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Hybridized dendrimer-loaded bimetal metal nanoparticle catalyst as well as preparation method and application thereof

A technology of metal nanoparticles and dendrimers, applied in organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problem of low catalytic activity and difficulty in recycling catalysts, etc. problems, to achieve high selectivity, excellent catalytic hydrogenation effect

Active Publication Date: 2015-02-11
YINGDE BOTE CHEM INDAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Therefore, in view of the problems that the current hydrogenated nitrile rubber method is difficult to recycle the catalyst, the gelation rate of HNBR is high, and the catalytic activity is low, a new compound with high selectivity, high catalytic activity, high cost performance, easy separation, recovery and recycling has been prepared. Hydrogen catalyst is a key problem that needs to be solved urgently in the research of NBR hydrogenation production technology

Method used

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  • Hybridized dendrimer-loaded bimetal metal nanoparticle catalyst as well as preparation method and application thereof
  • Hybridized dendrimer-loaded bimetal metal nanoparticle catalyst as well as preparation method and application thereof
  • Hybridized dendrimer-loaded bimetal metal nanoparticle catalyst as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Example 1 Second-generation hybrid dendritic polymer-loaded bimetallic nanoparticles and its catalytic hydrogenation of nitrile rubber

[0040] 1. Surface-modified second-generation polypropyleneimine dendrimers (G 2 PPI-M) take 2.155g (2.79×10 ‐3 mol)G 2 PPI (Netherlands SyMO-Chem B.V company) was dissolved in 10ml acetonitrile for later use. 0.48g (4.8×10 ‐4 mol)1,11‐di[2,4,6‐triisopropylbenzenesulfonyl]‐6‐[4‐(3‐bromopropyl)benzenesulfonyl]‐1,6,11‐triazacyclodeca Pentadecane‐3,8,13‐triene (MAC), 0.33g (2.4×10 ‐3 mol) of anhydrous potassium carbonate is placed in a reaction flask with a reflux and ventilation device. Connect the external ventilation device and replace the N 2 three times. Under normal temperature stirring, inject 0.24mlG into the flask successively 2 PPI / acetonitrile solution and 30ml acetonitrile. The temperature was raised to 107°C for 12 hours. After the reaction was completed, the solid powder was removed by filtration, and the solid powd...

Embodiment 2

[0053] Example 2 The third generation of hybrid dendrimers loaded with bimetallic nanoparticles and its catalytic hydrogenation of nitrile rubber

[0054] 1. G 3 Synthesis of PPI‐M

[0055] Accurately weigh 1.610g (9.54×10 ‐4 mol)G 3 PPI (Netherlands SyMO-Chem B.V company) was dissolved in 10ml acetonitrile for later use. Take 0.80g (8.0×10 ‐4 mol) MAC, 0.56g (4.1×10 ‐3 mol) of anhydrous potassium carbonate is placed in a reaction flask with a reflux and ventilation device. Connect the external ventilation device and replace the N 2 three times. Under stirring at room temperature, inject 0.56mlG into the flask successively 3 PPI / acetonitrile solution, 30ml acetonitrile. Then the temperature was raised to 107°C for 18 hours. After the reaction was completed, the solid powder was filtered out, and the solid powder was washed three times with tetrahydrofuran during filtration to obtain a filtrate. The filtrate was distilled under reduced pressure to obtain an oily liqu...

Embodiment 3

[0068] Example 3 The fourth generation of hybrid dendrimers loaded with bimetallic nanoparticles and its catalytic hydrogenation of nitrile rubber

[0069] 1. G 4 Synthesis of PPI-M

[0070] Take 0.654g (1.86×10 ‐4 mol) G 4 PPI (Netherlands SyMO-Chem B.V company) was dissolved in 17ml acetonitrile for later use. 0.84g (8.4×10 ‐4 mol) MAC, 0.62g (4.5×10 ‐3mol) of anhydrous potassium carbonate is placed in a reaction flask with a reflux and ventilation device. Connect the external ventilation device and replace the N 2 three times. Under normal temperature stirring, inject 1.92mlG into the flask successively 4 PPI / acetonitrile solution, 40ml of acetonitrile, heated to 107°C for 20h. After the reaction was completed, the solid powder was filtered out, and the solid powder was washed three times with 30 ml of tetrahydrofuran to obtain a filtrate. The filtrate was distilled under reduced pressure to obtain an oily liquid, which was subjected to silica gel column chromatog...

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Abstract

The invention discloses a hybridized dendrimer-loaded bimetal metal nanoparticle catalyst as well as a preparation method and application thereof. The hybridized dendrimer-loaded bimetal metal nanoparticle catalyst is a compound using hybridized polypropyleneimine (PPI) as a carrier and ruthenium and rhodium as metal nanoparticles. The preparation method comprises the following steps: modifying a primary amine group at the periphery of integral-algebra polypropyleneimine by using fifteen-element triene nitrogen heterocycle (MAC) to synthesize a novel hybridized dendrimer loading fifteen-element triolefin large ring on the surface and having different-algebra PPI; and then by adopting a method of co-complexing-reducing with two kinds of metal ions and using GnPPI-M (n=2, 3, 4, 5) as a carrier, preparing Ru / Rh bimetal DTNs with different Ru / Rh proportions, and by using the Ru / Rh bimetal DTNs as a catalyst, performing catalytic hydrogenation on butadiene-acrylonitrile rubber. The catalyst prepared by adopting the preparation method has excellent catalytic activity and selectivity, and can be recycled.

Description

technical field [0001] The invention relates to a catalyst for the preparation of hydrogenated nitrile rubber, in particular to a hybrid dendrimer-supported bimetal nanoparticle catalyst for catalytic hydrogenated nitrile rubber and a preparation method thereof. Background technique [0002] Hydrogenated nitrile rubber has good oil resistance (good resistance to fuel oil, lubricating oil, and aromatic solvents); and due to its highly saturated structure, it has good heat resistance and excellent chemical corrosion resistance (to Good resistance to freon, acid and alkali), excellent ozone resistance, high compression set resistance; at the same time, hydrogenated nitrile rubber also has high strength, high tear performance and excellent wear resistance. It is one of the rubbers with excellent comprehensive properties. Hydrogenated nitrile rubber (HNBR) is a highly saturated elastomer obtained by special hydrogenation of nitrile rubber, which can be prepared by catalyzing the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B82Y30/00B82Y40/00C07D255/02C08G73/04C08C19/02
Inventor 彭晓宏周为王洋
Owner YINGDE BOTE CHEM INDAL
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