CN104844408B - A kind of it is catalyzed the australene Hydrogenation method for cis-pinane - Google Patents
A kind of it is catalyzed the australene Hydrogenation method for cis-pinane Download PDFInfo
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- CN104844408B CN104844408B CN201510030412.4A CN201510030412A CN104844408B CN 104844408 B CN104844408 B CN 104844408B CN 201510030412 A CN201510030412 A CN 201510030412A CN 104844408 B CN104844408 B CN 104844408B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to the method that the metal nanoparticle hydrosol catalysis α pinene hydrogenation of a kind of polymer stabilizing efficiently prepares cis-pinane, belong to the preparation and application field of catalyst.Catalyst of the present invention is as stabilizer with P123 (polyoxyethylene polyoxypropylene polyoxyethylene triblock copolymer), the ruthenium nano particle hydrosol prepared by hydrogenating reduction method in aqueous medium.The ruthenium nano particle hydrosol of this polymer stabilizing can be catalyzed α pinene hydrogenation in a mild condition, high activity, high selectivity, prepares cis-pinane to high stability.The present invention metal nanoparticle hydrosol by polymer stabilizing first is used for the catalytic hydrogenation of α pinene, the preparation of catalyst and catalytic hydrogenation reaction mild condition, environmental friendliness, without any organic solvent, catalyst has prominent recycling performance, can be that terebinthine high value added utilization provides effective ways.
Description
Technical field
The metal nanoparticle hydrosol catalysis australene hydrogenation that the present invention relates to a kind of polymer stabilizing efficiently prepares cis-pinane
Method, specifically a kind of with ruthenium nanometer stable for P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer)
The particle hydrosol is catalyst, and catalysis australene Hydrogenation, for the method for cis-pinane, belongs to the preparation and application field of catalyst.
Background technology
Australene, as important renewable Colophonium class resource, can generate cis-pinane and trans pinane after hydrogenated reaction.Pinane
Reaction is in order to synthesize terpenoid spice and the series of downstream products thereof such as linalool, geraniol and dihydromyrcenol further.Wherein,
The reactivity of cis-pinane is higher than trans pinane, it is desirable to the pinane used on perfume industry is the highest along inverse ratio, with
Avoid the occurrence of the problems such as downstream product separating-purifying difficulty.And if think to obtain efficiently high selective cis-pinane, it is critical only that α-
The selection of pinene hydrogenation catalyst.
Current industrial conventional Pd/C and Raney-Ni catalyst often exist severe reaction conditions, product selectivity relatively low
With problems such as the easy cokings of catalyst.For many years, chemists continuously search for the selective catalyst system and catalyzing of high-cis
(CN1262263A;CN101884925A;CN102671711B;CN104003831A), but still suffer from catalytic body so far
System is complicated, reaction temperature and the shortcoming such as pressure is higher, environmental pollution is more serious, catalyst repeat performance is the best.
Water has the features such as abundance, cheap, pollution-free and not burning, has been applied to as " green medium " by water
Machine reaction has become as an important research direction in Green Chemistry field.Research finds, under some specific reaction system,
Water can significantly improve reaction rate and selectivity, and easily realizes the separation of product and recycling (the J Am Chem of catalyst
Soc,1980,102,7816-7817;Chem Soc Rev,2006,35,68-82).And since the nineties in last century, polymer
The application in catalytic hydrogenation reaction of the stable metal nanoparticle is paid close attention to widely.Block copolymer P123 is as a kind of two
The surfactant of parent, soluble in water, it is possible to promote the transition metal nanoparticle of synthesizing stable in aqueous medium and under the conditions of room temperature
The sub-hydrosol, and may be implemented under mild reaction conditions for alkene, α, beta-unsaturated aldehyde ketone and the high activity of nitrobenzene derivative
With high-selective and hydrogenating (Langmuir, 2004,20,8426-8430;Journal of Colloid and Interface Science,2014,
415,117-126).But up to now, use the transition metal nanoparticles hydrosol system of this polymer stabilizing as catalysis
Being not reported in agent catalysis australene hydrogenation reaction document at home and abroad, this technique is formulated in exploitation, is expected to the conjunction for cis-pinane
Become to provide a new way efficient, gentle, eco-friendly.
Summary of the invention
The invention aims to solve severe reaction conditions in existing australene hydrogenation technique, cis-pinane selectivity relatively
The problems such as the low and easy coking of catalyst, it is provided that the metal Ru Nanoparticles Hydrosol catalysis australene hydrogenation of a kind of polymer stabilizing is anti-
Should, the method the most efficiently preparing cis-pinane.
According to the present invention, it is provided that polymer stabilizing metal Ru Nanoparticles Hydrosol catalyst composition, function as follows:
In aqueous medium, with P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, molecular weight: 5800) shape
The micelle become is stabilizer, prepares the ruthenium nano particle hydrosol by the hydrogenating reduction of ruthenium salt.In this catalyst system, P123 exists
The micelle that water is formed not only can prevent ruthenium nano particle from assembling, at the same time as amphipathic microreactor, to turning in catalytic reaction
Rate and selective raising thereof play critical effect.
The metal Ru concrete preparation method of Nanoparticles Hydrosol catalyst of the polymer stabilizing that the present invention provides is as follows:
In stainless steel cauldron, add P123 and the 2mL deionized water of 30mg, be stirred at room temperature uniformly.Add 0.01
The RuCl of mmol3·3H2O, first uses H after being sufficiently stirred for2Air in still is replaced for several times, is filled with the H of 0.5MPa afterwards2,
60 DEG C are reacted 1 hour, obtain black ruthenium Nanoparticles Hydrosol stable for P123.
The technical scheme of the metal Ru Nanoparticles Hydrosol catalysis australene hydrogenation of the polymer stabilizing that the present invention provides is such reality
Existing:
In the above-mentioned ruthenium nano particle hydrosol system prepared, it is directly added into a certain amount of australene, is filled with certain pressure
H2Carry out hydrogenation reaction.Reaction terminate after, the catalyst hydrosol is layered mutually with organic product, remove upper strata product mutually after, water-soluble
Glue catalyst system then can directly be reused.
In the technical scheme that the present invention provides, raw material australene is 200 with the mol ratio of ruthenium nano particle hydrosol catalyst, reaction temperature
Degree is at 40 DEG C, and the response time is 2h, and reactive hydrogen atmospheric pressure is 0.7MPa.
The ruthenium nano particle hydrosol stable for P123 that the present invention provides is catalyzed the australene Hydrogenation method for cis-pinane with existing
Technology is compared has following feature:
(1) the invention provides a kind of method being medium preparation with stable alpha-pinene hydrogenation reacting metal catalyst with water, easy
Easy, cleaning is cheap;
(2) the catalysis australene hydrogen addition technology that the present invention provides has the highest catalysis activity and cis-pinane selectivity of product;
(3) the catalysis australene hydrogen addition technology that the present invention provides is not required to any organic solvent, and reaction condition is gentle, environmental friendliness;
(4), in the catalysis australene hydrogen addition technology that the present invention provides, hydrosol catalyst system can directly be reused, and it is urged
Change performance sufficiently stable.
Accompanying drawing explanation
Fig. 1 be the stable ruthenium nano particle of the polymer P 123 prepared by embodiment 1 transmission electron microscope (TEM) photo and
Corresponding grain size distribution.
Fig. 2 is x-ray photoelectron spectroscopy (XPS) figure of the stable ruthenium nano particle of the polymer P 123 prepared by embodiment 1.
Fig. 3 is that the laser confocal microscope (CLSM) of the micelle microreactor formed in embodiment 2 course of reaction irradiates figure.
Detailed description of the invention
The following example is used for further illustrating the present invention, but does not thereby limits the invention.
The preparation of the ruthenium nano particle hydrosol catalyst of [embodiment 1] P123 polymer stabilizing
30mg P123 and 2mL water are joined in stainless steel cauldron, is stirred at room temperature uniformly.Add 0.01mmol's
RuCl3·3H2O, first with the H of 1MPa after being sufficiently stirred for2Air in still is replaced 4 times, is filled with 0.5MPa H afterwards2, 60 DEG C
Reaction 1h, i.e. obtains ruthenium nano particle hydrosol catalyst stable for P123.
Accompanying drawing 1 shows, the ruthenium nano particle particle diameter prepared is at about 2.8nm, and dispersibility is preferable.Accompanying drawing 2 data show system
Being zero-valent metal ruthenium for ruthenium nano particle major part (≈ 91.5%) gone out, this is owing to the sample making course before detecting is exposed to air
In, there is a few part (≈ 8.5%) to be oxidized to ruthenium-oxide.
2mmol australene is joined the 0.010mmol of the P123 polymer stabilizing prepared equipped with embodiment 1 by [embodiment 2]
In the stainless steel cauldron of ruthenium nano particle hydrosol catalyst (australene is 200 with the mol ratio of ruthenium nano particle), mixing is all
Even, with the hydrogen of 1MPa, air in still is replaced 4 times, be filled with 0.7MPa H2, stirring reaction 2h at 40 DEG C.Reaction
After end, collect upper strata product phase, use gas chromatography to carry out quantitative analysis.The conversion ratio of australene is 99.9%, selects
Property is 98.9%.
The laser confocal microscope (CLSM) of accompanying drawing 3 irradiates characterization result and shows, in embodiment 2 course of reaction, and australene
Hydrogenation reaction be P123 hydrosol polymer formed micelle microreactor in carry out, its micelle microreactor size is 700
About nm.
Product, with embodiment 2, after reaction terminates, is removed by [embodiment 3-26] experiment condition and reactions steps mutually, bottom
Hydrosol catalyst the most then adds 2mmol australene, repeats the experimental procedure of embodiment 2, has carried out 24 times repeating experiment.
Catalyst is after recycling 14 times, and the conversion ratio of australene is still 98.1%;After reusing 24 times, the conversion ratio of australene
Being 95.6%, the selectivity of cis-pinane is 98.8%.
30mg P123 and 2mL methanol are joined in stainless steel cauldron by [comparative example 1], are stirred at room temperature uniformly.Add again
Enter the RuCl of 0.01mmol3·3H2O, first with the H of 1MPa after being sufficiently stirred for2Air in still is replaced 4 times, is filled with afterwards
0.5MPa H2, 60 DEG C of reaction 1h, obtain comparative catalyst 1.
2mmol australene is joined in the stainless steel cauldron of the comparative catalyst 1 prepared equipped with comparative example 1 (australene with
The mol ratio of ruthenium nano particle is 200), mix homogeneously, with the hydrogen of 1MPa, air in still is replaced 4 times, be filled with 0.7MPa
H2, stirring reaction 2h at 40 DEG C.After reaction terminates, collect upper strata product phase, use gas chromatography to carry out quantitative analysis.
The conversion ratio of australene is 33.2%, and selectivity is 98.5%.
[comparative example 2] is by the RuCl of 0.01mmol3·3H2O and 2mL water joins in stainless steel cauldron, is sufficiently stirred for
Rear first with the H of 1MPa2Air in still is replaced 4 times, is filled with 0.5MPa H afterwards2, 60 DEG C of reaction 1h, obtain contrast and urge
Agent 2.
2mmol australene is joined in the stainless steel cauldron of the comparative catalyst 2 prepared equipped with comparative example 2 (australene with
The mol ratio of ruthenium nano particle is 200), mix homogeneously, with the hydrogen of 1MPa, air in still is replaced 4 times, be filled with 0.7MPa
H2, stirring reaction 2h at 40 DEG C.After reaction terminates, collect upper strata product phase, use gas chromatography to carry out quantitative analysis.
The conversion ratio of australene is 21.7%, and selectivity is 93.5%.
Claims (3)
1. the metal nanoparticle hydrosol catalysis australene Hydrogenation of polymer stabilizing is for a method for cis-pinane, and its feature exists
In: the ruthenium nano particle hydrosol prepared by hydrogenating reduction method in aqueous medium with P123 polymer for stabilizer is for urging
Agent, in a mild condition direct efficient catalytic australene hydrogenation, high selectivity, high stability prepare cis-pinane, its
Described in P123 polymer be polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer.
2. a preparation method for the metal Ru Nanoparticles Hydrosol catalyst of the P123 polymer stabilizing described in claim 1, its
It is characterised by that preparation process is as follows:
In stainless steel cauldron, add P123 polymer and deionized water, be stirred at room temperature uniformly, add a certain amount of
RuCl3·3H2O, first uses H after being sufficiently stirred for2Air in still is replaced 4 times, is filled with 0.5MPa H afterwards2, 60 DEG C anti-
Answer 1h, obtain the black ruthenium Nanoparticles Hydrosol catalyst of P123 polymer stabilizing.
3. the method preparing cis-pinane described in a claim 1, it is characterised in that: at organic solvent-free, raw material australene with
The mol ratio of the metal Ru Nanoparticles Hydrosol catalyst of P123 polymer stabilizing is 200, reaction temperature 40 DEG C, reaction
Time 2h, under the mild reaction conditions of Hydrogen Vapor Pressure 0.7MPa, direct hydrogenation prepares cis-pinane.
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CN105198689B (en) * | 2015-10-30 | 2018-01-19 | 青岛科技大学 | A kind of method that α firpenes selective hydrogenation prepares cis-pinane |
CN105418355A (en) * | 2015-11-21 | 2016-03-23 | 青岛科技大学 | Method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation in aqueous medium |
CN105642279A (en) * | 2015-12-25 | 2016-06-08 | 北京化工大学 | Water-soluble nanoparticle catalyst and application thereof |
CN105566027B (en) * | 2016-02-22 | 2018-07-17 | 青岛科技大学 | Under a kind of normal temperature and pressure catalysis australene Hydrogenation for cis-pinane method |
CN105622328B (en) * | 2016-03-28 | 2017-12-22 | 青岛科技大学 | A kind of method that α pinene hydrogenations prepare cis-pinane |
CN105753653B (en) * | 2016-03-29 | 2018-12-21 | 青岛科技大学 | A method of preparing fatty alcohol |
CN106316747B (en) * | 2016-08-15 | 2019-01-11 | 青岛科技大学 | A kind of method that palladium nickel bimetal catalyst australene adds hydrogen to prepare cis-pinane |
CN106345456A (en) * | 2016-08-22 | 2017-01-25 | 青岛科技大学 | Method for preparing aniline through aqueous-phase catalysis nitrobenzene hydrogenation |
CN107188775A (en) * | 2017-07-07 | 2017-09-22 | 青岛科技大学 | A kind of method that amphipathic molecule sieve load Ru nano particle catalysis α pinene hydrogenations prepare cis-pinane |
CN107519867B (en) * | 2017-09-14 | 2020-05-15 | 江西省科学院应用化学研究所 | Preparation method of ruthenium-supported titanium dioxide catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene |
CN111545195A (en) * | 2020-05-19 | 2020-08-18 | 福州大学 | Recyclable Ru nano catalyst, preparation method thereof and application thereof in preparation of cis-pinane |
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