CN104338558B - Hydridization dendrimers supported bi-metallic nano-particle catalyst and preparation method and application - Google Patents
Hydridization dendrimers supported bi-metallic nano-particle catalyst and preparation method and application Download PDFInfo
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Abstract
The invention discloses hydridization dendrimers supported bi-metallic nano-particle catalyst and preparation method and application.The catalyst is the compound of ruthenium and rhodium as metal nanoparticle with hydridization PPI as carrier.The preparation method is first modified to the peripheral primary amine groups of whole algebraically PPI with 15 yuan of triolefin azacyclo-s, and synthesis difference algebraically PPI surfaces carry the novel hybride dendrimers of the big ring of 15 yuan of alkatrienes.Then using the method with the common complexation-reduction of two metal ion species, with GnPPI-M, (n=2,3,4,5) prepare the different Ru/Rh bimetallic DTNs of Ru/Rh ratios as carrier, and as catalyst, carry out catalytic hydrogenation to nitrile rubber.Catalyst prepared by the present invention not only has excellent catalysis activity and selectivity, and recyclable and recycling.
Description
Technical field
The present invention relates to catalyst prepared by a kind of hydrogenated nitrile-butadiene rubber, more particularly to a kind of catalytic hydrogenation butyronitrile rubber
Glue hydridization dendrimers supported bi-metallic nano-particle catalyst and preparation method thereof.
Background technology
Hydrogenated nitrile-butadiene rubber has good oil resistance (good to fuel oil, lubricating oil, fragrant series solvent resistance)；And
And due to its HI SA highly saturated structure so as to have a good heat resistance, excellent resistance to chemical corrosion (to freon, acid,
Alkali with good resistance), excellent ozone resistance, higher incompressible permanent deformation performance；While hydrogenated butyronitrile
Rubber also has high intensity, high tear energy, the features such as anti-wear performance is excellent, is one of supereminent rubber of combination property.
Hydrogenated nitrile-butadiene rubber (HNBR) is a kind of HI SA highly saturated elastomer by obtained from nitrile rubber carries out special hydrotreating, can
With obtained by the butadiene unit by being catalyzed on nitrile rubber (NBR) segment.HNBR not only has the elasticity of NBR, but also
With more excellent thermal oxidation resistance degradation property, and significantly improve the tensile strength of NBR, percentage elongation, wear resistance and hard
The mechanical performances such as degree.As HNBR has excellent process based prediction model, therefore it is widely used in automobile, oil well oil field and boat
The important field such as empty space flight.
Existing industrialized production hydrogenated nbr method has latex hydrogenation method and solution hydrogenation method.Latex hydrogenation method mainly has
Catalytic hydrogenation method and hydrogenation parent method.Catalytic hydrogenation method need to use noble metal, such as Rh, Ru and Pd, the method have hydrogenation degree it is high,
The advantages of selectivity is good and simplifies operation, but there is also the shortcoming that catalyst is difficult to reclaim；Hydrogenation parent rule is without the need for expensive
Metal, the hydro genation system for using are hydrazine hydrate/hydrogen peroxide/boric acid, and the method is simple to operate, but easily in the double bond not being hydrogenated
On crosslink side reaction, so as to cause machine-shaping difficult.Solution hydrogenation method is the main technology road of current NBR hydrogenations
Line, hydrogenation catalyst used therein have heterogeneous and homogeneous dividing.Heterogeneous catalysis has hydrogenation rear catalyst with hydrogenated products
Solution is susceptible to separate and the simple advantage of post processing, but there is also that catalysis activity is relatively low, catalyst amount is big
The harsh shortcoming with hydrogenation conditions, such catalyst are predominantly carried on above carbon black, silicon dioxide and barium sulfate etc.
Metal Pd；Homogeneous catalyst has the advantages that hydrogenation activity is high and consumption is few, has the disadvantage the abjection of catalyst in product and reclaims
More difficult, such catalyst mainly includes Wilkinson catalyst, such as three (triphenylphosphine) radium chloride.
Therefore exist that catalyst is difficult to reclaim, HNBR gel fractions are higher, be catalyzed for current hydrogenated nitrile-butadiene rubber method
The problems such as activity is relatively low, prepares the new of high selectivity, high catalytic activity, high performance-price ratio, easily separated recovery and recycling
Hydrogenation catalyst is the key issue for being badly in need of solving in terms of NBR hydrogenates production technology research.
The content of the invention
Present invention aims to prior art problem, has invented a kind of high selectivity, high catalytic activity, high sexual valence
Than, easily separated recovery and the hydridization dendrimers supported bi-metallic nano-particle catalyst and preparation method thereof for recycling
Another object of the present invention is to provide the hydridization dendrimers supported bi-metallic nano-particle catalyst urging
Change prepares the application of hydrogenated nitrile-butadiene rubber.
The purpose of the present invention is achieved through the following technical solutions：
1st, hydridization dendrimers supported bi-metallic nano-particle catalyst, it is characterised in that：The catalyst is with 15 yuan
The modified PPI (PPI) of triolefin azacyclo- (MAC) is carrier, the change of ruthenium (Ru) and rhodium (Rh) as metal nanoparticle
Compound, its general molecular formula is：
Wherein n1=2,3,4,5；n2=8,16,32,64；The integer of x=30～70.
The preparation method of the hydridization dendrimers supported bi-metallic nano-particle catalyst, comprises the steps：
1) 15 yuan of triolefin azacyclo-s (MAC) of bromopropyl and PPI (Gn will be contained1PPI, n1=2,3,4, rubbing 5)
You are than pressing 7:1～80:During 1 adds reactor, acetonitrile and Anhydrous potassium carbonate are subsequently adding；It is warming up to 100 DEG C～110 DEG C reactions
12h～26h；The PPI is the 2nd, 3,4, and 5 generation dendroid PPIs；
2) reaction is finished, and is removed by filtration pressed powder, is cleaned pressed powder with tetrahydrofuran during filtration, obtains filtrate, will
Filtrate decompression distills to obtain oily liquids, oily liquids is chromatographed with silicagel column, and it is 3 that eluent is volume ratio:7～5:7 acetic acid
Ethyl ester and petroleum ether；
3) vacuum distillation removes eluent, obtains product Gn after being dried1PPI-M；n1=2,3,4,5；
4) in N2Under protection, by Gn1PPI-M is added in reaction bulb；At room temperature, add tetrahydrofuran, rhodium chloride and
Solution of ruthenium trichloride stirring reaction 24h-26h；It is subsequently adding NaBH4Solution, continues stirring 1h-2h at room temperature；Described three
The mol ratio of radium chloride and ruthenium trichloride is 30:70～70:30；
5) to step 4) pH of Deca hydrochloric acid solution to reaction system is 7～8 in gained reactant, you can different algebraically
The tree-shaped PPI of hydridization loads ruthenium rhodium bimetal nano particles catalyst (Gn1-M(Ru100-xRhx)DTNs)；
Described is 1,11- bis- [2,4,6- tri isopropyl benzenesulfonyl bases] -6- [4- containing 15 yuan of triolefin azacyclo-s of bromopropyl
(3- bromoethyls) benzenesulfonyl] three azo-cycle pentadecane -3,8,13- triolefins of -1,6,11-；Bis- [2,4,6- triisopropylbenzenes of 1,11-
Sulfonyl] three azo-cycle pentadecane -3,8,13- triolefins of -6- [4- (3- bromopropyls) benzenesulfonyl] -1,6,11-；1,11- bis- [2,4,
6- tri isopropyl benzenesulfonyl bases] three azo-cycle pentadecane -3,8,13- triolefins of -6- [4- (3- brombutyls) benzenesulfonyl] -1,6,11-
In one kind.
Further to realize the object of the invention, it is preferable that the consumption of the acetonitrile and Anhydrous potassium carbonate is respectively brominated third
30～50 times and 0.5～1.0 times of 15 yuan of triolefin azepine ring qualities of base.
The consumption of the tetrahydrofuran is containing 15 yuan of bromopropyl, 15～35 times of triolefin azacyclo- quality.
The NaBH4Consumption be 20～25 times of rhodium chloride and ruthenium trichloride molal quantity.
The Gn1PPI-M accounts for the 5～30% of rhodium chloride and ruthenium trichloride total moles fraction.
The PPI Gn1The molecular weight of PPI is 700～7200.
The application of described hydridization dendrimers supported bi-metallic nano-particle catalyst：First NBR is dissolved in chlorobenzene, adds
NBR glues are made in reactor, under room temperature and 750r/min～900r/min stirrings, N is used2Displacement, then use high-purity H2Put
Change；100 DEG C～110 DEG C are warming up to, by Gn1‐M(Ru100‐xRhx) DTNs catalyst and triphenylphosphine H2It is depressed in reactor, and
In H2Pressure be 5.5～6.0MPa, temperature be 100 DEG C～110 DEG C and speed of agitator for 700r/min～900r/min condition
Lower reaction 6h～8h；After reaction terminates, glue is taken out in cooling, is flocculated with methanol, with centrifuge 0.5h～1h, by lower floor
Floccule vacuum drying obtains hydrogenated nitrile-butadiene rubber (HNBR), and supernatant decompression rotary distillation is removed methanol and chlorobenzene, and
The Gn reclaimed in alembic is dissolved with chlorobenzene1‐M(Ru100‐xRhx) DTNs catalyst；
The quality of the NBR is Gn1‐M(Ru100‐xRhx) 280～300 times of DTNs catalyst；
The triphenylphosphine consumption is Gn1‐M(Ru100‐xRhx) DTNs catalyst qualities 8-12%.
Preferably, the Gn of recovery1‐M(Ru100‐xRhx) DTNs catalyst carries out the catalytic hydrogenation of NBR again.
PPI dendrimers have the structure and composition of regular, highly branched, high-sequential, and it is right to pass through
Peripheral functional group modification is by the metal nanoparticle with catalysis activity stable on modified dendrimers surface.Therefore with poly-
The Ru/Rh bimetal nano particles catalyst (Ru/Rh DTNs) of propyleneimine dendrimers load mainly has two features:
A, dissolubility mainly by dendrimers surface chemical structure controlling, so as to the recovery and repetition that are conducive to Ru/Rh DTNs make
With；B, due to by stable Ru/Rh be located at dendrimers surface, it is easier to contact with substrate, and be passivated area it is little, catalysis work
Property it is high；C, as the electronegativity (2.28) of rhodium is bigger than the electronegativity (2.20) of ruthenium, the electron interaction of two kinds of metallic atoms makes
The cloud density for obtaining Ru is reduced, and produces electron deficiency effect.Double bond in NBR is more easy to mutually tie with the electron deficiency surface of catalyst
Close, therefore Ru/Rh DTNs catalyst has higher catalysis activity than corresponding physical mixed monometallic DTNs catalyst.
The present invention compared with prior art, has the advantage that：
1st, Gn prepared by the present invention1‐M(Ru100‐xRhx) DTNs catalyst to the catalysis of NBR with excellent activity, when urging
When agent consumption is 0.35wt%, the hydrogenation degree up to more than 99% of NBR can be made.
2nd, Gn prepared by the present invention1‐M(Ru100‐xRhx) hydrogenation of the DTNs catalyst to NBR has high selectivity, hydrogenated
There is in journey excellent catalytic hydrogenation to carbon-carbon double bond, and then will not catalytic hydrogenation to itrile group.
3rd, Gn prepared by the present invention1‐M(Ru100‐xRhx) DTNs catalyst have the advantages that it is recyclable and recycle.When
DTNs catalyst is recycled after 3 times, can still make the hydrogenation degree of HNBR reach more than 90%.
Description of the drawings
Fig. 1 is G in each embodiment and Application ExamplenThe infrared spectrum of PPI-M (n=2,3,4,5)；
Fig. 2 is G in each embodiment and Application ExamplenThe nucleus magnetic hydrogen spectrum figure of PPI-M (n=2,3,4,5)；
Fig. 3-1 is Gn-M, Ru3+、Rh3+Ultraviolet-visible spectrogram；
Fig. 3-2 is Gn-M (Ru100‐xRhx) ultraviolet-visible spectrogram (n=2,3,4,5)；
Fig. 4 is NBR and HNBR in embodiment 333Infrared spectrum；
Fig. 5 is the G for preparing in embodiment 34-M(Ru30Rh70) impact of the cycle-index to its catalysis activity.
Specific embodiment
For a better understanding of the present invention, the present invention is further illustrated with reference to the accompanying drawings and examples, but this
The embodiment not limited to this of invention.
1 second filial generation hydridization dendrimers supported bi-metallic nanoparticle of embodiment and its catalytic hydrogenation nitrile rubber
1st, the modified second filial generation PPI dendrimers (G in 15 yuan of triolefin nitrogen heterocyclic ring (MAC) surfaces2PPI-M)
Take 2.155g (2.79 × 10‐3mol)G2It is standby that PPI (Dutch SyMO-ChemB.V companies) is dissolved in 10ml acetonitriles.By 0.48g (4.8
×10‐4Mol) 1,11- bis- [2,4,6- tri isopropyl benzenesulfonyl bases] -6- [4- (3- bromopropyls) benzenesulfonyl] three nitrogen of -1,6,11-
Cyclopentadecane -3,8,13- triolefins (MAC), 0.33g (2.4 × 10‐3Mol) Anhydrous potassium carbonate is placed in backflow and air interchanger
Reaction bulb in.Outside air interchanger is connected, N is replaced2Three times.Under stirring at normal temperature, it is implanted sequentially in flask
0.24mlG2PPI/ acetonitrile solutions and 30ml acetonitriles.It is warming up to 107 DEG C of reaction 12h.After the completion of reaction, solid powder is removed by filtration
End, cleans pressed powder three times, obtains filtrate with tetrahydrofuran during filtration.Filtrate decompression is distilled into obtain oily liquids, silicon is used
Plastic column chromatography, eluent are ethyl acetate：Petroleum ether (V:V)=3:7.Product at reduced pressure is distilled off into eluent, is vacuum dried
2h obtains white solid product G2PPI-M (the tree-shaped PPI of second filial generation hydridization).
As shown in Figure 1 knowable to infrared spectrum analysis, G23320cm in PPI-1Place belongs to-NH2Base asymmetrical stretching vibration
With the bimodal basic disappearance of symmetrical stretching vibration, and G21600cm in PPI-M-1Place belongs to the stretching vibration of C=C and absorbs
Peak occurs, 2806cm-1And 1450cm-1Place belongs to the intensity of methylene characteristic peak and is remarkably reinforced, and thus illustrates G2PPI terminations
Bromine atoms on amino and 15 yuan of triolefin nitrogen heterocyclic rings there occurs reaction.Meanwhile, to G2The nucleus magnetic hydrogen spectrum (Fig. 2) of PPI-M enters
Row analysis, δ=3.4ppm belong to Br-CH 2- on proton peak disappear, δ=1.7ppm belongs to-NH 2On proton peak intensity
Significantly reduce, and the division peak for belonging to proton on phenyl ring is occurred in that at chemical shift δ=7.2-7.7ppm, and δ=
- C is belonged at 2.6-2.7ppmH 2-NH-CH 2- on number of hydrogen atoms 32H, illustrate G2It is big containing 15 yuan of triolefin azepines in PPI-M
Ring.Meanwhile, as shown in Table 2 (using the Vario EL III organic element analyzers of Elementar companies product, by product sample preparation
The content of tetra- kinds of elements of C, H, N, S in product is tested after numbering), G2The theoretical value of tetra- kinds of elements of C, H, N, S and measure in PPI-M
Between value relatively, provable G2PPI-M successfully synthesizes and its structure is than more complete.
2、G2PPI-M loads ruthenium rhodium bimetal nano particles (G2-M(Ru70Rh30) DTNs) and catalyst preparation
Take 0.12g G2PPI-M is placed in and is provided with the reaction bulb of air interchanger, connects outside air interchanger, replaces N2
Three times.Under stirring at normal temperature, 50ml tetrahydrofurans are added in bottle, be subsequently adding the tri-chlorination that 0.3ml concentration is 0.1mol/L
Rhodium and 0.7ml concentration are 0.1mol/L solution of ruthenium trichloride.After 24h is stirred at room temperature, 2.0ml concentration is added in reaction bulb
For the NaBH of 1.0mol/L4Solution.After continuing stirring 1h, the HCl solution of 0.2mol/L is slowly added dropwise in bottle to reaction system
PH be 7, you can G2-M(Ru70Rh30)DTNs。
G2-M(Ru70Rh30) DTNs ultra-violet absorption spectrum as shown in figure 3-2.Comparison diagram 3-1 can be seen that G2PPI-M's
Characteristic absorption peak at the 292nm, in complexation, after Ru and Rh metal nanoparticles, shift respectively by the position of characteristic absorption peak
To 296nm and 298nm.Additionally, G2-M(Ru70Rh30) the ultra-violet absorption spectrum curve shape of DTNs is similar to index variation,
This shows G2-M(Ru3+ 70Rh3+ 30) reduction is completely.
3rd, hydrogenated nitrile-butadiene rubber (HNBR1) preparation
3.6gNBR is dissolved in into 150ml chlorobenzenes it is added in reactor and makes NBR glues, closed reaction kettle, connection ventilation dress
Put, under conditions of room temperature and mixing speed are 750r/min, first use N2Displacement three times, then use high-purity H2Displacement three times.It is warming up to
95 DEG C, by 1.26 × 10-3g G2-M(Ru70Rh30) DTNs catalyst, 1.26 × 10-2G triphenylphosphine H2It is depressed in reactor,
In H2Pressure be 5.5MPa, 100 DEG C, react 8h under conditions of 800r/min.Reaction is cooled down after terminating, and is taken out glue, is used methanol
Flocculation, obtains HNBR after floccule vacuum drying 6h1, its hydrogenation degree is as shown in table 1.
From infrared test, 970cm in the infrared spectrum of NBR-1And 917cm-1Place is respectively belonging to 1,4-C=C and 1,
The relative intensity of the characteristic absorption peak of 2-C=C substantially weakens, and HNBR1Infrared spectrum in belong to-(CH2)n-(n>4)
723cm-1Characteristic absorption peak relative intensity increases, and 2236cm-1Place belongs to the characteristic absorption peak of-CN and is not changed in, thus
G can be confirmed2-M(Ru70Rh30) DTNs has excellent catalytic activity and catalytic selectivity.As known from Table 1, HNBR1Hydrogenation degree
It is above HNBR11Hydrogenation degree.This is to be more easy to combine with the electron deficiency surface of catalyst due to the carbon-carbon double bond in NBR.Root
According to the electronegativity principle of Pauling, the electronegativity (2.28) of Rh is bigger than the electronegativity (2.20) of Ru, the electronics phase of Rh and Ru atoms
Interaction causes the cloud density of Ru to reduce, generation electron deficiency effect, therefore G2-M(Ru70Rh30) DTNs have higher catalysis
Activity.The method of testing of hydrogenation degree in table 1：It is measured according to SH/T1762-2008.
Comparative example 1G2-M(Ru70Rh30)DTNs
1、G2-M(Ru70) DTNs and G2-M(Rh30) DTNs preparation
Take 0.12g G2PPI-M is placed in and is provided with the reaction bulb of air interchanger, connects outside air interchanger, replaces N2
Three times.Under stirring at normal temperature, 50ml tetrahydrofurans are added in bottle, be subsequently adding the tri-chlorination that 0.3ml concentration is 0.1mol/L
Rhodium or 0.7ml concentration are 0.1mol/L solution of ruthenium trichloride.After 24h is stirred at room temperature, 2.0ml concentration is added in reaction bulb
For the NaBH of 1.0mol/L4Solution.After continuing stirring 1h, the HCl solution of 0.2mol/L is slowly added dropwise in bottle to reaction system
PH be 7, obtain G2-M(Ru70) DTNs and G2-M(Rh30) DTNs, its physical mixed is obtained into G2-M(Ru70) DTNs and
G2-M(Rh30) DTNs physical mixed catalyst.
2nd, hydrogenated nitrile-butadiene rubber (HNBR11) preparation
3.6gNBR is dissolved in into 150ml chlorobenzenes it is added in reactor and make NBR glues, then closed reaction kettle, connection is changed
Device of air, under conditions of room temperature and mixing speed are 750r/min, first uses N2Displacement three times, then use high-purity H2Displacement three times.Rise
Temperature to 95 DEG C, by 1.26 × 10-3gG2-M(Ru70) and G2-M(Rh30) DTNs physical mixed catalyst, 1.26 × 10-2G triphenyls
Phosphine H2It is depressed in reactor, in H2Pressure be 5.5MPa, 100 DEG C, react 8h under conditions of 800r/min.It is after reaction terminates, cold
But, glue is taken out, is flocculated with methanol, after floccule vacuum drying 6h, obtain hydrogenated products HNBR11, its hydrogenation degree is as shown in table 1.
2 third generation hydridization dendrimers supported bi-metallic nanoparticle of embodiment and its catalytic hydrogenation nitrile rubber
1、G3The synthesis of PPI-M
1.610g (9.54 × 10 is weighed accurately‐4mol)G3It is standby that PPI (Dutch SyMO-ChemB.V companies) is dissolved in 10ml acetonitriles
With.Take 0.80g (8.0 × 10‐4mol)MAC、0.56g(4.1×10‐3Mol) Anhydrous potassium carbonate is placed in backflow and dress of taking a breath
In the reaction bulb put.Outside air interchanger is connected, N is replaced2Three times.Under stirring at normal temperature, it is implanted sequentially in flask
0.56mlG3PPI/ acetonitrile solutions, 30ml acetonitriles.Then 107 DEG C of reaction 18h are warming up to.Reaction is finished, and filters out pressed powder,
Pressed powder three times is cleaned during filtration with tetrahydrofuran, filtrate is obtained.Filtrate decompression distillation filtrate is obtained into oily liquids, silicon is used
Plastic column chromatography, eluent proportioning are ethyl acetate：Petroleum ether (V:V)=5:7.Last vacuum distillation removes eluent, after being dried
Obtain near-white solid product G3PPI-M (the tree-shaped PPI of third generation hydridization).
Analyzed from infrared spectrum (Fig. 1), G33310cm in PPI-1Place belongs to-NH2Base asymmetrical stretching vibration and
The bimodal basic disappearance of symmetrical stretching vibration, and G31600cm in PPI-M-1The stretching vibration absworption peak for belonging to C=C goes out
It is existing, 2790cm-1And 1465cm-1Place belongs to the intensity of methylene characteristic peak and is remarkably reinforced, and thus illustrates G3The amino of PPI terminations
Reaction be there occurs with the bromine atoms on 15 yuan of triolefin nitrogen heterocyclic rings.Meanwhile, to G3The nucleus magnetic hydrogen spectrum (Fig. 2) of PPI-M is carried out point
Analysis, δ=3.4ppm belong to Br-CH 2- on proton peak disappear, δ=1.9ppm belongs to-NH 2On proton peak intensity it is notable
Reduce, and the division peak for belonging to proton on phenyl ring is occurred in that at chemical shift δ=7.2-7.7ppm, and δ=2.6-
- C is belonged at 2.7ppmH 2-NH-CH 2- on number of hydrogen atoms 64H, illustrate in G2PPI-M containing 15 yuan of triolefin nitrogen heterocyclic rings.Together
When, as shown in Table 2, G3In PPI-M between the theoretical value and measured value of tetra- kinds of elements of C, H, N, S relatively, it is therefore provable
G3PPI-M successfully synthesizes and its structure is than more complete.
2、G3-M(Ru50Rh50) DTNs preparation
Take 0.12g G3PPI-M is placed in and is provided with the reaction bulb of air interchanger, connects outside air interchanger, replaces N2
Three times.Under stirring at normal temperature, 50ml tetrahydrofurans are added in bottle, 0.5ml rhodium chlorides and 0.5ml ruthenium trichlorides is subsequently adding
Solution.After 26h is stirred at room temperature, 5ml concentration is added in reaction bulb for the NaBH of 0.5mol/L4Solution.Continue stirring 2h
Afterwards, the pH that the HCl solution to reaction system of 0.2mol/L is slowly added dropwise in bottle is 7, you can obtain G3-M(Ru50Rh50)DTNs。
G3-M(Ru50Rh50) DTNs ultra-violet absorption spectrum as shown in figure 3-2.Comparison diagram 3-1 can be seen that G3PPI-M's
Characteristic absorption peak at the 291nm, in complexation, after Ru and Rh metal nanoparticles, shift respectively by the position of characteristic absorption peak
To 296nm and 298nm.Additionally, G3-M(Ru50Rh50) the ultra-violet absorption spectrum curve shape of DTNs is similar to index variation,
This shows G3-M(Ru3+ 50Rh3+ 50) reduction is completely.
3、HNBR2Preparation
3.6gNBR is dissolved in into 150ml chlorobenzenes it is added in reactor and make NBR glues, then closed reaction kettle, connection is changed
Device of air, under conditions of room temperature and mixing speed are 800r/min, first uses N2Displacement three times, then use high-purity H2Displacement three times.Rise
Temperature to 95 DEG C, by 1.26 × 10‐3gG3‐M(Ru50Rh50) DTNs catalyst, 1.26 × 10‐2G triphenylphosphine H2It is depressed into reactor
In, in H2Pressure be 6.0MPa, 100 DEG C, react 8h under conditions of 800r/min.After reaction terminates, glue is taken out in cooling, uses
Methanol flocculates, and obtains hydrogenated products HNBR after floccule vacuum drying 7h2, its hydrogenation degree is as shown in table 1.
From infrared test, 970cm in the infrared spectrum of NBR-1And 917cm-1Place is respectively belonging to 1,4-C=C and 1,
The relative intensity of the characteristic absorption peak of 2-C=C substantially weakens, and HNBR2Infrared spectrum in belong to-(CH2)n-(n>4)
723cm-1Characteristic absorption peak relative intensity increases, and 2236cm-1Place belongs to the characteristic absorption peak of-CN and is not changed in, thus
G can be confirmed3- M (Ru50Rh50) DTNs has excellent catalytic activity and catalytic selectivity.As known from Table 1, HNBR2Hydrogenation degree
With HNBR in embodiment 11Compare and improve.This is the collaboration electricity as one side is when Rh/Ru increases, between Rh and Ru
Sub- effect increases so that the activity increase of catalyst；On the other hand it is due to G3-M(Ru50Rh50) 15 yuan in DTNs molecules
Triolefin nitrogen heterocyclic ring increases, so catalysis activity point increases, so as to cause catalysis activity to increase.
Comparative example 2
1、G3-M(Ru50) DTNs and G3-M(Rh50) DTNs physical mixed catalyst preparation
Take 0.12g G3PPI-M is placed in and is provided with the reaction bulb of air interchanger, connects outside air interchanger, replaces N2
Three times.Under stirring at normal temperature, 50ml tetrahydrofurans are added in bottle, be subsequently adding the tri-chlorination that 0.5ml concentration is 0.1mol/L
Rhodium (or 0.5ml concentration is 0.1mol/L solution of ruthenium trichloride).After 26h is stirred at room temperature, in reaction bulb add 5.0ml dense
Spend the NaBH for 0.5mol/L4Solution.After continuing stirring 2h, the HCl solution of 0.1mol/L is slowly added dropwise in bottle to reactant
The pH of system is 7, you can obtain G3-M(Ru50) DTNs and G3-M(Rh50)DTNs。
2nd, hydrogenated nitrile-butadiene rubber (HNBR22) preparation
3.6gNBR is dissolved in into 150ml chlorobenzenes it is added in reactor and make NBR glues, then closed reaction kettle, connection is changed
Device of air, under conditions of room temperature and mixing speed are 800r/min, first uses N2Displacement three times, then use high-purity H2Displacement three times.Rise
Temperature to 95 DEG C, by 1.26 × 10-3gG3-M(Ru50) and G3-M(Rh50) DTNs physical mixed catalyst, 1.26 × 10-2G triphenyls
Phosphine H2It is depressed in reactor, in H2Pressure be 6.0MPa, 100 DEG C, react 8h under conditions of 800r/min.It is after reaction terminates, cold
But, glue is taken out, is flocculated with methanol, after floccule vacuum drying 6h, obtain hydrogenated products HNBR22, its hydrogenation degree is as shown in table 1.
3 forth generation hydridization dendrimers supported bi-metallic nanoparticle of embodiment and its catalytic hydrogenation nitrile rubber
1、G4The synthesis of PPI-M
Take 0.654g (1.86 × 10‐4mol)G4It is standby that PPI (Dutch SyMO-ChemB.V companies) is dissolved in 17ml acetonitriles.Will
0.84g(8.4×10‐4mol)MAC、0.62g(4.5×10‐3Mol) Anhydrous potassium carbonate is placed in anti-with air interchanger with backflow
In answering bottle.Outside air interchanger is connected, N is replaced2Three times.Under stirring at normal temperature, 1.92mlG is implanted sequentially in flask4PPI/
Acetonitrile solution, 40ml acetonitriles are warming up to 107 DEG C of reaction 20h.Reaction is finished, and filters out pressed powder, and 30ml tetrahydrochysenes are used during filtration
Furan cleaning pressed powder three times, obtains filtrate.Filtrate decompression distillation filtrate is obtained into oily liquids, silica gel column chromatography is used, is washed
De- liquid proportioning is ethyl acetate：Petroleum ether (V:V)=5:7.Last vacuum distillation removes eluent, and near-white solid is obtained after being dried
Product G4PPI-M (the tree-shaped PPI of forth generation hydridization).
Analyzed from infrared spectrum (Fig. 1), G43290cm in PPI-1Place belongs to-NH2Base asymmetrical stretching vibration and
The bimodal basic disappearance of symmetrical stretching vibration, and G41600cm in PPI-1The stretching vibration absworption peak for belonging to C=C occurs,
2806cm-1And 1450cm-1Place belongs to the intensity of methylene characteristic peak and is remarkably reinforced, and thus illustrates G4The amino of PPI terminations with
The bromine atoms of 15 yuan of triolefin nitrogen heterocyclic rings there occurs reaction.Meanwhile, to G4The nucleus magnetic hydrogen spectrum (Fig. 2) of PPI-M is analyzed, δ
=3.4ppm belongs to Br-CH 2- on proton peak disappear, δ=1.9ppm belongs to-NH 2On proton peak intensity significantly reduce,
And the division peak for belonging to proton on phenyl ring is occurred in that at chemical shift δ=7.2-7.7ppm, and at δ=2.6-2.7ppm
Belong to-CH 2-NH-CH 2- on number of hydrogen atoms 128H, illustrate G4Contain 15 yuan of triolefin nitrogen heterocyclic rings in PPI-M.Meanwhile, by table
2 understand, G4In PPI-M between the theoretical value and measured value of tetra- kinds of elements of C, H, N, S relatively, therefore provable G4PPI-M into
Work(synthesizes and its structure is than more complete.
2、G4-M(Ru30Rh70) DTNs preparation
Take 0.12g G4PPI-M is placed in and is provided with the reaction bulb of air interchanger, connects outside air interchanger, replaces N2
Three times.Under stirring at normal temperature, 50ml tetrahydrofurans are added in bottle, 0.7ml rhodium chlorides and 0.3ml ruthenium trichlorides is subsequently adding
Solution.After 24h is stirred at room temperature, 5.0ml concentration is added in reaction bulb for the NaBH of 0.5mol/L4Solution.Continue stirring
After 2h, the pH that the HCl solution to reaction system of 0.2mol/L is slowly added dropwise in bottle is 7, you can obtain G4-M(Ru30Rh70)DTNs。
G4-M(Ru70Rh30) DTNs ultra-violet absorption spectrum as shown in figure 3-2.Comparison diagram 3-1 can be seen that G4PPI-M's
Characteristic absorption peak at the 292nm, in complexation, after Ru and Rh metal nanoparticles, shift respectively by the position of characteristic absorption peak
To 296nm and 298nm.Additionally, G4-M(Ru30Rh70) the ultra-violet absorption spectrum curve shape of DTNs is similar to index variation,
This shows G4-M(Ru3+ 30Rh3+ 70) reduction is completely.
3、HNBR3Preparation
3.6gNBR is dissolved in into 150ml chlorobenzenes it is added in reactor and make NBR glues, then closed reaction kettle, connection is changed
Device of air, under conditions of room temperature and mixing speed are 750r/min, first uses N2Displacement three times, then use high-purity H2Displacement three times.Rise
Temperature to 100 DEG C, by 1.26 × 10-3gG4-M(Ru30Rh70) DTNs catalyst, 1.26 × 10-2G triphenylphosphines H2 is depressed into reaction
In kettle, in H2Pressure be 5.5MPa, 100 DEG C, react 8h under conditions of 900r/min.After reaction terminates, glue is taken out in cooling,
Flocculated with methanol, with methanol flocculation glue, use centrifuge 0.5h, collect the supernatant, decompression rotary distillation removes methanol
With the floccule of chlorobenzene, after floccule is vacuum dried 6h, hydrogenated products HNBR is obtained3, its hydrogenation degree is as shown in table 1.And use chlorine
The G in alembic is reclaimed in benzene dissolving4-M(Ru30Rh70)DTNs.Then by the catalyst for reclaiming as described in Example 1 and condition
The catalytic hydrogenation of NBR is carried out again, and circulation every time all adds 1.26 × 10-2The triphenylphosphine of g.
As shown in Figure 4,970cm in the infrared spectrum of NBR-1And 917cm-1Place is respectively belonging to 1,4-C=C and 1,2-C=
The relative intensity of the characteristic absorption peak of C substantially weakens, and HNBR3Infrared spectrum in belong to-(CH2)n-(n>4)
723cm-1Characteristic absorption peak relative intensity increases, and 2236cm-1Place belongs to the characteristic absorption peak of-CN and is not changed in, and thus may be used
To confirm G4-M(Ru30Rh70) DTNs has excellent catalytic activity and catalytic selectivity.As known from Table 1, HNBR3Hydrogenation degree phase
For HNBR2Have and further improve.This is that, as one side is when Rh/Ru increases, the coelectron effect between Rh and Ru increases
Plus so that the activity increase of catalyst；Another aspect G4-M(Ru30Rh70) metal nanoparticle in DTNs is evenly distributed, is catalyzed
The active site on agent surface increases, therefore catalysis activity has and further improves.
By Fig. 5 cycle-indexes to G4-M(Ru30Rh70) DTNs catalyst activities impact understand, G4-M(Ru30Rh70)DTNs
After recycling 2 times, still remain higher catalysis and live.After recycling 4 times, catalyst activity is decreased obviously.This
It is to lose due to as the increase of cycle-index is in flocculation process, there is partial catalyst be coated by HNBR.Additionally, urging
Change in hydriding process, there is also catalyst be oxidized and the factor such as normal loss impact.
Comparative example 3
1、G4-M(Ru30) DTNs and G4-M(Rh70) DTNs preparation
Take 0.12g G4PPI-M is placed in and is provided with the reaction bulb of air interchanger, connects outside air interchanger, replaces N2
Three times.Under stirring at normal temperature, 50ml tetrahydrofurans are added in bottle, be subsequently adding the tri-chlorination that 0.7ml concentration is 0.1mol/L
Rhodium (or 0.3ml concentration is 0.1mol/L solution of ruthenium trichloride).After 20h is stirred at room temperature, in reaction bulb add 5.0ml dense
Spend the NaBH for 0.5mol/L4Solution.After continuing stirring 2h, the HCl solution of 0.1mol/L is slowly added dropwise in bottle to reactant
The pH of system is 7, you can prepare G respectively4-M(Rh70) DTNs and G4-M(Ru30)DTNs。
2、HNBR33Preparation
3.6gNBR is dissolved in into 150ml chlorobenzenes it is added in reactor and make NBR glues, then closed reaction kettle, connection is changed
Device of air, under conditions of room temperature and mixing speed are 750r/min, first uses N2Displacement three times, then use high-purity H2Displacement three times.Rise
Temperature to 100 DEG C, by 1.26 × 10‐3gG4‐M(Ru30) and G4‐M(Rh70) DTNs physical mixed catalyst, 1.26 × 10‐2G triphens
Base phosphine H2It is depressed in reactor, in H2Pressure be 5.5MPa, 100 DEG C, react 8h under conditions of 750r/min.After reaction terminates,
Cooling, takes out glue, is flocculated with methanol, obtains hydrogenated products HNBR after floccule vacuum drying 6h33, its hydrogenation degree such as 1 institute of table
Show.
The 5th generation hydridization dendrimers supported bi-metallic nanoparticle of embodiment 4 and its catalytic hydrogenation nitrile rubber
1、G5The synthesis of PPI-M
5th generation PPI (G is taken accurately5PPI) (Dutch SyMO-ChemB.V companies) 0.346g (4.83 × 10‐ 5Mol) it is dissolved in 13.3ml acetonitriles standby.Take 0.84g (8.4 × 10‐4mol)MAC、0.82g(5.9×10‐3Mol) Anhydrous potassium carbonate
It is placed in reflux, in the reaction bulb of air interchanger.Outside air interchanger is connected, N is replaced2Three times.In stirring at normal temperature
Under, 3.82mlG is implanted sequentially in flask5PPI/ acetonitrile solutions and 40ml acetonitriles.It is warming up to 107 DEG C of reaction 26h.React
Finish, filter out pressed powder, clean pressed powder three times during filtration with 30ml tetrahydrofurans, obtain filtrate.Filtrate decompression is distilled
Filtrate obtains oily liquids, is used silica gel column chromatography, and eluent proportioning is ethyl acetate：Petroleum ether (V:V)=5:7.Decompression is steamed
Eluent is removed in distillation, and near-white solid product G is obtained after being dried5PPI-M (the tree-shaped PPI of the 5th generation hydridization).
Analyzed from infrared spectrum (Fig. 1), G53330cm in PPI‐1Place belongs to-NH2Base asymmetrical stretching vibration and
The bimodal basic disappearance of symmetrical stretching vibration, and G51600cm in PPI‐1The stretching vibration absworption peak for belonging to C=C occurs,
2800cm‐1And 1460cm‐1Place belongs to the intensity of methylene characteristic peak and is remarkably reinforced, and thus illustrates G5The amino of PPI terminations with
The bromine atoms of 15 yuan of triolefin nitrogen heterocyclic rings there occurs reaction.Meanwhile, to G5The nucleus magnetic hydrogen spectrum (Fig. 2) of PPI-M is analyzed, δ
=3.4ppm belongs to Br-CH2- on proton peak disappear, δ=1.9ppm belongs to-NH2On proton peak intensity significantly reduce,
And the division peak for belonging to proton on phenyl ring is occurred in that at chemical shift δ=7.2-7.7ppm, illustrate G5Contain 15 in PPI-M
First triolefin nitrogen heterocyclic ring.Meanwhile, as shown in Table 2, G5Compare between the theoretical value and measured value of tetra- kinds of elements of C, H, N, S in PPI-M
There is different, this shows G5Amino on PPI is not reacted completely with 15 yuan of triolefin nitrogen heterocyclic rings containing bromopropyl, but not shadow
Ring G5The integrally-built integrity of PPI-M, therefore G5PPI-M successfully synthesizes.
2、G5-M(Ru30Rh70) DTNs preparation
Take 0.12g G5PPI-M is placed in and is provided with the reaction bulb of air interchanger, connects outside air interchanger, replaces N2
Three times.Under stirring at normal temperature, 50ml tetrahydrofurans are added in bottle, 0.7ml rhodium chlorides and 0.3ml ruthenium trichlorides is subsequently adding
Solution.After 24h is stirred at room temperature, 10ml concentration is added in reaction bulb for the NaBH of 0.25mol/L4Solution.Continue stirring
After 2h, the pH that the HCl solution to reaction system of 0.2mol/L is slowly added dropwise in bottle is 7, you can obtain G5-M(Ru30Rh70)DTNs。
To G5-M(Ru30Rh70) DTNs ultra-violet absorption spectrum as shown in figure 3-2.Comparison diagram 3-1 can be seen that G5PPI-M
Characteristic absorption peak at the 294nm, in complexation, after Ru and Rh metal nanoparticles, the position of characteristic absorption peak turns respectively
Move at 297nm and 299nm.Additionally, G5-M(Ru30Rh70) DTNs ultra-violet absorption spectrum curve shape be similar to index change
Change, this shows G5-M(Ru3+ 30Rh3+ 70) reduction is completely.
3、HNBR4Preparation
3.6gNBR is dissolved in into 150ml chlorobenzenes it is added in reactor and make NBR glues, then closed reaction kettle, connection is changed
Device of air, under conditions of room temperature and mixing speed are 900r/min, first uses N2Displacement three times, then use high-purity H2Displacement three times.Rise
Temperature to 90 DEG C, by 1.26 × 10‐3gG5‐M(Ru30Rh70) DTNs catalyst, 1.26 × 10‐2G triphenylphosphine H2It is depressed into reactor
In, in H2Pressure be 6.0MPa, 100 DEG C, react 8h under conditions of 900r/min.After reaction terminates, glue is taken out in cooling, uses
Methanol flocculates, and obtains hydrogenated products HNBR after floccule vacuum drying 7h4, its hydrogenation degree is as shown in table 1.
From infrared test, 970cm in NBR-1And 917cm-1Place is respectively belonging to the spy of 1,4-C=C and 1,2-C=C
The relative intensity for levying absworption peak substantially weakens, and HNBR4Middle discovery belongs to-(CH2)n-(n>4) 723cm-1Characteristic absorption peak
Intensity increases, and 2236cm-1Place belongs to the characteristic absorption peak of-CN and is not changed in, it can be confirmed that G5-M(Ru70Rh30)
DTNs has excellent catalytic activity and catalytic selectivity.As shown in Table 1, G5-M(Ru30Rh70) DTNs activity relative to embodiment
Three have declined.This is likely due to dendrimers G5The big ring of 15 yuan of triolefins of PPI-M peripheries mutually tangles overlap, nanometer
Particle there occurs more serious agglomeration, so as to reduce its catalytic capability.
Comparative example 4
1、G5-M(Ru30) DTNs and G5-M(Rh70) DTNs preparation
Take 0.12g G5PPI-M is placed in and is provided with the reaction bulb of air interchanger, connects outside air interchanger, replaces N2
Three times.Under stirring at normal temperature, 50ml tetrahydrofurans are added in bottle, be subsequently adding 0.7ml rhodium chlorides (or 0.3ml tri-chlorinations
Ruthenium) solution.After 24h is stirred at room temperature, 10ml concentration is added in reaction bulb for the NaBH of 0.25mol/L4Solution.Continue to stir
After mixing 2h, the pH that the HCl solution to reaction system of 0.2mol/L is slowly added dropwise in bottle is 7, you can must prepare G respectively5-M
(Rh70) DTNs and G5-M(Ru30)DTNs。
2、HNBR44Preparation
3.6gNBR is dissolved in into 150ml chlorobenzenes it is added in reactor and make NBR glues, then closed reaction kettle, connection is changed
Device of air, under conditions of room temperature and mixing speed are 750r/min, first uses N2Displacement three times, then use high-purity H2Displacement three times.Rise
Temperature to 100 DEG C, by 1.26 × 10‐3gG5‐M(Ru30) and G5‐M(Rh70) DTNs physical mixed catalyst, 1.26 × 10‐2G triphens
Base phosphine H2It is depressed in reactor, in H2Pressure be 5.5MPa, 100 DEG C, react 8h under conditions of 800r/min.After reaction terminates,
Cooling, takes out glue, is flocculated with methanol, obtains hydrogenated products HNBR after floccule vacuum drying 6h33, its hydrogenation degree such as 1 institute of table
Show.
Impact of 1 different catalysts of table to HNBR hydrogenation degrees
| Hydrogenation degree (%) | |
| 1 (HNBR of embodiment1) | 92.1 |
| 2 (HNBR of embodiment2) | 93.5 |
| 3 (HNBR of embodiment3) | 99.5 |
| 4 (HNBR of embodiment4) | 95.5 |
| 1 (HNBR of comparative example11) | 82.8 |
| 2 (HNBR of comparative example22) | 88.9 |
| 3 (HNBR of comparative example33) | 89.7 |
| 4 (HNBR of comparative example44) | 91.8 |
The elementary analysiss result and value of calculation of 2 GnPPI-M of table
As known from Table 1, HNBR1、HNBR2、HNBR3And HNBR4Hydrogenation degree respectively apparently higher than HNBR11、HNBR22、
HNBR33And HNBR44Hydrogenation degree.As the carbon-carbon double bond in NBR is more easy to combine with the electron deficiency surface of catalyst, according to
The electronegativity principle of Pauling, the electronegativity (2.28) of Rh are bigger than the electronegativity (2.20) of Ru, and the electronics of Rh and Ru atoms is mutual
Effect causes the cloud density of Ru to reduce, generation electron deficiency effect, therefore G2‐M(Ru70Rh30) there is DTNs higher catalysis to live
Property.The method of testing of hydrogenation degree in table 1：It is measured according to SH/T 1762-2008.Also, it should be noted that in the present invention
The end of tree-shaped PPI introduces 15 yuan of nitrogenous triolefin azacyclo-s, so that the nano-particle catalyst of its load possesses
The advantage that can be recycled, so as to solve the problems, such as that noble metal catalyst is recycled.
Claims (10)
1. hydridization dendrimers supported bi-metallic nano-particle catalyst, it is characterised in that：The catalyst is with 15 yuan of triolefins
The modified PPI of azacyclo- is carrier, the compound of ruthenium and rhodium as metal nanoparticle, and its general molecular formula is：
Wherein n1=2,3,4,5；n2=8,16,32,64；The integer of x=30～70.
2. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst described in claim 1, its feature exist
In comprising the steps：
1) mol ratio containing 15 yuan of triolefin azacyclo-s of bromopropyl with PPI is pressed into 7:1～80:During 1 adds reactor,
It is subsequently adding acetonitrile and Anhydrous potassium carbonate；It is warming up to 100 DEG C～110 DEG C reaction 12h～26h；The PPI be the 2nd,
3rd, 4 or 5 generation dendroid PPI；
2) reaction is finished, and is removed by filtration pressed powder, is cleaned pressed powder with tetrahydrofuran during filtration, obtain filtrate, by filtrate
Vacuum distillation obtains oily liquids, oily liquids is chromatographed with silicagel column, and it is 3 that eluent is volume ratio:7～5:7 ethyl acetate
And petroleum ether；
3) vacuum distillation removes eluent, obtains product Gn after being dried1PPI-M；n1=2,3,4,5；
4) in N2Under protection, by Gn1PPI-M is added in reaction bulb；At room temperature, tetrahydrofuran, rhodium chloride and trichlorine are added
Change ruthenium solution stirring reaction 24h-26h；It is subsequently adding NaBH4Solution, continues stirring 1h-2h at room temperature；The tri-chlorination
The mol ratio of rhodium and ruthenium trichloride is 30:70～70:30；
5) to step 4) pH of Deca hydrochloric acid solution to reaction system is 7～8 in gained reactant, obtains Gn1-M(Ru100-xRhx)
DTNs catalyst；
Described is 1,11- bis- [2,4,6- tri isopropyl benzenesulfonyl bases] -6- [4- (3- bromines containing 15 yuan of triolefin azacyclo-s of bromopropyl
Ethyl) benzenesulfonyl] three azo-cycle pentadecane -3,8,13- triolefins of -1,6,11-；Bis- [2,4,6- tri isopropyl benzenesulfonyls of 1,11-
Base] three azo-cycle pentadecane -3,8,13- triolefins of -6- [4- (3- bromopropyls) benzenesulfonyl] -1,6,11-；Bis- [2,4,6- tri- of 1,11-
Isopropylbenzenesuifonyl] in three azo-cycle pentadecane -3,8,13- triolefins of -6- [4- (3- brombutyls) benzenesulfonyl] -1,6,11-
It is a kind of.
3. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 2, its
It is characterised by：The consumption of the acetonitrile and Anhydrous potassium carbonate respectively containing 15 yuan of triolefin azepine ring qualities of bromopropyl 30～50
Again with 0.5～1.0 times.
4. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 2, its
It is characterised by：The consumption of the tetrahydrofuran is containing 15 yuan of bromopropyl, 15～35 times of triolefin azacyclo- quality.
5. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 2, its
It is characterised by：The NaBH4Consumption be 20～25 times of rhodium chloride and ruthenium trichloride molal quantity summation.
6. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 2, its
It is characterised by：The Gn1PPI-M accounts for the 5～30% of rhodium chloride and ruthenium trichloride total mole number.
7. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 2, its
It is characterised by：The PPI Gn1The molecular weight of PPI is 700～7200.
8. the application of the hydridization dendrimers supported bi-metallic nano-particle catalyst described in claim 1, it is characterised in that：
First NBR is dissolved in chlorobenzene, and NBR glues are made in being added to reactor, under room temperature and 750r/min～900r/min stirrings, uses N2
Displacement, then use high-purity H2Displacement；100 DEG C～110 DEG C are warming up to, by Gn1‐M(Ru100‐xRhx) DTNs catalyst and triphenylphosphine use
H2It is depressed in reactor, and in H2It is 100 DEG C～110 DEG C and speed of agitator is 700r/min that pressure is 5.5～6.0MPa, temperature
6h～8h is reacted under conditions of～900r/min；After reaction terminates, glue is taken out in cooling, is flocculated with methanol, uses centrifuge
Lower floor's floccule vacuum drying is obtained hydrogenated nitrile-butadiene rubber (HNBR) by 0.5～1h, and supernatant decompression rotary distillation is removed
Methanol and chlorobenzene, and the Gn reclaimed in alembic is dissolved with chlorobenzene1‐M(Ru100‐xRhx) DTNs catalyst；
The quality of the NBR is Gn1‐M(Ru100‐xRhx) 280～300 times of DTNs catalyst；
The triphenylphosphine consumption is Gn1‐M(Ru100‐xRhx) DTNs catalyst qualities 8～12%.
9. the application of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 8, its feature
It is, the Gn of recovery1‐M(Ru100‐xRhx) DTNs catalyst carries out the catalytic hydrogenation of NBR again.
10. the application of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 8, its feature
It is to use N2The number of times of displacement is three times, then uses high-purity H2The number of times of displacement is three times.
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| "RuRh Bimetallic Nanoparticles Stabilized by 15-membered Macrocycles-terminated Poly(propylene imine) Dendrimer: Preparation and Catalytic Hydrogenation of Nitrile–Butadiene Rubber";Yang Wang等;《Nano-Micro Letters》;20140106;第6卷(第1期);第56页左栏第3段-右栏第4段、第57页右栏第1段 * |
| "杂化树形聚合物负载双金属纳米粒子的制备及其催化丁腈橡胶氢化研究";芦晓然;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20120115(第1期);第4.2.2节、4.3.1节、第4.2.2.5节 * |
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Effective date of registration: 20171204 Address after: 513058 fine chemical industry two road of overseas Chinese Industrial Park, Donghua Town, Yingde City, Qingyuan City, Guangdong Patentee after: Guangdong Potter new materials Co., Ltd. Address before: 510640 Tianhe District, Guangdong, No. five road, No. 381, Patentee before: South China University of Technology |