CN1048657C - Catalyst or prepn. of alcohol by hydrogen formylation of olefines - Google Patents
Catalyst or prepn. of alcohol by hydrogen formylation of olefines Download PDFInfo
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- CN1048657C CN1048657C CN94119949A CN94119949A CN1048657C CN 1048657 C CN1048657 C CN 1048657C CN 94119949 A CN94119949 A CN 94119949A CN 94119949 A CN94119949 A CN 94119949A CN 1048657 C CN1048657 C CN 1048657C
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Abstract
The present invention relates to a catalyst for preparing fatty alcohol by olefin one-step carbonyl synthesis, which is prepared from organic phosphine ligand and transitional metal by coordination, wherein the ligand is in the structure: R=P-R'; R is polycyclic alkyl or alkenyl and is generally bicyclic or tricyclic; R' is alcohol, ketone, carboxylic acid and ester and is generally derivatives of C2 to C30 at least containing a carboxy group, a ketone group, an aldehyde group and an ester substituting group. The catalyst prepared from the ligand and the transitional metal by coordination can be used as the catalyst for preparing fatty alcohol by olefin one-step hydroformylation and be especially suitable for one-step primary alcohol preparation from various kinds of internal olefin.
Description
The present invention relates to the catalyzer of a kind of alkene and carbon monoxide and H-H reaction system Fatty Alcohol(C12-C14 and C12-C18); catalyzer 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 catalyzer that generates of Co, Rh particularly; not only can be used as the catalyzer of olefin hydroformylation generation Fatty Alcohol(C12-C14 and C12-C18), be particularly suitable for the direct step manufacturing of internal olefin 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 atom 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 catalyzer.
To cobalt cobalt-based composition catalyst, more effective organic phosphine coordination body is a tributylphosphine.Through the cobalt carboxyl complex catalyzer of tributylphosphine modification, when being used for making alcohol by alkene and carbon monoxide and hydroformylation step reaction, though have active preferably, have in the boiling point of tributylphosphine lower, when being used to prepare the higher higher alcohols of boiling point, as C
12Above alcohol, in catalyzer and product separation process, the loss of tributylphosphine is more, causes the production cost of alcohol to raise.
In order to improve this class phosphine coordinate boiling point, people once adopted the alkyl tert phosphine ligand of macromolecule, for example: u.s.3,448,157; U.s.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 conditions, the dynamic structure easily of catalyzer 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 catalyzer, lose more than gain from increasing catalyzer ligand molecular weight.
At BP1, a kind of catalyzer of alkene oxo process system primary alconol is disclosed in 109,787.Its objective is when improving catalyzer phosphine ligand boiling point and do not reduce activity of such catalysts, to be suitable for preparing higher alcohols.The phosphine ligand of this catalyzer is actually the dicyclo organic phosphine, that is: the thermostability of phosphine ligand is not very good, decomposes when surpassing 200 ℃; This catalyst hydrogenation performance strong and to the double-bond isomerization ability a little less than, be used for internal olefin feed, n-alkanol content is not high in the product.Under empty temperature, be solid, bring inconvenience during use; Cost in order to the monocycle diolefin of preparation dicyclo phosphine is higher, causes the price of catalyzer more expensive.
U.s.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.In the hydroformylation process, generate catalyst precipitation easily, be an impediment to the conveying of pump.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.
Chinese patent 88108971.0,89100610.9 provide a kind of many ring phosphorus heterocycle organic phosphine coordination bodies and transition metal complex particularly with the alkene oxygen formylation catalyst for preparing alcohol of cobalt formation; should encircle phosphorus heterocycle organic phosphine coordination bodies more; not only make catalyzer have as far as possible little volume; reduced spatial obstacle; improved speed of response; and making catalyzer have active preferably and preferable thermostability, this catalyzer ligand also has higher boiling point simultaneously.Yet still there be the deficiency more weak to the double-bond isomerization ability.
The objective of the invention is, novel organic phosphine coordination body and olefin hydroformylation Preparation of catalysts method thereof is provided, make this catalyzer have double-bond isomerization performance and lower preparation cost preferably.
Purpose of the present invention can realize by the compound with following general structure (I):
Wherein L is novel organic phosphine coordination body, and the general structure of ligand L is:
R is dicyclo or multi-ring alkyl or thiazolinyl, is generally dicyclo or three rings, and R ' is for containing a hydroxyl or acyl group or substituent alkyl such as ester group or carboxyl at least.
This phosphine ligand is actually phosphine (PH
3) three H be substituted the result that the carbon atom of base replaces respectively.The phosphorus atom of ligand and substituting group 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 polynuclear hydrocarbon.Another key of phosphorus and another alcohol or copper or ester or carboxylic acid substituent R ' link to each other, thereby form (formation) phosphine (phosphorus) heterocyclic alcohol or copper or ester or carboxylic acid derivative.
The R=P part of above-mentioned ligand is actually the phosphorus heterocycle of being made up of plural ring, 2～5 of number of rings, and the carbonatoms of each ring is greater than 4, and less than 9, and the most common person is five or six-ring.The carbonatoms of R ' less than 30, is generally 20～35 greater than 4.And contain a Sauerstoffatom at least.
The total carbon atom number order of ligand is 16～50, is generally 20～35.
Above-mentioned activity of such catalysts center cobalt when the preparation catalyzer, is considered and is implemented conveniently generally to select the compound of transition metal for use, for example: Co
2(CO)
3, Co
3O
4, Co
2(CO
3)
3, cobalt naphthenate or all kinds of carboxylic acid cobalts etc.
The Preparation of catalysts process is that the above-mentioned phosphine ligand of preparation is made catalyzer by phosphine ligand and the reaction of above-mentioned transistion metal compound then earlier.The key of preparation catalyzer is the synthetic of phosphine ligand.
The preparation of ligand was divided into for two steps usually to be carried out, and at first much synthetic ring contains the organic secondary phosphine of oxygen, and the second step regeneration three replaces the derivative of alcohol, ketone, ester or the acid of 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 and contain substituent normal olefine.
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 isomer.The present invention is identical with patent 88108971.0 to the name of above-mentioned organic phosphine coordination body.
In be pressed into gas (H
2+ CO) exist down, can generate the transition-metal-carbonyl-complexes catalyzer (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.In be pressed under the gas condition, this catalyzer input is contained in the solution of toluene, normal heptane or the isooctyl alcohol of alkene or higher alcohols, the hydroformylation reaction of alkene promptly takes place.
Purpose of the present invention can also realize by following measure:
The source of catalyzer phosphine ligand phosphorus is PCl
3Or PCl
3Adopt PCl
3The time with Grignard and reduction method.
A 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-ring or six-ring, for example following many ring diolefins or alkatrienes.
Along [1,5]-cyclooctadiene
Anti-[1,5]-cyclooctadiene
Three rings [5,2,1,0
2,6] decyl-3, the 8-diene
Three rings [6,2,1,0
2,7] undecyl-4, the 9-diene
Three rings [4,2,2,0
2,5] decyl-3,7, the 9-triolefin
R wherein
1, R
2, R
3Be H or C
1～C
4Alkyl or Ph etc.
The another kind of raw material of synthetic above-mentioned ligand L is actually and contains a following substituent alkenes compounds at least.As hydroxyl, ketone group, ester group or carboxyl and can be converted into the substituting group of above-mentioned group, as halogen, itrile group, aldehyde radical.Usually end position alkenyl compound is faster than internal olefin speed of response; The straight chain derivative is than the synthetic yield height of branched derivative; Contain the product purity height of the derivative of unconjugated double bond than the derivative gained that contains conjugated double bond; The carbonatoms of this compound is 1～30, is generally 3～20 carbon atoms.Exemplify as follows as the raw material olefin derivative:
Vinylformic acid and ester class thereof, methacrylic ester, vinyl acetate between to for plastic and ester class thereof, propenyl chloride, vinylcarbinol and ester class thereof, methylene acetone, pentenone, Sulcatone, undecylenic acid and ester thereof or salt, oleic acid, linolic acid, fatty acids such as linolenic acid and timnodonic acid.
With above-mentioned PH
3During with the synthetic ligand of above-mentioned many rings diolefin or alkatrienes, 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 initiator can adopt low temperature modification, middle warm type or high temperature modification, perhaps causes with UV-light, and what wherein be suitable for is the low temperature modification initiator.When adopting the low temperature modification initiator, the selectivity of product increases, and in adopting when warm type or high temperature modification initiator, but required time of institute's short reaction then.
When adopting different many rings diolefins or alkatrienes, the reaction conditions that generates tertiary phosphine is different, and what have need be than exacting terms, as higher reaction pressure or temperature of reaction or long reaction times.
Pressurize is favourable to increasing reaction yield, the pressure range 1.0-10.0MPa that suits.Temperature of reaction becomes with selected initiator, is generally 20～170 ℃.
The concrete preparation method of catalyzer phosphine ligand of the present invention is as follows:
To encircle diolefin (or alkatrienes) and initiator more and add in the reactor, (freezing down at dry ice) adds solvent again, removes the interior oxygen of still with high purity nitrogen.Reacting used initiator generally has: Diisopropyl azodicarboxylate, tert-butyl hydroperoxide benzoyl etc., solvent for use generally has: Skellysolve A, normal hexane, toluene, n-dodecane etc.
Add PH then
3, warming-in-water also stirs, and makes PH
3With many rings diolefin or alkatrienes reaction, temperature of reaction is-10～130 ℃, and reaction pressure is 1.0～10.0MPa, 1～15 hour reaction times.
Above-mentioned reaction is cooled to room temperature after finishing, and discharges the PH of reaction
3Gas is evacuated to 10～0.1mmHg, obtains reactant.And then add the solution that contains substituent alkene and initiator, and be pressurized to 0.5～5.0MPa with high purity nitrogen, heat up and stir, 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 isomer to generate.Therefore may comprise several isomer with above-mentioned raw materials and method synthetic phosphine ligand, but this does not influence the catalytic performance of this catalyzer.
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 phosphine and the multi-ring alkyl, mark with Arabic numerals, if from the raw material that contains into phosphine ligand-encircle diolefin or alkatrienes more, contain alcohol, ketone, acid or the ester of unsaturated double-bond, the position of the one-tenth key carbon atom that Arabic numerals mark in the above-mentioned agreement is actually the many rings diolefin that marks with Arabic numerals 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, 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 a series of phosphine ligands, its part exemplifies as follows:
Undecane-carboxylic acid base-dicyclo [2,2,1] heptane base (2,5)-phosphine 1.
Ethyl acetate base-dicyclo [2,2,1] heptane base (2,5)-phosphine 2.
2-methylheptanone-(2) base-dicyclo [2,2,1] heptane base (2,5)
-phosphine 3.
Undecane-carboxylic acid base-dicyclo [3,3,1] octyl (2,6)-phosphine 4.
Ethyl acetate base-dicyclo [3,3,1] octyl (2,6)-phosphine 5.
2-methylheptanone-(2) base-dicyclo [3,3,1] octyl (2,6)
-phosphine 6.
Above-mentioned six ligands also can be done following name:
But as 4. called after 9-phosphine bicyclic nonane-9-undecane-carboxylic acid
But 5. called after 9-phosphine bicyclic nonane-9-ethyl acetate
But 6. called after 9-phosphine bicyclic nonane-9-2-methylheptane ketone
To each above-mentioned ligand, say in a sense, use following each representative formula may be more appropriate respectively:
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
C
1Be terminal hydroxy group, ethanoyl, first, second, third or the butyl ester base, carboxyl and its esters; N is 1～30.
With above-mentioned various phosphine ligands,, can make this catalyzer with the transistion metal compound reaction.
In reactor, when synthetic 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 cobaltous carbonates etc. react in solution such as isooctyl alcohol or normal heptane, generate catalyzer, and catalyst activity species HCo (CO) appears belonging in its in-situ ft-ir
3The 2045cm of L
-1Absorption peak.
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 is got dicyclo [2,2,1] the heptane base-2 that 10 grams (about 10ml) newly distill out, and 5-diene (being norbornadiene, 86 ℃ of boiling points) and 1 gram Diisopropyl azodicarboxylate add in the stirring autoclave of 0.3 liter capacity.Four interfaces of autoclave respectively with PH
3Press bullet, high pure nitrogen bottle, slotting low pipe and blow-down pipe to link to each other.Under the dry ice freezing conditions, add the 50ml Skellysolve A,, remove the oxygen in the autoclave with high pure nitrogen displacement three times.Then, at room temperature suppress PH into 3.8MPa by pressure
3, warming-in-water also stirs, control reaction temperature in 65～75 ℃ of scopes, 5 hours reaction times.After being cooled to room temperature, discharge unreacted PH
3Gas is evacuated to 20mmHg pressure, obtains HPC
7H
10Compound.Then, be pressed into the mixing solutions that contains 15 gram undecylenic acids and 1 gram Diisopropyl azodicarboxylate and 50mml Skellysolve A, boost to 1.0MPa with high purity nitrogen after, heat up and stir also that 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
12O
2H
25Pc
7H
10Deng 13 grams, i.e. undecane-carboxylic acid base-dicyclo [2,2,1] heptane base (2,5)-phosphine and isomer mixture thereof etc., productive rate 86% (weight).
IR tests γ
c=0 1709.4cm
-1(VS)
P-NMR spectrum-2.4PPm dicyclo [2,2,1] heptane base (2,
6)-phosphine-derivatives
-37.2PPm dicyclo [2,2,1] heptane base
(2,5)-phosphine-derivatives
C-NMR spectrum 178.9PPm (COOH), 34.3PPm
(-CH
2COOH)
29.1PPm(-P-CH
2-)
Example 2 is got the C of example 1 preparation
12H
25O
2PC
7H
104.0 gram and 0.66 gram Co
2(CO)
8Be dissolved in altogether in the 150ml2-ethylhexanol, 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 synthetic gas displacement three times, to drive away the oxygen in the autoclave.Be pressurized to 1.0MPa with synthetic 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 synthetic gas again, keeps 1 hour.Detect catalyst solution with in-situ ft-ir simultaneously, as the characteristic absorbance 2045cm of catalyst activity species
-1After reaching the full value of closing, confirm that Preparation of Catalyst finishes.
With the catalyzer that aforesaid method makes, its catalytic activity is estimated in available laurylene-(1).Evaluation method is: suppress into 60 gram laurylene-(1) with pressing, reaction pressure keeps 5.0MPa, temperature of reaction 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 86% (mol), and wherein the content of positive structure tridecanol is 82%.
Example 3 is with three rings [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 conditions is identical with example 1 with working method, can make ligand undecane-carboxylic acid base-three ring [5,2,1,0
2,6] decyl (3,8)-phosphine-(C
12H
25O
2PC
10H
14) several isomer mixtures.
Get phosphine ligand 4.2 grams and cobalt octoate 0.88 gram produced above, be dissolved in the 150ml 2-Ethylhexyl Alcohol.Use then with example 1 similar methods and make hydroformylation catalyst.
Estimate above-mentioned catalyzer with laurylene-(1).Drop into 60 gram laurylene-(1), with the synthetic 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, the total recovery 84% (mol) of products of oxo synthesis, and wherein the content of positive structure tridecanol is 83%.
Example 4 is in the 100ml three neck round-bottomed flasks that reflux condensing tube and constant pressure funnel are housed; under high purity nitrogen protection; add 8.6 gram 9-phosphine bicyclic nonanes; 16 milliliters of undecane-carboxylic acids and 20 milliliters of toluene; under 70～75 ℃ of agitation conditions; dropping contains 15 milliliters of the toluene solutions of 0.5 gram 2,2'-Azobis(2,4-dimethylvaleronitrile), dropwises to continue reaction 3 hours.After normal pressure steamed volatile matters such as toluene, underpressure distillation went out unreacted C
3H
14PH and undecane-carboxylic acid (136～140 ℃/0.5mmHg), flaxen product is at room temperature separated out solid.Obtain clear crystal with the refining crude product of chloroform.39～40 ℃ of fusing points, ultimate analysis C
19H
35O
2P measured value (%) C:69.55, H:10.88; Calculated value (%) C:69.90, H; 10.81.Analyze through IR and NMR, record product C
19H
35O
2Be the mixture of [4,2,1]-9-phosphine bicyclic nonane-9-undecane-carboxylic acid and [3,3,1]-9-phosphine bicyclic nonane-9-undecane-carboxylic acid among the P, the two mol ratio is 74: 26%.
Example 5. adopts method and the catalyst concn and the proportioning of example 2, carries out the reaction of positive laurylene-(1) oxo process system alcohol, makes C
13Alcohol, yield are 86% (mole).
Example 6. adopts method and the catalyst concn and the proportioning of example 2, carries out C
11～C
11One step of mixed olefins (wherein the propylene hydrocarbon content reaches 85% (weight)) oxo process system Fatty Alcohol(C12-C14 and C12-C18), at 6.0 ± 0.5MPa, H
2/ CO=2 (mol) under 180 ± 5 ℃ the reaction conditions, reacted 120 minutes, and olefin conversion can reach 99%, C
12～C
13The Fatty Alcohol(C12-C14 and C12-C18) yield reaches 83% (mol).
Example 7 adopts the method for example 2, catalyst concn and same Co: the proportioning of P solvent, replace 11 carbon carboxylic acid-9-phosphine bicyclic nonane ligand with octadecyl-9-phosphine bicyclic nonane, and be used to estimate C
11～C
12The synthetic step Fatty Alcohol(C12-C14 and C12-C18) of mixed olefins (wherein internal olefin content reaches 85% (weight)) carboxyl under the same reaction conditions of example 6, reacts 180 minutes olefin conversions and reaches 96%, C
12～C
13The Fatty Alcohol(C12-C14 and C12-C18) yield reaches 82% (mol).
Example 8 is being equipped with reflux condensing tube; in 100 milliliters of round-bottomed flasks of constant pressure funnel; under high purity nitrogen protection; add 12.8 gram 9-phosphine bicyclic nonanes; 16 milliliters of vinyl acetate between to for plastics and 20 milliliters of toluene; stirring is warming up to 20 milliliters of the toluene solutions that 70 ℃ of droppings contain 1.4 gram Diisopropyl azodicarboxylates, isothermal reaction 1 hour.Steam unreacted vinyl acetate between to for plastic and toluene under the normal pressure, decompression steams remaining 9-phosphine bicyclic nonane, gets 9-phosphine bicyclic nonane 9-ethyl acetate faint yellow solid 15 grams, 135～138 ℃ of fusing points.Refining back ultimate analysis C
12H
21O
2P measured value (%) C:632, H:9.11; Calculated value (%) C:63.18, H:9.21.
With 9-phosphine bicyclic nonane-9-ethyl acetate ligand and Co
2(CO)
8In toluene solution, at H
2Under+CO synthetic gas the pressure, autoclave made acid-stable in situ CoP catalyzer (cobalt concentration is identical with example 2 with catalyst proportion) carries out laurylene-(1) oxo process system 13 carbon fatty alcohols, yield 76% (mol).
Claims (9)
1. catalyst for preparing alcohol from olefin, its structure is:
It is characterized in that ligand L has following structure:
Wherein: (1) R is dicyclo or trinucleated alkyl or thiazolinyl, the phosphorus heterocycle that R=P constitutes, 3～5 of number of rings, the atomicity of each ring greater than 4 less than 9;
(2) R ' is alcohol, ketone, carboxylic acid and ester group, its carbon subnumber greater than 2 less than 30;
(3) total carbon atom number of ligand L is 15～45.
2. catalyzer as claimed in claim 1 is characterized in that the catalyzer ligand is:
C
1-(CH
2)
m-P＝C
8H
12
Wherein: m is 2～30, C
8H
12Be [3,3,1] and/or [4,2,1] bicyclic nonane, C
1For-COC
nH
2n+2, n is 1～5.
3. catalyzer as claimed in claim 1, the total carbon atom number that it is characterized in that ligand L is 17～35, and the atomicity of R is 5 or 6, and the carbonatoms of R ' is 10～25.
4. catalyzer as claimed in claim 1 is characterized in that: the catalyzer ligand is:
C
1-(CH
2)
m-P＝C
8H
12
Wherein: m is 2～30, C
8H
12Be dicyclo [3,3,1] nonane, C
1For-CH
2OCOC
JH
2J+1, J is 1～4.
5. catalyzer as claimed in claim 1 is characterized in that, the catalyzer ligand is:
C
1-(CH
2)
m-P＝C
8H
12
Wherein: m is 1～30, C
8H
12Be [3,3,1] and/or [4,2,1] bicyclic nonane, C
1For-COOM, M is H or Na, K.
6. catalyzer as claimed in claim 1 is characterized in that, the catalyzer ligand is:
C
1-(CH
2)
m-P＝C
7H
10
Wherein: m is 1～30, C
7H
10Be dicyclo [2,2,1] heptane, C
1Be hydroxyl-OH; Acyl group-C-C
JH
2J+1, J is 1～4;-CH
2OCOC
QH
2Q+1, Q is 1～4; Or-COOM, M is H or Na, K.
7. catalyzer as claimed in claim 1 is characterized in that, the catalyzer ligand is:
C
1-(CH
2)
m-P＝C
10H
14
Wherein: m is 1～30, C
10H
14Be dicyclo [3,3,0] decane, C
1Be hydroxyl-OH; Acyl group-C-C
JH
2J+1, J is 1～4;-CH
2COC
QH
2Q+1, Q is 1～4; Or-COOM, M is H or Na, K.
8. the preparation method of catalyst for preparing alcohol from olefin as claimed in claim 1 comprises:
(1) in the presence of initiator, in solvent, by cycloolefin and PH
3Reaction;
(2) in the presence of initiator, in solvent, above-mentioned reactant again with unsaturated alcohol, ketone, carboxylic acid and ester reaction;
(3) organic tertiary phosphine of above-mentioned reactant and Co
2(CO)
8, Co
3O
4, CO
2(CO
3)
3, the reaction of cobalt naphthenate or all kinds of carboxylic acid cobalt, it is characterized in that:
1. cycloolefin is dicyclo or trinucleated diolefin or alkatrienes;
When 2. preparing organic tertiary phosphine, PH
3Be respectively with temperature of reaction, reaction pressure and the reaction times of many rings diolefin and alkene:
20～170 ℃, 10～10.0MPa, 1～15 hour and 60～170 ℃, 0.5～5.0MPa, 5～50 hours.
3. the temperature of reaction, reaction pressure and the reaction times that prepare catalyzer are:
120～175 ℃, 0.5～5.0MPa and infrared in position on 2045cm appears
-1Saturated absorption.
9. method for preparing catalyst as claimed in claim 8 is characterized in that, used initiator is a Diisopropyl azodicarboxylate, or 2,2'-Azobis(2,4-dimethylvaleronitrile), and the solvent of selecting for use is saturated alkane and aromatic hydrocarbons; Many ring diolefins are: dicyclo [2,2,1] heptane base-2,5-diene or three rings [5,2,1,0
2,6] decyl 3,8-diene or [1,5]-cyclooctadiene; The temperature of reaction, reaction pressure and the reaction times that prepare organic tertiary phosphine are respectively:
65～75 ℃, 3.8～5.0MPa, 5～10 hours and 65～75 ℃, 1.0～1.5MPa, 12～15 hours;
Temperature of reaction, reaction pressure and the reaction times of preparation catalyzer are: 165～175 ℃, 2.5～3.0MPa and 1 hour.
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| CN94119949A CN1048657C (en) | 1994-12-29 | 1994-12-29 | Catalyst or prepn. of alcohol by hydrogen formylation of olefines |
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| CN94119949A CN1048657C (en) | 1994-12-29 | 1994-12-29 | Catalyst or prepn. of alcohol by hydrogen formylation of olefines |
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| CN1126108A CN1126108A (en) | 1996-07-10 |
| CN1048657C true CN1048657C (en) | 2000-01-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527818A (en) * | 1965-11-26 | 1970-09-08 | Shell Oil Co | Oxo alcohols using catalysts comprising ditertiary phosphines |
| SU1020420A1 (en) * | 1980-10-27 | 1983-05-30 | Предприятие П/Я Р-6913 | Process for preparing aldehydes and alcohols by hydroformylation of olefins |
| DD206370A1 (en) * | 1982-01-05 | 1984-01-25 | Leuna Werke Veb | METHOD FOR HYDROFORMYLATION OF LONG-CHAIN OLEFINES |
| CN1020680C (en) * | 1988-12-26 | 1993-05-19 | 中国科学院兰州化学物理研究所 | Catalyst for preparing alcohol from olefin |
-
1994
- 1994-12-29 CN CN94119949A patent/CN1048657C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527818A (en) * | 1965-11-26 | 1970-09-08 | Shell Oil Co | Oxo alcohols using catalysts comprising ditertiary phosphines |
| SU1020420A1 (en) * | 1980-10-27 | 1983-05-30 | Предприятие П/Я Р-6913 | Process for preparing aldehydes and alcohols by hydroformylation of olefins |
| DD206370A1 (en) * | 1982-01-05 | 1984-01-25 | Leuna Werke Veb | METHOD FOR HYDROFORMYLATION OF LONG-CHAIN OLEFINES |
| CN1020680C (en) * | 1988-12-26 | 1993-05-19 | 中国科学院兰州化学物理研究所 | Catalyst for preparing alcohol from olefin |
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| CN1126108A (en) | 1996-07-10 |
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