CN1120850C - Process for removing hydrocatalyst from unsaturated copolymer - Google Patents
Process for removing hydrocatalyst from unsaturated copolymer Download PDFInfo
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- CN1120850C CN1120850C CN00103779A CN00103779A CN1120850C CN 1120850 C CN1120850 C CN 1120850C CN 00103779 A CN00103779 A CN 00103779A CN 00103779 A CN00103779 A CN 00103779A CN 1120850 C CN1120850 C CN 1120850C
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Abstract
The present invention provides a process for removing a copolymer through a water phase technical line, particularly a residual noble metal catalyst after the homogeneous phase catalysis and hydrogenation of a butyronitrile rubber solution. The present invention is characterized in that an organic compound containing-NH2 or (and) C=S is used as a complexing agent, and carboxylic acid is used as an extraction agent; the residual noble metal catalyst in a copolymer hydrogenation solution, particularly the hydrogenization butyronitrile rubber solution, is converted into a metallic organic complex capable of dissolving in an extraction agent water solution to enter an aqueous solution from the viscous copolymer hydrogenation solution; a one-step removing rate of noble metal rhodium in the hydrogenation solution can reach more than 98%. The process also has an effect on a homogeneous phase catalysis hydrogenization solution of the polymer solution by a bimetallic catalyst, the one-step removing rate of the noble metal rhodium can reach 95.5%, and simultaneously, the one-step removing rate of noble metal ruthenium reaches 57%. The process is suitable for removing catalysts of the noble metal rhodium and the ruthenium in the organic compound hydrogenation solution, the one-step removing rate of the rhodium reaches more than 98%, and the one-step removing rate of the ruthenium reaches more than 77%.
Description
The invention provides a kind of catalyzer and from the heavy-gravity unsaturated copolymer hydrogenation solution, be removed to method in the aqueous solution precious metal organic coordination compounds such as rhodium-containing, rutheniums, particularly remove the method for rhodium, ruthenium catalyst in butyronitrile class rubber homogeneous hydrogenation solution, this method also is applicable to removing of rhodium, ruthenium catalyst in the organic compound hydrogenation solution.
Unsaturated copolymer and nitrile group-containing unsaturated copolymer (as perbutan) are because of containing carbon-carbon double bond (C=C), and its Application Areas is restricted.With carbon-carbon double bond, particularly the carbon-carbon double bond of nitrile group-containing makes it both keep original performance after selecting hydrogenation, has improved thermotolerance, anti-H again
2S, O
3Etc. ageing-resistant performance, thereby its over-all properties is improved.Selective hydrogenation for the carbon-carbon double bond in the perbutan just has report as far back as nineteen fifty-two, up to the present, realizes that its industrialized method of hydrotreating mainly contains homogeneous phase solution shortening method and heterogeneous solution shortening method.Correspondingly, the catalyst system that these two kinds of methods are used can be divided into homogeneous catalyst system and heterogeneous catalyst systems, they all selected for use the higher group VIII noble metals of cost, and its esters or its a metal-organic complex be catalyzer.They mainly are the catalyzer that is made of monometallic or bimetal and one or more part.Behind unsaturated copolymer and the nitrile group-containing unsaturated copolymer homogeneous phase solution hydrogenation, these metal residuals are in hydrogenation products, not only influence product appearance but also under effect such as heat, oxygen, ultraviolet ray, can quicken polymer degradation, aging etc., thereby product performance are had potential impact; Simultaneously, the cost height of noble metal catalyst need to recycle, otherwise the cost of hydrogenation products improves greatly.Therefore, for improving the quality of products, reduce product cost, the Separation and Recovery noble metal catalyst is just very necessary from hydrogenation of polymer solution.
Behind the heterogeneous catalysis hydrogenation, the separation removal of catalyzer, recovery are made with extra care and are utilized than being easier to again, although the homogeneous catalytic hydrogenation catalyzer is active relative with selectivity higher,, make the separation removal of residual homogeneous catalyst, recycling all very difficult owing to hydrogenation solution viscosity is big.
The reported in literature that catalyst separating removes in unsaturated copolymer and the nitrile group-containing unsaturated copolymer homogeneous catalytic hydrogenation solution seldom only has several pieces of patents.USP 3,700, and 637 have mentioned the aftertreatment of hydrogenated nitrile-butadiene rubber (HNBR) glue, after degree of hydrogenation reaches requirement, with methyl alcohol repetitive scrubbing glue, removing catalyzer, up to washings be colourless till.This method methanol usage is big, and is loaded down with trivial details, and exists bulk thickness micelle to be difficult for being disperseed, and causes difficult that catalyst detergent is complete; USP 4,944, and 926 have introduced the method that removes rhodium-containing catalyst in hydrogenated nitrile-butadiene rubber (HNBR) glue with the precipitator method.This method need add a large amount of fine organic precipitants, forms precipitation with rhodium catalyst under certain condition, by filtering or centrifuging, will precipitate with glue and separate.This method adds that precipitation dosage is big, and it is little to generate the precipitation granularity, and gelatin viscosity is big, filters very difficultly, and as not removing fully, precipitation agent has the possibility of polluted product; USP4,985,540 have reported a kind of method of directly adsorbing rhodium-containing homogeneous hydrogenation catalyzer with wide aperture, functionalized ion exchange resin from the chemigum hydrogenation glue, USP 5,403,566 have also introduced the method for directly adsorbing rhodium-containing and/or ruthenium homogeneous hydrogenation catalyzer with organosiloxane copolymer as sorbent material from the HNBR glue, though these two kinds of methods are continuous operation easily, and can not bring impurity into, but all have unfavorable factors such as gelatin viscosity is big, resistance to mass transfer big, absorption is slow, resin is low to the primary sorption rate of catalyzer, length consuming time; In addition, USP 4,857, and 635 also disclose a kind of kneader and a kind of method of separating the noble metal catalyst in the HNBR glue in this device with extraction agent, and there are long, unfavorable factors such as decreasing ratio is low, complex operation of operating time in this method.
Situation in view of above prior art, the present inventor is in the art through after the experiment extensively and profoundly, discovery adds some complexing agent in the HNBR glue, be easy to generate throw out with the catalyzer of rhodium-containing, ruthenium, this class throw out is soluble in the carboxylic-acid aqueous solution again and separates with the HNBR glue.Therefore, the present invention adopts the water technological line that homogeneous catalyst separation in the HNBR thickness glue is removed to method in the extraction agent aqueous solution.The present invention has overcome the toughness of the drawback, the especially glue that exist in above-mentioned all methods to the difficulty that the Separation and Recovery catalyzer brings, and has not only improved the decreasing ratio of catalyzer, and has simplified technology.
Therefore, an object of the present invention is to provide a kind of with unsaturated copolymer, the residual catalyzer method of separation removal in the aqueous solution from the heavy-gravity hydrogenation solution efficiently in the butyronitrile class rubber homogeneous hydrogenation solution particularly.
Another object of the present invention provides a kind of with above-mentioned hydrogenation catalyst separation removal removing process in the extraction agent aqueous solution efficiently from the heavy-gravity hydrogenation solution.
Above and other objects of the present invention, feature and advantage can obtain embodying in further elaboration of the present invention.
The objective of the invention is to realize: to contain-NH by following method
2Or/and the organic compound of C=S is a complexing agent, be extraction agent with the carboxylic acid, in copolymer hydrogenation solution, particularly in the hydrogenated nitrile-butadiene rubber glue residual noble metal catalyst separation removal in the extraction agent aqueous solution.
Method of the present invention comprises following processing step: (1) adds above-mentioned complexing agent in copolymer hydrogenation solution or in the hydrogenated nitrile-butadiene rubber glue, react under certain condition; (2) remove reacted viscous solution with the carboxylic-acid aqueous solution extraction is above-mentioned, catalyzer is entered in the extraction agent aqueous solution, then the extraction agent aqueous solution is separated with polymers soln.
According to the present invention, provide a kind of, particularly the residual hydrogenation catalyst method of separation removal in the extraction agent aqueous solution from viscous solution in the butyronitrile class rubber homogeneous catalytic hydrogenation solution with unsaturated copolymer.Unsaturated copolymer described in the present invention can be copolymer, comprise divinyl-(methyl) vinyl cyanide, 2-methyl isophthalic acid, 3-divinyl-(methyl) vinyl cyanide, styrene-butadiene copolymer and styrene-butadiene-styrene (SBS) and styrene-isoprene-phenylethene (SIS) segmented copolymer are preferably perbutan (paracril), styrene-butadiene copolymer and styrene-butadiene-styrene block copolymer (SBS); And terpolymer, comprise divinyl-(methyl) vinyl cyanide-(methyl) vinylformic acid, divinyl-(methyl) vinyl cyanide-[N-(4-anilino phenyl) Methacrylamide], be preferably butadiene-acrylonitrile-Sipacril 2739OF (carboxy nitrile rubber).Typical example is paracril (NBR), and its composition can contain 15～50% vinyl cyanide, and the degree of hydrogenation of described hydrogenated nitrile-butadiene rubber (HNBR) is 60～100%.Its degree of hydrogenation adopts bromine iodine method to measure, and analytical procedure is seen CNS GB-1676-81; Japan JISK0070-1966.
Homogeneous hydrogenation catalyzer described in the present invention is the group VIII transition metal organic coordination compound, especially the hydrogenation catalyst of nitrile group-containing multipolymer is required catalyzer with high reactivity, highly selective, be that the C=C unsaturated double-bond is saturated by hydrogenation, and C ≡ N group is unaffected.The a metal-organic complex catalyzer that some are relatively inexpensive, as catalyzer such as nickel naphthenate/aluminum alkyls, cobalt naphthenate/aluminum alkylss to the hydrogenation activity of the two keys of C=C and unsatisfactory to the selectivity of C ≡ N, and rhodium, ruthenium, palladium precious metal can constitute a metal-organic complex catalyzer, especially homogeneous rhodium catalyst such as RhCl (PPh with one or more parts
3)
3, RhH (PPh
3)
4Deng having high reactivity and highly selective.In addition, it is suitable with single rhodium organic coordination compound catalyst activity to the hydrogenation activity of nitrile group-containing unsaturated copolymer that Chinese patent application publication number CN1199051A has reported a kind of Rh-Ru bimetallic catalyst system, cheap, and can be than hydrogenation under the mild conditions and gel-free produces.Described butadiene rubber catalyzed by novel Rh-Ru bimetallic agent general formula is M
1 aM
2 bX
m(L
1)
n, M in the formula
1Be rhodium, M
2Be ruthenium, X is a chlorine, L
1Be triphenylphosphine, 1≤a≤4; B=1; 3≤m≤6; 6≤n≤15.But the price of these catalyzer still belongs to costliness, experimental results show that they remain in the product product performance are had potential impact.Therefore must develop a kind of method that can remove noble metal catalyst in the hydrogenation polymers soln efficiently, reach the target that product cost and quality are all optimized.
Term used herein " water technological line " is meant in the hydrogenation copolymer solution and adds complexing agent, the homogeneous hydrogenation catalyzer is converted into a metal-organic complex that dissolves in the extraction agent aqueous solution, under the effect of water-soluble extraction agent, enter water, and separate with polymers soln.The present invention has overcome the precipitator method and ion-exchange-resin process because of the big filtration difficulty that brings of polymer solution viscosity, deficiency such as rate of adsorption is slow, resistance to mass transfer is big.
Used complexing agent is to contain-NH among the present invention
2Or/and the organic compound of C=S.Contain-NH
2Or/and the example of C=S organic compound has ocean current because of, thiocarbamide, rhodanine, thiobarbituric acid etc., preferred thiocarbamide and thiobarbituric acid.This complexing agent can directly add in the glue, also can the solution form add in the glue.Solvent for use is a protic solvent, comprises C
1～C
4Alcohol, particular methanol or ethanol.The consumption of described solvent is the required minimum of the described complexing agent of dissolving.
Used extraction agent is the carboxylic acid extractant among the present invention, and described carboxylic acid comprises C
1～C
4The straight-chain carboxylic acid, preferable formic acid and acetate.
The hydrogenation solution concentration of the multipolymer that the present invention is mentioned, particularly nitrile group-containing multipolymer is to contain 1～15 gram multipolymer in the 100ml solvent.The consumption of hydrogenation catalyst is 0.05～5.0% of a copolymer quality.Solvent for use solubilized multipolymer and catalyzer comprise aromatic hydrocarbons and by derivative, halogenated alkane, ketone, naphthenic hydrocarbon or acid amides and the mixed solvent thereof of alkyl or halogen replacement, are preferably dimethylbenzene, chlorobenzene and composition thereof.
The mentioned complexing agent consumption of the present invention is a catalyzer: complexing agent=1: 3～1: 60 (mol ratio), preferred 1: 6～1: 30 (mol ratio); The extraction agent amount of aqueous solution used is 25～300% of a copolymer solution volume, preferred 50～100%; The concentration of the extraction agent aqueous solution is 10～100%, preferred 70～90%; Removing temperature of reaction is 30～160 ℃, preferred 90～130 ℃; Removing the reaction times is 0.1～6hr, is preferably 0.5～3hr.Extraction agent can be added in the copolymer hydrogenation solution simultaneously with complexing agent, also can add complexing agent earlier, adds extraction agent in removing the reaction back.
After removing reaction,, can use this area ion exchange resin commonly used in order to reclaim the noble metal catalyst in the extraction agent aqueous solution.
Elaboration is listed among the following embodiment.Following embodiment is used to further specify the present invention, rather than is used for limiting the scope of the invention.Except as otherwise noted, all umber and per-cents all are based on weight.
The general step of catalyst removal reaction:
7% xylene solution of paracril carries out hydrogenation reaction under rhodium catalyst and hydrogen effect, obtain hydrogenated nitrile-butadiene rubber (HNBR) glue behind the hydrogenation, its degree of hydrogenation is 98.7% (hydrogenation process is referring to the comparative example 2-1 among the Chinese patent application publication number CN1199051A).Get 40mlHNBR glue (its catalyst metal content is known by analysis), place three mouthfuls of reaction flasks that stirring and reflux exchanger are housed, add complexing agent, under temperature of reaction behind the stirring and refluxing certain hour, stop heated and stirred, be cooled to room temperature, add the extraction agent aqueous solution, vibration or stirring certain hour, static layering is separated extraction liquid with glue.Glue is become light yellow or colourless by deep yellow, the extraction liquid aqueous solution is yellow or deep yellow.With HNBR glue precipitating in ethanol, 60 ℃ of vacuum-dryings.Respectively with the content of catalyst rhodium in dried glue of atomic absorption spectrochemical analysis and the extraction liquid.
Embodiment 1.
By above-mentioned removal method of catalyst, get HNBR glue 40ml, Rh content 23.08mgRh/1 glue wherein, the ethanolic soln that adds thiocarbamide, thiocarbamide wherein: catalyzer=15: 1 (mol ratio), 120 ℃ of reactions 2 hours, the aqueous formic acid that the cooling back adds 20ml 88% extracted catalyzer in the glue.Analytical results is listed in table 1.Comparative Examples 1.
By above-mentioned removal method of catalyst,, do not add thiocarbamide with the experiment condition of embodiment 1.The results are shown in table 1.Comparative Examples 2.
By above-mentioned removal method of catalyst, with the experiment condition of embodiment 1, do not add aqueous formic acid, and add the extraction of 20ml deionized water, it is light yellow that water is, and the Vandyke brown precipitation is arranged in the water.Divide Rh amount in bleed and the glue, the results are shown in the table 1.
Table 1
*: owing to technological operation, analyze the loss of sample preparation, glue reason such as precipitating in ethanol.*: mainly be thiocarbamide-water-fast precipitation of rhodium catalyst complex compound.
| Experimental example | Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of %, % | 2.51 92.78 97.49 4.71 * | 96.36 2.88 3.64 0.76 * | 38.80 10.09 61.20 51.11 ** |
Table 1 comparing result shows that adding thiocarbamide among the present invention is complexing agent, is the necessity of extraction agent in the water removal methods with the aqueous formic acid.
Embodiment 2.
Repeat embodiment 1, add the ethanolic soln 4ml of thiocarbamide, reacted 2 hours down, the results are shown in table 2 at 110 ℃.Comparative Examples 3.
Repeat embodiment 2, add the aqueous solution 4ml of thiocarbamide, the results are shown in table 2.
Table 2
| Experimental example | Embodiment 2 | Comparative Examples 3 |
| The solvent of complexing agent | Ethanol | Water |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of %, % | 2.51 92.95 97.49 4.54 * | 23.30 37.97 (precipitation is arranged) 62.03 38.73 ** |
*, * *: with * in the table 1 and * *.
Embodiment 3.
Repeat embodiment 2, the ethanolic soln consumption of thiocarbamide reduces to 0.6ml, the results are shown in table 3.
Embodiment 4.
Repeat embodiment 2, the ethanolic soln consumption of thiocarbamide is increased to 8.0ml, the results are shown in table 3.
Table 3
*: with * in the table 1.
| Experimental example | Embodiment 3 | Embodiment 2 | Embodiment 4 |
| The thiourea solution amount, ml | 0.6 | 4.0 | 8.0 |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of % *，％ | 3.01 92.91 97.00 4.08 | 2.51 92.95 97.49 4.54 | 2.62 93.04 97.38 4.34 |
Embodiment 5.
Repeat embodiment 2,, the results are shown in table 4 90 ℃ of reactions 2 hours.
Embodiment 6.
Repeat embodiment 2,, the results are shown in table 4 130 ℃ of reactions 2 hours.Table 4
| Experimental example | Embodiment 5 | Embodiment 2 | Embodiment 1 | Embodiment 6 |
| Remove temperature of reaction, ℃ | 90 | 110 | 120 | 130 |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of % *，％ | 13.35 83.89 86.65 2.76 | 2.51 92.95 97.49 4.54 | 2.51 92.78 97.49 4.71 | 13.20 83.30 86.80 3.50 |
*: with * in the table 1.
Embodiment 7.
By above-mentioned removal method of catalyst, thiocarbamide: catalyzer=3: 1 (mol ratio), 110 ℃ of reactions 2 hours, all the other conditions the results are shown in table 5 with embodiment 1.
Embodiment 8.
Repeat embodiment 7, thiocarbamide: catalyzer=6: 1 (mol ratio) the results are shown in table 5.
Embodiment 9.
Repeat embodiment 7, thiocarbamide: catalyzer=30: 1 (mol ratio) the results are shown in table 5.
Table 5
| Experimental example | Embodiment 7 | Embodiment 8 | Embodiment 2 | Embodiment 9 |
| Thiocarbamide: catalyzer, mol ratio | 3∶1 | 6∶1 | 15∶1 | 30∶1 |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of % *，％ | 32.41 65.72 67.59 1.87 | 16.35 82.10 83.65 1.55 | 2.51 92.95 97.49 4.54 | 1.20 91.49 98.80 7.31 |
*: with * in the table 1.
Embodiment 10.
By above-mentioned removal method of catalyst, thiocarbamide: catalyzer=15: 1 (mol ratio) was 110 ℃ of reactions 30 minutes, and all the other conditions the results are shown in table 6 with embodiment 1.
Embodiment 11.
Repeat embodiment 10, in 1 hour reaction times, the results are shown in table 6.
Embodiment 12.
Repeat embodiment 10, in 3 hours reaction times, the results are shown in table 6.
Embodiment 13.
Repeat embodiment 10, in 6 hours reaction times, the results are shown in table 6.
Table 6
| Experimental example | Embodiment 10 | Embodiment 11 | Embodiment 2 | Embodiment 12 | Embodiment 13 |
| Remove the reaction times, hour | 0.5 | 1.0 | 2.0 | 3.0 | 6.0 |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of % *，％ | 31.92 67.10 68.08 0.98 | 20.95 73.47 79.05 5.58 | 2.51 92.95 97.49 4.54 | 2.54 92.27 97.46 5.19 | 2.55 92.22 97.45 5.23 |
*: with * in the table 1.
Embodiment 14.
By above-mentioned removal method of catalyst, get the 120mlHNBR glue, wherein Rh content is 41.2mgRh/l, adds thiocarbamide: catalyzer=15: 1 (mol ratio) in 110 ℃ of following stirring reactions 2 hours, is divided into three equal parts with glue.With catalyzer in 70%, 60%, 50% the aqueous formic acid 20ml extraction glue, measure Rh content in the extraction water solution respectively, all the other conditions the results are shown in table 7 with embodiment 2.
Table 7
Embodiment 15.
| Aqueous formic acid concentration, % | 88 | 70 | 60 | 50 |
| Rh in the extraction water solution, % | 92.95 | 68.79 | 43.24 | 20.04 |
Repeat embodiment 2, with catalyzer in the 88% aqueous formic acid extraction glue, Rh content is 92.16% in the extraction water solution as a result.With glue with after the aqueous solution separates, extract glue for the second time with 88% aqueous formic acid, Rh content is 7.8% in the extraction water solution, and the result shows the glue with twice extraction of 88% aqueous formic acid HNBR, 99.96% of catalyzer Rh in the glue can be extracted in the aqueous solution.
Embodiment 16.
Repeat embodiment 2,88% aqueous formic acid 20ml and thiocarbamide are added simultaneously, remove reaction under 110 ℃, the results are shown in table 8.
Table 8
| Experimental example | Embodiment 2 | Embodiment 16 |
| Extraction agent adds mode | Removing the reaction back adds | Complexing agent and thiocarbamide add simultaneously |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of % *，％ | 2.51 92.95 97.49 4.54 | 2.61 92.89 97.39 4.50 |
*: with * in the table 1.
Embodiment 17.
Repeat embodiment 2, complexing agent is used thiobarbituric acid instead, and add-on is a thiobarbituric acid: catalyzer=15: 1 (mol ratio) the results are shown in table 9.
Table 9
| Experimental example | Embodiment 2 embodiment 17 |
| Complexing agent | The thiocarbamide thiobarbituric acid |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of % *，％ | 2.51 24.04 92.95 71.50 97.49 75.96 4.54 4.46 |
*: with * in the table 1.
Embodiment 18.
Paracril 7% xylene solution carries out hydrogenation reaction under Rh-Ru bimetallic catalyst and hydrogen effect, obtain hydrogenated nitrile-butadiene rubber (HNBR) glue behind the hydrogenation, its degree of hydrogenation is 98.5% (hydrogenation process is referring to Chinese patent application publication number CN1199051A embodiment 2-2).Get the 40mlHNBR glue, Rh content 13.35mgRh/l glue in its glue, Ru content 8.43mgRu/l glue, by above-mentioned removal method of catalyst, experiment condition the results are shown in table 10 with embodiment 2.
Table 10
| Embodiment | Embodiment 18 | Embodiment 2 | |
| Metal in the catalyzer | Rh | Ru | Rh |
| Residual Rh in the dried glue, Rh in the % extraction water solution, Rh decreasing ratio in the % glue, all the other Rh of % *，％ | 4.57 90.06 95.43 5.37 | 42.92 52.64 57.08 4.44 | 2.51 92.95 97.49 4.54 |
*: with * in the table 1.
Table 10 is the result show, the technology that the aqueous solution of the present invention removes catalyzer not only is suitable for containing the Rh catalyzer, and suitable equally to the Rh-Ru bimetallic catalyst.
Above experimental result all is once to remove result of experiment.
The isolating embodiment that removes of above Rh, Ru catalyzer is exemplary, feature of the present invention is a kind ofly from the bigger copolymer solution of viscosity catalyzer to be changed into a metal-organic complex that dissolves in the extraction agent aqueous solution, be extracted in the aqueous solution with water-soluble extraction agent, reach and the isolating water removal methods of multipolymer organic solution.Those skilled in the art can remove water of the present invention-and concentration process carries out appropriate change, for example change a metal-organic complex in the extraction agent alcoholic solution extraction glue into, the removing etc. of organic compound hydrogenation liquid hydrogenation catalyst that maybe this method is used for non-toughness, all within the scope of the invention.
Claims (16)
1. a method that is used for removing behind the unsaturated copolymer solution homogeneous catalytic hydrogenation the residual ruthenium of hydrogenation solution, rhodium, triphenylphosphine palladium phosphine composition catalyst comprises and will contain-NH
2Or/and remove reaction in the hydrogenated copolymer solution behind the complexing agent of the C=S group adding hydrogenation, add C then
1-C
4Straight-chain carboxylic acid's extraction agent aqueous solution, after reacting again, the title complex that removes reaction formation is extracted in the aqueous solution, the consumption of wherein said complexing agent makes catalyzer: complexing agent=1: 3～1: 60 (mol ratio), the consumption of the extraction agent aqueous solution is 25～300% of a hydrogenated copolymer solution volume, extractant concentration is 10～100% weight, and removing temperature of reaction is 30 ℃～160 ℃, and the reaction times is 0.1～6.0 hour.
2. according to the method for claim 1, it is characterized in that used complexing agent is for containing-NH
2Or/and the organic compound of C=S group, be selected from ocean current because of, thiobarbituric acid, thiocarbamide, rhodanine.
3. according to the method for claim 2, it is characterized in that complexing agent is thiocarbamide and thiobarbituric acid.
4. according to each method of claim 1～3, it is characterized in that described complexing agent uses with the solution form in protic solvent, described solvent is selected from C
1～C
4Alcohol.
5. according to the method for claim 4, it is characterized in that described solvent is methyl alcohol or ethanol.
6. according to the method for claim 1, it is characterized in that described extraction agent is formic acid or acetate.
7. according to the method for claim 1, it is characterized in that in the hydrogenated copolymer solution after the described extraction agent aqueous solution and described complexing agent add hydrogenation simultaneously.
8. according to the method for claim 1, the hydrogenation thing that it is characterized in that described unsaturated copolymer is a copolymer, comprise divinyl-(methyl) vinyl cyanide, 2-methyl isophthalic acid, 3-divinyl-(methyl) vinyl cyanide, styrene-butadiene copolymer, and styrene-butadiene-styrene, styrene isoprene styrene block copolymer (SIS), and terpolymer, comprise the hydride of divinyl-(methyl) vinyl cyanide-(methyl) vinylformic acid, divinyl-(methyl) vinyl cyanide-[N (4-anilino phenyl) Methacrylamide].
9. according to the method for claim 1 or 8, the hydride that it is characterized in that described unsaturated copolymer is the hydride of perbutan or styrene-butadiene copolymer or styrene-butadiene-styrene block copolymer.
10. according to the method for claim 1, it is characterized in that described homogeneous hydrogenation catalyzer is for being selected from RhCl (PPh
3)
3, RhH (PPh
3)
4, and M
1 aM
2 bX
m(L
1)
nCatalyzer, M wherein
1Be rhodium, M
2Be ruthenium, X is a chlorine, L
1Be triphenylphosphine, 1≤a≤4, b=1,3≤m≤6,6≤n≤15, its consumption is 0.05～5.0% of a copolymer quality.
11. according to the method for claim 1, the consumption that it is characterized in that complexing agent is a catalyzer: complexing agent=1: 6～1: 30 (mol ratio).
12., it is characterized in that the consumption of described solvent is the required minimum of the described complexing agent of dissolving according to the method for claim 4.
13., it is characterized in that the consumption of described solvent is the required minimum of the described complexing agent of dissolving according to the method for claim 5.
14. according to the method for claim 1, it is characterized in that extraction agent water solvent consumption is 50～100% of a hydrogenated copolymer solution volume, extractant concentration is 70～90% weight.
15. according to the method for claim 1, it is characterized in that removing temperature of reaction is 90～130 ℃.
16. according to the method for claim 1, it is characterized in that removing the reaction times is 0.5～3 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10240775A1 (en) * | 2002-08-30 | 2004-03-11 | Röhm GmbH & Co. KG | Process for removing metal ions from polymers or polymer solutions |
| JP4691046B2 (en) | 2004-12-28 | 2011-06-01 | 日本曹達株式会社 | Method for removing metal and method for producing polymer |
| CN101704926B (en) * | 2009-11-27 | 2011-06-22 | 北京化工大学 | Method for removing noble metal catalyst in hydrogenated copolymer solution |
| CN102924726B (en) * | 2012-11-13 | 2015-05-20 | 北京化工大学 | Method for recycling rhodium (Rh) from glue solution of polyamidoamine (PAMAN) dendrimer packaged Rh nanoparticle catalytic NBR (nitrile-butadiene rubber) hydrogenation |
| TWI653297B (en) * | 2013-12-30 | 2019-03-11 | 艾朗希歐德意志有限公司 | Hydrogenated nitrile rubber containing phosphine oxide or diphosphine oxide (1) |
| TWI653246B (en) * | 2013-12-30 | 2019-03-11 | 艾朗希歐德意志有限公司 | Hydrogenated nitrile rubber containing phosphine oxide or diphosphine oxide (2) |
| CN105985456B (en) * | 2015-02-05 | 2017-11-07 | 中国石油天然气股份有限公司 | A kind of method of metal rhodium in removal hydrogenated nitrile-butadiene rubber |
| CN111533831B (en) * | 2020-06-01 | 2023-05-30 | 浙江众立合成材料科技股份有限公司 | Method for removing residual metal after hydrogenation of unsaturated polymer |
| CN114426588A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Method for removing noble metal catalyst from unsaturated copolymer hydrogenation solution |
| CN116239711B (en) * | 2023-01-13 | 2023-09-12 | 华东理工大学 | Method for removing SBS homogeneous hydrogenation catalyst in SEBS solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4857632A (en) * | 1988-06-13 | 1989-08-15 | Polysar Limited | Residue removal process |
| US4944926A (en) * | 1988-08-01 | 1990-07-31 | Polysar Limited | Method to treat rhodium-containing solutions |
| US4985540A (en) * | 1989-11-20 | 1991-01-15 | Polysar Limited | Process for removing rhodium-containing catalyst residue from hydrogenated nitrile rubber |
-
2000
- 2000-03-10 CN CN00103779A patent/CN1120850C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4857632A (en) * | 1988-06-13 | 1989-08-15 | Polysar Limited | Residue removal process |
| US4944926A (en) * | 1988-08-01 | 1990-07-31 | Polysar Limited | Method to treat rhodium-containing solutions |
| US4985540A (en) * | 1989-11-20 | 1991-01-15 | Polysar Limited | Process for removing rhodium-containing catalyst residue from hydrogenated nitrile rubber |
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| CN1313344A (en) | 2001-09-19 |
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