CN1222900A

CN1222900A - Processes for producing 1,6-hexanediols

Info

Publication number: CN1222900A
Application number: CN 97195720
Authority: CN
Inventors: A·S·古拉姆; J·R·布里格斯; D·L·帕克特; K·D·奥尔森; T·C·埃森施米德; E·B·特雅登
Original assignee: Union Carbide Chemicals and Plastics Technology LLC
Current assignee: Union Carbide Chemicals and Plastics Technology LLC
Priority date: 1996-04-24
Filing date: 1997-04-23
Publication date: 1999-07-14

Abstract

This invention relates to processes for producing one or more substituted or unsubstituted 1,6-hexanediols, e.g., 1,6-hexanediol, which comprise subjecting one or more substituted or unsubstituted alkadienes to hydrocarbonylation in the presence of a hydrocarbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and a promoter and optionally free ligand to produce said one or more substituted or unsubstituted 1,6-hexanediols. The substituted and unsubstituted 1,6-hexanediols produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof, e.g., epsilon caprolactone. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted 1,6-hexanediols as principal product(s) of reaction.

Description

Preparation 1, the method for 6-hexylene glycol

The invention overview

Technical field

The present invention partly relates to selectivity and produces one or more replacements or unsubstituted 1, the method for 6-hexylene glycol.The present invention also part relates to and containing as one or more replacements of required reaction product or unsubstituted 1, the reaction mixture of 6-hexylene glycol.

Background of invention

1, the 6-hexylene glycol is useful, a valuable intermediate in producing polyester for example.Use at present and produce 1, the method for 6-hexylene glycol has many shortcomings.For example, be used to produce 1, the raw material of 6-hexylene glycol is valuable relatively.In addition, to 1, the selectivity of 6-hexylene glycol is low in the method for prior art.Therefore, hope is optionally to produce 1, the 6-hexylene glycol from relatively inexpensive raw material and the economic method of use.

The present invention is open

Found alkadiene to be changed into straight diol with single step reaction.Found that also the unsaturated alcohol that will have interior alkene changes into straight diol.Particularly be surprisingly found out that and use catalyzer amylene-1-ol can be changed into 1 as the 3-amylene-1-ol with hydroformylation (hydrocarbonylation)/isomer ability, 6-hexylene glycol class, as 1, the 6-hexylene glycol.Further find in metal-ligand coordination catalyst and optional free ligand; the existence of the organic phosphine coordination body of the strong and low spatial loose density of the preferred alkalescence of wherein said ligand is descended and at promotor, promptly has pKa and carries out hydroformylation reaction under the existence of the organic or inorganic compound of the ionizable hydrogen of about 1-about 35 and can obtain highly selective and high straight chain: the branched chain isomer ratio.

The present invention relates to produce one or more replacements or unsubstituted 1; the 6-hexylene glycol; as 1; the method of 6-hexylene glycol; it is included in hydroformylation catalysts; under the existence as metal-organophosphorus ligand coordination catalyst and promotor and optional free ligand, it is described one or more replacements or unsubstituted 1 that one or more replacements or unsubstituted alkadiene are produced through hydroformylation, the 6-hexylene glycol.

The present invention also relates to produce one or more replacements or unsubstituted 1; the 6-hexylene glycol; as 1; the method of 6-hexylene glycol; it is included in hydroformylation catalysts; under the existence as metal-organophosphorus ligand coordination catalyst, promotor and optional free ligand, it is described one or more replacements or unsubstituted 1 that one or more replacements or unsubstituted pentenals are produced through hydroformylation, the 6-hexylene glycol.

The invention further relates to and produce one or more replacements or unsubstituted 1; the 6-hexylene glycol; as 1; the method of 6-hexylene glycol; it is included in hydroformylation catalysts; exist down as metal-organophosphorus ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted amylene-1-ol produce described one or more replacements or unsubstituted 1,6-hexylene glycol through hydroformylation.

The present invention also further relates to production one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of 6-hexylene glycol, it comprises: (a) at hydroformylation catalysts, under the existence as metal-organophosphorus ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene, produce amylene-1-ol one or more replacements or unsubstituted through hydroformylation as divinyl; (b) at hydroformylation catalysts; under the existence as metal-organophosphorus ligand coordination catalyst, promotor and optional free ligand; it is described one or more replacements or unsubstituted 1 that described one or more replacements or unsubstituted amylene-1-ol are produced through hydroformylation, the 6-hexylene glycol.In step (a) and (b) reaction conditions of hydroformylation can be identical or different can be identical or different with hydroformylation catalysts in step (a) and (b).

The present invention also relates to produce one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of 6-hexylene glycol, it is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1,6-hexylene glycol.In preferred embodiments, described metal-ligand coordination catalyst is one or more raw materials, intermediate or the product that metal-organophosphorus ligand coordination catalyst and described promotor are this laws.

The invention further relates to and produce one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of 6-hexylene glycol, it is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted pentenals and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1,6-hexylene glycol.In preferred embodiments, described metal-ligand coordination catalyst is one or more raw materials, intermediate or the product that metal-organophosphorus ligand coordination catalyst and described promotor are this laws.

The present invention also further relates to production one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of 6-hexylene glycol, it is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1,6-hexylene glycol.In preferred embodiments, described metal-ligand coordination catalyst is one or more raw materials, intermediate or the product that metal-organophosphorus ligand coordination catalyst and described promotor are this laws.

The present invention also relates to produce one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of 6-hexylene glycol, it comprises: (a) at metal-ligand coordination catalyst, under the existence of promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene and carbon monoxide and H-H reaction produce one or more replacements or unsubstituted amylene-1-ol and (b) at metal-ligand coordination catalyst, under the existence of promotor and optional free ligand, make described one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1,6-hexylene glycol.The hydroformylation reaction condition can be identical or different in step (a) and (b), can be identical or different with hydroformylation catalysts in step (a) and (b).In preferred embodiments, described metal-ligand coordination catalyst is one or more raw materials, intermediate or the product that metal-organophosphorus ligand coordination catalyst and described promotor are this laws.

The present invention further part relates to the method for the reaction mixture that production produces in batches or continuously, and this reaction mixture comprises:

(1) one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the 6-hexylene glycol;

(2) choose any one kind of them or multiple replacement or unsubstituted amylene-1-ol, as suitable-2-amylene-1-ol, anti--the 2-amylene-1-ol, suitable-the 3-amylene-1-ol, anti--3-amylene-1-ol and/or 4-amylene-1-ol;

(3) choose any one kind of them or multiple replacement or unsubstituted 6-hydroxyl hexanal, as 6-hydroxyl hexanal;

(4) choose any one kind of them or multiple replacement or unsubstituted 5-hydrogenation of hydroxypentylaldehyd, and/or its ring lactol derivative, as 2-methyl-5-hydrogenation of hydroxypentylaldehyd;

(5) choose any one kind of them or multiple replacement or unsubstituted 4-acetaldol and/or its ring lactol derivative, as 2-ethyl-4-acetaldol;

(6) choose any one kind of them or multiple replacement or unsubstituted penta-1-alcohol;

(7) choose any one kind of them or multiple replacement or unsubstituted valeral;

(8) choose any one kind of them or multiple replacement or unsubstituted pentenals, as suitable-2-pentenals, anti--the 2-pentenals, suitable-the 3-pentenals, anti--3-pentenals and/or 4-pentenals;

(9) choose any one kind of them or multiple replacement or unsubstituted 1, the 6-hexanedial is as hexanedial;

(1 0) choose any one kind of them or multiple replacement 1, the 5-glutaraldehyde is as 2-methylpent dialdehyde;

(11) choose any one kind of them or multiple replacement 1, the 4-suceinic aldehyde, as 2,3-dimethyl butyrate dialdehyde and 2-ethyl suceinic aldehyde; With

(12) one or more replacements or unsubstituted divinyl are as divinyl; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is greater than about 0.1, be preferably greater than about 0.25, more preferably greater than about 1.0; And the weight ratio of component (12) and component (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is that about 0-is about 100, preferably about 0.001-about 50; Wherein method is included in metal-ligand coordination catalyst, promotor and optional free ligand existence down, makes one or more replacements or unsubstituted divinyl and carbon monoxide and H-H reaction produce the described reaction mixture that produces in batches or continuously.In preferred embodiments, described metal-ligand coordination catalyst is one or more raw materials, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention also further part relates to the method for the reaction mixture that production produces in batches or continuously, and this reaction mixture comprises:

(7) choose any one kind of them or multiple replacement or unsubstituted valeral; With

(8) choose any one kind of them or multiple replacement or unsubstituted pentenals, as suitable-2-pentenals, anti--the 2-pentenals, suitable-the 3-pentenals, anti--3-pentenals and/or 4-pentenals; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6) and (7) summation is greater than about 0.1, be preferably greater than about 0.25, more preferably greater than about 1.0; And the weight ratio of component (8) and component (1), (2), (3), (4), (5), (6) and (7) summation is that about 0-is about 100, preferably about 0.001-about 50; Wherein method is included in metal-ligand coordination catalyst, promotor and optional free ligand existence down, makes one or more replacements or unsubstituted pentenals and carbon monoxide and H-H reaction produce the described reaction mixture that produces in batches or continuously.In preferred embodiments, described metal-ligand coordination catalyst is one or more raw materials, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention also part relates to the method for the reaction mixture that production produces in batches or continuously, and this reaction mixture comprises:

(2) one or more replacements or unsubstituted amylene-1-ol are as suitable-2-amylene-1-ol, anti--the 2-amylene-1-ol, suitable-the 3-amylene-1-ol, anti--3-amylene-1-ol and/or 4-amylene-1-ol;

(5) choose any one kind of them or multiple replacement or unsubstituted 4-acetaldol and/or its ring lactol derivative, as 2-ethyl-4-acetaldol; With

(6) choose any one kind of them or multiple replacement or unsubstituted valeral; Wherein the weight ratio of component (1) and component (3), (4), (5) and (6) summation is greater than about 0.1, be preferably greater than about 0.25, more preferably greater than about 1.0; And the weight ratio of component (2) and component (1), (3), (4), (5) and (6) summation is that about 0-is about 100, preferably about 0.001-about 50; This method is included in metal-ligand coordination catalyst, promotor and optional free ligand and exists down, makes one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction produce the described reaction mixture that produces in batches or continuously.In preferred embodiments, described metal-ligand coordination catalyst is one or more raw materials, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention further partly relates to the production proportion by subtraction or produces the method for reaction mixture continuously, and described reaction mixture comprises:

(10) choose any one kind of them or multiple replacement 1, the 5-glutaraldehyde is as 2-methylpent dialdehyde;

(12)-kind or multiple replacement or unsubstituted divinyl, as divinyl; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is greater than about 0.1, be preferably greater than about 0.25, more preferably greater than about 1.0; And the weight ratio of component (12) and component (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is that about 0-is about 100, preferably about 0.001-about 50; This method comprises: (a) in the presence of metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted divinyl and carbon monoxide and H-H reaction produce one or more replacements or unsubstituted amylene-1-ol and (b) in the presence of metal-ligand coordination catalyst, promotor and optional free ligand, make described one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction produce the described reaction mixture of generation in batches or continuously.The hydroformylation reaction condition can be identical or different in step (a) and (b), can be identical or different with hydroformylation catalysts in step (a) and (b).In preferred embodiments, described metal-ligand coordination catalyst is one or more raw materials, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention also further relates to production and comprises one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of the reaction mixture of 6-hexylene glycol, this method is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, makes one or more replacements or unsubstituted alkadiene and carbon monoxide and H-H reaction production described that comprise one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the reaction mixture of 6-hexylene glycol.In preferred embodiments, described metal-ligand coordination catalyst is one or more replacements or unsubstituted raw material, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention also relates to produce and comprise one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of the reaction mixture of 6-hexylene glycol, this method is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, makes described one or more replacements or unsubstituted 1, the 6-hexylene glycol of comprising of one or more replacements or unsubstituted pentenals and carbon monoxide and H-H reaction production, as 1, the reaction mixture of 6-hexylene glycol.In preferred embodiments, described metal-ligand coordination catalyst is one or more replacements or unsubstituted raw material, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The invention further relates to produce and comprise one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of the reaction mixture of 6-hexylene glycol, this method is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, makes described one or more replacements or unsubstituted 1, the 6-hexylene glycol of comprising of one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction production, as 1, the reaction mixture of 6-hexylene glycol.In preferred embodiments, described metal-ligand coordination catalyst is one or more replacements or unsubstituted raw material, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention also further relates to production and comprises one or more replacements or unsubstituted 1, the 6-hexylene glycol, as 1, the method of the reaction mixture of 6-hexylene glycol, this method comprises: (a) at metal-ligand coordination catalyst, under the existence of promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene and carbon monoxide and H-H reaction production comprise the reaction mixture of one or more replacements or unsubstituted amylene-1-ol and (b) at metal-ligand coordination catalyst, promotor and optional free ligand exist down, make described one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol of comprising.The reaction conditions of hydroformylation can be identical or different in step (a) and (b), can be identical or different with hydroformylation catalysts in step (a) and (b).In preferred embodiments, described metal-ligand coordination catalyst is one or more replacements or unsubstituted raw material, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

Method of the present invention can obtain alkadiene to 1, and the highly selective of 6-hexylene glycol is as obtaining divinyl to 1 by method of the present invention, 6-hexylene glycol as many as 10% (weight) or higher selectivity.Equally, the inventive method can obtain high straight chain: the branched chain isomer ratio, as with high straight chain: the branched chain isomer ratio makes the butadiene hydrogenation formylation get 1, the 6-hexylene glycol.

The present invention also part relates to the reaction mixture that produces in batches or continuously, and this mixture comprises:

(12)-kind or multiple replacement or unsubstituted divinyl, as divinyl; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is greater than about 0.1, be preferably greater than about 0.25, more preferably greater than about 1.0; And the weight ratio of component (12) and component (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is that about 0-is about 100, preferably about 0.001-about 50;

The present invention further part relates to the reaction mixture that produces in batches or continuously, and this mixture comprises:

(8) choose any one kind of them or multiple replacement or unsubstituted pentenals, as suitable-2-pentenals, anti--the 2-pentenals, suitable-the 3-pentenals, anti--3-pentenals and/or 4-pentenals; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6) and (7) summation is greater than about 0.1, be preferably greater than about 0.25, more preferably greater than about 1.0; And the weight ratio of component (8) and component (1), (2), (3), (4), (5), (6) and (7) is that about 0-is about 100, preferably about 0.001-about 50;

The present invention also further partly relates to the reaction mixture that produces in batches or continuously, and this mixture comprises:

(6) choose any one kind of them or multiple replacement or unsubstituted valeral; Wherein the weight ratio of component (1) and component (3), (4), (5) and (6) summation is greater than about 0.1, be preferably greater than about 0.25, more preferably greater than about 1.0; And the weight ratio of component (2) and component (1), (3), (4), (5) and (6) summation is that about 0-is about 100, preferably about 0.001-about 50;

The present invention also partly relates to and comprises one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol, wherein exist down by being included in metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene and carbon monoxide and H-H reaction production comprise one or more replacements or unsubstituted 1, the method for the described reaction mixture of 6-hexylene glycol prepares described reaction mixture.In preferred embodiments, described metal-ligand coordination catalyst is one or more replacements or unsubstituted raw material, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention further partly relates to and comprises one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol, wherein exist down by being included in metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted pentenals and carbon monoxide and H-H reaction production comprise one or more replacements or unsubstituted 1, the method for the described reaction mixture of 6-hexylene glycol prepares described reaction mixture.In preferred embodiments, described metal-ligand coordination catalyst is one or more replacements or unsubstituted raw material, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention also further partly relates to and comprises one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol, wherein exist down by being included in metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction production comprise one or more replacements or unsubstituted 1, the method for the described reaction mixture of 6-hexylene glycol prepares described reaction mixture.In preferred embodiments, described metal-ligand coordination catalyst is one or more replacements or unsubstituted raw material, intermediate or the product that metal-organic phosphine coordination body coordination catalyst and described promotor are this laws.

The present invention also partly relates to and comprises one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol, the method that wherein prepares described reaction mixture comprises: (a) at metal-ligand coordination catalyst, under the existence of promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene and carbon monoxide and H-H reaction produce one or more replacements or unsubstituted amylene-1-ol and (b) at metal-ligand coordination catalyst, under the existence of promotor and optional free ligand, make described one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1, the described reaction mixture of 6-hexylene glycol of comprising.The hydroformylation reaction condition can be identical or different in step (a) and (b), can be identical or different with hydroformylation catalysts in step (a) and (b).In preferred embodiments, described metal-ligand coordination catalyst is one or more replacements or unsubstituted raw material, intermediate or the product that metal-organophosphorus ligand coordination catalyst and described promotor are this laws.

Reaction mixture of the present invention is characteristic, produces 1 of highly selective because this preparation method can obtain, the 6-hexylene glycol, and its mode is fit to be applied to produce 1, in the industrial process of 6-hexylene glycol.Reaction mixture particularly of the present invention is characteristic, because this preparation method makes 1, the relative yield of 6-hexylene glycol production is high and do not produce a large amount of byproducts, as amylalcohol and 2-methyl 1,5-pentanediol.Describe in detail

Hydroformylation process of the present invention comprises one or more replacements or unsubstituted alkadiene is changed into one or more replacements or unsubstituted 1; the 6-hexylene glycol; one or more replacements or unsubstituted alkadiene are changed into one or more replacements or unsubstituted amylene-1-ol and/or one or more replacements or unsubstituted amylene-1-ol are changed into one or more replacements or unsubstituted 1,6-hexylene glycol.The method of hydroformylation of the present invention can be carried out in a step or multistep (or stage), preferred one step process.The hydroformylation process that comprises that all are allowed can be imagined in term " hydroformylation " just as used in this; it comprises one or more replacements or unsubstituted alkadiene is changed into one or more replacements or unsubstituted 1; the 6-hexylene glycol; one or more replacements or unsubstituted alkadiene are changed into one or more replacements or unsubstituted amylene-1-ol and/or one or more replacements or unsubstituted amylene-1-ol are changed into one or more replacements or unsubstituted 1,6-hexylene glycol.It is open in U.S. Patent Application Serial (D-17761) to be applied to preferred hydroformylation process among the present invention, application (filed on aneven date herewith) meanwhile, and the content of the disclosure is done concrete reference at this in conjunction with the present invention.

Hydroformylation process is included under the existence of metal-ligand coordination catalyst and optional free ligand; in the liquid medium that also contains promotor, make alkadiene and/or undersaturated alcohol and carbon monoxide and H-H reaction produce 1,6-hexylene glycol and/or undersaturated alcohol.Can be in continuous single pass mode with continuous gas Recycle design or more preferably described as followsly carry out described reaction with the continuous liquid catalyst Recycle design.In this applicable hydroformylation processing technology corresponding to any known processing technology.

Mixture at the hydroformylation process of this application comprises any solution that is derived from any corresponding hydroformylation process; it contains at least one quantitative 4 kinds of different main components or component; be glycol product, metal-ligand coordination catalyst, promotor and optional free ligand; described composition is equivalent to the composition that hydroformylation process utilizes and/or produces, and therefrom can obtain the raw material of hydroformylation process mixture.So-called " free ligand " is meant the ligand that does not cooperate the coordination catalyst of (being connected or bonding) with metal such as rhodium atom.Will be understood that to form and can and generally contain a small amount of other composition as composition intended application in hydroformylation process or that in described method, form on the spot at the mixture of the hydroformylation process of this application.The example of this constituents that can exist comprises unreacted alkadiene or unsaturated alcohol raw material, carbon monoxide and hydrogen, the unreacted isomerized alkene of by product of Xing Chenging such as saturated alcohol and/or corresponding alkadiene or unsaturated alcohol raw material, high boiling liquid by product on the spot, and other inertia cosolvent type raw material or hydrocarbon additive (when using).

The catalyzer that is applied to hydroformylation process comprises metal-ligand coordination catalyst.The permissible metal that constitutes metal-ligand compositions comprises and is selected from 8,9 and 10 following family's metals: rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and its mixture, preferable alloy is rhodium, cobalt, iridium and ruthenium, more preferably rhodium, cobalt and ruthenium, particularly rhodium.Permissible ligand comprises for example organophosphorus, organoarsenic and antimony organic ligand or its mixture, preferred organic phosphorus ligand.Constituting the permissible organophosphorus ligand of metal-organophosphorus ligand complex and free organophosphates ligand comprises one-, two-, three-and more high-grade poly--(organophosphorus) compound, the compound of preferred high basicity and low spatial loose density.Illustration as permissible organophosphorus ligand comprises for example organophosphorus, organophosphite, Organophosphonate, organic phosphinate, the nitrogenous ligand of organophosphorus, organophosphorus sulfur-bearing ligand, the siliceous ligand of organophosphorus etc.Other permissible ligand comprises and for example contains the heteroatoms ligand, the ligand described in U.S. Patent Application Serial (D-17646-) (application on March 10th, 1997), and the content of the disclosure is done concrete reference at this in conjunction with the present invention.If need, in metal-ligand coordination catalyst and/or free ligand, can use the mixture of this class ligand, they can be identical or different.The enforcement that can notice success of the present invention is not depended on and not based on the definite structure of metal-ligand compositions kind, this structure can exist with monokaryon, double-core and/or higher nuclear (nuclearity) form.In fact, do not know precise structure.Though do not want to be subject to any theory or mechanism at this, seem the kind of described catalyzer can combine with ligand and employed carbon monoxide by metal in the title complex substantially and form with simple form.

Employed term " title complex " meaning is for by having the one or more electron rich molecules that independently there are ability or atom and having the coordination compound that the one or more electron-deficient molecules that independently have ability or atom combine formation respectively in this and claims.For example, ligand as used herein, promptly the organophosphorus ligand can have one or more phosphorus donor atoms, and each atom has one and can utilize or unshared electron pair, wherein the every pair of electronics have independent form the coordinate-covalent bond ability or can combine with metal is collaborative (as, pass through sequestering action).Carbon monoxide (but also proper classification is a ligand) also can exist and cooperate with metal.The final elementary composition of coordination catalyst also can contain additional ligand, as hydrogen or satisfy the coordination position or the negatively charged ion of metal core electric charge.Illustration as additional ligand comprises as halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl group, CF ₃, C ₂F ₅, CN, (R) ₂PO and RP (O) be O (wherein each R is identical or different and is to replace or unsubstituted alkyl, as alkyl or aryl), acetate, acetylacetonate, SO (OH) ₄, BF ₄, PF ₆, NO ₂, NO ₃, CH ₃O, CH ₂=CHCH ₂, CH ₃CH=CHCH ₂, C ₆H ₅CN, CH ₃CN, NO, NH ₃, pyridine, (C ₂H ₅) ₃N, monoolefine, diolefin and alkatrienes, tetrahydrofuran (THF) etc.Certainly will be understood that the title complex kind does not preferably contain any other organic ligand or the negatively charged ion that can make poisoning of catalyst and catalyst performance be had undue disadvantageous effect.Preferred active catalyst is the halogen and the sulphur of no Direct Bonding metal in the hydroformylation process of metal-ligand coordination catalysis, though this is not indispensable.Preferred metal-ligand coordination catalyst comprises rhodium-organic phosphine coordination body coordination catalyst.

Known in the art in such metal the number of available coordination position.Thereby this class catalyst type can comprise with single poly-, the double focusing or the mixture of the coordination catalyst of multinuclear form more, and its preferable feature is that each metal such as rhodium cooperate a phosphorated molecule at least.As mentioned above, owing to use carbon monoxide and hydrogen in the hydroformylation process, can think that the catalysis kind of the preferred catalyst used except the organophosphorus ligand, can cooperate with carbon monoxide and hydrogen in hydroformylation process.

As the organic phosphine of the free organic phosphine coordination body of the metal-ligand of organic phosphine coordination catalyzer and/or the mixing raw material of hydroformylation process can be one-; two-; three-and poly--(organic phosphine) as three organic phosphines; trialkyl phosphine; alkyl diaryl phosphine; dialkyl aryl phosphine; the bicyclic alkyl aryl phosphine; cycloalkyl diaryl phosphine; tris(aralkyl)phosphine; tricyclic alkyl phosphine and triaryl phosphine; alkyl and/aryl diphosphine and diphosphine monoxide, and contain and be selected from sulfonate; carboxylate salt; ion three organic phosphines of at least one ion part of phosphonate and quaternary ammonium compound salt etc.Certainly, such uncle's nonionic and any alkyl of ion organic phosphine are if need available any substituting group suitable, that the result of required hydroformylation process is not produced excessive disadvantageous effect to replace.Employed organic phosphine coordination body is well known in the art in hydroformylation process and/or its preparation method.

Illustrative three organic phosphine coordination bodies can be represented by following formula: Each R wherein ¹Be identical or different and be to replace or unsubstituted univalence hydrocarbyl, as alkyl, cycloalkyl or aryl.In preferred embodiments, each R ¹Be identical or different and be selected from one-level alkyl, secondary alkyl, three grades of alkyl and aryl.The alkyl that is fit to can contain from 1-24 or more a plurality of carbon atoms.Being present in illustrative substituting group on the alkyl comprises as replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted silyl as-Si (R ²) ₃Amino as-N (R ²) ₂Acyl group is as-C (O) R ²Carboxyl is as-C (O) OR ²Acyloxy is as-OC (O) R ²Amido is as-C (O) N (R ²) ₂With-N (R ²) C (O) R ²Radical ion is as-SO ₃M, wherein inorganic or organic cation atom or group of M representative; Alkylsulfonyl is as-SO ₂R ²Ether is as-OR ²Sulfinyl is as-SOR ²Selenyl is as-SeR ²Sulfenyl is as-SR ²And halogen, nitro, cyano group, trifluoromethyl and hydroxyl etc., wherein each R ²Represent identical or different replacement or unsubstituted univalence hydrocarbyl separately, but must be at amino substituting group as-N (R ²) ₂In, each R ²Also can represent the divalent abutment that forms heterocyclic radical jointly with nitrogen-atoms and at the amido substituting group as-C (O) N (R ²) ₂With-N (R ²) C (O) R ²In, the R of each bonding N ²Also can be hydrogen.Comprise as methyl, ethyl, propyl group, butyl, octyl group, cyclohexyl, sec.-propyl etc. as the alkyl illustration.Comprise as phenyl, naphthyl, fluorophenyl, difluorophenyl, benzoyloxy phenyl, carbonyl ethoxyl phenenyl, acetyl phenyl, phenelyl, phenoxy phenyl, hydroxy phenyl as the aryl illustration; Carboxyl phenyl, trifluoromethyl, methoxyethyl phenyl, acetylamino phenyl, dimethylamino formylphenyl, tolyl, xylyl, 4-dimethylaminophenyl, 2,4,6-2,4,5-trimethoxyphenyl etc.

Comprise as trimethyl-phosphine as specific organic phosphine illustration, triethyl phosphine, tributylphosphine, tri octyl phosphine, the diethyl butyl phosphine, diethyl-just-the propyl group phosphine, diethyl sec.-propyl phosphine, diethyl benzyl phosphine, diethyl cyclopentyl phosphine, diethyl cyclohexyl phosphine, triphenyl phosphine, three-right-toluene phosphine, three-right-methoxy phosphniline, three-dimethylamino phosphniline, the propyl group diphenyl phosphine, the tert-butyl diphenyl phosphine, just-the butyl diphenyl phosphine, just-the hexyl diphenyl phosphine, the cyclohexyl diphenyl phosphine, the dicyclohexyl phosphniline, tricyclohexyl phosphine, three benzyl phosphines, DIOP i.e. (4R, 5R)-(-)-O-isopropylidene-2,3-dihydroxyl-1, two (diphenyl phosphine) butane of 4-and/or (4S, 5S)-(+)-O-isopropylidene-2,3-dihydroxyl-1, two (diphenyl phosphine) butane of 4-and/or (4S, 5R)-(-)-O-isopropylidene-2,3-dihydroxyl-1, two (diphenyl phosphine) butane of 4-, the two phosphines of replacement or unsubstituted dicyclo are as 1,2-two (1, the inferior ring of 4-octyl group phosphino-) ethane, 1,3-two (1, the inferior ring of 4-octyl group phosphino-) propane, 1,3-two (1, the inferior ring of 5-octyl group phosphino-) propane and 1,2-two (2,6-dimethyl-1, the inferior ring of 4-octyl group phosphino-) ethane, replace or unsubstituted pair (2,2 '-diphenyl phosphine methyl) biphenyl such as two (2,2 '-diphenylphosphine ylmethyl) biphenyl and two { 2,2 '-two (4-fluorophenyl) phosphinomethyl } biphenyl, MeC (CH ₂PPh ₂) ₃(triphos), NaO ₃S (C ₆H ₄) CH ₂C (CH ₂PPh ₂) ₃(sulphos), two (diphenyl phosphine) ferrocene, two (di-isopropyl phosphino-) ferrocene, two (diphenyl phosphine) ruthenocene and sulfonation triphenyl phosphine are as the basic metal of (three--sulfophenyl) phosphine and (-sulfophenyl) diphenyl phosphine and alkaline earth salt etc.

The preferred organic phosphorus ligand that constitutes metal-organophosphorus ligand coordination catalyst and free organophosphates ligand is the high alkalinity ligand.Say that generally the alkalescence of organophosphorus ligand should be more than or equal to the alkalescence (pKb2.74) of triphenyl phosphine as from about 2.74-about 15.The organophosphorus ligand that is fit to has pKb about 3 or greater than 3, and preferred pKb is about 12 for about 3-, and more preferably pKb is about 5, about 12.As the pKb value that the is used for illustrative organophosphorus ligand of the present invention I that is listed in the table below.In addition, the organophosphorus ligand that is used for the present invention has the space loose density that is enough to promote hydroformylation reaction.One closes coordinate organophosphorus ligand space loose density should be less than or equal to 210 ° of Tolman cone angles, preferably is less than or equal to tricyclohexyl phosphine space loose density (Tolman cone angle=170 °).Organophosphorus ligand with required alkalescence and space loose density comprises that for example replacement or unsubstituted three-Bai-alkylphosphines are (as tri octyl phosphine, the diethyl butyl phosphine, diethyl isobutyl-phosphine), two-second month in a season-alkylaryl phosphine is (as the diethyl phosphniline, diethyl-right-N, the N-dimethylphenylphosphine), two-Bai-alkyl-one-second month in a season-alkylphosphines is (as diethyl sec.-propyl phosphine, diethyl cyclohexyl phosphine), two-Bai-alkyl-uncle-alkylphosphines (as diethyl-tert-butyl phosphine), one-Bai-alkyl-diaryl phosphine (as the diphenyl-methyl phosphine), one-Bai-alkyl-two-second month in a season-alkylphosphines (as dicyclohexyl ethyl phosphine), miyoshi phosphine (as three-right-N, N-dimethylamino phosphniline), three-secondary alkylphosphines (as tricyclohexyl phosphine), one-primary alkyl-one-secondary alkyl-one-tertiary alkyl phosphine (as ethyl sec.-propyl tert-butyl phosphine) etc.Permissible organophosphorus ligand can and can comprise following promotor with any suitable functionality replacement.

Table I organophosphor ligand PKb trimethyl-phosphine 8.7 triethyl phosphines 8.7 3-just-propyl group phosphine 8.7 3-just-butyl phosphine 8.4 3-just-octyl group phosphine 8.4 3-tert-butyl phosphine 11.4 diethyl-tert-butyl phosphine 10.1 tricyclohexyl phosphines 10 diphenyl methyl phosphines 4.5 diethyl phenyl phosphine 6.4 diphenylcyclohexyl phosphines, 5 diphenyl-ethyl phosphines 4.9 3 (right-anisyl) phosphine 4.6 triphenyl phasphines 2.74 three (right-N, N-dimethylaminophenyl) phosphines 8.65 three (right-aminomethyl phenyl) phosphines 3.84

More particularly, comprise as metal-organic phosphine coordination catalyzer illustration with as free organic phosphine coordination style card and for example be disclosed in United States Patent (USP) 3239566; 3527809; 4148830; 4247486; 4283562; 4400548; In 4482749 and 4861918 those, content disclosed herein is in conjunction with doing concrete reference among the present invention.

Comprise as being disclosed in United States Patent (USP) 4567306 as other the permissible organophosphorus ligand illustration that constitutes metal-organophosphorus ligand complex and free organophosphates ligand, 4599206,4668651,4717775,3415906,4567306,4599206,4748261,4769498,4717775,4885401,5202297,5235113,5254741,5264616,5312996,5364950,5391801, in U.S. Patent Application Serial (D-17646) (application in November 26 in 1996) and the U.S. Patent Application Serial (D-17459-1) (application meanwhile) those, content disclosed herein is in conjunction with doing concrete reference among the present invention.

Can form metal-ligand coordination catalyst of using in the present invention with methods known in the art.Described metal-ligand coordination catalyst can be homogeneous phase or heterogeneous form.For example, can be prepared into shaped metal hydrogenation-carbonyl-organophosphorus ligand catalyzer and introducing in the reaction mixture of hydroformylation process.More preferably described metal-ligand coordination catalyst can be derived from introducing metal catalysts precursors in the reaction medium to form active catalyst on the spot.For example, rhodium catalyst precursor such as rhodium dicarbapentaborane acetylacetonate, Rh ₂O ₃, Rh ₄(CO) ₁₂, Rh ₆(CO) ₁₆, Rh (NO ₃) ₃Deng introducing jointly in the reaction mixture to form active catalyst on the spot with the organophosphorus ligand.In a preferred embodiment of the invention, rhodium dicarbapentaborane acetylacetonate is used as the rhodium precursor and in the presence of promotor, form catalytic rhodium-organic phosphine coordination body title complex precursor with organic phosphine coordination precursor reactant, and introduce jointly in the reactor so that form active catalyzer on the spot with excessive free organic phosphine coordination body.In any case carbon monoxide, hydrogen and organo phosphorous compounds all are the ligands that can cooperate with metal and reactive metal-organophosphorus ligand catalyzer is present in hydroformylation process is enough to satisfy purpose of the present invention in the reaction mixture under institute's working conditions.

More particularly, can form the catalyst precursor composition of the preceding body catalyst of the metal-ligand compositions that comprises solubilising substantially, promotor and free ligand.By forming raw material as metal oxide, hydride, carboxide or the salt precursor composition as the solution of nitrate can prepare, it can or cannot be in title complex combines with organophosphorus ligand in this definition.Can use any proper metal raw material, as rhodium dicarbapentaborane acetylacetonate, Rh ₂O ₃, Rh ₄(CO) ₁₂, Rh ₆(CO) ₁₆, Rh (NO ₃) ₃With organophosphorus ligand rhodium carbonyl hydride.If carbonyl and organophosphorus ligand also do not cooperate with metal originally, they can cooperate with metal before the hydroformylation process or in its process on the spot so.

By illustrating, preferred catalyst precursor composition of the present invention comprises substantially by forming rhodium dicarbapentaborane acetylacetonate, promotor and body catalyst, promotor and free organic phosphine coordination body before the solubilising rhodium carbonyl organic phosphine coordination body title complex of the formulations prepared from solutions of the ligand of this definition.As by discharge CO (carbon monoxide converter) gas proved, at room temperature, organic phosphine coordination body is replaced a carbonyl ligand of rhodium acetylacetonate title complex precursor easily.As needs, can promote this substitution reaction by heating this solution.The suitable organic solvent of any solubilized rhodium dicarbapentaborane acetylacetonate title complex precursor and rhodium organic phosphine coordination body title complex precursor all can use.Rhodium coordination catalyst precursor, organic solvent and organic phosphine coordination body, and the embodiment preferred consumption that is present in such catalyst precursor composition is obviously consistent with the amount of using in hydroformylation process of the present invention.Experience show described before the acetyl pyruvate ligand of body catalyst after hydroformylation reaction begins, replaced by a kind of different ligand such as hydrogen, carbon monoxide or organic phosphine coordination body, form above-described active coordination catalyst.In the successive method, under the hydroformylation condition, the free methyl ethyl diketone migrates out from reaction medium with product alcohol in the body catalyst in the past, therefore can't cause disadvantageous effect to hydroformylation reaction.The precursor composition of using so preferred rhodium coordination catalysis provides simple economy and effectively handles the method that rhodium precursor metal and hydroformylation start.

Therefore, employed in the method for the invention metal-ligand coordination catalyst is made up of the metal that cooperates with carbon monoxide and ligand substantially, and described ligand is with chelating and/or this metal of non-chelated forms bonding (cooperation).In addition, " comprise substantially " except that carbon monoxide and ligand, do not get rid of but comprise the hydrogen that cooperates with metal at this employed term.Further, other organic ligand and/or the anionic possibility that yet cooperates with this metal do not got rid of in such term.To make poisoning of catalyst inadequately or to make the material of the amount of catalyst deactivation inadequately is deleterious, therefore the described catalyzer utmost point be necessary not contain pollutent as with metal link halogen (as chlorine etc.), although this is not to be indispensable.The hydrogen of reactive metal-organic phosphine coordination body coordination catalyst and/or carbonyl ligand can be used as be body catalyst ligand before the bonding the result and/or as the result that forms on the spot because in hydroformylation process of the present invention, use hydrogen and CO (carbon monoxide converter) gas and existing.

As described, hydroformylation process comprises uses metal described herein-ligand coordination catalyst.Certainly, if need also use such mixture of catalysts.The consumption that is present in the metal-ligand coordination catalyst in the reaction medium of given hydroformylation process only needs for the minimum necessary consumption that the required metal concentration that uses is provided and will comprise the amount that the basis is provided as the required catalytic amount at least of disclosed specific hydroformylation process metal in above-mentioned patent as catalysis.Say that generally catalyst concn can be from ppm to percentum (weight).The mol ratio of spendable organophosphorus ligand is generally from about 0.5: 1 or be less to about 1000: 1 or bigger in above-mentioned catalyzer.Catalyst concentration will depend on the condition of hydroformylation process and used solvent.

Say that generally the organophosphorus ligand concentration can be the scope between about 0.005 and 25% (weight) based on the gross weight of its reaction mixture in the hydroformylation process mixture.Preferred in view of the above ligand concentration is between 0.01 and 15% (weight), more preferably between about 0.05 and 10% (weight).

Say that generally the metal concentration in the mixture of hydroformylation process can be up to about 2,000/1000000ths (weight) based on the weight of reaction mixture.Preferable alloy concentration based on the weight of reaction mixture be about 50/1000000ths and 1,500 (weight) between, more preferably between about 70/1000000ths and 1,200 (weight) based on reaction mixture weight.

Except that metal-ligand coordination catalyst, free ligand (i.e. the ligand that does not cooperate with rhodium metal) also may reside in the hydroformylation reaction medium.Free ligand is consistent with ligand in any above-mentioned definition of this applied above-mentioned discussion.Preferred free ligand is same as the ligand of used metal-ligand coordination catalyst.Yet such ligand needs not to be identical in any given method.In the hydroformylation process medium, hydroformylation process can contain 100 moles of every mole metal as many as or more free ligand.Preferred described hydroformylation process in reaction medium every mole metal from the about 50 moles coordination phosphorus of about 1-, more preferably from the about 20 moles of coordination phosphorus of about 1-with most preferably under the existence of the about 8 moles of coordination phosphorus of about 1-, carry out; The consumption of described coordination phosphorus be the coordination phosphorus consumption that exists of bonding (cooperation) rhodium metal and free (non-cooperation) but the two summation of consumption that coordination phosphorus exists.Certainly, if need, at any time and in any appropriate manner will replenish or other coordination phosphorus is added in the reaction medium of hydroformylation process, to remain on the predeterminated level of free ligand in the reaction medium.

As implied above, hydroformylation catalysts can be heterogeneous form in reaction process and/or in the product separation process.Such catalyzer produces particularly advantageous in high boiling point or the temperature-sensitive alcohol at the hydroformylation of alkadiene, so that catalyzer can separate from product by filter at low temperature or decant.For example, rhodium catalyst can adhere to carrier so that catalyzer keeps its solid form or be dissolved in the liquid reaction medium precipitation when cooling off then when high temperature in hydroformylation and separation phase.

As described, rhodium catalyst can be immersed on any solid carrier, as inorganic oxide (as aluminum oxide, silicon-dioxide, titanium dioxide or zirconium white), charcoal or ion exchange resin.With catalyst cupport or embed the hole inside of zeolite or glass; Also can be in the liquid film that covers described zeolite or glass hole with catalyst dissolution.Zeolite-loaded catalyzer like this is particularly conducive to the alcohol that highly selective is produced one or more regional isomers, as by zeolite the aperture determined.The technology of supported catalyst on solid as tentatively wetting, is known to those skilled in the art.The solid catalyst of Xing Chenging still can cooperate with one or more ligands of above-mentioned definition like this.The description of this class solid catalyst is found in as J.Mol.Cat.1991,70,363-368; Catal.Lett.1991,8,209-214; J.Organomet.Chem.1991,403,221-227; Nature, 1989,339,454-455; J.Catal.1985,96,563-573; J.Mol.Cat.1987,39,243-259.

Rhodium catalyst can be attached to film or membrane carrier, as cellulose acetate or PPSU, and as described in J.Mol.Cat.1990,63,213-221.

Ligand by containing organophosphorus such as phosphine or phosphorous acid ester mix polymkeric substance, can be with rhodium catalyst attached on the insoluble polymer support.The ligand of this base polymer load is known, and comprises the commercially available kind such as the triphenyl phosphine of Vinylstyrene/loaded by polystyrene.Polymkeric substance or the selection of sneaking into phosphorous kind wherein do not limit the load ligand.For example the description of the catalyzer of polymkeric substance load is found in: J.Mol.Cat.1993,83,17-35; Chemtech 1983,46; J.Am.Chem.Soc.1987,109,7122-7127.

In above-mentioned heterogeneous catalyst, in the process of whole hydroformylation and catalyst separating, catalyzer can keep its heterogeneous form.In another embodiment of the invention, catalyzer can be carried on the polymkeric substance, because the molecular weight character of polymkeric substance dissolves in the reaction medium when elevated temperature, but cools off precipitablely to go out, and helps catalyzer like this and isolates from reaction mixture.The catalyzer of this class " solvable " polymkeric substance load is described in as Polymer, 1992,33,161; J.Org.Chem.1989,54, among the 2726-2730.

When rhodium catalyst is heterogeneous or during its load form, this reaction can be carried out in gas phase.Because the high boiling point of product, more preferably be reflected at slurry and carry out in mutually, decompose to avoid product alcohol.By filtration or decant catalyzer is isolated from product mixtures then.

Method of the present invention can running in very wide speed of response scope (m/L/h=product mole number/reaction soln rise number/hour).Say that generally speed of response is 0.01m/L/h or higher at least, preferably 0.1m/L/h or higher and more preferably 0.5m/L/h or higher at least at least.Higher speed of response is preferred generally from economic angle as less reactor specification etc.

The replacement and the unsubstituted alkadiene raw material that are applied in the hydroformylation process comprise (but being not limited thereto) any conjugated aliphatic by the following formula representative:

R wherein ₁And R ₂Be identical or different also be hydrogen, halogen or replacement or unsubstituted alkyl.Described alkadiene can be straight or branched and can contain substituting group (as alkyl, halogen atom, amino or silyl).Suitably the illustration of alkadiene raw material is divinyl, isoprene, dimethylbutadiene, cyclopentadiene and chloroprene.Most preferably described alkadiene raw material is divinyl (CH itself ₂=CH-CH=CH ₂).Be in purpose of the present invention, term " alkadiene " will comprise replacement and the unsubstituted conjugated diolefine that all are allowed, comprise that all allow that containing one or more replaces and the mixture of unsubstituted conjugated diolefine.The illustration of suitable replacement and unsubstituted alkadiene (comprising the alkadiene derivative) is included in the Encyclopedia ofChemicalTechnology of Kirk-Othmer, those that describe among the Fourth Edition (1996) allow and replace and unsubstituted alkadiene, and its relevant part is done concrete reference at this in conjunction with the present invention.

Specific hydroformylation reaction condition is unimportant, can be enough to produce one or more 1, any effective hydroformylation technology of 6-hexylene glycol and/or unsaturated alcohol.Obtain high catalyst selectivity, activity, life-span and easy handling by taking into account best, and the raw material inherent reactive behavior of being considered and raw material and required reaction product decide definite reaction conditions to the relation between the stability of reaction conditions.The condition of hydroformylation process can comprise used so far hydroformylation condition of producing any suitable type of alcohol.Employed total pressure is generally from the scope of the about 10000psia of about 1-in hydroformylation process, preferably from about 20-3000psia with more preferably from about 50-2000psia.The total pressure of hydroformylation process will depend on employed specific catalyst system.

More precisely, the carbon monoxide pressure of tension of hydroformylation process generally can be from the scope of the about 3000psia of about 1-, and preferably from the about 1500psia of about 3-, and the hydrogen dividing potential drop generally can be from the about 3000psia of about 1-with preferably from the about 1500psia of about 3-.Say that generally the mol ratio of carbon monoxide and gaseous hydrogen can be from about 100: 1 or bigger to about 1: 100 or littler scope, preferred carbon monoxide and gaseous hydrogen mol ratio are from about 1: 10 to about 10: 1.Carbon monoxide and hydrogen dividing potential drop will depend in part on employed special catalyst system.Will be understood that carbon monoxide and hydrogen can use respectively, mix separately or mutually and use (being synthetic gas), or under reaction conditions, produce and/or be derived from promotor or solvent (needn't contain free hydrogen or carbon monoxide) on the spot.In one embodiment, hydrogen dividing potential drop and carbon monoxide pressure of tension are enough to prevent or make derivatization, reduce to minimum as the hydrogenation of amylene-1-ol or the hydrogenation of alkadiene.

Further, the temperature of reaction that can carry out hydroformylation process is from about 20 ℃-Yue 200 ℃, preferably from about 50 ℃-Yue 150 ℃, more preferably from 65 ℃-Yue 115 ℃.Temperature must satisfy reaction (changing with employed catalyst system) takes place, but can not be too high so that ligand or catalyzer decompose.High temperature (changing with employed catalyst system), amylene-1-ol can take place change into unwanted byproduct.

Certainly, the condition that also will be understood that employed hydroformylation process will be determined by the type of required pure product.

In order to make 3-amylene-1-ol and/or 4-amylene-1-ol reach highest level and to make the 2-amylene-1-ol minimum, wish to keep certain alkadiene dividing potential drop or transform when complete when alkadiene, carbon monoxide and hydrogen dividing potential drop will be enough to prevent or make derivatization, reduce to minimum as the hydrogenation of amylene-1-ol or the hydrogenation of alkadiene.

In preferred embodiments, be enough to prevent or make derivatization in the dividing potential drop of alkadiene dividing potential drop and/or carbon monoxide and hydrogen, as the hydrogenation of amylene-1-ol hydrogenation or alkadiene reduce to carry out under the minimum condition as described in the alkadiene hydroformylation.In a more preferred embodiment, greater than 0psi, be preferably greater than 5psi and in the alkadiene dividing potential drop more preferably greater than 9psi; Greater than 0psi, be preferably greater than 25psi and at carbon monoxide pressure of tension more preferably greater than 40psi; With in the hydrogen dividing potential drop greater than 0psi, be preferably greater than 25psi and more preferably greater than the hydroformylation that carries out alkadiene such as divinyl under the 80psi.

In the presence of promotor, also can carry out hydrogenation formyl process." promotor " means and has the organic or inorganic compound of pKa from the ionized hydrogen of about 1-about 35 as used in this.Illustrative promotor for example comprise protonic solvent, organic and mineral acid, alcohol, water, phenol, mercaptan, thiophenol, nitro-paraffin, ketone, nitrile, amine (as pyrroles and pentanoic), acid amides (as ethanamide) ,-, two-and trialkyl ammonium salts etc.The about pKa value that is used for the present invention's illustrative promotor is listed in the table below in the II.Described promotor can separately exist in the hydroformylation reaction mixture or incorporate in the ligand structure, as metal-ligand coordination catalyst or as free ligand, or incorporates in the alkadiene structure.Required promotor will depend on the metal-ligand of ligand coordination catalyst and the character of metal.Generally say to have the promotor that will need low concentration and/or weaker acid with the catalyzer of the acyl group of more alkaline metal link or other intermediate.

Though, show that promotor can have the function of the catalyzer that shifts hydrogen ion function or phase deactivation connection acyl group or other intermediate in this discussion of not planning to be confined to any theory or mechanism.Anyly allow that the mixture of bonded promotor can be used among the present invention.A preferred class promotor comprises and carries out hydrogen bonding, as contains the group of NH, OH and SH and the material of Lewis acid, because be sure of that they help that hydrogen ion shifts or activation connects acyl group or other intermediate of metal.Say that generally the consumption of promotor can be based on the mixture material gross weight of hydroformylation process from about 10/1000000ths or as many as about 99 percent (weight) or more.

The table II

Promotor pKa

ROH (R=alkyl) 15-19

ROH (R=aryl) 8-11

RCONHR (the R=hydrogen or alkyl is as ethanamide) 15-19

R ₃NH-, R ₂NH ₂+ (R=alkyl) 10-11

RCH ₂NO ₂ 8-11

RCOCH ₂R (R=alkyl) 19-20

RSH (R=alkyl) 10-11

RSH (R=aryl) 8-11

CNCH ₂CN 11

Diaryl-amine 21-24

The pyrroles 20

Tetramethyleneimine 34

The concentration of employed promotor will depend on the details of the catalyst system that uses.Do not wishing to be limited by theory down, the component of promotor must have enough acidity and enough concentration to be connected acyl group or other intermediate of catalyzer with transfer hydrogen ion or phase deactivation.What can be sure of is that cocatalyst component acidity or concentration are not enough to shift hydrogen ion or the phase deactivation connects the acyl group of catalyzer or formation rather than the preferred pure product that other intermediate will cause the aldehyde product.Cocatalyst component shifts hydrogen ion or the phase deactivation connects the acyl group of catalyzer or the ability of other intermediate is determined by Several Factors, for example the composition (as reaction solvent) and the temperature of the intrinsic acidity of the concentration of cocatalyst component, cocatalyst component (pKa), reaction medium.The selection of promotor will be in the formation that is enough to cause pure product; but be unlikely high to the reaction conditions of the disadvantageous pair of reaction that causes described catalyzer, reagent or product, shift the hydrogen ion or the acyl group of phase deactivation connection catalyzer or the ability of other intermediate according to it and carry out.If when the acidity of cocatalyst component or concentration are not enough to reach requirement, begin formation aldehyde product (as pentenals) can maybe can not be changed into alcohol, subsequently as amylene-1-ol.

Say that generally the acyl group that connects the weakly alkaline metal will need the cocatalyst component of higher concentration or more highly acid cocatalyst component so that protonated or it is fully activated; So that product is more required alcohol; Rather than aldehyde.Component by suitable selection promotor can reach this point.For example; The cocatalyst component of the medium acidity by using high density; or by use low concentration more the component of strong acidity can obtain concentration that can be protonated or can activate acyl group or other intermediate that connects catalyzer on the contrary.Cocatalyst component produces ability protonated or phase deactivation connection catalyzer acyl group or other intermediate desired concn and selects according under reaction conditions in reaction medium.Say that generally the inherent strength of acidic substance rather than is defined as pKa in the normally used reaction medium normally in the aqueous solution in hydroformylation.Promotor and concentration thereof are selected part separately according to promotor with pH theory or suitable ( equivalent ) that this concentration provides in 22 ℃ of aqueous solution.The theory that cocatalyst component solution is required or suitable pH should be greater than 0； Preferably from about 1-12, more preferably from about 2-10 with most preferably from 4-8. by normative reference table such as E.P Serjeant and Boyd Dempsey " Ionization Constants of Organic Acids in Aqueous Solution " (IUPAC Chemical Data Series-No.23) [Pergamon publishing house (1979)] and " Dissociation Constants of Inorganic Acids and Bases inAqueous Solution " (IUPAC Chemical Data Series-No.19) (the Pergamon publishing house) of D.D.Perrin in the standard scale put down in writing; Under suitable cocatalyst component concentration, by the pKa value pH theory of computation or suitable easily.

According to used specific catalyst and reactant, the promotor that is fit to preferably includes solvent, for example alcohol (as pure product as amylene-1-ol or hexylene glycol), mercaptan, thiophenol, selenol, Supreme Being's alcohol (tellurol), alkene, alkynes, aldehyde, higher by product, ketone, ester, acid amides, firsts and seconds amine, alkane aromatic hydrocarbons etc.Can use any suitable promotor that disturbs specified hydroformylation process unfriendly within reason.Permissible protonic solvent has the pKa of about 1-35, the preferably pKa of about 3-30 and the more preferably from about pKa of 5-25.If need to use the mixture of one or more different solvents.

Generally say, for producing 1,6-hexylene glycol, preferred pure promotor consistent and/or the main protonic solvent of higher by product conduct of using with the pure product of required generation.Also can prefabricated such by product and thereby use if need.Producing alcohol, comprise alcohol (as pentenol, octanol, hexylene glycol), amine, mercaptan, thiophenol, ketone (as acetone and methylethylketone), hydroxy aldehyde (as the 6-hydroxy aldehyde), lactonaphthol (as 2-methylpent lactonaphthol), ester (as ethyl acetate), hydrocarbon (as ditan, triphenyl methane), nitro-hydrocarbon (as Nitromethane 99Min.), 1,4-butyleneglycol and tetramethylene sulfone as spendable preferred protonic solvent illustration in the hexylene glycol.Suitable protonic solvent is disclosed in the United States Patent (USP) 5312996.

As implied above, promotor can be incorporated in the ligand structure, as metal-ligand coordination catalyst or as free ligand.The organophosphorus ligand promotor that is fit in can be used for the present invention comprises as three (2-hydroxyethyl) phosphine, three (3-hydroxypropyl) phosphine, three (2-hydroxyphenyl phosphine), three (4-hydroxyphenyl phosphines), three (3-carboxylic propyl group) phosphine, three (3-formamido-propyl group) phosphine, phenylbenzene (2-hydroxyphenyl) phosphine, diethyl (2-anilino phenyl) phosphine and three (3-pyrryl) phosphine.When pure product can not be effective as promotor, using the ligand promotor in these cases is particularly advantageous, when using the organophosphorus ligand that constitutes metal-organophosphorus ligand coordination catalyst and free organophosphates ligand, preferred organophosphorus ligand promotor be high basicity and have the space loose density of being less than or equal to 210 ° of Tolman cone angles, preferably be less than or equal to the ligand of tricyclohexyl phosphine (Tolman cone angle=170 °).Really, organophosphorus ligand promotor can be used as the organophosphorus ligand of formation metal-organophosphorus ligand coordination catalyst and free organophosphates ligand.Can use the catalyst mixture that comprises one or more ligand promotors in the present invention and comprise one or more ligand promotors and the mixture of one or more other promotors such as protonic solvent.

In embodiments of the invention, the mixture of hydroformylation process can be made up of one or more liquid phases such as polarity and nonpolar phase.For example such method usually helps product being separated from catalyzer and/or reactant in mutually by being assigned to any one.In addition, can increase the selectivity of product that depends on solvent property by in described solvent, reacting.The application of present technique is the water hydroformylation that uses the alkadiene of sulfonated phosphine ligand, hydroxylation phosphine ligand and amination phosphine ligand for rhodium catalyst.The method of carrying out in water-containing solvent is particularly conducive to preparation alcohol, because product enters in the solvent and can separate from catalyzer by extraction.

As said, can contain the substituting group of any number as the phosphorated ligand of rhodium hydroformylation catalysts, as positively charged ion or anion substituent, they will be provided at soluble catalyzer in polar phase such as the water.Optional phase-transfer catalyst is joined is beneficial to catalyzer, reactant or product and is transferred in the required solvent phase in the reaction mixture.The structure of ligand or phase-transfer catalyst is not crucial, and should depend on the selection of reaction conditions, reaction solvent and required product.

When catalyzer is present in the multiphase system, as extraction or decant catalyzer is separated from reactant and/or product by ordinary method.Reaction mixture self also comprises a phase or heterogeneous; In addition, when reaction finishes, produce multiphase system and from catalyzer, isolate product by for example adding second kind of solvent.As see, United States Patent (USP) 5180854, content disclosed herein is in conjunction with doing concrete reference among the present invention.

In embodiments of the invention, use above-mentioned metal ligand coordination catalyst, with alkadiene with the hydrogenation of olefins formylation.In such a case, also produce alkene alcohol derivate and alcohol as hexylene glycol.

In hydroformylation process, if need to use the mixture of different alkene raw materials.More preferably described hydroformylation process is containing 2-30; the alpha-olefin (comprising iso-butylene) of preferred 4-20 carbon atom and contain the internal olefin of 4-20 carbon atom and the existence of the raw mix of this class alpha-olefin and internal olefin under make the alkadiene hydroformylation and be particularly useful for producing 1, the 6-hexylene glycol.The commercially available alpha-olefin that contains 4 or more a plurality of carbon atoms can contain a small amount of corresponding internal olefin and/or its corresponding stable hydrocarbon and the commercially available alkene of this class needn't purifying before hydroformylation.

The illustration of other olefin feedstock comprises alpha-olefin, internal olefin, 1, the 3-diene, 1, the 2-diene, alkyl chain acid ester, alkenyl alkanoate, alkenyl alkyl ethers, alkenols, chain olefine aldehydr etc., as ethene, propylene, 1-butylene, the 1-amylene, the 1-hexene, the 1-octene, the 1-nonene, 1-decene, the 1-undecylene, the 1-dodecylene, the 1-tridecylene, tetradecene, 1-15 carbenes, cetene, the 1-heptadecene, the 1-vaccenic acid, 1-19 carbenes, the 1-eicosylene, 2-butylene, 2-methacrylic (iso-butylene), the 2-methyl butene, the 2-amylene, the 2-hexene, the 3-hexane, the 2-heptene, tetrahydrobenzene, propylene dimer, propylene trimer, the propylene tetramer, piperylene, isoprene, 2-ethyl-1-hexene, the 2-octene, vinylbenzene, 3-phenyl-1-propylene, 1, the 4-hexadiene, 1, the 7-octadiene, 3-cyclohexyl-1-butylene, allyl alcohol, allyl butyrate, oneself-1-alkene-4-alcohol, suffering-1-alkene-4-alcohol, vinyl-acetic ester, allyl acetate, acetate 3-butene esters, propionate, allyl propionate, methyl methacrylate, EVE, vinyl methyl ether, vinyl cyclohexene, allyl ethyl ether, amylene-4 acid methyl ester, the 7-octylenic acid just-propyl ester, pentenals, as the 2-pentenals, 3-pentenals and 4-pentenals; Amylene-1-ol such as 2-amylene-1-ol, 3-amylene-1-ol and 4-amylene-1-ol, 3-crotononitrile, 3 pentene nitrile, 5-hexene acid amides, 4-vinyl toluene, 4-isopropyl benzene ethene, 4-t-butyl styrene, alpha-methyl styrene, 4-tert-butyl-alpha-methyl styrene, 1,3-di isopropenylbenzene, oxymethoxyallylbenzene, different-oxymethoxyallylbenzene, safrole, different-safrole, methyl allylphenol, 4-allyl group phenylmethylether, indenes, limonene, beta-pinene, dicyclopentadiene, cyclooctadiene, amphene, linalool etc.For example right-isobutyl-benzene ethene that other illustrative olefin(e) compound can comprise, 2-vinyl-6-methoxynaphthalene, 3-ethenylphenyl phenyl ketone, 4-ethenylphenyl-2-thienyl ketone, 4-vinyl-2-fluorine biphenyl, 4-(1,3-dihydro-1-oxo-2H-isoindole-2-yl) vinylbenzene, 2-vinyl-5-benzoyl thiophene, 3-ethenylphenyl phenyl ether, propenylbenzene, isobutyl--4-propenylbenzene, Vinyl phenyl ether etc.The aryl ethylene that other olefin(e) compound comprises replacement is as at described in the United States Patent (USP) 4329507 those, and the content of the disclosure is done concrete reference at this in conjunction with the present invention.

At promotor is not under the situation of solvent, and the included hydroformylation process of the present invention is to carry out in the presence of the organic solvent that is used for metal-ligand coordination catalyst and free ligand.This solvent also can contain dissolved water until limit of saturation.The suitable organic solvent that depends on employed special catalyst and reactant comprises for example alcohol, alkane, alkene, alkynes, ether, aldehyde, higher hydroformylation by product, ketone, ester, acid amides, tertiary amine, aromatic hydrocarbons etc.Any suitable solvent of the hydroformylation reaction that will carry out that disturbs unfriendly within reason all can use.If need, can use the mixture of one or more different solvents.The illustration of employed preferred solvent comprises ketone (as acetone and methylethylketone), ester (as ethyl acetate), hydrocarbon (as toluene), nitro-hydrocarbon (as oil of mirbane), ether (as tetrahydrofuran (THF) (THF) and tetramethylene sulfone) in producing alcohol.The solvent that is fit to is disclosed in the United States Patent (USP) 5312996.For the purpose of the present invention, the consumption of the solvent that uses is unimportant and only need to be enough to the catalyzer of the hydrogenation formyl reaction mixture that solubilising need handle and the consumption of free ligand.Say that generally the consumption of solvent is the scope from about 5% (weight) as many as about 99% (weight) based on hydroformylation reaction mixture material total amount.

Be used for the replacement of the inventive method and the illustration of unsubstituted unsaturated alcohol intermediate and raw material and comprise following one or more materials: alkenols such as suitable-3-amylene-1-ol, anti--the 3-amylene-1-ol, 4-amylene-1-ol, suitable-2-amylene-1-ol and/or anti--2-amylene-1-ol comprise the mixture that contains one or more above-mentioned unsaturated alcohols.The replacement that is fit to and the illustration of unsubstituted unsaturated alcohol (comprising the unsaturated alcohol derivative) comprise the Encyclopedia ofChemical Technology of Kirk-Othmer, those permissible replacements and unsubstituted unsaturated alcohol described in the Fourth Edition (1996), its relative section is done concrete reference at this in conjunction with the present invention.

The replacement that can prepare by the inventive method and unsubstituted 1, the illustration of 6-hexylene glycol comprises alkanediol as 1,1 of 6-hexylene glycol and replacement, 6-hexylene glycol (as the 2-methyl isophthalic acid, 6-hexylene glycol and 3,4-dimethyl-1,6-hexylene glycol) etc.Suitably replacement and unsubstituted 1, the 6-hexylene glycol (comprises 1, the derivative of 6-hexylene glycol) illustration is included in the Encyclopedia ofChemical Technology of Kirk-Othmer, those permissible replacements and unsubstituted 1 described in the Fourth Edition (1996), the 6-hexylene glycol, its relevant part is done concrete reference at this in conjunction with the present invention.

As mentioned above, the general preferred hydroformylation process of the present invention that carries out in a continuous manner.Say that generally the successive hydroformylation process can comprise: (a) in the liquid homogeneous phase reaction mixture that contains solvent, metal-ligand coordination thing catalyzer and free ligand, use carbon monoxide and hydrogen to make alkadiene raw material hydroformylation; (b) maintain the temperature of reaction of the hydroformylation that is beneficial to the alkadiene raw material and the condition of pressure; (c) when alkadiene raw material, carbon monoxide and hydrogen exhaust, these materials that magnitude of recruitment is provided are in reaction medium; (d) reclaim required glycol hydroformylation products in any required mode.Successive reaction can single pass mode be carried out, promptly from liquid reaction mixture, migrate out the vapourous mixture (therefrom reclaiming this diol product) of the diol product that comprises unreacted alkadiene raw material and vaporization and provide additional alkadiene raw material, carbon monoxide and hydrogen in the liquid reaction medium as using in the next one way, and the unreacted alkadiene raw material of not recirculation.Yet, generally need to use the successive reaction that comprises liquid and/or gas circulation step.Circulation step of known the type and the liquid circulation that comprises isolating metal from required glycol reaction product-ligand coordination catalysis agent solution in this area.

As described above, hydroformylation process can comprise the liquid catalyst circulation step.Liquid catalyst round-robin step in well known this class.For example; in this class I liquid I catalyst recirculation step; usually can be continuously or from the hydroformylation reaction device, shift off and on and contain as pure product; the metal of solubilising-ligand coordination catalyst; free ligand and organic solvent; and by hydroformylation by product that produces on the spot and the unreacted alkadiene raw material that is dissolved in the described medium; if the partially liq reaction product medium of carbon monoxide and hydrogen (synthetic gas) is to distillation zone such as vaporizer/separator, wherein suitably at normal pressure; decompression or boost down and isolate required diol product with one or more levels distillation with from liquid medium.Concentrate then and reclaim the required diol product that this evaporation or fractionation by distillation go out with any above-mentioned common method.As required; with or need not further handle; by product in still being dissolved in described circulating liquid residue and non-vaporized gas reactant; the remaining non-evaporated liquid residue of the diol product that will contain metal-ligand coordination catalyst, solvent, free ligand and not distill out more usually; return in the hydroformylation reaction device with any required usual manner, as disclosed content in the above-mentioned patent.Therefore, the reactant gases that shifts out through distillation from vaporizer also can be circulated back in the reactor as required.

The recovery of diol product and purifying can and can comprise distillation, be separated, extract, precipitate by any appropriate means, absorption, crystallization, membrane sepn, formation derivative and other proper method.For example, under normal pressure or decompression, the crude reaction product is carried out fractionation by distillation by the distillation column of filling.Reaction distillation can be used for carrying out hydroformylation reaction.

As implied above, finish (or in process) at hydroformylation process, from the reaction mixture that is used for the inventive method, reclaim needed glycol as 1, the 6-hexylene glycol.For example, in the continuous liquid catalyst circulating reaction, the partially liq reaction mixture that shifts out from reactor (contains 1,6-hexylene glycol product, catalyzer etc.), by vaporizer/separator, wherein, use one or more levels through distillation, at normal pressure, reduce pressure or boost and down from liquid reaction solution, isolate required pure product, in the product receptor, concentrate and collect and can be further purified if need.With any usual way from spissated 1,6-hexylene glycol product is as by after the fractionation by distillation, the nonvolatile catalyst recirculation of residue that will contain liquid reaction mixture is got back in the reactor, if need any other volatility raw material such as unreacted alkadiene to return together with any hydrogen and the carbon monoxide that are dissolved in the liquid reactions liquid.Generally need to use the molecular weight of organophosphorus ligand to surpass 1 of in hydroformylation process corresponding generation, the higher alcohol oligopolymer by product molecular weight of 6-hexylene glycol phosphorus ligand arranged.Another recovery technology that is fit to is solvent extraction or crystallization.Generally say, preferably decompression with from the reaction mixture that contains catalyzer, separate requiredly 1 at low temperatures, the 6-hexylene glycol is to avoid may degrading of organophosphorus ligand and reaction product.When also using α-monoene reactant, by also separable its alcohol derivate of aforesaid method.

More particularly, from the product solution of containing metal-ligand coordination catalyst distillation with separate required diol product and can suitable carry out under temperature required any.Generally say, advise that such distillation under relative low temperature, as below 150 ℃, more preferably carrying out under the temperature of about 50 ℃-Yue 130 ℃ of scopes.General advise that also such glycol distillation under reduced pressure carries out, for example ought comprise that low-boiling point alcohol is (as C ₅And C ₆) time, advise that its total gaseous tension is actual and be lower than total gaseous tension used in the hydroformylation and ought comprise that maybe high-boiling point alcohol is (as C ₇Or higher) time, suggestion is carried out under vacuum.For example; method commonly used is that the liquid reacting product medium decompression of will shift out from the hydroformylation reaction device is so that the evaporation major part is dissolved in the unreacting gas in the liquid medium; thereby making it contain the synthesis gas concentration ratio is present in and delivers to the distillation zone; much lower as the concentration in the hydroformylation process medium in vaporizer/separator, wherein required pure product is distilled.Say that generally the distillation pressure range satisfies most purpose from the high extremely about 50psig total gas pressure of vacuum.

When not wishing to be confined to any specific reaction mechanism; can be sure of whole hydroformylation reaction generally with one the step carry out; be that one or more replacements or unsubstituted alkadiene (as divinyl) directly or by one or more intermediates (as 3-amylene-1-ol and/or 4-amylene-1-ol) are converted to one or more replacements or unsubstituted glycol (as 1, the 6-hexylene glycol).The present invention is confined to any specific reaction mechanism by any way; but comprise and relating in the presence of metal-ligand coordination catalyst, promotor and optional free ligand; one or more replacements or unsubstituted alkadiene and/or unsaturated alcohol are produced one or more replacements or unsubstituted 1, whole reaction mechanisms of allowing of 6-hexylene glycol with carbon monoxide and hydrogen through hydroformylation.

The reductibility hydroformylation that comprises one or more replacements or unsubstituted alkadiene is produced one or more replacements or unsubstituted 1; the one step process of 6-hexylene glycol is disclosed in the common unsettled U.S. Patent Application Serial 60/016287 (application on April 24th, 1996), and the content of the disclosure is done concrete reference at this in conjunction with the present invention.The reductibility hydroformylation that comprises one or more replacements or unsubstituted alkadiene produces one or more replacements or unsubstituted 1; the other method of 6-hexylene glycol; be disclosed in the common unsettled U.S. Patent Application Serial (D-17775); application meanwhile, the content of the disclosure is done concrete reference at this in conjunction with the present invention.

Embodiment of the present invention relate to produces one or more replacements or unsubstituted 1, the method for 6-hexylene glycol, and it comprises:

(a) in the presence of hydroformylation catalysts such as metal-organophosphorus ligand coordination catalyst, promotor and optional free ligand, one or more replacements or unsubstituted alkadiene such as butadiene hydrogenation formylation are produced one or more replacements or unsubstituted unsaturated alcohol, comprise the 3-amylene-1-ol, 4-amylene-1-ol and/or 2-amylene-1-ol;

(b) optional 3-amylene-1-ol, 4-amylene-1-ol and/or the 2-amylene-1-ol of from hydroformylation catalysts, separating; With

(c) in the presence of hydroformylation catalysts such as metal-organophosphorus ligand coordination catalyst, promotor and optional free ligand; with described one or more replacements or replace the unsaturated alcohol hydroformylation comprise 3-amylene-1-ol, 4-amylene-1-ol and/or 2-amylene-1-ol and produce one or more replacements or unsubstituted 1,6-hexylene glycol.In step (a) and the hydroformylation reaction condition (c) can be identical or different and in step (a) and the hydroformylation catalysts (c) can be identical or different.

Another embodiment of the invention relates to and produces one or more replacements or unsubstituted 1, the method for 6-hexylene glycol, and it comprises:

(a) in the presence of hydroformylation catalysts such as metal-organophosphorus ligand coordination catalyst, promotor and optional free ligand, one or more replacements or unsubstituted alkadiene such as butadiene hydrogenation formylation are produced one or more replacements or do not replace, comprise the unsaturated alcohol of 3-amylene-1-ol, 4-amylene-1-ol and/or 2-amylene-1-ol;

(b) optional 3-amylene-1-ol, 4-amylene-1-ol and/or the 2-amylene-1-ol of from hydroformylation catalysts, separating;

(c) in the presence of heterogeneous or homogeneous phase olefin isomerization catalyst, optional with 2-amylene-1-ol and/or the isomerization of 3-amylene-1-ol, make 2-amylene-1-ol and/or 3-amylene-1-ol partially or even wholly be isomerizated into 3-amylene-1-ol and/or 4-amylene-1-ol; With

(d) in the presence of hydroformylation catalysts such as metal-organophosphorus ligand coordination catalyst, promotor and optional free ligand; described one or more replacements or unsubstituted unsaturated alcohol are comprised that 2-amylene-1-ol, 3-amylene-1-ol and/or 4-amylene-1-ol hydroformylation produce one or more replacements or unsubstituted 1,6-hexylene glycol.In step (a) and (d) the hydroformylation reaction condition can be identical or different and in step (a) and the hydroformylation catalysts (d) can be identical or different.

Olefin isomerization catalyst in the step (c) can be that the homogeneous phase of any kind of or the catalyzer of heterogeneous transition metal base (particularly Ni, Rh, Pd, Pt, Co, Ru or Ir) maybe can be heterogeneous or homogeneous acid catalyst (particularly any acid zeolite, polymer resin or H ⁺The source, wherein any one available one or more are transition metal modified).Carry out isomerization reaction at well known such olefin isomerization catalyst and available common method known in the art.(but being not limited thereto) all isomerization methods of allowing planned to comprise in term " isomerization " as used in this, and they comprise one or more replacements or unsubstituted 2-amylene-1-ol and/or 3-amylene-1-ol are changed into one or more replacements or unsubstituted 4-amylene-1-ol.

When dividing 2 stages to carry out, method of the present invention (at first under a series of conditions, produces 2-amylene-1-ol, 3-amylene-1-ol and/or 4-amylene-1-ol, under another sets of conditions, produce 1 then from 2-amylene-1-ol, 3-amylene-1-ol and/or 4-amylene-1-ol (or acetal), the 6-hexylene glycol), the preferred fs in temperature from 75 ℃-110 ℃ with carry out under the 250psi-1000psi with subordinate phase in temperature from 60 ℃-100 ℃ with under 100psi-500psi, carry out at pressure in total pressure.In first and second stages, can use identical or different catalyzer.Other condition can be identical or different in two stages.

1,6-hexylene glycol product has in extensive fields well known in the art to be used, as be used as raw material/intermediate in producing polyester.In producing caprolactone and hexanolactam, 1, the 6-hexylene glycol also can be used as raw material/intermediate.Cyclisation step

Described cyclization method comprises one or more replacements or unsubstituted 1, the 6-hexylene glycol is as 1, the 6-hexylene glycol or comprise one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol changes into one or more replacements or unsubstituted 6-caprolactone or comprises the reaction mixture of one or more replacements or unsubstituted 6-caprolactone.Term " cyclisation " is intended to comprise that all allow cyclization method as used in this, they comprise one or more replacements or unsubstituted 1, the 6-hexylene glycol is as 1,6-hexylene glycol or comprise one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol changes into one or more replacements or unsubstituted 6-caprolactone or comprises the reaction mixture of one or more replacements or unsubstituted 6-caprolactone.Term " 6-caprolactone " plan comprises replacement or the unsubstituted 6-caprolactone that all are allowed as used in this, they can be derived from one or more replacements or unsubstituted 1, the 6-hexylene glycol is as 1,6-hexylene glycol or comprise one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol.

Replace or unsubstituted 1, the illustration of 6-hexylene glycol for example comprises 1,6-hexylene glycol or its acetal etc.Be used for 1 of cyclization method, the 6-hexylene glycol is known raw material and can prepares by ordinary method.For example, can prepare 1, the 6-hexylene glycol by above-mentioned hydroformylation and step of hydrogenation or by other common method.Can use at this and to contain 1, the reaction mixture of 6-hexylene glycol.Use 1 in cyclisation step, the consumption of 6-hexylene glycol there is no strict restriction and can be to satisfy any consumption of preferably producing 6-caprolactone with highly selective.

Specific cyclization condition there is no strict restriction but can satisfy any effective cyclization method of producing 6-caprolactone.

Cyclization can temperature from about 50 ℃-Yue 400 ℃ carried out about 1 hour or following to about 4 hours or the longer time (low temperature is long more duration of service more), preferably about 100 ℃-Yue 350 ℃ carried out about 1 hour or following to about 2 hours or the longer time with more preferably carried out about 1 hour or shorter time at about 150 ℃-Yue 300 ℃.

Described cyclization can carry out in the wide pressure range of the about 2000psig of about 15psig-.The preferred pressure of carrying out cyclization is from the about 1000psig of about 15psig-.Described cyclization preferably carries out under liquid state or gaseous state or its mixed state.

Use known catalyzer can carry out this cyclization with conventional amount used.The illustration of the cyclization catalyst that is fit to comprises for example promoted copper chromite of barium (barium promoted copperchromite), with barium, manganese, copper, calcium, the promoted chromium of zinc, for example, the promoted copper chromite of barium, carrying alumina silver, carrying alumina molybdenum oxide, the copper/zinc oxide, carrying alumina platinum/tin, copper/chromium/barium, the alumina/silica that are carried on aluminum oxide or the bulk oxidation thing are carried cobalt.Preferred cyclization catalyst comprise the promoted copper chromite of barium and aluminum oxide copper-loaded/zinc oxide etc.Employed special catalyst should have under mild conditions with high yield and transforms 1, and the 6-hexylene glycol is the ability of 6-caprolactone.Catalyzer can be homogeneous phase or heterogenetic.Ligand that is fit to or promotor can be sneaked in this catalyzer to change activity of such catalysts, selectivity, work-ing life or ease for operation.This class ligand and promotor are known substances and use with conventional amount used.

The consumption of the cyclization catalyst that uses depends on employed specific cyclization catalyst and for about 0.01% (weight) of described raw material gross weight or more be low to moderate about 10% (weight) or higher.

In any appropriate solvent, under any suitable pressure, or in gas phase, carry out this class cyclization.Select the solvent of this class and pressure to obtain the performance of optimal catalyzer.For example, can under hydrogen, react so that rugged catalyst avoids decomposition reaction to become unproductive catalyzer.Suitable solvent comprises ether, ester, lactone (as 6-caprolactone), ketone, aliphatic series or aromatic hydrocarbon, fluorocarbon, siloxanes, polyethers, hydrochloric ether etc.

Can separate by common technology such as distillation, extraction, precipitation, crystallization, membrane sepn or other proper method by the 6-caprolactone that cyclisation step of the present invention is produced.For example, under normal pressure or decompression, by filling distillation column with crude reaction product fractionation by distillation.Reaction distillation can be applied in the cyclization step.

The illustrative 6-caprolactone that can prepare by method of the present invention comprises the 6-caprolactone (6-caprolactone that replaces as α, β, γ and δ) of 6-caprolactone and replacement.Replacement that is fit to and the illustration that does not replace 6-caprolactone (comprising epsilon-caprolactone derivative) are included in the Encyclopedia of Chemical Technology of Kirk-Othmer, those permissible replacements or unsubstituted 6-caprolactone described in the Third Edition (1984), its relevant part is done concrete reference at this in conjunction with the present invention.

Replacement or unsubstituted 6-caprolactone product have in widespread use well known in the art, as can be used as raw material/intermediate in producing ε-Ji Neixianan and polyester.

For example, can use fixed-bed reactor, fluidized-bed reactor, continuous stirred tank reactor (CSTR) or slurry-phase reactor to finish hydroformylation process of the present invention.The optimum size of catalyzer and shape will depend on the type of the reactor that uses.Generally say, fluid bedreactors, preferred little, spherical catalyst particle is to be easy to fluidisation.When using fixed-bed reactor, preferably bigger catalyst particle is so that the counterpressure in the reactor remains on low degree rationally.

The process of hydroformylation of the present invention can be carried out in mode in batches or continuously, the raw material that does not consume can be recycled as needs.Described reaction can the single reaction district carry out or with the serial or parallel connection mode a plurality of reaction zones carry out the elongation pipe line area or series such district in carry out in batches or continuously.The material that exists in the manufactured materials reply reaction process that is adopted shows that the manufacturing of inertia and equipment should be able to the tolerance response temperature and pressure.The device that raw material or component is imported in batches or continuously the importing of amount of reaction zone and/or adjusting in reaction process can be used in particular for keeping the required molar ratio of raw material in the method easily.For example, add hydrogen and carbon monoxide according to appointment at 2: 1 to keep required dividing potential drop with suitable mol ratio.By incremental change add a kind of former expect in the another kind of raw material can carry out reactions steps.Equally, can merge reactions steps by uniting the adding raw material.When not needing or can not get transforming fully, can for example from product, isolate raw material and then raw material is circulated back to reaction zone by distillation.

Can in the conversion unit of enamel, stainless steel or similar type, carry out hydroformylation reaction.Reaction zone can be installed one or more inside and/or external heat exchanger, so that control undue temperature fluctuation, or prevents any possibility " disengaging control " temperature of reaction.

Can carry out hydroformylation process of the present invention with one or more steps or stage.Definite reaction step number or number of stages will be decided by the high catalyst selectivity, activity, work-ing life and the ease for operation that obtain and consider that the inherent reactivity of raw material and raw material and required reactor product are to the optimal coordination scheme between the stability of reaction conditions.

The replacement of producing by method of the present invention and unsubstituted 1, the 6-hexylene glycol can further react to obtain its required derivative.According to carry out such derivative reaction of allowing with common method known in the art.Illustrative derivative reaction comprises reactions such as for example cyclisation, dehydration reaction, cyclocarbonylization, carbonyl esterification (carboesterification), hydrogenation, esterification, etherificate, amination, alkylation, dehydrogenation, reduction, acidylate, condensation, carboxylated, carbonylation, oxidation, silylanizing, comprises the association response that it is allowed.Preferred derivative reaction and 1,6-hexane diol derivatives for example comprise that amination reaction obtains hexamethylene-diamine, oxidizing reaction and obtains that hexanodioic acid, oxidation and cyclization obtain 6-caprolactone and oxidation, cyclisation and amination reaction obtain ε-Ji Neixianan.The present invention also is confined to the derivative reaction of allowing or the replacement of allowing and unsubstituted 1, the derivative of 6-hexylene glycol never in any form.

For purposes of the invention, term " hydrocarbon " plans to comprise that all have the compound of allowing of at least one hydrogen and a carbon atom.Permissible compound so also can have one or more heteroatomss.In broad aspect, that permissible hydrocarbon comprises is acyclic (have or do not have heteroatoms) and can being substituted or unsubstituted organic compound of ring-type, side chain and unbranched, carbocyclic ring and heterocycle, aromatics and non-aromatics.

The organic compound substituting group that all are allowed unless otherwise indicated planned to comprise in term " replacement " as used in this.In broad aspect, the substituting group of allowing comprises the substituting group of acyclic and ring-type, side chain and unbranched, carbocyclic ring and heterocycle, aromatics and non-aromatics organic compound.Substituent illustration comprises for example alkyl, alkoxyl group, aryl, aryloxy, hydroxyl, hydroxyalkyl, amino, aminoalkyl group, halogen etc., and wherein carbonatoms can be from 1-about 20 or more, preferably from 1-about 12.For suitable organic compound, the substituting group of allowing can be one or more and identical or different.The present invention also is confined to permissible organic compound substituting group never in any form.

For purposes of the invention, determine chemical element according to the periodic table of elements that F.Albert Cotton.Geoffrey Wilkinson and Paul L.Gaus reprint in " Basic Inorganic Chemistry " (John Wiley and Sons Inc. publishes, the 3rd edition 1995).

Provide more following embodiment to further specify the present invention.

Embodiment 1-19

In 100 milliliters of high-pressure reactors that the top band stirs, pack into 0.25mmol dicarbapentaborane Acetyl Acetone rhodium (dicarbonylacetylacetonato rhodium) (I), defined trialkyl phosphine in the following Table A of 0.9mmol, 3 milliliters of divinyl, 26 milliliters as Table A target diglyme in defined solvent and the 1 milliliter of work.With the hydrogen/carbon monoxide pressurized reactor of 1/1 ratio of 5-10psi and be heated to the temperature required of Table A defined.Under required temperature, reactor is forced into the ratio of required hydrogen/carbon monoxide set in the Table A and monitors gas absorption.Pressure reduces after 10%, in order to 1/1 ratio hydrogen/carbon monoxide again pressurized reactor to initial value.In the predetermined distance time, answer blend sample through the negate of sample thief pipeline, place dry ice refrigerative phial, use gas chromatographic analysis.After reacting end in 90 minutes, emit gas and discharge reaction mixture.Further details and analytical results are listed in the Table A.

Table A embodiment solvent/promotor phosphine temperature H ₂/CO ( ％ ) ( ℃ ) ( psi ) ( ％ ) n/L/h 34 1 60 300/300 27 0.2 92 2 80 300/300 90 1.6 87 3 80 500/500 87 1.3 91 4 80 75/75 75 0.3 71 5 80 600/200 98 1.9 88 6 3- 80 600/200 89 nd 90 7 80 300/300 65 nd 93 8 80 600/200 90 1.4 88 9 80 300/300 55 1.0 70 10 /THF 80 600/200 84 2.0 55 11 120 250/250 99 nd 38 ( 15min rxn.time ) 12 120 250/250 97 nd 42 ( 2h rxn.time ) 13 --N,N-80 600/200 70 1.2 64

Dimethylphenylphosphine 14 ethanol/acetonitrile triethyl phosphines 80 3,00/,300 68 1.1 82 15 ethanol/tetraethylene glycol dimethyl ether triethyl phosphine 80 3,00/,300 64 1.0 91 16 diphenylamines tri octyl phosphines 80 6,00/,200 80 0.8 54 17 acetamide tri octyl phosphines 80 6,00/,200 85 0.9 34 18 methylacetamide tri octyl phosphines 80 6,00/,200 73 0.8 59 19 N-METHYLFORMAMIDE tri octyl phosphines 80 6,00/,200 33 0.1 19 nd=do not detect

Embodiment 20-26

Target diglyme in defined trialkyl phosphine among the following tabulation B of dicarbapentaborane Acetyl Acetone rhodium (I), 0.9mmol of 0.25mmol, 3 milliliters of divinyl, the 26 milliliters of ethanol of in 100 milliliters of high-pressure reactors that the top band stirs, packing into and the 1 milliliter of work.With the hydrogen/carbon monoxide pressurized reactor of 1/1 ratio of 5-10psi and be heated to 80 ℃.Under required temperature, reactor is forced into the ratio of required hydrogen/carbon monoxide set among the table B and monitors gas absorption.Pressure reduces after 10%, in order to 1/1 ratio hydrogen/carbon monoxide again pressurized reactor to initial value.In the predetermined distance time, answer blend sample and place dry ice refrigerative phial through the negate of sampling pipeline, use gas chromatographic analysis.After reacting end in 120 minutes, emit gas and discharge reaction mixture.Further details and analytical results are listed among the table B.

Table B embodiment phosphine H ₂/ CO divinyl speed 3 and 4 pentenol sequence number (psi) transformation efficiency (m/L/ selectivity (%)

(％) h)

(%) 20 tert-butyl group diethyl phosphines, 3,00/,300 60 0.8 1321 tert-butyl group diethyl phosphines, 8,00/,200 69 1.1 1922 cyclohexyl diethyl phosphines, 3,00/,300 76 0.7 7523 cyclohexyl diethyl phosphines, 8,00/,200 82 1.4 8024 normal-butyl diethyl phosphines, 3,00/,300 77 1.1 8225 ethylphenyl phosphines, 2,00/,800 53 0.9 7726 ethyl diphenylphosphines 2,00/,800 38 0.6 27

Embodiment 27

With 1: 1 H ₂160 milliliters of magnetic agitation autoclaves of/CO purge and packing into comprise 0.1125 gram (0.44mmol) dicarbapentaborane Acetyl Acetone rhodium (I), 0.3515 gram (2.94mmol) P (CH ₂CH ₂CH ₂OH) ₃Catalyst solution with 44.1 gram tetrahydrofuran (THF)s.With 40psig 1: 1H ₂/ CO makes the autoclave pressurization and is heated to 80 ℃.Add the 1,3-butadiene of 6 milliliters (3.73 grams) and with 1: 1 H with volume pump ₂/ CO is forced into 1000psig with reactor.In 1000psi1: 1H ₂The maintenance reaction mixture is at 80 ℃ under the/CO.Negate answers blend sample to obtain listed result among the following tabulation C after 90 minutes and 170 minutes.

Table C time-temperature H ₂/ CO divinyl speed 3 and 4 pentenols (minute) (℃) are (m/L/h) selectivity (%) 90 80 5,00/,500 81 0.7 66 170 80 5,00/,500 96 0.4 72 of transformation efficiency (%) (psig)

Embodiment 28

With 1: 1 H ₂160 milliliters of magnetic agitation autoclaves of/CO purge and packing into comprise 0.1126 gram (0.44mmol) dicarbapentaborane Acetyl Acetone rhodium (I), 0.6120 gram (1.69mmol) P (CH ₂CH ₂CH ₂OH) ₃With 39.9 gram alcoholic acid catalyst solutions.With 1: 1 H of 40psig ₂/ CO makes the autoclave pressurization and is heated to 80 ℃.Add the 1,3-butadiene of 6 milliliters (3.73 grams) and with 1: 1 H with volume pump ₂/ CO is forced into 1000psig with reactor.In 1000psi1: 1 H ₂The maintenance reaction mixture is at 80 ℃ under the/CO.Negate answers blend sample to obtain the result who lists among the following tabulation D after 15 minutes and 43 minutes.

Table D time-temperature H ₂/ CO divinyl speed 3 and 4 pentenols (minute) (℃) are (m/L/h) selectivity (%) of transformation efficiency (%) (psig)

15 80 500/500 53 2.6 70

43 80 500/500 89 1.5 78

Embodiment 29

With 1: 1 H ₂160 milliliters of magnetic agitation autoclaves of/CO purge and packing into comprise 0.1125 gram (0.44mmol) dicarbapentaborane Acetyl Acetone rhodium (I), 0.3515 gram (2.94mmol) P (CH ₂CH ₂CH ₂OH) ₃Catalyst solution with 44.1 gram tetrahydrofuran (THF)s.With 40psig 1: 1H ₂/ CO makes the autoclave pressurization and is heated to 80 ℃.Add the 1,3-butadiene of 6 milliliters (3.73 grams) and with 1: 1 H with volume pump ₂/ CO is forced into 1000psig with reactor.In 1000psi 1: 1H ₂The maintenance reaction mixture is at 80 ℃ under the/CO.Negate answers blend sample to obtain the result who lists among the following tabulation E after 90 minutes.

Table E time-temperature H ₂/ CO divinyl speed 1,6-hexylene glycol (minute) (℃) is (m/L/h) selectivity (%) 90 80 5,00/,500 81 0.7 2 of transformation efficiency (%) (psig)

Embodiment 30

With 1: 1 H ₂160 milliliters of magnetic agitation autoclaves of/CO purge and packing into comprise 0.1126 gram (0.44mmol) dicarbapentaborane Acetyl Acetone rhodium (I), 0.6120 gram (1.69mmol) P (CH ₂CH ₂CH ₂OH) ₃With 39.9 gram alcoholic acid catalyst solutions.With 1: 1 H of 40psig ₂/ CO makes the autoclave pressurization and is heated to 80 ℃.Add the 1,3-butadiene of 6 milliliters (3.73 grams) and with 1: 1 H with volume pump ₂/ CO is forced into 1000 psig with reactor.In 1000 psi1: 1 H ₂The maintenance reaction mixture is at 80 ℃ under the/CO.Negate answers blend sample to obtain the result who lists among the following tabulation F after 60 minutes.

Table F time-temperature H ₂/ CO divinyl speed 1,6-hexylene glycol (minute) (℃) is (m/L/h) selectivity (%) 60 80 5,00/,500 89 1.1 4 of transformation efficiency (%) (psig)

Embodiment 31-34

The target diglyme in dicarbapentaborane Acetyl Acetone rhodium (I), the 0.9mmol trialkyl phosphine (as defining among the following table G) of 0.25mmol, 3 milliliters of divinyl, 26 milliliters ethanol and the 1 milliliter of conduct of in 100 milliliters of high-pressure reactors that the top band stirs, packing into.With the hydrogen/carbon monoxide pressurized reactor of 1/1 ratio of 5-10psi and be heated to 80 ℃.Under required temperature, reactor is forced into the ratio of the required hydrogen/carbon monoxide that is provided with among the table G and monitors gas absorption.Reactor pressure descends after 10%, in order to 1/1 ratio hydrogen/carbon monoxide again pressurized reactor to initial value.After finishing 120 minute reaction time, emit gas and discharge reaction mixture and use gas chromatographic analysis.Further details and analytical results are listed among the table G.

Table G embodiment trialkyl phosphine H ₂/ Co, (psi) butadiene speed is to 1.6-hexylene glycol sequence number conversion ratio, (%), (m/L/h) selective, (%) 31 cyclohexyl diethyl phosphines, 3,00/,300 76 0.7 7.232 hexyl diethyl phosphines 8,00/,200 82 1.4 7.233 just-butyl diethyl phosphine 3,00/,300 77 1.1 5.934 diethyl phenyl phosphines 2,00/,800 53 0.9 3.0

Embodiment 35-52

In the Schlenk flask, by under nitrogen, mixing dicarbapentaborane acetylacetonate rhodium (I), [Co ₂(CO) ₈] and ethanol (30 milliliters) prepare catalyzer with the metal concentration that this obtains to show among the H separately.1.0M solution in the tetrahydrofuran (THF) that adds triethyl phosphine (labelled amount among the table H) as the quantitative diglyme of interior mapping.Be transferred to after stirring the mixture 5-10 minute in 100 milliliters of stainless Parr autoclaves.The divinyl that adds aequum then through syringe.After required carbon monoxide resulting pressure with about 25% and about 25% required final hydrogen dividing potential drop make the autoclave pressurization, be heated to final required temperature of reaction, add a certain amount of carbon monoxide and hydrogen then to obtain required final dividing potential drop (all are indicated among the table H).Make and react the time shown in carrying out.When total pressure drop to required stagnation pressure 90% the time, (mixture of hydrogen and carbon monoxide makes stagnation pressure go back up to 100% of required pressure to add 2: 1 synthesis gass.Cooling reactor is to room temperature and be deflated to normal pressure, must show the result shown in the I by the gas chromatographic analysis content.

Table H embodiment [Rh] [Co] PEt ₃Divinyl temperature P (CO) P (H ₂) time

( ppm ) ( ppm ) ( mmol ) ( mmols ) ( ℃ ) ( psig ) ( psig ) ( ) 35 309 315 0.3 34.8 100 250 400 11336 604 313 1.0 36.7 125 550 600 12037 911 311 1.6 33.8 150 400 800 14838 965 654 1.0 33.3 100 400 600 12439 297 599 2.1 33.1 125 250 800 11040 594 593 0.3 36.9 150 400 550 13841 300 892 2.1 27.6 100 550 600 11542 606 892 0.3 34.2 150 400 800 13843 900 900 1.1 33.7 150 250 400 12044 600 300 1.7 67.0 100 400 400 12145 916 312 0.3 68.1 125 250 600 9946 330 332 1.0 31.5 150 550 800 12247 911 597 0.3 66.7 100 550 800 12048 307 586 1.2 66.7 125 400 400 13849 600 600 1.9 69.6 150 250 600 11250 601 910 1.2 68.6 100 250 800 13851 885 874 1.9 69.5 150 400 600 13852 324 789 0.4 71.9 150 400 600 120

Table I embodiment amylene-1-aldehyde amylene-1-ol 6-hydroxyl hexanal 1,6-hexylene glycol 35 1.7 68.7 2.0 3.736 0.0 29.4 0.0 8.737 3.8 3.3 0.0 0.038 0.0 79.3 0.0 7.539 0.0 62.5 0.9 8.540 4.6 0.0 1.6 2.441 2.5 13.0 0.0 0.042 6.1 0.0 1.8 0.043 0.0 0.0 0.0 9.844 0.0 74.8 0.7 5.245 1.9 0.0 2.5 1.046 0.0 4.4 0.6 10.247 0.0 42.0 0.6 7.848 0.0 53.1 1.0 7.349 0.0 1.3 0.4 9.550 0.4 79.2 0.9 5.451 0.0 54.8 0.6 8.552 5.8 1.0 0.0 0.0

Embodiment 53-60

In the Schlenk flask by under nitrogen, mix dicarbapentaborane acetylacetonate rhodium (I) (0.11mmol), PEt ₃(1.0M is in tetrahydrofuran (THF)) and PhP (CH ₂CN) ₂, diglyme (gas phase in mark: 1 milliliter) and ethanol (23 milliliters), below obtaining with this among table J ligand/metal molar than preparing catalyzer.Be transferred to after stirring the mixture 5-10 minute in 100 milliliters of stainless Parr autoclaves.The divinyl that adds aequum then through injection.After making the autoclave pressurization with about 25% required carbon monoxide resulting pressure and about 25% required final hydrogen dividing potential drop, be heated to final required temperature of reaction, add a certain amount of carbon monoxide and hydrogen then to obtain required final dividing potential drop (all are indicated among the table J).Make and react the time shown in carrying out.When total pressure drop to required stagnation pressure 90% the time, add 2: 1 synthetic gas (mixture of hydrogen and carbon monoxide), make stagnation pressure 100% of the required pressure that gos up.Cooling reactor to room temperature must be shown the result shown in the K with exitting to normal pressure with by the gas chromatographic analysis content.

Table J embodiment PhP (CH ₂CN) ₂/ Rh PEt ₃/ Rh divinyl temperature P (CO) P (H ₂) time

(mmols) (℃) (psig) (psig) (minute) 53 21 68.1 70 800 150 138 54 25 100.6 70 200 150 138 55 85 68.5 70 800 150 123 56 21 67.4 100 800 450 110 57 81 67.4 100 200 450 110 58 25 68.1 100 200 450 127 59 85 68.1 100 800 450 128 60 53 68.4 85 500 300 127

Table K embodiment amylene-1-aldehyde amylene-1-ol 6-hydroxyl hexanal 1,6-hexylene glycol 53 11.0 74.9 0.0 0.054 5.2 70.8 0.0 0.055 43.4 47.3 0.0 0.056 65.1 3.4 0.0 0.057 71.3 1.4 0.0 0.058 0.5 69.1 0.9 6.359 5.4 68.8 2.5 3.560 14.9 49.9 3.4 1.2

Embodiment 61-66

In 100 milliliters of high-pressure reactors that the top band stirs, pack into 0.25mmol dicarbapentaborane Acetyl Acetone rhodium (I), 0.9-2.6mmol below target diglyme in the phosphine shown in the table L, 3 milliliters divinyl, the solvent shown in 26 milliliters the table L and the 1 milliliter of conduct.With 1/1 hydrogen/carbon monoxide pressurized reactor of 5-10psi be heated to required temperature.Under required temperature, with hydrogen and carbon monoxide pressurized reactor to required ratio and pressure and monitor gas absorption.After the gas absorption 10%, with 1/1 hydrogen/carbon monoxide again pressurized reactor to initial value.Answer blend sample to place dry ice refrigerative phial and through gas chromatographic analysis in pitch time of regulation through sampling pipeline negate.After finishing 90 minute reaction time, in emitting gas and discharging reaction mixture and under nitrogen, be stored in bottle.Further details and presentation of results are in table L.

Table L embodiment solvent/promotor phosphine (phosphine: Rh) temperature H ₂/ CO divinyl speed 1,6-hexylene glycol sequence number

(℃) (psi) conversion ratio (%) m/L/h (%) 61 diphenylamines tri octyl phosphines (4) 80 6,00/,200 80 0.6 662 ethanol triethyl phosphines (10.5) 100 3,00/,300 74 1.4 763 ethanol triethyl phosphines (3.5) 80 3,00/,300 71 1.0 564 acetamide tri octyl phosphines (4) 90 6,00/,200 84 0.8 365 N-methylacetamide tri octyl phosphines (4) 90 6,00/,200 73 0.5 866 pyrroles's tri octyl phosphines (4) 80 6,00/,200 90 1.4 5

Embodiment 67 and 68

In 100 milliliters of high-pressure reactors that the top band stirs, pack into 0.25mmol dicarbapentaborane Acetyl Acetone rhodium (I), 0.9mmol below the solvent shown in the unsaturated Substrate (valeral or amylalcohol) shown in the phosphine shown in the table M, 2 milliliters of table M, 26 milliliters of table M and as 1 milliliter of diglyme of interior target.With 1/1 hydrogen/carbon monoxide pressurized reactor of 100 psi and be heated to required temperature.Under required temperature, with 1/1 hydrogen and carbon monoxide pressurized reactor to required pressure and stirred reaction mixture 2-4 hour.When finish reaction time, emit gas and discharge reaction mixture and through gas chromatographic analysis.Further details and presentation of results are in table M.

Table M embodiment Substrate solvent/promotor phosphine (phosphine: Rh) temperature H ₂/ CO 1,6-hexylene glycol sequence number (℃) (psi) (%) 67 4-pentenol ethanol triethyl phosphines (3.5) 120 3,00/,300 69 68 4-pentenals pyrroles tri octyl phosphines (4) 120 3,00/,300 59

Embodiment 69 reactor assemblies

Reactive system comprises being furnished with 3/8 inch * the Applied Test Systems Inc. stove of 22 inches silica tube reaction zones.Described pipe is with following order pack into 2 centimetres of glass tampons, 2 millimeters crown glass pearls of 3 centimetres, 1/8 inch pelleted catalyst of Engelhard Cu-1186 T of 12 centimetres and 2 milliliters of crown glass pearls of 20 centimetres.Described silica tube is placed stove, make catalyzer be positioned at the stove center.Described pipe is equipped with 2 thermopairs, and one at the top of catalyst bed, and another is in the bottom of catalyst bed.This system is furnished with nitrogen and hydrogen metering opening for feed.Use the product of cold-trap condensation from air-flow.Reactor moves under normal pressure.Through syringe pump reactant is input in the system and drops on the granulated glass sphere and vaporize.The catalyst activation effect

Open the nitrogen gas stream of 51 cubic centimetres of per minutes.Furnace temperature is heated to 230 ℃.In case temperature-stable, the hydrogen stream that the unlatching per minute is 5 cubic centimetres.With the time more than 2 hours, hydrogen flowing quantity is increased to 51 cubic centimetres of per minutes.Can observe the heat release of following the catalyst reduction reaction by the top thermopair.When bottom thermopair and sinking (subside) when observing heat release, show that catalyst activation is complete.Catalyst bed temperature rises to 260 ℃.Beginning is with per minute 0.012 milliliter of diglycol material of input and make its operation 24 hours.After 24 hours, from the sampling of product condensation product and through gas chromatographic analysis.Analyze to show greater than 90% by glycol ether to 1, the transformation efficiency and the selectivity of 4-Er Evil ketone (dioxanone).Whether carry out the glycol ether dehydrogenation reaction activates to measure catalyzer.1,6-hexylene glycol dehydrogenation

Off-response thing feed cuts out the hydrogen feed, cleans syringe pump, charging line and product receptor.Syringe pump injects 75 gram glyme and 50g 1, the solution of 6-hexylene glycol.Start the hydrogen feed and keep 50 cubic centimetres of per minutes.The nitrogen feed remains on 51 cubic centimetres of per minutes.The beginning per minute provides 0.024 milliliter 1, the feed of 6-hexylene glycol.Top electric thermo-couple temperature reading is 264 ℃.Keep all the other working times catalyst bed temperature at about 260 ℃ (as the top thermocouple assays).Under such condition, make reactor operation 24 hours.Through atmospheric condenser condensed product and unreacted raw material from air-flow.After 24 hours reaction times, off-response device and taking-up 5.0 gram crude products from the product that condenser is collected.Through the gas chromatographic analysis crude product.The crude product analysis shows 13.2% glyme, 25.0%1, several undetermined other by product of 6-hexylene glycol, 30.9% caprolactone and formation sample remainder.Gas chromatography is not calibrated with its result and is area percentage.Through gas chromatography/infrared/mass spectrum confirmation caprolactone product.

Though by more aforesaid embodiment the present invention has been described, has not therefore constituted limitation ot it; On the contrary, the present invention includes as above-mentioned disclosed entire area.Under the prerequisite that does not deviate from the spirit and scope of the present invention, can carry out various changes and formulate various embodiments.

Claims

1. produce one or more replacements or unsubstituted 1, the method of 6-hexylene glycol, it is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1,6-hexylene glycol.

2. produce one or more replacements or unsubstituted 1, the method of 6-hexylene glycol, it is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted pentenals and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1,6-hexylene glycol.

3. produce one or more replacements or unsubstituted 1, the method of 6-hexylene glycol, it is included under the existence of metal-ligand coordination catalyst, promotor and optional free ligand, make one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1,6-hexylene glycol.

4. produce one or more replacements or unsubstituted 1, the method of 6-hexylene glycol, it comprises: (a) at metal-ligand coordination catalyst, under the existence of promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene and carbon monoxide and H-H reaction produce one or more replacements or unsubstituted amylene-1-ol and (b) at metal-ligand coordination catalyst, under the existence of promotor and optional free ligand, make described one or more replacements or unsubstituted amylene-1-ol and carbon monoxide and H-H reaction produce described one or more replacements or unsubstituted 1,6-hexylene glycol.

5. claim 1 and 4 method, wherein said replacement or unsubstituted alkadiene comprise divinyl, described replacement or unsubstituted amylene-1-ol comprise suitable-3-amylene-1-ol, anti--the 3-amylene-1-ol, 4-amylene-1-ol, suitable-2-amylene-1-ol and/or anti--2-amylene-1-ol and described replacement or unsubstituted 1, the 6-hexylene glycol comprises 1, the 6-hexylene glycol.

6. the method for claim 4, wherein step (a) and (b) described in hydroformylation (hydrocarbonylation) reaction conditions can be identical or different, and hydroformylation catalysts can be identical or different in step (a) with (b).

7. claim 1,2,3 and 4 method, wherein said metal-ligand coordination catalyst comprise be selected from 8,9 and 10 family's metals and be selected from one-, two-, three-and the metal that cooperates of the organic phosphine coordination body of poly--(organic phosphine) ligand.

8. claim 1,2,3 and 4 method, wherein said metal-ligand coordination catalyst comprise and are selected from the metal that 8,9 and 10 family's metals cooperate with the organic phosphine coordination body of the three organic phosphine coordination bodies that are selected from the following formula representative:

Each R wherein ¹Identical or different and for replacing or unsubstituted monovalence alkyl.

9. the method for claim 7, wherein said organic phosphine coordination body have more than or equal to the alkalescence of triphenyl phosphine (pKb=2.74) alkalescence and are less than or equal to the space loose density of 210 ° of Tolman cone angles.

10. claim 1,2,3 and 4 method, wherein said promotor is incorporated in the ligand structure as metal-ligand coordination catalyst or as free ligand.

11. claim 1,2,3 and 4 method, wherein said promotor have the pKa of about 1-35 and comprise protonic solvent, organic and mineral acid, alcohol, water, phenol, mercaptan, selenol, nitro-paraffin, ketone, nitrile, amine, acid amides or-, two-or trialkyl ammonium salts or its mixture.

12. claim 1,2,3 and 4 method, it is from about 50 ℃-150 ℃ temperature with carrying out under the stagnation pressure of the about 3000psig of about 20psig-.

13. claim 1,2,3 and 4 method, wherein said method produces the reaction mixture that comprises following ingredients in batches or continuously:

(1) one or more replacements or unsubstituted 1, the 6-hexylene glycol;

(2) choose any one kind of them or multiple replacement or unsubstituted amylene-1-ol;

(3) choose any one kind of them or multiple replacement or unsubstituted 6-hydroxyl hexanal;

(4) choose any one kind of them or multiple replacement or unsubstituted 5-hydrogenation of hydroxypentylaldehyd, and/or its ring lactol derivative;

(5) choose any one kind of them or multiple replacement or unsubstituted 4-acetaldol and/or its ring lactol derivative;

(8) choose any one kind of them or multiple replacement or unsubstituted pentenals;

(9) choose any one kind of them or multiple replacement or unsubstituted 1 the 6-hexanedial;

(10) choose any one kind of them or multiple replacement 1, the 5-glutaraldehyde;

(11) choose any one kind of them or multiple replacement 1, the 4-suceinic aldehyde; With

(12) one or more replacements or unsubstituted divinyl; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is greater than about 0.1; And the weight ratio of component (12) and component (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is about 0-about 100; Or comprise the reaction mixture of following ingredients:

(1) one or more replacements or unsubstituted 1, the 6-hexylene glycol;

(8) choose any one kind of them or multiple replacement or unsubstituted pentenals; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6) and (7) summation is greater than about 0.1; And the weight ratio of component (8) and component (1), (2), (3), (4), (5), (6) and (7) summation is about 0-about 100; Or comprise the reaction mixture of following ingredients:

(1) one or more replacements or unsubstituted 1, the 6-hexylene glycol;

(2) one or more replacements or unsubstituted amylene-1-ol;

(5) choose any one kind of them or multiple replacement or unsubstituted 4-acetaldol and/or its ring lactol derivative; With

(6) choose any one kind of them or multiple replacement or unsubstituted valeral; Wherein the weight ratio of component (1) and component (3), (4), (5) and (6) summation is greater than about 0.1; And the weight ratio of component (2) and component (1), (3), (4), (5) and (6) summation is about 0-about 100; Or comprise the reaction mixture of following ingredients:

(1) one or more replacements or unsubstituted 1, the 6-hexylene glycol;

(12) one or more replacements or unsubstituted divinyl; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is greater than about 0.1; And the weight ratio of component (12) and component (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is about 0-about 100.

Comprise one or more replacements or unsubstituted 1 14. produce, the method for the reaction mixture of 6-hexylene glycol, this method comprise claim 1,2,3 and 4 method.

15. the composition of producing by claim 1,2,3 and 4 method comprises:

(1) one or more replacements or unsubstituted 1, the 6-hexylene glycol;

(12) one or more replacements or unsubstituted divinyl; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is greater than about 0.1; And the weight ratio of component (12) and component (1), (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) summation is about 0-about 100; Or comprise the composition of following ingredients:

(1) one or more replacements or unsubstituted 1, the 6-hexylene glycol;

(8) choose any one kind of them or multiple replacement or unsubstituted pentenals; Wherein the weight ratio of component (1) and component (2), (3), (4), (5), (6) and (7) summation is greater than about 0.1; And the weight ratio of component (8) and component (1), (2), (3), (4), (5), (6) and (7) summation is about 0-about 100; Or comprise the composition of following ingredients:

(1) one or more replacements or unsubstituted 1, the 6-hexylene glycol;

(2) one or more replacements or unsubstituted amylene-1-ol;

(6) choose any one kind of them or multiple replacement or unsubstituted valeral; Wherein the weight ratio of component (1) and component (3), (4), (5) and (6) summation is greater than about 0.1; And the weight ratio of component (2) and component (1), (3), (4), (5) and (6) summation is about 0-about 100.

16. produce one or more replacements or unsubstituted 1, the method for 6-hexylene glycol, it comprises:

(a) in the presence of hydroformylation catalysts, promotor and optional free ligand, make one or more replacements or unsubstituted alkadiene hydroformylation produce the unsaturated alcohol of one or more replacements or the unsubstituted 3-of comprising amylene-1-ol, 4-amylene-1-ol and/or 2-amylene-1-ol;

(c) in the presence of hydroformylation catalysts, promotor and optional free ligand; make the unsaturated alcohol hydroformylation of described one or more replacements or the unsubstituted 3-of comprising amylene-1-ol, 4-amylene-1-ol and/or 2-amylene-1-ol produce one or more replacements or unsubstituted 1,6-hexylene glycol.

17. produce one or more replacements or unsubstituted 1, the method for 6-hexylene glycol, it comprises:

(d) in the presence of hydroformylation catalysts, promotor and optional free ligand; make the unsaturated alcohol hydroformylation of described one or more replacements or the unsubstituted 2-of comprising amylene-1-ol, 3-amylene-1-ol and/or 4-amylene-1-ol produce one or more replacements or unsubstituted 1,6-hexylene glycol.

18. comprise one or more replacements or unsubstituted 1, the reaction mixture of 6-hexylene glycol wherein prepares described reaction mixture by claim 1,2,3 and 4 method.

19. claim 1,2,3 and 4 method further comprise described one or more replacements of derivatize or unsubstituted 1; the step of 6-hexylene glycol, wherein said derivative reaction comprise cyclisation, dehydration, cyclocarbonylization, carbonyl ester (carboesterification) change, hydrogenation, esterification, etherificate, amination, alkylation, dehydrogenation, reduction, acidylate, condensation, carboxylated, carbonylation, oxidation, silylanizing and its composite reaction of allowing.

20. one or more replacements of claim 19 or unsubstituted 1, the derivative of 6-hexylene glycol.