CA1163750A - Process for hydrogenation of conjugated diene polymers - Google Patents

Process for hydrogenation of conjugated diene polymers

Info

Publication number
CA1163750A
CA1163750A CA000366233A CA366233A CA1163750A CA 1163750 A CA1163750 A CA 1163750A CA 000366233 A CA000366233 A CA 000366233A CA 366233 A CA366233 A CA 366233A CA 1163750 A CA1163750 A CA 1163750A
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CA
Canada
Prior art keywords
catalyst
weight
polymer
carrier
supported
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000366233A
Other languages
French (fr)
Inventor
Yoichiro Kubo
Kiyomori Ohura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Nippon Zeon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP15857579A external-priority patent/JPS5681305A/en
Priority claimed from JP15857679A external-priority patent/JPS5681306A/en
Application filed by Nippon Zeon Co Ltd filed Critical Nippon Zeon Co Ltd
Application granted granted Critical
Publication of CA1163750A publication Critical patent/CA1163750A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00Chemical modification of rubber
    • C08C19/02Hydrogenation

Abstract

Abstract The invention relates to a process for hydrogenating a conjuated diene polymer using a Pd-containing catalyst having improved activity. The catalyst is composed of a porous powdery of granular carrier and supported thereon both Pd nd at least one metal selected from the group consisting of the metals of Groups Ia, IIa, IIIa, IVa, Va and VIa of the periodic table, Ge and Sb.

Description

1 ~3750 This invention relates to a process for hydroge-nating a conjugated diene polymer using a Pd-containing catalyst having improved activity.
Catalysts composed of a metal of Group VIII of the periodic table supported on a porous carrier such as carbon, silica or alumina have generally been used to catalyze hydrogenation of the carbon-carbon double bonds of conjugated diene polymers. An unsaturated bond of a polymer is hydrogenated for the purpose of improving the properties of the polymer. If, however, the inherent properties of the polymer are degraded as a result of the hydrogenation, there is no significance in modifying the polymer by hydrogenation. For example, when modification of a styrene/butadiene random or block copolymer proceeds so far as to hydrogenate the benzene ring of styrene, the polymer will lose its rubber-like properties. In the case of an acrylonitrile/butadiene random or block copolymer, reduction of its nitrile group as a result of hydrogenation will markedly reduce the oil resistance of the copolymer. Accordingly, in so modifying a con~ugated diene polymer, it is necessary to selectively hydrogenate only the double bonds of its con~ugated diene portion.
Noble metals such as Pt and Pd are frequently used as catalytic metals having such selectivity. Since these noble metals are expensive, they are desirably used in the smallest possible amounts in performing selective hydrogenation. Furthermore, because in hydrogenating a high-molecular-weight polymer in solvent, the viscosity of the system should be minimized in order to stir it I 16375~

well and perform uniform hydrogenation reaction. Consequently, the amount of the catalyst has to be decreased. It has been desired therefore to develop a catalyst having high activity and high selectivity.
It is an object of this invention therefore to provide a Pd-containing catalyst which has activity in catalyzing hydrogenation of conjugated diene polymers and can selectively hydrogenate carbon-carbon double bonds in the main chain or side chains of the polymers.
On extensive investigation, the present inventors have found that when a conjugated diene polymer is hydrogenated by using a catalyst containing Pd and another metal supported together on a carrier, the catalyst shows much higher activity and much higher selectivity than a catalyst containing only Pd supported on a carrier.
Thus, the present invention provides in a process which comprises catalytically hydrogenating the carbon-carbon double bonds of a conjugated diene polymer, the improvement which comprises using a catalyst composed of a porous powdery or granular carrier and supported thereon 0.001 to 30% by weight Pd based on the weight of the carrier, and at least one metal selected from the group consisting of the metals of Groups Ia, IIa, IIIa, IIIb, IVa, Va and VIa of the periodic table, Ge and Sb.
The catalyst used in the process of this invention is prepared by supporting both Pd and at least one metal selected from the group consisting of the metals of Groups Ia, IIa, IIIa, IIIb, IVa, Va and VIa of the periodic table, Ge and Sb on a porous powdery or - 2a -; ,j ~ 1637 50 granular carrier, such as silica, silica-alumina, alumina, diatomaceous earth, activated carbon or carbon blac~ used for rubber compounding or coloration. When used alone, the metals of Groups Ia, IIa and IIIa do not have hydrogenating ability, The metals of Groups IVa and Va, on the other hand, have little or no hydrogenating ability when used alone.
The above metals can be supported on the carrier by any ordinary supporting methods. For example, these metals can be supported in the elemental state on the carrier. Or the carrier may be dipped in an aqueous solution of a halide, oxide, hydroxide, acid chloride, sulfate, carbonate, etc. of these metals, followed by reduction to provide the desired catalyst.
The amount of Pd deposited on the carrier is 0,001 to ~ by weight, preferably 0.01 to 10~ by weight, based on the carrier. If the amount of Pd supported is too small, the supported catalyst must be used in a great quantity in the reaction. Consequently, the vis-cosity of the reaction system becomes so high that it is difficult to stir. ~Tence, the catalyst is not effec-tively used. On the other hand, if the amount of Pd supported on the carrier is too large, dispersion of the metals on the carrier becomes poor, and the dimmeter of the metal particles increases to reduce the catalytic activity of the resulting catalyst.
The atomic ratio of the metal supported together with Pd to Pd is in the range of from 0.001 to 50, preferably from 0.005 to 10.

The amount of the supported catalyst used is in the range of 5 to 2000 ppm, preferably 10 to 1000 ppm, calculated as Pd based on the polymer. Amounts larger than 2000 ppm may be used, but are not economically feasible.
The conjugated diene polymer used in this invention is composed of 10 to 100~ by weight of a conjugated diene monomer unit and ~0 to ~ by weight of an ethylenically unsaturated monomer unit. Specific examples of the conjugated diene monomer are 1,~-butadiene, 2,3-dimethylbutadiene, isoprene and 1,3-pentadiene. Specific examples of the ethylenically unsaturated monomer include unsaturated nitriles such as acrylonitrile and methacrylonitrile; mono~inylidene aromatic hydrocarbons such as styrene, (o-, m- and p-) alkylstyrenes; unsaturated carboxylic acids and the esters thereof, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate; vinylpyridine; and vinyl esters such as vinyl acetate.
The conjugated diene polymer may be the one prepared by any method of preparation, such as emulsion polymerization, solution polymerization or bulk polyme-rization. Specific examples of the conjugated dienepolymer include polyisoprene, polybutadiene, a styrene/
butadiene (random or block) copolymer, an acrylonitrile/
butadiene ~random or blocked) copolymer, a butadiene/
isoprene copolymer, and an isoprene-isobutylene copolymer.

1 ~637 5 The conjugated diene polymer may be hydroge-nated as such. Good results, however, can be obtained when the polymer is used in the form of a solution. The concentration of the polymer solution is 1 to 70yU by weight, preferably 1 to 40~ by weight. Any solvent which does not adversely affect the catalyst and can dissolve the polymer to be hydrogenated may be used to provide the polymer solution. ~here may usually be employed benzene, toluene, xylene, hexane, cyclohexane, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, and cyclonexanone. When the polymer is prepared by a solution-polymerization method, the resulting solut$on may be used as such for hydrogenation.
The hydrogenation reaction is carried out in an autoclave. The reaction temperature is 0 to 300C, preferably 20 to 150C. Temperatures of not more than 150C are preferred in order to ensure proceeding of selective hydrogenation and inhibit undesirable side-reactions. The pressure of hydrogen is not particularly limited. Usually, it is from atmospheric pressure to 300 kg/cm2, preferably 5 to 200 kg/cm2. Pressures higher than 300 kg/cm are not feasible in view of the equipment and operation of the reaction.
The hydrogenated polymer has excellent weather-ability, ozone resistance, heat resistance and coldclimate resistance, and can be used in a wide range of fields.
The following ~xamples illustrate the present invention more specifically.

1 i~37 50 _ ~ _ ~ n acrylonitrile/butadiene copolymer was hydrogenated using a catalyst having supported on an active carbon carrier Pd, Pd/Ma, Pd/Ca, Pd/Sc, Pd/Ti or Pd/V. In the two-component systems, the atomic ratio of the respective metal to Pd was 1:1. In any of the catalysts, the amount of Pd was 1,~ by weight based on the carrier.
Pre~aration of the catalyst Activated carbon was dipped in an aqueous solution of each of PdC12, PdC12/NaC1, PdC12/CaC12, PdC12/ScC13, PdC12/TiC14, and PdC12/VC14 to impregnate the aqueous solution fully in the activated carbon. The impregnated carbon carrier was subjected to reduction with formaldeh~de-sodium hydroxide to prepare a carrier-supported catalyst.
Procedure of the hydro~enation A 100 ml autoclave was charged with a solution of 3 g of an acrylonitrile/butadiene copolymer (the amount of bonded acrylonitrile 41.1~ by weight; MLl+4, 100C=53; abbreviated NBR) in 17 g of acetone and 0.075 g of the supported catalyst (corresponding to 2.5 parts by weight per 100 parts by weight of the polymer).
The inside of the autoclave was purged with nitrogen, and pressurized with hydrogen to 50 kg/cm2. The polymer was thus hydrogenated at 50C for 4 hours.
Separately the same autoclave was charged with a solution of 3 g of polybutadiene (cis-1,4-content 98~; MLl+4, 100C-409 abbreviated BR) in 27 g of cyclohexane 1 ~6:~50 and the same amount of the same supported catalyst as above, The inside of the autoclave was purged with nitrogen, and pressurized with hydrogen to 50 kg/cm2.
Thus, the polymer was hydrogenated at 90C for 4 hours.
The results are shown in Table 1. Infrared absorption spectrcscopy showed no reduction of the nitrile group, Table 1 _ Run Polymer Catalyst Degree o ~ _............... hydroge-Type Amount in part nation by weight per (~)*
100 parts by weight of the . polymer Comparlson ~R Pd 2.5 68.1 .
.~ r~R Pd-Na 2.5 88.5 NBR Pd-Ca 2.5 95.3 Invention ~R Pd-Sc 2.5 81.7 NBR Pd-Ti 2.5 94.7 NBR Pd-V 2.5 92.6 Comparison . BR Pd 2.5 52.4 . , BR Pd-Ca 2.5 73.3 Invention BR Pd-Ti 2.5 72.9 . - ..
* Measured by the iodine value method.
Example 2 Catalysts were prepared in the same way as in Example 1 except that Zr was used as a metal to be deposited together with Pd. ZrC14 was used as a source 1 1637S~

of Zr, The atomic ratio of Zr to Pd was adjusted to 0.1, 0.5, 1, 2 and 10, respectively. Using each of the supported catalysts, the same ~R as used in ~xample 1 was hydrogenated under the same conditions as in ~xample 1. The amount of Pd supported in these catalysts was 1~ by weight based on the activated carbon. In all runs, reduction of the nitrile group was not noted.
Table 2 Run Zr-Pd Amount of the Degree of atomic ratio catalyst (parts by hydrogenation weight per 100 (o~)*
parts by weight of the polymer) son Pd alone 2.5 67.7 _ .
0.1 0.63 97.8 0.5 0.63 96.5 tion 1 1.25 94.5
2 2.5 83.0 2.5 75.4 * Measur~d by the iodine method.
xample 3 The same BR as used in Example 1, a styrene!
butadiene random copolymer (the amount of bonded styrene 23.5~ by weight; MI,1+4, 100C=50; abbreviated SBR), and polyisoprene (cis-1,4 content 97/,; MLl+4, 100C=80;
abbreviated IR) were each dissolved in cyclohexane in a concentration o~ 10~ by weight. ~ach of these polymers in solution was hydrogenated under the same conditions as ~ ~6375~
g _ in the hydrogenation of BF' in Example 1 using the supported catalyst prepared in Example 2 (Zr/Pd atomic ratio=0.5; 1~ by weight of Pd deposited on activated carbon). The amount of the catalyst was 2.5 parts by weight per 100 parts by weight of the polymer.
The results are shown in Table 3. In the SBR
run, hydrogenation of the benzene ring was not noted.
Table 3 _ Run Polymer Catalyst Y (g~) ComparisonBR Pd 52.4 Invention Pd-Zr 78.3 _ ComparisonSBR Pd 70.3 , Invention Pd-Zr 85.7 .
ComparisonIR Pd 39.2 Invention Pd-Zr 52.9 xample 4 An acrylonitrile/butadiene copolymer was hydrogenated using a catalyst having supported on an activated carbon carrier Pd alone, and both Pd and B, Al, Ga, Ge, Sb, M0 or ~J. In the two-component systems, the atomic ratio of the respective metal to Pd was 1:1.
The amount of Pd deposited on the carrier was 1~ in any of these catalysts.
Preparation of the catalyst Activated carbon was dipped in an aqueous 1 ~637 5~

solution of the chlorides of these metals to impregnate them fully in the activated carbon. Reduction with formaldehyde-sodium hydroxide afforded a carrier-supported catalyst.
Procedure of the hydro~enation A 100 ml autoclave was charged with a solution of 3 g of an acrylonitrile-butadiene random copolymer (the amount of bonded acrylonitrile 41.1~ by weight;
MLl+4, 100C=53; abbreviated NBR) in 17 g of acetone and 0.075 g of the supported catalyst (corresponding to 2.5 parts by weight per 100 parts by weight of the polymer).
m e inside of the autoclave was purged with nitrogen, and then pressurized with hydrogen to 50 kg/cm2. Thus, the polymer was hydrogenated at 50C for 4 hours.
The results are shown in Tàble 4. In all runs, reduction of the nitrile group was not noted.
Tab -............... Catalyst jDegree of h~drogenation Comparison 67.6 _ Pd-B 90.4 Pd-~l 92.2 Pd-Ga 76.3 Invention Pd-Ge 93.9 Pd-Sb 94.3 Pd-Mo 91.3 Pd-W 89.7 ~163750 Example 5 In the same way as in ~xample 4, a catalyst having supported on an activated carbon Pd alone or Pd and Al (atomic ratio 1:1) was prepared.
~ 100 ml autoclave was charged with a solution of 3 g of polybutadiene (cis-1,4-content 98~; MLl+4, 100C=40) in 27 g of cyclohexane and each of the catalyst prepared. The inside of the autoclave was purged with nitrogen, and pressurized to 50 kg/cm2 with hydrogen.
0 ~lUS, the polymer was hydrogenated at 90C for 4 hours.
The amount of the catalyst was 3 parts by weight per 100 parts by weight of the polymer The results are shown in Table 5.
Table 5 RunCatalyst Degree of .
hydrogenatlon ComparisonPd 60.3 . l Invention Pd-Al 80.2

Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process which comprises catalytically hydrogenating the carbon-carbon double bonds of a conjugated diene polymer, the improvement which comprises using a catalyst composed of a porous powdery or granular carrier and supported thereon 0.001 to 30% by weight Pd based on the weight of the carrier, and at least one metal selected from the group consisting of the metals of Groups Ia, IIa, IIIa, IIIb, IVa, Va and VIa of the periodic table, Ge and Sb.
2. The process of claim 1 wherein the carrier is silica, silicaalumina, alumina, diatomaceous earth, activated carbon or carbon black.
3. m e process of claim 1 wherein the atomic ratio of said at least one metal to Pd is in the range of from 0.001 to 50.
4. The process of claim 1 wherein the amount of the catalyst is
5 to 2000 ppm calculated as Pd based on the weight of the polymer.
CA000366233A 1979-12-06 1980-12-05 Process for hydrogenation of conjugated diene polymers Expired CA1163750A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP158,576/79 1979-12-06
JP15857579A JPS5681305A (en) 1979-12-06 1979-12-06 Hydrogenation of conjugated diene type polymer
JP15857679A JPS5681306A (en) 1979-12-06 1979-12-06 Hydrogenation of conjugated diene type polymer
JP158,575/79 1979-12-06

Publications (1)

Publication Number Publication Date
CA1163750A true CA1163750A (en) 1984-03-13

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CA (1) CA1163750A (en)
DE (1) DE3046008C2 (en)

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DE3046008A1 (en) 1981-09-03
DE3046008C2 (en) 1990-10-04
US4337329A (en) 1982-06-29

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