロニトリル−ブタジエン共重合体に対して、パラジウム量が150重量ppmとなる量に変更した以外は、実施例1と同様にして、水素化アクリロニトリル−ブタジエン共重合体を得た。得られた水素化アクリロニトリル−ブタジエン共重合体について、上記方法にしたがって、水素添加率を測定したところ93.8%であった。
製造例2で得られた粉砕Pd/SiO2触媒の使用量を、アクリロニトリル−ブタジエン共重合体に対して、パラジウム量が180重量ppmとなる量に変更した以外は、実施例1と同様にして、水素化アクリロニトリル−ブタジエン共重合体を得た。得られた水素化アクリロニトリル−ブタジエン共重合体について、上記方法にしたがって、水素添加率を測定したところ95.4%であった。
製造例2で得られた粉砕Pd/SiO2触媒に代えて、製造例1で得られた未粉砕Pd/SiO2触媒を用いるとともに、未粉砕Pd/SiO2触媒の使用量を、アクリロニトリル−ブタジエン共重合体に対して、パラジウム量が180重量ppmとなる量に変更した以外は、実施例1と同様にして、水素化アクリロニトリル−ブタジエン共重合体を得た。得られた水素化アクリロニトリル−ブタジエン共重合体について、上記方法にしたがって、水素添加率を測定したところ88.2%であった。
Claims (6)
- 金属および/または金属化合物を担体に担持させてなる金属担持型触媒であって、
2.3重量%のポリビニルピロリドン水溶液中において、水素雰囲気下、温度50℃、36rpmの条件で1時間振とうさせた際における、前記金属担持型触媒中に含まれる金属および/または金属化合物の減少率が20重量%以上である金属担持型触媒。 - 前記金属および/または金属化合物として、白金族元素および/または白金族元素含有化合物を担体に担持させてなるものである請求項1に記載の金属担持型触媒。
- 前記ポリビニルピロリドン水溶液中に含まれるポリビニルピロリドンのポリスチレン換算での重量平均分子量が8,000〜12,000である請求項1または2に記載の金属担持型触媒。
- 体積基準で求めた粒子径分布における50%累積径が、0μm超、100μm以下である請求項1〜3のいずれかに記載の金属担持型触媒。
- 個数基準で求めた粒子径分布における50%累積径が、0μm超、2μm以下である請求項1〜4のいずれかに記載の金属担持型触媒。
- 溶媒中、請求項1〜5のいずれかに記載の金属担持型触媒の存在下で、共役ジエン系重合体を水素化する水素化共役ジエン系重合体の製造方法。
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JP2004051721A (ja) * | 2002-07-18 | 2004-02-19 | Nippon Zeon Co Ltd | 水素化触媒安定化剤、水素化触媒溶液及びその調製方法、水素化反応方法 |
JP2012040515A (ja) * | 2010-08-19 | 2012-03-01 | Mazda Motor Corp | 排気ガス浄化用触媒及び排気ガス浄化用触媒の製造方法 |
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CN101780406B (zh) * | 2009-01-19 | 2012-06-27 | 中国科学院化学研究所 | 一种纳米金属催化剂及其制备方法与应用 |
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JP2012040515A (ja) * | 2010-08-19 | 2012-03-01 | Mazda Motor Corp | 排気ガス浄化用触媒及び排気ガス浄化用触媒の製造方法 |
JP2013180235A (ja) * | 2012-03-01 | 2013-09-12 | Nissan Motor Co Ltd | 排ガス浄化触媒及びその製造方法 |
JP2015163387A (ja) * | 2014-01-30 | 2015-09-10 | 積水化学工業株式会社 | 合成用の触媒及びその製造方法、酸素化物の製造装置ならびに酸素化物の製造方法 |
JP2016000686A (ja) * | 2015-06-29 | 2016-01-07 | 旭化成ケミカルズ株式会社 | シリカ系材料及びその製造方法、並びに貴金属担持物及びそれを触媒として用いるカルボン酸類の製造方法 |
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US20220023840A1 (en) | 2022-01-27 |
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