CN1043640A - Catalyst for preparing alcohol from olefin - Google Patents
Catalyst for preparing alcohol from olefin Download PDFInfo
- Publication number
- CN1043640A CN1043640A CN 88108971 CN88108971A CN1043640A CN 1043640 A CN1043640 A CN 1043640A CN 88108971 CN88108971 CN 88108971 CN 88108971 A CN88108971 A CN 88108971A CN 1043640 A CN1043640 A CN 1043640A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ring
- ligand
- reaction
- phosphine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Catalyst for preparing alcohol from olefin.Catalyst is cooperated with transition metal by organic phosphine coordination body and constitutes; the structure of its ligand is: R=P-R '; R is multi-ring alkyl or thiazolinyl; be generally dicyclo or three rings; R ' is alkyl, aromatic radical or cycloalkyl; this class not only can be used as the catalyst that olefin hydroformylation generates aldehyde by the catalyst that ligand and transition-metal coordination generate, and also can be used for step manufacturing primary alconol.
Description
The present invention relates to the catalyst of a kind of alkene and carbon monoxide and H-H reaction system fatty alcohol; catalyst is cooperated with transition metal by phosphine ligand and forms; this class is by ligand and transition metal Co, Rh, Ir, Ni, Pd, Pt etc.; the catalyst that generates of Co, Rh particularly; not only can be used as the catalyst of olefin hydroformylation generation aldehyde, also can a direct step make primary alconol.
The transition metal compound catalizer of producing primary alconol about alkene and carbon monoxide and H-H reaction had many reports, and many kinds of organic phosphines all can be used as the ligand of transition metal compound catalizer, wherein are preferably organic tertiary phosphine.The phosphorus atoms of ligand organic phosphine can be respectively links to each other with three alkyl with carbon number or different carbon numbers, and the alkyl that links to each other can be simple alkyl, aryl or cycloalkyl, also can be among them any two kinds.The effect of organic phosphine coordination body mainly is the stability of the catalytic performance that improves transition metal compound catalizer, particularly catalyst.
To cobalt carbonyl-complexes catalyst, more effective organic phosphine coordination body is a tributylphosphine.Through the cobalt carbonyl-complexes catalyst of tributylphosphine modification, when being used for making alcohol by alkene and carbon monoxide and hydroformylation step reaction, though have active preferably because the boiling point of tributylphosphine is lower, when being used to prepare the higher higher alcohols of boiling point, as C
12Above alcohol, in catalyst and product separation process, the loss of tributylphosphine is more, causes the production cost of alcohol to raise.
In order to improve the boiling point of this class phosphine ligand, people once adopted the alkyl tert phosphine ligand of macromolecule, for example: US.3,448,157; US.3,488,296 etc.The organic phosphine coordination body of this class macromolecule, though boiling point increases, but the spatial volume of ligand obviously increases, under reaction condition, the dynamic structure easily of catalyst produces stronger spatial obstacle, influence the collision of reactant molecule and catalyst active center's atom, make activity of such catalysts that significant decline be arranged.Obviously, only consider, improve the performance of catalyst, lose more than gain from increasing catalyst ligand molecular weight.
At BP 1,109, the catalyst of the synthetic system of a kind of alkene carbonyl primary alconol is disclosed in 787.Its purpose is not reduce activity of such catalysts when improving catalyst phosphine ligand boiling point, to be suitable for preparing higher alcohols.The phosphine ligand of this catalyst is actually the dicyclo organic phosphine, that is: the phosphorus atoms of phosphine ligand simultaneously with a carbocyclic ring hydrocarbon on two carbon atom Cheng Jian, another key of phosphorus atoms and alkyl or aryl Cheng Jian, formation dicyclo phosphine heterocycle structure.The composition catalyst that generates with this ligand and cobalt atom has boiling point and active higher characteristics.Weak point is that the heat endurance of phosphine ligand is not very good, decomposes when surpassing 200 ℃; Be solid at room temperature, bring inconvenience during use; Cost in order to the monocycle diolefin of preparation dicyclo phosphine is higher, causes the price of catalyst more expensive.
US.3,527,818 disclose the another kind of two phosphine ligands of dicyclo that are used for preparing alcohol from olefin cobalt phosphine catalyst, and its catalytic activity and primary alconol yield are all better, but the synthesis yield of this organic phosphine coordination body is lower, and required raw material is difficult for making, and price is more expensive.Decrease although produce the norm quota of consumption of the organic phosphine of alcohol per ton, the cost of producing the organic phosphine that pure product per ton consumes increases.
The objective of the invention is to avoid the weak point of above-mentioned prior art and provide a kind of many ring phosphorus heterocycle organic phosphine coordination bodies and transient metal complex particularly with the olefin hydroformylation catalyst for preparing alcohol of cobalt formation; should encircle phosphorus heterocycle organic phosphine coordination bodies more; not only make catalyst have as far as possible little volume; reduced spatial obstacle; improved reaction speed; and making catalyst have active preferably and preferable heat endurance, this catalyst ligand also has higher boiling point simultaneously.
Another object of the present invention is, this Preparation of catalysts method is provided, and makes catalyst have lower preparation cost.
Purpose of the present invention can realize by the compound with following general structure (I):
Wherein L is many ring phosphorus heterocycle organic phosphine coordination bodies, and M is a transition metal atoms, and the general structure of ligand L is:
R is multi-ring alkyl or thiazolinyl, is generally dicyclo or three rings, and R ' is alkyl, aromatic radical or cycloalkyl, also can be thiazolinyl.
This phosphine ligand is actually phosphine (PH
3) three results that H is replaced by alkyl respectively.The phosphorus atoms of ligand and alkyl form three chemical bonds, wherein have at least two keys simultaneously with a multi-ring alkyl or thiazolinyl in two carbon atoms become key respectively, these two carbon atoms can also can be generally the secondary carbon atom from different rings from the same ring of polycyclic hydrocarbon.Another key of phosphorus and another hydro carbons substituent R ' link, thus form (formation) phosphine (phosphorus) Hete rocyclic derivatives.
The R=P part of above-mentioned ligand is actually the phosphorus heterocycle of being made up of the ring more than three, 3～5 of number of rings, and the atomicity of each ring is greater than 4, and less than 9, the most common person is a five-membered ring.The carbon number of R ' less than 30, is generally 10～25 greater than 4.
The total carbon atom number order of ligand is 16～50, is generally 20～35.
Above-mentioned activity of such catalysts central metal M can be selected from transition metal, for example Co, Rh, Ir, Ni, Pd, Pt etc., wherein preferably Co, Rh, preferably Co.When the preparation catalyst, consider the convenience of enforcement, when the preparation catalyst, generally select the compound of transition metal for use, for example: Co
2(CO)
8, Co
3C
4, Co
2(CO
3)
3, cobalt naphthenate or all kinds of carboxylic acid cobalts etc., or the above-claimed cpd of rhodium.
The Preparation of catalysts process is that the above-mentioned phosphine ligand of preparation is made catalyst by phosphine ligand and the reaction of above-mentioned transistion metal compound then earlier.The key of preparation catalyst is the synthetic of phosphine coordination.
The preparation of ligand was divided into for two steps usually to be carried out, and at first synthetic one replaces or dibasic hydrogeneous organic phosphine, and the second step regeneration three replaces tertiary phosphines.Above-mentioned reaction all can be carried out under free radical causes.The raw material of preparation phosphine ligand substituent R and R ', R can be selected many ring diolefins or alkatrienes for use, and preferably non-conjugated alkene, R ' are generally alkene or substituent linear alkene is arranged.
The ligand of obvious said structure (II), this body structure are complicated, are the phosphine (phosphorus) of ring more than heterocycles, and preparing in the above-mentioned ligand process with many ring diolefins or alkatrienes, also may form more isomers, make the present invention difficult to narrate.Consider the convenience of narration and should be readily appreciated that the present invention that the present invention is to the name of above-mentioned organic phosphine coordination body and possible structure is made following agreement and hypothesis is necessary:
1, above-mentioned trisubstituted organic phosphine coordination body, as phosphine (PH
3) derivative name called after: certain base-certain base-phosphine;
2, to phosphine PH
3The situation that replaced by two carbon atoms in the multi-ring alkyl simultaneously of two H, also make following agreement:
(1) cycloalkyl is pressed the systematic nomenclature name;
(2) order of each carbon atom of cycloalkyl being arranged by Arabic numerals according to the cycloalkyl systematic nomenclature, mark the phosphorus atoms possible carbon atom of Cheng Jian simultaneously with this Ah position uncle numeral, and being arranged in above-mentioned each substituent back, the front of phosphine is simultaneously with writing in " () ".
3, above-mentioned each substituting group is pressed the straight chain substituting group, branched straight chain substituting group, the order of many ring substituents is arranged;
For example, by above-mentioned agreement, the organic phosphine coordination body of following structure is named as: octadecyl (1)-dicyclo [2.2.1] heptane base (2,5)-phosphine
What need here further to emphasize is, by carbon atom that above-mentioned agreement marked and multi-ring alkyl phosphorus atoms while Cheng Jian, only be a kind of possibility structure or the one-tenth key situation of this phosphine ligand, because, when synthesizing phosphine ligand with many ring diolefins or alkatrienes, multiple isomers may appear, so, the public is understanding when of the present invention, should be not only in the possible structure that oneself is confined to the phosphine ligand that this specification proposed.Obviously, if necessary, can also exemplify out many kinds of isomers in this specification.
In be pressed into gas (H
2+ CO) exist down, can generate the transition-metal-carbonyl-complexes catalyst (I) of organic phosphine coordination by above-mentioned phosphine ligand L and above-mentioned transistion metal compound.The transition metal compound catalizer of this organic phosphine coordination body both can original position generate in reactor, also can press in synthesis gas under the protection and make catalyst.In be pressed under the gas condition, this catalyst input is contained in the solution of toluene, normal heptane or isooctanol of alkene, the hydroformylation reaction of alkene promptly takes place.
Purpose of the present invention can also realize by following measure:
The source of catalyst phosphine ligand phosphorus is PCl
3Or PH
3Adopt PCl
3The time with Grignard and reducing process.
The another kind of reaction reagent of synthetic above-mentioned phosphine ligand L is for containing the polycyclic olefin of two two keys at least, and comparatively ideal polycyclic olefin is the diolefin or the alkatrienes of five-membered ring or hexatomic ring, for example following many ring diolefins or alkatrienes
Three ring [4.2.2.0
2.5] decyl-3,7, the 9-triolefin
R wherein
1, R
2, R
3, R
4Be H or C
1～C
4Alkyl or Ph etc.
With above-mentioned PH
3During with the synthetic ligand of above-mentioned many rings diolefin or alkatrienes and alkene, at first synthetic one replaces or dibasic hydrogeneous organic phosphine, and further reaction generates three and replaces tertiary phosphines then.Two-step reaction all can carry out under free radical causes, and initator can adopt low form, middle warm type or high temperature modification, perhaps causes with ultraviolet light, and what wherein be suitable for is the low form initator.When adopting the low form initator, the selectivity of product increases, and in adopting when warm type or high temperature modification initator, then can shorten the required time of reaction.
When adopting different many rings diolefins or alkatrienes, the reaction condition that generates tertiary phosphine is different, and what have need be than exacting terms, as higher reaction pressure or reaction temperature or long reaction time.
It is favourable to increasing reaction yield to improve pressure, and suitable pressure limit is 1.0～10.0MPa.Reaction temperature becomes with selected initator, is generally 20 ℃～170 ℃.
The concrete preparation method of catalyst phosphine ligand of the present invention is as follows:
To encircle diolefin (or alkatrienes) and initator more and add in the reactor, (freezing down at dry ice) adds solvent again, directly changes three times with high purity nitrogen, removes the oxygen in the still.Reacting used initator generally has: azodiisobutyronitrile, tert-butyl hydroperoxide benzoyl etc., solvent for use generally has: pentane, n-hexane, toluene, n-dodecane etc.
Add PH then
3, water-soluble intensification and stirring make PH
3Or with the reaction of many rings diolefin or alkatrienes, reaction temperature is 65～75 ℃, reaction pressure is 1.0～10.0MPa, 1～15 hour reaction time.
Above-mentioned reaction is cooled to room temperature after finishing, and discharges unreacted PH
3Gas is evacuated to 10～0.1mmHg, obtains reactant.And then add straight chain or the solution of substituent linear alkene and initator is arranged,, heat up and stir to being depressed into 0.5～5.0MPa with high purity nitrogen, and 60～170 ℃ of reactions 5～50 hours.
Under 3～0.1mmHg condition, distill out impurity and unreacted reactant, can obtain required phosphine ligand.
Above-mentioned many rings diolefin or alkatrienes with PH
3During reaction, generally all there is isomers to generate.Therefore, may comprise several isomers with above-mentioned raw materials and the synthetic phosphine ligand of method, but this does not influence the catalytic performance of this catalyst.
The phosphine ligand that makes as stated above, when the naming method name of the phosphine ligand of arranging by the present invention, become the position of key carbon atom in phosphorus and the multi-ring alkyl, mark with Arabic numerals, if from the raw material of synthetic phosphine ligand-encircle diolefin or alkatrienes more, the position of the one-tenth key carbon atom that Ah position uncle numeral marks in the above-mentioned agreement is actually with the digital many rings diolefin that marks of Ah position uncle or the position of double bond of alkatrienes.Therefore, agreement and the hypothesis that the name and the possible structure of organophosphite ligand position body are made above is be the structure of sure phosphine ligand.Not equal to be to help us to understand the present invention better.
By above-mentioned raw material and synthetic method, can obtain following phosphine ligand:
Octadecyl-dicyclo [2.2.1] heptane base (2,5)-phosphine
Cetyl-dicyclo [2.2.1] heptane base (2,5)-phosphine
Eicosyl-dicyclo [2.2.1] heptane base (2,5)-phosphine
Octadecyl-dicyclo [3.2.1] octyl (2,6)-phosphine
Myristyl-dicyclo [3.2.1] octyl (2,6)-phosphine
Cetyl-dicyclo [3.2.1] octyl (2,6)-phosphine
Octadecyl-three ring [5.2.1.0
2,6] decyl (3,8)-phosphine
Cetyl-three ring [4.4.0.0
1,4] decyl (2,5)-phosphine
Eicosyl-three ring [4.2.1.1
2,5] decyl (3,7)-phosphine
Octadecyl-three ring [6.2.1.0
2.7] undecyl (4,9)-phosphine
Octadecyl-three ring [4.2.2.0
2,5] decyl-9-alkene (3,7)-phosphine
To each above-mentioned ligand, say in a sense, respectively with following various express possibility more appropriate:
C
nH
2n+1-P=C
7H
10(dicyclo [2.2.1] heptane base)
C
nH
2n+1-P=C
8H
12(dicyclo [3.2.1] octyl)
C
nH
2n+1-P=C
10H
14(three ring [5.2.1.0
2,6] decyl)
C
nH
2n+1-P=C
10H
14(three ring [4.4.0.0
1,4] decyl)
C
nH
2n+1-P=C
10H
14(three ring [4.2.1.1
2,5] decyl)
C
nH
2n+1-P=C
11H
16(three ring [6.2.1.0
2,7] undecyl)
C
nH
2n+1-P=C
10H
13(three ring [4.2.2.0
2,5] decyl-9-alkene)
Wherein n is 4～30, is generally 10～25, is 16～22 preferably.
C
nH
2n+1Alkyl also can be by aromatic radical, and alcyl replaces, promptly
C
1-（CH
2）
n-P＝C
7H
10
C
1-（CH
2）
n-P＝C
8H
12
C
1-（CH
2）
n-P＝C
10H
14
C
1-（CH
2）
n-P＝C
10H
14
C
1-（CH
2）
n-P＝C
10H
14
C
1-（CH
2）
n-P＝C
11H
16
C
1-（CH
2）
n-P＝C
10H
13
Wherein l is 5～6, C
1Be phenyl ring or alicyclic ring, n is 1～4.
With above-mentioned various phosphine ligands,, can make this catalyst with the transistion metal compound reaction.
In reactor, when synthesis gas pressure is 0.5MPa, the compound of phosphine ligand and cobalt, for example: Co
2(CO)
8, Co
3O
4, Co
2(CO
3)
3, cobalt naphthenate or all kinds of carbonyl acid cobalt etc. reacts in solution such as isooctanol or normal heptane, generates catalyst, and following absworption peak appears in its in-situ ft-ir:
2045cm
-12010cm
-11985cm
-11970cm
-11950cm
-1
1930cm
-11900cm
-1
Under the hydroformylation reaction condition, component main in the reactant liquor is:
Co
2（CO）
6L
2[Co（CO）
4]
-Co
2（CO）
7L HCo（CO）
2L
2HCo（CO）
3L
Wherein: L is a phosphine ligand, HCo(CO)
3L and [Co(CO)
4] be the catalyst activity species.
Above-mentioned catalyst with preparation method's preparation of the present invention can be used for C
= 5～C
= 18Hydroformylation reaction.Table 1 has been listed two kinds of catalyst of the present invention and has been aligned laurylene-(1) and carry out the result of hydroformylation reaction, has also listed file names with the result of prior art, so that relatively.
The hydroformylation reaction of table 1, positive laurylene
A B C D
Catalyst source BP1,109,787 US.3,527818 this patent this patents
Cobalt concentration (% weight) 0.2 0.2 0.2 0.2
The P/Co(mole) 2222
Phosphine part * 1234
H
2/CO 2 2.1 2 2
The KOH/CO(mole) 0.75 0.75 0.75 0.75
Reaction temperature (℃) 183～185 182～184 180 ± 5 180 ± 5
Reaction pressure (MPa) 8.2 8.2 6.0 ± 0.5 6.0 ± 0.5
Reaction time (hour) 6.0 4.9 3.5 6.0
Positive laurylene 99.0 99.4 99.0 99.0
Conversion ratio (%)
Alkane production rate 14.3 12.1 11.0 14.0
(% mole)
Primary alconol production rate 84.7 87.2 88.0 85.0
(% mole)
* 1.9-eicosyl-9-phosphine bicyclic nonane tertiary phosphine
2. two-the 9-phosphine-bicyclic nonane octane two tertiary phosphines
3. octadecyl-dicyclo [2.2.1] heptane base (2,5)-phosphine and mixture of isomers thereof
4. octadecyl-three encircles [5.2.1.0
2,6] decyl (3,8)-phosphine and mixture of isomers thereof
Table 1 is the result show: by octadecyl-dicyclo [2.2.1] heptane base (2,5)-the cobalt carbonyl-complexes catalyst of phosphine ligand coordination compares with the catalyst of dicyclo phosphine coordination, it is fast to have reaction speed, the advantage that reaction time is short helps reducing the volume of reactor and improves reactor production capacity.
Be further narration the present invention, the present invention proposes following embodiment.Obviously embodiments of the present invention are not limited to following embodiment.
Example 1.
Get dicyclo [2.2.1] the heptane base-2 that 10 grams (about 10ml) newly distill out, 5-diene (being norbornadiene, 86 ℃ of boiling points) and 1 gram azodiisobutyronitrile add in the stirring autoclave of 0.3 liter capacity.Four interfaces of autoclave press bullet, high pure nitrogen bottle, bottom insert canal and blow-down pipe to link to each other with PH3 respectively.Under the dry ice freezing conditions, add the 50ml pentane, use high-purity N
2Replace three times, remove the oxygen in the autoclave.Then, at room temperature suppress PH into 3.8MPa by pressure
3, warming-in-water also stirs, and the control reaction temperature is in 65～75 ℃ of scopes, and the reaction time is 5 hours.Be cooled to room temperature, discharge unreacted PH
3Gas is evacuated to 20mmHg pressure, obtains HPC
7H
10Compound.Then, be pressed into the mixed solution that contains 20 gram octadecylene-(1) and 1 gram azo dibutyronitrile and 50ml pentane, boost to 1.0MPa with high purity nitrogen after, heat up stirring also constant temperature kept 12 hours at 70 ± 5 ℃.Keep condition of negative pressure, distill out boiling range, obtain C at the unreacted reactant below 160 ℃ and other impurity
18H
37PC
7H
10Deng 12 grams, i.e. octadecyl-dicyclo [2.2.1] heptane base (2,5)-phosphine and isomer mixture thereof etc., productive rate thing 75%(mol).
The results of elemental analyses of above-mentioned ligand is as follows:
Element theory value (wt) measured value (wt)
P 0.082 0.088
C 0.793 0.802
H 0.125 0.120
Get the C for preparing above
18H
37PC
7H
104.26 gram and 0.66 gram Co
2(CO)
8Be dissolved in altogether in the 150ml 2-Ethylhexyl Alcohol, under vacuum, add in 0.5 liter of stainless steel hot pressing still of charged magnetic stirring.Find time to outgas and use H
2/ CO mol ratio is 2 synthesis gas displacement three times, to drive away the oxygen in the autoclave.Be pressurized to 1.0MPa with synthesis gas again, stir, intensification and constant temperature are at 170 ± 5 ℃, and the still internal pressure increases this moment, is pressurized to 2.5MPa with synthesis gas again, keeps 1 hour.Detect catalyst solution with in-situ ft-ir simultaneously, as the characteristic absorption 2045cm of catalyst activity species
-1After the value of reaching capacity, confirm that Preparation of Catalyst finishes.
With the catalyst that said method makes, its activity is estimated in available laurylene～(1).Evaluation method is: suppress into 60 gram laurylene-(1) with pressing, reaction pressure keeps 5.0MPa, reaction temperature is kept 95～105 ℃, reacted 3.5 hours, to drop into laurylene-(1) serves as to calculate benchmark, the total recovery of products of oxo synthesis is 88%(mol), wherein the content of positive structure tridecanol is 83%.
Example 2
With three ring [5.2.1.0
2,6] decyl-3,8-diene (double focusing cyclopentadiene) replaces dicyclo [2.2.1] heptane base-2,5-diene (mol ratio is constant).Reaction condition is identical with example 1 with method of operating, can make ligand octadecyl-three ring [5.2..1.0
2,6] decyl (3,8)-phosphine (C
18H
37PC
10H
14) several isomer mixtures.
Get the C that produces above
18H
37PC
10H
145.14 gram and cobalt octoate 0.88 gram are dissolved in the 150ml2-ethyl hexanol.Use then with example 1 similar methods and make hydroformylation catalyst.
Estimate above-mentioned catalyst with laurylene-(1).Drop into 60 gram laurylene-(1), with the synthesis gas pressurising and keep 6.0MPa pressure, constant temperature (180 ± 5 ℃) reacted 6 hours.With laurylene-(1) of dropping into serves as to calculate benchmark, and carbonyl closes the total recovery 85%(mol of product), wherein the content of positive structure tridecanol is 82%.
Example 3
Method with being similar to example 1 and example 2 also can make following phosphine ligand:
Octadecyl-dicyclo [3.2.1] octyl (2,6)-phosphine and isomer mixture etc., that is: C
18H
37-P=C
8H
12
Cetyl-three ring [6.2.1.0
2,7] hendecane (4,9)-phosphine and isomer mixture etc., that is:
C
16H
33-P＝C
11H
16
Octadecyl-three ring [4.2.1.12,5] decyls (3,7)-phosphine and isomer mixture etc., that is:
C
18H
37-P＝C
10H
14
Example 4
Adopt the preparation method of example 1 or example 2, will make ligand in above-mentioned each example, and Co
2(CO)
8, Co
3O
4, Co
2(CO
3)
3, reactions such as cobalt naphthenate or all kinds of carbonyl acid cobalt just can make various hydroformylation reaction catalyst.
Claims (10)
1, catalyst for preparing alcohol from olefin is made of phosphorus heterocycle organic phosphine compound and transient metal complex coordination, and its structure is:
It is characterized in that ligand L has following structure:
Wherein: (1) R is the alkyl or the thiazolinyl of dicyclo or three rings, the phosphorus heterocycle that R-P constitutes, and 3～5 of number of rings, the atomicity of each ring less than 9, are generally 5 or 6 greater than 4;
(2) R ' is alkyl, aromatic radical or cycloalkyl (alcyl), and its carbon number less than 30, is generally 10～25 greater than 4;
(3) total carbon atom number of ligand L is 17～45, is generally 20～35.
2, catalyst as claimed in claim 1 is characterized in that, the catalyst ligand is:
C
nH
2n+1-P＝C
7H
10
C
1-（CH
2）
m-P＝C
7H
10
Wherein: n is 14～22, and m is 1～4, and l is 5～6, C
7H
10Be dicyclo [2.2.1] octane, C
1Be phenyl ring or alicyclic ring.
3, catalyst as claimed in claim 1 is characterized in that, the catalyst ligand is:
C
nH
2n+1-P＝C
8H
12
C
1-（CH
2）
m-P＝C
8H
12
Wherein: n is 14～22, and m is 1～4, and l is 5～6, C
8H
12Be dicyclo [3.2.1] heptane, C
1Be phenyl ring or alicyclic ring.
4, catalyst as claimed in claim 1 is characterized in that, the catalyst ligand is:
C
nH
2n+1-P＝C
10H
14
C
1-（CH
2）
m-P＝C
10H
14
Wherein: n is 14～22, and m is 1～4, and l is 5～6, C
10H
14Be three ring [5.2.1.0
2.6] decane, C
1Be phenyl ring or alicyclic ring.
5, catalyst as claimed in claim 1 is characterized in that, the catalyst ligand is:
C
nH
2n+1-P＝C
11H
16
C
1-（CH
2）
m-P＝C
11H
16
Wherein: n is 14～22, and m is 1～4, and l is 5～6, C
11H
16Be three ring [6.2.1.0
2.7] hendecane, C
1Be phenyl ring or alicyclic ring.
6, catalyst as claimed in claim 1 is characterized in that, the catalyst ligand is:
C
nH
2n+1-P＝C
10H
14
C
1-（CH
2）
m-P＝C
10H
14
Wherein: n is 14～22, and m is 1～4, and l is 5～6, C
10H
14Be three ring [4.2.1.1
2.5] decane, C
1Be phenyl ring or alicyclic ring.
7, catalyst as claimed in claim 1 is characterized in that, the catalyst ligand is:
C
nH
2n+1-P＝C
9H
14
C
1-（CH
2）
m-P＝C
9H
14
Wherein: n is 14～22, and m is 1～4, and l is 5～6, C
9H
14Be dicyclo [3.3.0], C
1Be phenyl ring or alicyclic ring.
8, catalyst as claimed in claim 1 is characterized in that, the catalyst ligand is:
C
nH
2n+1-P＝C
10H
13
C
nH
2n+1-P＝C
10H
14
Wherein: n is 14～22, C
10H
13Be three ring [4.2.2.0
2.5] decyl-3-alkene, C
10H
14Be three rings [three ring [4.2.2.0
2.5] decane.
9, the preparation method of catalyst for preparing alcohol from olefin comprises:
(1) in the presence of initator, in solvent, by cycloolefin and PH
3Reaction;
(2) in the presence of initator, in solvent, above-mentioned reactant again with;
(3) organic tertiary phosphine of above-mentioned reactant and transistion metal compound reaction,
It is characterized in that:
(1) cycloolefin is the diolefin or the alkatrienes of dicyclo or three rings;
(2) during the organic tertiary phosphine of preparation, PH
3Be respectively with reaction temperature, reaction pressure and the reaction time of many rings diolefin and alkene:
20～170 ℃, 1.0～10.0MPa, 1～15 hour and 60～170 ℃, 0.5～5.0MPa and 5～50 hours.
(3) reaction temperature, reaction pressure and the reaction time of preparation catalyst are:
120 ℃～175 ℃, 0.5～5.0MPa and infrared in position on 2045cm appears
-1Saturated absorption.
10, method for preparing catalyst as claimed in claim 11 is characterized in that, used initator is an azodiisobutyronitrile, and the solvent of selecting for use is a pentane, encircles diolefin more and is: dicyclo [2.2.1] octyl-2,5-diene or three ring [5.2.1.0
2.6] decyl-3, reaction temperature, reaction pressure and reaction time that the 8-diene prepares organic tertiary phosphine are respectively: 65～75 ℃, 3.8～5.0MPa, 5～10 hours and 65～75 ℃, 1.0～1.5MPa, 12～15 hours; Reaction temperature, reaction pressure and the reaction time of preparation catalyst are: 165～175 ℃, and 2.5～3.0MPa and 1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88108971 CN1020680C (en) | 1988-12-26 | 1988-12-26 | Catalyst for preparing alcohol from olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88108971 CN1020680C (en) | 1988-12-26 | 1988-12-26 | Catalyst for preparing alcohol from olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1043640A true CN1043640A (en) | 1990-07-11 |
| CN1020680C CN1020680C (en) | 1993-05-19 |
Family
ID=4835278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88108971 Expired - Fee Related CN1020680C (en) | 1988-12-26 | 1988-12-26 | Catalyst for preparing alcohol from olefin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020680C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060412C (en) * | 1997-10-24 | 2001-01-10 | 中国石油化工总公司 | Phosphine ligand with temp. controlled phase transfer function, and application thereof |
| WO2015085506A1 (en) * | 2013-12-11 | 2015-06-18 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst used for olefin hydroformylation reaction, preparation method and use thereof |
| WO2015085503A1 (en) * | 2013-12-11 | 2015-06-18 | 中国科学院大连化学物理研究所 | Method for olefin hydroformylation reaction using solid heterogeneous catalyst |
| CN108126717A (en) * | 2017-12-10 | 2018-06-08 | 江苏师范大学 | A kind of preparation method of olefin hydroformylation porous rare earth catalyst |
| CN109985667A (en) * | 2017-12-29 | 2019-07-09 | 内蒙古伊泰煤基新材料研究院有限公司 | The device and method for preparing organophosphine ligand catalyst online |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048657C (en) * | 1994-12-29 | 2000-01-26 | 中国科学院兰州化学物理研究所 | Catalyst or prepn. of alcohol by hydrogen formylation of olefines |
-
1988
- 1988-12-26 CN CN 88108971 patent/CN1020680C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060412C (en) * | 1997-10-24 | 2001-01-10 | 中国石油化工总公司 | Phosphine ligand with temp. controlled phase transfer function, and application thereof |
| WO2015085506A1 (en) * | 2013-12-11 | 2015-06-18 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst used for olefin hydroformylation reaction, preparation method and use thereof |
| WO2015085503A1 (en) * | 2013-12-11 | 2015-06-18 | 中国科学院大连化学物理研究所 | Method for olefin hydroformylation reaction using solid heterogeneous catalyst |
| US9586197B2 (en) | 2013-12-11 | 2017-03-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Solid heterogeneous catalyst for olefin hydroformylation reaction and production method and use thereof |
| US9611203B2 (en) | 2013-12-11 | 2017-04-04 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for olefin hydroformylation reaction using solid heterogeneous catalyst |
| CN108126717A (en) * | 2017-12-10 | 2018-06-08 | 江苏师范大学 | A kind of preparation method of olefin hydroformylation porous rare earth catalyst |
| CN109985667A (en) * | 2017-12-29 | 2019-07-09 | 内蒙古伊泰煤基新材料研究院有限公司 | The device and method for preparing organophosphine ligand catalyst online |
| CN109985667B (en) * | 2017-12-29 | 2024-03-26 | 内蒙古伊泰煤基新材料研究院有限公司 | Device and method for preparing organic phosphine ligand catalyst on line |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1020680C (en) | 1993-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1020448C (en) | Diethers usable in preparation of zieglernatta catalysts | |
| CN1291996C (en) | Ruthenium complexes as (pre)catalysts for metathesis reactions | |
| CN1230406C (en) | Multi-stage preparation process of carbonyl synthesizing aldehyde and/or alcohol | |
| CN1068307C (en) | Catalyzed vapor phase hydrocyanation of diolefinic compounds | |
| CN1233648C (en) | Chiral salen catalyst and methods for prepn. of chirol compounds from racemic epoxides by using new catalyst | |
| CN1527834A (en) | Method for producing diphosphines and the use thereof | |
| CN1131850C (en) | Process to prepare terminal aldehyde | |
| CN1636950A (en) | Process for the preparation of TCD-alcohol DM | |
| CN1056865A (en) | Be used to produce 1, the catalyzer of 3-glycol and/or 3-hydroxy aldehyde and preparation method and application thereof | |
| CN1228404A (en) | Preparation of propene and, if desired, 1-butene | |
| CN1890203A (en) | Method for producing tricyclodecandialdehyde | |
| CN1303049C (en) | Process for producing isononyl aldehyde from mixed octene and synthetic gas | |
| CN1020680C (en) | Catalyst for preparing alcohol from olefin | |
| CN1636955A (en) | Process for the preparation of TCD-dialdehyde | |
| CN1064344C (en) | Process for producing N-butyraldehyde and/or N-butanol | |
| CN1071302C (en) | Process to prepare 5-formylvaleric acid | |
| CN1124468A (en) | New method and catalysts on inorganic carriers for converting C1-C4 Hydrocarbons to C2-olefinic hydrocarbons | |
| CN1027631C (en) | Process for decomposition of methanol | |
| CN1162221C (en) | Catalyst containing complex of group VIII metal, and hydroformylation process | |
| CN1069960A (en) | The preparation method of alcohols | |
| CN1319917C (en) | Method of 1-hexene one-step synthesizing straight chain olefin hydrocarbon and catalyst | |
| CN1123557C (en) | Process for synthesizing aldehyde from olefine, CO and hydrogen | |
| CN1071159A (en) | Produce the method for hexanodioic acid by the hydrogenation carboxylation of pentenoic acid | |
| CN1150152C (en) | Acetals, their preparation and their use | |
| CN1048657C (en) | Catalyst or prepn. of alcohol by hydrogen formylation of olefines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |