CN109092355A - A kind of catalyst and the method for preparing carboxyl HNBR - Google Patents
A kind of catalyst and the method for preparing carboxyl HNBR Download PDFInfo
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- CN109092355A CN109092355A CN201810844224.9A CN201810844224A CN109092355A CN 109092355 A CN109092355 A CN 109092355A CN 201810844224 A CN201810844224 A CN 201810844224A CN 109092355 A CN109092355 A CN 109092355A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
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Abstract
The present invention relates to a kind of catalyst and the methods for preparing carboxyl HNBR.The catalyst is platinum group metal ion-HMD/GO, is made of graphene oxide, hexamethylene diamine and platinum group metal, and the platinum group metal is selected from one of Ru, Rh, Pd.Using the effect of catalyst, carboxyl HNBR can be prepared.This method operating method is simple, it is environmentally protective simultaneously, atom utilization reaches 100%, meet the requirement of Green Chemistry, it can guarantee again simultaneously and obtain higher degree of hydrogenation in unsaturated rubber hydrogenation process and obtain the HNBR containing carboxyl, therefore this method has important application value in no hydrogen carboxyl hydrorubber preparation field.
Description
Technical field
The present invention relates to a kind of catalyst and the methods for preparing carboxyl HNBR.
Background technique
Hydrogenated carboxylated nitrile rubber (HXNBR) is a kind of novel synthetic rubber, by conjugated diene, acrylonitrile and unsaturated carboxylic
Acid copolymerization formed terpolymer, selective hydrogenation under conditions of hydrogen and be made.Compared with HNBR, HXNBR has more
Excellent mechanical property, bond properties and wearability and excellent high temperature tearing strength, can be used for rubber roller, the oil of press
The dedicated packer of well, drill bit sealing ring, explosion-proof apparatus and drill pipe wiper etc..
Carbon dioxide is as a kind of common carboxylation reaction carbon source in organic chemistry.CN102884025A discloses one
Kind utilize carbon dioxide as carbon source, nickel system provides a kind of direct carboxylated of alkene as catalyst and prepares salt unsaturated carboxylic acid
Method.CN107698435A discloses a kind of ionic iron catalyst Terminal Acetylenes based compound and the carboxylated of carbon dioxide is anti-
Application in answering.Thus, we can use the CO generated in situ2And H2It is carried out while to nitrile rubber add in-place hydrogen in situ
Carboxylated realizes atom economy and Green Chemistry, and opens up a kind of new method for synthesizing carboxyl HNBR.
Summary of the invention
The object of the present invention is to provide a kind of catalyst and the methods for preparing carboxyl HNBR.
Technical scheme is as follows:
A kind of catalyst, the catalyst is platinum group metal ion-HMD/GO, by graphene oxide (GO), hexamethylene diamine
(HMD) it is made with platinum group metal, the platinum group metal is selected from one or more of Ru, Rh, Pd;It is preferred that Ru.
The catalyst is prepared in raw material, and the weight ratio of the graphene oxide, hexamethylene diamine and platinum group metal ion is
100:(100-600): (1-20).
Under aforementioned proportion, preparation-obtained multifunction catalyst has uniform particle diameter, the excellent advantage of catalytic effect.
Catalyst of the present invention, the platinum group metal provide preferably in the form of chloride;When the platinum group metal
For Ru.It provides in a chloride-form, having dissolution in the preparation, the uniform advantage of particle diameter distribution, products therefrom has catalysis rapidly
It is active high, the advantages such as not easy to reunite.
The present invention provides the preparation method of above-mentioned any one catalyst together, is that graphene oxide, hexamethylene diamine is abundant
The chloride of the platinum group metal is added after stirring, through reduction reaction to obtain the final product.
Preferably, described that 10-24h is sufficiently stirred in graphene oxide, hexamethylene diamine;More preferably carry out at normal temperature.
Preferably, after the halide of the platinum group metal is added, continue to stir 10-24h;More preferably carry out at normal temperature.
Preferably, the reduction reaction is 5-10% with sodium borohydride reduction, the preferably dosage of 1-2mol/L sodium borohydride.
In the preparation method of above-mentioned catalyst, preferably using deionized water as reaction system solvent.
The present invention provides platinum group metal-HMD/GO catalyst described in above-mentioned any one technical solution in rubber carboxylic together
Application in base.
The rubber is selected from one of butadiene-styrene rubber (SBR) or nitrile rubber (NBR).
The method that the present invention further provides a kind of to prepare carboxylated HNBR using rubber as raw material, using above-mentioned any one
Catalyst described in item technical solution.
The rubber is selected from one of butadiene-styrene rubber (SBR) or nitrile rubber (NBR);It is highly preferred that the rubber is molten
Solution in organic solvent, mass fraction 5-30%;
Preferably, the organic solvent be include short chain alcohol, and selected from chloroform, n-hexane, chlorobenzene, benzene, dimethylbenzene,
Tetrahydrofuran, carbon tetrachloride, the mixed solvent of one or more of toluene;
The short chain alcohol is selected from one or more of methanol, ethyl alcohol, propyl alcohol, butanol.
The organic solvent for selecting above-mentioned compounding has the high advantage of activity;And when short chain alcohol and the organic solvent are complete
The volume ratio in portion is (1-10): when (51-60), having the hydrogen of generation and carbon dioxide sufficient, more conducive to the advantage of reaction.
The method of preparation carboxylated HNBR of the present invention, it is preferable that the mass ratio of the catalyst and the rubber
For (1-4): (100-150), further preferably 3.5: 100.
The method of preparation carboxylated HNBR of the present invention, including by rubber solutions under the catalyst action,
50-100 DEG C, hydrogenation reaction 2-8h under conditions of revolving speed 300-1000r/min adjust reaction temperature to 100-200 DEG C of continuation carboxylic
Glycosylation reaction 4-20h to get.
Preferably, the rubber solutions are to be dissolved in the in the mixed solvent of dimethylbenzene and methanol with NBR and SBR quality point is made
The solution of number 5-30%;It is further preferred that the volume ratio of methanol and dimethylbenzene is (1-10) in above-mentioned mixed solution: 50, it is further excellent
It is selected as 1:10.
The hydrogenation time is preferably 2-8h.
The carboxylation reaction preferably carries out 2-10h at 100-150 DEG C;More preferable 2-6h.
The above method generates CO using platinum group metal-HMD/GO as catalyst in situ in mixed organic solvents2And H2, lead to
Carboxylated HNBR is prepared in situ in excess temperature regulation directly catalysis NBR, this method technical process is simple, reaction process controllability is high,
Production cost is low and production security is high, meets the requirement of Green Chemistry, realizes atom economy.The invention also includes above-mentioned
Platinum group metal-HMD/GO multifunction catalyst production carbon dioxide method: by Ru-HMD/GO multifunction catalyst be dissolved in from
It in sub- water, pours into the Solutions Solution dissolved, is stirred and heated to 50-150 DEG C, is i.e. generation CO2And H2。
The invention also includes the methods that above-mentioned catalyst produces carbon dioxide: the catalyst is dissolved in organic solvent,
It is heated to 50-150 DEG C, i.e. generation CO2And H2;
The organic solvent be include short chain alcohol, and be selected from chloroform, n-hexane, chlorobenzene, benzene, dimethylbenzene, tetrahydro furan
It mutters, carbon tetrachloride, the mixed solvent of one or more of toluene;
The short chain alcohol is selected from one or more of methanol, ethyl alcohol, propyl alcohol, butanol.
The method that carboxyl hydrogenated nitrile-butadiene rubber (HNBR) is prepared in situ in one kettle way of the invention, using mixed organic solvents,
Catalytic mixing solvent generates hydrogen and carbon dioxide under the effect of the catalyst, and it is anti-that hydrogen can carry out addition to unsaturated double-bond
It answers, the active carbon dioxide just generated can then be reduced to carboxyl under given conditions, and it is partially grafted in double bond, it completes
Carboxylated.This method operating method is simple, while the carbon dioxide and hydrogen generated is decomposed using mixed solvent, environmentally protective,
Atom utilization reaches 100%, meets the requirement of Green Chemistry, at the same can guarantee again obtained in unsaturated rubber hydrogenation process compared with
High degree of hydrogenation and the HNBR containing carboxyl is obtained, therefore this method has in no hydrogen carboxyl hydrorubber preparation field
Important application value.
Detailed description of the invention
Fig. 1 is that embodiment 2 generates the relationship of hydrogen at any time.
Fig. 2 is that embodiment 13-17 prepares the infrared spectrum before and after carboxyl HNBR.
Fig. 3 prepares the nuclear-magnetism carbon spectrum before and after carboxyl HNBR for embodiment 13-17.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions, described technology or conditions according to the literature in the art, or carried out according to product description.Examination used
Production firm person is not specified in agent or instrument, is the conventional products that can be commercially available by regular distributor.
Embodiment 1
The present embodiment provides a kind of catalyst and preparation method thereof, the specific steps are as follows:
The hexamethylene diamine (HMD) of 2.17g is added to suspension (solvent is water) 500ml containing 1g graphene oxide (GO)
In, the RuCl that concentration is 20g/L is added dropwise in ultrasound2Aqueous solution 10ml, be added NaBH430ml reacts at room temperature 60min, is centrifuged, 50
DEG C vacuum drying for 24 hours, obtains Ru-HMD/GO.
Embodiment 2
The present embodiment provides a kind of methods of hydrogen producing and carbon dioxide, the specific steps are as follows:
Compound concentration is methanol/dimethylbenzene mixed liquor (methanol/dimethylbenzene=1/5) of 4mol/L, and embodiment 1 is prepared into
To Ru-HMD/GO catalyst 2% be added in mixed liquor, be warming up to 50 DEG C, revolving speed 300r/min can produce gas,
The gas of generation is collected, gas-chromatography test is shown in Table 1.
Table 1, which decomposes to generate, obtains gas with various content
Embodiment 3-7
Embodiment 3-7 provides a kind of method for preparing carboxyl HNBR respectively, the specific steps are as follows:
10gNBR is dissolved in the dimethylbenzene of 100ml and the mixed solution (methanol/dimethylbenzene=1/5) of methanol, is configured to
The NBR glue that mass fraction is 10%.It takes the 60ml NBR glue to be placed in 100mL reaction kettle and be added and is equivalent to glue quality
The Ru-HMD/GO multifunction catalyst (preparation of embodiment 1) of score 2%, under the conditions of revolving speed 300r/min respectively at temperature 50 C,
It is reacted 5 hours in 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C.
Its carboxylated the results are shown in Table 2.
Degree of hydrogenation under 2 embodiment 3- embodiment of table, 7 different temperatures
Embodiment 8-12
Embodiment 8-12 provides a kind of method for preparing carboxyl HNBR respectively, the specific steps are as follows:
The mixed solution (methanol/dimethylbenzene=1/5) of 12%, 14%, 16%, 18%, 20% volume fraction is prepared respectively,
Prepare the NBR glue of mass fraction 10% again using mixed solution.It takes the 60ml glue to be added in 100ml reaction kettle, is added
It is equivalent to the Ru-HMD/GO multifunction catalyst (preparation of embodiment 1) of NBR mass fraction 2%, under the conditions of revolving speed 500r/min
In temperature 50 C, react 6 hours.Temperature is adjusted to 120 DEG C, the reaction was continued 4 hours, and the result is shown in tables 3.
The degree of hydrogenation and carboxylated degree of 3 embodiment 8-12 of table
Embodiment 13-17
Embodiment 13-17 provides a kind of method for preparing carboxyl HNBR respectively, the specific steps are as follows:
NBR is dissolved in the mixed solution of (volume ratio of dimethylbenzene and methanol is 5/1), being configured to mass fraction is 10%
NBR glue.Take the 60ml NBR glue to be placed in 100mL reaction kettle and be added be equivalent to glue mass fraction 1.5%, 2%,
2.5%, 3%, 3.5% Ru-HMD/GO multifunction catalyst (preparation of embodiment 1), under the conditions of revolving speed 500r/min with temperature
50 DEG C of degree reacts 6 hours, raises the temperature to 120 DEG C the reaction was continued 6 hours.Its product the results are shown in Table 4, Fig. 2 and Fig. 3.
The degree of hydrogenation and carboxylated degree of 4 embodiment 13-17 of table
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of catalyst, which is characterized in that the catalyst be platinum group metal ion-HMD/GO, be by graphene oxide, oneself
Diamines and platinum group metal are made, and the platinum group metal is selected from one of Ru, Rh, Pd.
2. catalyst according to claim 1, which is characterized in that the graphene oxide, hexamethylene diamine and platinum group metal from
The weight ratio of son is 100:(100-600): (1-20).
3. a kind of method for preparing catalyst of any of claims 1 or 2, which is characterized in that fill graphene oxide, hexamethylene diamine
Divide the chloride that the platinum group metal is added after stirring, through reduction reaction to obtain the final product;
Preferably,
10-24h is sufficiently stirred in graphene oxide, hexamethylene diamine at normal temperature;
And/or
After the chloride of the platinum group metal is added, continue to stir 10-24h at normal temperature;
And/or
The reduction reaction is 5-10% with sodium borohydride reduction, the dosage of more preferable 1-2mol/L sodium borohydride.
4. application of the catalyst according to claim 1 or 2 in rubber carboxylated;
Preferably, the rubber is selected from one of butadiene-styrene rubber or nitrile rubber.
5. a kind of method for preparing carboxylated HNBR using rubber as raw material, which is characterized in that using described in as claimed in claim 1 or 22
Catalyst;
Preferably, the rubber is selected from one of butadiene-styrene rubber or nitrile rubber;It is highly preferred that the rubber solution is organic
In solvent, mass fraction 5-30%.
6. according to the method described in claim 5, it is characterized in that, the organic solvent be include short chain alcohol, and be selected from trichlorine
Methane, n-hexane, chlorobenzene, benzene, dimethylbenzene, tetrahydrofuran, carbon tetrachloride, the mixed solvent of one or more of toluene;
Preferably, it is (1-10): (51-60) that the short chain alcohol, which accounts for the volume ratio of the organic solvent,.
7. method according to claim 5 or 6, which is characterized in that the mass ratio of the catalyst and the rubber is (1-
4): (100-150), preferably 3.5: 100.
8. according to the described in any item methods of claim 5-7, which is characterized in that including urging the solution of the rubber described
Agent effect under, first hydrogenation reaction, be further continued for carboxylation reaction to get;
Preferably, hydrogenation reaction 2-8h under conditions of 50-100 DEG C, revolving speed 300-1000r/min, adjust reaction temperature to
100-200 DEG C of continuation carboxylation reaction 2-20h.
9. according to the described in any item methods of claim 5-8, which is characterized in that the rubber solutions are dissolved in the rubber
The solution of mass fraction 5-30% is made in the in the mixed solvent of dimethylbenzene and methanol;It is preferred that the in the mixed solvent methanol and two
The volume ratio of toluene is (1-10): 50, further preferably 1:10.
10. method according to claim 8 or claim 9, which is characterized in that the carboxylation reaction carries out at 100-150 DEG C
2-10h;It is preferred that 2-6h.
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Title |
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