CN100584822C - Preparation of acrylic acid derivatives from alpha or beta-hydroxycarboxylic acids - Google Patents
Preparation of acrylic acid derivatives from alpha or beta-hydroxycarboxylic acids Download PDFInfo
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- CN100584822C CN100584822C CN200580010291A CN200580010291A CN100584822C CN 100584822 C CN100584822 C CN 100584822C CN 200580010291 A CN200580010291 A CN 200580010291A CN 200580010291 A CN200580010291 A CN 200580010291A CN 100584822 C CN100584822 C CN 100584822C
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Abstract
The present invention relates to a process for the preparation of α, β -unsaturated acids, esters and amides from α or β -hydroxycarboxylic acids or esters or precursors in high yield and high selectivity. The alpha, beta-unsaturated acids or esters are optionally prepared in the presence of a specific dehydration and/or esterification catalyst. The alpha, beta-unsaturated amides or substituted amides are optionally prepared in the presence of a dehydration and/or amidation catalyst. The source of the alpha or beta-hydroxycarboxylic acid or precursor is preferably derived from renewable resources. Precursors are defined herein.
Description
The present invention relates to high yield and highly selective, prepare α, the method for beta-unsaturated acid, ester and acid amides by other derivative of α or beta-hydroxycarboxylic acids, multi-hydroxy ester or α or beta-hydroxycarboxylic acids.Choose wantonly in the presence of dehydration and/or esterifying catalyst and prepare α, beta-unsaturated acid and ester.Choose wantonly in the presence of amidation and/or dehydration catalyst and prepare α, the acid amides of β-undersaturated acid amides or replacement.The source of α or beta-hydroxycarboxylic acids can obtain or derive from renewable resources for synthesizing.
α or beta-hydroxycarboxylic acids are the compounds with height applicability.They have difunctionality, and therefore can carry out many chemical conversions.Acidic group can change the acid amides of various esters, acid amides and replacement into.Hydroxyl can be removed with adjacent hydrogen, causes unsaturated compound thus.It is lactone or lactide that the difunctionality character of this compounds can also be polymerized to polyester, oligopolymer and cyclisation.
To the concrete interest of this compounds is the commercially important α of preparation, and beta-unsaturated carboxylic acid and their derivative be the acid amides of ester, salt or acrylate and methacrylic ester family for example.(methyl) vinylformic acid and its derivative are used as monomer in the preparation of polymkeric substance and multipolymer.Formed polymkeric substance and multipolymer have many application, for example papermaking, solid/liquid separation method, oil recovery and refining of petroleum, mineral processing, municipal and Industrial Wastewater Treatment, paper, top coat, individual's care products, tackiness agent, sealing agent, sorbent material, textiles, nonwoven fabric and as rheology modifier.
Vinylformic acid is the oxidation preparation by propylene.At present acrylate is that acrylic acid esterification by derived from propylene prepares.It also is known preparing vinylformic acid by propane.The most frequently used method of preparation methacrylic acid is to be prepared by acetone cyanohydrin.Although propylene is obtained from mineral fuel easily, synthesize (methyl) vinylformic acid by renewable resources and ester is an ideal with equal or lower expense.
Acrylamide is prepared by the catalytic hydration of vinyl cyanide usually, and the acrylamide that replaces is prepared by vinyl cyanide and alkene or pure the reaction under strong acidic condition.The method of other practical application of preparation acrylamide comprises three tediously long one step process at present, and it originates in the Michael addition of C=C key, and it in last deprotection steps thermoreversion can take place.In some cases, the Ritter reaction is a method selected, and it uses the vitriol oil.Therefore, by renewable resources with (methyl) acrylamide of produced in high yields (methyl) acrylamide and replacement, technology simply and greatly economic method also be ideal.
The purpose of this invention is to provide inexpensive method, this method is used a kind of raw material, and if necessary, this raw material stems from these monomeric whole renewable resourcess of preparation.According to the present invention, (methyl) vinylformic acid and ester are with high yield and highly selective, by the precursor preparation of the hydroxycarboxylic acid of the hydroxycarboxylic acid of α or beta substitution or corresponding α or beta substitution.The dehydration of α or beta-hydroxycarboxylic acids or dehydration/esterification can be carried out in the presence of water, and optional can carrying out in the presence of dehydration catalyst and/or esterifying catalyst.
(methyl) acrylamide is by α-or beta-hydroxycarboxylic acids or derivative preparation, wherein one or two-stage process in amidation and dehydration take place.Optional amidation and/or dehydration catalyst can be used for this reaction.
In addition, (methyl) vinylformic acid, ester and acid amides can origin come from the α or the beta-hydroxycarboxylic acids preparation of biological origin.It can be as the α of the part generation of zymotechnique or the form of beta-hydroxycarboxylic acids, or it can comprise poly-hydroxy alkane carboxylicesters for example poly-hydroxy propionic ester or multi-hydroxybutyrate, can be derived from biomass examples such as microorganism cells or vegetable cell, this is a most economical approach of considering non-petroleum sources.Poly-hydroxy alkane carboxylicesters can or come from sugar by microorganism, and for example plant, agriculture material and useless agriculture material and other biomass of carbohydrate are synthesized.
For example, processing poly-hydroxy alkane carboxylicesters has been discussed to form ester, acid amides and chain acid derivative among the PCT application No.WO03/051813.
U.S. apply for that No.20020055650 discloses the preparation method of methacrylic acid and ester, it is in the presence of pure and mild solid catalyst, prepares by handling hydroxy-iso-butyric acid or ester.
U.S. patent No.5,250,729 disclose preparation α, the method for beta-unsaturated acid or ester, it is from α or beta-hydroxycarboxylic acids ester.Be reflected under the existence of acidic dehydration catalyst and carry out.
U.S. patent No.2,469,701 have described a kind of method, wherein contacting with sour dehydration catalyst, hydroxy-propionic acid are being dewatered under the condition of from 130 to 190 ℃ of temperature.
PCT application No.WO03/82795 discloses in the presence of pure and mild dehydration catalyst, has prepared α by beta-hydroxycarboxylic acids or ester, β-undersaturated carboxylicesters.
U.S. patent No.3,639,466 disclose a kind of preparation acrylic acid, and this method is that the resistates that will contain hydroxy-propionic acid in the presence of amine or tertiary phosphine heats.
U.S. patent No.3,658,895 disclose in the presence of acid, and the diluting soln of vinylformic acid and beta-hydroxycarboxylic acids forms polyester, and this polyester is through adding thermosetting vinylformic acid.
Spain patent application No.ES 515891 discloses following content: in the presence of solvent, stopper and carrier gas, by means of II, IIIA, IVB and/or VIII family metal sulfate and/or phosphoric acid salt as catalyzer, dehydration by alpha-hydroxy carboxylic acid compounds or its ester, preparation α, β-undersaturated carboxylic acid and/or their ester.
German application No.3141173 discloses α, the preparation method of beta-unsaturated acid or their ester, and this method is by Alpha-hydroxy methane amide R
1R
2C (OH) CONH
2Contact with Fatty Alcohol(C12-C14 and C12-C18) or with Fatty Alcohol(C12-C14 and C12-C18) separately or with water or with water with solid catalyst and to prepare.
U.S. patent No.3,954,854 disclose from the crude product vinylformic acid resistates of processing and have reclaimed monomer vinylformic acid.This resistates contains β-acryloxy oxygen base propionic acid, β-acetoxyl group propionic acid, hydroxy-propionic acid, dilactic acid and polymeric hydroxy-propionic acid.This resistates is under less than 1 atmospheric pressure, is heated under 150 to 215 ℃ the temperature and handles with catalyst for cracking.
U.S. patent No.2,464,768 have described the preparation method of low molecular weight propylene acid esters, and this method is led to the solution of anhydrous ethylene lactic acid in alcohol excess in the mixture of strong acid and copper powder under 130 to 170 ℃, and distills out acrylate and water.
European application No.1,186,592 have described under hot conditions, and Alpha-hydroxy isobutyric acid and alcoholic solution are prepared methacrylic ester by catalyst bed.
U.S. patent No.2,466,501 have described and will mix by the propiolactone and the alcohol of activated carbon catalyst, produce acrylate, thus preparation α, β-undersaturated monocarboxylic ester.
Wislicenus, Justus von, Liebig ' s Ann.Chem, 166 (1873), 1-64 and Wislicenus, Justus von, Liebig ' s Ann Chem, 174, (1974), 285-301 has described ethylene lactic acid to acrylic acid conversion.This conversion obtains by forming vinylformic acid with lead or silver salt distillation.
U.S. patent No.2,649,438 described by handle lactone with amine, then through overheated dehydrogenation, form acrylamide by beta-propiolactone.Do not describe in detail for this conversion.
Britain application No.648,886 have described by beta-propiolactone and uncle or secondary amine reaction post-heating and dehydration forms the acrylamide that replaces and prepares undersaturated substituted amide.
U.S. patent No.4,237,067 disclose α, the preparation method of β-undersaturated acid amides and substituted amide.Raw material is the beta-hydroxycarboxylic acids acid amides.Remove step and need have acid or alkali.
U.S. patent No.5,268,507 have described the preparation of the amide derivatives of alcohol acid.
German application No.2,819,735 have described by suitable saturated beta-hydroxy acid amides and the heating of suitable amine, dehydration are then prepared α, β-undersaturated N-replacing acid acid amides.
U.S. patent No.2,548,155 have described by handling beta-propiolactone and form the hydroxy propylene amide derivatives with replacing amine.
Also need a kind of method, this method can by optional derived from renewable resources biological example material α or beta-hydroxycarboxylic acids or α or the beta-hydroxycarboxylic acids polymkeric substance, oligopolymer, lactide or the lactone that form come efficient, gentle with prepare (methyl) vinylformic acid and its derivative for example ester, salt and acid amides simply.Need a kind of simple method, utilize this method can be in the presence of water, under simple, gentle reaction conditions, efficiently and effectively dewater.Wish that further the preparation of ester, acid or acid amides can carry out in same reactor, and, in fact do not have byproduct or a large amount of harmful waste to produce as reaction result.
According to the present invention, α, the derivative of beta-unsaturated acid and they is by will suitable α or beta-hydroxycarboxylic acids heating and dehydration or suitable polymers, oligopolymer, lactide or the lactone of α or beta-hydroxycarboxylic acids chosen wantonly to be hydrolyzed in the presence of catalyzer and to dewater prepare, and described catalyzer can be oxide compound or other the suitable catalysts of Si, Ti or Al.α or beta-hydroxycarboxylic acids or the α that forms by dehydration reaction, beta-unsaturated acid, can use appropriate catalyst for example aluminosilicate carry out esterification.Can reclaim (methyl) vinylformic acid or ester by distillation, if or in gas phase, react, can collect product by concentrating.
The present invention also comprises α, beta-unsaturated acyl amine, α, acid amides and α that β-unsaturated N-replaces, β-unsaturated N, the preparation of N-disubstituded amide, this preparation by with suitable α-or beta-hydroxycarboxylic acids, α-or beta-hydroxycarboxylic acids ester, α-or beta-hydroxycarboxylic acids salt or their polymerization (polyester), oligopolymer, lactide or precursors for lactones thing add the thermosetting amidate with amine, dewater subsequently or simultaneously.When dehydration was finished, (methyl) acrylamide of (methyl) acrylamide or replacement can reclaim by distillation, if or be reflected in the gas phase and carry out, can collect product by concentrating.
Correspondingly,
Preparation α, the method for beta-unsaturated acid comprises
A) provide at least a aqueous solution that comprises in following
α-or beta-hydroxycarboxylic acids or its salt;
The polyester of α or beta-hydroxycarboxylic acids, oligopolymer, lactide or lactone derivatives;
Or
Derived from the α or the beta-hydroxycarboxylic acids of microorganism or vegetable cell, this microorganism or vegetable cell contain or produce the polyester of α or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids, maybe can change other derivative of α or beta-hydroxycarboxylic acids into,
With
B) heat this aqueous solution, choose wantonly in the presence of suitable dehydration catalyst.
Also find α, beta-unsaturated acid can not have under the situation of catalyzer by heating α or beta-hydroxycarboxylic acids or precursor formation.
Being used for the object of the invention precursor is meant
The polyester of α or beta-hydroxycarboxylic acids, oligopolymer, lactide or lactone derivatives;
Or
Derived from the α or the beta-hydroxycarboxylic acids of microorganism or vegetable cell, this microorganism or vegetable cell contain or produce the polyester of α or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids, maybe can change other derivative of α or beta-hydroxycarboxylic acids into.
The present invention includes in addition,
Preparation α, the method for beta-unsaturated carboxylic acid ester comprises
A) provide at least a aqueous solution that comprises in following
α-or beta-hydroxycarboxylic acids or its salt;
The polyester of α or beta-hydroxycarboxylic acids, oligopolymer, lactide or lactone derivatives;
Or
Derived from the α or the beta-hydroxycarboxylic acids of microorganism or vegetable cell, this microorganism or vegetable cell contain or produce the polyester of α or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids, maybe can change other derivative of α or beta-hydroxycarboxylic acids into,
With
B) choose wantonly in the presence of catalyzer and heat aqueous solution, step b) is to carry out in the presence of alcohol.
Catalyzer can be dehydration and/or esterifying catalyst.
The unexpected discovery can only use a kind of catalyzer to dewater and esterification.
Correspondingly,
Preparation α, the method for beta-unsaturated carboxylic acid ester comprises
A) provide at least a aqueous solution that comprises in following
α or beta-hydroxycarboxylic acids or salt;
The polyester of α or beta-hydroxycarboxylic acids, oligopolymer, lactide or lactone derivatives;
Or
Derived from the α or the beta-hydroxycarboxylic acids of microorganism or vegetable cell, this microorganism or vegetable cell contain or produce the polyester of α or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids, maybe can change other derivative of α or beta-hydroxycarboxylic acids into,
With
B) in the presence of catalyzer, heat aqueous solution,
Wherein step b) is to carry out in the presence of alcohol, and catalyzer is an aluminosilicate.
Preferred aluminosilicate is a zeolite.
Correspondingly,
Preparation α, beta-unsaturated acyl amine, α, acid amides or α that β-unsaturated N-replaces, β-unsaturated N, the method for N-disubstituded amide comprises
A) form the aqueous solution comprise at least a compound in following
α or beta-hydroxycarboxylic acids or salt;
α-or the beta-hydroxycarboxylic acids ester;
The polyester of α or beta-hydroxycarboxylic acids, oligopolymer, lactide or lactone derivatives;
Or
Derived from the α or the beta-hydroxycarboxylic acids of microorganism or vegetable cell, this microorganism or vegetable cell contain or produce the polyester of α or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids, maybe can change other derivative of α or beta-hydroxycarboxylic acids into,
With
B) amine or α-or the amine salt of beta-hydroxycarboxylic acids in the presence of, heating aqueous solution a),
Choose wantonly in the presence of amidation and/or dehydration catalyst.
Amine or amine salt are selected from ammonia, primary amine and secondary amine.
Another embodiment of the invention is to prepare α by the polyester of β or alpha-hydroxy carboxylic acid compounds or its lactide, beta-unsaturated acyl amine, α, acid amides or α that β-unsaturated N-replaces, the method for β-unsaturated disubstituded amide.
Correspondingly,
Preparation α, beta-unsaturated acyl amine or α, the method for β-acid amides that unsaturated N-replaces comprises
A) form the aqueous solution that comprises α or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids ester or α or beta-hydroxycarboxylic acids salt,
B) polymerization forms polyester, oligopolymer, or cyclisation formation cyclic lactide,
With
C) in the presence of amine, with formed b) polyester or ring-type lactide heating,
Choose wantonly in the presence of amidation and/or dehydration catalyst.
The aqueous solution that comprises α or beta-hydroxycarboxylic acids or precursor, the zymotechnique that can randomly stem from sugar, or stemming from the zymotechnique that comprises biomass, biomass can be to contain or the polyester that produces α or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids maybe can change the microorganism or the vegetable cell of other precursor of α or beta-hydroxycarboxylic acids into.
The aqueous solution dehydration of beta-hydroxycarboxylic acids can be (methyl) vinylformic acid, or dehydration and esterification simultaneously in the presence of alcohol, both can be in gas phase with their reactor heatings by containing the catalysis weighting material, also can in containing the liquid phase of catalyzer, carry out this reaction.
By the α that the inventive method forms, beta-unsaturated carboxylic acid or ester are the compounds of formula (I)
R wherein
1Be H, C
1-C
8Alkyl,
R
2Be H or C
1-C
4Alkyl and
R
3Be H, methyl or ethyl.
C
1-C
4Alkyl can be side chain or unbranched carbon-based group, for example, and methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl-.
The C that is used for the object of the invention
1-C
8Alkyl can be side chain or unbranched group, for example, and methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, 2-ethyl-butyl, isopentyl, 1-methyl amyl, 1,3-dimethylbutyl, n-hexyl, different heptyl, 2-ethylhexyl, 1-methyl hexyl, the tertiary butyl, and n-pentyl.
Preferably, by the α of this method preparation, beta-unsaturated carboxylic acid is vinylformic acid, methacrylic acid or Ba Dousuan.
Initial α-or beta-hydroxycarboxylic acids or precursor can be α-or beta-hydroxycarboxylic acids, for example 3-hydroxy-propionic acid, lactic acid, 3-hydroxybutyric acid, 3-hydroxy-2-methyl propionic acid or 2-hydroxy-2-methyl propionic acid.
Preferred α-or beta-hydroxycarboxylic acids be α, beta-hydroxycarboxylic acids.Most preferably, beta-hydroxycarboxylic acids is the 3-hydroxy-propionic acid, 3-hydroxy-2-methyl propionic acid, or 3-hydroxybutyric acid.
Because α or beta-hydroxycarboxylic acids are dual functional, it can form polyester, oligopolymer, lactone and lactide.The precursor that therefore will be used for the object of the invention is defined as polyester, oligopolymer, lactide or the lactone derivatives of α or beta-hydroxycarboxylic acids.Perhaps, also precursor is defined as α or beta-hydroxycarboxylic acids derived from microorganism or vegetable cell, microorganism or vegetable cell contain or the polyester that produces α or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids maybe can change other precursor derivative of α or beta-hydroxycarboxylic acids into.
These precursors can be derived from the zymotechnique of sugar, or comprises the zymotechnique of biomass.
α-or beta-hydroxycarboxylic acids source or precursor preferentially be aqueous solution or the fermentation broth that contains hydroxycarboxylic acid.
The concentration of solution can be low to moderate high density from the utmost point of hydroxycarboxylic acid or precursor and change.For example, concentration from based on total solution weight 10 to 90% between change.Preferably, can be based on about concentration of 20 to 85% of total solution weight as the raw material among the present invention.
The aqueous solution that is used for the object of the invention is meant that big water gaging is present in the raw material.For example, greater than trace or greater than since the quantity of the water yield that obtains of dehydration reaction be present in the raw material.
Water in aqueous solution, preferably it exists quantity greater than 1%, and more preferably its quantity greater than 3%.
The aqueous solution of beta-hydroxycarboxylic acids, the solution in the gas phase can be dewatered by the optional reactor heating that contains the catalysis weighting material is α, beta-unsaturated carboxylic acid.
The catalysis weighting material can play dehydration catalyst, and can comprise metal oxide and/or aluminosilicate, preferable alloy oxide compound and/or zeolite.
Preferably, metal oxide is γ-AI
2O
3, SiO
2, TiO
2
Dehydration catalyst is the γ-AI with special high surface area
2O
3Or the silica of high surface area, wherein silica is SiO basically
2The SiO basically that is used for the object of the invention
2Be meant for example H of strong acid of no use
3PO
4, CuSO
4, NaH
2PO
4Or H
2SO
4The silica of handling.Silica can not serve as the carrier of metal catalyst, but it is SiO basically
2
Most preferred dehydration catalyst is the γ-AI of high surface area
2O
3Or zeolite.
The high surface area that is used for the object of the invention is meant about 100m
2/ g or above surface.Preferably, surface-area is at least about 125m
2/ g, particularly about at least 135m
2/ g.
α-or the dehydration of beta-hydroxycarboxylic acids or precursor also can carry out under the situation of dehydration catalyst not having.For example, reaction can be in gas phase, inert filler for example glass, pottery, resin, porcelain, plastics, metal or brick powder weighting material in the presence of move, and form α, beta-unsaturated carboxylic acid with good productive rate and purity.Especially beat all is because raw material is aqueous.
The unexpected discovery, aluminosilicate can play dehydration and esterifying catalyst.In other words, by using aluminosilicate, reaction raw materials can directly change α, beta-unsaturated carboxylic acid ester into.
Esterification or built-up type dehydration/esterifying catalyst are aluminosilicates.It can synthesize or natural existence.For example aluminosilicate can be selected from naturally occurring clay and feldspar, kaolinite for example, polynite, attapulgite clay (atapulgite), illite, wilkinite, halloysite and acidic white earth.Perhaps, aluminosilicate can be synthetic or natural zeolite, and it is a crystal type aluminosilicate structure, has to run through solid aperture (from the diameter of 1-20 dust).The example of natural zeolite is abalcite, chabazite, heulandite, naturolite, stilbite and thomosonite.
Preferred esterification or built-up type dehydration/esterifying catalyst are to have the aluminosilicate zeolites that diameter is a 1-20 dust pore size.Most preferably, zeolite is medium or large pore zeolite.
For example, ZSM-12 is a medium hole zeolite, has the aperture of about 5.6 * 6.0 dusts.Think that also ZSM-5 is a medium hole zeolite, has the aperture of about 5.1 * 5.5 to 5.3 * 5.6 dusts.By contrast, mordenite has shown the bigger aperture of 6.5 * 7.0 dusts.The particularly preferred catalyzer that is used for esterification or dehydration/esterification combination is the ZSM-12 zeolite catalyst.
Molecular sieve is the subclass of zeolite, and they also are the crystal type aluminosilicates, but when dewatering, its crystalline structure does not almost change.The aperture is in the scope of about 5 to 10 dusts.Therefore, the term " zeolite " that is used for the object of the invention is meant and comprises molecular sieve.
Zeolite can be variant aspect acid.Be used for preferred zeolite of the present invention and only have appropriateness acidity, for example when zeolite is suspended in the water, show pH value from 4 to 7.
Preferably, zeolite is medium or large pore zeolite.Most preferably, esterifying catalyst is the ZSM-12 zeolite.
The preparation of top acid and ester can be carried out in liquid phase or gas phase.Liquid phase or vapour-phase reaction can be carried out with batch, batch feed (fed-batch) or continuous mode.Preferably, carry out in dehydration and the gas phase of esterification on heatable catalyst.
The dehydration of α or beta-hydroxycarboxylic acids and esterification can be in same reactor order or carry out simultaneously.For example, by introducing dehydration and esterifying catalyst as heating weighting material or having the inert filler of esterifying catalyst bed by introducing, two reactions can be carried out in same reactor.With inert material and/or the catalyzer of raw material by heating.Perhaps, reaction can be carried out with the order of dewater esterification subsequently or esterification subsequent dewatering.
Be elected to be dehydration and/or catalyst for esterification, under the condition as mild as a dove and in the presence of water, make α, beta-unsaturated acid or ester form with high yield, and byproduct seldom.
Dehydration and/or esterification are preferably carried out in gas phase.Preferred reaction is carried out in a continuous manner equally, especially.
α, the beta-unsaturated carboxylic acid ester is C
1-C
8Alkyl (methyl) acrylate or C
1-C
8The alkyl crotonate.
The formed ester of the present invention can be for example methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, 2-ethyl-butyl, isopentyl, 1-methyl amyl, 1,3-dimethylbutyl, n-hexyl, different heptyl, 1-methyl hexyl, the tertiary butyl, 2-ethylhexyl and n-pentyl (methyl) acrylate or crotonate.
For example, C
1-C
8Alkyl (methyl) acrylate can be selected from methyl (methyl) acrylate, ethyl (methyl) acrylate, n-propyl (methyl) acrylate, sec.-propyl (methyl) acrylate, normal-butyl (methyl) acrylate, isobutyl-(methyl) acrylate, sec-butyl (methyl) acrylate, 2-ethyl-butyl (methyl) acrylate, isopentyl (methyl) acrylate, 1-methyl amyl (methyl) acrylate, 1,3-dimethylbutyl (methyl) acrylate, n-hexyl (methyl) acrylate, different heptyl (methyl) acrylate, 1-methyl hexyl (methyl) acrylate, the tertiary butyl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate and n-pentyl (methyl) acrylate.
Most preferred (methyl) acrylate is methyl (methyl) acrylate, ethyl (methyl) acrylate, and butyl (methyl) acrylate.
C
1-C
8The alkyl crotonate can be selected from the methylcrotonic acid ester, ethyl crotonic acid ester, n-propyl crotonate, the sec.-propyl crotonate, normal-butyl crotonate, isobutyl-crotonate, the sec-butyl crotonate, 2-ethyl-butyl crotonate, isopentyl crotonate, 1-methyl amyl crotonate, 1,3-dimethylbutyl crotonate, the n-hexyl crotonate, different heptyl crotonate, 1-methyl hexyl crotonate, tertiary butyl crotonate, 2-ethylhexyl crotonate and n-pentyl crotonate.
Most preferred crotonate is the methylcrotonic acid ester, ethyl crotonic acid ester and butyl crotonate.
Alcohol directly can be joined α-or the beta-hydroxycarboxylic acids aqueous solution in, then simultaneously the dehydration and esterification.After the dehydrating step, can also add alcohol, make itself and α then, the beta-unsaturated carboxylic acid reaction forms ester.
Can also with pure and mild α-or beta-hydroxycarboxylic acids from contain α-or the aqueous solution of beta-hydroxycarboxylic acids be input in the Gas-phase reactor respectively.
The quantity of reactant is not crucial, and rangeability can be very big.Usually, preferred excessive alcohol, and when mol ratio be about 5 moles alcohol than about 1 mole α-or during beta-hydroxycarboxylic acids, can obtain best productive rate, but can use from 10 mol of alcohol than 1 or even higher ratio, have good result.
The dehydrating step that forms unsaturated acid can be in gas phase or liquid phase, about 100 ℃ to about 400 ℃, preferably approximately 100 to about 350 ℃, most preferably carry out under about 175 to about 325 ℃.In addition, reaction can be carried out in postcritical reaction medium.Vapour-phase reaction needs higher temperature than liquid phase reaction usually.
Esterif iotacation step is carried out under the temperature lower than dehydrating step usually.This temperature can change, from about 100 ℃ to about 300 ℃, and 100 ℃ to about 250 ℃ of preferably approximatelies, most preferably about 125 ℃ to about 225 ℃.
For esterification of carrying out with a kind of catalyzer and dehydration, for example use zeolite, be reflected in the gas phase and carry out, temperature can change, from about 100 ℃ to about 300 ℃, 100 ℃ to about 250 ℃ of preferably approximatelies, most preferably about 125 ℃ to about 225 ℃.
The transformation time of acid or ester can change.Reaction in the gas phase is faster than the reaction of carrying out in the liquid phase usually, and in seconds takes place, and the reaction in liquid phase can need about 1 to about 6 hours.Therefore, transform the time of needs usually from extremely about 6 hours about several seconds.
When reaction was carried out in gas phase by reactant is exposed to heating surface, dehydration catalyst and/or esterifying catalyst can be the surfaces of heating, or it can be for example pottery or glass of inert filler material, resin, porcelain, plastics, metal or brick powder.
The quantity of dehydration and/or esterifying catalyst can alter a great deal, and is not crucial.
Optionally require is during heat-processed, and existence can prevent α, the material of beta-unsaturated acid or polyisocyanate polyaddition.The suitable substance that is used for this purpose comprises copper, mantoquita, Resorcinol, p methoxy phenol and other stopper well known to those skilled in the art.
By with α-or the aqueous solution of beta-hydroxycarboxylic acids and amine salt thermal reactor by containing inertia and/or catalysis weighting material or in gas phase by reacting in the liquid phase of catalyzer having or do not have, can be acrylamide or the N that acrylamide, N-replace with their amidations simultaneously and dehydration, the dibasic acrylamide of N-.Liquid phase or vapour-phase reaction can be carried out with batch, batch feed or continuous mode.
Be meant all reactants that participate in initial action in batches; Batch feed is meant that Substrate during reaction is input in the reactor, but outwards flowing of product do not taken place; Be meant continuously Substrate is sent in the reactor continuously, and during reaction from reactor, extract product continuously.
α-or the liquid-phase reaction solution of beta-hydroxycarboxylic acids and amine can also carry out with the clearly two-stage process of amidation subsequent dewatering.In this case, dewater with distillation after the amidation.
By the α that the inventive method forms, β-undersaturated Carboxylamide or α, β-undersaturated replacement or disubstituded amide are the compounds of formula (I)
R wherein
1And R
2Be H, C independently
1-C
8Alkyl, cycloalkyl, or R
1And R
2Can form ring, for example morpholine.
R
3Be H or C
1-C
4Alkyl.
R
4Be H, methyl or ethyl.
C
1-C
4Alkyl can be side chain or unbranched carbon-based group, for example, and methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl-.
The C that is used for the object of the invention
1-C
8Alkyl can be side chain or unbranched group, for example, and methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, 2-ethyl-butyl, isopentyl, 1-methyl amyl, 1, the 3-dimethylbutyl, n-hexyl, different heptyl, 1-methyl hexyl, the tertiary butyl, 2-ethylhexyl and n-pentyl.
Initial α-or beta-hydroxycarboxylic acids for example can be, the 3-hydroxypropionic acid, lactic acid, the 3-hydroxybutyric acid, 3-hydroxy-2-methyl propionic acid, 2-hydroxy-2-methyl propionic acid, acid C
1-C
4Ester or salt.
α-or the beta-hydroxycarboxylic acids source can also be derived from aqueous solution that contains hydroxycarboxylic acid or precursor or fermentation broth, and during dehydration reaction, can be hydrolyzed to monomer component.
In addition, α-or beta-hydroxycarboxylic acids, α or beta-hydroxycarboxylic acids C
1-C
4Ester or α-or beta-hydroxycarboxylic acids salt can amidation and the dehydration before carry out polymerization, oligomeric or cyclisation.For example, lactic acid can polymerization forms poly(lactic acid), or dimerization is its corresponding ring-type lactide, and 3,6-dimethyl-1,4-diox-2,5-diketone.
There is the various α of being used to form-or the polyester of beta-hydroxycarboxylic acids or simple method of dimerization ring-type lactide, for example use acid treatment.The polycondensation of lactic acid can contain various catalyzer for example in the solution of methylsulfonic acid, tin compound, CaO or BaO, metal alcoholate or enzyme or finish in melt.
R
1And R
2Can be H, C independently
1-C
8Alkyl, cycloalkyl, or R
1And R
2Can form ring, for example morpholine.
R
3And R
4Can be H, C independently
1-C
4Alkyl.
N=0 to 5000.
Be used for α-or the amidated amine of beta-hydroxycarboxylic acids be ammonia, uncle or secondary amine.Amine can be further by for example alcohol replacement of other functional group, for example thanomin and diethanolamine.
Preferred amine of the present invention can comprise ammonia, methylamine, and dimethylamine, ethamine, diethylamine, n-propyl amine, Isopropylamine, n-Butyl Amine 99, sec-butylamine, TERTIARY BUTYL AMINE, the second month in a season-n-pentyl amine, tert.-amylamine and cyclammonium be morpholine for example.
Can use pure or be dissolved in amine in the inert solvent.Preferably, solvent is water and/or lower alkyl alcohol.The mol ratio of amine and acid or ester units can be about 10: 0.8.Preferably, the mol ratio of amine and acid or ester units is about 1: 1 to 2: 1.
Preferred excessive amine, because it helps amidation, but it is too expensive too much to cause amine to reclaim.The optional catalyzer that uses, but that it can quicken the releasing of the depolymerization of polyester or lactide is oligomeric.
Lower alkyl alcohol can be for example methyl alcohol, ethanol, propyl alcohol, butanols, the trimethyl carbinol or Virahol.
Amidation step can or be equal to or less than under the normal pressure at pressure carries out.Reaction can be carried out in the presence of water or under anhydrous condition.Preferred α or beta-hydroxycarboxylic acids, α-or beta-hydroxycarboxylic acids salt or α-or the aqueous solution of beta-hydroxycarboxylic acids ester, polyester or lactide.Reaction can be carried out in steam or liquid phase.
Amine directly can be joined α or beta-hydroxycarboxylic acids, α-or beta-hydroxycarboxylic acids ester or α-or beta-hydroxycarboxylic acids salt, polyester or lactide solution in.Perhaps, can adopt α-or beta-hydroxycarboxylic acids or α-or the neutral amine salt of beta-hydroxycarboxylic acids, and directly be added to the water, then carry out amidation and dehydration.Equally can with α or beta-hydroxycarboxylic acids, α-or beta-hydroxycarboxylic acids ester, α-or beta-hydroxycarboxylic acids salt, polyester or lactide solution join in the amine aqueous solution.
Amine and α or beta-hydroxycarboxylic acids can also be input into respectively in gas phase or the Liquid-phase reactor.
Amidation and dehydrating step are carried out under from 100 ℃ to 400 ℃ in temperature.Vapour-phase reaction needs higher temperature than liquid phase reaction usually.
Being used for the time that acid, salt, ester, lactide or polyester be converted into acid amides can change, and this depends on employed amine and acid derivative.Reaction in the gas phase is faster than the reaction of carrying out in the liquid phase usually, and in seconds takes place, and the reaction in liquid phase can need about 1 to about 6 hours.Therefore, transform the time of needs usually from extremely about 6 hours several seconds.
In case amidation is finished, oxyamide dehydration is for example (methyl) acrylamide, can be in steam or liquid phase, having or do not having and carrying out under the condition of catalyzer.
Amidation can take place before dehydration or after the dehydration.Perhaps, amidation and dehydration can take place simultaneously.
Catalyzer can be selected from multiple dehydration catalyst.Preferred catalyzer is an acidic solid catalyst, its in the preparation of acrylic acid or the like be known, have a very good optionally dewatering agent.Yet the present invention does not need their purposes.
Randomly, dehydration catalyst can be joined in the aqueous solution, be heated, form α, beta-unsaturated acyl amine to increase the dehydration of acid amides.Acidity, alkalescence or neutral substance can be used for the catalytic dehydration flow process in water medium.When excessive use amine, itself can the catalytic dehydration flow process.Perhaps, when reaction was carried out in gas phase by reactant being exposed to heating surface, dehydration catalyst can be a heating surface.
During solution reaction, can fill activated carbon in the distillation tower or promote the dehydration catalyst of dehydration equally.
Optionally require is during heat-processed, and existence can prevent α, beta-unsaturated acyl amine polymeric material.The suitable substance that is used for this purpose comprises copper, mantoquita, Resorcinol, p methoxy phenol and other stopper well known to those skilled in the art.Preferably, existence prevents the polymeric material.
Determine the percentage ratio productive rate of acid amides by high pressure liquid chromatography, use
4.6 * 150mm post, 70: 30 acetonitrile/water elutriants, flow velocity 1ml/min, detector is at the wavelength place of 220 nanometers.
The productive rate of vinylformic acid, acrylate or acrylamide and substituted amide can for example GC or HPLC determine by any suitable analytical method.The percentage ratio productive rate of vinylformic acid and ester is determined by vapor-phase chromatography, uses PE-FFAP, 30m * 0.538 PERKIN ELMER post, N2 carrier gas, the FID temperature of 230 ℃ injector temperature and 250 ℃.
(3-HP) forms vinylformic acid by the 3-hydroxy-propionic acid.
Reaction in embodiment 1-10 is all carried out in gas phase.
Embodiment 1
Will be at the 20%3-hydroxy-propionic acid solution in the water that contains the 100ppm p methoxy phenol, be injected into the top of the vertical silica gel reaction tubes that contains 500mm ceramic packing bed with the speed of 15 grams per hour, there is the nitrogen gas stream of 60ml/min simultaneously.Utilize the concentric tube type stove that this pipe is heated to 300 ℃.The waste gas of pipe bottom is concentrated and collection analysis.The GC of liquid analyzes and shows that 83% is converted into vinylformic acid.
Embodiment 2
Repeat the experiment of embodiment 1, except bottom 25mm bed by high surface area-alumina filled thing forms with temperature of reactor be 250 ℃.The GC of collected liquid analyzes and shows that 97% is converted into vinylformic acid, does not have unconverted 3-hydroxy-propionic acid.
Embodiment 3
Repeat embodiment 2, except bottom 250mm bed is made up of the high surface area silica gel filler.The analysis of product liquid shows that 97% is converted into vinylformic acid, and does not have unconverted 3-hydroxy-propionic acid basically.
Embodiment 4,5 and 6
Repeat embodiment 2, except the injection solution of 3-hydroxy-propionic acid in water that uses 40,60 and 80% weight successively.With regard to all situations, shown acrylic acid conversion is 97-98%.
Embodiment 7
Repeat the experiment of embodiment 1, except bed by low surface area TiO
2Weighting material is formed and temperature of reactor is outside 250 ℃.The GC of the liquid of collecting analyzes and shows that 93.6% is converted into vinylformic acid.
Embodiment 8
Repeat the experiment of embodiment 1, except bed by low surface area SiO
2Weighting material is formed and temperature of reactor is outside 250 ℃.The GC of the liquid of collecting analyzes and shows that 80.6% is converted into vinylformic acid.
Embodiment 9
Repeat the experiment of embodiment 1, except bed by the Alpha-alumina weighting material forms with temperature of reactor be 250 ℃.The GC of the liquid of collecting analyzes and shows that 83.6% is converted into vinylformic acid.
Embodiment 10
With pretreated γ-AI
2O
3Fill quartz column (φ 12mm, embedding has the pipe of the φ 3mm of thermal sensing element), form the catalyst bed of 10 cm lengths.Should be heated to about 260 ℃ by effective tube furnace, and the nitrogen of 7.5ml/min was passed through this post." perfusion " pump that deionized water is used in the catalyst bed top is introduced.In case the internal temperature of catalyst bed is constant in about 250 ℃, the aqueous solution (19.9%w/w, stable with 0.1% p methoxy phenol) of 3-HP is introduced with the speed of 7.5ml/hr.Gaseous reaction mixture is collected in the deionized water (containing p methoxy phenol as stablizer).After the dosage of the 3-HP of 33.7g solution, end experiment, determine that by GC yield is 92.7%AA.
Table I
Dehydration reaction in gas phase
| Embodiment | Catalyzer | Fill the degree of depth (mm) | Temperature (℃) | 3-HP rate of injection (g/hr) | % vinylformic acid (GC area normalization) |
| 1 | There is not the inactive ceramic weighting material | 250 | 300 | 15 | 83.1 |
| 2 | Gama-alumina 1 | 25 | 250 | 15 | 97.3 |
| 3 | High surface area SiO 2 2 | 250 | 250 | 15 | 97.0 |
| 4 | Gama-alumina | 25 | 250 | 15 (the 40% 3-HP aqueous solution) | 97.5 |
| 5 | Gama-alumina | 25 | 250 | 15 (the 60% 3-HP aqueous solution) | 97.9 |
| 6 | Gama-alumina | 25 | 250 | 15 (the 80% 3-HP aqueous solution) | 98.2 |
| 7 | TiO 2 3 | 250 | 250 | 15 | 93.6 |
| 8 | Low surface area SiO 2 4 | 250 | 250 | 15 | 80.6 |
| 9 | Alpha-alumina 5 | 250 | 250 | 15 | 83.6 |
| 10 | Gama-alumina 6 | 100 | 250 | 7.5ml/hr | 92.7 |
1. buy gama-alumina, 1/8 " piller, 255m from Alfa Aesar
2The surface-area of/g, 70-micron aperture.
2. buy high surface area SiO from Alfa Aesar
2, 1/8 " piller has 144m
2Surface-area, handle with 0.2%NaO.
3. buy low surface area TiO from AlfaAesar
2, 1/8 " piller, surface-area are 37m
2/ g, octahedrite, intermediate value pore diameter 270 dusts.
4. buy low surface area SiO from Alfa Aesar
2, 1/8 " piller, 0.11m
2The surface-area of/g.
5. buy Alpha-alumina, 3/16 " piller, 0.82m from Alfa Aesar
2The surface-area of/g, 1,10 and 250-micron aperture.
6. with γ-Al
2O
3(the T-1894 type, the 3mm piller derives from Sud-Chemie, Munich) 500 ℃ of calcination 5 hours.
In gas phase, form acrylate
Embodiment 11-16
Vinylformic acid (AA) is to the esterification of methyl acrylate (MA)
The popular response condition
Quartz column (φ 12mm embeds the φ 3mm pipe that has thermal sensing element) is filled with various catalyzer, form the catalyst bed of 10 cm lengths.Should be heated to 150 ℃ to about 200 ℃ by effective tube furnace, the nitrogen that makes 2.5ml/min is by this post (embodiment 12 is with the 5ml/min operation)." perfusion " pump that moisture MeOH (about 30% water) is used in the catalyst bed top is introduced.In case the internal temperature of catalyst bed is constant in about 150 ℃ to 200 ℃, add moisture AA solution (15g AA, 35gMeOH, 17g deionized water) to the about speed of 5ml/hr with about 2ml/hr.Gaseous reaction mixture is collected in the deionized water,, analyzes the composition of measuring product by GC along with the past of time.
Table 2
| Embodiment | Catalyst type | Temperature (℃) | Working time (h) | AA-adds speed (ml/h) | N2-gas velocity (ml/min) | Transform % (GC area %) |
| 11 | Fullcat 1(polynite) | 200 | 2 | 5 | 2.5 | 84.3 |
| 12 | 2NAFION SAC- 25 | 180 | 3.5 | 5 | 5 | 88.9 |
| 13 | 3The EM-1500 zeolite | 150 | 2 | 2 | 2.5 | 98 |
| 14 | The EM-1500 zeolite | 170 | 1 | 3 | 2.5 | 95.9 |
| 15 | The EM-1500 zeolite | 150 | 7 | 2 | 2.5 | 96.7 |
| 16 | 4The ACC clay that has all (wilkinite, polynites) | 180 | 2 | 2 | 2.5 | 8.4 |
| 17 | 5ATC granule (zeolite) | 180 | 3 | 2 | 2.5 | 14.4 |
| 18 | 2Nafion NR 50 | 160 | 2 | 2 | 2.5 | 86.1 |
1. Fuller's earth is obtained from Fluka.
2.NAFION 50 two of SAC-25 and NR are the perfluorosulfonic acid polymkeric substance.SAC-25 is commercial can't to be obtained, but NR 50 is obtained from Fluka.
3. the synthetic aluminium silicate zeolite is provided by Exxon Mobile, has the pore size of 5.6 * 6.0 dusts.The pH value is 4.78, in 10% aqeous suspension.
4. naturally occurring calcium-base bentonite is obtained from American Colloid Company.Aqueous pure aluminium silicate mainly comprises the clay mineral polynite.Surface-area is 30m
2/ g, the pH value is 8.0 to 10.0.
5. synthetic titanosilicate is provided by Engelhard.
6. has SO
3The storng-acid cation exchange resin of functional group is prepared by DuPont.
The dehydration of 3-hydroxy-propionic acid (3-HP) and esterification subsequently are methyl acrylate (MA)
Embodiment 19-20
Quartz column (φ 12mm embeds the φ 3mm pipe that has thermal sensing element) is filled with molecular sieve spherolite (EM-1500, pH value 4.78), form the catalyst bed of 10 cm lengths.Should be heated to about 150 ℃ by effective tube furnace, and the nitrogen of 2.5ml/min was passed through this post." perfusion " pump that moisture MeOH (about 30% water) is used in the catalyst bed top is introduced.In case the internal temperature of catalyst bed is constant in about 150 ℃, 3-HP solution (75.2g 3-HP, 25.4% aqueous solution, 35g MeOH, 5mg p methoxy phenol) is introduced with the speed of 2ml/hr.Gaseous reaction mixture is collected in the deionized water,, analyzes the composition of measuring product by GC along with the past of time.
Table 3
| Embodiment | Catalyst type | Temperature (℃) | Working time (h) | 3-HP adds speed (ml/h) | N2-gas velocity (ml/min) | Transform % (GC area %) |
| 19 | EM-1500 | 150 | 1 | 2 | 2.5 | 97.4 |
| 20 | EM-1500 | 150 | 2.5 | 2 | 2.5 | 98.9 |
Form the acid amides of acid amides and replacement by 3-hydroxy-propionic acid (3-HP)
Embodiment 21
30% weightaqueous solution of 5 gram 3-hydroxy-propionic acids (3-HP) is neutralized with 1.5g anhydrous dimethyl amine.With solution in high pressure pipe, 180 ℃ the heating 5 hours.Distillating liquid product under normal pressure removes and anhydrates.Continue distillation in a vacuum, obtain N,N-DMAA and acrylic acid 1: 1 mixture (0.7g).This expression is based on the 22-23% yield of the N,N-DMAA of 3-HP.
Embodiment 22
88% aqueous solution of 3g lactic acid is neutralized with 2.6g anhydrous dimethyl amine.With solution in high pressure pipe, 160 ℃ the heating 5 hours.Distillating liquid product under normal pressure removes and anhydrates.Continue distillation in a vacuum, obtain 1.7g 2-hydroxy-n, N-dimethyl propylene acid amides (productive rate 50%).
Embodiment 23
With lactide (3,6-dimethyl-1,4-diox-2,5-diketone; 5 grams) join in the round-bottomed flask, and in oil bath, be heated to 130 ℃.The gasiform dimethylamine with the lactide of slow, stable speed bubbling by melting, was carried out 5 hours, analyze the demonstration amidate action up to 1H NMR and finish.Distill the mixture that obtains in a vacuum, obtain 6.7 gram 2-hydroxy-ns, N-dimethyl propylene acid amides (productive rate 82%).
Embodiment 24
With in nitrogen atmosphere, pack into the top of the tubular reactor that contains calcium phosphate of the 5g N,N-dimethylacetamide that comes from embodiment 23, and 350 ℃ of heating.With the gaseous state ejecta condensation that obtains, obtain 2 gram N,N-DMAAs.
Embodiment 25
30% 3-HP aqueous solution is neutralized with Isopropylamine, and the solution that obtains is injected the top of Gas-phase reactor (VPR).The bed of 250mm pottery weighting material is contained at the top of vertical silica gel reaction tubes, contains the bed of the high surface area silica gel filler of 250mm in the bottom.The nitrogen gas stream that has 60ml/min simultaneously.By the concentric tube type stove pipe is heated to 250 ℃.The gaseous state ejecta that comes from the pipe bottom is concentrated, and collection analysis.The GC of liquid analyzes and shows, analyzes 24.1% N-N-isopropylacrylamide yield and 36.4% vinylformic acid yield based on GC.
Embodiment 26
According to embodiment 25 similar modes, will be input among the VPR with isobutylamine neutral 3-HP solution, and concentrate, collect product and analyze.Show that N-isobutyl-acrylamide and acrylic acid transformation efficiency are respectively 17.6% and 34.2%.
Embodiment 27
Mode according to being similar to embodiment 25 neutralizes 3-HP with morpholine, and is input among the VPR.Show that acryloyl morpholine and acrylic acid transformation efficiency are respectively 22.2% and 32.2%.
Embodiment 28
Mode according to being similar to embodiment 25 neutralizes 3-HP with dimethylamine, and is input among the VPR.The transformation efficiency that shows is 50%N, N-DMAA and 18.2% vinylformic acid.
Claims (14)
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| US60/649,461 | 2005-02-02 |
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| FR2931822B1 (en) * | 2008-05-30 | 2012-11-02 | Arkema France | BIOMASS - DERIVED METHYL METHACRYLATE, PROCESS FOR PRODUCING THE SAME, USES AND CORRESPONDING POLYMERS. |
| JP6173314B2 (en) * | 2012-06-27 | 2017-08-02 | 株式会社日本触媒 | (Meth) acrylic acid production method and hydrophilic resin production method |
| DE102013209821A1 (en) * | 2013-05-27 | 2014-11-27 | Evonik Industries Ag | Process for the dehydration of alpha-substituted carboxylic acids |
| DE102014213016A1 (en) * | 2014-07-04 | 2016-01-07 | Evonik Röhm Gmbh | Dehydration of alpha-substituted carboxylic acids in the presence of water at high pressures |
| CN115925652A (en) * | 2022-12-08 | 2023-04-07 | 南通沃兰化工有限公司 | A kind of preparation method of acryloylmorpholine |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB751750A (en) * | 1952-11-06 | 1956-07-04 | Minnesota Mining & Mfg | Process of producing acrylic acid and its esters and nitrile |
| CN1109865A (en) * | 1993-12-02 | 1995-10-11 | 罗姆和哈斯公司 | High yield process for the production of methacylic acid esters |
| CN1121505A (en) * | 1994-06-06 | 1996-05-01 | 三井东压化学株式会社 | A new method for the continuous production of methyl methacrylate |
| CN1162589A (en) * | 1996-01-31 | 1997-10-22 | 弗·哈夫曼-拉罗切有限公司 | α, the preparation method of β-unsaturated organic carboxylic acid |
| WO2003066815A2 (en) * | 2002-02-05 | 2003-08-14 | E.I. Du Pont De Nemours And Company | Method for producing 2-hydroxyisobutyric acid and methacrylic acid from acetone cyanohydrin |
-
2005
- 2005-03-23 CN CN200580010291A patent/CN100584822C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB751750A (en) * | 1952-11-06 | 1956-07-04 | Minnesota Mining & Mfg | Process of producing acrylic acid and its esters and nitrile |
| CN1109865A (en) * | 1993-12-02 | 1995-10-11 | 罗姆和哈斯公司 | High yield process for the production of methacylic acid esters |
| CN1121505A (en) * | 1994-06-06 | 1996-05-01 | 三井东压化学株式会社 | A new method for the continuous production of methyl methacrylate |
| CN1162589A (en) * | 1996-01-31 | 1997-10-22 | 弗·哈夫曼-拉罗切有限公司 | α, the preparation method of β-unsaturated organic carboxylic acid |
| WO2003066815A2 (en) * | 2002-02-05 | 2003-08-14 | E.I. Du Pont De Nemours And Company | Method for producing 2-hydroxyisobutyric acid and methacrylic acid from acetone cyanohydrin |
Non-Patent Citations (2)
| Title |
|---|
| 丙烯酸及其酯的合成方法及催化体系. 杨先贵等.天然气化工，第23卷第4期. 1998 |
| 丙烯酸及其酯的合成方法及催化体系. 杨先贵等.天然气化工，第23卷第4期. 1998 * |
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