Heterogeneous two-component hydrogenation catalyst, hydrogenated nitrile rubber and preparation method thereof

A hydrogenation catalyst, nitrile rubber technology, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve the problem of difficult separation, waste of precious metal resources, accelerated Rubber aging and other issues

Active Publication Date: 2020-10-20
CHINA UNIV OF PETROLEUM (BEIJING) +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the difficulty in separating homogeneous catalysts from hydrogenation products, the investment in catalyst separation equipment greatly increases production costs
At the same time, the catalyst remaining in the hydrogenation product causes waste of precious metal resources, accelerates the aging of rubber and shortens the product life cycle

Method used

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  • Heterogeneous two-component hydrogenation catalyst, hydrogenated nitrile rubber and preparation method thereof
  • Heterogeneous two-component hydrogenation catalyst, hydrogenated nitrile rubber and preparation method thereof
  • Heterogeneous two-component hydrogenation catalyst, hydrogenated nitrile rubber and preparation method thereof

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preparation example Construction

[0052] The specific embodiment of the present invention provides the preparation method of the heterogeneous two-component hydrogenation catalyst, and this preparation method specifically comprises the following steps:

[0053] The modification of SHMs can be carried out according to the following steps, but not limited thereto:

[0054] Take 1g of SHMs and dry at 100°C, cool to room temperature, and disperse in a certain solvent; dissolve a certain amount of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane to prepare a precursor liquid; Body fluid and SHMs dispersion were mixed, stirred at room temperature for 10 min, then transferred to a constant temperature water bath at 80°C for 24 h; after cooling to room temperature, centrifuged, washed with a solvent to remove unreacted substances on the surface of the carrier; after washing, the sample was dispersed in in ethanol, stirred in a 60°C water bath for 8h, cooled to room temperature, separated, and dried in an oven at 100°C t...

Embodiment 1

[0061] This embodiment provides a method for preparing a heterogeneous two-component hydrogenation catalyst, which comprises the following steps:

[0062] N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane amino-modified silica hollow microspheres SHMs, and then, using amino-modified SHMs as a carrier, Pd(OAc) 2 The solution is the precursor liquid of the active component, and Pd is loaded by chemical bonding method, and Zr(C 3 h 7 O) 4 The solution is the precursor liquid of the auxiliary component, and Zr is loaded by the solvent evaporation method to prepare a heterogeneous two-component hydrogenation catalyst Pd-Zr / SHMs with a total loading of 7wt% and a Pd:Zr atomic ratio of 7:1. .

[0063] The present embodiment also provides the preparation method of HNBR, and this preparation method comprises the following steps:

[0064] Dissolve 1g of NBR in 100mL of acetone solvent to obtain glue, take 1g of heterogeneous two-component hydrogenation catalyst Pd-Zr / SHMs into the glue...

Embodiment 2

[0068] This embodiment provides a method for preparing a heterogeneous two-component hydrogenation catalyst, which comprises the following steps:

[0069] N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane amino-modified silica hollow microspheres SHMs, and then, using amino-modified SHMs as a carrier, Pd(OAc) 2 The solution is the precursor liquid of the active component, and Pd is loaded by chemical bonding method, and Zr(C 3 h 7 O) 4 The solution is the precursor liquid of the auxiliary component, and the Zr is loaded by the solvent evaporation method, and finally, after drying, H 2 Reduction and other treatments prepared a heterogeneous two-component hydrogenation catalyst Pd-Zr / SHMs with a total loading of 7wt% and a Pd:Zr atomic ratio of 5:1.

[0070] The preparation method of HNBR is as embodiment 1, and the hydrogenation degree of this method, selectivity and the Pd content that exist in the prepared HNBR are listed in table 2.

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Abstract

The present invention relates to a heterogeneous two-component hydrogenation catalyst, a hydrogenated nitrile butadiene rubber, and preparation methods of the heterogeneous two-component hydrogenation catalyst and the hydrogenated nitrile butadiene rubber. The heterogeneous two-component hydrogenation catalyst preparation method specifically comprises: carrying out amino modification on a silica hollow microsphere carrier by using a coupling agent, loading an active component M1 and an auxiliary agent component M2 on the carrier, drying, and carrying out H2 reduction treatment to obtain the heterogeneous two-component hydrogenation catalyst, wherein the active component M1 is selected from Pd or Rh, preferably Pd, and the auxiliary agent component M2 is selected from Zr or Ti, preferably Zr. According to the present invention, the prepared heterogeneous two-component hydrogenation catalyst has advantages of high catalytic activity, high selectivity, good stability, relatively low preparation cost, mild hydrogenation condition, simple process and precious metal consumption reducing; the synthesis cost of the catalyst is effectively reduced by completely using the synergetic effect between the precious metal and the auxiliary agent; and the hydrogenation degree of the hydrogenated nitrile butadiene rubber preparation method is high, and the selectivity can achieve 100%.

Description

technical field [0001] The invention relates to a heterogeneous two-component hydrogenation catalyst, hydrogenated nitrile rubber and a preparation method thereof, belonging to the field of preparing special rubber by catalytic hydrogenation. Background technique [0002] Nitrile rubber (NBR) is called butadiene-acrylonitrile rubber, which is prepared by emulsion copolymerization of butadiene and acrylonitrile. It is one of the main synthetic rubber varieties widely used at present. The presence of nitrile groups in the NBR molecular chain makes it resistant to non-polar oils and low aromatic solvents, but the presence of a large number of unsaturated C=C makes it heat resistant, oxidation resistant, aging resistant and resistant Ozone performance is poor. Under the premise of retaining the nitrile group, hydrogenated nitrile rubber (HNBR) with high performance and high added value can be prepared by selectively hydrogenating and saturating the unsaturated C=C. HNBR inheri...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/44C08C19/02
CPCB01J23/44C08C19/02
Inventor 袁珮鲍晓军王建龚光碧郑聚成艾纯金
Owner CHINA UNIV OF PETROLEUM (BEIJING)
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