TWI564077B - 選擇性氫化共聚物的觸媒與方法 - Google Patents
選擇性氫化共聚物的觸媒與方法 Download PDFInfo
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- TWI564077B TWI564077B TW104134635A TW104134635A TWI564077B TW I564077 B TWI564077 B TW I564077B TW 104134635 A TW104134635 A TW 104134635A TW 104134635 A TW104134635 A TW 104134635A TW I564077 B TWI564077 B TW I564077B
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- Prior art keywords
- copolymer
- catalyst
- selectively hydrogenating
- metal oxide
- porous carrier
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- 229920001577 copolymer Polymers 0.000 title claims description 48
- 239000003054 catalyst Substances 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims description 25
- 150000004706 metal oxides Chemical class 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000004291 polyenes Chemical class 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 70
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 22
- 229910052772 Samarium Inorganic materials 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 13
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920001400 block copolymer Polymers 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 229920002633 Kraton (polymer) Polymers 0.000 description 10
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 10
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000005060 rubber Substances 0.000 description 5
- 229920006132 styrene block copolymer Polymers 0.000 description 5
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- ULFUTCYGWMQVIO-PCVRPHSVSA-N [(6s,8r,9s,10r,13s,14s,17r)-17-acetyl-6,10,13-trimethyl-3-oxo-2,6,7,8,9,11,12,14,15,16-decahydro-1h-cyclopenta[a]phenanthren-17-yl] acetate;[(8r,9s,13s,14s,17s)-3-hydroxy-13-methyl-6,7,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthren-17-yl] pentano Chemical compound C1CC2=CC(O)=CC=C2[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)CCCC)[C@@]1(C)CC2.C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 ULFUTCYGWMQVIO-PCVRPHSVSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- -1 styrene-ethylene-butylene-styrene Chemical class 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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Description
本發明係關於非勻相觸媒，更特別關於此觸媒於選擇性氫化共聚物的應用。
SBS及SIS皆為苯乙烯系熱塑性彈性體(稱為苯乙烯系嵌段式聚合物Styrenic Block Copolymers，簡稱SBCs)，兼具了熱塑性塑膠及橡膠的優點，在室温下柔軟像橡膠，具有韌性及彈性，在高溫時具有流動性，能塑化成形，是繼天然橡膠、合成橡膠後的第三代橡膠，是目前是世界產量最大、與橡膠性能最相似的一種熱塑性彈體；目前共有四種SBCs系列產品：苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)；苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)；苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)；苯乙烯-乙烯-丙烯-苯乙烯型嵌段共聚物(SEPS)。SEBS和SEPS分別是SBS和SIS的氫化型共聚物，性能卓越，價格約為原來原料(SBS及SIS)的2至4倍。SBS是SBCs中產量最大(佔70%以上)、成本最低應用較廣的產品種，是以苯乙烯、丁二烯為單體的三嵌段共聚物，兼有塑料和橡膠的特性，具有良好的抗化學性質，優良的拉伸強度，表面摩擦系数大，低温性能好，電性能優良，加工性能好等特性，成為目前產量最大熱塑性彈
性體。
SBS的聚丁二烯鏈段與SIS的聚異戊二烯鏈段皆
具有雙鍵，因此SBS及SIS材料都存在抗熱性差及耐候(抗臭氧、紫外線及氧)性差之缺點。上述缺點可經由氫化聚丁二烯或聚異戊二烯的雙鍵改善，而SBS及SIS的雙鍵氫化產物分別為SEBS(見式1)及SEPS(見式2)，具有更優異的耐候性及性能，在工程及醫療材料上有許多應用。
綜上所述，目前亟需新的方法與觸媒，可選擇性氫化SBS及SIS的雙鍵而不氫化其芳環，以形成SEBS與SEPS。
本發明一實施例提供之選擇性氫化共聚物的觸媒，包括：孔洞狀載體；金屬氧化物，披覆於孔洞狀載體之部份表面上；以及多個Pd粒子，位於孔洞狀載體與金屬氧化物上，其中孔洞狀載體之孔徑介於0.02μm至1.2μm之間，且Pd粒子之粒徑介於1nm至3nm之間。
本發明一實施例提供之選擇性氫化共聚物的方
法，包括：提供共聚物，且共聚物具有一芳香環與一雙鍵；使共聚物接觸觸媒，並通入氫氣以選擇性氫化共聚物之雙鍵且實質上不氫化共聚物之芳香環，其中觸媒包括：孔洞狀載體；金屬氧化物，披覆於孔洞狀載體之部份表面上；以及多個Pd粒子，位於孔洞狀載體與金屬氧化物上。
本發明一實施例提供選擇性氫化共聚物的方法。首先，提供共聚物，其具有一芳香環與一雙鍵。舉例來說，多烯單體可為丁二烯、異戊二烯、其他具有至少兩個雙鍵的單體、或上述單體之組合。乙烯基芳族單體可為苯乙烯、α-甲基苯乙烯、其他乙烯基芳族單體、或上述單體之組合。上述共聚物具有一芳環與一雙鍵，比如苯乙烯與丁二烯共聚形成的SBS，或苯乙烯與異戊二烯共聚形成的SIS。在本發明一實施例中，共聚物之數目平均分子量介於3萬至40萬之間。共聚物之數目平均分子量範圍取決於產品所需之性質及其應用領域。
接著使共聚物接觸觸媒，並通入氫氣以選擇性氫化共聚物之雙鍵且實質上不氫化共聚物之芳香環。上述觸媒包括：孔洞狀載體、披覆於孔洞狀載體之部份表面上的金屬氧化物、以及位於孔洞狀載體與金屬氧化物上的Pd粒子。在本發明一實施例中，孔洞狀載體之孔徑介於0.02μm至1.2μm之間。若孔洞狀載體之孔徑過小，則共聚物難以進入孔洞以接觸孔洞表
面上的Pd粒子，即氫化反應之效果不佳。若孔洞狀載體之孔徑過大，則載體之比表面積過小而無法負載足夠量的Pd粒子。在本發明一實施例中，Pd粒子之粒徑介於1nm至3nm之間。若Pd粒子之粒徑過大，則Pd粒子之比表面積過小而降低催化活性。
在本發明一實施例中，孔洞狀載體可為氧化鋁、
氧化矽、氧化鈦、氧化鋯、或類似物。在本發明一實施例中，金屬氧化物包括氧化釤、氧化釹、氧化鑭、或上述金屬氧化物之組合。在本發明一實施例中，孔洞狀載體與金屬氧化物之重量比介於1：1至1：0.025之間。若金屬氧化物之比例過低，則無法有效避免Pd粒子聚集而降低比表面積的問題。若金屬氧化物之比例過高，則可能堵塞孔洞狀載體之孔洞，使共聚物難以進入孔洞以接觸孔洞表面上的Pd粒子。在本發明一實施例中，Pd粒子占觸媒的0.1wt%至5wt%之間。若Pd粒子之比例過低，則觸媒活性不足致產率偏低。若Pd粒子之比例過高，則觸媒的成本偏高，缺乏經濟效益。
在本發明一實施例中，上述觸媒的形成方法如
下。首先將金屬鹽類溶於水中，再將孔洞狀載體加入上述金屬鹽類的水溶液，攪拌均勻後加熱至110℃並抽真空將水去除，得到粉體。接著高溫煆燒粉體，使金屬氧化物披覆於多孔載體之部份表面上。接著取Pd鹽類溶於水中，再將部份表面上批覆有金屬氧化物之多孔載體加入Pd鹽類的水溶液中，使Pd鹽類吸附於多孔載體上，再加熱並抽真空除水，即形成Pd粒子於多孔載體及金屬氧化物上。
在本發明一實施例中，氫化共聚物之溫度介於40℃
至150℃之間，而氫氣壓力介於10Kg/cm2至50Kg/cm2之間。在本發明另一實施例中，氫化反應之溫度介於70℃至120℃之間，而氫氣壓力介於30Kg/cm2至40Kg/cm2之間。若氫化反應之溫度過低及/或氫氣壓力過低，則無法進行氫化反應。若氫化反應之溫度過高及/或氫氣壓力過高，除了氫化共聚物之雙鍵外，還會氫化共聚物之芳環。
上述觸媒可選擇性氫化共聚物之雙鍵，且實質上
不氫化共聚物之芳環。舉例來說，上述氫化反應只會氫化共聚物中不到5%的芳環，但可氫化97%以上的雙鍵。
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明如下：
取9.55g之SiO2(購自Fuji silysia之Q50)作為孔洞狀載體，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.735g之H2PtCl6及0.155g之IrCl3溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於Al2O3上，再加熱至110℃並抽真空以去除水形成粉體。之後將乾燥粉體置於玻璃管中，通入2vol%氫氣並加熱至200℃後維持4小時以還原SiO2上的金屬鹽。待降至室溫後再通入空氣鈍化觸媒表面，即形成Pt3.5Ir1/SiO2觸媒。
取9.55g之Al2O3載體(購自Norpro之SD alumina)，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.411g之醋酸鈀溶於
水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於Al2O3上，再加熱至110℃並抽真空將水去除，生成粉體Pd2/Al2O3觸媒。
取9.55g之Al2O3載體(購自Alfa之44693)，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.411g之醋酸鈀溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於Al2O3上，再加熱至110℃並抽真空將水去除，生成粉體Pd2/Al2O3觸媒。
將2.524g之Sm(NO3)3溶於水中，加入7.92g之SD alumina，攪拌均勻後再加熱至110℃並抽真空將水去除，生成之粉體在600℃煆燒，生成20wt%Sm2O3-alumina。取9.9g之20%Sm2O3-alumina，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.213g之醋酸鈀溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於20wt%Sm2O3-alumina上，再加熱至110℃並抽真空將水去除，生成粉體Pd1/20wt%Sm2O3-alumina觸媒。
取9.984g之20%Sm2O3-alumina，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.034g之醋酸鈀溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於20wt%Sm2O3-alumina上，再加熱至110℃並抽真空將水去除，生成粉體Pd0.16/20wt%Sm2O3-alumina觸媒。
將1.271g之Sm(NO3)3溶於水中，加入8.973g之SD-Al2O3，攪拌均勻後再加熱至110℃並抽真空將水去除，生成之粉體在
600℃煆燒，生成10wt%Sm2O3-alumina。取9.97g之10wt%Sm2O3-alumina，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.063g之醋酸鈀溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於10wt%Sm2O3-alumina上，再加熱至110℃並抽真空將水去除，生成粉體Pd0.3/10wt%Sm2O3-alumina觸媒。
將0.636g之Sm(NO3)3溶於水中，加入8.973g之SD-Al2O3，攪拌均勻後再加熱至110℃並抽真空將水去除，生成之粉體在600℃煆燒，生成5wt%Sm2O3-alumina。取9.9g之5wt%Sm2O3-alumina，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.213g之醋酸鈀溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於5wt%Sm2O3-alumina上，再加熱至110℃並抽真空將水去除，生成粉體Pd1/5wt%Sm2O3-alumina觸媒。
將2.922g之Nd(NO3)3溶於水中，加入8.973g之SD alumina，攪拌均勻後再加熱至110℃並抽真空將水去除，生成之粉體在600℃煆燒，生成20wt%Nd2O3-alumina。取9.97g之20wt%Nd2O3-alumina，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.063g之醋酸鈀溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於20wt%Nd2O3-alumina上，再加熱至110℃並抽真空將水去除，生成粉體Pd0.3/20wt%Nd2O3-alumina觸媒。
將2.524g之La(NO3)3溶於水中，加入7.92g之SD-Al2O3，攪拌均勻後再加熱至110℃並抽真空將水去除，生成之粉體在600
℃煆燒，生成20wt%La2O3-alumina。取9.9g之20wt%La2O3-alumina，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.213g之醋酸鈀溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於20wt%La2O3-alumina上，再加熱至110℃並抽真空將水去除，生成粉體Pd1/20wt%La2O3-alumina觸媒。
取9.97g之20wt%La2O3-alumina，置入110℃之烘箱乾燥隔夜後置入圓底瓶中。取0.063g之醋酸鈀溶於水中後加入圓底瓶中，靜置2小時後使金屬鹽吸附於20wt%La2O3-alumina上，再加熱至110℃並抽真空將水去除，生成粉體Pd0.3/20wt%La2O3-alumina觸媒。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例1中1.8g之Pt3.5Ir1/SiO2加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至120℃後反應156分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為98%及<2%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例2中1.8g之Pd2/Al2O3加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至120℃後反應228分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵
及芳香環之轉化率分別為92%及<5%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例3中1.8g之Pd2/Al2O3加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至120℃後反應250分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為85%及<5%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例4中1.8g之Pd1/20wt%Sm2O3-alumina加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應41分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>98%及<2%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例5中1.8g之Pd0.16/20wt%Sm2O3-alumina加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應41分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>98%及<2%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例6中1.8g之Pd0.3/10wt%Sm2O3-alumina加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應41分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>98%及<2%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例7中1.8g之Pd1/5wt%Sm2O3-alumina加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應41分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>97%及<2%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例8中1.8g之Pd0.3/20wt%Nd2O3-alumina加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應41分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>98%及<2%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例9中1.8g之Pd1/20wt%La2O3-alumina加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應39分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>97%及<2%(如第1表所示)。
取9g之聚苯乙烯-異戊二烯-聚苯乙烯之嵌段共聚物(SIS，Kraton D1161)溶於111g之環己烷中形成7.5wt%之SIS溶液後，置入反應釜中。取製備例10中1.8g之Pd0.3/20wt%La2O3-alumina加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應37分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>97%及<2%(如第1表所示)。
取9g之聚苯乙烯-正丁二烯-聚苯乙烯之嵌段共聚物(Mn=62000)溶於111g之環己烷中形成15wt%之SBS溶液後，置入反應釜中。取製備例2中1.8g之Pd2/Al2O3加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應130分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>96%及<2%。
取9g之聚苯乙烯-正丁二烯-聚苯乙烯之嵌段共聚物(Mn=62000)溶於111g之環己烷中形成15wt%之SBS溶液後，置入反應釜中。取製備例10中1.8g之Pd0.3/20wt%La2O3-alumina加入反應釜後，密封反應釜並通入40Kg/cm2之氫氣。將反應釜升溫至80℃後反應35分鐘，停止加熱並以FTIR及UV-VIS量測轉化率，雙鍵及芳香環之轉化率分別為>98%及<2%。
由比較例2與3可知，載體之孔徑過小會降低氫化選擇性並增加氫化時間。由比較例2與實施例1可知，金屬氧化物可提升氫化選擇性並縮短氫化時間。
雖然本發明已以數個實施例揭露如上，然其並非用以限定本發明，任何本技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (15)
- 一種選擇性氫化共聚物的觸媒，係由一孔洞狀載體、一金屬氧化物、與多個Pd粒子所組成，其中該金屬氧化物披覆於該孔洞狀載體之部份表面上；且該些Pd粒子位於該孔洞狀載體與該金屬氧化物上，其中該孔洞狀載體之孔徑介於0.02μm至1.2μm之間，且該些Pd粒子之粒徑介於1nm至3nm之間。
- 如申請專利範圍第1項所述之選擇性氫化共聚物的觸媒，其中該孔洞狀載體包括氧化鋁、氧化矽、氧化鈦、或氧化鋯。
- 如申請專利範圍第1項所述之選擇性氫化共聚物的觸媒，其中該金屬氧化物包括氧化釤、氧化釹、氧化鑭、或上述金屬氧化物之組合。
- 如申請專利範圍第1項所述之選擇性氫化共聚物的觸媒，其中該孔洞狀載體與該金屬氧化物之重量比介於1：1至1：0.025之間。
- 如申請專利範圍第1項所述之選擇性氫化共聚物的觸媒，其中該些Pd粒子占該觸媒的0.1wt%至5wt%之間。
- 一種選擇性氫化共聚物的方法，包括：提供一共聚物，且該共聚物具有一芳香環與一雙鍵；使該共聚物接觸一觸媒，並通入氫氣以選擇性氫化該共聚物之該雙鍵且實質上不氫化該共聚物之該芳香環，其中該觸媒包括：一孔洞狀載體； 一金屬氧化物，披覆於該孔洞狀載體之部份表面上；以及多個Pd粒子，位於該孔洞狀載體與該金屬氧化物上。
- 如申請專利範圍第6項所述之選擇性氫化共聚物的方法，其中該孔洞狀載體之孔徑介於0.02μm至1.2μm之間。
- 如申請專利範圍第6項所述之選擇性氫化共聚物的方法，其中該些Pd粒子之粒徑介於1nm至3nm之間。
- 如申請專利範圍第6項所述之選擇性氫化共聚物的方法，其中該共聚物係由一多烯單體與一乙烯基芳族單體共聚而成。
- 如申請專利範圍第9項所述之選擇性氫化共聚物的方法，其中該多烯單體包括丁二烯、異戊二烯、或上述單體之組合，且該乙烯基芳族單體包括苯乙烯、α-甲基苯乙烯、或上述單體之組合。
- 如申請專利範圍第6項所述之選擇性氫化共聚物的方法，其中該共聚物之數目平均分子量介於3萬至40萬之間。
- 如申請專利範圍第6項所述之選擇性氫化共聚物的方法，其中該孔洞狀載體包括氧化鋁、氧化矽、氧化鈦、或氧化鋯。
- 如申請專利範圍第6項所述之選擇性氫化共聚物的方法，其中該金屬氧化物包括氧化釤、氧化釹、氧化鑭、或上述金屬氧化物之組合。
- 如申請專利範圍第6項所述之選擇性氫化共聚物的方法，其中該孔洞狀載體與該金屬氧化物之重量比介於1：1至 1：0.025之間。
- 如申請專利範圍第6項所述之選擇性氫化共聚物的方法，其中該些Pd粒子占該觸媒的0.1wt%至5wt%之間。
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| TW104134635A TWI564077B (zh) | 2015-10-22 | 2015-10-22 | 選擇性氫化共聚物的觸媒與方法 |
| CN201610375005.1A CN106607027A (zh) | 2015-10-22 | 2016-05-30 | 选择性氢化共聚物的催化剂与方法 |
| US15/202,819 US20170114175A1 (en) | 2015-10-22 | 2016-07-06 | Heterogeneous catalyst and method for selectively hydrogenating copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906602A (en) * | 1987-10-28 | 1990-03-06 | Sud-Chemie Aktiengesellschaft | Catalyst for the selective hydrogenation of polyunsaturated hydrocarbons and process for preparing the catalyst |
| CN102728354A (zh) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | 可高温再生的选择加氢催化剂及其制备方法 |
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| US6725031B2 (en) * | 2000-07-21 | 2004-04-20 | Telemac Corporation | Method and system for data rating for wireless devices |
| GB0312769D0 (en) * | 2003-06-04 | 2003-07-09 | Johnson Matthey Plc | Process for selective hydrogenation of acetylenic compounds and catalyst therefor |
| JP2007254413A (ja) * | 2006-03-24 | 2007-10-04 | Sumitomo Chemical Co Ltd | オレフィンの水添方法 |
| CN103551180B (zh) * | 2013-11-19 | 2015-03-18 | 中国海洋石油总公司 | 一种c10+双环重芳烃选择性加氢裂解催化剂的制备方法 |
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2015
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2016
- 2016-05-30 CN CN201610375005.1A patent/CN106607027A/zh active Pending
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906602A (en) * | 1987-10-28 | 1990-03-06 | Sud-Chemie Aktiengesellschaft | Catalyst for the selective hydrogenation of polyunsaturated hydrocarbons and process for preparing the catalyst |
| CN102728354A (zh) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | 可高温再生的选择加氢催化剂及其制备方法 |
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