CN114505072B - 一种大孔氧化硅材料的制备方法及其在不饱和聚合物非均相加氢中的应用 - Google Patents
一种大孔氧化硅材料的制备方法及其在不饱和聚合物非均相加氢中的应用 Download PDFInfo
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- CN114505072B CN114505072B CN202210239757.0A CN202210239757A CN114505072B CN 114505072 B CN114505072 B CN 114505072B CN 202210239757 A CN202210239757 A CN 202210239757A CN 114505072 B CN114505072 B CN 114505072B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 21
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 21
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
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- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
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- 239000002243 precursor Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
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- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- -1 amino trimethylene phosphonate Chemical compound 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
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- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
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- 230000000694 effects Effects 0.000 abstract description 8
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- 239000000376 reactant Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 4
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- 229910000510 noble metal Inorganic materials 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
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
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- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 3
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种大孔氧化硅材料的制备方法及其在不饱和聚合物非均相加氢中的应用。该方法利用简单的溶胶凝胶过程,创新性地在加入硅酸盐的同时加入硅烷偶联剂,通过精准控制硅酸盐与水的比例及溶液的pH,合成了稳定的表面功能化的大孔氧化硅材料,该方法成本低廉、制备简单、绿色环保。以此为载体负载金属后可制备得到大孔负载型催化剂,用于不饱和聚合物非均相加氢,表现出优异的加氢活性和选择性。
Description
技术领域
本发明属于材料制备技术领域,具体涉及一种大孔氧化硅材料的制备方法,以该材料为载体制备得到的大孔催化剂用于不饱和聚合物加氢时表现出优异的加氢活性和选择性。
背景技术
不饱和聚合物由于存在易老化的碳碳双键,导致其耐候、耐老化等性能较差,对聚合物中的C=C选择性加氢得到的氢化聚合物是具有特殊性质和结构的弹性体。与未加氢前相比,氢化聚合物的耐热、耐老化、耐臭氧、抗氧化性、热稳定性及在特殊环境下耐候性、耐腐蚀性等性能均可得到明显提升。氢化聚合物被广泛应用于其他普通聚合物难以胜任的诸多领域,如汽车传送带、汽车用燃料胶管和航天器的输油管道、石油钻探套管等特殊零部件中。
在不饱和聚合物加氢反应中,按照是否使用催化剂可分为催化和非催化加氢法。非催化加氢法主要是采用二酰亚胺(HN=NH)原位加氢的方法,反应过程中原料消耗量大,而且副反应严重,严重限制了该方法的大规模应用。对于催化加氢法,根据加氢体系不同,主要分为聚合物均相和非均相加氢法。均相溶液加氢法的特点是催化剂和反应物处于同一相,活性组分与反应物分子充分接触,无扩散传质问题,因此反应条件温和,加氢效率较高。US4978771采用 Ru 的三苯基膦配合物为催化剂,该类催化剂对 NBR 具有良好的加氢活性,在最佳反应条件下 NBR 转化率均能达 95%以上。但均相溶液加氢普遍存在的问题是贵金属催化剂分离回收困难、制备过程复杂,贵金属在产品中的残留会影响加工和使用性能。相比之下,非均相溶液加氢的优势在于催化剂和反应物处于固液两相,加氢反应完成后可直接采用过滤或离心分离技术将产物与催化剂分离,催化剂易于回收,可循环利用。
聚合物非均相溶液加氢催化剂一般是以二氧化硅(SiO2),炭黑(C),二氧化钛(TiO2)等为载体的催化剂。US04384081A公开了一种Pd/C催化剂,该催化剂具有较好的C=C选择性,US4452951A以Pd/SiO2作为催化剂,此催化剂表现出很高的催化活性和选择性,US4954576A公开了Pd/TiO2负载型催化剂,此催化剂具有催化活性高、选择性好以及重复使用性能优异的特点,CN103418413A利用多巴胺对二氧化硅改性后负载贵金属Rh,该催化剂表现出较高的催化活性。众多材料中,二氧化硅由于热稳定性优异、孔径和比表面积可调、表面含有丰富的硅羟基官能团可用于改性等特点,被广泛用于负载型催化剂的载体。
聚合物的加氢不同于普通小分子的加氢,其分子量大、构型复杂,因而反应物大分子在催化剂孔道中的扩散限制及与活性位的可接近性是影响加氢效率的关键。需要开发大孔结构的催化剂,以减小聚合物的内扩散阻力、增加孔内活性位点利用率,从而提高催化活性。但是结合目前已报道的文献,大孔催化剂的制备步骤繁琐(通常需要加入模板剂或造孔剂)、成本较高,且制备过程需要使用大量的有机溶剂,严重污染环境。
发明内容
为解决上述技术问题,本发明的目的在于开发一种大孔氧化硅材料的制备方法及其在不饱和聚合物非均相加氢中的应用。该方法利用简单的溶胶凝胶过程,创新性地在加入硅酸盐的同时加入硅烷偶联剂,合成了稳定的表面功能化大孔氧化硅材料,通过调节硅酸盐与水的比例、老化温度及溶液的pH等条件精准控制大孔孔径尺寸,该方法成本低廉、制备简单、绿色环保。以此材料为载体制备得到的大孔催化剂用于不饱和聚合物非均相加氢时表现出优异的加氢活性和选择性。
为了实现上述目的,本发明采用如下技术方案:
(a) 大孔氧化硅载体的制备:首先将硅酸盐和硅烷偶联剂溶解于适量去离子水中,以一定浓度的硝酸滴至溶液保持一定pH,然后将混合溶液置于水热合成釜中在一定温度下老化一段时间,将老化后的样品分离、干燥,即可合成表面功能化的大孔氧化硅载体。
(b) 金属负载:以上述表面功能化大孔氧化硅为载体,以金属盐为前驱体,利用浸渍法进行金属负载得到大孔氧化硅负载金属基催化剂。
步骤(a)中所述水和硅酸盐的摩尔比为5-30:1,优选摩尔比5-20:1。
步骤(a)中所述硅酸盐和硅烷偶联剂的摩尔比为10-100:1,优选20-60:1。
步骤(a)中所述硅酸盐为硅酸钠或硅酸钾,所述硅烷偶联剂为γ-氨乙基氨丙基三甲氧基硅烷、氨基三亚甲基膦酸盐和γ-氨丙基三乙氧基硅烷中的一种。
步骤(a)中所述硝酸浓度是1-5 mol/L,优选1-3 mol/L。
步骤(a)中所述硅源溶解温度是25-60 oC,优选温度30 oC。
步骤(a)中所述溶液pH保持在6-8区间,优选pH 7-8。
步骤(a)中所述混合液老化温度是60-200 oC,老化时间是5-30 h。优选老化时间20-30 h,老化温度60-120 oC。
步骤(a)中所述大孔氧化硅载体孔径为50-200 nm。
步骤(b)所述金属盐前驱体是醋酸盐和氯化盐,金属为Pd,Rh,Ni,Ru,优选Pd或Rh,金属负载量为0.5wt%-3wt%。
一种大孔氧化硅材料在不饱和聚合物非均相加氢中的应用,具体为:将制备得到的大孔氧化硅负载金属基催化剂和不饱和聚合物溶液同时置于高压反应釜中,通入一定量氢气,根据不同聚合物调节各反应参数后进行加氢反应,反应结束后对反应液进行离心分离、洗涤、烘干,回收大孔催化剂用于下一次加氢反应。
所述不饱和聚合物可以是丁腈橡胶、聚苯乙烯及苯乙烯类共聚物。
所述大孔氧化硅负载金属基催化剂与不饱和聚合物的质量比为0.1-1:1。
硅烷偶联剂作用原理:硅酸盐水解缩聚的同时与γ-氨丙基三乙氧基硅烷等偶联剂一起聚合,形成Si-O-Si骨架,因而在形成氧化硅时表面就会嫁接氨丙基三乙氧基硅。本发明在合成氧化硅的同时嫁接这个偶联剂的目的是想利用偶联剂中的氨基,由于它跟金属有很好的配位作用,因此可以锚定和分散金属颗粒,增强载体和金属间的相互作用,防止金属在后续的催化反应中脱落。
水的添加量决定氧化硅颗粒间的距离,适量的水可以增加颗粒间距离,从而在一定程度上促进形成大孔结构;但是当水量过多时,凝胶过程中形成的大孔会破裂,反而不利于大孔的产生。
氧化硅凝胶老化过程中,会经历溶解和沉淀过程,此过程溶解的氧化硅会迁移到氧化硅胶体颗粒间的颈部区域,导致孔径减小。这主要是由于颈部区域的溶解度低于体相,适当提高温度可以提升颈部氧化硅的溶解度,从而控制颈部生长,优化大孔孔径。
氧化硅老化过程中,硅羟基基团容易发生脱水缩合,导致氧化硅孔径进一步减小,酸性条件会促进这一现象的产生,因此通过调节pH条件优化氧化硅孔径。
本发明的有益效果在于:
1) 本发明提供的上述大孔氧化硅为载体的负载型催化剂对不饱和聚合物非均相加氢具有优异的催化活性和选择性。
2) 该催化剂的特点是:(1)利用简单的溶胶凝胶过程,同时加入硅酸盐和硅烷偶联剂,一步合成了稳定的表面功能化的大孔氧化硅材料;(2)通过调节硅酸盐与水的比例、老化温度及溶液的pH等可以精准调控大孔孔径尺寸;(3)偏硅酸钠水解缩聚的同时与氨基硅烷偶联剂一起聚合,一步合成表面嫁接氨基的氧化硅载体,利用氨基和金属的配位作用,更好地分散和锚定金属颗粒,防止金属在反应中脱落,进而降低产物中活性组分残留量、提升产品性能;(4)该方法成本低廉、制备简单、绿色环保;(5)以该材料为载体制备得到的大孔催化剂用于不饱和聚合物加氢时表现出优异的加氢活性和选择性。
附图说明
图1为实施例1、2和3中催化剂的N2吸附-脱附等温线图;
图2为对比例1中催化剂的N2吸附-脱附等温线和孔径分布图;
图3为实施例2和3中催化剂的孔径分布图(压汞法);
图4为实施例2和对比例1中所得产物HNBR及反应物NBR的1H NMR图。
具体实施方式
为了使本发明所述的内容更加便于理解,通过以下实施例对本发明所述的技术方案进一步阐述,但下面实施例仅为本发明优选实例,并非对本发明实施范围的限定。基于实施方式中的实施例,本领域技术人员在没有做出创造性劳动的前提下所获得的其他实施例,均属于本发明的保护范围。
在以下实施例中N2吸脱附等温线和孔径分布数据由美国麦克ASAP 2460全自动物理吸附仪获得;大孔孔径分布数据由美国康塔Poremaster33全自动压汞法测试仪获得;1HNMR数据由日本AVANCE NEO 600核磁共振波谱仪获得。
实施例1
催化剂制备过程如下:首先配制3 mol/L的硝酸待用。将9.46 g Na2SiO3·9H2O和0.1 g γ-氨丙基三乙氧基硅烷溶解在17.99 g水中,30 oC下向溶液中滴加硝酸至中性,再将此混合溶液置于水热合成釜中在60 oC恒温干燥箱中老化20 h,最后抽滤、干燥得到表面功能化的大孔氧化硅载体;接着将1.50 g大孔氧化硅分散在50 mL二氯甲烷中,再称取0.03g醋酸钯溶解在8 mL二氯甲烷中,将醋酸钯溶液逐滴加入上述氧化硅悬浮液中,搅拌后转移至60 oC水浴锅中老化24 h,离心分离得到样品;最后将样品在140 oC、体积分数10% H2/Ar气氛下还原2 h,即可得到大孔氧化硅为载体的负载型催化剂。非均相加氢过程如下:将0.5g NBR溶解在40 g丙酮中,取0.5 g催化剂加入到NBR胶液中,在高压反应釜中进行加氢反应。反应条件为:反应温度60 oC,氢气压力1 MPa,反应时间2 h。反应结束后,将混合反应液离心分离,向胶液中添加去离子水聚沉得到产品HNBR,产物加氢度列于表1中。
实施例2
把实施例1中水的质量换成6.00 g,其他同实施例1,结果见表1。
实施例3
把实施例1中水的质量换成3.00 g,其他同实施例1,结果见表1。
实施例4
把实施例2中硅烷偶联剂换成0. 2 gγ-氨乙基氨丙基三甲氧基硅烷,其他同实施例2,结果见表1。
实施例5
把实施例2中醋酸钯换成三氯化铑,具体过程如下:称量1.5 g上述功能化大孔氧化硅载体和50 mL乙酸乙酯置于烧杯中搅拌分散,再称取0.03 g三氯化铑溶解在5 mL乙酸乙酯中,将三氯化铑溶液逐滴加入上述氧化硅悬浮液中,其他同实施例2,结果见表1。
实施例6
把实施例2中所制备的催化剂用于聚苯乙烯(PS)加氢,具体过程为:称取PS溶解在80.0 g环己烷中配置成浓度为5wt%的PS胶液,再将其转移至反应釜中,同时加入1.0 g上述催化剂,将釜内空气排空后,设置氢气反应压力为4.0 MPa、反应时间为8.0 h、反应温度为150 oC、搅拌速率1000 r/min。反应结束后,将混合反应液离心分离得到产物,其他同实施例2,结果见表1。
实施例7
把实施例2中所制备的催化剂用于苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)加氢,具体过程为:称取1.0 g SBS溶解在80.0 g环己烷中,再将其转移至反应釜中,同时加入1.0g上述催化剂,将釜内空气排空后,设置氢气反应压力为3.0 MPa、反应时间为6.0 h、反应温度为140 oC、搅拌速率800 r/min。反应结束后,将混合反应液离心分离得到产物,其他同实施例2,结果见表1。
对比例1
为验证大孔结构的作用,本对比例将氧化硅载体合成过程中水的质量变为53.97g,其他同实施例1,结果见表1。
对比例2
为验证本发明硅烷偶联剂的作用,本对比例不添加硅烷偶联剂,其他同实施例2,结果见表2。
实施例2和对比例2的产物中金属残留量分别是0.46ppm和51.92ppm,即氨基修饰的催化剂中活性组分流失现象明显改善。
图1为实施例1、2和3中大孔氧化硅催化剂的N2吸附-脱附等温线和比表面积数据。从图中可以观察到,三种催化剂的比表面积分别为158 m2/g、95 m2/g和83 m2/g,三种催化剂均表现为IV型等温线和H3型滞后环,说明催化剂中可能含有大孔结构。
图2为对比例1中催化剂的N2吸附-脱附等温线和孔径分布图。从图中可以看到,该催化剂比表面积达321 m2/g,孔径是12.6 nm左右的介孔。
图3为实施例2和3中催化剂的孔径分布图。从图中可以观察到,两种催化剂均为大孔结构,孔径分别位于70.0 nm和120.8 nm左右。
图4为实施例2和对比例1中所得产物HNBR及反应物NBR的1H NMR对比图。从图中可以看到,相比于反应物NBR,实施例2和对比例1中产物HNBR位于4.9-5.6 ppm左右属于烯烃上氢原子的化学位移峰都大幅减弱,位于0.9-1.8 ppm左右属于碳碳单键上氢原子的化学位移峰增强,说明发生了加氢反应。其中实施例2中产物HNBR在4.9-5.6 ppm处的氢化学位移峰几乎消失,说明氢化度更高。
表1实施例 1-7 和对比例1-2的加氢度和选择性
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (4)
1.一种大孔氧化硅材料的制备方法,其特征在于:首先将硅酸盐和硅烷偶联剂溶解于适量去离子水中,滴入一定浓度的硝酸保持一定的pH,然后将混合溶液置于水热合成釜中在一定温度下老化一段时间,将老化后的样品分离、干燥,得到表面功能化的大孔氧化硅材料;
所述去离子水和硅酸盐的摩尔比为5-30:1,所述硅酸盐为硅酸钠或硅酸钾;
所述硅酸盐和硅烷偶联剂的摩尔比为10-100:1,所述硅烷偶联剂为γ-氨乙基氨丙基三甲氧基硅烷、氨基三亚甲基膦酸盐和γ-氨丙基三乙氧基硅烷中的一种;
硝酸浓度是1-3 mol/L,溶液pH保持在6-8区间;
硅酸盐溶解温度是25-60 oC;
老化温度是60-200 oC,老化时间是5-30 h;
所述大孔氧化硅材料孔径为50-200 nm。
2.根据权利要求1所述的制备方法,其特征在于:以大孔氧化硅材料为载体,以金属盐为前驱体,利用浸渍法进行金属负载得到大孔氧化硅负载金属基催化剂;所述金属盐前驱体是醋酸盐或氯化盐,金属为Pd,Rh,Ni,Ru中的一种或多种,金属负载量为0.5wt%-3wt%。
3.根据权利要求2所述的制备方法,其特征在于:将大孔氧化硅负载金属基催化剂用于不饱和聚合物非均相加氢反应中。
4.根据权利要求3所述的制备方法,其特征在于:所述不饱和聚合物非均相加氢反应是在高压反应釜内进行,用适当有机溶剂溶解不饱和聚合物后加入反应釜,然后加入一定量的大孔氧化硅负载金属基催化剂,通入一定的氢气压力,根据不同聚合物升至一定温度进行加氢反应,反应结束后对反应液进行离心分离,回收得到的催化剂用于下一次加氢反应;
所述不饱和聚合物是丁腈橡胶、聚苯乙烯、苯乙烯-丁二烯-苯乙烯嵌段共聚物;大孔氧化硅负载金属基催化剂与不饱和聚合物的质量比为0.1-1:1。
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CN109277112B (zh) * | 2017-07-20 | 2020-05-08 | 万华化学集团股份有限公司 | 一种基于silicalite-1分子筛的催化剂及用其制备1,2-戊二醇的方法 |
CN108380171A (zh) * | 2018-03-26 | 2018-08-10 | 武汉理工大学 | 一种氨基功能化磁性二氧化硅吸附材料的制备方法 |
CN112871199A (zh) * | 2021-02-27 | 2021-06-01 | 福州大学 | 一种非均相负载型加氢催化剂、其制备方法以及其在加氢制备聚环己烷基乙烯上的应用 |
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