CN104338558A - Hybridized dendrimer-loaded bimetal metal nanoparticle catalyst as well as preparation method and application thereof - Google Patents
Hybridized dendrimer-loaded bimetal metal nanoparticle catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hybridized dendrimer-loaded bimetal metal nanoparticle catalyst as well as a preparation method and application thereof. The hybridized dendrimer-loaded bimetal metal nanoparticle catalyst is a compound using hybridized polypropyleneimine (PPI) as a carrier and ruthenium and rhodium as metal nanoparticles. The preparation method comprises the following steps: modifying a primary amine group at the periphery of integral-algebra polypropyleneimine by using fifteen-element triene nitrogen heterocycle (MAC) to synthesize a novel hybridized dendrimer loading fifteen-element triolefin large ring on the surface and having different-algebra PPI; and then by adopting a method of co-complexing-reducing with two kinds of metal ions and using GnPPI-M (n=2, 3, 4, 5) as a carrier, preparing Ru/Rh bimetal DTNs with different Ru/Rh proportions, and by using the Ru/Rh bimetal DTNs as a catalyst, performing catalytic hydrogenation on butadiene-acrylonitrile rubber. The catalyst prepared by adopting the preparation method has excellent catalytic activity and selectivity, and can be recycled.
Description
Technical field
The present invention relates to catalyst prepared by a kind of hydrogenated nitrile-butadiene rubber, particularly relate to a kind of catalytic hydrogenation acrylonitrile-butadiene rubber 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, aromatic series solvent resistance); And due to its HI SA highly saturated structure, make the heat resistance that its tool is good, excellent resistance to chemical corrosion (to freon, acid, alkali there is good resistance), excellent ozone resistance, higher incompressible permanent deformation performance; The features such as hydrogenated nitrile-butadiene rubber also has high strength simultaneously, and high tear energy, anti-wear performance are excellent are one of supereminent rubber of combination property.Hydrogenated nitrile-butadiene rubber (HNBR) is the HI SA highly saturated elastomer of one carrying out special hydrotreatment by acrylonitrile-butadiene rubber and obtain, can by obtained by the butadiene unit on catalysis acrylonitrile-butadiene rubber (NBR) segment.HNBR not only has the elasticity of NBR, but also has more excellent thermal oxidation resistance degradation property, and significantly improves hot strength, percentage elongation, the mechanical performance such as mar proof and hardness of NBR.Because HNBR has excellent process based prediction model, be therefore widely used in the field that automobile, oil well oil field and Aero-Space etc. are important.
Existing suitability for industrialized production hydrogenated nbr method has latex hydrogenation method and solution hydrogenation method.Latex hydrogenation method mainly contains catalytic hydrogenation method and hydrogenation parent method.Catalytic hydrogenation method need use noble metal, and as Rh, Ru and Pd, it is high, selective good and simplify the advantages such as operation that the method has hydrogenation degree, but also there is the shortcoming that catalyst is difficult to reclaim; Hydrogenation parent rule is without the need to noble metal, and the hydro genation system of use is hydrazine hydrate/hydrogen peroxide/boric acid, and the method is simple to operate, but easily in the double bond be not hydrogenated, crosslinking side reaction occurs, thus causes machine-shaping difficulty.Solution hydrogenation method is the main technology path of current NBR hydrogenation, hydrogenation catalyst used therein have heterogeneous and homogeneous phase point.Heterogeneous catalysis has hydrogenation rear catalyst and is easily separated and the simple advantage of post processing with the solution of hydrogenated products, but also there is the shortcoming that catalytic activity is relatively lower, catalyst amount is large and hydrogenation conditions is harsh, such catalyst is mainly the metal Pd be carried on above carbon black, silica and barium sulfate etc.; Homogeneous catalyst has the advantage that hydrogenation activity is high and consumption is few, shortcoming be in product catalyst deviate from recovery more difficult, such catalyst mainly comprises Wilkinson catalyst, as three (triphenylphosphine) radium chloride.
Therefore for the current hydrogenated nitrile-butadiene rubber method problem that also exists that catalyst is difficult to reclaim, HNBR gel fraction is higher, catalytic activity is lower etc., high selectivity, high catalytic activity, high performance-price ratio, easily separated recovery is prepared and the novel hydrogenation catalyst that recycles is the key issue that NBR hydrogenation production technology research aspect is badly in need of solving.
Summary of the invention
The object of the invention is to for prior art problem, invented a kind of high selectivity, high catalytic activity, high performance-price ratio, easily separated recovery and hydridization dendrimers supported bi-metallic nano-particle catalyst of recycling and preparation method thereof
Another object of the present invention is to provide described hydridization dendrimers supported bi-metallic nano-particle catalyst to prepare the application of hydrogenated nitrile-butadiene rubber in catalysis.
Object of the present invention is achieved through the following technical solutions:
1, hydridization dendrimers supported bi-metallic nano-particle catalyst, it is characterized in that: this catalyst with the PPI (PPI) of 15 yuan of triolefin azacyclo-s (MAC) modification for carrier, ruthenium (Ru) and rhodium (Rh) are as the compound of metal nanoparticle, and its general molecular formula is:
Wherein n
1=2,3,4,5; n
2=8,16,32,64; The integer of x=30 ~ 70.
The preparation method of described hydridization dendrimers supported bi-metallic nano-particle catalyst, comprises the steps:
1) will containing bromopropyl 15 yuan of triolefin azacyclo-s (MAC) and PPI (Gn
1pPI, n
1=2,3,4,5) mol ratio adds in reactor by 7:1 ~ 80:1, then adds acetonitrile and Anhydrous potassium carbonate; Be warming up to 100 DEG C ~ 110 DEG C reaction 12h ~ 26h; Described PPI is the 2nd, 3,4, and 5 generation dendroid PPI;
2) react complete, removed by filtration pressed powder, during filtration, clean pressed powder with oxolane, obtain filtrate, filtrate decompression is distilled to obtain oily liquids, with silicagel column to oily liquids chromatography, ethyl acetate and the benzinum of eluent to be volume ratio be 3:7 ~ 5:7;
3) decompression distillation removing eluent, obtains product Gn after drying
1pPI-M; n
1=2,3,4,5;
4) at N
2under protection, by Gn
1pPI-M joins in reaction bulb; At room temperature, oxolane, rhodium chloride and ruthenium trichloride solution & stir reaction 24h-26h is added; Then NaBH is added
4solution, at room temperature continues to stir 1h-2h; The mol ratio of described rhodium chloride and ruthenium trichloride is 30:70 ~ 70:30;
5) to step 4) to drip hydrochloric acid solution in gained reactant to the pH of reaction system be 7 ~ 8, different algebraically hydridization tree-shaped PPI load ruthenium rhodium bimetal nano particles catalyst (Gn
1-M (Ru
100-xrh
x) DTNs);
Described is 1,11 ?bis-[2,4,6 ?tri isopropyl benzenesulfonyl base] ?6 ?[4 ?(3 ?bromoethyl) benzenesulfonyl] ?1,6,11 ?tri-nitrogen cyclopentadecane ?3,8,13 ?triolefins containing bromopropyl 15 yuan of triolefin azacyclo-s; 1,11 ?bis-[2,4,6 ?tri isopropyl benzenesulfonyl base] ?6 ?[4 ?(3 ?bromopropyl) benzenesulfonyl] ?1,6,11 ?tri-nitrogen cyclopentadecane ?3,8,13 ?triolefins; One in 1,11 ?bis-[2,4,6 ?tri isopropyl benzenesulfonyl base] ?6 ?[4 ?(3 ?brombutyl) benzenesulfonyl] ?1,6,11 ?tri-nitrogen cyclopentadecane ?3,8,13 ?triolefins.
For realizing the object of the invention further, preferably, the consumption of described acetonitrile and Anhydrous potassium carbonate is respectively 30 ~ 50 times and 0.5 ~ 1.0 times containing bromopropyl 15 yuan of triolefin azacyclo-quality.
The consumption of described oxolane is for containing bromopropyl 15 yuan of triolefin azacyclo-s 15 ~ 35 times of quality.
Described NaBH
4consumption be rhodium chloride and ruthenium trichloride molal quantity 20 ~ 25 times.
Described Gn
1pPI ?M account for 5 ~ 30% of rhodium chloride and the total molar fraction of ruthenium trichloride.
Described PPI Gn
1the 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, joins in reactor and makes NBR glue, under room temperature and 750r/min ~ 900r/min stir, uses N
2displacement, then use high-purity H
2displacement; Be warming up to 100 DEG C ~ 110 DEG C, by Gn
1?M (Ru
100 ?xrh
x) DTNs catalyst and triphenylphosphine H
2be depressed in reactor, and at H
2pressure is 5.5 ~ 6.0MPa, temperature be 100 DEG C ~ 110 DEG C and speed of agitator is react 6h ~ 8h under the condition of 700r/min ~ 900r/min; After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, with centrifuge 0.5h ~ 1h, lower floor's floccule vacuum drying is obtained hydrogenated nitrile-butadiene rubber (HNBR), rotary distillation that supernatant liquor is reduced pressure removing methyl alcohol and chlorobenzene, and the Gn reclaimed in cucurbit is dissolved with chlorobenzene
1?M (Ru
100 ?xrh
x) DTNs catalyst;
The quality of described NBR is Gn
1?M (Ru
100 ?xrh
x) 280 ~ 300 times of DTNs catalyst;
Described triphenylphosphine consumption is Gn
1?M (Ru
100 ?xrh
x) DTNs catalyst quality 8 ?12%.
Preferably, the Gn of recovery
1?M (Ru
100 ?xrh
x) DTNs catalyst carries out the catalytic hydrogenation of NBR again.
PPI dendrimers has structure and the composition of regular, highly branched, high-sequential, by the metal nanoparticle with catalytic activity being stabilized in peripheral functional group modification the dendrimers surface of modification.Therefore mainly contain two feature: a with the Ru/Rh bimetal nano particles catalyst (Ru/Rh DTNs) of PPI dendrimers load, dissolubility controls primarily of dendrimers surface chemical structure, thus be conducive to the recovery of Ru/Rh DTNs and reuse; B, owing to being positioned at dendrimers surface by stable Ru/Rh, more easily and substrate contact, and passivation area is little, and catalytic activity is high; C, because the electronegativity (2.28) of rhodium is larger than the electronegativity (2.20) of ruthenium, the electron interaction of two kinds of metallic atoms makes the cloud density of Ru reduce, generation electron deficient effect.Double bond in NBR more easily combines with the electron deficient surface of catalyst, therefore Ru/Rh DTNs catalyst has higher catalytic activity than corresponding physical mixed monometallic DTNs catalyst.
Compared with prior art, tool has the following advantages in the present invention:
1, the Gn for preparing of the present invention
1?M (Ru
100 ?xrh
x) catalysis of DTNs catalyst to NBR has excellent activity, when catalyst amount is 0.35wt%, the hydrogenation degree of NBR can be made to be up to more than 99%.
2, the Gn for preparing of the present invention
1?M (Ru
100 ?xrh
x) hydrogenation of DTNs catalyst to NBR has high selectivity, has excellent catalytic hydrogenation in hydrogenation process to carbon-carbon double bond, then can not catalytic hydrogenation to itrile group.
3, the Gn for preparing of the present invention
1?M (Ru
100 ?xrh
x) DTNs catalyst has recyclable and advantage that is that recycle.When DTNs catalyst circulation uses after 3 times, the hydrogenation degree of HNBR still can be made to reach more than 90%.
Accompanying drawing explanation
Fig. 1 is G in each embodiment and Application Example
nthe infrared spectrum of PPI-M (n=2,3,4,5);
Fig. 2 is G in each embodiment and Application Example
nthe nucleus magnetic hydrogen spectrum figure of PPI-M (n=2,3,4,5);
Figure 3 ?1 be Gn ?M, Ru
3+, Rh
3+ultraviolet-visible spectrogram;
Figure 3 ?2 be Gn ?M (Ru
100 ?xrh
x) the ultraviolet-visible spectrogram of (n=2,3,4,5);
Fig. 4 is NBR and HNBR in embodiment 3
33infrared spectrum;
Fig. 5 is the G of preparation in embodiment 3
4-M (Ru
30rh
70) cycle-index on the impact of its catalytic activity.
Detailed description of the invention
For a better understanding of the present invention, below in conjunction with drawings and Examples, the present invention is further illustrated, but embodiments of the present invention are not limited thereto.
Embodiment 1 second generation hydridization dendrimers supported bi-metallic nano particle and catalytic hydrogenation acrylonitrile-butadiene rubber thereof
1,15 yuan of triolefin nitrogen heterocyclic ring (MAC) surface modification second generation PPI dendrimers (G
2pPI-M) 2.155g (2.79 × 10 is got
?3mol) G
2it is for subsequent use that PPI (Dutch SyMO ?ChemB.V company) is dissolved in 10ml acetonitrile.By 0.48g (4.8 × 10
?4mol) 1,11 ?bis-[2,4,6 ?tri isopropyl benzenesulfonyl base] ?6 ?[4 ?(3 ?bromopropyl) benzenesulfonyl] ?1,6,11 ?tri-nitrogen cyclopentadecane ?3,8,13 ?triolefins (MAC), 0.33g (2.4 × 10
?3mol) Anhydrous potassium carbonate is placed in the reaction bulb with backflow and air interchanger.Connect outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in flask, inject 0.24mlG successively
2pPI/ acetonitrile solution and 30ml acetonitrile.Be warming up to 107 DEG C of reaction 12h.After having reacted, removed by filtration pressed powder, cleans pressed powder three times with oxolane during filtration, obtains filtrate.Filtrate decompression is distilled to obtain oily liquids, is used silica gel column chromatography, eluent is ethyl acetate: benzinum (V:V)=3:7.By product at reduced pressure distillation removing eluent, vacuum drying 2h obtains white solid product G
2pPI ?M (the tree-shaped PPI of second generation hydridization).
Infrared spectrum is analyzed known as shown in Figure 1, G
23320cm in PPI
-1place belongs to-NH
2base asymmetric stretching vibration and symmetrical stretching vibration bimodal basic disappearance, and G
21600cm in PPI-M
-1the stretching vibration absworption peak that place belongs to C=C occurs, 2806cm
-1and 1450cm
-1the intensity that place belongs to methylene characteristic peak obviously strengthens, and thus G is described
2bromine atoms on the amino of PPI termination and 15 yuan of triolefin nitrogen heterocyclic rings there occurs reaction.Meanwhile, to G
2the nucleus magnetic hydrogen spectrum (Fig. 2) of PPI-M is analyzed, and δ=3.4ppm belongs to Br-C
h 2-on proton peak disappear, δ=1.7ppm belongs to-N
h 2on proton peak intensity significantly reduce, and occurred the division peak belonging to proton on phenyl ring at chemical shift δ=7.2-7.7ppm place, and δ=2.6-2.7ppm place belongs to-C
h 2-NH-C
h 2-on number of hydrogen atoms 32H, G is described
2containing 15 yuan of triolefin nitrogen heterocyclic rings in PPI-M.Meanwhile, (the Vario EL III organic element analyzer that Elementar company produces is adopted, the content by C, H, N, S tetra-kinds of elements in test product after product sample preparation numbering) as shown in Table 2, G
2in PPI-M between the theoretical value of C, H, N, S tetra-kinds of elements and measured value relatively, provable G
2pPI-M successfully synthesizes and its structure comparison is complete.
2, G
2pPI-M load ruthenium rhodium bimetal nano particles (G
2-M (Ru
70rh
30) DTNs) preparation of catalyst
Get 0.12g G
2pPI-M is placed in the reaction bulb being provided with air interchanger, connects outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in bottle, add 50ml oxolane, then add rhodium chloride that 0.3ml concentration is 0.1mol/L and 0.7ml concentration is 0.1mol/L ruthenium trichloride solution.After at room temperature stirring 24h, in reaction bulb, add the NaBH that 2.0ml concentration is 1.0mol/L
4solution.Continue to stir after 1h, the HCl solution slowly dripping 0.2mol/L in bottle is 7 to the pH of reaction system, G
2-M (Ru
70rh
30) DTNs.
G
2-M (Ru
70rh
30) DTNs ultra-violet absorption spectrum as shown in figure 3-2.Comparison diagram 3-1 can find out, G
2the characteristic absorption peak of PPI-M is positioned at 292nm place, and in complexing, after Ru and Rh metal nanoparticle, the position of characteristic absorption peak is transferred to 296nm and 298nm place respectively.In addition, G
2-M (Ru
70rh
30) the ultra-violet absorption spectrum curve shape of DTNs is all similar to index variation, this shows G
2-M (Ru
3+ 70rh
3+ 30) reduction completely.
3, hydrogenated nitrile-butadiene rubber (HNBR
1) preparation
3.6gNBR is dissolved in 150ml chlorobenzene to join in reactor and make NBR glue, closed reaction still, connects air interchanger, under room temperature and mixing speed are the condition of 750r/min, first use N
2replace three times, then use high-purity H
2replace three times.Be warming up to 95 DEG C, by 1.26 × 10
-3g G
2-M (Ru
70rh
30) DTNs catalyst, 1.26 × 10
-2g triphenylphosphine H
2be depressed in reactor, at H
2pressure be 5.5MPa, 100 DEG C, react 8h under the condition of 800r/min.Reaction terminates rear cooling, takes out glue, with methyl alcohol flocculation, obtains HNBR after floccule vacuum drying 6h
1, its hydrogenation degree is as shown in table 1.
From infrared test, 970cm in the infrared spectrum of NBR
-1and 917cm
-1the relative intensity that place belongs to the characteristic absorption peak of Isosorbide-5-Nitrae-C=C and 1,2-C=C respectively obviously weakens, and HNBR
1infrared spectrum in belong to-(CH
2)
nthe 723cm of-(n>4)
-1characteristic absorption peak relative intensity increases, and 2236cm
-1the characteristic absorption peak that place belongs to-CN does not change, and it can be confirmed G
2-M (Ru
70rh
30) DTNs has excellent catalytic activity and catalytic selectivity.As known from Table 1, HNBR
1hydrogenation degree all higher than HNBR
11hydrogenation degree.This is because the carbon-carbon double bond in NBR more easily combines with the electron deficient surface of catalyst.According to the electronegativity principle of Pauling, the electronegativity (2.28) of Rh is larger than the electronegativity (2.20) of Ru, and the electron interaction of Rh and Ru atom makes the cloud density of Ru reduce, and produces electron deficient effect, therefore G
2-M (Ru
70rh
30) DTNs has higher catalytic activity.The method of testing of hydrogenation degree in table 1: measure according to SH/T 1762-2008.
Comparative example 1G
2-M (Ru
70rh
30) DTNs
1, G
2-M (Ru
70) DTNs and G
2-M (Rh
30) preparation of DTNs
Get 0.12g G
2pPI-M is placed in the reaction bulb being provided with air interchanger, connects outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in bottle, add 50ml oxolane, then add rhodium chloride that 0.3ml concentration is 0.1mol/L or 0.7ml concentration is 0.1mol/L ruthenium trichloride solution.After at room temperature stirring 24h, in reaction bulb, add the NaBH that 2.0ml concentration is 1.0mol/L
4solution.Continue to stir after 1h, the HCl solution slowly dripping 0.2mol/L in bottle is 7 to the pH of reaction system, obtains G
2-M (Ru
70) DTNs and G
2-M (Rh
30) DTNs, its physical mixed can be obtained G
2-M (Ru
70) DTNs and G
2-M (Rh
30) DTNs physical mixed catalyst.
2, hydrogenated nitrile-butadiene rubber (HNBR
11) preparation
3.6gNBR is dissolved in 150ml chlorobenzene to join in reactor and make NBR glue, then closed reaction still, connects air interchanger, under room temperature and mixing speed are the condition of 750r/min, first use N
2replace three times, then use high-purity H
2replace three times.Be warming up to 95 DEG C, by 1.26 × 10
-3gG
2-M (Ru
70) and G
2-M (Rh
30) DTNs physical mixed catalyst, 1.26 × 10
-2g triphenylphosphine H
2be depressed in reactor, at H
2pressure be 5.5MPa, 100 DEG C, react 8h under the condition of 800r/min.After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, obtains hydrogenated products HNBR after floccule vacuum drying 6h
11, its hydrogenation degree is as shown in table 1.
Embodiment 2 third generation hydridization dendrimers supported bi-metallic nano particle and catalytic hydrogenation acrylonitrile-butadiene rubber thereof
1, G
3pPI ?the synthesis of M
Accurately take 1.610g (9.54 × 10
?4mol) G
3it is for subsequent use that PPI (Dutch SyMO ?ChemB.V company) is dissolved in 10ml acetonitrile.Get 0.80g (8.0 × 10
?4mol) MAC, 0.56g (4.1 × 10
?3mol) Anhydrous potassium carbonate is placed in the reaction bulb with backflow and air interchanger.Connect outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in flask, inject 0.56mlG successively
3pPI/ acetonitrile solution, 30ml acetonitrile.Then 107 DEG C of reaction 18h are warming up to.React complete, filters solid powder, clean pressed powder three times with oxolane during filtration, obtain filtrate.Filtrate decompression is distilled filtrate and obtains oily liquids, used silica gel column chromatography, eluent proportioning is ethyl acetate: benzinum (V:V)=5:7.Last decompression distillation removing eluent, obtains near-white solid product G after drying
3pPI ?M (the tree-shaped PPI of third generation hydridization).
Analyzed from infrared spectrum (Fig. 1), G
33310cm in PPI
-1place belongs to-NH
2the bimodal basic disappearance of base asymmetric stretching vibration and symmetrical stretching vibration, and G
31600cm in PPI-M
-1the stretching vibration absworption peak belonging to C=C occurs, 2790cm
-1and 1465cm
-1the intensity that place belongs to methylene characteristic peak obviously strengthens, and thus G is described
3bromine atoms on the amino of PPI termination and 15 yuan of triolefin nitrogen heterocyclic rings there occurs reaction.Meanwhile, to G
3the nucleus magnetic hydrogen spectrum (Fig. 2) of PPI-M is analyzed, and δ=3.4ppm belongs to Br-C
h 2-on proton peak disappear, δ=1.9ppm belongs to-N
h 2on proton peak intensity significantly reduce, and occurred the division peak belonging to proton on phenyl ring at chemical shift δ=7.2-7.7ppm place, and δ=2.6-2.7ppm place belongs to-C
h 2-NH-C
h 2-on number of hydrogen atoms 64H, illustrate in G2PPI-M containing 15 yuan of triolefin nitrogen heterocyclic rings.Meanwhile, as shown in Table 2, G
3in PPI-M between the theoretical value of C, H, N, S tetra-kinds of elements and measured value relatively, therefore provable G
3pPI-M successfully synthesizes and its structure comparison is complete.
2, G
3-M (Ru
50rh
50) preparation of DTNs
Get 0.12g G
3pPI-M is placed in the reaction bulb being provided with air interchanger, connects outside air interchanger, displacement N2 tri-times.Under stirring at normal temperature, in bottle, add 50ml oxolane, then add 0.5ml rhodium chloride and 0.5ml ruthenium trichloride solution.After at room temperature stirring 26h, in reaction bulb, add the NaBH that 5ml concentration is 0.5mol/L
4solution.Continue to stir after 2h, the HCl solution slowly dripping 0.2mol/L in bottle is 7 to the pH of reaction system, G
3-M (Ru
50rh
50) DTNs.
G
3-M (Ru
50rh
50) DTNs ultra-violet absorption spectrum as shown in figure 3-2.Comparison diagram 3-1 can find out, G
3the characteristic absorption peak of PPI-M is positioned at 291nm place, and in complexing, after Ru and Rh metal nanoparticle, the position of characteristic absorption peak is transferred to 296nm and 298nm place respectively.In addition, G
3-M (Ru
50rh
50) the ultra-violet absorption spectrum curve shape of DTNs is all similar to index variation, this shows G
3-M (Ru
3+ 50rh
3+ 50) reduction completely.
3, HNBR
2preparation
3.6gNBR is dissolved in 150ml chlorobenzene to join in reactor and make NBR glue, then closed reaction still, connects air interchanger, under room temperature and mixing speed are the condition of 800r/min, first use N
2replace three times, then use high-purity H
2replace three times.Be warming up to 95 DEG C, by 1.26 × 10
?3gG
3?M (Ru
50rh
50) DTNs catalyst, 1.26 × 10
?2g triphenylphosphine H
2be depressed in reactor, at H
2pressure be 6.0MPa, 100 DEG C, react 8h under the condition of 800r/min.After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, obtains hydrogenated products HNBR after floccule vacuum drying 7h
2, its hydrogenation degree is as shown in table 1.
From infrared test, 970cm in the infrared spectrum of NBR
-1and 917cm
-1the relative intensity that place belongs to the characteristic absorption peak of Isosorbide-5-Nitrae-C=C and 1,2-C=C respectively obviously weakens, and HNBR
2infrared spectrum in belong to-(CH
2)
nthe 723cm of-(n>4)
-1characteristic absorption peak relative intensity increases, and 2236cm
-1the characteristic absorption peak that place belongs to-CN does not change, and it can be confirmed G
3-M (Ru50Rh50) DTNs has excellent catalytic activity and catalytic selectivity.As known from Table 1, HNBR
2hydrogenation degree with HNBR in embodiment 1
1compare and improve.This is that the coelectron effect between Rh and Ru increases, and the activity of catalyst is increased due on the one hand when Rh/Ru increases; Due to G on the other hand
3-M (Ru
50rh
50) 15 yuan of triolefin nitrogen heterocyclic rings in DTNs molecule increase, so catalytic activity point increases, thus cause catalytic activity to increase.
Comparative example 2
1, G
3-M (Ru
50) DTNs and G
3-M (Rh
50) preparation of DTNs physical mixed catalyst
Get 0.12g G
3pPI-M is placed in the reaction bulb being provided with air interchanger, connects outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in bottle, add 50ml oxolane, then add the rhodium chloride (or 0.5ml concentration is 0.1mol/L ruthenium trichloride solution) that 0.5ml concentration is 0.1mol/L.After at room temperature stirring 26h, in reaction bulb, add the NaBH that 5.0ml concentration is 0.5mol/L
4solution.Continue to stir after 2h, the HCl solution slowly dripping 0.1mol/L in bottle is 7 to the pH of reaction system, G
3-M (Ru
50) DTNs and G
3-M (Rh
50) DTNs.
2, hydrogenated nitrile-butadiene rubber (HNBR
22) preparation
3.6gNBR is dissolved in 150ml chlorobenzene to join in reactor and make NBR glue, then closed reaction still, connects air interchanger, under room temperature and mixing speed are the condition of 800r/min, first use N
2replace three times, then use high-purity H
2replace three times.Be warming up to 95 DEG C, by 1.26 × 10
-3gG
3-M (Ru
50) and G
3-M (Rh
50) DTNs physical mixed catalyst, 1.26 × 10
-2g triphenylphosphine H
2be depressed in reactor, at H
2pressure be 6.0MPa, 100 DEG C, react 8h under the condition of 800r/min.After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, obtains hydrogenated products HNBR after floccule vacuum drying 6h
22, its hydrogenation degree is as shown in table 1.
Embodiment 3 forth generation hydridization dendrimers supported bi-metallic nano particle and catalytic hydrogenation acrylonitrile-butadiene rubber thereof
1, G
4pPI ?the synthesis of M
Get 0.654g (1.86 × 10
?4mol) G
4it is for subsequent use that PPI (Dutch SyMO ?ChemB.V company) is dissolved in 17ml acetonitrile.By 0.84g (8.4 × 10
?4mol) MAC, 0.62g (4.5 × 10
?3mol) Anhydrous potassium carbonate is placed in the reaction bulb with backflow and air interchanger.Connect outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in flask, inject 1.92mlG successively
4pPI/ acetonitrile solution, 40ml acetonitrile, is warming up to 107 DEG C of reaction 20h.React complete, filters solid powder, clean pressed powder three times with 30ml oxolane during filtration, obtain filtrate.Filtrate decompression is distilled filtrate and obtains oily liquids, used silica gel column chromatography, eluent proportioning is ethyl acetate: benzinum (V:V)=5:7.Last decompression distillation removing eluent, obtains near-white solid product G after drying
4pPI ?M (the tree-shaped PPI of forth generation hydridization).
Analyzed from infrared spectrum (Fig. 1), G
43290cm in PPI
-1place belongs to-NH
2the bimodal basic disappearance of base asymmetric stretching vibration and symmetrical stretching vibration, and G
41600cm in PPI
-1the stretching vibration absworption peak belonging to C=C occurs, 2806cm
-1and 1450cm
-1the intensity that place belongs to methylene characteristic peak obviously strengthens, and thus G is described
4the bromine atoms of the amino of PPI termination and 15 yuan of triolefin nitrogen heterocyclic rings there occurs reaction.Meanwhile, to G
4the nucleus magnetic hydrogen spectrum (Fig. 2) of PPI-M is analyzed, and δ=3.4ppm belongs to Br-C
h 2-on proton peak disappear, δ=1.9ppm belongs to-N
h 2on proton peak intensity significantly reduce, and occurred the division peak belonging to proton on phenyl ring at chemical shift δ=7.2-7.7ppm place, and δ=2.6-2.7ppm place belongs to-C
h 2-NH-C
h 2-on number of hydrogen atoms 128H, G is described
4containing 15 yuan of triolefin nitrogen heterocyclic rings in PPI-M.Meanwhile, as shown in Table 2, G
4in PPI-M between the theoretical value of C, H, N, S tetra-kinds of elements and measured value relatively, therefore provable G
4pPI-M successfully synthesizes and its structure comparison is complete.
2, G
4-M (Ru
30rh
70) preparation of DTNs
Get 0.12g G
4pPI-M is placed in the reaction bulb being provided with air interchanger, connects outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in bottle, add 50ml oxolane, then add 0.7ml rhodium chloride and 0.3ml ruthenium trichloride solution.After at room temperature stirring 24h, in reaction bulb, add the NaBH that 5.0ml concentration is 0.5mol/L
4solution.Continue to stir after 2h, the HCl solution slowly dripping 0.2mol/L in bottle is 7 to the pH of reaction system, G
4-M (Ru
30rh
70) DTNs.
G
4-M (Ru
70rh
30) DTNs ultra-violet absorption spectrum as shown in figure 3-2.Comparison diagram 3-1 can find out, G
4the characteristic absorption peak of PPI-M is positioned at 292nm place, and in complexing, after Ru and Rh metal nanoparticle, the position of characteristic absorption peak is transferred to 296nm and 298nm place respectively.In addition, G
4-M (Ru
30rh
70) the ultra-violet absorption spectrum curve shape of DTNs is all similar to index variation, this shows G
4-M (Ru
3+ 30rh
3+ 70) reduction completely.
3, HNBR
3preparation
3.6gNBR is dissolved in 150ml chlorobenzene to join in reactor and make NBR glue, then closed reaction still, connects air interchanger, under room temperature and mixing speed are the condition of 750r/min, first use N
2replace three times, then use high-purity H
2replace three times.Be warming up to 100 DEG C, by 1.26 × 10
-3gG
4-M (Ru
30rh
70) DTNs catalyst, 1.26 × 10
-2g triphenylphosphine H2 is depressed in reactor, at H
2pressure be 5.5MPa, 100 DEG C, react 8h under the condition of 900r/min.After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, to flocculate glue, use centrifuge 0.5h with methyl alcohol, collect supernatant liquor, and the floccule of decompression rotary distillation removing methyl alcohol and chlorobenzene, obtains hydrogenated products HNBR by after floccule vacuum drying 6h
3, its hydrogenation degree is as shown in table 1.And the G reclaimed in cucurbit is dissolved with chlorobenzene
4-M (Ru
30rh
70) DTNs.Then the catalyst of recovery is carried out again the catalytic hydrogenation of NBR by the method for embodiment 1 and condition, each circulation all adds 1.26 × 10
-2the triphenylphosphine of g.
As shown in Figure 4,970cm in the infrared spectrum of NBR
-1and 917cm
-1the relative intensity that place belongs to the characteristic absorption peak of Isosorbide-5-Nitrae-C=C and 1,2-C=C respectively obviously weakens, and HNBR
3infrared spectrum in belong to-(CH
2)
nthe 723cm of-(n>4)
-1characteristic absorption peak relative intensity increases, and 2236cm
-1the characteristic absorption peak that place belongs to-CN does not change, and it can be confirmed G
4-M (Ru
30rh
70) DTNs has excellent catalytic activity and catalytic selectivity.As known from Table 1, HNBR
3hydrogenation degree relative to HNBR
2there is further raising.This is that the coelectron effect between Rh and Ru increases, and the activity of catalyst is increased due on the one hand when Rh/Ru increases; G on the other hand
4-M (Ru
30rh
70) metal nanoparticle in DTNs is evenly distributed, the active site of catalyst surface increases, and therefore catalytic activity has further raising.
By Fig. 5 cycle-index to G
4-M (Ru
30rh
70) impact of DTNs catalyst activity is known, G
4-M (Ru
30rh
70) DTNs after recycling 2 times, still remain higher catalysis and live.After recycling 4 times, catalyst activity obviously declines.This is owing to being increased in flocculation process along with cycle-index, has partially catalyzed agent can be coated and lose by HNBR.In addition, in catalytic hydrogenation process, also there is the impact of the factors such as the oxidized and normal loss of catalyst.
Comparative example 3
1, G
4-M (Ru
30) DTNs and G
4-M (Rh
70) preparation of DTNs
Get 0.12g G
4pPI-M is placed in the reaction bulb being provided with air interchanger, connects outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in bottle, add 50ml oxolane, then add the rhodium chloride (or 0.3ml concentration is 0.1mol/L ruthenium trichloride solution) that 0.7ml concentration is 0.1mol/L.After at room temperature stirring 20h, in reaction bulb, add the NaBH that 5.0ml concentration is 0.5mol/L
4solution.Continue to stir after 2h, the HCl solution slowly dripping 0.1mol/L in bottle is 7 to the pH of reaction system, can prepare G respectively
4-M (Rh
70) DTNs and G
4-M (Ru
30) DTNs.
2, HNBR
33preparation
3.6gNBR is dissolved in 150ml chlorobenzene to join in reactor and make NBR glue, then closed reaction still, connects air interchanger, under room temperature and mixing speed are the condition of 750r/min, first use N
2replace three times, then use high-purity H
2replace three times.Be warming up to 100 DEG C, by 1.26 × 10
?3gG
4?M (Ru
30) and G
4?M (Rh
70) DTNs physical mixed catalyst, 1.26 × 10
?2g triphenylphosphine H
2be depressed in reactor, at H
2pressure be 5.5MPa, 100 DEG C, react 8h under the condition of 750r/min.After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, obtains hydrogenated products HNBR after floccule vacuum drying 6h
33, its hydrogenation degree is as shown in table 1.
Embodiment 4 the 5th generation hydridization dendrimers supported bi-metallic nano particle and catalytic hydrogenation acrylonitrile-butadiene rubber thereof
1, G
5pPI ?the synthesis of M
Accurately get the 5th generation PPI (G
5pPI) (Dutch SyMO ?ChemB.V company) 0.346g (4.83 × 10
?5mol) 13.3ml acetonitrile is dissolved in for subsequent use.Get 0.84g (8.4 × 10
?4mol) MAC, 0.82g (5.9 × 10
?3mol) Anhydrous potassium carbonate is placed in reflux, in the reaction bulb of air interchanger.Connect outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in flask, inject 3.82mlG successively
5pPI/ acetonitrile solution and 40ml acetonitrile.Be warming up to 107 DEG C of reaction 26h.React complete, filters solid powder, clean pressed powder three times with 30ml oxolane during filtration, obtain filtrate.Filtrate decompression is distilled filtrate and obtains oily liquids, used silica gel column chromatography, eluent proportioning is ethyl acetate: benzinum (V:V)=5:7.Decompression distillation removing eluent, obtains near-white solid product G after drying
5pPI ?M (the tree-shaped PPI of the 5th generation hydridization).
Analyzed from infrared spectrum (Fig. 1), G
53330cm in PPI
?1place Gui Shu Yu ?NH
2the bimodal basic disappearance of base asymmetric stretching vibration and symmetrical stretching vibration, and G
51600cm in PPI
?1the stretching vibration absworption peak belonging to C=C occurs, 2800cm
?1and 1460cm
?1the intensity that place belongs to methylene characteristic peak obviously strengthens, and thus G is described
5the bromine atoms of the amino of PPI termination and 15 yuan of triolefin nitrogen heterocyclic rings there occurs reaction.Meanwhile, to G
5pPI ?the nucleus magnetic hydrogen spectrum (Fig. 2) of M analyze, δ=3.4ppm belong to Br ?CH
2?on proton peak disappear, δ=1.9ppm Gui Shu Yu ?NH
2on proton peak intensity significantly reduce, and in chemical shift δ=7.2 ?7.7ppm place there is the division peak belonging to proton on phenyl ring, G is described
5pPI ?in M containing 15 yuan of triolefin nitrogen heterocyclic rings.Meanwhile, as shown in Table 2, G
5pPI ?in M between the theoretical value of C, H, N, S tetra-kinds of elements and measured value than there being different, this shows G
5amino on PPI does not have complete reaction with containing bromopropyl 15 yuan of triolefin nitrogen heterocyclic rings, but does not affect G
5pPI ?the integrally-built integrality of M, therefore G
5pPI ?M successfully synthesize.
2, G
5-M (Ru
30rh
70) preparation of DTNs
Get 0.12g G
5pPI-M is placed in the reaction bulb being provided with air interchanger, connects outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in bottle, add 50ml oxolane, then add 0.7ml rhodium chloride and 0.3ml ruthenium trichloride solution.After at room temperature stirring 24h, in reaction bulb, add the NaBH that 10ml concentration is 0.25mol/L
4solution.Continue to stir after 2h, the HCl solution slowly dripping 0.2mol/L in bottle is 7 to the pH of reaction system, G
5-M (Ru
30rh
70) DTNs.
To G
5-M (Ru
30rh
70) DTNs ultra-violet absorption spectrum as shown in figure 3-2.Comparison diagram 3-1 can find out, G
5the characteristic absorption peak of PPI-M is positioned at 294nm place, and in complexing, after Ru and Rh metal nanoparticle, the position of characteristic absorption peak is transferred to 297nm and 299nm place respectively.In addition, G
5-M (Ru
30rh
70) the ultra-violet absorption spectrum curve shape of DTNs is all similar to index variation, this shows G
5-M (Ru
3+ 30rh
3+ 70) reduction completely.
3, HNBR
4preparation
3.6gNBR is dissolved in 150ml chlorobenzene to join in reactor and make NBR glue, then closed reaction still, connects air interchanger, under room temperature and mixing speed are the condition of 900r/min, first use N
2replace three times, then use high-purity H
2replace three times.Be warming up to 90 DEG C, by 1.26 × 10
?3gG
5?M (Ru
30rh
70) DTNs catalyst, 1.26 × 10
?2g triphenylphosphine H
2be depressed in reactor, at H
2pressure be 6.0MPa, 100 DEG C, react 8h under the condition of 900r/min.After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, obtains hydrogenated products HNBR after floccule vacuum drying 7h
4, its hydrogenation degree is as shown in table 1.
From infrared test, 970cm in NBR
-1and 917cm
-1the relative intensity that place belongs to the characteristic absorption peak of Isosorbide-5-Nitrae-C=C and 1,2-C=C respectively obviously weakens, and HNBR
4middle discovery belongs to-(CH
2)
nthe 723cm of-(n>4)
-1characteristic absorption peak intensity increases, and 2236cm
-1the characteristic absorption peak that place belongs to-CN does not change, and it can be confirmed G
5-M (Ru
70rh
30) DTNs has excellent catalytic activity and catalytic selectivity.As shown in Table 1, G
5-M (Ru
30rh
70) activity of DTNs declines to some extent relative to embodiment three.This may be due to dendrimers G
515 yuan of large rings of triolefin of PPI-M periphery tangle overlap mutually, and nano particle there occurs more serious agglomeration, thus reduces its catalytic capability.
Comparative example 4
1, G
5-M (Ru
30) DTNs and G
5-M (Rh
70) preparation of DTNs
Get 0.12g G
5pPI-M is placed in the reaction bulb being provided with air interchanger, connects outside air interchanger, displacement N
2three times.Under stirring at normal temperature, in bottle, add 50ml oxolane, then add 0.7ml rhodium chloride (or 0.3ml ruthenium trichloride) solution.After at room temperature stirring 24h, in reaction bulb, add the NaBH that 10ml concentration is 0.25mol/L
4solution.Continue to stir after 2h, the HCl solution slowly dripping 0.2mol/L in bottle is 7 to the pH of reaction system, prepare G respectively
5-M (Rh
70) DTNs and G
5-M (Ru
30) DTNs.
2, HNBR
44preparation
3.6gNBR is dissolved in 150ml chlorobenzene to join in reactor and make NBR glue, then closed reaction still, connects air interchanger, under room temperature and mixing speed are the condition of 750r/min, first use N
2replace three times, then use high-purity H
2replace three times.Be warming up to 100 DEG C, by 1.26 × 10
?3gG
5?M (Ru
30) and G
5?M (Rh
70) DTNs physical mixed catalyst, 1.26 × 10
?2g triphenylphosphine H
2be depressed in reactor, at H
2pressure be 5.5MPa, 100 DEG C, react 8h under the condition of 800r/min.After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, obtains hydrogenated products HNBR after floccule vacuum drying 6h
33, its hydrogenation degree is as shown in table 1.
Table 1 different catalysts is on the impact of HNBR hydrogenation degree
| Hydrogenation degree (%) | |
| Embodiment 1 (HNBR 1) | 92.1 |
| Embodiment 2 (HNBR 2) | 93.5 |
| Embodiment 3 (HNBR 3) | 99.5 |
| Embodiment 4 (HNBR 4) | 95.5 |
| Comparative example 1 (HNBR 11) | 82.8 |
| Comparative example 2 (HNBR 22) | 88.9 |
| Comparative example 3 (HNBR 33) | 89.7 |
| Comparative example 4 (HNBR 44) | 91.8 |
Table 2 GnPPI ?the results of elemental analyses of M and calculated value
As known from Table 1, HNBR
1, HNBR
2, HNBR
3and HNBR
4hydrogenation degree respectively apparently higher than HNBR
11, HNBR
22, HNBR
33and HNBR
44hydrogenation degree.Because the carbon-carbon double bond in NBR more easily combines with the electron deficient surface of catalyst, according to the electronegativity principle of Pauling, the electronegativity (2.28) of Rh is larger than the electronegativity (2.20) of Ru, the electron interaction of Rh and Ru atom makes the cloud density of Ru reduce, produce electron deficient effect, therefore G
2?M (Ru
70rh
30) DTNs has higher catalytic activity.The method of testing of hydrogenation degree in table 1: according to SH/T 1762 ?2008 to measure.Also it should be noted that, introduce 15 yuan of nitrogenous triolefin azacyclo-s at the end of tree-shaped PPI in the present invention, thus make the nano-particle catalyst of its load possess the advantage that can be recycled, thus solve the problem of noble metal catalyst recycling.
Claims (10)
1. hydridization dendrimers supported bi-metallic nano-particle catalyst, is characterized in that: this catalyst is with the PPI of 15 yuan of triolefin azacyclo-s modification for carrier, and ruthenium and rhodium are as the compound of metal nanoparticle, and its general molecular formula is:
Wherein n
1=2,3,4,5; n
2=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, is characterized in that comprising the steps:
1) mol ratio containing bromopropyl 15 yuan of triolefin azacyclo-s and PPI is added in reactor by 7:1 ~ 80:1, then add acetonitrile and Anhydrous potassium carbonate; Be warming up to 100 DEG C ~ 110 DEG C reaction 12h ~ 26h; Described PPI is the 2nd, 3,4, and 5 generation dendroid PPI;
2) react complete, removed by filtration pressed powder, during filtration, clean pressed powder with oxolane, obtain filtrate, filtrate decompression is distilled to obtain oily liquids, with silicagel column to oily liquids chromatography, ethyl acetate and the benzinum of eluent to be volume ratio be 3:7 ~ 5:7;
3) decompression distillation removing eluent, obtains product Gn after drying
1pPI-M; n
1=2,3,4,5;
4) at N
2under protection, by Gn
1pPI-M joins in reaction bulb; At room temperature, oxolane, rhodium chloride and ruthenium trichloride solution & stir reaction 24h-26h is added; Then NaBH is added
4solution, at room temperature continues to stir 1h-2h; The mol ratio of described rhodium chloride and ruthenium trichloride is 30:70 ~ 70:30;
5) to step 4) to drip hydrochloric acid solution in gained reactant to the pH of reaction system be 7 ~ 8, obtains Gn
1-M (Ru
100-xrh
x) DTNs catalyst;
Described is 1,11 ?bis-[2,4,6 ?tri isopropyl benzenesulfonyl base] ?6 ?[4 ?(3 ?bromoethyl) benzenesulfonyl] ?1,6,11 ?tri-nitrogen cyclopentadecane ?3,8,13 ?triolefins containing bromopropyl 15 yuan of triolefin azacyclo-s; 1,11 ?bis-[2,4,6 ?tri isopropyl benzenesulfonyl base] ?6 ?[4 ?(3 ?bromopropyl) benzenesulfonyl] ?1,6,11 ?tri-nitrogen cyclopentadecane ?3,8,13 ?triolefins; One in 1,11 ?bis-[2,4,6 ?tri isopropyl benzenesulfonyl base] ?6 ?[4 ?(3 ?brombutyl) benzenesulfonyl] ?1,6,11 ?tri-nitrogen cyclopentadecane ?3,8,13 ?triolefins.
3. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 1, is characterized in that: the consumption of described acetonitrile and Anhydrous potassium carbonate is respectively 30 ~ 50 times and 0.5 ~ 1.0 times containing bromopropyl 15 yuan of triolefin azacyclo-quality.
4. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 1, is characterized in that: the consumption of described oxolane is for containing bromopropyl 15 yuan of triolefin azacyclo-s 15 ~ 35 times of quality.
5. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 1, is characterized in that: described NaBH
4consumption be rhodium chloride and ruthenium trichloride molal quantity 20 ~ 25 times.
6. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 1, is characterized in that: described Gn
1pPI ?M account for 5 ~ 30% of rhodium chloride and the total molar fraction of ruthenium trichloride.
7. the preparation method of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 1, is characterized in that: described PPI Gn
1the molecular weight of PPI is 700 ~ 7200.
8. the application of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 1, is characterized in that: first NBR is dissolved in chlorobenzene, joins in reactor and make NBR glue, under room temperature and 750r/min ~ 900r/min stir, uses N
2displacement, then use high-purity H
2displacement; Be warming up to 100 DEG C ~ 110 DEG C, by Gn
1?M (Ru
100 ?xrh
x) DTNs catalyst and triphenylphosphine H
2be depressed in reactor, and at H
2pressure is 5.5 ~ 6.0MPa, temperature be 100 DEG C ~ 110 DEG C and speed of agitator is react 6h ~ 8h under the condition of 700r/min ~ 900r/min; After reaction terminates, cooling, takes out glue, with methyl alcohol flocculation, with centrifuge 0.5 ~ 1h, lower floor's floccule vacuum drying is obtained hydrogenated nitrile-butadiene rubber (HNBR), rotary distillation that supernatant liquor is reduced pressure removing methyl alcohol and chlorobenzene, and the Gn reclaimed in cucurbit is dissolved with chlorobenzene
1?M (Ru
100 ?xrh
x) DTNs catalyst;
The quality of described NBR is Gn
1?M (Ru
100 ?xrh
x) 280 ~ 300 times of DTNs catalyst;
Described triphenylphosphine consumption is Gn
1?M (Ru
100 ?xrh
x) DTNs catalyst quality 8 ~ 12%.
9. the application of hydridization dendrimers supported bi-metallic nano-particle catalyst according to claim 8, is characterized in that, the Gn of recovery
1?M (Ru
100 ?xrh
x) 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, is characterized in that, use N
2the number of times of displacement is three times, then uses high-purity H
2the number of times of displacement is three times.
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| CN106179504A (en) * | 2016-07-11 | 2016-12-07 | 华南理工大学 | Hydridization dendrimers metal supported catalyst and preparation method and application |
| CN108144649A (en) * | 2017-12-15 | 2018-06-12 | 华南理工大学 | Big ring is modified preparation method and the application of dendrimers load Pd-Pt bimetal nano particles catalyst |
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| EP1219640A2 (en) * | 2000-12-28 | 2002-07-03 | Bayer Inc. | Hydrogenation of nitrile rubber |
| CN103224591A (en) * | 2013-04-24 | 2013-07-31 | 北京化工大学 | Bimetallic catalytic hydrogenation method of nitrile rubber |
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2014
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| EP1219640A2 (en) * | 2000-12-28 | 2002-07-03 | Bayer Inc. | Hydrogenation of nitrile rubber |
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| CN106179504A (en) * | 2016-07-11 | 2016-12-07 | 华南理工大学 | Hydridization dendrimers metal supported catalyst and preparation method and application |
| CN106179504B (en) * | 2016-07-11 | 2018-10-09 | 华南理工大学 | Hydridization dendrimers metal supported catalyst and the preparation method and application thereof |
| CN108144649A (en) * | 2017-12-15 | 2018-06-12 | 华南理工大学 | Big ring is modified preparation method and the application of dendrimers load Pd-Pt bimetal nano particles catalyst |
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