CN103073683A - Method for synthesizing hydrogenated butadiene-acrylonitrile rubber by nano-Pd/C catalyst - Google Patents
Method for synthesizing hydrogenated butadiene-acrylonitrile rubber by nano-Pd/C catalyst Download PDFInfo
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- CN103073683A CN103073683A CN2013100046195A CN201310004619A CN103073683A CN 103073683 A CN103073683 A CN 103073683A CN 2013100046195 A CN2013100046195 A CN 2013100046195A CN 201310004619 A CN201310004619 A CN 201310004619A CN 103073683 A CN103073683 A CN 103073683A
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Abstract
The invention provides a method for synthesizing hydrogenated butadiene-acrylonitrile rubber (HNBR) by a nano-Pd/C catalyst. According to the invention, NBR (nitrile-butadiene rubber) is taken as a raw material, Pd/C (dihydroxy polyether/carbon) is taken as the catalyst, a solvent is added, and the HNBR is synthesized by performing catalytic hydrogenation in a high-pressure reaction kettle. According to the invention, the 3 wt% of Pd/C is adopted as the catalyst, and in the reaction, hydrogenation is performed for C and C joined by a double bond in orientation selection while being not performed for C and N joined by a triple bond, so that the problems of high cost, rigorous reaction conditions, poor purity, low yield, incomplete conversion and the like for synthesis of HNBR are radically solved; and the method is environment-friendly and efficient, the conversion rate is nearly 100%, and the hydrogenation rate reaches 99.5%.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to the method for the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer.
Background technology
Hydrogenated nitrile-butadiene rubber (HNBR) is a kind of hi-tech, the novel elastomer of high added value, the butadiene unit on paracril (NBR) segment to be carried out selectable Hydrogenation get, its irreplaceable high-performance, be widely used in aerospace, the oil field, the fields such as automobile, such as the sealing member of using as space flight and aviation, cushioning material, the oil sealing of automobile and transmission belt, the system component of fuel oil, the maintenance case of drilling well and the piston that mud is used, the rubber roll of printing and weaving usefulness etc., the traditional field of NBR has been broken through in its utilization field, so that chlorosulfonated polyethylene, the specialty elastomers such as chlorinatedpolyethylene also have certain impact.Mainly from Petrochina Lanzhou Petrochemical Company and external import, imported product is mainly from the auspicious father-in-law of Japan in the supply of domestic HNBR.Along with China's automobile component standard is more and more higher, adopt V-type transmission belt, the tooth-like belt of traditional material C R rubber manufacturing can not satisfy material powerful high, modulus is large, the requirement of Heat stability is good etc., the demand of these special dimensions will further strengthen the demand to hydrogenated nitrile-butadiene rubber.The demand that expects the year two thousand twenty HNBR has raising by a larger margin more at present.
About the main synthetic method of HNBR has NBR latex hydrogenation method, NBR solution hydrogenation method and Bing Xi Jing – ethylene copolymer method.When wherein the third alkene nitrile – ethylene copolymer legal system is for HNBR, very large (the γ AN=0. 04 of the speed of reaction difference of vinyl cyanide and vinyl monomer in the copolyreaction; γ E=0. 8), cause the component control ratio difficult owing to differ greatly, and the side chain in the polymerisate and gel quality affects mark height, product strength is low, and poor processability still is in the lab scale conceptual phase at present.NBR latex hydrogenation method refers to catalyzer and additive are directly joined preparation HNBR method in the latex of NBR, and that has reported at present has hydrazine hydrate hydrogenated nbr emulsion method and a water-soluble Wilkinson catalyst emulsion hydrogenation method.NBR solution hydrogenation method is the main production method that at present industrialization is both at home and abroad adopted, and its process is at first pulverized NBR, is dissolved in suitable solvent, and in high temperature, high-pressure reactor, wherein catalyzer is the key of synthetic HNBR.Wherein, NBR solution hydrogenation method is the most efficient, environmental protection, succinct method, mainly both at home and abroad come synthesizing hydrogenated paracril with rhodium base catalyst and homogeneous catalysis, but at the bottom of can not fundamentally solving synthesizing hydrogenated paracril cost height, severe reaction conditions, purity difference, yield, the shortcoming such as conversion is incomplete.
Summary of the invention
The method that the purpose of this invention is to provide the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer.This inventive method reaction orientation selective hydrogenation C=C, and to C ≡ N hydrogenation not, overcome synthesizing hydrogenated paracril cost height, severe reaction conditions, purity difference, yield at the bottom of, transform the problems such as incomplete; And have the characteristics such as technique is succinct, efficient, environmental protection.
In order to reach above purpose, Technical Design of the present invention is as follows:
The method of the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer is characterized in that, take NBR as raw material, Pd/C is catalyzer, adds solvent, the synthetic HNBR of shortening in autoclave.
The method of the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer is characterized in that the charge capacity of Pd is 1～10wt% in the Pd/C catalyzer, preferred 2～5wt%.
The method of the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer is characterized in that the mass ratio of NBR and Pd/C catalyzer is 1: 0.001～1.
The method of the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer is characterized in that solvent can be one or both in Virahol, benzene,toluene,xylene, hexanaphthene, the tetrahydrofuran (THF), the mass ratio of NBR and solvent 1: 5～100.
The method of the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer is characterized in that reaction pressure is 2～8MPa in autoclave, and temperature of reaction is 30～150 ℃, and the reaction times is 3～10h.
Reaction equation is as follows:
Beneficial effect of the present invention:
1, the present invention uses the 3wt% Pd/C catalyzer of independent development, easily separated in synthesizing hydrogenated paracril process, reclaim, regeneration.
2, the method for the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer of the present invention, reaction conditions are relatively gentle, and reaction solvent is reusable, environment-friendly high-efficiency, and the hydrogenation ratio of HNBR reaches 99.5%.
Description of drawings
Fig. 1 hydrogenated nitrile-butadiene rubber
13C NMR spectrogram;
Fig. 2 hydrogenated nitrile-butadiene rubber
1H NMR spectrogram;
The Infrared Characterization figure of Fig. 3 hydrogenated nitrile-butadiene rubber sample.
Embodiment
For advance and the innovative point of illustrating the technology of the present invention, make the technology of the present invention characteristics be more readily apparent from understanding, the spy is further described in conjunction with specific examples.
Adopt nucleus magnetic resonance and infrared spectra that hydrogenated nitrile-butadiene rubber is detected in following examples.Wherein Fig. 1, Fig. 2 and Fig. 3 are the detected result figure of embodiment 5.
The catalyzer of the Pd/C catalyzer that the present invention adopts for making according to the Chinese patent of publication number CN 101966455 B " a kind of method by adhering to depositing technology and prepare the highly selective palladium carbon catalyst ", the preparation method is as follows:
(1), the modification of activated carbon capillary internal surface is processed
At normal temperatures, be 1: 5～30 with the mass ratio of gac and deionized water, be drawn into together in the reactor, under agitation drip modifier with 60～120mL/min, stir balance 1～12h, wherein:
Adsorption temp is 15～35 ℃, and stirring velocity is 50～200r/min;
Above-mentioned coating materials is that one or more components in hydrazine, Vanillin, Trisodium Citrate, aldose, potassium acetate, the oxyacetic acid are in the arbitrary volume ratio solution formulated with deionized water at normal temperatures, concentration is 0.01～5mol/L, and add-on is 1: 0.01～15 according to the mass ratio of gac and modifier;
(2), the preparation of palladium presoma
It is some to take by weighing the calculated amount Palladous chloride, adds the concentrated hydrochloric acid dissolve complete of 0.5～5 times of volume, adds deionized water and is diluted to 10～30g/L, and add protective material in palladium liquid, under agitation, regulates pH to 1～5, wherein:
Above-mentioned Palladous chloride solubilizing reaction equation is:
PdCl
2?+?2HCl?=?H
2PdCl
4
Above-mentioned protective material is that one or more components of polyvinyl alcohol, tetraethylene-glycol, Tween-20, polyvinylpyrrolidone, Brij-35, ethylene glycol, xitix are formulated, and protectant consumption is 0.1～5% of reaction system massfraction;
The solvent of above-mentioned adjusting pH is Na
2CO
3, NaOH or NaHCO
3In one or both, the massfraction of solution is 5～10%;
(3), the palladium presoma adheres to-precipitates
The palladium presoma of preparation in the step (two) is added in the step (), adding speed is 50～200mL/min, stirring velocity is 50～200r/min, adhere to 15～25 ℃ of temperature, adhere to starting time 1～24h, adhere to and add calculated amount urea after balance finishes, still temperature rise to 50～90 ℃ even hydrolytic precipitation 1～3 h, wherein:
Urea calculates consumption to precipitate palladium ion afterreaction system pH to 6～9 fully;
(4), injection reduction
The reductive agent injection of in advance preparation is added in the step (three), wherein:
Reductive agent is the formulated mixture of one or more components of formaldehyde, sodium acetate, Trisodium Citrate, hydrazine hydrate, sodium borohydride, and reductive agent pH is 4～11, and concentration is 0.05～2mol/L, and reductive agent adds 0.5～50 milliliter consumption calculating by 1 gram palladium;
The mode that injection port is lower than liquid level adds reductive agent, and reduction temperature is 40～60 ℃;
(5), ageing, filtration, washing and drying
Be 0.5～10% palladium carbon catalyst of high activity with the material ageing in the step (four), filtration, washing and the dry charge capacity that makes palladium, wherein:
The material Aging Temperature is 15～35 ℃, time 1～10 h, and material was 2～6 with 0.05～1.5mol/L hydrochloric acid or acetic acid accent pH after ageing finished, and used the deionized water filtration washing extremely without Cl
–Till;
Filter cake enters the dehydration of removal moisture drying room, and the drying shed dehydration removes 15～35 ℃ of wet temps, dehumidifier model C F10K, and moisture removal 5～10Kg/h, removal moisture drying room humidity transfers to 40～55% dehydrations, 1～3 h.
Accurately take by weighing 25 g NBR, 2.5 g by the standby 3wt% Pd/C catalyzer of CN 101966455 B patent systems, one or both solvents in 175g Virahol, benzene,toluene,xylene, hexanaphthene, the tetrahydrofuran (THF), join in the 0.5L autoclave, extract first the air in the reactor, repeatedly replace for several times with hydrogen, be heated with stirring to 60 ℃, and fill hydrogen and react 5 h to 4MPa, after having reacted, filtration, washing, evaporating solvent, sample uses 1H NMR spectrum analysis, and the hydrogenation ratio of HNBR reaches 97.8%.
Accurately take by weighing 25 g NBR, 2.5 g by the standby 3wt% Pd/C catalyzer of CN 101966455 B patent systems, one or both solvents in 175g Virahol, benzene,toluene,xylene, hexanaphthene, the tetrahydrofuran (THF), join in the 0.5L autoclave, extract first the air in the reactor, repeatedly replace for several times with hydrogen, be heated with stirring to 60 ℃, and fill hydrogen and react 6 h to 4MPa, after having reacted, filtration, washing, evaporating solvent, sample uses 1H NMR spectrum analysis, and the hydrogenation ratio of HNBR reaches 98.5%.
Embodiment 3
Accurately take by weighing 25 g NBR, 2.5 g by the standby 3wt% Pd/C catalyzer of CN 101966455 B patent systems, one or both solvents in 175g Virahol, benzene,toluene,xylene, hexanaphthene, the tetrahydrofuran (THF), join in the 0.5L autoclave, extract first the air in the reactor, repeatedly replace for several times with hydrogen, be heated with stirring to 70 ℃, and fill hydrogen and react 5 h to 4MPa, after having reacted, filtration, washing, evaporating solvent, sample uses 1H NMR spectrum analysis, and the hydrogenation ratio of HNBR reaches 98.8%.
Accurately take by weighing 25 g NBR, 2.5 g by the standby 3wt% Pd/C catalyzer of CN 101966455 B patent systems, one or both solvents in 225g Virahol, benzene,toluene,xylene, hexanaphthene, the tetrahydrofuran (THF), join in the 0.5L autoclave, extract first the air in the reactor, repeatedly replace for several times with hydrogen, be heated with stirring to 60 ℃, and fill hydrogen and react 5 h to 4MPa, after having reacted, filtration, washing, evaporating solvent, sample uses 1H NMR spectrum analysis, and the hydrogenation ratio of HNBR reaches 99.1%.
Accurately take by weighing 25 g NBR, 2.5 g by the standby 3wt% Pd/C catalyzer of CN 101966455 B patent systems, one or both solvents in 225g Virahol, benzene,toluene,xylene, hexanaphthene, the tetrahydrofuran (THF), join in the 0.5L autoclave, extract first the air in the reactor, repeatedly replace for several times with hydrogen, be heated with stirring to 70 ℃, and fill hydrogen and react 6 h to 4MPa, after having reacted, filtration, washing, evaporating solvent, sample uses 1H NMR spectrum analysis, and the hydrogenation ratio of HNBR reaches 99.8%.
Claims (5)
1. the method for the synthesizing hydrogenated paracril of nanometer Pd/C catalyzer, it is characterized in that: take paracril NBR as raw material, Pd/C is catalyzer, adds solvent, the synthesizing hydrogenated paracril HNBR of shortening in autoclave.
2. the method for the synthesizing hydrogenated paracril of described a kind of nanometer Pd/C catalyzer according to claim 1, it is characterized in that: the charge capacity of Pd is 1～10wt% in the Pd/C catalyzer, preferred 2～5wt%.
3. the method for the synthesizing hydrogenated paracril of described a kind of nanometer Pd/C catalyzer according to claim 1, it is characterized in that: solvent can be one or both in Virahol, benzene,toluene,xylene, hexanaphthene, the tetrahydrofuran (THF), the mass ratio of NBR and solvent 1: 5～100.
4. the method for the synthesizing hydrogenated paracril of a kind of nanometer Pd/C catalyzer according to claim 1, it is characterized in that: reaction pressure is 2～8MPa in autoclave, and temperature of reaction is 30～150 ℃, and the reaction times is 3～10h.
5. according to claim 1 or the method for the synthesizing hydrogenated paracril of 2 described a kind of nanometer Pd/C catalyzer, it is characterized in that: the mass ratio of NBR and Pd/C catalyzer is 1: 0.001～1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722145A (en) * | 2016-08-10 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenated nitrile-butadiene rubber |
| CN110449151A (en) * | 2019-09-03 | 2019-11-15 | 福州大学 | A kind of loading type Pd/ZrO2The preparation method and applications of catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954278A (en) * | 2010-09-15 | 2011-01-26 | 郴州高鑫铂业有限公司 | Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof |
| CN101966457A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-activity carbonyl hydrogenation ruthenium-carbon catalyst |
| CN101966455A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process |
| CN101987874A (en) * | 2010-09-15 | 2011-03-23 | 郴州高鑫铂业有限公司 | Method for synthesizing hydrogenated nitrile-butadiene rubber by using nanometer Pd/C catalyst |
-
2013
- 2013-02-26 CN CN2013100046195A patent/CN103073683A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954278A (en) * | 2010-09-15 | 2011-01-26 | 郴州高鑫铂业有限公司 | Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof |
| CN101987874A (en) * | 2010-09-15 | 2011-03-23 | 郴州高鑫铂业有限公司 | Method for synthesizing hydrogenated nitrile-butadiene rubber by using nanometer Pd/C catalyst |
| CN101966457A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-activity carbonyl hydrogenation ruthenium-carbon catalyst |
| CN101966455A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722145A (en) * | 2016-08-10 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenated nitrile-butadiene rubber |
| CN107722145B (en) * | 2016-08-10 | 2020-07-24 | 中国石油化工股份有限公司 | Preparation method of hydrogenated nitrile rubber |
| CN110449151A (en) * | 2019-09-03 | 2019-11-15 | 福州大学 | A kind of loading type Pd/ZrO2The preparation method and applications of catalyst |
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Application publication date: 20130501 |