CN106622374B - 一种树脂基固载化铑膦配合物催化剂及其制备方法与应用 - Google Patents
一种树脂基固载化铑膦配合物催化剂及其制备方法与应用 Download PDFInfo
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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Abstract
本发明公开了一种树脂基固载化铑膦配合物催化剂及其制备方法与应用,其是以树脂性聚合物作为载体,采用膦配体对其进行改性后,在其上键合铑配合物,合成固载化的铑膦配合物催化剂。该催化剂通过氧桥键将铑膦配合物固载在载体树脂表面,从而可在其载体表面形成具有较高催化活性和选择性的铑膦配位催化活性中心,并使所得催化剂具有反应条件温和,选择性好,催化性能稳定以及易于分离可循环使用等特点,可用于催化1‑辛烯氢甲酰化反应。
Description
技术领域
本发明属于催化剂制备领域,具体涉及一种树脂基固载化铑膦配合物催化剂及其制备方法与应用。
背景技术
氢甲酰化反应是在1938年由Otto Roelen(1897-1993)发现的,是当今产能最大的均相催化过程,其产物醛是非常重要的精细化学品,也是合成合成醇、酯和胺的中间体,年产量已有近10000多万吨。到目前为止,工业上大多采用均相的Rh和Co作为催化剂,其反应条件较为苛刻,仅适用于低碳链的烯烃,且反应结束后,催化剂难于与产物分离,因此合成非均相的铑膦络合物催化剂已成为当今研究的热点。
目前,均相金属络合物催化剂多相化方法主要包括以下两大类:一类是将催化剂动态“担载”在与产物互不相溶的液相而实施的液/液两相催化;另一类是将催化剂静态固定在有机高分子或无机载体上的固载化。但当两相催化工艺扩展到高碳烯烃时,由于高碳烯烃的水溶性太低,反应过程中传质受到限制,使反应难以进行。
为实现氢甲酰化催化剂的均相固载化,Kausik Mukhopadhyay 等(Chem Mater,2003,15:1766-1777)以MCM-41和MCM-48为载体,采用磷钨酸对载体表面改性,以磷钨酸为链接基团将Wilkinson催化剂HRh(CO)(PPh3)3锚定于分子筛内而用于高碳烯烃的氢甲酰化反应。但从反应效果看,对于线性醛的选择性依然较低。
L. Huang等(Applied Catalysis A: General,2004,265:247-257)利用胺化后的SiO2负载HRh(CO)(PPh3)3,研究表明,由于膦和胺配体的空间效应,在相同反应条件下,SiO2负载催化剂活性大大超过了HRh(CO)(PPh3)3催化的均相体系,且Rh流失量较少。
Yasan He等(Journal of Porous Mater,2009,16:721-729)以MCM-41为载体,利用含膦和含氮有机硅耦合试剂对载体表面改性后浸渍RhCl3,以苯乙烯为底物,为达到较高的反应活性和支链醛的选择性还需要额外添加三苯基膦,但由于配体具有还原性,Rh(III)被部分还原为活性更低的氧化态,因此催化效果较差。
Ki-Chang Song等(Catalysis Today,2011,164:561-565)胺化处理SBA-15后利用膦配体对载体表面修饰,将铑的络合物封装在SBA-15中,由于膦配体的配位作用,铑可以特定的固定在介孔内部和表面,因此具有较高的选择性,而且无铑流失,但相较于均相催化效果,还有很大的差距。
Banothile C. E. Makhubela等(Green Chemistry,2012,14:338-347)以无毒、生物可降解的壳聚糖为载体,由于载体表面具有活性胺基,用希夫碱改性后可络合铑催化剂。反应温度为70℃,反应压力为30bar时,反应活性、线性选择性达到最高,但依然有少量Rh析出。
N. Sudheesh等(Applied Catalysis A:General,2012,415-416:124-131)将HRh(CO)(PPh3)3原位封装在六方介孔硅中,封装过程中加入十二烷胺异构化Rh络合物。在非均相催化剂体系中,包埋在胶束中的Rh-络合物在孔道内形成均相催化体系,反应过程中详细考察了催化剂用量、Rh-络合物/TEOS、温度、H2和CO分压对丙烯氢甲酰化的影响。研究表明,Rh-络合物/TEOS和H2分压对催化效果影响最大,增加Rh-络合物/TEOS和H2分压可提高正丁醛的选择性。
发明内容
本发明的目的在于提供一种树脂基固载化铑膦配合物催化剂及其制备方法与应用,该催化剂选择性好、催化性能稳定,且无铑流失,可用于高碳烯烃的氢甲酰化反应。
为实现上述目的,本发明采用如下技术方案:
一种树脂基固载化铑膦配合物催化剂,其是以有机聚合物作为载体,采用膦配体对其进行改性后,在其上键合铑配合物,合成固载化的铑膦配合物催化剂;所述有机聚合物为酚醛树脂、含磷酚醛树脂或间苯二酚树脂。
所述有机聚合物具有规整六方介孔结构,其比表面积为220m2/g,孔容为0.34cm3/g,孔径集中分布在3.7nm。
所述膦配体为二苯基氯化膦;所述铑配合物为乙酰丙酮二羰基铑。
所得催化剂中Rh的含量为2%。
所述树脂基固载化铑膦配合物催化剂的制备方法包括以下步骤:
1)将0.5g有机聚合物加入到体积浓度为10%的100mL稀硝酸溶液中,于100℃回流3h后,用蒸馏水清洗至滤液呈中性,再于50℃进行真空干燥,得活化的载体;
2)将0.2g活化的载体加入到20mL四氢呋喃(THF)中,再加入3.3mol三乙胺、2.58mmol二苯基氯化膦,在N2气氛中常温回流24h,所得产物用无水乙醇洗涤后,在真空条件下除去溶剂,然后于50℃进行真空干燥,得改性后的载体;
3)将0.2g改性后的载体加入到20mL甲苯中,再加入5.1mg乙酰丙酮二羰基铑[Rh(acac)(CO)2],在N2气氛中常温回流24h,所得产物用甲苯洗涤后,于50℃进行真空干燥,取出后在N2气氛下保存。
所得树脂基固载化铑膦配合物催化剂可用于催化1-辛烯氢甲酰化反应,其反应在高压反应釜内进行,反应温度为60-110℃,优选80℃,反应压力为1-4MPa,优选2MPa,反应时间为2-8h,优选4h。
本发明采用具有规整六方介孔结构的树脂性聚合物作为载体,其表面具有丰富的羟基,经膦配体改性后,能产生较多的活性位点,可在其上锚定铑配合物,并利用载体表面丰富的膦配位中心与铑形成稳定催化活性中心,有效减少铑流失,提高催化活性。
本发明制备方法简单,所得固载化铑膦配合物催化剂可应用于高碳烯烃反应中,其反应条件温和,催化剂易回收,且产物醛的选择性高。
附图说明
图1为实施例1所得酚醛树脂的等温吸-脱附曲线图。
图2为实施例1所得酚醛树脂的孔径分布图。
图3为实施例1所得酚醛树脂的XRD图。
图4为实施例1所得活化载体(a)、改性载体(b)及铑膦配合物催化剂(c)的FTTR图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
1、酚醛树脂的合成
1)称取2.44g苯酚,在40-42℃溶化后,在搅拌条件下加入0.52g 20wt%的NaOH溶液,然后在50℃下滴加4.2g甲醛(37wt%的甲醛溶液),再在70℃下反应1h,用0.6M的HCl溶液调节pH至7.0,50℃蒸发除去水分;
2)称取3.2g F127溶解于20mL乙醇中,在40℃下搅拌1h后得到澄清的溶液,加入步骤1)所得酚醛低聚物,在40℃下搅拌1h,过滤除去溶液中析出的盐;
3)将步骤2)所得溶液倒入平盘中,在40℃烘箱中放置过夜,以蒸发除去乙醇,然后在100℃下固化24h,取出研磨成粉;
4)将所得粉末放入管式炉中,通入N2,并以1℃/min的速率升温至350℃,恒温焙烧3h,所得固体自然降温后取出,存放于干燥器内,记为RF。
将所得聚合物先在473K脱气处理6h,再在液氮下进行氮吸附测试,其测试结果如图1所示。从图1可见,所得聚合物具有典型的IV型等温曲线,P/P0 =0.6-0.8出现毛细凝聚现象,表明该材料为介孔材料。
采用ASAP 2020型吸附仪对所得聚合物的比表面积和孔径分布进行测定,其测试结果如图2所述,从图2可见,其孔径集中分布在3.7nm左右。
采用XRD检测RF的结构。XRD测试在X'Pert PRO型X射线衍射仪,测试条件为:CuKα1辐射源,扫描范围2θ=0.5°-5°,扫描速度为0.2°/s,测试结果如图3所示,从图3可见,其出现一个强衍射峰,两个弱衍射峰,由衍射特征角可知,该聚合物为规整的2-D六方结构。
2、固载化铑膦配合物催化剂的制备
1)将0.5g所制备的酚醛树脂加入到100mL体积浓度为10%的稀硝酸溶液中,于100℃回流3h后,用蒸馏水洗涤至溶液为中性,再于50℃进行真空干燥,得到活化的载体,放入干燥器内存放;
2)取0.2g活化的载体,加入20mL THF和3.3mmol三乙胺,并滴加2.58mmol二苯基氯化膦,在室温下、N2气氛中回流24h,所得产物在N2保护下,用无水乙醇过滤洗涤除去三乙胺盐酸盐后,再蒸发除去乙醇,然后于50℃进行真空干燥,得到改性后的载体;
3)将0.2g改性后的载体加入到20mL甲苯中,再加入5.1mg Rh(acac)(CO)2,在室温下、N2气氛中回流24h后,所得产物用过量的甲苯洗涤后,蒸发除去甲苯,再在50℃进行真空干燥,得固载化铑膦配合物催化剂,将其取出后在N2的保护下密封保存。
采用Nicolet 6700型傅里叶红外光谱仪对所得活化载体(a)、改性载体(b)及铑膦配合物催化剂(c)进行测定,测得结果如图4所示。从图4中可见,经过膦配体改性键合铑配合物后,在波数为693cm-1左右有吸收峰,表明该载体成功固载铑膦络合物。
实施例2
含磷酚醛树脂的合成
1)称取2.44g苯酚,在40-42℃溶化后,在搅拌条件下加入0.52g 20wt%的NaOH溶液,然后在50℃下滴加4.2g甲醛(37wt%的甲醛溶液),再在70℃下反应1h,用0.6M的HCl溶液调节pH至~7.0,50℃蒸发除去水分;
2)称取3.2g F127溶解在20.0mL乙醇中,在40℃下搅拌1h后得到澄清的溶液,然后加入4mL蒸馏水和4mL 0.6mol/L的HCl,再加入0.72g磷酸和步骤1)所得酚醛低聚物,搅拌1h后,倒入平盘,在室温下蒸发除去水分,然后在100℃烘箱中固化24h;
3)将所得固体放入管式炉中,通入N2,并以1℃/min的速率升温至350℃,恒温焙烧3h,所得固体自然降温后取出,存放于干燥器内,记为RFP。
除使用载体为含磷酚醛树脂(RFP)外,其催化剂制备操作同实施例1。
实施例3
间苯二酚树脂的合成
1)称取0.55g间苯二酚、0.35g HMTA、1.00g F127和0.20g 1,3,5-三甲苯,将其溶解于18g水中,在室温下剧烈搅拌2h,将所得到的均相溶液倒入100mL的高压釜中,在100℃下反应12h,过滤得到橘红色的聚合物颗粒,清洗后在空气中干燥;
2)将所得聚合物颗粒放入管式炉中,通入N2,并以每分钟1℃的速率升温至350℃,恒温焙烧3h后,所得固体自然降温后取出,存放于干燥器内,记为RS。
除使用载体为间苯二酚树脂(RS)外,其催化剂制备操作同实施例1。
分别测定实施例1-3所得铑膦配合物催化剂对1-辛烯氢甲酰化反应的催化效果,其测定操作为:在100mL高压反应釜中,加入铑膦配合物催化剂0.0129g、1-辛烯0.5611g、甲苯10mL,安装好反应釜;先后用N2和合成气(CO和H2的混合气,CO/H2=1/1)置换反应釜中的空气三次,然后将反应釜加热至70℃,充入合成气至压力为1Mpa,反应4h后停止运行,迅速用冰水将反应釜冷却至室温,打开出口阀,泄压至常压,然后打开釜盖,取出反应液,过滤后得到产物。加入0.3g的正葵烷作为内标进行分析,所得结果见表1。
对比例1
在1-辛烯氢甲酰化反应中,以实施例2所得铑膦配合物催化剂进行催化,并在原料中加入0.0375g三苯基膦,其他按上述氢甲酰化反应进行操作,所得结果见表1。
对比例2
在1-辛烯氢甲酰化反应中,以实施例3所得铑膦配合物催化剂进行催化,并在原料中加入0.0375g三苯基膦,其他按上述氢甲酰化反应进行操作,所得结果见表1。
表1 不同铑膦配合物催化剂对1-辛烯氢甲酰化反应的催化效果
由表1可见,使用本发明制备的固载化铑膦配合物催化剂在1-辛烯氢甲酰化反应中具有最好的催化性能,对线性醛具有较高的选择性,适用于高碳烯烃的氢甲酰化过程。
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 (1)
1.一种树脂基固载化铑膦配合物催化剂的制备方法,其特征在于:包括以下步骤:
1)将有机聚合物加入到体积浓度为10%的稀硝酸溶液中,于100℃回流3h后,用蒸馏水清洗至滤液呈中性,再于50℃进行真空干燥,得活化的载体;
2)将0.2g活化的载体加入到20mL四氢呋喃中,再加入3.3mmol三乙胺,2.58mmol二苯基氯化膦,在N2气氛中常温回流24h,所得产物用无水乙醇洗涤后,在真空条件下除去溶剂,然后于50℃进行真空干燥,得改性后的载体;
3)将0.2g改性后的载体加入到20mL甲苯中,再加入5.1mg乙酰丙酮二羰基铑,在N2气氛中常温回流24h,所得产物用甲苯洗涤后,于50℃进行真空干燥,取出后在N2气氛下保存;
所述有机聚合物为酚醛树脂、含磷酚醛树脂或间苯二酚树脂。
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