CN1111546C - Hydrogenation catalyst, its method for making and the application in unsaturated copolymer hydrogenating - Google Patents
Hydrogenation catalyst, its method for making and the application in unsaturated copolymer hydrogenating Download PDFInfo
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Abstract
The present invention relates to a kind of empirical formula is M
a 1M
b 2X
m(L
1)
c(L
2)
dThe two ligand catalysts of bimetal, M in the formula
1, M
2, X, L
1, L
2, a, b, m, c, d in the specification sheets definition; This catalyzer and solution thereof are very stable to air, are applicable to unsaturated copolymer, particularly the hydrogenation of butyronitrile class rubber.The invention still further relates to this Preparation of catalysts method and at unsaturated copolymer, the particularly application in the butyronitrile class rubber hydrogenation.
Description
The present invention relates to a kind of novel hydrogenation catalyzer, more specifically to a kind of two ligand catalysts of bimetal that contain or do not contain organic phosphine or organic arsine, and at unsaturated copolymer, particularly in the unsaturated copolymer of nitrile group-containing to the application of carbon-carbon double bond (C=C) hydrogenation.
To carbon-carbon double bond hydrogenation in the unsaturated copolymer, the selective hydrogenation that reaches carbon-carbon double bond in the nitrile group-containing unsaturated copolymer (as perbutan) all early has report, mainly is the metallo-organic complex of rhodium, ruthenium or palladium to the employed catalyzer of latter's selective hydrogenation.This hydrogenation catalyst has the catalyzer (monometallic list ligand catalyst) of a kind of metal and a kind of part formation and the catalyzer of a kind of metal and two or more part formation (two parts of monometallic or multiple ligand catalyzer).Monometallic list ligand catalyst such as English Patent GB1,558,491 disclosed RhX
n(R
mB)
3, X=Cl in the formula, B=P or As compound; U.S. Pat 4,503,196 disclosed RhHLx, in the formula during x=3, L=As or Sb compound, during x=4, the L=phosphine compound; U.S. Pat 3,454,644 disclosed ML
nZ
2, M=Ru or Os in the formula, Z=Cl, Br or H, L=CO or tertiary phosphine; The two ligand catalysts of monometallic or multiple ligand catalyzer such as U.S. Pat 4,631,315 and US4,673,757 disclosed RuXL
1(L
2)
2And RuXL
1(L
2)
n, X=H, Cl or Br in the formula, L
1=H, Cl, Br or by H, CH
3, C
2H
5, the cyclopentadienyl that replaces of Ph, L
2=phosphine, diphosphine or arsonium compound; U.S. Pat 4,816,525 disclosed Ru (CO) XY (Z)
2, Y=H, Cl, Br or ester group in the formula, X=ester group, Z=PPh
3The disclosed RhH of clear 64-45402
m(A)
n(L)
1(Y)
p, A=PR in the formula
3, L=neutral ligand (as vinyl, propenyl, cycloalkyl, benzene nitrile), Y=contains the compound of P, S or N (as triphenyl phosphite, CS
2, dimethyl sulfoxide (DMSO), pyridine, triethylamine); U.S. US4,795,788 disclosed RuX (L
1) (L
2)
n, X=SnCl in the formula
3, halogen, H, L
1=indenyl or fluorenyl, L
2=phosphine, or diphosphine, arsonium compound.
Rhodium metal organic complex catalyzer is to the selectivity height of carbon-carbon double bond hydrogenation in the nitrile group-containing unsaturated copolymer in the above-mentioned catalyst system, the hydrogenation activity height, but cost an arm and a leg, make product cost too high.Ruthenium metallo-organic complex catalyzer is also very high to the hydrogenation activity of carbon-carbon double bond, because of its price than rhodium considerably cheaper, replace the patent of metallo-organic complex catalyzer of rhodium also a lot of with ruthenium, but side reaction can take place in its hydrogenation to carbon-carbon double bond in the nitrile group-containing unsaturated copolymer, generates gel.
Nearest disclosed the applicant's Chinese patent application publication number CN1199051A proposed a kind of have with monometallic rhodium organic complex catalyst hydrogenation activity quite, hydrogenation reaction do not produce gel and inexpensive bimetal list ligand catalyst, and be used for unsaturated copolymer, the particularly hydrogenation of butyronitrile class rubber.This catalyzer is by empirical formula M
1 aM
2 bX
m(L
1)
nExpression, M in the formula
1=Rh or Ru, M
2=Ru or lanthanide rare metal, X=H, Cl, Br, L
1=phosphine or diphosphine, arsonium compound.
The part of above-mentioned catalyst system all is the compounds that contain phosphine or arsine, except that Chinese patent application publication number CN1199051A, all is single-metal reforming catalyst, and catalyst solution all needs preparation and storage under high purity nitrogen protection.
In view of above prior art situation, when the present inventor carries out extensively and profoundly research in this area, be surprised to find that not to be to contain organic phosphine compound, especially PPh as the mentioned rhodium of background technology or the part of ruthenium metallo-organic complex catalyzer
3, its hydrogenation activity is just high, be not yet as the applicant's Chinese patent application publication number CN1199051A disclosed have only in the bimetal organic complex catalyzer between two kinds of metal complexs synergy is arranged.The inventor finds, to contain two kinds of metal halides of crystal water and two kinds of ligand mixtures that do not contain the organic compound of phosphine or arsine reacts the two ligand catalysts of a kind of bimetal that makes and can be used for unsaturated copolymer hydrogenating in mixed solvent, particularly the nitrile group-containing unsaturated copolymer hydrogenating had high hydrogenation activity, highly selective, hydrogenation activity is suitable with bimetal list ligand catalyst, price is also suitable, and finds between two kinds of parts synergy is arranged also; This catalyzer and solution thereof need not preparation and storage under high purity nitrogen protection; very stable in air, these many catalyzer that are different from the background technology and mentioned must be kept away the oxygen storage, therefore; the operation of catalyst solution preparation of the present invention is just very easy, also is beneficial to storage.The inventor finds also that simultaneously even one of two kinds of parts are for containing the organic compound of phosphine or arsine in this catalyzer, it still keeps high hydrogenation activity, highly selective and cheap cost.
The inventor finds that also this catalyzer to unsaturated copolymer, when particularly the nitrile group-containing multipolymer carries out hydrogenation, does not produce gel yet under mild conditions.The present invention just is being based on that above-mentioned discovery finishes.
Therefore, an object of the present invention is to provide a kind of two part hydrogenation catalysts of bimetal that do not contain phosphine or arsine, it has high hydrogenation activity, highly selective and low cost, and has high stability in air, thereby make the preparation of this catalyst solution and storage convenient, need not to use high purity nitrogen.
Another object of the present invention provides a kind of two part hydrogenation catalysts of bimetal that contain phosphine or arsine, and it still has high hydrogenation activity, highly selective and low cost.
Another purpose of the present invention provides the hydrogenation technique that above-mentioned catalyzer is used for unsaturated copolymer hydrogenating, and hydrogenation products does not produce gel.
An also purpose of the present invention provides a kind of method for preparing above-mentioned catalyzer.
Above and other objects of the present invention, feature and advantage can obtain embodying in further elaboration of the present invention.
According to a first aspect of the invention, provide a kind of unsaturated copolymer that is used for, the particularly bimetal of nitrile group-containing unsaturated copolymer hydrogenating two ligand catalysts, it has following empirical formula:
M
1 aM
2 bX
m(L
1)
c(L
2)
dM in the formula
1Be Rh or Ru, M
2Be Ru or lanthanide series metal; Work as M
1During for Rh, M
2Be Ru or lanthanide series metal; M
1During for Ru, M
2Be lanthanide series metal;
X is H, Br, Cl or its combination;
L
1And L
2Different and be respectively the organic compound that contains 1～3 N, O or S, or contain the organic compound of N and O, S and N or S and O simultaneously; Perhaps L
2And L
2One of also can be for containing the organic compound of phosphine, diphosphine or arsine; With
1≤a≤6；1≤b≤2；1≤a∶b≤4；3≤m≤6，1≤c≤6，1≤d≤6，c∶d＝1～6∶6～1。
The lanthanide series metal that can be used among the present invention comprises the 57th～60,62～No. 71 elements in the periodic table of elements.For reducing catalyzer cost, the lanthanide series metal that the preferred price of the present invention is more cheap.
According to the present invention, preferred M
1Be rhodium, M
2Be ruthenium or lanthanide series metal.
According to the present invention, X=H, Cl, Br or its combination, preferred X=H, Cl or its combination, more preferably hydrogen or chlorine.
According to the present invention, L
1And L
2Be can with the part of metal rhodium, ruthenium or lanthanide metal-complexed, they can be respectively the organic compound that contains 1～3 N, S or O, or contain the organic compound of N and O, S and N or S and O simultaneously.L
1And L
2Example comprise triphenylamine, Trimethylamine 99, triethylamine, hexichol ethylamine, N, accelerine, N, N-Diethyl Aniline, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetraphenyl quadrol, by CH
3, C
2H
5, C
3H
7, the thioether (as diphenyl sulfide, dipropyl thioether, diethyl thioether, dimethyl thioether) that replaces of phenyl; Acetyl Acetone; benzophenone; thiocarbamide; dimethyl amido ethyl-diphenyl-methyl ether hydrochloride (popular name diphenhydramine), N, N '-diphenyl ethylene diamine, N, N '-di-o-tolyl-ethylene-diamine; N, N '-two-betanaphthyl Ursol D.Preferred diphenyl sulfide, N, N, N ', N '-Tetramethyl Ethylene Diamine, triphenylamine, dimethyl amido ethyl-diphenyl-methyl ether hydrochloride or N, the N '-diphenyl ethylene diamine of using.
According to the present invention, ligand L
1And L
2One of also can be for containing the organic compound of phosphine, diphosphine or arsine.For example, L
1And L
2One of can be formula PR
1R
2R
3, R
1R
2P (CH)
nPR
3R
4And AsR
1R
2R
3Shown compound, R in the formula
1, R
2, R
3, R
4Can be identical or different, be respectively C
1～C
6Alkyl, C
6～C
12Cycloalkyl, aryl, C
7～C
12Aralkyl, aryloxy, n are the integer of 2-4.Example comprises triphenylphosphine (arsine), triethyl phosphine (arsine), diphenyl-ethyl phosphine (arsine), triple phenoxyl phosphine, dibutyl Phenylphosphine (arsine), three-right-p-methoxy-phenyl phosphine, 1,2-2-2 phenyl phosphine ethane, 1,4-2-2 phenyl phosphine butane.
According to the present invention, reach desired activity for making catalyzer, make the hydrogenation products of nitrile group-containing multipolymer not produce gel, and the catalyzer cost is lower, preferred 1≤a: b≤4, more preferably 1≤a: b≤2.
According to the present invention, 3≤m≤6; 1≤c≤6; 1≤d≤6; C: d=1～6: 6～1, preferred c: d=2～4: 4～2.
According to a further aspect in the invention, provide a kind of method for preparing catalyzer of the present invention, comprised and from the halogenide of rhodium, ruthenium or lanthanide series metal, select two kinds of metal halides for use, preferably contained the metal chloride of crystal water, selected two kinds of different ligand L again for use
1And L
2, they reacted under the reflux temperature of mixed solvent make catalyzer of the present invention.
For example, with selected L
1And L
2Add reaction flask with mixed solvent, under reflux temperature, will be dissolved in the M in the hot mixed solvent
1And M
2Halogenide add reaction flask and make catalyzer of the present invention.
Particularly, with M
1The source rhodium metal halogenide of crystal water (as contain) and M
2Mix with certain mol proportion in the source ruthenium metal halide of crystal water (as contain), simultaneously and the organic compound ligand L that contains or do not contain phosphine or arsine
1And L
2Mix, they react 0.5～2.0 hour under reflux temperature in the mixed solvent of two kinds of solvents after, removing desolvates makes catalyzer of the present invention.Wherein preferably use M
1And M
2Muriate, more preferably contain the muriate of crystal water, the preferred a of its mol ratio: b 〉=1, more preferably 1～2.(L
1+ L
2) and (M
1+ M
2) mol ratio greater than 3, preferred 6～12; L
1With L
2Mol ratio be that c: d is 1: 6～6: 1, be preferably 2～4: 4～2.
Operable solvent should be able to dissolve two kinds of metal halides that contain crystal water in Preparation of catalysts method of the present invention, also can dissolve simultaneously two kinds of parts with metal complex.The used solvent of the present invention for example can be the mixed solvent of two kinds of solvents in alcohols (as 95% ethanol, dehydrated alcohol), ketone (as methylethylketone, acetone), ethers (as ether), the aromatic hydrocarbons (as benzene, toluene), is preferably the alcohols that is selected from 95% ethanol and dehydrated alcohol and the mixture of ether.
According to a third aspect of the invention we, provide a kind of method of using above-mentioned catalyzer unsaturated copolymer to be carried out hydrogenation.This method comprises unsaturated copolymer is dissolved in the solvent, adds an amount of anti-aging agent on demand, auxiliary agents such as stablizer, and its consumption is 1～3% of a polymer weight, is mixed with unsaturated copolymer solution; This solution is added in the reactor, fill and get rid of gas, the solution of the described catalyzer that will prepare in advance adds in the reactor again, and described catalyst solution also can add with the polymers soln for the treatment of hydrogenation, fills and gets rid of gas; Start and stir, be warming up to temperature of reaction, charge into hydrogen, the stopped reaction of lowering the temperature behind the reaction certain hour.The preferred catalytic agent solution is prepared in air atmosphere.
In method of hydrotreating of the present invention, temperature of reaction is 40～200 ℃, is preferably 100～170 ℃.
In method of hydrotreating of the present invention, the hydrogen pressure of reaction is 0.05～5.0MPa, is preferably high-purity hydrogen pressure 0.1～1.5MPa.
In method of hydrotreating of the present invention, the reaction times is 0.5～10 hour, is preferably 1～5 hour.
Two ligand complex catalyzed dose of the bimetal of preferred rhodium of catalyzer of the present invention and ruthenium, wherein hydrogenation products gel-free when Rh: Ru 〉=1 (mol ratio).
In method of hydrotreating of the present invention, catalyst levels is represented with the bimetallic metal quality in the catalyzer and the ratio of copolymer quality, is 1 * 10
-5～5 * 10
-3, preferred 1 * 10
-4～2 * 10
-3
In method of hydrotreating of the present invention, used solvent should be able to dissolve polymer and catalyzer, comprises aromatic hydrocarbons and derivative, halogenated alkane, ketone, naphthenic hydrocarbon or amides of being replaced by alkyl or halogen and composition thereof.Specific examples is benzene,toluene,xylene, chlorobenzene, orthodichlorobenzene, trichlorobenzene, ethylene dichloride, hexanaphthene, acetone, butanone, N, dinethylformamide, N,N-dimethylacetamide and composition thereof.Preferred dimethylbenzene, chlorobenzene and composition thereof.
According to the present invention, described unsaturated copolymer can be copolymer and terpolymer, copolymer comprises divinyl-(methyl) vinyl cyanide, butadiene-styrene, 2-methyl isophthalic acid, 3-divinyl-(methyl) vinyl cyanide, styrene-butadiene-styrene block copolymer (SBS), preferred perbutan (paracril) and SBS; Terpolymer comprises divinyl-(methyl) vinyl cyanide-(methyl) vinylformic acid, divinyl-(methyl) vinyl cyanide-(N-(4-phenyl amino phenyl) Methacrylamide), preferred butadiene-acrylonitrile-(methyl) acrylic copolymer (carboxy nitrile rubber).The molecular weight of multipolymer is unimportant.
The concentration of polymkeric substance is 1～20 gram polymkeric substance/100ml solvent in method of hydrotreating of the present invention, preferred 1～10 gram polymkeric substance/100ml solvent.
Catalyzer of the present invention reacts applicable to homogeneous hydrogenation, and also available methods known in the art are carried out modification to catalyzer, makes it be applicable to heterogeneous hydrogenation reaction.
Catalyzer of the present invention is specially adapted to the hydrogenation of nitrile group-containing unsaturated copolymer, especially the homogeneous hydrogenation of paracril.Hydrogenation rate definition and degree of unsaturation analytical procedure
Bromine iodine method is adopted in the degree of unsaturation analysis among the present invention, with reference to CNS GB-1676-81, makes polymer solvent with trichloromethane, and adopts the bromine iodine reagent, adjusts compound concentration, to meet analysis precision.
The following example is used to further specify the present invention, but the present invention is not limited.
Preparation of Catalyst Embodiment 1
In the 100ml of charged magnetic stirrer and reflux condensing tube reaction flask, add an amount of ether and alcohol mixed solvent, place water bath with thermostatic control.The part that adds kind shown in the table 1 and consumption starts and stirs and intensification; Metal halide with consumption shown in the table 1 is dissolved in the mixed solvent of heat then, under reflux temperature, add in the reaction flask, under agitation back flow reaction 0.5-2 hour, removing desolvates made Rh: Ru=3: 2 (A～F, H～K) or the catalyzer various of the present invention of 2: 3 (G).
Table 1
In the table: T=N, N, N ', N '-Tetramethyl Ethylene Diamine
| Sequence number | The catalyzer code name | Metal halide (add-on) | Part (add-on) |
| 1 | A | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | T(3.0mmol) Y(3.0mmol) |
| 2 | B | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | T(3.0mmol) N(3.0mmol) |
| 3 | C | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | T(3.0mmol) S(3.0mmol) |
| 4 | D | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | N(3.0mmol) S(3.0mmol) |
| 5 | E | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | Y(6.0mmol) |
| 6 | F | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | T(6.0mmol) |
| 7 | G | RhCl 3·3H 2O(0.4mmol) RuCl 3·xH 2O(0.6mmol) | T(3.0mmol) Y(3.0mmol) |
| 8 | H | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | P(4.0mmol) T(2.0mmol) |
| 9 | I | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | P(4.0mmol) S(2.0mmol) |
| 10 | J | RhCl 3·3H 2O(0.6mmol) RuCl 3·xH 2O(0.4mmol) | P(4.0mmol) Y(2.0mmol) |
S=diphenyl sulfide N=triphenylamine P=triphenylphosphine
Y=dimethyl amido ethyl-diphenyl-methyl ether hydrochloride
The hydrogenation of unsaturated copolymer
The universal program of method of hydrotreating: with nitrile content is that 33% Nancar 1052 paracrils (NANTEX Industry Co.LTD) are dissolved in dimethylbenzene, and adds auxiliary agents such as an amount of anti-aging agent, stablizer on demand, is made into 7 gram/100ml xylene solutions.Get the above-mentioned glue of 50ml and add in 0.1 liter of autoclave, add the catalyst solution of desired concn, close kettle cover, fill with high purity nitrogen or High Purity Hydrogen and get rid of gas.Start and stir and intensification, charge into High Purity Hydrogen when reaching temperature of reaction to certain pressure, still interior hydrogen pressure in reaction beginning back descends, and needs continuous hydrogen make-up, to keep constant pressure.Behind the reaction certain hour, cooling finishes reaction, and hydrogenation products is separated out with ethanol or hot water or the cohesion of steam distillation method, separates, dry, to be measured.
Embodiment 2
By above-mentioned method of hydrotreating,,, to Nancar 1052 NBR hydrogenation 4 hours, the results are shown in table 2 under the 0.8MPa hydrogen pressure at 145 ℃ with catalyzer shown in the table 2 and consumption thereof.
Table 2
| Sequence number | Catalyzer | Catalyst levels *，(wt) | Hydrogenation rate, % |
| 1 2 3 4 | A RhCl(PPh 3) 3RhRuXP **RhRuXP ** | 4.40×10 -4 3.23×10 -4 3.27×10 -4 4.36×10 -4 | 99.0 94.2 95.1 98.5 |
*Catalyst levels is with (M
1+ M
2/ NBR) mass ratio is represented.
*Containing its part of Rh-Ru bimetallic catalyst is triphenylphosphine, Rh: Ru=3: 1 (mol)
RhCl (PPh
3)
3The preparation method translated the 60th page of " inorganic synthetic " the tenth volume 1977 referring to Zhang Jinghua etc., Science Press.
The RhRuXP catalyzer synthesizes sees Chinese patent application publication number CN1199051A.
By embodiment 2 as seen, although the A catalyzer does not contain phosphine or arsine, because two kinds of part (L
1With L
2) between synergy is arranged, the hydrogenation activity height of this catalyzer, it is active all suitable with similar Rh-Ru bimetal list ligand catalyst with single rhodium organic complex catalyzer, and the first gel of product.
Embodiment 3
By above-mentioned method of hydrotreating, to have Different L shown in the table 3
1And L
2The catalyzer of part and consumption thereof, under 145 ℃, 1.4MPa hydrogen pressure, to Nancar 1052 NBR hydrogenation 4 hours, the results are shown in Table 3.
Table 3
| Sequence number | Catalyzer | Catalyst levels *，(wt) | Hydrogenation rate, % |
| 1 2 3 4 | A B C D | 4.40×10 -4 4.42×10 -4 4.46×10 -4 4.40×10 -4 | 98.6 96.0 98.1 98.6 |
| 5 6 | RhCl(PPh 3) 3RhRuX(P) | 3.23×10 -4 4.36×10 -4 | 97.5 98.5 |
| 7 8 9 10 | J J H I | 4.20×10 -4 3.58×10 -4 3.30×10 -4 3.28×10 -4 | 98.9 98.7 98.0 98.8 |
*With table 2.
By table 3 as seen, sequence number 1～4,7～10 catalyzer is respectively the two ligand catalysts of the Rh-Ru bimetal that does not contain phosphine and contain phosphine, they all have high hydrogenation rate under same catalyst consumption and identical hydroconversion condition, and hydrogenation rate is close, and the hydrogenation activity of the catalyzer of their hydrogenation activity and sequence number 5,6 is also suitable.In the table 3 in sequence number 5 and the table 2 catalyzer of sequence number 2 all identical with consumption, and the high reason of hydrogenation rate is that hydrogen pressure in the table 3 is than the height in the table 2.
Embodiment 4
By above-mentioned method of hydrotreating, under 145 ℃, 1.4MPa hydrogen pressure, to Nancar 1052 NBR hydrogenation 4 hours, the results are shown in Table 4 with the two ligand catalyst consumptions of the Rh-Ru bimetal that does not contain phosphine shown in the table 4.
Table 4
| Sequence number | Catalyzer | Catalyst levels *，(wt) | Hydrogenation rate, % |
| 1 2 3 4 | A A A A | 6.60×10 -4 4.40×10 -4 2.75×10 -4 2.00×10 -4 | 99.2 98.8 96.2 96.0 |
| 5 6 7 | B B B | 6.60×10 -4 4.40×10 -4 1.65×10 -4 | 98.3 96.0 81.0 |
| 8 9 | C C | 4.46×10 -4 1.67×10 -4 | 98.1 95.9 |
*With table 2.
By embodiment 4 as seen, catalyst levels increases, and hydrogenation rate increases; Catalyst B is lower slightly than the hydrogenation activity of A and C, and reason may be that two kinds of parts of catalyst B all are organic compounds containing nitrogen, and its synergy is not as in two parts of catalyst A and C between oxygen and the nitrogen or the synergy between sulphur and the nitrogen.
Embodiment 5
By above-mentioned method of hydrotreating, the ratio of component of Rh and Ru in the change catalyzer, to Nancar 1052NBR hydrogenation, the results are shown in Table 5.
Table 5
| Sequence number | Catalyzer | Catalyst levels *，(wt) | Hydrogenation rate, % | Remarks |
| 1 | A | 4.40×10 -4 | 98.8 | Rh∶Ru＝3∶2 |
| 2 | G | 4.40×10 -4 | 98.7 | Rh∶Ru＝2∶3 |
*With table 2.
Hydroconversion condition: 145 ℃ of hydrogenation reaction temperature, high-purity hydrogen pressure 1.4MPa, 4 hours reaction times.
By embodiment 5 as seen, even the mol ratio of Rh and Ru was reduced to 2: 3 in the catalyzer, hydrogenation rate is still very high, the product gel-free, show with N N, N ', N '-Tetramethyl Ethylene Diamine (T) and dimethyl aminoethyl-diphenyl-methyl ether hydrochloride (Y) is the hydrogenation activity height that does not contain the two ligand catalysts of phosphine bimetal of part, selectivity height.
Embodiment 6
By above-mentioned method of hydrotreating, the results are shown in Table 6 to its activity influence storage period in air for catalyst solution.
Table 6
| Sequence number | Catalyzer | Catalyst levels *，(wt) | Hydrogenation rate, % | Remarks |
| 1 | A | 3.18×10 -4 | 98.5 | Cat. solution stores 28 days, places 17 hours in air then |
| 2 | A | 3.18×10 -4 | 98.3 | Cat. solution stores 3 days |
| 3 | A | 3.18×10 -4 | 98.6 | Cat. solution stores 27 days |
*With table 2.Hydroconversion condition: with table 5.
By embodiment 6 as seen, catalyzer of the present invention and solution thereof are very stable to air, so hydrogenation activity almost is not affected, it is different from many catalyzer mentioned in the background technology need keep away the oxygen storage, the operation of therefore preparing this catalyst solution is just very easy, also is beneficial to storage.
Embodiment 7
By above-mentioned method of hydrotreating, under the hydroconversion condition of table 5, with the hydrogenation activity comparison of the two ligand catalyst A of bimetal and bimetal list ligand catalyst E, F, the results are shown in Table 7.
Table 7
| Sequence number | Catalyzer | Catalyst levels *，(wt) | Hydrogenation rate, % |
| 1 | A | 3.18×10 -4 | 98.3 |
| 2 | E | 3.18×10 -4 | 80.5 |
| 3 | F | 3.70×10 -4 | 91.9 |
*With table 2.
By embodiment 7 as seen, catalyzer E and F are respectively the catalyzer of Rh-Ru bimetal and the preparation of a kind of part, their amount of ligand is identical with catalyst A part total amount, and the hydrogenation activity of catalyst A is higher than E, F, and showing between two kinds of parts in the catalyst A has synergy.
Embodiment 8
By above-mentioned method of hydrotreating, under the hydroconversion condition of table 5, with paracril (NBR) hydrogenation of catalyst A to different nitrile content.Nancar 1051 NBR, Nancar 1052 NBR and Nancar 6004 NBR are NANTEX Industry Co.LTD product, and the results are shown in Table 8 for its hydrogenation.
Table 8
| Sequence number | Catalyzer | The NBR trade mark ** | Nitrile content, % | Catalyst levels *，(wt) | Hydrogenation rate, % |
| 1 | A | 1052 | 33.0 | 4.40×10 -4 | 98.8 |
| 2 | A | 1051 | 41.0 | 4.40×10 -4 | 97.9 |
| 3 | A | 6004 | 19.0 | 4.40×10 -4 | 96.6 |
*With table 2.
*Nancar 1051 NBR solvents are chlorobenzene, and Nancar 1052 and 6004 NBR solvents are dimethylbenzene.
Above experimental result shows, catalyzer of the present invention is to unsaturated copolymer, particularly in the hydrogenation of nitrile group-containing unsaturated copolymer (as paracril), not only with in the background technology contain the Rh-Ru bimetallic catalyst and single rhodium metal organic complex catalyzer has suitable high reactivity, highly selective, and catalyzer of the present invention is very stable to air, makes the operation of Preparation of Catalyst and catalyst solution preparation more easy.
Above description is exemplary, and those skilled in the art can carry out suitable change, for example M to catalyzer of the present invention and hydrogenation technique thereof
1And M
2Change (the M of mol ratio
1: M
2＜1, M
1: M
2＞4) ligand L that, does not contain phosphine, arsine
1And L
2The expansion of example ranges etc., all within the scope of the invention.
Claims (10)
1. two ligand catalysts of the bimetal that is used for the unsaturated copolymer shortening, this catalyzer has following empirical formula:
M
1 aM
2 bX
m(L
1)
c(L
2)
dM in the formula
1Be rhodium or ruthenium, M
2Be ruthenium or lanthanide series metal; Work as M
1During for rhodium, M
2Be ruthenium or lanthanide series metal; M
1During for ruthenium, M
2Be lanthanide series metal;
X is H, Br, Cl or its combination;
L
1And L
2Different and be respectively the organic compound that contains 1～3 N, O or S, or contain the organic compound of N and O, S and N or S and O, perhaps L simultaneously
1And L
2One of for being selected from formula PR
1R
2R
3Phosphine, formula R
1R
2P (CH
2)
nPR
3R
4Diphosphine or formula AsR
1R
2R
3The compound of arsine, R wherein
1, R
2, R
3, R
4Can be identical or different, be respectively C
1～C
6Alkyl, C
6～C
12Cycloalkyl, aryl, C
7～C
12Aralkyl, aryloxy, n are the integer of 2-4; With
1≤a≤6；1≤b≤2；1≤a∶b≤4；3≤m≤6；1≤c≤6，1≤d≤6，c∶d＝1～6∶6～1。
2. according to the catalyzer of claim 1, it is characterized in that M
1Be rhodium, M
2Be ruthenium or lanthanide series metal, X is hydrogen or chlorine.
3. according to the catalyzer of claim 1 or 2, it is characterized in that L
1And L
2Be selected from triphenylamine, Trimethylamine 99, triethylamine, hexichol ethylamine, N; accelerine, N; N, N ', N '-Tetramethyl Ethylene Diamine, N; N; N ', N '-tetraphenyl quadrol, N, N '-diphenyl ethylene diamine, N; N '-di-o-tolyl-ethylene-diamine, N, N '-two-betanaphthyl Ursol D, dimethyl amido ethyl-diphenyl-methyl ether hydrochloride, Acetyl Acetone, benzophenone, diphenyl sulfide, dimethyl thioether, diethyl thioether, dipropyl thioether, thiocarbamide.
4. according to the catalyzer of claim 3, it is characterized in that L
1And L
2Be selected from diphenyl sulfide, N, N, N ', N '-Tetramethyl Ethylene Diamine, triphenylamine, dimethyl amido ethyl-diphenyl-methyl ether hydrochloride, N, N '-diphenyl ethylene diamine.
5. a method for preparing according to each catalyzer in the claim 1～4 comprises selected L
1And L
2Add reaction flask with mixed solvent, under reflux temperature, will be dissolved in the M in the hot mixed solvent
1And M
2Halogenide add reaction flask and make described catalyzer, wherein L
1, L
2, M
1And M
2Such as claim 1 definition, it is characterized in that L
1And L
2Mol ratio be 1: 6～6: 1; M
1And M
2Halogenide be the muriate that contains crystal water, M
1And M
2Mol ratio be 1～2; (L
1+ L
2) and (M
1+ M
2) mol ratio be 6～12; Described mixed solvent is the mixed solvent of any two kinds of solvents in alcohols, ketone, ethers, the aromatic hydrocarbons.
6. according to the method for claim 5, it is characterized in that described mixed solvent is to be selected from the alcohols of 95% ethanol and dehydrated alcohol and the mixture of ether.
7. the method for hydrotreating of a unsaturated copolymer, the catalyst solution that comprises the copolymer solution that will contain anti-aging agent, stablizer and preparation adds reactor, fill and get rid of gas, reach temperature of reaction, filling high-purity hydrogen reacts to certain pressure, it is characterized in that described catalyzer for according to any one catalyzer in the claim 1～4, and wherein copolymer concentration is 1～10 gram multipolymer/100 milliliter solvent, described solvent is selected from dimethylbenzene, chlorobenzene and composition thereof; High Purity Hydrogen pressure is 0.1～1.5MPa, and temperature of reaction is 100～170 ℃, and the reaction times is 1～5 hour, and catalyst levels is expressed as 1 * 10 with the ratio of bimetallic metal quality in the catalyzer and copolymer quality
-4-2 * 10
-3, the catalyzer solvent is chlorobenzene, dimethylbenzene, N, dinethylformamide and composition thereof.
8. according to the method for hydrotreating of claim 7, it is characterized in that described catalyst solution prepares in air atmosphere.
9. according to the method for hydrotreating of claim 7 or 8, it is characterized in that described unsaturated copolymer for being selected from divinyl-(methyl) vinyl cyanide, 2-methyl isophthalic acid, the copolymer of 3-divinyl-(methyl) vinyl cyanide, butadiene-styrene and styrene-butadiene-styrene block copolymer and be selected from the terpolymer of divinyl-(methyl) vinyl cyanide-(methyl) vinylformic acid, divinyl-(methyl) vinyl cyanide-[N-(4-anilino phenyl) Methacrylamide].
10. according to the method for hydrotreating of claim 9, it is characterized in that described unsaturated copolymer is perbutan or styrene-butadiene-styrene block copolymer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99102148A CN1111546C (en) | 1999-02-12 | 1999-02-12 | Hydrogenation catalyst, its method for making and the application in unsaturated copolymer hydrogenating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99102148A CN1111546C (en) | 1999-02-12 | 1999-02-12 | Hydrogenation catalyst, its method for making and the application in unsaturated copolymer hydrogenating |
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| CN1111546C true CN1111546C (en) | 2003-06-18 |
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| CN100469802C (en) * | 2004-11-12 | 2009-03-18 | 江苏圣杰实业有限公司 | High polymer carbon-carbon double bond hydrogenation ruthenium complex catalyst and hydrogenation method thereof |
| CN101870744A (en) * | 2010-06-11 | 2010-10-27 | 北京化工大学 | Hydrogenation method of butadiene-acrylonitrile rubber |
| CN106423283B (en) * | 2016-08-31 | 2019-05-17 | 北京化工大学 | Diamine transition metal complex catalyst and the preparation method and application thereof |
| CN116041621B (en) * | 2021-10-28 | 2023-08-01 | 中国石油化工股份有限公司 | Hydrogenated nitrile rubber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4241013A (en) * | 1979-10-09 | 1980-12-23 | Basf Wyandotte Corporation | Hydroxybenzoic acid as pH buffer and corrosion inhibitor for antifreeze containing aminosilicone-silicate polymers |
| US5075388A (en) * | 1990-12-13 | 1991-12-24 | Rempel Garry L | Amine modified hydrogenation of nitrile rubber |
| US5210151A (en) * | 1992-09-02 | 1993-05-11 | Polysar Rubber Corporation | Hydrogenation of nitrile rubber |
-
1999
- 1999-02-12 CN CN99102148A patent/CN1111546C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4241013A (en) * | 1979-10-09 | 1980-12-23 | Basf Wyandotte Corporation | Hydroxybenzoic acid as pH buffer and corrosion inhibitor for antifreeze containing aminosilicone-silicate polymers |
| US5075388A (en) * | 1990-12-13 | 1991-12-24 | Rempel Garry L | Amine modified hydrogenation of nitrile rubber |
| US5210151A (en) * | 1992-09-02 | 1993-05-11 | Polysar Rubber Corporation | Hydrogenation of nitrile rubber |
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|---|---|
| CN1263111A (en) | 2000-08-16 |
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