CN1481348A - Process for prepn. of polyhydric alcohols - Google Patents

Process for prepn. of polyhydric alcohols Download PDF

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Publication number
CN1481348A
CN1481348A CNA018207804A CN01820780A CN1481348A CN 1481348 A CN1481348 A CN 1481348A CN A018207804 A CNA018207804 A CN A018207804A CN 01820780 A CN01820780 A CN 01820780A CN 1481348 A CN1481348 A CN 1481348A
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reaction
polyalcohols
manufacture method
acetal
olefines
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CN100488927C (en
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高原润
亨
濑户山亨
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Provided is a method for producing polyhydric alcohols by efficiently oxidizing olefins having carbonyl groups by molecular oxygen, and hydrolyzing and reducing the oxidation product. This method for producing the polyhydric alcohols comprises reacting the olefins having ethylenic double bonds, and the carbonyl groups or protective groups thereof in the same molecules, with the oxygen and alcohols to provide a reaction product containing an acetal and/or a ketal compound, and hydrolyzing and reducing the acetal and/or the ketal compound.

Description

The manufacture method of polyalcohols
Technical field
The present invention relates to the polyalcohols manufacture method; it is olefines and oxygen and the alcohols reaction that same intramolecularly is had carbonyl and/or its protecting group and two keys; obtain containing the compound of acetal and/or ketal, be hydrolyzed again and reduction reaction is made the manufacture method of polyalcohols.
Background technology
Hydroxyl, epoxy group(ing) or carbonyl etc. are incorporated on the two key positions of alkene of olefines that same intramolecularly has carbonyl and/or its protecting group,, just can obtain polyalcohols its reduction.For their research of synthesis method, be primarily aimed at synthetic as polyester raw material, useful 1, the method for ammediol.Specifically, with acrolein hydration, make 3-hydroxypropyl aldehyde, again through be disclosed in United States Patent (USP) No. 5093537, Japan the special permission open flat 10-212253 of communique number (No. 6140543, United States Patent (USP)) of reductive manufacture method and Japan's special permission openly in the flat 8-143502 of communique number.
In addition, as 1, other synthetic methods of ammediol will be disclosed in Japan through the reductive method of the glycidaldehyde that hydrogen peroxide aqueous solution chlorination propenal forms and specially permit in open the flat 9-20703 of communique number.
But No. 5093537, above-mentioned United States Patent (USP), Japan the special permission open flat 10-212253 of communique number (No. 6140543, United States Patent (USP)) and the Japan's special permission reaction conversion ratio when openly there is hydration reaction in disclosed method such as the flat 8-143502 of communique number is not high; Moreover if reaction conversion ratio is improved, selectivity is then relatively poor; If reaction mesostroma concentration reaches 17% when above, the problem that by product then increases.In addition, be to be solvent with water because of this reaction, 1 after the 3-hydroxypropyl aldehyde of generation or the reduction, ammediol is soluble in water, is difficult to water and resultant extraction separation must be distilled the problem of separating big water gaging so also have.
In addition,, promptly, also there is necessary this hydrogen peroxide of excessive use for utilizing on high price hydrogen peroxide this aspect as oxygenant for the open flat 9-20702 of the communique number disclosed method of Japan special permission, otherwise, the problem of glycidaldehyde just can not high-level efficiency be obtained.On the contrary, if excessive use hydrogen peroxide also exists side reaction takes place, aldehyde is oxidized to the problem of carboxylic acid.
As mentioned above, people wish to develop as polyester raw material useful, 1, the industrial effective manufacture method of polyalcohols such as ammediol.
On the other hand, alkene is industrial effective means through the reaction of molecular oxygen oxidation, and wherein, useful especially is general known Wacker reaction.That is, as catalyzer, ethene is made the manufacture method that acetaldehyde, propylene are made acetone with molecular oxygen, also be applied to industrial with the aqueous solution that contains Palladous chloride and cupric chloride.
Though for example J.Org.Chem is arranged, 1987,52,1758-64 and Bul1.Chem.Soc.Jpn., 63,166-169 examples such as (1990) is used as the example that this reaction is applicable to compounds such as aforesaid propylene aldehyde, and the result is that reactivity is very low, and TOF is below 1.
That is, it is believed that the Wacker reactive applications is when the olefines of the electron withdrawing group that has carbonyl and so on is synthetic as mentioned above, its reactivity is very low, is the flow process that is difficult to be suitable for industrial operation as the polyalcohols synthesis flow.
Summary of the invention
In order to solve above-mentioned related problems, the present inventor is through further investigation, found that: even have the olefines of the carbonyl of electron withdrawing group, also can set up tool hyperergy, good oxidizing reaction system optionally, again by expeditiously with the acetal of gained and/or ketal compound hydrolysis, reduction, even use the olefines of the carbonyl that has electron withdrawing group, also can high conversion, highly selective makes polyalcohols, finish the new synthesis flow that can be suitable for industry, finish the present invention at this point.
Promptly; main points of the present invention are polyalcohols manufacture method; it has carbonyl and/or its protecting group with same intramolecularly; olefines and oxygen and alcohols reaction with the two keys of alkene; obtain containing the resultant of reaction of the compound of acetal and/or ketal; this acetal and/or ketal compound are hydrolyzed and reduction reaction; make the manufacture method of polyalcohols; in addition; olefines and protective material that it also makes same intramolecularly have carbonyl and the two keys of alkene react; after the protection carbonyl; to have this olefines and oxygen and alcohols reaction through the carbonyl and the two keys of alkene of protection; obtain corresponding acetal and/or ketal compound, and this acetal and/or ketal compound are carried out deprotection; the polyalcohols manufacture method of hydrolysis and reduction reaction.
Embodiment
The present invention has carbonyl with same intramolecularly, and the olefines with the two keys of alkene is as reaction raw materials, perhaps with the carbonyl of this olefines olefines after with the protecting group protection as raw material.Then, utilize these raw materials to make corresponding polyvalent alcohol through oxidizing reaction, hydrolysis and reduction reaction.
The present invention roughly is divided into 2 kinds of reaction process.
The 1st reaction process is: same intramolecularly is had the olefines oxidation of carbonyl and/or its protecting group and the two keys of alkene, obtain acetal and/or ketal compound, polyvalent alcohol is made in its hydrolysis, reduction.The 2nd reaction process is: the olefines and the protective material that same intramolecularly are had carbonyl and/or the two keys of alkene react, and after carbonyl is protected, its oxidation are obtained acetal and/or ketal compound, then, with its deprotection, hydrolysis, reduction, make polyvalent alcohol.In the 1st and the 2nd reaction process, oxidizing reaction, hydrolysis and reduction reaction are common operation.
An example with regard to reaction formula in the present invention's the 2nd reaction process describes.In addition, in the formula, R ' and R " the expression alkyl.
At first, the reaction formula with initial protective reaction is expressed as (1-a).
Figure A0182078000061
Formula (1-a)
The protected compound of the carbonyl of above-mentioned reaction gained is carried out oxidation, an example of this reaction formula is expressed as 1-b.
Figure A0182078000062
Formula (1-b)
The example that resultant deprotection after the oxidation forms the reaction formula of carbonyl is expressed as formula 2-a.
Formula (2-a)
With acetal behind the deprotection and/or ketal hydrolysis, form an example of the reaction formula of carbonyl, 2-b is represented with formula.
Formula (2-b)
In addition, the formula 2-c of utilization represents the carbonyl reduction with gained, forms hydroxyl, obtains an example of the reaction formula of polyalcohols.
Above-mentioned reaction process is the situation of the 2nd reaction process, if the 1st reaction process, the protective reaction of formula 1-a is omitted, and as starting raw material, carries out the oxidizing reaction of formula 1-b with olefines with carbonyl.At this moment, the deprotection reaction that does not need formula 2-a certainly.
According to different situations, also can be out of order with deprotection reaction (formula 2-a) and hydrolysis (formula 2-b).In addition, the protecting group of carbonyl is carried out deprotection when becoming carbonyl as acetal, ketal and so on through hydrolysis, can carry out deprotection and hydrolysis simultaneously.In addition, during through the reduction reaction deprotection, deprotection and reduction become simultaneously and carry out, and when reduction reaction can directly become hydroxyl, even do not carry out deprotection, also can obtain required polyvalent alcohol in protecting group in the protecting group of carbonyl.
(starting raw material)
Starting raw material of the present invention is that same intramolecularly has olefines carbonyl, that have the two keys of alkene.
Olefines of the present invention can be a chain, also can be ring-type.If during chain alkene, the carbonatoms of olefines is generally more than 2, is preferably more than 3; In addition, usually below 25, more fortunately below 10.If cyclic olefin, usually more than 4, more fortunately more than 5, in addition, usually below 10, more fortunately below 8.Though 1 intramolecular double key number order of olefines is not had special restriction, usually below 8, more fortunately below 3.In addition, position of double bond where can.As carbonyl, can use aldehyde radical, ketone group etc., carboxyl etc., be preferably aldehyde radical.Moreover, though the number of 1 olefines intramolecularly ketone group is not particularly limited, usually below 8, more fortunately below 3.
As long as the position of two keys and carbonyl relation is to have it to exist at same intramolecularly, though there is not any restriction, between two groups, better carbonatoms is below 3, and adjoining position preferably is so that carbonatoms is 0.Be preferably α, the β beta-unsaturated carbonyl compounds.
For these chains or cyclic olefin, in any position of main chain substituting group can be arranged, also can have fused rings.As substituting group, can be that carbonatomss such as the alkyl of 1-23, alkoxyl group that carbonatoms is 1-23, phenyl are halogen radical, nitros etc. such as the aryl, chlorine, bromine of 6-22 with carbonatoms.The substituting group number also can be more than 1.
Though can former state offers oxidizing reaction without variation with above-mentioned olefines, also can become the protecting group of carbonyl making carbonyl-protection after, provide it to oxidizing reaction.The protecting group of so-called carbonyl refers to: in the oxidizing reaction operation, for preventing the protected carbonyl of carbonyl reaction, in addition, it also can be the group that becomes hydroxyl through deprotection, hydrolysis and/or reduction.
As the protecting group of carbonyl, for example can be acetal radical, thioacetal base, ketal group, thio ketal ization base, ester group etc.Wherein, acetal radical, ester group wherein, are preferably acetal radical for well.
Even these carbonyls can react at the pure and mild oxygen that the oxidizing reaction neutralization is used to react, but if can become hydroxyl in the operation afterwards, just no problem.
When utilization has the olefines of a plurality of carbonyls, can not will its whole carbonyls protect.
As the above-mentioned olefines that has the olefines of carbonyl and have protected carbonyl, can enumerate following material: α such as propenal, metacrolein, crotonic aldehyde, 2-hexenoic aldehyde, phenylacrolein, 2-tetrahydrobenzene formaldehyde, β unsaturated aldehyde; Propenal dimethylacetal, propenal diethyl acetal, 2-vinyl-1,3-dioxolane or 2-vinyl-1, acetalses such as 3-diox; Ethenyl methyl ketone, vinyl ethyl ketone, 3-amylene-α such as 2-ketone, the beta unsaturated ketone class; Ethenyl methyl ketone dimethyl ketal, 2,2-ethyl vinyl-1, ketal classes such as 3-dioxolane; α such as vinylformic acid, methacrylic acid, styracin, 2-cyclohexene carboxylate, the β unsaturated carboxylic acid; α such as maleic anhydride, the β acid anhydrides; Methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 3-hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester; Also have lactone such as γ-crotonolactone in addition; Also have ester classes such as vinyl ester such as vinyl acetate between to for plastic base ester, butyric acid vinyl ester.Wherein, the most handy α, β unsaturated aldehyde.
(protective reaction operation)
The protective reaction operation is to have carbonyl at same intramolecularly and to have the reaction raw materials and the protective material reaction of the olefines of the two keys of alkene, the operation of the protecting group of synthesizing carbonyl.
For the reaction method of this operation, can there be restriction especially with the method for known protection carbonyl.In addition, for the protecting group among the present invention, as not returning to carbonyl, as long as become hydroxyl through deprotection, hydrolysis and/or reduction reaction through deprotection reaction.
Formed protecting group can be by deprotection operation deprotection in this operation; but if select can with deprotection reaction with hydrolysis the same terms under carry out protecting group the time; deprotection reaction and hydrolysis can be carried out simultaneously, from reducing reactor quantity, help operation.As can with the hydrolysis same reaction conditions under carry out the object lesson of deprotection reaction, the carbonyl of starting raw material can be enumerated formyl radical, that is, compound is an aldehyde, the protection back is an acetal.The reaction that aldehyde is become acetal is an acetalation, is used as the reaction of protection carbonyl usually.In addition, under conditions such as heating, according to the difference of carbonyl kind, carbonyl can in the case, be protected carbonyl acetalation or esterification owing to decarboxylation is lost.As object lesson, the carbonyl that can enumerate starting raw material is a carboxyl, that is, compound is a carboxylic acid, and the protection back is an ester.The reaction that carboxylic acid is become ester is everybody known esterification.
In the present invention; though also can not carry out carbonyl-protection; and make it be converted to hydroxyl by oxidation, hydrolysis and reduction reaction; but during the reduction after the functional group that oxidation forms is hydrolyzed again; more hydrogen etc. when wanting consumption rate protection carbonyl; if when reduction reaction needs high temperature and high pressure, preferably carbonyl is become its protecting group in advance, this is because its protecting group returns to original carbonyl easily in the deprotection operation.Moreover, even identical carbonyl, as carboxyl and ester group, by the esterification of carboxyl, esterolytic reaction, can be easily conversion mutually, so, become protecting group in advance for well.In addition, utilization becomes protecting group and also easily purpose resultant and other compounds is carried out fractionation by distillation, and can solve the material problem of equipment therefor of the present invention, so, preferably become protecting group.
As such olefines, can following material specifically be arranged: α such as propenal, metacrolein, crotonic aldehyde, 2-hexenoic aldehyde, phenylacrolein, 2-tetrahydrobenzene formaldehyde, β unsaturated aldehyde with aldehyde and carboxylic acid; Ethenyl methyl ketone, vinyl ethyl ketone, 3-amylene-α such as 2-ketone, the beta unsaturated ketone class; α such as vinylformic acid, methacrylic acid, styracin, 2-cyclohexene carboxylate, β unsaturated carboxylic acid etc.
For protective material, can suitably select according to the purpose resultant, though can form protected carbonyl with known protective material, more handy alcohol, the most handy polyvalent alcohol identical with the purpose resultant is used as protective material.For the kind of alcohol, do not have restriction especially, but if,, be ideal from the angle that transformation efficiency increases with making the alcohol of the balanced deflection of pure and mild resultant in resultant.
Be under the situation of acetalation for example, use carbonatoms usually more than 1 in protective reaction, the alcohol below 10, wherein, more handy polyvalent alcohol, special handy carbonatoms are the glycols of 2-5.Be specially: ethylene glycol, 1, ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,3-pentanediol, 2 etc.
If when protective reaction is esterification, use carbonatoms more than 1 usually, the alcohol below 10 is specifically used methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, ethylene glycol, 1, ammediol etc.
Because of in deprotection reaction, generate used alcohol here, so the purpose resultant must be separated with this alcohol, therefore, better be to select easily and the isolating alcohols of purpose resultant.That is, if for example adopt the separation method of fractionation by distillation, better employing and resultant boiling point differ bigger alcohols.If use the alcohols identical with desirable polyalcohols, just need not separate, help operation.When for example using propenal and vinylformic acid etc. as olefin feedstock, if use purpose resultant 1, ammediol is optimal as alcohols, because behind the deprotection reaction, will not separate from resultant by alcohol.
Acetalation and esterification are balanced reaction, so usually with the excessive use of one of carbonyl compound or protective material.When if excessive use protective material is pure, then after the protective reaction, this alcohol can be residual.Usually before supplying with next oxidizing reaction operation, this alcohol must be removed, still,, just needn't remove this alcohol, and make easy and simple to handlely, also save the expense of removing if when should alcohol also using in the oxidation operation after the protection operation, economical and practical.
As the carbonyl-protection base of oxidizing reaction, can use known group usually, but protected mode is not had special restriction.So-called carbonyl through protection is meant the group that can become original carbonyl, can use acetal radical, thioacetal base, ketal group, thio ketal ization base, ester group etc.More handy acetal radical or ketal group and ester group.Specifically available: propenal dimethylacetal, propenal diethyl acetal class; 2-vinyl-1,3-dioxolane, 2-vinyl-1, acetalses such as 3-diox; Ethenyl methyl ketone dimethyl ketal, 2,2-ethyl vinyl-1, ketal classes such as 3-dioxolane; Ester classes such as methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 3-hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester etc.
As the protection carbonyl example, dehydration condensation below is described, concrete is: have formyl radical aldehyde acetalation and have the esterification of the carboxylic acid of carboxyl.In addition, for the acetalation of utilizing dehydration condensation and esterification, except the kind difference of just carbonyl kind and better protecting agent alcohol, other all adopt identical reaction conditions to react.For the dehydration condensation that has catalyzer to exist, be that the olefines that will have carbonyl reacts under the effect of pure and mild catalyzer, obtain having the olefines of carbonyl-protection base.
The content of the olefines in the reaction system more than 1vol%, more than the 5vol%, can also be selected below the 99vol%, more fortunately below the 50vol% usually more fortunately in addition usually.
In these olefin feedstocks, also have because polymerization takes place in heating etc., or the alkene of free radical autoxidation takes place easily.At this moment, can in reaction system, add free radical scavengers such as quinhydrones, thiodiphenylamine, polymerization retarder etc.
Corresponding to the entire reaction volume, alcohols content is usually more than 1vol%, more fortunately more than the 5vol% in the reaction system.In addition, usually below 99vol%, more fortunately below the 80vol%.
The raw material carbonyl in the reaction system of initial reaction stage and the mol ratio of alcohols, though there is not special restriction, can be in the scope of 1/1-1/100.More fortunately 1/1-1/95 is in the scope of special 1/1.2-1/90 fortunately.
The protective reaction of olefines is normally carried out under the effect of acid catalyst.As the acid catalyst of this moment, can use: mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Lewis acids such as lanthanon trifluate, polyacid such as heteropolyacid, solid peracids such as ion exchange resin, zeolite, clay.From separating the simple and easy degree of resultant, comparatively convenient with solid peracid.About the addition of acid, with minute quantity promptly effectively, there is not restriction especially, corresponding to matrix, the addition of acid is more fortunately more than 0.001 weight ratio, better more than 0.01 weight ratio, in addition, more fortunately below 100 weight ratios, be preferably in below 70 weight ratios, the spy is fortunately below 60 weight ratios.
For temperature of reaction, according to the difference of reaction formation and difference.Dewatering or azeotropic mixture in the one side steaming, when one side is reacted, must be to steam the temperature of removing, and in addition, is not removing outside reaction system under the situation of resultant, and for reaching balance, low temperature is more favourable.Temperature of reaction is usually more than-100 degree, more fortunately-50 more than the degree, better more than-20 degree.In addition, normally below 200 degree, below 180 degree, be more preferably below 150 degree more fortunately.
For the reaction formation of protective reaction, can carry out according to common form.When each composition of catalyzer is in solution state, in the specific reaction times, utilize batch reactor, matrix is contacted with alcohols and react; Utilize the external phase reactor that matrix and alcohols are provided continuously, also can react.On the other hand, if catalyzer of the present invention is insoluble to matrix and pure time-like, promptly, when being immobilized with solid peracid and/or catalyzer composition, also can use above-mentioned liquid phase reaction, or adopt the trickle bed system, be about to catalyzer and be filled in fixed bed, and corresponding matrix and the alcohols of supplying with liquid phase state are given fixed bed.
Acetalation and esterification all are balanced reaction.Therefore, can adopt reacted raw material is separated with the purpose resultant, the method for the promotion reaction that water that will generate in maybe will reacting or acetal or ester are removed from reaction system.As the method for from reaction system, removing, can adopt: add and the pure solvent that forms 2 layers the acetal that extraction generates or the method for ester; The method that the water distillation that generates is removed in heating; Or add the solvent can generate azeotropic mixture with water, azeotropic mixture is steamed the method removed etc.Resultant is not being steamed from reaction system under the situation about removing, be to improve transformation efficiency, can use raw material ratio is improved, or temperature of reaction is reduced so that balance shift to generation etc. method.
(oxidation operation)
Describe with regard to oxidation operation below.
Oxidation operation has carbonyl and/or protecting group with same intramolecularly and olefines and the oxygen and the alcohols reaction of the two keys of alkene is arranged, and main is the synthesis procedure of the compound of acetal and/or ketal with the alkene partial oxidation.
That is, under the situation of chain olefines, if terminal olefin mainly generates the ketal of acetal or methyl ketone, if inner alkene mainly generates corresponding ketal.
In addition; in the present invention; for having manufacturing protecting group, that contain the olefines of the two keys of alkene, not necessarily to carry out in identical place with oxidation operation, also can with in advance that make in other place, that have protecting group, contain the olefines of the two keys of alkene as raw material.
General oxidizing reaction is in solvent, in the presence of alcohol, comes the oxyalkylene hydro carbons with catalyzer, and the amount of olefines is generally more than the 1vol% in the reaction system, more fortunately more than the 5vol%, and below 99vol%, more fortunately below the 50vol%.
In these olefin feedstocks, comprise because heating waits meeting generation polymerization or causes the alkene of free radical autoxidation easily, at this moment, and can be in reaction system, free radical scavenger, polymerization retarders etc. such as interpolation quinhydrones, thiodiphenylamine.
As the alcohols that is present in the oxidizing reaction, by reacting main generation acetal and/or ketal, they are in equilibrium state with aldehyde and/or ketone, so can be difficult to oxidized alcohol but better adopt with the alcohol that makes this balanced deflection resultant acetal or ketal.
Wish to use energy and aliphatics or aromatic hydrocarbons equal solvent to form two layers alcohols.This is because add such alcohols in reaction, reacts the back layering and with alcohols and separated from solvent, and after reaction because the extraction of these hydrocarbon solvents etc., just easily with resultant from being dissolved in the catalyzer of alcohol layer, i.e. separation such as palladium, iron, copper.
Separate and during carrying out these 2 layers, for being separated effectively, or improve the extraction yield of resultant, also can add additive resultant and catalyst separating.In addition, before being separated, after also by product that obstruction can be separated and extract and water etc. are removed, separate again.In addition, can adopt will hinder the by product that extracts and water etc. to remove from each layer that carried out flash liberation after, or desolvate and alcohol removing, the concentration of each composition is improved after, again with 2 layers of mixing, to improve the method for extraction yield.
From the above point of view, use alcohols as reaction, generally use carbonatoms more than 1, the alcohol below 10 wherein is preferably methyl alcohol and polyvalent alcohol, and good especially is the dibasic alcohol of 2-5 for carbonatoms.Specifically can enumerate methyl alcohol, ethylene glycol, 1, ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,3-pentanediol, 2 etc.
In this operation, obtain acetal and/or ketal, utilize hydrolysis, generate the alcohols that this operation is used.From the viewpoint of economy, when alcohols is separated with the purpose resultant, wish to select segregative alcohols.That is,, be preferably the alcohols bigger with the boiling-point difference of required matrix if when adopting the separation method of fractionation by distillation.In addition, be preferably the alcohols identical with required polyalcohols.For example when using propenal or its acetal as olefin feedstock, if with 1, ammediol this purpose resultant is as pure time-like, behind the hydrolysis reaction, because of need not from resultant alcohol to be separated, so with 1, ammediol is best as alcohols.
The content of alcohols in the reaction system, corresponding to the entire reaction volume, generally more than 1vol%, more fortunately more than the 5vol%, in addition, generally below 99vol%, more fortunately in the following scope of 80vol%.
Though do not have special restriction for the mol ratio of raw material olefines and alcohols in the reaction system of initial reaction stage, but as long as in the scope of 1/1-1/100,1/1-1/95 more fortunately is especially fortunately in the scope of 1/1.2-1/90.
As the catalyzer of this operation,, both can be with homogeneous phase though there is not special restriction, again can be with heterogeneous system, but wherein as long as add palladium, with containing copper or iron at least, or contain copper and both catalyzer of iron for well, especially with the catalyzer of palladium, copper and iron three combination for well.As the starting compound of these palladiums, copper and iron, the known compound of selling on the market of people has multiple can the selection arbitrarily from these compounds.
As the compound of palladium, for example can use: halogenation palladiums such as Palladous chloride, palladium bromide; Na 2PdCl 4, Li 2PdCl 4Deng palladate; Mineral acid or organic acid palladium salt such as Palladous nitrate, palladous sulfate, acid chloride, trichoroacetic acid(TCA) palladium, palladium acetylacetonate; Inorganic palladium such as palladous oxide, palladium hydroxide; In addition, have from these metal-salt deutero-base coordination compoundes, for example: PdCl 2(CH 3CN) 2, PdCl 2(PhCN) 2, PdCl 2(PPh 3) 2, Pd (en) 2Cl 2, Pd (Phen) Cl 2Deng, but unrestrictedly (the en here refers to quadrol, and phen is 1,10-phenantrorine) to this.From above-mentioned solvent and the stratified viewpoint of alcohols, wherein better be to use Na 2PdCl 4, Li 2PdCl 4Deng palladate, base coordination compound, for example: PdCl 2(CH 3CN) 2, PdCl 2(PhCN) 2, PdCl 2(PPh 3) 2, Pd (en) 2Cl 2, Pd (Phen) Cl 2Difficulty is dissolved in the palladium compound of hydrocarbon Deng easily being dissolved in alcohols.
As iron cpd, for example can use: the various salt or the coordination compound form of iron(ic) chloride (II), iron(ic) chloride muriates such as (III), iron bromide (II), iron bromide bromides such as (III), ferric sulfate (II), ferric sulfate (III), iron nitrate (II), iron nitrate inorganic acid salts such as (III), ironic acetate (II), ironic acetate (III), ironic oxalate (II), ironic oxalate (III), ironic formiate, ferric acetyl acetonade etc. are supplied to reaction, wherein, be preferably iron(ic) chloride (III).
As copper compound, for example can use: cupric chloride (I), cupric chloride muriates such as (II); Cupric bromide (I), cupric bromide bromides such as (II); The various salt of copper sulfate (I), copper sulfate (II), cupric nitrate (I), cupric nitrate inorganic acid salts such as (II), venus crystals (I), venus crystals (II), cupric oxalate (I), cupric oxalate (II), Tubercuprose, acetylacetone copper etc. or the form supply of coordination compound reaction, wherein, more handy cupric chloride (I), cupric chloride (II).
Catalyst concn, from the viewpoint of economy, general lower concentration is better, but from the productivity angle, as long as in speed of response with in catalyst concn does not become the zone of negative correlation, high density to a certain degree is comparatively desirable.Thus, for entire reaction liquid weight, generally more than the 0.001wt%, more fortunately more than the 0.01wt%, in addition, generally below 10wt%, select in the following scope of 5wt% more fortunately as [Pd] of palladium concentration.But, in speed of response under the high density condition interdependence of concentration is different under low consistency conditions speed of response to the interdependence of concentration, and the trend of the deterioration of efficiency of catalyzer is arranged, so, should carry out concentration and select from economy and high-level efficiency angle.
The concentration of iron or copper can be used with respect to the relative concentration of palladium and represent in the reaction solution.Use the amount of recently representing iron and copper with respect to the mole of palladium,, more than 0.1, in addition,, select in the scope below 10 more fortunately generally below 100 generally respectively more than 0.01.If iron or copper ion concentration are when being lower than these scopes regional, not only speed of response reduces, and main effect suppresses the trend that effect that Pd separates out has reduction, and is undesirable.In addition, if though can not hinder reaction, there is the trend that meltage reduces in the reaction system in more interpolation, undesirable.
In the reaction system in this operation, better be to have halide-ions to exist, especially have Cl ion or Br ion to exist.Here " ion " refers in the reaction system, can be dissociative ionic form, also can not dissociate, and exists with the form of salt.As the method that halide-ions exists, wish to be used as being selected from least a kind of starting compound in palladium, copper and the iron as catalyzer with haloids such as muriate and bromides.In addition, also can in reaction system, add other halogen compounds.As halogen compounds, can use NaCl, LiCl, SnCl 2In inorganic salt.With the amount of the relative concentration of Pd being represented the halide-ions in these reaction systems, promptly more fortunately 0.1＜[Cl and/or Br]) in the scope/[Pd]＜100 (mol ratio), better 0.3＜[Cland/or Br)/[Pd]＜50, but under the situation of halogen concentration, though the concentration of the water in the reactor is low, but the corrosion of the equipment matter that might react so halogen ion concentration should be low as far as possible, and guarantees the function of catalyzer simultaneously.In addition, have the composition that contains halogen sometimes in the part of by product from catalyzer.At this moment, for example better be that the continuous or periodic form of metal-salt of utilizing is replenished the halogen that is consumed.
In the reaction of this operation, though also can be excessive the alcohols of use reaction as solvent,, be effective if add other solvents different with alcohols.At first, add solvent and can suppress production of by-products, especially alcohols adds to alkene and partly generates ether.In addition, when these solvents of alcohols and other form two layers, can utilize aforesaid be separated separating catalyst and resultant.Especially in the reaction system of using homogeneous catalyst, the big problem of more difficult separating catalyst of industrial existence and resultant can be avoided these problems and be had very big meaning.
As other solvents that are different from alcohols, can use aliphatics, aromatic hydrocarbon solvents and halocarbon.Concrete available benzene,toluene,xylene, ethylbenzene, pentane, hexane, heptane, octane, pentamethylene, hexanaphthene, methylene dichloride, trichloromethane, tetracol phenixin, ethylene dichloride, fluorobenzene etc.There is not special restriction though be different from the addition of other solvents of alcohols for this class, for the total amount of alcohol and olefines, more fortunately more than 0.05, better in the weight ratio more than 0.1, in addition, the weight ratio below 100 is better in the weight ratio below 25 more fortunately.
Mainly obtain in the reaction of acetal or ketal compound in the 1st stage, though temperature of reaction is as long as can react more than 0 degree, because of the present invention's reaction depends on temperature of reaction very much, so be preferably high temperature.But for fear of the condition that forms explosive mixture and increase the free radical autoxidation of carrying out easily in the high-temperature area and the quantity of the by product that produces and the polyreaction of matrix, just must select temperature of reaction, usually the temperature range of this reaction is preferably 20 degree between 200 degree, more preferably 40 degree are to the scopes of 180 degree, just not only economy but also obtain required speed of response effectively.
In this operation, though can use oxygen, in certain temperature, certain pressure and compositing range, oxygen and organic compound might produce explosive mixture, so must avoid this danger.Oxygen partial pressure is generally as long as just can react more than 0.001MPa, but oxygen partial pressure is lower, has the trend of speed of response step-down, might make catalyst deactivation, so must decide oxygen partial pressure according to the relation of temperature and catalyst concn, oxygen partial pressure is preferably 0.01-10MPa among the present invention.If possible, oxygen partial pressure is higher, is preferably 0.05-5MPa, should select pressure preferably from the angle of safety, economy.
The reactive mode of this operation is to decide according to common method for oxidation.When each composition of catalyzer exists with solution state, both can be in the specific reaction times, utilize batch reactor that olefines is contacted with the gas that contains aerobic and carry out oxidizing reaction; Also can utilize the external phase reactor that gas and the olefines that contains aerobic is provided continuously, carry out oxidizing reaction.On the other hand, if when the catalysts in the 1st stage is immobilized, both can use above-mentioned liquid phase reaction; Or adopt so-called trickle bed system, be about to catalyzer and be filled on the fixed bed, and the olefines and the oxygen of corresponding liquid phase state are provided.
As the method that oxygen is provided, can adopt the means that effectively oxygen are dissolved in the reaction soln system, for example: make the gas that contains aerobic become the method for micro-bubble by agitating vane; In the inboard of reactor, arrangement of baffles makes oxygen become the method for micro-bubble; The method of utilizing nozzle to spray in the system with high linear speed.
In addition, in these reactions, the water that acetals or ketal class are produced when generating makes the balance between acetals or ketal class and aldehydes or the ketone help aldehydes or ketone.Because of these free carbonyl compound are higher than alcohol adducts to the reactivity of oxidizing reaction, so oxidized successively easily.Therefore, as far as possible the water that is generated in the system is discharged to outside the system to well, the water yield in the reaction system better is to maintain below the 50 weight %, better maintains below the 20 weight %.As its method, can be in order to following method: make the anhydrous metal salt of planar water and the method for zeolite equimolecular sieve coexistence; Add and water azeotropic composition, through the method for dephlegmate; By containing oxygen or oxygen-free gas distills the method for removing together; Or and water reaction, become the method that the compound that reaction is had no adverse effects for example adds metal alcoholate etc.
For the reaction solution after the oxidizing reaction,, also can make pressure release to a certain degree, low pressureization if it is in the situation of pressurized state.If the boiling point of material composition and resultant is different from reaction solvent very much, during for lower boiling, can directly lower boiling composition fractionation by distillation from reaction solution be come out.In addition, if the boiling point of material composition and resultant is higher than reaction solvent, when being high boiling point, interpolation can form reaction solvent the solvent of two-phase, carry out liquid-liquid phase separation, and make catalyst component be included in wherein one mutually in, from the solvent phase that contains catalyzer hardly, reclaim raw material, can resultant be taken out selectivity.After being separated, in resultant, sneak under the situation of catalyst component of trace, also can carry out extraction separation more than 2 times, the residual quantity of catalyst component is reduced to negligible degree.Also can be raw material and resultant after being separated of the 1st stage are recovered to a certain degree, and distill operation, after being increased to residual catalyst concn to a certain degree, extract once more, should take to think more economical, high efficiency method.Be separated and the separated alcohol catalyzer in mutually can recycle the reactor in oxidation operation for utilization.
In addition, the interior minor amount of water that generates successively along with the carrying out of oxidizing reaction of reactor.Better be as possible it to be discharged to outside the reaction system, but exist, just may corrode reactor as if halogenic ingredients such as Cl are arranged in the reaction system.Thus, for caustic acid such as hydrogenchloride, must use stronger erosion resistance material in required place.
Reaction pressure can be used the container of materials such as glass, pottery, fluoro-resin in not too high scope the time; If under the high situation of reaction pressure, generally use the reaction vessel of erosion resistance, promptly various Stainless Steel Alloies, especially be commonly called as, contained titanium alloy, contained the container of the alloy etc. of zirconium to the anti-corrosion nickel-base alloy of Kazakhstan department Troy; Or coating of these alloys and pressure be attached to lip-deep container.Reactor particularly, it is higher to be corroded possibility, but also is being equipped with when leaving standstill groove, separator tank, and these positions are subjected to the corrosive possibility higher.Moreover, containing the oil phase of resultant in distillation, under the residual situation of catalyst component, because of halogenic ingredient can be concentrated, its corrodibility can be higher.For the material of these main containers and attached pipe arrangement, preferably in the scope that economy allows, use the material of erosion resistance according to the size of the possibility that is corroded.
For the main component of gained compound in this operation reaction, be that the alkene part is oxidized, further with the alcohol reaction and acetal or ketal.Specifically: with propenal or 2-vinyl-1, this acetal of 3-diox (VDO) is as raw material, just can obtain mda two (1,3-diox-2-yl) acetal (DAC), mda list (1,3-diox-2-yl) acetal (MAC) as main resultant.Except these main components, can also obtain 1, the 3-dioxane oneself-2-guanidine-acetic acid 3-hydroxypropyl acrylate (PDE), 2-hydroxyethyl-1,3-diox (HDO) etc.The hydrolysis of ensuing second operation and reduction reaction not only can also all become required compound with these compounds with the acetal of main component, and promptly polyvalent alcohol 1, ammediol.
In above-mentioned reaction, can observe minor by-products, promptly under the anaerobic, alcohol directly is inserted into the alkene part and generates ether.Specifically: with the 2-vinyl-1 of propenal or its acetal, 3-diox (VDO) is 2-(6-hydroxyl-3-oxa-hexyl)-1,3-diox (HEDO) etc. during as raw material.In addition, for oxidizing reaction, the material that requisite composition alcohols is not complete non-activity in the reaction system.Can observe and also have the oxidized compound of alcohol to exist.
But most these by products and purpose resultant are hydrolyzed in the operation of back together and reduce, and become original alcohols, or resolve into lower boiling compound.Usually the boiling point majority as the oxide compound of by product of gained is higher in oxidizing reaction, when distillation is removed etc., need to consume big energy, but in the present invention, these by products can be become effective constituent or be decomposed into segregative compound, therefore can constitute very efficient commercial run.
On the other hand, repeat for a long time in intermittent reaction or the successive reaction, may the oxide compound of above-mentioned alcohols be arranged in mutually and accumulate down at the alcohol that contains catalyst component from the composition of olefines oxide compounds at different levels.In order to make operation energy steady operation, must the whole material balance of strict control.Therefore, according to the formation speed of these impurity and the formation speed of oxydised component step by step, the part that must will contain the pure phase of catalyzer is discharged to outside the system, additional then new catalysagen feed liquid.At this moment,, cause bigger economical load, so catalyst component must be reclaimed because of the rate of removing that catalyst component is discharged to outside the system is bigger.Unrestricted for its method, but can be with removing organism, cleaning, reclaim the effective ways of metal ingredient.
In addition, the situation that the separation solvent in the isolating organic phase that contains resultant of two-phase has same impurity to accumulate when reclaiming at this moment, also must be discharged to outside the system separation solvent that restock is new with a part of separating solvent.
(deprotection operation)
Through acetal and/or ketal compound that oxidation gets, must recover carbonyl for the olefines that has protecting group that carries out protective reaction by above-mentioned operation by deprotection.For deprotection method, use the known correlation method of people according to the protecting group of the formed carbonyl of protection operation.
By the be protected used protective material of operation and contain the compound of carbonyl of deprotection,,, when can original shape making protective material and using, can in the protection operation, utilize again through Separation and Recovery for the protective material of this operation gained.If in the time of can not utilizing as protective material with original shape after the Separation and Recovery, need to make protective material regeneration through suitable reaction, can also utilize again.
According to the kind of protecting group, the deprotection operation also can be carried out behind hydrolyzing process.If because the existence of protecting group can hinder hydrolyzing process; Or in hydrolyzing process, protecting group changes, and appears at the situation that can not become hydroxyl in the reduction operation; Deprotection operation and can not become the situation of hydroxyl in the operation of back perhaps has the acetal that generates in the oxidation operation and/or ketal owing to will be carried out before hydrolyzing process.If hydrolyzing process is not produced aforesaid influence, which is passable in the provisional capital of advancing for deprotection and hydrolysis.
If deprotection not, protecting group also can become hydroxyl in hydrolysis or reduction operation, also can save the deprotection operation.Specifically, carboxylic acid is carried out under the situation of esterification in the operation in protection, even return to carboxylic acid without deprotection, ester also can be reduced and become hydroxyl.Because of the ester reduction is most than the carboxylic acid reduction easily usually, so better be to omit the deprotection operation this moment.In addition,, can in hydrolyzing process, become carbonyl together, deprotection operation and hydrolyzing process are carried out simultaneously with the acetal and/or the ketal that generate in the oxidation operation if the protecting group that the protection operation generates is acetal and/or ketal.Like this, in technology, just can reduce the quantity of reactor etc.,, cut down pork barrel preferably industrial.Moreover the deprotection for acetal and/or ketal is elaborated at hydrolyzable moiety.
(hydrolyzing process)
Hydrolyzing process is that acetal and/or the ketal with above-mentioned oxidation operation or deprotection operation gained is hydrolyzed, and becomes the operation of carbonyl.
Normally when catalyzer exists, be hydrolyzed,, more effectively use acid as this catalyzer.As the acid catalyst of this moment, can use following material: Lewis acids such as mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, lanthanon trifluate, polyacid such as heteropolyacid, solid peracids such as ion exchange resin, zeolite, clay.Consider from the easy degree that separates resultant, easy with solid peracid.The addition of acid, minute quantity promptly effectively do not have special restriction to this, still, for the addition of matrix more fortunately more than 0.001 weight ratio, better more than 0.01 weight ratio, in addition, more fortunately below 100 weight ratios, better below 70 weight ratios, especially fortunately below 60 weight ratios.
The water yield that is used for hydrolysis is generally acetal and/or ketal is decomposed more than the essential chemical theory amount.But when acetal and/or ketal hydrolysis, this reaction that generates aldehyde and/or ketone is balanced reaction.Therefore, in order to promote balanced reaction, just essential a large amount of water.But after adding a large amount of like this water, the problem that the cost that water is removed with regard to existence from resultant increases from economic angle, should be discussed for this amount.Specifically, the amount of water is in the reaction system: for the entire reaction volume, the water yield is usually more than the 1vol%, more fortunately more than the 5vol%, in addition, and usually below 99vol%, more fortunately below the 80vol%.There is not special restriction for the mol ratio of raw material in the initial reaction stage reaction system and water, but as long as in the scope of 1/1-1/100.Wherein, 1/1-1/95 is better in the scope of 1/1.2-1/90 more fortunately.Moreover, when alcohol that generates in hydrolysis or carboxide boiling point are lower than water, when removing them, distillation reacts, can change balance, and the water yield of use tails off, and is favourable.
In order to change balance, the solvent that utilizes solubilized resultant carbonyl compound is discharged to outside the system as with solvent carboxide being extracted during reaction as solvent, can obtain same effect.As solvent,, acid and reductive agent do not get final product so long as not causing the solvent of variation.
As hydrolysis temperature, though can confirm as long as more than 0 degree, just can react,, because of reaction of the present invention depends on temperature of reaction more greatly, so, be preferably high temperature.In general, hydrolysis in the temperature provinces of 20 degree-200 degree for well.Better, just can obtain favourable economically speed of response in 40 degree-180 degree temperature ranges.
For the reaction formation of this operation, can carry out according to common form.When each composition of catalyzer is in solution state, in the specific reaction times, utilize batch reactor, matrix is contacted with water and react; In addition, utilize the external phase reactor that matrix and water are provided continuously, also can react.On the other hand,, or adopt the trickle bed system, be about to catalyzer and be filled on the fixed bed, and provide the matrix of corresponding liquid phase state and water to fixed bed if catalyzer of the present invention when being fixed, also can use above-mentioned liquid phase reaction.
Because the alcohol that has oxidation operation to use generates,, can also in the reactor of oxidation operation, utilize again so in this operation, it is reclaimed.In addition, in the protection operation, utilize acetals and ketal class, omitted under the situation of deprotection operation, also the use alcohol that is closed by aldehyde, the synthetic acetals of ketone and ketal class in the protection operation can be reclaimed as protecting group.This alcohol can utilize in the reactor of synthetic acetal of protection operation and ketal again.
The pure and mild acetals that is used to protect operation, the ketal class of using at oxidation operation is synthetic used when pure identical, just needn't carry out the separation of these alcohol, can it be utilized in the reactor of the reactor of protecting operation and oxidation operation again according to required ratio.
Identical at above-mentioned 2 kinds of pure and mild purpose resultant polyvalent alcohols, or wherein a kind of when identical, just needn't carry out the separation of each alcohol or isolating kind is reduced, refining can simplifying, industrial be favourable technology.
If the reaction solution behind the hydrolyzing process is under the pressurized state, can carry out to a certain degree pressure release, make its low pressureization.The purpose resultant is separated from catalyst component, water and by product, and common working method for example can be utilized: method such as fractionation by distillation, extraction separation, Crystallization Separation, settlement separate, filtering separation.
In addition, by product that also separation can be generated or the purpose resultant that contains by product turn back in the reactor once more.For example, by hydrolysis the by product that boiling point is higher than the purpose compound after the fractionation by distillation is decomposed once more, a part becomes carboxide and alcohols etc., and the transformation efficiency of whole resultant, the rate of recovery of alcohol are improved.
(reduction operation)
The reduction operation is the carbonyl compound reduction with the hydrolyzing process gained, becomes the operation of polyvalent alcohol.
As the reduction reaction reductive agent, can therefrom select to use with everybody known carbonyl reduction agent or the reductive agent of selling on the market.Because of hope as mentioned above hydrolyzing process and ensuing reduction operation in same reactor, carry out simultaneously, so, wish reductive agent with reducing power acid and alkali and water influence.From economic and isolating easy degree consideration, more wish hydrogen to contact reduction as reductive agent.
If as reductive agent, though the dividing potential drop of hydrogen needs only more than 0.001MPa, reaction just can be carried out with hydrogen, but if the branch of hydrogen forces down, then the speed of response step-down might make catalyzer lose activity, so must decide the dividing potential drop of hydrogen according to the relation with temperature and catalyst concn.Usually more than 0.01MPa, more fortunately more than the 0.05MPa, better more than 0.1MPa.In addition, usually below 50MPa, more fortunately below the 20MPa, better below 10MPa.
As contact reductive catalyzer, people know the catalyzer of selling on the market, and for example Ruan's catalyzer of coming nickel, platinum, rhodium, palladium, ruthenium etc. and load these metals on carriers such as carbon, silica, zeolite can therefrom be selected arbitrarily.Especially with the ruthenium catalyzer of principal constituent, because its side reaction is few, better.The amount of these catalyzer though minute quantity is also effective, does not have special restriction to this, corresponding to the catalytic amount of matrix, is preferably the 0.0001-100 weight ratio, more preferably 0.001-70 weight ratio, particularly preferably 0.01%-50 weight ratio.
For the temperature of reaction of reduction reaction, can confirm in addition,, also can obtain enough speed of response industrial even about room temperature as long as more than 0 degree, just can react.Though when higher temperature, can obtain hyperergy, but,, increased by product by aldehyde, acetal, ketone, ketal, the pure hydrogenation carried out are easily decomposed in high-temperature area, so, should select to temperature of reaction from the angle that prevents that by product from increasing.Reduction reaction is carried out in the temperature range of 10 degree-200 degree usually, better in the temperature range of 25 degree-180 degree, just can obtain economical and effective speed of response.
The reaction formation of this operation can carry out according to common form.When each composition of catalyzer is in solution state, in the specific reaction times, utilize batch reactor, the gas that just can make matrix and water and contain hydrogen contacts and reacts, and utilizes the external phase reactor that water is provided continuously, contains the gas and the matrix of hydrogen, also can react.On the other hand,, or adopt the trickle bed system, be about to catalyzer and be filled on the fixed bed, and matrix, water and hydrogen that corresponding liquid phase state is provided are to fixed bed if catalyzer of the present invention when being fixed, also can use above-mentioned liquid phase reaction.
If the reaction solution after the reduction reaction is under the pressurized state, can carry out to a certain degree pressure release, make its low pressureization.For the separation of purpose resultant from catalyst component, water and by product, common working method for example can be utilized: method such as fractionation by distillation, extraction separation, Crystallization Separation, settlement separate, filtering separation.Exist as having carbonyl compound impurity in the polyvalent alcohol of polyester raw material once in a while, and become problem, utilize simple distillation to wait and it can not be removed fully, at this moment aforesaid operations can be made up, adopt optimal process for purification.In addition, if also when being difficult to be removed, the pressure that can more increase, high temperature reduce to be made with extra care, and makes the density loss of the carbonyl compound in the resultant.
Can once more by product that generates through separation or the polyvalent alcohol that contains by product be turned back in the reactor.The by product that the boiling point that is produced during fractionation by distillation is higher than the purpose polyvalent alcohol passes through hydrolysis once more, and hydrogenation makes its decomposition etc., a part becomes the purpose polyvalent alcohol, in addition, becomes more lower boiling by product, the boiling point mean value of whole resultant descends, so it is just low to distill required cost of energy.
(relation of hydrolysis and reduction operation)
Though the present invention both can adopt hydrolyzing process and the reduction operation method of carrying out in reactor separately, can adopt again in same container, adding water is hydrolyzed, afterwards, add reductive agent, carry out the reductive method, but people wish that in the presence of water and reductive agent hydrolysis and reduction reaction after this can be carried out simultaneously in same reactor.Its reason is: acetal and/or ketal be hydrolyzed with aldehyde and/or ketogenetic reaction be balanced reaction, in order to promote this balanced reaction, just need a large amount of water.
If there are so a large amount of water to exist, the cost that water is removed from resultant is risen.Yet, if hydrolysis and reduction reaction are after this carried out in same reactor simultaneously, because of aldehyde and/or the ketone that hydrolysis generated can be reduced to alcohol very soon, so reaction is disequilibrated, and depart from toward generation structure, just can only need a spot of interpolation water.At this moment, hydrolysis institute water consumption only is that the required chemical theory amount of hydrolysing substrate gets final product.Certainly, also can excessively use, also can add entry solvent in addition.
With resultant behind the above-mentioned oxidation operation and catalyst separating the time, sometimes be to have used to form 2 layers solvent with alcohol, form the state that is dissolved with resultant in the solvent this moment, is dissolved at this resultant under the state of solvent, also can carry out and the contacting of water and hydrogen, be hydrolyzed and reduce operation.At this moment, the alcohol that deprotection generated is alcohol used in the oxidation operation, so can be separated with solvent.In addition, during as protecting group, generate alcohol, or resultant also be polyvalent alcohol, so most applications is to want the while separate with solvent phase through hydrolysis at acetal and/or ketal.After oxidizing reaction; solvent is in the state that is dissolved with resultant; at this moment steam and desolventize; or utilize method such as distillation that resultant is taken out afterwards, carries out deprotection, hydrolysis, reduction reaction; in contrast to this; with the method that the resultant etc. after the reduction is separated, on simplicity, cost, be favourable.And, utilize this method also easily unreacted carbonyl compound to be separated with the object polyvalent alcohol, improve the purity of polyvalent alcohol.
Better mode to can be hydrolyzed simultaneously operation and reduction operation describes.
Wish to be used for hydrolysis catalyzer, be used for reduction reaction reductive agent, be used for the catalyzer of reduction reaction and the solvent that added any not can because of acid, and water, hydrogen change, its catalytic capability can not reduce.In addition, in the case, can add aforesaid hydrolyst and contact reducing catalyst as catalyzer respectively, also can add their physical mixture, but also can add a kind of catalyzer that chemical bond is arranged between the two with dualism, for example: as carrier, the precious metal that will have the contact reducing power is carried in this supported catalyst with solid peracids such as zeolites.Moreover the known metal catalyst that contains Pt, Ru and Pd etc. of people is in the presence of hydrogen, and the addition catalyst that can be used as acid, hydrogen works, by being hydrolyzed and reduction reaction with so single catalyzer.
As reaction formation, can in the specific reaction times, utilize batch reactor, the gas that makes matrix and water and contain hydrogen contacts and reacts; Also can utilize the external phase reactor to provide continuously and contain water, hydrogenous gas and matrix, react.On the other hand,, or adopt the trickle bed system, be about to catalyzer and be filled on the fixed bed, and matrix, water and hydrogen that corresponding liquid phase state is provided are to fixed bed if catalyzer of the present invention when being immobilized, also can use above-mentioned liquid phase reaction.
When protecting operation acetals, ketal class as protecting group; if protection is hydrolyzed in the operation simultaneously and the words of reduction reaction; then deprotection reaction also can carry out simultaneously; can generate by aldehyde, the synthetic acetals of ketone, the used alcohol of ketal class, the alcohol of pure and mild the object of the invention compound that oxidation operation is used.In these 3 kinds of different occasions, separable and can carry out recirculation to these operations respectively, identical, or have two when identical, just will not separate mutually by alcohol, so just reducing must isolating kind, makes refining the simplification, to industrial be favourable.
Concrete example as: with propenal as raw material, with 1; 3 one propylene glycol are as the protective material in the protection operation, with 1; ammediol is during as pure in the oxidation operation; when deprotection operation, hydrolyzing process and reduction operation are carried out in same reactor simultaneously; become 1 all; ammediol just will not separate by alcohols.
Though set forth the basic constituent element of reaction system of the present invention above, but these integrants just make olefines carry out the condition that comparatively is fit to of oxidizing reaction and hydrolysis and reduction reaction effectively, in addition for each reaction process, can also add other compositions, reactive behavior and reactivity are further improved.Promptly, even add the additive of energy promotes oxidn reaction, for example, the compound of copper compound, basic metal, alkaline-earth metal and rare earth metal etc., free radical scavenger suppresses side reaction, dissolved oxygen concentration increases the solvent that uses in the solution in order to make with adding, the use of supercutical fluid, improve mechanical stirring intensity, with activeconstituents immobilization, the whole bag of tricks that the dispersiveness of catalyst component is increased, also be in the above-mentioned invention scope of the present invention that only contains catalyst component of the present invention.
Among the present invention, utilize propenal and acetal thereof as olefines, wherein use 2-vinyl-1, the 3-diox produces 1 as matrix, the method for ammediol industrial be useful especially, this be because resultant be effective as polyester raw material.By 1, ammediol is made the general method that the manufacture method of polyester can adopt WO9823662, WO9815559 etc. to be put down in writing.
Embodiment
Below, utilize embodiment to come the present invention is further specified.But the present invention is not subjected to the restriction of these embodiment.
In embodiment and comparative example, the following following compound of abbreviation statement:
VDO:2-vinyl-1, the 3-diox
HDO:2-hydroxyethyl-1, the 3-diox
Figure A0182078000222
MAC: mda list (1,3-diox-2-yl) acetal
Figure A0182078000223
DAC: mda two (1,3-diox-2-yl) acetal
Figure A0182078000224
HEDO:2-(6-hydroxyl-3-oxa-hexyl)-1, the 3-diox
Figure A0182078000225
PDE:1, the 3-dioxane oneself-2-guanidine-acetic acid 3-hydroxypropyl acrylate
13PD:1, ammediol
In embodiment and comparative example, the selectivity in the time of can calculating oxidizing reaction by following formula.
The selectivity of purpose compound (%)=(the generation mole number of HDO, MAC, DAC, PDE and)/(all total mole numbers of resultants)
The selectivity of DAC (%)=(total generation mole number of DAC)/(total generation mole number of HDO, MAC, DAC, PDE)
The selectivity of HEDO=(total generation mole number of HEDO)/(total mole number of whole resultants)
(reference example) same intramolecularly has the protective reaction of carbonyl of the olefines of the two keys of carbonyl and alkene.
(reference example 1)
With arbitrary proportion (mol ratio) is the propenal and 1 of 5g with total amount, ammediol mixes, the acidic ion exchange resin Amberlyst15 (doing) (making) that adds 175mg by Rohm and Haas Co., stirring at room (just example (a) stirred 60 minutes in ice bath), after 20 minutes, utilize gas chromatography that it is analyzed, the result is illustrated in the table 1.
Table 1
Charging is than (mol ratio) (1, ammediol/propenal) The productive rate of VDO (is benchmark with ACR) %
????3.91 ????80.7
????3.12 ????79.7
????1.48 ????71.8
????0.92 ????58.0
????0.33 ????27.1
????0.26 ????21.5
????1.50 ????82.0???????????a
A=0 ℃ 60 minutes
(reference example 2)
(internal diameter is 11mm to the glass column that overlaps from strap clamp, length is 120mm) inlet side about 7ml granulated glass sphere of packing into, mix with the acidic ion exchange resin (Amberlyst15) of 175mg with the glass grain of particle diameter then, the whole volume of packing into is the catalyst layer of 5ml, with granulated glass sphere post is filled up afterwards, by the LC pump, with propenal and 1, it is 1: 1.5 solution that ammediol is made mol ratio, and the flow that divides with 0.494g/ flows through (being approximately 7 minutes duration of contact).Chuck partly flows through the other water of stipulating temperature, so that column jecket remains on 25 ℃ temperature.In the exit, collect liquid, utilize GC to analyze, the productive rate of VDO is 64.8% as a result.
(reference example 3)
Pack into the Amberlyst15 of 3ml of discord glass grain flows with 0.29g/min (being approximately 6 minutes duration of contact) with mixing, and the temperature of chuck is decided to be 0 ℃, and other and reference example 2 are reacted equally, and the productive rate of VDO is 78.3%.
(embodiment 1)
With propenal and 1, ammediol with 1: 3 mixed in molar ratio and mixture in, adding mixture is the acidic ion exchange resin (exsiccant Amberlyst15) of 2wt%, after carrying out under the room temperature stirring in 20 minutes, with the catalyzer filtering.In reaction mixture, the methylene dichloride that adds 4 times of volumes extracts.Behind the separatory, utilize the anhydrous magnesium sulfate drying dichloromethane layer after, siccative is filtered out, the distillation.With propenal as benchmark, purpose compound 2-vinyl-1,3-diox (VDO), productive rate are 70%.
At 6g1, be dissolved with Na in the ammediol fully 2PdCl 40.1mmol, CuCl 0.1mmol, FeCl 30.1mmol solution in, add the VDO 9.7mmol of above-mentioned reaction gained.This solution is joined in the stainless steel pressure kettle that has special teflon inner core and agitator, add benzene 6g again, will make the pressure of oxygen be decided to be 0.7MPa wherein with after the oxygen displacement.Put it in 80 ℃ the water-bath, stir.At this moment, replenish the dividing potential drop that is consumed oxygen, to guarantee the constant pressure of oxygen.After beginning to stir 25 minutes, cool off suddenly while stir with ice bath.With gas chromatography reaction mixture is analyzed, the transformation efficiency of VDO is 98.2%, and the selectivity of purpose compound is 79.4% (selectivity of DAC is 75.0%), and the selectivity of HEDO is 7.0%.
The purpose compound here refers to HDO, MAC, DAC, PDE, in following each example too.The benzene layer is separated, benzene is removed the back from this benzene layer distillation material is made with extra care, obtain the mixture of purpose resultant.In this mixture, add the 5%Ru/C of 0.25g zeolite USY (ratio of silicon/aluminum oxide is 50) and 0.38g, the water of 2.5g, and put it in the pressure kettle.After replacing with hydrogen, the pressure of hydrogen is decided to be 0.9MPa, is put into then in 80 ℃ the oil bath, be consumed up to no hydrogen, can't see hydrogen pressure decline, be hydrolyzed and reduction reaction by stirring.Need about 30 minutes during this.HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 2)
At 6g 1, be dissolved with Na in the ammediol fully 2PdCl 40.1mmol, CuCl 0.1mmol, FeCl 30.1mmol solution in, add propenal 19mmol, stirred 30 minutes.This solution is joined in the stainless steel pressure kettle that has special teflon inner core and agitator, add 6g benzene again, after oxygen displacement wherein, make the pressure of oxygen be decided to be 0.7MPa.Put it in 80 ℃ the water-bath, stir.At this moment, replenish the oxygen partial pressure that is consumed, to guarantee the constant pressure of oxygen.After beginning to stir 25 minutes, cool off suddenly while stir with ice bath.With gas chromatography reaction mixture is analyzed, the transformation efficiency of propenal is 100%, and the selectivity of purpose compound is 77.5% (selectivity of DAC is 73.9%), and the selectivity of HEDO is 14.4%.
The benzene layer is separated, benzene is removed the back from this benzene layer distillation material is made with extra care, obtain HDO (2.6mmol), DAC (9.96mmol).In this mixture, add the 5%Ru/C of 0.25g zeolite USY (ratio of silica/alumina is 50) and 0.38g, the water of 2.5g, and put it in the pressure kettle.After replacing with hydrogen, hydrogen pressure is decided to be 0.9MPa, is put into then in 80 ℃ the oil bath, be consumed up to no hydrogen, can't see hydrogen pressure decline, be hydrolyzed and reduction reaction by stirring.Need about 30 minutes during this.HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 3)
Except using PdCl 2(CH 3CN) 2Replace Na 2PdCl 4, with 1, the amount of ammediol is decided to be 10g, replace beyond the propenal with the VDO of 15.9mmol, other all with embodiment 2 in the same method react.The transformation efficiency of VDO is 100%, and the selectivity of purpose compound is 65.7% (selectivity 78.4% of DAC), and the selectivity of HEDO is 27.9%, and HDO, the transformation efficiency of DAC are 99.5%, and the selectivity of 13PD is 99.7%.
(embodiment 4)
Except replacing propenal with 9.7mmol VDO, replace beyond the benzene with hexane, other all with embodiment 2 the same reactions.The transformation efficiency of VDO is 100%, and the selectivity of purpose compound is 73.0% (selectivity 73.3% of DAC), and the selectivity of HEDO is 14.4%, and HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 5)
Except replace propenal with 9.7mmol VDO, with 1, the amount of ammediol is decided to be 1g, replace beyond the benzene of 6g with the ethylene dichloride of 10g, other all with embodiment 2 identical reactions.The transformation efficiency of VDO is 85.8%, and the selectivity of purpose compound is 85.1% (selectivity 71.6% of DAC), and the selectivity of HEDO is 0.9%, and HDO, the transformation efficiency of DAC are 99.4%, and the selectivity of 13PD is 99.5%.
(embodiment 6)
Except replace propenal with 9.7mmol VDO, with 1, the amount of ammediol is decided to be 2g, replaces the benzene of 6g with the ethanol of 10g, stir beyond beginning cooled off later in 10 minutes, other all with embodiment 2 identical reactions.The transformation efficiency of VDO is 100%, and the selectivity of purpose compound is 75.2% (selectivity 71.3% of DAC), and the selectivity of HEDO is 1.1%, and HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 7)
Except replace propenal with 9.7mmol VDO, with 1, the amount of ammediol is decided to be 2g, replace with methyl alcohol beyond the benzene of 6g, other all with embodiment 3 identical reactions.The transformation efficiency of VDO is 98.7%, and the selectivity of purpose compound is 68.9% (selectivity 74.3% of DAC), and the selectivity of HEDO is 4.6%, and HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 8)
Except replace propenal with 9.7mmol VDO, with 1, the amount of ammediol is decided to be 2g, makes the amount of benzene be decided to be 8g, begin to stir cool off after 35 minutes beyond, other all with embodiment 2 identical reactions.The transformation efficiency of VDO is 100%, and the selectivity of purpose compound is 87.9% (selectivity 83.4% of DAC), and the selectivity of HEDO is 3.5%, and HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 9)
Except replace propenal with 9.7mmol VDO, without FeCl 3, begin to stir cool off after 60 minutes beyond, other all with embodiment 2 identical reactions.The transformation efficiency of VDO is 96.1%, and the selectivity of purpose compound is 59.1% (selectivity 69.1% of DAC), and the selectivity of HEDO is 27.5%, and HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 10)
Except replace propenal with 9.7mmol VDO, when the tetrem oxygen silicon of 2g is dissolved in oxidizing reaction in the added benzene, other all with embodiment 2 identical reactions.The transformation efficiency of VDO is 97.8%, and the selectivity of purpose compound is 84.5% (selectivity 78.7% of DAC), and the selectivity of HEDO is 2.9%, and HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 11)
Except with 1, the amount of ammediol is decided to be 4g, makes the amount of benzene be decided to be 8g, begin to stir cool off after 15 minutes beyond, other all with embodiment 9 identical reactions.The transformation efficiency of VDO is 97.2%, and the selectivity of purpose compound is 91.8% (selectivity 80.4% of DAC), and the selectivity of HEDO is 2.6%, and HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 12)
Except replace propenal with 9.7mmol VDO, with 2,6-two-t-butyl-when this polymerization retarder of 4-cresylol 0.5g is dissolved in oxidizing reaction in the added benzene beyond, other all with embodiment 2 identical reactions.The transformation efficiency of VDO is 98.1%, and the selectivity of purpose compound is 77.5% (selectivity 72.0% of DAC), and the selectivity of HEDO is 14.4%, and HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 13)
At 6g 1, be dissolved with Na in the ammediol fully 2PdCl 40.1mmol, CuCl 0.1mmol, FeCl 30.1mmol solution in, add 6g benzene.This solution is joined in the stainless steel pressure kettle that has special teflon inner core and agitator, after oxygen displacement wherein, again it is positioned in 80 ℃ the water-bath, in pressure kettle, become 80 ℃.Add the VDO of 10mmol in this solution, the pressure that makes oxygen is 0.7MPa, stirs.At this moment, replenish the oxygen partial pressure that is consumed so that its pressure keeps constant.After beginning to stir 10 minutes, cooling utilizes gas chromatography that reaction mixture is analyzed, and the transformation efficiency of VDO is 100%, and the selectivity of purpose compound is 78.4% (selectivity 76.0% of DAC), and the selectivity of HEDO is 8.4%.
After this, be hydrolyzed and hydrogenation with the method identical with embodiment 2.HDO, the transformation efficiency of DAC are 99.6%, and the selectivity of 13PD is 99.6%.
(embodiment 14)
Except replacing propenal with 9.7mmol VDO, the tungstosilicic acid mixture replaced the zeolite USY, other all with embodiment 2 identical reactions.HDO, the transformation efficiency of DAC are 91.0%, and the selectivity of 13PD is 96.5%.
(comparative example 1)
Except replacing propenal with 9.7mmol VDO and not adding Na 2PdCl 40.1mmol, CuCl 0.1mmo1, FeCl 30.1mol in addition, other all with embodiment 2 identical reactions.Consequently: do not have DAC fully and generate, raw material is recovered.
(comparative example 2)
Except replacing propenal with 9.7mmol VDO and replace the oxygen with nitrogen, other are all identical with embodiment 2, only obtain HEDO.
The possibility of using on the industry
By the present invention, just can suppress side reaction, and high conversion and highly selective will make polyalcohol with the olefines of carbonyl, industrial value is high.

Claims (18)

1. the manufacture method of polyalcohols; it is characterized in that; make same intramolecularly have carbonyl and/or its protecting group and have the olefines of the two keys of alkene and oxygen and alcohols react; obtain containing the resultant of reaction of acetal and/or ketal compound; then, with this acetal and/or ketal compound is hydrolyzed and reduction reaction makes polyalcohols.
2. the manufacture method of polyalcohols; it is characterized in that; the olefines and the protective material that make same intramolecularly have carbonyl and the two keys of alkene react; after carbonyl protected; olefines with the two keys of protected carbonyl and alkene and oxygen and alcohols are reacted; obtain corresponding acetal and/or ketal compound, then this acetal and/or ketal compound are carried out deprotection, hydrolysis and reduction reaction make polyalcohols.
3. the manufacture method of polyalcohols according to claim 1 is characterized in that, described carbonyl and/or its protecting group are the groups that is selected from aldehyde radical and acetal radical, ketone group and ketal group thereof, carboxyl, comprises the ester group of lactone.
4. according to claim 1 or 3 described polyalcohols manufacture method, it is characterized in that described olefines is to be selected from α, β unsaturated aldehyde and acetal thereof, α, beta unsaturated ketone and ketal thereof, α, the compound of β unsaturated carboxylic acid and ester thereof.
5. polyalcohols manufacture method according to claim 4 is characterized in that, described olefines is propenal and/or its acetal.
6. polyalcohols manufacture method according to claim 5 is characterized in that, described olefines is to be selected from 2-vinyl-1,3-dioxolane, 2-vinyl-1,3-diox and 2-vinyl-1, the acetal of the propenal of 3-dioxepin.
7. polyalcohols manufacture method according to claim 4 is characterized in that, described olefines is vinylformic acid and/or its ester.
8. according to each described polyalcohols manufacture method among the claim 1-7, it is characterized in that described alcohols is a di-alcohols.
9. according to each described polyalcohols manufacture method among the claim 1-8, it is characterized in that, when described olefines and oxygen and alcohols react, use the catalyzer that contains palladium and copper and/or iron.
10. according to the described polyalcohols manufacture method of each kind among the claim 1-9, it is characterized in that, when described olefines and oxygen and alcohols react, have halide-ions in the reaction system.
11. polyalcohols manufacture method according to claim 10 is characterized in that, is selected from a kind of halogenide that forms in palladium, copper and the iron as catalyst component at least.
12. according to each described polyalcohols manufacture method among the claim 1-11, it is characterized in that, when described olefines and oxygen and alcohols react, have in the reaction system can and this alcohols form two layers solvent.
13. polyalcohols manufacture method according to claim 12 is characterized in that, the solvent that energy and the formation of described alcohols are two layers is selected from aromatic hydrocarbons, aliphatic hydrocarbon and halohydrocarbon.
14. according to each described polyalcohols manufacture method among the claim 1-13, it is characterized in that, at the acetal that makes described olefines and oxygen and alcohols reaction gained and/or ketal compound is hydrolyzed and reduction reaction when making polyalcohols, hydrolysis and reduction reaction are carried out in same reactor.
15., it is characterized in that the deprotection of described acetal and/or ketal compound, hydrolysis and reduction reaction are all carried out in same reactor according to each described polyalcohols manufacture method among the claim 2-14.
16. according to claim 14 or 15 described polyalcohols manufacture method, it is characterized in that, when in same reactor, being hydrolyzed, use the zeolite that is loaded with as the precious metal of catalyzer with reduction reaction.
17., it is characterized in that the polyalcohols of making is 1, ammediol according to each described polyalcohols manufacture method among the claim 1-16.
18. a polyester is characterized in that, utilizes the polyvalent alcohol that each described polyalcohols manufacture method obtains among the claim 1-17 to make.
CNB018207804A 2000-12-18 2001-12-18 Process for preparation of polyhydric alcohols Expired - Fee Related CN100488927C (en)

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US3963754A (en) * 1974-07-31 1976-06-15 E. I. Du Pont De Nemours And Company 2-Vinyl-5-methyl-1,3-dioxane
US3929915A (en) * 1974-07-31 1975-12-30 Du Pont Process for the production of butanediol
US4200765A (en) * 1976-09-17 1980-04-29 National Distillers And Chemical Corporation Glycol aldehyde and ethylene glycol processes
EP0055108B1 (en) * 1980-12-23 1984-09-05 Ube Industries, Ltd. Process for producing an acetal
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JPH06234759A (en) * 1993-02-10 1994-08-23 Mitsubishi Petrochem Co Ltd Production of 1,4-butanedial monoacetal
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JPH0881396A (en) * 1994-09-13 1996-03-26 Denki Kagaku Kogyo Kk Production of acetal
JP3781059B2 (en) * 1995-07-07 2006-05-31 三菱瓦斯化学株式会社 Method for producing 1,3-propanediol
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