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Method for removing residual rhodium catalyst from hydrogenated nitrile rubber

A technology for hydrogenating nitrile butadiene rubber and rhodium catalysts, which is applied in the field of removing residual rhodium catalysts, can solve the problems of long processing cycle time, secondary pollution of hydrogenated nitrile butadiene rubber, large consumption, etc., to reduce consumption, improve desorption efficiency, The effect of reducing the processing cycle

Inactive Publication Date: 2005-03-30
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] U.S. Patent 4,944,926 mentions a method for removing the rhodium catalyst in the hydrogenated nitrile rubber by adding organic additives, but if these additives are not completely separated from the hydrogenated nitrile rubber, it will cause damage to the hydrogenated nitrile rubber Secondary pollution
U.S. Patent 4,985,540 discloses a kind of chelating resin with a single functional group such as mercapto, thiourea, primary amine, secondary amine to remove rhodium catalyst in hydrogenated nitrile rubber, but its resin is used for continuous treatment of glue. Very large (1:3 resin:glue (dry basis)), long processing cycle time (54 hours)

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] The macroporous chelating resin is a copolymer of benzenediene-divinylbenzene with a specific surface area of ​​500m 2 / g, pore volume is 0.75ml / g, average pore size: 200; particle size distribution: 1~1.5mm (dry basis); bulk density: 880g / l (wet basis), with thiourea group, isosulfide Urea functional group.

[0017] Use the above macroporous chelating resin with thiourea group and isothiourea group to remove the rhodium complex catalyst in HNBR. The specific process is as follows:

[0018] Hydrogenation of 6-25% nitrile rubber in chlorobenzene solution in the presence of rhodium catalyst and triphenylphosphine co-catalyst can obtain HNBR.

[0019] About 10g of macroporous chelating resin with thiourea group and isothiourea group functional group is arranged in an ion exchange column with a length of about 20cm and an inner diameter of about 1.0cm. The ion exchange column is preheated at 60-90°C, and 1000 g of 6% HNBR glue is passed through the ion exchange column at a flo...

Embodiment 2

[0022] Use about 10g of the same macroporous chelating resin of the benzenediene-divinylbenzene copolymer as in Example 1 but with mercapto and isothiourea functional groups to remove the residual rhodium catalyst in the HNBR glue. Process As described in Example 1, the rhodium content in the treated HNBR was 20 ppm, and the rhodium removal rate was 87%.

Embodiment 3

[0024] Use about 10g of the same macroporous chelating resin of benzodiene-divinylbenzene copolymer as in Example 1, but with mixed functional groups of mercapto, thiourea and isothiourea (mercapto: thiourea: isothiourea = 90-98:2-8:0-3). Using it to remove the residual rhodium catalyst in the HNBR glue solution, the process is the same as that described in Example 1. The rhodium content in the treated HNBR is 8 ppm, and the rhodium removal rate is 94.8%.

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PUM

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Abstract

The present invention provides a process for removing rhodium catalyst from rubber liquor of hydrogenated nitrile rubber, and is characterized by that it adopts macroporous resin with special functional group to treat the above-mentioned rubber liquor or the hydrogenated nitrile rubber so as to can remove residual catalyst. Said functional group is the functional group containing two kinds of more than two kinds of mercapto-group, thiourea and isothiourea. It is specially suitable for industrial equipment, for industrial equipment, for example exchange column, to continuously treat rubber liquor.

Description

Technical field [0001] The invention provides a process for removing residual rhodium catalyst from hydrogenated nitrile rubber glue. technical background [0002] Hydrogenated nitrile rubber (HNBR) refers to nitrile rubber (NBR) through hydrogenation, at least 80% (preferably 90-99.5%) of carbon-carbon double bonds are hydrogenated. Unsaturated nitrile rubber is a copolymer of monomers with nitrile groups (-C≡N) containing 3 to 5 α, β unsaturated carbons and conjugated diene monomers containing 4 to 6 carbons, a typical example It is an acrylonitrile-butadiene copolymer. Unsaturated nitrile rubber is obtained by free radical emulsion polymerization. A typical example is obtained by free radical emulsion polymerization of acrylonitrile and butadiene, where the combined amount of butadiene and acrylonitrile is 80-85:20-50. [0003] Hydrogenated nitrile rubber is prepared by catalytic hydrogenation of nitrile rubber with rhodium complex as a catalyst, because most non-noble metals ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F6/08
Inventor 刘志才陈彩云龚光碧李锦山苏玲李晓鹏韩者芬王月霞周志平宋中勤苟文甲汤海鲲
Owner PETROCHINA CO LTD