CN105985456A - Method for removing metal rhodium in hydrogenated butadiene-acrylonitrile rubber - Google Patents
Method for removing metal rhodium in hydrogenated butadiene-acrylonitrile rubber Download PDFInfo
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Abstract
The invention provides a method for removing metal rhodium in hydrogenated butadiene-acrylonitrile rubber. The method is characterized in that under existence of an olefin metathesis catalyst, an alkene nonsaturated substituent-containing thiourea or mercapto compound and an alkene nonsaturated substituent-containing organosiloxane monomer are subjected to a reaction to prepare a silicon-supported ion complexing agent for removing metal rhodium in the hydrogenated butadiene-acrylonitrile rubber, and the clearance of rhodium in a hydrogenated butadiene-acrylonitrile rubber solution can reach more than 95%.
Description
Technical field
The present invention relates to a kind of method removing metal rhodium in hydrogenated nitrile-butadiene rubber, specifically a kind of removing hydrogenation
The minimizing technology of metal rhodium in the rhodium catalyst of nitrile rubber residual.
Background technology
During hydrogenated nitrile-butadiene rubber (HNBR) produces, use homogeneous rhodium series catalysts, residual catalysis after reaction
Agent is difficult to remove, and affects properties of product.Traditional handicraft uses ion exchange resin to be removed metal rhodium.
The removal methods of 02104394.9 hydrogenated nitrile-butadiene rubber residual rhodium catalyst, use with sulfydryl, thiocarbamide,
In isothiourea, the macroporous type chelating resin of two or more functional groups is fully contacted with hydrogenated butyronitrile glue, by from
Sub-exchange process removes triphenyl phosphorus radium chloride catalyst.The silane coupler modified SiO2 of CN103537304A
The preparation of supported rhodium catalyst and the selective hydrogenation application to nitrile rubber, the invention discloses silane even
The preparation of the modified SiO2 supported rhodium catalyst of connection agent and the selective hydrogenation application to nitrile rubber.To NBR
Hydrogenation research shows, hydrogenation efficiency improves a lot, and under equal conditions, degree of hydrogenation can have original 52% to carry
High to more than 98%, and after reaction completes, catalyst recycling is also greatly improved.
CN200810187875.1 removes iron-residues, rhodium-containing from optionally hydrogenated nitrile rubber and is catalyzed containing ruthenium
The method of agent residue, provide a kind of by iron-residues, rhodium-containing and/or ruthenium-containing catalyst residues from containing
Have in the optionally hydrogenated nitrile rubber solution of this kind of iron-residues, rhodium-containing and/or residue containing ruthenium and remove
Method, this is removed by making (the sense of at least one type of this solution and a kind of specific functionalization
Group's modification, this functional group is selected from a primary amine, secondary amine, mercaptan, dithio formate, thiocarbamide and two sulphur
For carbamate groups) contacts ionic exchange resin and carry out.Use ion exchange resin to hydrogenated butyronitrile
In glue, triphenyl phosphorus radium chloride removes, and because resin portion is dissolved or swelling, also has HNBR molecule
Block resin duct or be wound around with molecular resin, affecting removal efficiency.CN101868467A intermediary
A kind of formula that continued is [(R4O)3SiCH2CH2The compound of SX, X is (CR1R2)eNR5CONHR、
(CR1R2)e NR5The compounds such as CSNHR, the monomer containing thiol functionalities and olefin-containing in the method
Reaction between siloxanes is the reactions such as free radical addition, replacement or esterification, the sense containing S after reaction
Group is sandwiched in the centre of compound, causes functional group's free degree by sterically hindered restriction, affects it
Reaction efficiency during complexing inorganic ions.
Content of the invention
It is an object of the present invention to provide a kind of method removing metal rhodium in hydrogenated nitrile-butadiene rubber, the method is to use
Silicon support type ionic complexing agent absorption rhodium ion simultaneously separates, specifically by unsaturated silane, unsaturated ion network
Mixture reacts the using method generating silicon support type ionic complexing agent under olefin metathesis catalyst effect.
In removal HNBR of the present invention, the method for metal rhodium comprises the following steps:
(1) testing rhodium content in HNBR dry glue, the molal quantity calculating metal rhodium is calculated as MRhodiumAnd after conduct
The foundation of continuous charging；
(2) weigh HNBR glue, add the water of dry glue quality 0.1-1 times；
(3) molal quantity is added to be MRhodiumThe acidulant of 5-20 times amount (preferably 5-8 times)；
(4) molal quantity is added to be MRhodiumThe ionic complexing agent of 5-20 times amount (preferably 5-8 times)；
(5) molal quantity is added to be MRhodiumThe carrier of 50-100 times amount (preferably 50-60 times)；
(6) stirring 0.5-1.5h, being warming up to 50-80 DEG C, sending into supercentrifuge at rotating speed is
Centrifuging 15-30min under 10000-50000rpm, separating upper strata glue and test its rhodium content, rhodium content reduces
More than 95%.
Silicon support type ionic complexing agent of the present invention is in the presence of olefin metathesis catalyst, by containing alkene
The thiocarbamide of unsaturated substituent or sulfhydryl compound and the organosiloxane monomer containing the unsaturated substituent of alkene are anti-
Should prepare.
Described silicon support type ionic complexing agent its preparation method comprises the steps: containing the unsaturated substituent of alkene
Thiocarbamide or sulfhydryl compound and the organosiloxane monomer containing the unsaturated substituent of alkene with 1:(1-5) mol ratio
(preferably 1:(1-1.5)) mixing, it is configured to 2-10% mass concentration (preferably 8-10%) with toluene solvant
Monomer solution, adds in solution and accounts for monomer molar fraction 0.01-0.1% (preferably 0.05-0.0.08%mol)
Olefin metathesis catalyst, isolation air and water, after reaction 0.5-2h, use vacuum desolvation agent device
Toluene solvant is deviate from, prepares silicon support type ionic complexing agent.
The thiocarbamide containing the unsaturated substituent of alkene described in ionic complexing agent preparation or sulfhydryl compound can be
Allylthiourea, ethylene thiourea, alkene butyl thiourea, sulfydryl propylene, sulfydryl styrene, sulfydryl acrylic acid etc.
The thiocarbamide of different carbon chain lengths and the unsaturated substituent of alkene, thiol compound, preferably allylthiourea
Its structural formula of organosiloxane monomer containing the unsaturated substituent of alkene is:
Wherein:
Y-contains the unsaturated olefin aliphatic segment of 2～18 carbon, can be vinyl, acrylic,
Isopropenyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, 1-heptenyl, methyl
Acryloxypropyl, methacryloxy, preferred vinyl；
R1、R3-containing the alkoxyl of 1～12 carbon, the aryloxy group of 6～12 carbon, the silicon of 3～12 carbon
Epoxide, can be methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, penta oxygen
Base, epoxide in positive heptan, different octyloxy, positive nonyl epoxide, phenoxy group, chlorophenoxy, allyloxy, benzyloxy,
Acetoxyl group, trimethylsiloxy group, preferably methoxyl group, ethyoxyl；R1And R3It is set as containing alkoxyl
Purpose be to make alkoxyl hydrolyze by the effect of heat and acid, thus form-O-Si-spacial framework, make
Complexing agent volume increases readily removed.
R2Can be and R1Identical group, can also is that the saturated segment containing 1～20 carbon, 3～8
Cyclic alkane, aromatic hydrocarbon；Preferably methyl, ethyl, methoxyl group, ethyoxyl；
The organosiloxane monomer containing the unsaturated substituent of alkene described in ionic complexing agent preparation can be second
Thiazolinyl triethoxysilane, vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, ethene
Base two amoxys-hexyl silane, isopropenyl two n-butoxyethyl silane etc..
Olefin metathesis catalyst agent described in ionic complexing agent preparation can be Etc. the Grubbs catalyst series with identity function or other there is olefin metathesis
The metal carbene catalyst of function.
Acidulant of the present invention preferably employs inorganic acid, as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid,
Selenic acid, hydrobromic acid, hydroiodic acid, chloric acid etc., preferably hydrochloric acid.
Carrier of the present invention is the inorganic particle of bigger serface, increases it for adion complexing agent
Quality and volume thus be beneficial to separate, be chosen in particular from carbon black, montmorillonite, calcium carbonate, attapulgite, illiteracy take off
The inorganic particles, preferably white carbon such as soil, white carbon.
The particle size of carrier is not limited by the present invention, but in order to reduce its secondary agglomeration and at glue
Middle fine dispersion and can adion complexing agent, preferably average grain diameter is the white carbon of 700-900nm.
The know-why of foundation of the present invention is:
1. the preparating mechanism of ionic complexing agent is with the alkene subdivision of thiosinamine and vinyltrimethoxy silane
As a example by solving reaction, explaination is as follows:
As shown in above-mentioned chemical equation, in the present invention thiourea compound containing the unsaturated substituent of alkene and
Organosiloxane monomer generation olefin metathesis reaction containing the unsaturated substituent of alkene, with thiosinamine and ethene
Base trimethoxy silane is made under solvent Grubbs bis-generation catalyst action at toluene, occurs olefin metathesis anti-
Should react, the thiocarbamide substituted propenyl trimethoxy silane of generation.The thiourea functional group of this compound is in
End, the free degree is high, it is simple to catch inorganic ions；Acrylic connects the free degree after segment length proper extension
Higher.
2. acidulant effect is to dissociate out by the rhodium ion of complex status:
[(C6H5)3P]3RhCl+HCl——[(C6H5)3P]3HCl+RhCl
3. the effect that carrier adds is explained such as Fig. 1 complexing and Composite mechanism signal as a example by silicon dioxide microsphere
Figure, is initially charged acidulant in course of reaction, make the rhodium in triphenyl phosphorus radium chloride dissociate out the free shape of formation
State, adds ionic complexing agent and passes through high-speed stirred, enabling the thiourea group of complexing agent by free rhodium
Ion-catching is simultaneously complexed, and then adds silicon dioxide microsphere, the silica of its surface hydroxyl and ionic complexing agent
Groups generation hydrolysis, thus will be combined with carrier, the rhodium so dissociating is just by ionic complexing agent
Bridge joint used load is to the surface of carrier, and so big quality and volume can be carried by means such as centrifugal sedimentations
The efficiency of high later separation.
Specifically, the present invention contains the thiourea compound of the unsaturated substituent of alkene and containing the unsaturated substituent of alkene
Organosiloxane monomer generation olefin metathesis reaction, the thiocarbamide substituted propenyl trimethoxy silicon of generation
Alkane, can be combined with the carrier being added thereto after the hydrolysis of thiocarbamide substituted silane, generates surface and contains a large amount of ghiourea group
The complexing agent of group.Use it for homogeneous rhodium catalyst removing in HNBR glue, add acidulant by metal
Rhodium is converted into ionic forms, and thiourea group can be complexed rhodium ion, is performing centrifugal separation on the removal of rhodium in rear glue
Rate reaches more than 95%.
Brief description
Fig. 1 is that the present invention is complexed and Composite mechanism schematic diagram.
Detailed description of the invention
It is as described below that the present invention is embodied as required material auxiliary agent:
(1) preparation of ionic complexing agent: Allyl thiourea and VTES monomer are with 1:1
Mixed in molar ratio, is configured to the monomer solution of 10% mass concentration with toluene solvant, adds single in solution
Body 0.01%mol'sCatalyst, isolation air and water, after 25 DEG C of reaction 2h, use
Toluene solvant is deviate from by vacuum desolvation agent device, prepares silicon support type ionic complexing agent.
(2) hydrochloric acid, SILVER REAGENT, West Asia reagent Co., Ltd；Silica, SILVER REAGENT, Shanghai is converged general
Siloxanes Co., Ltd；
(3) chemical research center, HNBR glue Lanzhou 20L rubber hydrogenation plant lab scale sample, solvent is
Chlorobenzene.
(4) high-speed stirred is the T25 model of IKA company, and centrifuge is Beijing medical equipment company
LG10-3A model.
In the present invention, metal rhodium assay uses flame atomic absorption spectrometry to be measured.
Embodiment 1:
In test HNBR dry glue, rhodium content is 180mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0174mol, and add the ionic complexing agent of 0.2mol, 0.2mol hydrochloric acid and
The white carbon of 1mol, adds the deionized water of 3kg, stirs 0.5h, is warming up to 50 DEG C, send at a high speed from
Centrifuging 15min under scheming 10000rpm, separating upper strata glue and being dried and test its rhodium content is 5mg/kg,
Rhodium content clearance 97.2%.
Comparative example 1: be not added with ionic complexing agent
In test HNBR glue, rhodium content is 180mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0174mol, and adds the hydrochloric acid of 0.2mol and the white carbon of 1mol, adds 3kg
Deionized water, stir 0.5h, be warming up to 50 DEG C, send into centrifugal 15min under supercentrifuge 10000rpm,
Being dried and measure rhodium content the sampling of upper strata glue is 175mg/kg, poor removal effect.
Embodiment 2:
In test HNBR dry glue, rhodium content is 160mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0155mol, and add the ionic complexing agent of 0.3mol, 0.3mol sulfuric acid and
The white carbon of 1.5mol, adds the deionized water of 10kg, stirs 1.5h, is warming up to 80 DEG C, sends at a high speed
Centrifuging 30min under centrifuge 50000rpm, being dried and measure rhodium content the sampling of upper strata glue is 5mg/kg,
Clearance is 96.9%.
Comparative example 2: not acid adding
In test HNBR dry glue, rhodium content is 160mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0155mol, and adds the ionic complexing agent of 0.3mol and the white carbon of 1.5mol,
Add the deionized water of 10kg, stir 1.5h, be warming up to 80 DEG C, send into supercentrifuge 50000rpm
Centrifuging down 30min, glue sampling in upper strata being dried and measured rhodium content is still 110mg/kg, removal effect
Difference.
Embodiment 3:
In test HNBR dry glue, rhodium content is 175mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0169mol, and add the ionic complexing agent of 0.33mol, 0.33mol nitric acid and
The carbon black of 0.8mol, adds the deionized water of 5kg, stirs 0.6h, is warming up to 60 DEG C, send at a high speed from
Centrifuging 20min under scheming 30000rpm, being dried and measure rhodium content the sampling of upper strata glue is 6mg/kg,
Clearance is 96.6%.
Comparative example 3: no carrier added
In test HNBR dry glue, rhodium content is 175mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0169mol, and adds the nitric acid of the ionic complexing agent of 0.33mol, 0.33mol,
Add the deionized water of 5kg, stir 0.6h, be warming up to 60 DEG C, send under supercentrifuge 30000rpm
Centrifugal 20min, being dried and measure rhodium content the sampling of upper strata glue is 115mg/kg, poor removal effect.
Embodiment 4
In test HNBR dry glue, rhodium content is 170mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0165mol, and add the ionic complexing agent of 0.25mol, 0.25mol nitric acid and
The carbon black of 0.5mol, adds the deionized water of 5.5kg, stirs 0.6h, is warming up to 60 DEG C, sends at a high speed
Centrifuging 15min under centrifuge 25000rpm, being dried and measure rhodium content the sampling of upper strata glue is 4mg/kg,
Clearance is 97.6%.
Comparative example 4: use commercially available sulfydryl polystyrene resin
By the HNBR that commercially available sulfydryl polystyrene resin addition rhodium content is 170mg/kg (relative dry glue)
In glue, after stirring 3h, separate with filter screen, glue sampling is dried and measures rhodium content and be
80mg/kg, clearance is 52.9%, poor removal effect.
Embodiment 5:
In test HNBR dry glue, rhodium content is 155mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0150mol, and add the ionic complexing agent of 0.09mol, 0.09mol selenic acid and
The carbon black of 0.9mol, adds the deionized water of 1.0kg, stirs 0.65h, is warming up to 63.5 DEG C, sends into height
Glue sampling in upper strata is dried and measures rhodium content and is by centrifugal 23min under speed centrifuge 25370rpm
4.6mg/kg, clearance is 97.0%.
Comparative example 5: use commercially available ghiourea group polystyrene resin
By the HNBR that commercially available ghiourea group polystyrene resin addition rhodium content is 155mg/kg (relative dry glue)
In glue, after stirring 3h, separate with filter screen, glue sampling is dried and measures rhodium content and be
90mg/kg, clearance is 41.9%, poor removal effect.
Embodiment 6:
In test HNBR dry glue, rhodium content is 149mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0144mol, and adds the height of the ionic complexing agent of 0.2592mol, 0.2016mol
Chloric acid and the montmorillonite of 1.152mol, add the deionized water of 1.43kg, stirs 0.93h, is warming up to 77.4
DEG C, send into centrifugal 18min under supercentrifuge 45120rpm, glue sampling in upper strata is dried and measures rhodium
Content is 6.9mg/kg, and clearance is 95.3%.
Comparative example 6: add weak acid, acetic acid
In test HNBR dry glue, rhodium content is 149mg/kg, and weighing dry glue is 10kg glue, calculates gold
The molal quantity belonging to rhodium is calculated as 0.0144mol, and adds the second of the ionic complexing agent of 0.2592mol, 0.2016mol
Acid and the montmorillonite of 1.152mol, add the deionized water of 1.43kg, stirs 0.93h, is warming up to 77.4
DEG C, send into centrifugal 18min under supercentrifuge 45120rpm, glue sampling in upper strata is dried and measures rhodium
Content is 145mg/kg, poor removal effect.
Embodiment 7:
In test HNBR dry glue, rhodium content is 170mg/kg, weighs the HNBR glue that dry glue is 10kg
Liquid, calculate metal rhodium molal quantity 0.0165mol, and add the ionic complexing agent of 0.082mol, 0.082
The hydrochloric acid of mol and the white carbon of 0.82mol, add the deionized water of 3kg, stirs 0.5h, heats up
To 50 DEG C, send into centrifugal 15min under supercentrifuge 10000rpm, after isolating lower sediment thing,
Being 4mg/kg by upper strata glue sampling and measuring rhodium content, clearance is 97.6%.
Comparative example 7:
Method in CN101868467A embodiment 1 is used to prepare ionic complexing agent, will be containing at toluene
(2.5L) 2-aminoethyl hydrochloride 2 '-trimethoxysilylethylgroup group thioether (1.54 moles) in
Under agitation reflux 4 hours with the mixture of silica (lkg).This mixture is cooled to room temperature, so
Rear filtration.With toluene (1L), methyl alcohol (1L), aqueous alkali (2 × 2L), deionized water (2L) and methyl alcohol
(2L) wash solid, be then dried under reduced pressure and obtain fixing amino thioether (1.lkg).By this ammonia
Base sulfide oxidation silicon (100g, 0.1 mole) and methylisothiocyanate ester (0.25 mole) are at toluene (300mL)
In mixture under agitation heat 3 hours.When cooling, filter this mixture and fully washed by water
Washing solid and obtaining the thiocarbamide (105g) of formula 1, wherein c and d is O, R1、R2And R5It is hydrogen,
R is methyl.
According to the minimizing technology of the present invention, in test HNBR dry glue, rhodium content is 170mg/kg, claims
Take the HNBR glue that dry glue is 10kg, calculate the molal quantity 0.0165mol of metal rhodium, and add 0.082
The white carbon of comparative example 7 ionic complexing agent of mol, the hydrochloric acid of 0.082mol and 0.82mol, adds
The deionized water of 3kg, stirs 0.5h, is warming up to 50 DEG C, sends under supercentrifuge 10000rpm
Centrifugal 15min, after isolating lower sediment thing, is 58mg/kg by upper strata glue sampling and measuring rhodium content,
Clearance is 65.8%, poor removal effect.
Embodiment 8:
In test HNBR dry glue, rhodium content is 160mg/kg, weighs the HNBR glue that dry glue is 10kg
Liquid, calculate metal rhodium molal quantity 0.0155mol, and add the ionic complexing agent of 0.077mol, 0.077
The hydrochloric acid of mol and the white carbon of 0.77mol, add the deionized water of 3kg, stirs 0.5h, heats up
To 50 DEG C, send into centrifugal 15min under supercentrifuge 10000rpm, after isolating lower sediment thing,
Being 5mg/kg by upper strata glue sampling and measuring rhodium content, clearance is 96.9%.
Comparative example 8:
Method in CN101868467A embodiment 2 is used to prepare ionic complexing agent, will be containing at toluene
(250mL) 2-aminoethyl hydrochloride 2 '-trimethoxysilylethylgroup group thioether (0.154 mole) in
Under agitation reflux 4 hours with the mixture of silica (l00g).This mixture is cooled to room temperature,
Then filter.Wash this solid with toluene, methyl alcohol, aqueous alkali, deionized water and methyl alcohol, then
It is dried under reduced pressure and obtain fixing amino thioether (l10g).By this amino sulfide oxidation silicon (50g,
0.05 mole) and ethyl isothiocyanate 0.125 mole) mixture in toluene (150mL) Shen stirring
Mix lower heating 3 hours.When cooling, filter this mixture and wash solid with water and obtain formula l
Thiocarbamide (55g), wherein c and d is 0, R1、R2And R5Being hydrogen, R is ethyl.
According to the minimizing technology of the present invention, in test HNBR dry glue, rhodium content is 160mg/kg, claims
Take the HNBR glue that dry glue is 10kg, calculate the molal quantity 0.0155mol of metal rhodium, and add 0.077
The white carbon of comparative example 8 ionic complexing agent of mol, the hydrochloric acid of 0.077mol and 0.77mol, adds
The deionized water of 3kg, stirs 0.5h, is warming up to 50 DEG C, sends under supercentrifuge 10000rpm
Centrifugal 15min, after isolating lower sediment thing, is 53mg/kg by upper strata glue sampling and measuring rhodium content,
Clearance is 66.9%, poor removal effect.
Embodiment 9:
In test HNBR dry glue, rhodium content is 175mg/kg, weighs the HNBR glue that dry glue is 10kg
Liquid, calculate metal rhodium molal quantity 0.0169mol, and add the ionic complexing agent of 0.085mol, 0.085
The hydrochloric acid of mol and the white carbon of 0.85mol, add the deionized water of 3kg, stirs 0.5h, heats up
To 50 DEG C, send into centrifugal 15min under supercentrifuge 10000rpm, after sub-argument goes out lower sediment thing,
Being 8mg/kg by upper strata glue sampling and measuring rhodium content, clearance is 95.4%.
Comparative example 9:
Use method in CN101868467A embodiment 27 to prepare ionic complexing agent, under agitation will
Methylisothiocyanate ester (0.35 mole) and 2-aminoethyl hydrochloride 2 '-trimethoxysilylethylgroup group
Solution in toluene (50mL) for the thioether (0.154 mole) refluxes 4 hours and obtains
(CH3O)3SiCH2CH2SCH2CH2NHC (=S) NHCH3.Then add this solution in first to
Silica (l00g) Shen in benzene (200mL) under agitation backflow gained mixture 4 hours.This is mixed
Compound is cooled to room temperature, then filters.With toluene (1L), methyl alcohol (1L), aqueous alkali (2 × 2L),
Deionized water (2L) and methyl alcohol (2L) washing solid, be then dried under reduced pressure and obtain the thiocarbamide of formula l
(115g), wherein c and d is 0, R1、R2And R5Being hydrogen, R is methyl.
According to the minimizing technology of the present invention, in test HNBR dry glue, rhodium content is 175mg/kg, claims
Take the HNBR glue that dry glue is 10kg, calculate the molal quantity 0.0169mol of metal rhodium, and add 0.085
The white carbon of the ionic complexing agent of mol, the hydrochloric acid of 0.085mol and 0.85mol, adds going of 3kg
Ionized water, stirs 0.5h, is warming up to 50 DEG C, sends into centrifugal 15min under supercentrifuge 10000rpm,
After isolating lower sediment thing, being 48mg/kg by upper strata glue sampling and measuring rhodium content, clearance is
72.5%, removal effect is poor.
Certainly, the present invention also can have other various embodiments, without departing substantially from present invention spirit and essence thereof
In the case of, those of ordinary skill in the art can make various corresponding change according to the present invention and become
Shape, but these change accordingly and deform the protection domain that all should belong to the claims in the present invention.
Claims (17)
1. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber, it is characterised in that comprise the following steps:
Rhodium content in step (1) test hydrogenated nitrile-butadiene rubber dry glue, calculates the molal quantity of metal rhodium, is calculated as
MRhodium；
Step (2) weighs hydrogenated nitrile-butadiene rubber glue, adds water；
Step (3) is sequentially added into acidulant, silicon support type ionic complexing agent and carrier；
Step (4) stirs 0.5～1.5h, is warming up to 50～80 DEG C, and Centrifugal dispersion 15～30min, in separation
Its rhodium content tested by layer glue；Described silicon support type ionic complexing agent is to exist at olefin metathesis catalyst
Under, by the thiocarbamide containing the unsaturated substituent of alkene or sulfhydryl compound and the organic silica containing the unsaturated substituent of alkene
Alkane monomer reaction prepares.
2. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 1, its feature exists
In the preparation method of described silicon support type ionic complexing agent comprises the steps: containing the unsaturated substituent of alkene
Thiocarbamide or sulfhydryl compound monomer and the organosiloxane monomer containing the unsaturated substituent of alkene are with 1:(1～5) mole
It than mixing, is configured to the monomer solution of 2～10% mass concentrations with toluene solvant, add in solution and account for institute
State the olefin metathesis catalyst of two kinds of monomer total amount 0.01～0.1%mol numbers, completely cut off air and water, instead
After answering 0.5～2h, use vacuum desolvation agent device to deviate from toluene solvant, prepare silicon support type ion complexation
Agent.
3. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 2, its feature exists
In the described organosiloxane monomer structure formula containing the unsaturated substituent of alkene is:
Wherein:
Y is the unsaturated olefin aliphatic segment containing 2～18 carbon；R1、R3For containing 1～12 carbon
Alkoxyl, the siloxy of the aryloxy group of 6～12 carbon or 3～12 carbon；R2For with R1Identical group,
Or containing 1～20 carbon saturated segment, 3～8 cyclic alkane or aromatic hydrocarbon.
4. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 3, its feature exists
In in the described organosiloxane monomer structure formula containing the unsaturated substituent of alkene, Y is selected from vinyl, propylene
Base, isopropenyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, 1-heptenyl,
Methacryloxypropyl or methacryloxy.
5. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 3, its feature exists
In R in the described organosiloxane monomer structure formula containing the unsaturated substituent of alkene1、R3Selected from methoxyl group,
Ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, epoxide in positive heptan, different pungent oxygen
Base, positive nonyl epoxide, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group or trimethyl silicane
Epoxide.
6. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 3, its feature exists
In R in the described organosiloxane monomer structure formula containing the unsaturated substituent of alkene2Selected from methyl, ethyl,
Methoxy or ethoxy.
7. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 1 and 2, it is special
Levy and be, the described organosiloxane monomer containing the unsaturated substituent of alkene selected from VTES,
Vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, vinyl two amoxys-hexyl silane
Or isopropenyl two n-butoxyethyl silane.
8. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 1 and 2, it is special
Levying and being, the described thiocarbamide containing the unsaturated substituent of alkene or sulfhydryl compound are selected from allylthiourea, ethene sulphur
Urea, alkene butyl thiourea, sulfydryl propylene, sulfydryl styrene or sulfydryl acrylic acid, preferably allylthiourea.
9. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 1 and 2, it is special
Levying and being, described olefin metathesis catalyst agent is selected from
10. the method removing metal rhodium in hydrogenated nitrile-butadiene rubber according to claim 1, its feature exists
In described acidulant is inorganic acid.
The method of metal rhodium in 11. removal hydrogenated nitrile-butadiene rubbers according to claim 1, its feature exists
In described acidulant is selected from sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, selenic acid, hydrobromic acid, hydroiodic acid or chlorine
Acid, preferably hydrochloric acid.
The method of metal rhodium in 12. removal hydrogenated nitrile-butadiene rubbers according to claim 1, its feature exists
In described carrier is selected from carbon black, calcium carbonate, attapulgite, montmorillonite or white carbon, preferably white carbon.
The method of metal rhodium in 13. removal hydrogenated nitrile-butadiene rubbers according to claim 1, its feature exists
In the thiocarbamide containing the unsaturated substituent of alkene or sulfhydryl compound and the organosiloxane containing the unsaturated substituent of alkene
The mol ratio of monomer is 1:(1～1.5).
14. the method for claim 1, it is characterised in that the addition of olefin metathesis catalyst is
Thiocarbamide containing the unsaturated substituent of alkene or sulfhydryl compound and the organosiloxane list containing the unsaturated substituent of alkene
The 0.05-0.08%mol of the total molfraction of body.
The method of metal rhodium in 15. removal hydrogenated nitrile-butadiene rubbers according to claim 1, its feature exists
In described acidulant molal quantity is MRhodium5-20 times, preferably 5-8 times.
The method of metal rhodium in 16. removal hydrogenated nitrile-butadiene rubbers according to claim 1, its feature exists
In described silicon support type ionic complexing agent molal quantity is MRhodium5-20 times, preferably 5-8 times amount.
The method of metal rhodium in 17. removal hydrogenated nitrile-butadiene rubbers according to claim 1, its feature exists
It is M in described carrier molal quantityRhodium50-100 times amount, preferably 50-60 times.
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