JPH05503948A - Azeotropically assisted transvinylation technology - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Azeotropically assisted transvinylation technology 1.1 Mamedateokae The present invention provides a second Brønsted acid of an alkenyl derivative of a first Brønsted acid. Alkenyl derivatives of Brønsted acids are produced by transvinylation reaction with acids. In particular, it relates to methods for producing the desired transvinylated alkenyl-producing derivatives. by azeotropic distillation for economical and efficient separation from lance-vinylation reaction mixtures. assisted transvinylation.

2-L11 Kodanjo I Transvinylation or vinyl exchange techniques are well known.

The reaction is as follows: a vinyl-containing compound (R' CH=CH,) and activated water This can be explained by the reaction with an element-containing compound (RX): catalyst RX + R’CHIICHx −→RCH”C) It + R”X (in the formula, R is carboxy, aroxy, alkoxy, etc., and X is hydrogen, hydroxyl, alkyl, aryl, etc., and R' is carboxy, amido, alkyl, substituted alkyl, aryl or substituted aryl Adelman, Jour al Organic Chemistry, 14. pp, 1057-107 7. In 1949, on page 1057, transvinylation was defined as “typical transesterification”. It was called the ``vinyl exchange reaction'' to distinguish it from the conversion and ester acid exchange reactions.Adel man, for example, very mild reaction conditions, low yields of by-products and acetylene Monomers with higher purity and activity compared to monomers produced by reacting with Regarding the preparation of vinyl monomers by transvinylation, including relatively high yields of We focused on some of the advantages of

Adelman also found that vinyl esters of dibasic acids are Vinegar catalyzed with mercury salts, noting that it is much easier to produce by exchanging The reaction of vinyl acid is not limited to carboxylic acids and can be used with other compounds containing active hydrogen (acetate). This was shown to occur with acetic acid esters, glycolic acid esters, etc.).

Other researchers have demonstrated the versatility of transvinylation reactions using a variety of different catalysts. Brønsted acids and Brønsted acid derivatives. The applicability of the method was demonstrated. For example, McKeon et al., Tetrahedron, 28゜pp, 227-232 f1972) uses a palladium catalyst to produce vinyl The vinyl exchange reaction between a ether and an alcohol is shown. Other sources include salt reported the transvinylation reaction between vinyl chloride and carboxylic acid.

The literature indicates that the preferred catalysts for transvinylation reactions are based on mercury and palladium. This suggests that it was a compound. However, pt, (II) and Rh(III ) catalyzes this reaction A, 5abel, J, Sm1dt, R.

Jira and H. Prigge, Chem. Ber, 102. pp, 2939-2950 (reported by 19691. Also, August 26, 1973) Young's U.S. Patent No. 3,755,387 apor Phase Transvinylation Process”) is the supported Hg, Pd, Pt, Ir, Rh in the vapor phase transvinylation process. , claims the use of Ru or Os salt catalysts. The experimental part consisted of palladium alone or carbon alone, copper on carbon, iron on carbon, palladium/copper on carbon, silica Discloses the use of palladium/copper/iron, mercury acetate on carbon, and mercury chloride on carbon ing. Hg and Pd are cited as preferred metals in column 1, line 67. ing.

More recently, it was filed on June 30, 1988 and assigned to the assignee of the present application. As disclosed in U.S. Patent Application No. 213,697, ruthenium compositions are Useful transvinyl acids for many Brønsted acids and Brønsted acid derivatives. was discovered to be a catalyst. The invention disclosed therein is based on the first For the transvinylation of the vinyl derivative of the compound acid with a second Brønsted acid. (This step involves transvinylation in the presence of a ruthenium compound. a vinyl derivative of a first Brønsted acid and a second Brønsted acid at a temperature at which a second blend, which is the product of transvinylation; (including recovering the vinyl derivative of Stead acid) for the transvinylation process. The advantageous use of ruthenium-containing compounds as catalysts is in the transvinylation process. This overcomes several deficiencies observed with other catalysts used in

Various methods provide a vinyl derivative of the desired second Brønsted acid (vinyl-forming derivative). other compounds in the transvinylation reaction mixture (initiating reactant, first blend) (including the conjugate acid of the Stead acid vinyl derivative and other by-products produced by this reaction) It was used to separate from For example, distillation, fractional distillation, vacuum distillation and rotary evaporation. used. For example, in U.S. Pat. No. 3,188,319, vacuum distillation Examples 1-3), fractional distillation (Example 4.7) and distillation (Example 13) Various distillation techniques for conductor recovery are described. British Patent No. 1゜486.4 No. 43 describes a method for producing high-boiling vinyl esters, the separation of which This is facilitated by fractional distillation as the reaction progresses. Solvent extraction techniques also was used for the separation and recovery of derivatives.

Vinyl-forming derivatives, especially vinyl esters of carboxylic acids, are used as starting reactants and reaction agents. Significant obstacles to the separation process from by-products have been known for several years. 1967 In the early years, such problems were addressed by Bearden, U.S. Pat. No. 3.337, No. 611 (see column 1, lines 55-70). This °611 In patents, reactants of transvinylation reactions of vinyl-forming derivatives, such as distillation. Conventional techniques for separation from and by-products specifically use mercury catalysts for polymerization. This can result in high losses of vinyl-forming derivatives as well as losses of starting material when It was recognized that The loss of vinyl-forming derivatives, especially high-boiling esters, is due to the near-boiling It has also been recognized that separations involving distillation of mixtures of substances are enhanced.

Obstacles in the separation of near-boiling materials have also been recognized. U.S. Patent No. 3°337.611 The solution to this separation problem taught by Involves utilizing a molar excess of carboxylic acid compared to the molar concentration of the ester reactant. vinyl Distillation of the product derivatives left the method of choice for recovery of the total ester. 2nd column , lines 48-51, column 4, lines 50-59, and Example 1.

Therefore, transvinylation technology was used to make vinyl derivatives of Brønsted acids. Despite the recognition of the benefits of utilizing transvinylation technology, Conventionally used to separate and recover derivatives from transvinylation reaction mixtures. It has become less commercially important because of its inefficient and economically unattractive methods. not present. Fractionation or fractional distillation was typically used to recover vinyl-forming derivatives. Therefore, the separation and recovery of the vinyl-forming derivatives is important because the vinyl-forming derivatives are transcribed. The conjugate acid of the transvinylation reaction mixture (i.e., as the starting material during the transvinylation) acids formed from the vinyl derivatives of the Brønsted acids used) and/or other compounds It has been found that this is difficult in the case where the boiling point is very close to that of the substance. the In such cases, separation by fractional distillation requires a very large, complex and expensive distillation column. This can only be achieved by using ram, otherwise it cannot be achieved at all. like that The cost of columns and the investment to run them is therefore make the use of transvinylation technology for manufacturing commercially unattractive.

Therefore, alkenyl-forming derivatives, especially vinyl-forming derivatives, can be subjected to transvinylation reaction. from the conjugate acid of the alkenyl derivative of the first Brønsted acid. There continues to be a need for an economically separable transvinylation process. like that The requirements of the process are that when the conjugate acid and the alkenyl-forming derivative are near-boiling substances, i.e. , whose boiling points are close to each other (within 15 degrees of each other, especially within 5 degrees of each other) It is particularly strong when it has This field involves determining the desired transvinylation reaction product. economical separation of monomers and monomer mixtures, thereby allowing and enable the commercial manufacture of monomer mixtures (where they would otherwise be manufactured). or may not be manufactured without considerable expense). There is also a requirement for a transvinylation process. Alkenyl derivative of the first Brønsted acid Enables commercial production of alkenyl-forming derivatives that boil near the boiling point of the conductor's conjugate acid There are even more special requirements for the transvinylation process.

Light” [Ωl Leopard The present invention provides an improved protocol for the production of alkenyl derivatives of Brønsted acids. provides a vinylation process. The improved transvinylation process of the present invention Assists in the transvinylation process and converts alkenyl-forming derivatives into transvinylation reaction mixtures. Other compounds in the compound (starting reactants and especially the brake used as one of the starting reactants) (containing the conjugate acid) of alkenyl derivatives of This includes the use of azeotropic distillation to facilitate recovery of the product derivatives. trans vinyl The use of azeotropic distillation to assist in the oxidation process was not recognized until this invention.

Furthermore, this can be achieved through the use of azeotropic distillation to separate and recover alkenyl-forming derivatives. The benefits achieved have hitherto gone unrecognized.

Efficient generation of alkenyl derivatives from other compounds in the transvinylation reaction mixture Alkenyl production assisted by azeotropic distillation to achieve both economical and economical separations It is a first aspect of the present invention to provide a transvinylation process for the production of derivatives. It is a purpose.

Transvinylation process with improved productivity, lower equipment costs and lower operating costs It is also an object of this invention to provide.

Improved throughput due to simplified separation and recovery of alkenyl-generating derivatives It is a further object of this invention to provide a transvinylation process that

Alkenyl derivatives and alkenyl derivatives of Brønsted acids used as reactants For the production of alkenyl-forming derivatives when the conjugate acid of the conductor has a similar boiling point It is yet another object of this invention to provide a transvinylation process. Al A transvinylation process in which kenyl-forming derivatives can be produced in a single-stage reactor in the container, the conjugate acid and the alkenyl-forming derivative are near-boiling substances). is a related object of this invention.

of carboxylic acids that allows continuous removal of vinyl esters of carboxylic acids in isolated form. It is a further object of the invention to provide a continuous process for the production of vinyl esters. It is.

Highly pure alkenyl-forming derivatives can be produced with low residual acidity. It is yet another object of the present invention to provide a transvinylation process. low acid Provides a transvinylation process that can produce highly pure vinyl-forming derivatives in one step It is -1 special object of this invention.

Transvinyl is versatile (and can produce mixtures of alkenyl derivatives) It is also an object of this invention to provide a process for oxidation.

These and other objects and advantages of this invention will become apparent from the following description of the invention. There will be.

As used herein, the term alkenyl-producing derivative refers to the first Brønsted From the transvinylation reaction between an alkenyl derivative of an acid and a second Brønsted acid The resulting formula R(CH,), , CR” = CR’ R”c has a flu’y nyl containing (wherein R is carboxy, amido, aroxy, etc.) , n is 0 or 1, and R', R' and R2 are each independently hydrogen, 1 ~12 carbon atoms alkyl, cycloalkyl, aryl, alkyl ether, etc. transvinylation, as used here, refers to vinyl exchange and The novel process of the present invention is equivalent to both types of exchange reactions. It fits perfectly.

Accordingly, the present invention provides a method for preparing a second derivative of an alkenyl derivative of a first Brønsted acid. The Brønsted acid atom formed by the transvinylation reaction with the Brønsted acid Provided is a method for producing alkenyl derivatives, the method comprising: in the presence of a catalyst capable of catalyzing the transvinylation reaction of rukenyl derivatives. a second Brønsted acid; Transvinyl enzymatic agents capable of forming azeotropes with kenyl-forming derivatives and add the alkenyl derivative of the second Brønsted acid to the reaction mixture. (including recovery by azeotropic distillation as a product of the transvinylation reaction), The boiling agent and the alkenyl-forming derivative have a boiling point at least as high as that of the first Brønsted acid. The conjugate acid of the rukenyl derivative forms an azeotrope that is sufficiently different from the boiling point of the conjugate acid. It makes it possible to separate the boiling mixture and the conjugate acid by distillation.

The azeotrope-assisted transvinylation process according to the invention is versatile. The method is To produce a single monomer of relatively high purity or to produce a mixture of monomers. It can be used to The desired product can be obtained by appropriate selection of an azeotropic agent and by transcribing before azeotropic distillation. This can be accomplished by separation work carried out in the subvinylation reaction mixture.

Brief description of the drawing FIG. 1 is a schematic illustration of the transvinylation process of the present invention (by azeotropic distillation). (including recovery of alkenyl-forming derivatives and recycling of Brønsted acids).

Detailed description of the invention The present invention provides a first Brønsted acid alkenyl derivative R'(CHi)n CR”=CR’　R’ and the second Brønsted acid (RX) transvinyl Many Brønsted acid alkenino derivatives are easily formed by oxidation reactions. a process for the preparation and separation of alkenyl acids of a second Brønsted acid; (R(CHz), CR” = CR’ R’) To separate the alkenyl derivative of Brønsted acid from the conjugate acid (R'X) The process is assisted by azeotropic distillation of the transvinylation reaction mixture.

The method may be continuous, semi-continuous, batch, or semi-batch; The case of rukenyl derivatives can generally be described as follows: catalyst RX + R’(CHz)llCR”=CR’R’-+RCR”=CR’R’ + R'X (wherein, R is carboxy, amide, aroxy, etc., and X is hydrogen , hydroxyl, alkyl, aryl, etc., n is 0 or 1, and Ro is , carboxyl, amido, alkyl, substituted alkyl, aryl or substituted aryl and R', R' and R2 are each independently hydrogen, 1 to about 12 carbon atoms atomic alkyl, cycloalkyl, aryl, alkyl ether, etc.).

The transvinylation reaction is an equilibrium exchange reaction with an equilibrium constant of about 1. Therefore, isomo of the alkenyl derivative of the first Brønsted acid (R'CCH2), CR2 =CR0R1) and the second Bronsted acid (RX) until almost equilibrium is reached. If the reaction is completed, the reactants (i.e., the alkylene of the first Brønsted acid) are Nyl derivative (R(CH2).CR''=CR' R') and the second Bränst acid (R’X)) and the transvinylation product (i.e., the second alkenyl-forming derivatives of do-acids (R(CH snow), CR” = CR’ R’) and Equimole with the conjugate acid (R'X)) of the alkenyl derivative of the first Brønsted acid A mixture exists. Since all four compounds are present in the reaction mixture, this mixture The compound is referred to herein as the transvinylation reaction mixture. As is well known, the equilibrium reaction is , by appropriate adjustment of the reactants and/or removal of one or both of the reaction products. It can be turned into one advantageous production of reaction products. Therefore, the design parameters - and the desired product determine whether and how the equilibrium should be turned. in addition Nevertheless, the transvinylation reaction mixture contains alkenyl-forming derivatives (R(CH ,).

It is expected to contain both CR” = CR’ R’) and conjugate acid (R’ It will be done.

This invention enables azeotropic distillation to Comparison for recovery of ru-forming derivative (R(CH,).CR' = CR' R') transvinylation process by providing a simple, easy and economical method. Used to assist. The primary purpose of azeotropic distillation is to extract alkenyl-forming derivatives or The mixture of the alkenyl-forming derivative and the alkenyl derivative of the first Brønsted acid It is a profit. Alkenyl-forming derivatives or alkenyl-forming derivatives, even if otherwise indicated The mixture of the derivative and the alkenyl derivative of the first Brønsted acid is prepared before azeotropic distillation. Recovery regardless of how the transvinylation reaction mixture is processed It should be. Therefore, an entrainer can be added to the transvinylation reaction mixture to forms an azeotrope with the kenyl-forming derivative, thereby reducing the At least the alkenyl-forming derivative can be recovered. For that purpose, azeotropic The mixture is characterized in that at least the azeotrope is converted into a transvinylation reaction mixture by azeotropic distillation. The boiling point of the conjugate acid (R' It has a boiling point of

a mixture of an alkenyl-forming derivative and an alkenyl derivative of the first Brønsted acid; If recovery is desired, the alkenyl derivative in the transvinylation reaction mixture Depending on the relative boiling points of the conductor, alkenyl-forming derivative azeotrope and other compounds, It is also possible to form an azeotrope with the alkenyl derivative of the first Brønsted acid. Necessary or not necessary. Boiling of the alkenyl derivative of the first Brønsted acid The point is the conjugate acid or other compound in the reaction mixture from which it is to be separated (or the boiling point of both the conjugate acid and the other compound). It is not necessary to form an azeotrope with the alkenyl derivative of the Insted acid.

It is possible to separate the alkenyl derivative of the first Brønsted acid from the azeotrope and even desirable. However, the alkenium of the first Brønsted acid the boiling point of the compound in the transvinylation reaction mixture from which it is to be separated. If the points are too close, the alkenyl derivative or alkenyl derivative of the first Brønsted acid The derivative mixture is separated by forming an azeotrope with either or both of the derivatives forming the derivative. It is desirable to select an entrainer or a mixture of entrainers that allows the Delicious.

The entrainer selected must be compatible with the alkenyl-forming derivative. Furthermore , an entrainer is used to combine the alkenyl-forming derivative and other compounds in the transvinylation reaction mixture. azeotropic evaporation in a suitable column by forming an azeotrope with a sufficiently specific boiling point. It is possible to separate the co-ifB1ff1 compound from those compounds by distillation. do. For that purpose, the boiling point of the azeotrope and the transport in which the azeotrope is to be separated are determined. Preferably, the difference in boiling point from the other compounds in the subvinylation reaction mixture is several degrees Celsius. Most preferably, the temperature is about 10 degrees Celsius or higher. Separation by azeotropic distillation Generally, the greater the difference in boiling points, the less difficult and cheaper it will be.

The entrainer and the alkenyl-forming derivative are the lowest boiling azeotrope or the highest boiling azeotrope. It is recognized that either of these can be formed. The entrainer is an alkenyl-forming derivative and an inorganic Homogeneous or homogeneous azeotropes can be formed. Entrainers and alkenyl formation If the derivative forms a heterogeneous azeotrope, the azeotropic agent and alkenyl formation inducer The solubility of the bodies in each other is minimal. In the condensation of the azeotrope after distillation, the azeotropic agent and alkenyl-forming derivatives separate into two phases, therefore the alkenyl-forming entrainer Separation from derivatives is easy. Therefore, the entrainer is asymmetric with the alkenyl-forming derivative. It is preferred to form a single azeotrope. azeotrope forming a heterogeneous azeotrope The use of agents facilitates the separation, recovery, and production of alkenyl-generating derivatives.

The azeotropic distillation-assisted transvinylation process according to the present invention is extremely versatile ( an alkenyl-forming derivative and an alkenyl-forming derivative and a first Brønsted acid; Enables the production, separation and recovery of mixtures with lukenyl derivatives. Specific to be generated The product or product mixture is obtained by treating the transvinyl reaction product prior to azeotropic distillation. Decide how to For example, processing the transvinylation reaction product before azeotropic distillation to remove all or only a portion of the alkenyl derivative of the first Brønsted acid. Rukoto can.

If all the alkenyl derivatives of the first Brønsted acid are removed before azeotropic distillation The alkenyl-forming derivative is removed from the transvinylation reaction mixture by azeotropic distillation. separation and subsequent recovery by separation of the alkenyl-forming derivative from the entrainer. Ru. Only a portion of the alkenyl derivative of the first Brønsted acid is removed before azeotropic distillation , the alkenyl-generating derivative and the alkenyl derivatization of the first Brønsted acid The mixture with the body is separated and collected.

Entrainers can form azeotropes with alkenyl-forming derivatives; azeotrope with both the nyl-forming derivative and the alkenyl derivative of the first Brønsted acid. It is recognized that entrainers which form compounds of h6°alkenyl may also be satisfactorily used. an azeotrope with both the derivative and the alkenyl derivative of the first Brønsted acid. The choice of an entrainer that can be formed transcribes a mixture of the two derivatives. Allows for separation and recovery from the subvinylation reaction mixture. Of course, the boiling point is the same is higher or lower than the boiling point of the conjugate acid. of the first Brønsted acid without the initial formation of an azeotrope of the alcohol derivative. It is also possible to separate and recover a mixture of kenyl derivatives and alkenyl-forming derivatives. It is.

The transvinylation reaction is preferably carried out in the presence of a catalyst. any lap Known transvinylation catalysts can be used (e.g. mercury and palladium). (based on catalysts). A particularly preferred transvinylation catalyst is No. 213.697, filed in and assigned to the same assignee as the present application. Disclosed under the title “Transvinylation Reaction”) and The claimed ruthenium-based catalyst.

FIG. 1 illustrates a schematic representation of a preferred embodiment of the invention. Illustrated construction In Step 1o, the reactants, namely the alkenyl derivative of the first Brønsted acid and The second Brønsted acid is supplied to the reactor via feed lines 12 and 14, respectively. 16. Polymerization inhibitors are typically included to inhibit the vinyl monomer. Prevents unwanted polymerization. Reactor 16 contains a catalyst for the transvinylation reaction. 0 reactor 16 containing sufficient temperature and pressure to accomplish the transvinylation reaction. After reacting the zero reactants maintaining the power, the transvinylation reaction mixture (the first Alkenyl derivatives of Bronsted acids, second Bronsted acids, alkenyl derivatives and a concentrate of a conjugate acid of an alkenyl derivative of the first Brønsted acid; from reactor 16 through transfer line 17 to separation zone 18. Transport.

In separation zone 18, the transvinylation reaction mixture is seeded prior to azeotropic distillation. can perform various separation tasks.

By way of example, separation zone 18 may include a mixture of an alkenyl-forming derivative and a conjugate acid as a catalyst and It can be used to separate from any unreacted second Brønsted acid. reaction eyes The product is the unreacted alkenyl derivative of the first Brønsted acid in separation zone 1. 8, completely or partially separated from the alkenyl-forming derivative and the conjugate acid. Decide whether to be separated. To produce pure alkenyl-forming derivatives, separation is required. Separation zone 18 separates the unreacted alkenyl derivative of the first Brønsted acid and , optionally recycling the alkenyl derivative to the reactor via transfer line 20. Design as follows. Alkenyl-generating derivatives and alkenyl of the first Brønsted acid In order to produce a mixture with a derivative, the separation zone 18 can be is designed to separate only the alkenyl-forming derivative (or not at all). In an illustrated embodiment, the alkenyl derivative of the first Bronsted acid is All or at least a portion of the transvinylation reaction mixture in separation zone 18 and recycled to the reactor via transfer line 20. second brenste The acid is recovered from the separation zone 18 along with the catalyst and transferred to the reactor 16 via a transfer line 22. recirculate to.

For example, a separation zone can be used to separate the alkenyl-forming derivative from the transvinylation reaction mixture. If used for the first time for separation and recovery of the catalyst after separation, the separation zone 18 is It is recognized that it is included after azeotropic distillation.

of the alkenyl-forming derivative, the conjugate acid and, optionally, the unreacted first Brønsted acid. A line transports the alkenyl derivative from separation zone 18 to distillation column 24 for azeotropic distillation. 23. The entrainer can separate the alkenyl-forming derivative from the conjugate acid. In order to make it possible to form an azeotrope with I can do it.

The azeotrope and the conjugate acid (as well as the trans This invention Although azeotropic distillation-assisted transvinylation steps are useful, azeotropic The compound preferably has a boiling point that differs by less than 10'C from the boiling point of the conjugate acid.

For example, the invention particularly provides that if the monomers to be recovered are commercially useful and When the boiling point difference between the azeotrope and the conjugate acid (or components) is about 2 or 3 degrees Celsius Even useful.

Alkenyl derivatives, alkenyl-forming derivatives and conjugate acids of the first Brønsted acid The alkenyl derivative of the first Brønsted acid is determined from the conjugate acid by the relative boiling points of form an azeotrope with the alkenyl derivative of the first Brønsted acid to separate the It may or may not be necessary to use an entrainer to achieve this. first brain The boiling point of the alkenyl derivative of Stead's acid and the boiling point of the conjugate acid are relatively close (i.e., 15 (to a lesser extent), the conjugation of the alkenyl derivative of the first Brønsted acid Alkenyl derivatives of the first Brønsted acid to achieve efficient separation from the acid. Forming an azeotrope with the conductor is highly preferred. However, the first The boiling points of the alkenyl derivative of the Bronsted acid and the conjugate acid are not close to each other, and the first but Azeotroping between alkenyl derivatives of Rönsted acids and entrainers and alkenyl-forming derivatives If the boiling point of the mixture is lower or higher than the boiling point of the conjugate acid, the first Brønsted of the first Brønsted acid without the use of an entrainer for the alkenyl derivative of the acid. The alkenyl derivative can be separated from the conjugate acid along with the alkenyl-forming derivative. Ru.

The boiling point of the alkenyl derivative of the first Brønsted acid is sufficiently different from the boiling point of the conjugate acid. alkenyl derivatives and alkenyl-forming inducers of the first Brønsted acid. To ensure that the azeotrope of the conductor both boils hotter or colder than the conjugate acid. and thereby further aid in the separation of those components from the conjugate acid. It is preferred to form an azeotrope of the alkenyl derivative of the first Brønsted acid. It is acknowledged that it is true. Alkenyl-generating derivatives and first Brønsted Using one entrainer that can form an azeotrope with both alkenyl derivatives of the acid I can do it. Enzymes and first Brønsted acids for alkenyl-generating derivatives It is also contemplated that mixtures of entrainers for the alkenyl derivatives of may be used.

In the illustrated embodiment, the entrainer is placed near the top of column 24 in feed line 25. It is shown that it is supplied through. Furthermore, the rotation from decanter 30 (described later) The collected entrainer can be recycled to the azeotropic distillation column 24 and is preferred, regardless of the source of the entrainer, to compensate for the separation of undesired components during distillation. It is preferred to feed an entrainer near the top of the azeotropic distillation column to assist. mosquito The temperature of the liquid near the top of the ram is lower than at other locations, so the entrainer is placed at the top. Adding them close together cools the agent, thereby reducing the Knocks down boiling components. Even when the entrainer is water, water is the azeotrope's alkyl There is little time and opportunity to contact and hydrolyze the diyl-forming derivative as much as possible. stomach. However, the entrainer may be present in the distillation column 24, e.g., in the middle or near the bottom. It will be recognized by those skilled in the art that the column can be fed at other points on the column. azeotrope Agents can also be added to the feed to distillation column 24.

In the illustrated embodiment, the entrainer and the alkenyl-generating derivative are heterogeneous minimum boiling points. Forms a point azeotrope. As a result, the azeotrope is transferred from the top of column 24 to the transfer tube. through inlet 28 and transferred to decanter 30 (where the azeotrope is removed). It separates into two phases: the alkenyl-forming derivative and the entrainer). Alkenyl-forming derivatives and The mixture of Brønsted acid and alkenyl derivative of No. 1 is not separated from the conjugate acid. , one phase consists of the alkenyl-forming derivative and the alkenyl of the first Brønsted acid. Note that one phase consists of a mixture with a derivative and the other phase consists of a co-drug. Both The boiling agent is transferred to the distillation column 24 (as illustrated by transfer line 32). Recirculate for use. Some of the entrainer is discarded through transfer line 34. It can be removed as an object. An alkenyl-generating derivative phase also enhances rectification, if desired. may be refluxed (e.g., returned to distillation column 24 through transfer line 33 to vinegar).

The alkenyl-generating derivative is transferred to drying column 36 via transfer line 38.

In the drying column 36, the alkenyl-forming derivative is dried by azeotropic drying ( The azeotrope is removed from the column and transferred to the first decanter 30 as described above. or transferred to a second decanter 40 together with the alkenyl-forming derivative. phase separation of the boiling agent), alkenyl formation induction from the second decanter 40 The waste is returned to the drying column 36 via transfer line 42, while the entrainer is returned to the drying column 36 via transfer line 42. Process as .

The entrainer from decanter 40 is also recycled for use in distillation column 24. It can be done. The dried alkenyl-generating derivative is purified to recover the alkenyl-generating derivative. Transfer to column 44. If desired, alkenyl-generating derivatives can be treated with sodium bicarbonate. The residual acid can be removed by neutralization with a suitable radical such as um.

For the azeotropic distillation column 24, the first brake produced during the transvinylation reaction is The conjugate acid of the vinyl ester of the Insted acid remains at the bottom of the column. Azeotropic conjugate acid Acid separation column that separates and recovers the conjugate acid from the distillation column 24 via the transfer line 25 Transfer to 46. The conjugate acid is recovered for subsequent use. second brain The Stead acid is completely separated from the conjugate acid and the alkenyl-forming derivative in separation zone 18. If not separated, the second Brønsted acid is separated in the azeotropic distillation column 24. It is observed that it is separated and passed along with the conjugate acid to the acid separation column 46.

In the acid separation column 46, the second Brønsted acid is separated from the conjugate acid and transferred. Recycle to reactor 16 via line 48.

The operating temperature and pressure of the azeotropic distillation column are not particularly critical to the practice of this invention. However, there are relationships, and they are highly dependent on the particular separation to be performed. Azeotropic distillation is , at atmospheric pressure, or under vacuum or pressure. under operating pressure The limits are related to economic limitations in the condenser. The upper limit of the pressure is the column bottom temperature. depends on the limit (which in turn depends on the decomposition temperature of the components). The operating temperature is even more It depends on the condensing temperature of the condenser and the decomposition temperature of the components. The lower end of the operating temperature is The temperature is generally about 10°C higher than the temperature of the coolant. On the other hand, the upper end of the operating temperature The temperature is about 10°C lower than the decomposition temperature of most decomposable components in the system. Operating temperature and pressure is preferably selected such that the condenser cools easily and does not decompose any components. Ru. If water is the entrainer and the alkenyl-forming derivative is hydrolyzable (or (if the conjugate acid is an unsaturated acid), carry out azeotropic distillation under vacuum, thereby Preferably, the column can be operated at low pressure.

The type of azeotropic distillation column used to perform azeotropic distillation is non-critical, color The column may be a tray column or a packed column. The packed column preferably comprises: This is due to low pressure droplets crossing the column.

The rate at which the entrainer is fed to the azeotropic distillation column is determined by the rate at which the alkenyl-forming derivative is formed. depending on both the degree of production and the concentration of the alkenyl-forming derivative in the azeotrope. given a For alkenyl-forming derivatives and entrainers, the feed rate of the entrainer is preferably All alkenyl-forming derivatives fed to the ram are sufficient to form an azeotrope. It's a minute.

Some excess of entrainer can be used, but the rate of entrainer feed should be controlled to It is preferable to match the production rate of the derivative. After the first loading, preferably , the entrainer supplied to the distillation column is mixed with the alkenyl-forming derivative in the decanter. It is recovered from the two-phase separation of the entrainer. The azeotropic agent from the decanter is sent to the azeotropic distillation column. Simply recirculate it to meet the distillation column demand and, if necessary, remove it from the system. Refill only the amount of entrainer.

The azeotropic distillation assisted transvinylation process of the present invention involves poly(vinyl moieties) A suitable entrainer can be selected and used for the production of alkenyl-forming derivatives that do not have the following properties.

By way of illustration, compounds of the formula below are suitable alkenyl derivatives, where n is 0 or 1. and R', R' and R2 are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms. cycloalkyl, aryl, alkyl ether, etc.). Appropriate a Examples of lekenyl-forming derivatives 1-propenyl benzoate (cis and trans) , 1-propenyl bivalate (cis and trans), 2-propenyl benzoate and 2-propenyl bivalate, allyl bivalate, allyl benzoate, Lyl propionate, methallyl benzoate, methallyl bivalate, methyl ali Lupropionate, allyl crotonate, allyl methacrylate, allyl acrylate Rate et al.

Azeotropic distillation-assisted transvinylation is a suitable entrainer for many vinyl-forming derivatives. It can also be used for manufacturing using selected materials. As an illustration, the alkenyl-generating derivative is It can be any compound with a vinyl group attached to a Brønsted acid. That's it Such compounds can be identified as vinylated Bronsted acids. Vinyl inclusion in the formula below Group R' R' C=CR"- (In the formula, R5, R1 and R2 are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms) cycloalkyl, aryl, alkyl ether, etc.). breth A ted acid is any species that acts as a source of protons.

Examples of suitable alkenyl derivatives of Bronsted acids for the practice of this invention include: Vinyl acetate, vinyl bivalate, vinyl benzoate, vinyl methacrylate, Vinyl acrylate, vinyl propionate, vinyl cinnamate, vinyl sic lohexanoate, vinyl crotonate, vinyl butyrate, vinyl 2-methyl butyrate, vinyl isobutyrate, vinyl 2-valerate, vinyl 2-valerate Ethylhexanoate, vinyl octanoate, vinyl bibalate, vinylsic Roheras-3=enoate, vinyl neodecanoate, vinyl octanoate, Vinyl 2-propylheptanoate and other vinyl esters or neoesters , N-vinylpyrrolidinone, N-vinylsuccinimide, vinyl phenyl ether vinyl methyl ether, vinyl ethyl ether, 2-chloroethyl vinyl ether ether, ethyl vinyl ether, 2-vinyloxyethanol, allyl vinyl ether ether, isopropyl vinyl ether, propyl vinyl ether, 1-vinyl ether, isopropyl vinyl ether, xy-2-propatol, 3-vinyloxy-1-propatol, butylvinyl Ether, isobutyl vinyl ether, bis(2-vinyloxyethyl) ether 2-butylthioethyl vinyl ether, 2-butoxyethyl vinyl ether , 2-ethoxyethyl-2-vinyl-oxyethyl ether, 2-ethylhexy Rubinyl ether, 2-butoxyethyl 2-vinyl-oxyethyl ether, Limethyl nonyl vinyl ether, N-vinyl 2-oxazolidinone, 2-vinyl Oxyethyl acetate, 2-vinyloxyethyl acetate, 2-vinyloxy These include ethyl acrylate, vinyl chloride, vinyl sulfonamide, etc.

Preferred alkenyl derivatives are vinyl esters of carboxylic acids and vinyl alkyl or are aryl ethers, primarily because they are commercially available.

Examples of suitable Bronsted acids for the practice of this invention include monocarboxylic acids and Carboxylic acids such as polycarboxylic acids (acetic acid, propionic acid, butyric acid, isobutyric acid, 2-methyl Tylbutyric acid, crotonic acid, pivalic acid and other neoacids, stearic acid, benzoic acid, te Phthalic acid, isophthalic acid, phthalic acid, adipic acid, succinic acid, malic acid, male Inic acid, polyacrylic acid, acrylic acid, methacrylic acid, seed coat acid, 2-ethylhexyl (exemplified by sanoic acid, cyclohexanoic acid, and cyclohexenoic acid), amino acid (2-pyrrolidinone, 2-pyrrolidone, ε-caprolactam, 2-oxazoli alcohols (methanol, ethanol, n-propylene, etc.), alcohols (methanol, ethanol, Ropatool, isobutanol, fluorinated alkanol (1,1,1,3°3.3 -hexafluoro-2-propatool, etc.), monoethanolamine, jetano phenolic compounds (phenol, triethanolamine, etc.), phenolic compounds (phenol, triethanolamine, etc.), zorcinol, and bisphenol A [2,2-bis(4-hydroxyphenyl ) propane], etc.), sufficiently acidic amino compounds (secondary aromatic amines, azoles, etc.), ), hydroxy esters (hydroxyalkyl acrylates (e.g. 2-hydro (oxyethyl acrylate, 2-hydroxyethyl methacrylate) and hydro xyalkyl alkanoates (e.g. 2-hydroxyethyl acetate, 2- hydroxyethyl bivalate), silanol (dimethylsilanediol, (e.g., trimethylsilane monool).

Preferred Brønsted acids are carboxylic acids, alcohols, amides, imides, phenates, etc. Nols, etc.

Examples of transvinylation reactions that can be carried out by the process of this invention are as follows: is: Otsuko L1111 Dan 2 Noyo Mue 1! Charcoal 1 Vinyl acetate + Bivalic acid → vinyl Vivarate Vinyl acetate + methacrylic acid - vinyl methacrylate Vinyl acetate + acrylic acid → vinyl acrylate Vinyl acetate Decabenzoic acid → Vinyl benzoate Vinyl acetate + propionic acid - vinyl propionate Vinyl acetate + salicylic acid - vinyl salicylate Vinyl acetate + cinnamic acid → vinyl Cinnamate As previously indicated, entrainers are used to interact with alkenyl-generating derivatives of transvinylation reactions. It can be any compound that can form an azeotrope. For example, an entrainer is an alkenyl may form a two-component azeotrope with the product derivative or may form a fraction of the mixture of esters. If release is desired, the alkenyl-forming derivative and the alkenyl-forming derivative of the first Brønsted acid are may form azeotropes with nil derivatives. The azeotrope and the conjugate acid (and the first Alkenyl derivatives of Stead acids, which are not separated from the reaction mixture before azeotropic distillation and are If an azeotrope is required for the separation of )), the difference in boiling point between (approximately 10°C, as a non-limiting example) Suitable entrainers include water (liquid or vapor), cyclohexane, heptane, impregnated Contains lopatur, methanol and alkyl ethers.

A transvinylation reaction is performed between the alkenyl derivative of the first carboxylic acid and the second carboxylic acid. When producing vinyl esters of carboxylic acids by reaction with acids, water is Both the kenyl-forming derivative and the alkenyl derivative of the first Brønsted acid and the asymmetric In the condensation of an azeotrope, which is particularly preferred since it can form a single azeotrope, water and alkenyl-forming derivatives (and, if present, of the first Brønsted acid) The alkenyl derivative) separates into two separable phases in decanter 1.

Water is an organic acid having 1 to 12 carbon atoms, and an alkali of the first carboxylic acid of the following formula. R” is a preferred entrainer in transvinylation reactions involving kenyl derivatives. -C-OCH+ = CH* (wherein R'' is alkyl, aryl, cycloalkyl, from 1 to about 12 carbon atoms atoms). The water contains the alkenyl-forming derivative and the first carbon, if present. Forms the lowest boiling azeotrope with alkenyl derivatives of rubonic acids. lowest boiling point azeotrope The compound has a boiling point that differs by more than 10°C from the boiling point of the conjugate acid, and the boiling point of its azeotrope point is lower than the boiling point of the conjugate acid.

According to a preferred embodiment of the invention, a carboxylic acid having 1 to 12 carbon atoms Lukenyl derivatives include vinyl acetate and a second carboxylic acid having from 1 to about 7 carbon atoms. As described in pending application No. 213,697, produced in the presence of a ruthenium catalyst. Alkenyl-forming derivatives are The transvinylation reaction mixture is effectively and separated efficiently. Therefore, in the transvinylation reaction described, acetic acid (having a boiling point of about 116-118°C) is one of the reaction products. water, a Used to produce the lowest boiling point heterogeneous azeotrope with the rukenyl-forming derivative. azeotrope The mixture has a boiling point below that of acetic acid. Other components of alkenyl-forming derivatives It is easy to remove from.

The present invention relates to the combination of vinyl acetate with bivaric acid, butyric acid, propionic acid and crotonic acid. Vinyl vivalate, vinyl butyrate, vinyl It is particularly useful in the production of lupropionate and vinyl crotonate. Transbi The products of the nylation reaction (i.e., alkenyl-forming derivative and acetic acid) have similar boiling points. However, as shown in the table below, it is very difficult to separate by fractional distillation. It is.

Excuse me Vinyl 112 86 17 Viparate Addition of sufficient water to the alkenyl-forming derivative in the co-fpz distillation unit with vinylbutyrate, vinylpropionate and vinylcrotonate. Forms an aqueous azeotrope. Vinyl propionate, vinyl butyrate and vinyl Lucrotonate can be mixed with water at boiling points of about 94.9°C, about 87°C and about 92°C, respectively. It is known that vinyl vivalate and water form an azeotrope with a point It was discovered that an azeotrope was formed with a boiling point of about 86°C. in all cases In , the azeotrope has a boiling point substantially lower than that of acetic acid (which is , allowing the vinyl ester to be easily separated from the acetic acid).

Water forms a heterogeneous azeotrope with the vinyl ester in the condensation of the azeotrope. As a result, it separates into two phases (i.e. water and vinyl ester), thereby Facilitates easy recovery of esters. Therefore, we describe here an azeotropic distillation assisted The transvinylation process consists of vinyl vivalate, vinyl butyrate, and vinyl chloride. nate and vinylpropionate by direct transvinylation from vinyl acetate. It can be used for manufacturing. This process is relatively easy to convert vinyl ester into acetic acid. It is more economical than conventionally known transvinylation techniques because it can be separated from be.

The following examples are illustrative of the invention, but not limiting.

These examples illustrate the separability of vinyl esters and carboxylic acids, and vinyl from carboxylic acids by the azeotropic distillation assisted transvinylation process of the present invention. describes the production of ester-forming esters.

Xma1eyu This example separates vinyl acetate, vinyl propionate, acetic acid and propionic acid. demonstrating the feasibility of separating After removal of the catalyst, this mixture is mixed with vinyl acetate. Resulting from the production of vinyl propionate by transvinylation of propionic acid It is considered to be typical of a transvinylation reaction mixture. Using water as an azeotropic agent Ta.

28% by weight vinyl acetate, 30% by weight vinyl propionate, 18% by weight vinegar A mixture consisting of acid and 24% by weight propionic acid was packed into a 2 liter reactor. . The reaction vessel includes a 15-tray O1dershaw distillation column and an outlet of the distillation column. A condensation column connected to the (top) and a collection flask connected to the outlet end of the condensation column. I installed this.

The mixture was heated and an initial reflux rate of 10 was established. As the temperature of the reaction vessel increases, Low boiling vinyl acetate was seen to separate from the mixture. vinyl acetate mixture After separation, approximately 15.4 g of water was added dropwise to the top of the distillation column.

An aqueous azeotrope of vinyl propionate was formed, which was approximately 78-79°C. There was a roaring sound (observed) extending to (observed). The azeotrope was analyzed by gas chromatography. was analyzed and found to be 98.11% vinyl propionate, 0.689% acetic acid and 0. ．． It was found to contain 326% propionic acid.

Mitate Yu This example shows a mixture of vinyl acetate, acetic acid, vinyl crotonate and crotonic acid. The separation of vinyl acetate and vinyl crotonate by azeotropic distillation from child The mixture is the transvinylation reaction mixture (croton of vinyl acetate) after catalyst separation. Expected to result from the production of vinyl crotonate by transvinylation reaction with acid conduct a simulation experiment.

Vinyl acetate (7,0 g), vinyl crotonate (7,0 grams), acetic acid (4,0 ), and a solution (8.8 ml) prepared from crotonic acid (2.0 g). It was packed into the reaction kettle of a single-stage distillation apparatus. Gas chromatography analysis of this solution As shown in Table II below.

The reaction kettle was heated to 75°C and 1 ml of water was added through the addition funnel. Vinyl acetate/water and vinyl crotonate/water azeotrope at overhead temperatures ranging from 67 to 94°C. It was distilled at. Both of the following fractions were collected and analyzed by gas chromatography. It was discovered that it had the composition (area %) shown in Table III below.

21 worker 67-. 71°C 5.04% 92J1% --1,78% 67° 7.50% 92.81% --0,58%69-73° 10.56%87.4% 0. 39% 0.11% 0.78% 76-84 @ 16.38% 82.3% ~ -0.58% 84-90 @ 42.17% 54.9% 0.65% - 0.38% 90-93° 82.24% 13.8% 0.78% 0.19 % 0.37%94°’95.9% 1.33% 0.60% 0.13% 0.10% vinyl crotonate and vinyl acetate are prepared by simple azeotropic distillation. Separation and removal from transvinylation reaction mixtures without the use of synthetic rectification columns I understand that it is possible.

Mitate Eyu This example shows azeotropic distillation assisted transvinyl acetate and acrylic acid. The production of vinyl acrylate by chemical reaction will be explained.

Three separate transvinylation runs were performed. In each operation, 1,500 grams of acrylic acid, 1.91 grams of formula [Ru　(Co)-0COCH-]- of ruthenium catalyst, 1,500 grams of vinyl acetate, and 6.0 grams of The phenothiazine was packed into a 1 gallon autoclave. Pressurize the reactor and -oxidize Purge with carbon (50 psig) three times and then pressurize to 50 psig. reaction The vessel was heated to 130-136°C for a total of 4 hours. Cool the reactor, evacuate and catalyst, vinyl acrylate, acetic acid, acrylic acid and vinyl acetate. The vinylation mixture was discharged from the reactor.

Transvinylation mixture for each run, 2,848 grams and 2,938 grams, respectively. rum, 2,778 grams, were combined and then flash distilled under vacuum to transcribe. subvinylation mixture (vinyl acetate, vinyl acrylate, acetic acid and some acrylic acrylic acid) was removed from the acrylic acid/ruthenium catalyst residue. The distillate was collected.

The flash distilled transvinylation mixture was transferred to 24 trays of Odersha. A fractional distillation apparatus containing a 12 L reaction vessel equipped with a W column and a rectification head was loaded.

Removal of vinyl acetate from flash distilled transvinylation mixtures prior to azeotropic distillation did. During a vinyl acetate distillation run, a phenothiazine inhibitor (dissolved in vinyl acetate) was added to the reaction vessel and fed to the column using an addition funnel. Unreacted vinyl acetate (b , 9.72-73°C) from the transvinylation mixture at a reflux ratio of 10/1. Ta. Most of the remaining vinyl acetate was removed by gradually and briefly increasing the head temperature to 82°C. The column was purged at a high (10/1) reflux rate by letting the solution flow. of the result Gas chromatography area % analysis of the mixture is shown in Table IV below.

The reaction vessel is cooled and thereby withdrawn into a vapor column. Then the water is distilled Pack into the addition funnel on top of the ram and have the lowest boiling point (observed) of 77-78°C. A water/vinyl acrylate azeotrope was formed. In condensation, water/vinyl ac The rylate azeotrope separated into organic (top) and aqueous (bottom) phases. Azeotropic fraction gas The chromatographic analysis (area %) is shown in Table 1 below.

1ヱ 1 (77@) 96.013 3.301 0.367 0.0592 (7 g @) 911.360 1.168 Trace” 0.0913 (78°) 9 8.541 1.012 Trace" 0.091114 (7g-94°l"97 ．． 319 0.995 0.489 0.2445 (94°) 97.148 1.072 0.489 0.254 Combine the vinyl acrylate fractions and azeotropically (280 mm Hg, 78-79 °C) and distilled through a short-path column. This gave 2L of product. Gas chromatography of purified vinyl acrylate Table VI below shows the analysis according to Table VI below.

Gas chromatographic analysis shows that high purity, low acidity products are obtained by azeotropic distillation. It was shown that this can be obtained by utilizing transvinylation. Therefore, this Examples show that the present invention has low acidity and does not require further treatment to remove acid. provides a relatively simple method to directly obtain high-purity alkenyl-forming derivatives. to show that

Husband” 11A This example demonstrates the azeotropically assisted transvinylation of vinyl acetate with crotonic acid. The production of vinyl crotonate will be explained below.

In a 1 gallon autoclave, 1,350 grams of crotonic acid, 0.9 grams of Ruthenium catalyst with formula [Ru (Co) 20COCH3] 7, 1.350 A reactor packed with 2.0 grams of vinyl acetate and 2.7 grams of phenothiazine was added Pressurize and purge three times with nitrogen (50 psig), then pressurize to 25 psig. The reactor was heated to 127-133°C for a total of 12 hours. Cool the reactor and drain it. air, transvinylation mixture (catalyst, vinyl crotonate, acetic acid, crotonic acid) and vinyl acetate) were discharged from the reactor.

The transvinylated mixture is flash distilled under vacuum to produce the transvinylated product. (vinyl acetate, vinyl crotonate, acetic acid, and some crotonic acid) was removed from the phosphoric acid/ruthenium catalyst residue.

The flash distilled transvinylation mixture was transferred to 25 trays of Odersha. A fractional distillation apparatus including a 3000 ml reaction vessel equipped with a W column and a rectification head. Stuffed. During the vinyl acetate distillation run, add the phenothiazine inhibitor to the reaction kettle and Addition funnel was used to feed the column (phenothiazine was dissolved in vinyl acetate). Reactive vinyl acetate (b, p, 72-73°C) from the transvinylation mixture 5/1 Fractionation was carried out at reflux rates ranging from (initial) to 10/1 (end of distillation). The last remaining few amount of vinyl acetate to gradually and briefly raise the head temperature to 93°C. Therefore, the column was purged at a high (10/1) reflux rate.

The reaction vessel was briefly cooled, thereby allowing vapors to retreat into the column. water (fenochi) saturated with azine) at the top of the distillation column (the same location used for the inhibitor feed). Lowest boiling water/vinyl crotonate packed into a funnel and having a boiling point of 92°C (observed) An azeotrope was formed. In condensation, the water/vinyl crotonate azeotrope has Separated into organic (top) and aqueous (bottom) phases. Gas chromatograph the six azeotropic fractions It was analyzed by The compositions (area%) of both parts are shown in the table below. vinegar.

1 98.473% 0.067% 0.452% 0.473% 2 96.8g 5 0.014 2.942 0.0373 95.145 0.990 3. 581 0.0324 99.071 0.159 0.501 0.1575 98.410 Not measured 0.734 0.577 0.0416 44. 985 Not measured 25.007 14.594 0.523 fractions 2 and 3 In both cases, the column flooded, but the water feed rate did not fully share the vinyl crotonate. After the 0 fraction 3, which was considered too low to form a boiling mixture, the O1dershaw filter was The column was replaced with a Vigreux column to reduce overflow. After replacing the column, Good separation was obtained.

11 clay balls This example demonstrates the azeotropically assisted transvinylation of vinyl acetate with bivaric acid. The production of vinyl vivalate will be explained below.

A reactor was charged with 5,082 bonds of vinyl acetate, 4,854 bonds of bivaric acid, and Ruthenium dihydroponyl acetate homopolymer (530 g) was packed. reactor in the reactor at 25 psi of carbon monoxide (as the inhibitor hydroquinone requires) 500-11000 pp oxygen atmosphere) and 150°C for 7 hours. Heated. Analysis of reactor samples by gas chromatography indicates that the reaction has reached equilibrium. I showed that I did it. The reactor was cooled to 50°C and the contents were flash evaporated under vacuum. I stayed. The distillation residue (containing catalyst and bivaric acid) was discharged from the reactor.

Vinyl acetate was then separated from the distillate. After removal of vinyl acetate, reaction mixture The material was subjected to azeotropic distillation to separate and recover the vinyl vivalate.

The column bottoms from the vinyl acetate removal step were distilled by azeotropic distillation. Koc An h-5eltzer column was used with a 30 gallon decanter. coarse vinyl vinyl The column residue containing barreto (preheated to 90°C) is supplied to the center of the column, and the water is evaporated. The top of the ram was fed via a reflux line. Vinyl vivalate/water azeotrope ( b, p, = 86°C, water 17% by weight) was fractionated and distilled overhead. B Baric acid, acetic acid, and heavy materials were removed from the bottom of the column. 1 The azeotrope product is It was collected in a decanter that separates the phases.

The bottom aqueous layer is returned to the top of the azeotropic distillation column, and the top vinyl vivalate counterfeit is removed for final drying. collected for drying. During the run, crude material was fed to the column (approximately 50% -head distillation, removing approximately 50% from the column bottom). the top of the column throughout the separation. Keep the bottom temperature at 89.6-94.5°C and the bottom temperature at 120.8-126.2°C. I held it.

The yield of azeotropic distillation was 97.3%.

The compositions of the nine fractions from the azeotropic distillation are shown below in Table VII11 0.480 0.19 7 99.3132 0.096 0.064 99.813 0.0263 0.076 0.018 9L875 0.0064 0.079 0.087 98.863 0.9365 0.091 0.123 98.748 1. 0146 0.079 0.011 99.828 0.0687 0.0g2 0.010 99.874 0.0348 0.080 0.013 99. 877 0.0319 0.0119 0.033 99.559 0.022 From the analysis of fractions 2.3.6.7.8 and 9, it appears that azeotropic distillation produces particularly high purity and acid-containing It was found to be useful for the recovery of vinyl vivalate in low quantities, and also for removing acids. It is believed that there is no need for further processing of these fractions to remove them. Fraction 4 and During the period 5, the water feed to the azeotropic distillation column was unfavorably fast. water too early The feed resulted in higher than desired bivalic acid and acetic acid contents in the pivalic acid fraction.

This example demonstrates the significant advantages of the azeotropic distillation assisted transvinylation process of the present invention. shows. According to the invention, vinyl bivalate and acetic acid having very similar boiling points 112°C and 116-118°C, respectively) is much easier and cheaper; The production of vinyl bivalate by transvinylation of vinyl acetate and bivalic acid is economically and commercially attractive.

Therefore, the present invention provides efficient and economical separation and recovery of alkenyl-forming derivatives. An improved transvinylation process is provided. Azeotropic distillation assisted transformer Vinylation is at least partially responsible for the efficiency of separation and recovery of alkenyl-generating derivatives. Improved productivity, lower equipment costs than traditional fractionation or distillation due to ease and and has low operating costs. This process induces the production of high purity alkenyl with low acidity. bodies can be generated directly without the need for further processing. Furthermore, this The combination of the alkenyl-forming derivative and the alkenyl derivative of the first Brønsted acid alkenylation by transvinylation in a single-stage reactor where the role acid is a near-boiling material. To make the production of fluorine-generating derivatives economical.

About the animal of the alkenyl derivative of the first Brønsted acid with the second Brønsted acid. Method for producing alkenyl derivatives of Brønsted acids by vinylation reaction separates and recovers the alkenyl derivative of the second Bronsted acid as a product. azeotropic distillation of the transvinylation reaction mixture to obtain

-111-^----Naka II PCT/US 91108757

Claims (19)

[Claims] 1. of the alkenyl derivative of the first Brønsted acid in the second Brønsted acid. A method for producing alkenyl derivatives of Brønsted acids by transvinylation reaction. said alkenyl derivative of said first Brønsted acid in the presence of a catalyst. The azeotropic agent is then reacted with the second Brønsted acid to undergo a transvinylation reaction. the second Brønsted acid alkyl by azeotropic distillation. recovering the vinyl derivative as a product of transvinylation; can catalyze the transvinylation reaction, thereby allowing the aforementioned second an alkenyl derivative of a Bronsted acid and said alkyl derivative of said first Bronsted acid; forming a reaction mixture comprising the conjugate acid of the Lukenyl derivative, said entrainer being at least forming an azeotrope with said alkenyl derivative of said second Bronsted acid; The above manufacturing method allows 2. said alkenyl derivative of said entrainer and said second Bronsted acid; has a boiling point lower than the boiling point of the conjugate acid of the alkenyl derivative of the first Brønsted acid. or forming an azeotrope with said azeotrope and said second blend step. the above-mentioned alkenyl derivatives of the bronsted acid or the alkenyl derivatives of the first bronsted acid; forming an azeotrope having a boiling point higher than the boiling point of the conjugate acid, or and said alkenyl derivative of said second Bronsted acid is a heterogeneous azeotrope of the entrainer and the second Brønsted acid, thereby forming a compound of the entrainer and the second Brønsted acid. Phase separation of the alkenyl derivative occurs in the condensation of the azeotrope after distillation or wherein the entrainer is the alkenyl derivative of the second Bronsted acid and the alkenyl derivative of the second Bronsted acid; of the first Brønsted acid by forming an azeotrope with said alkenyl derivative of the first Brønsted acid. separating and recovering the mixture of derivatives described above from the transvinylation reaction mixture; The method described in claim 1. 3. After the transvinylation reaction and before the addition of the entrainer, the transvinylation reaction The mixture is fed to a separation zone to combine the catalyst and the second Brønsted acid in the transvinylation reaction. 2. The method of claim 1, comprising separating from other components of the reaction mixture. 4. produced by the transvinylation reaction, and the second Brønsted acid Alke of the first Brønsted acid remaining after azeotropic distillation of the rukenyl derivative 2. The method of claim 1, wherein the conjugate acid of the nil derivative is recovered. 5. The method according to claim 1, wherein the alkenyl-forming derivative is a compound of the following formula: Law: R-(CH2)n-CR2=CR0R1 (wherein R is carboxy, amide, aromatic xy, and alkoxy, n is 0 or 1, and R0, R1 and R2 each independently represents hydrogen, alkyl of 1 to about 12 carbon atoms, cycloalkyl, alkyl, lyles and alkyl ethers). 6. The alkenyl-producing derivatives include allyl pivalate, allyl benzoate, Allyl propionate, allyl crotonate, allyl methacrylate, allylua Acrylate, methallyl benzoate, methallyl pivalate, methallyl propione and mixtures thereof. Method described. 7. Triplication of the vinyl derivative of the first Brønsted acid with the second Brønsted acid 1. A method for producing a vinyl derivative of Brønsted acid by a vinylation reaction, the method comprising: Said vinyl derivative of said first Bronsted acid is added to said vinyl derivative of said first Brønsted acid in the presence of a catalyst. 2 with a Brønsted acid and an entrainer added to the transvinylation reaction mixture. , and the vinyl derivative of said second Brønsted acid is truncated by azeotropic distillation. said catalyst is recovered as a product of transvinylation. of the second Brønsted acid. the vinyl derivative and the conjugate acid of the vinyl derivative of the first Bronsted acid. forming a reaction mixture containing said entrainer at least in said second blend step; The above-mentioned production method is capable of forming an azeotrope with the above-mentioned vinyl derivative of the do-acid. Law. 8. the vinyl derivative of the entrainer and the second Bronsted acid, a conjugate having a boiling point lower than the boiling point of the conjugate acid of the vinyl derivative of the first Brønsted acid; or before said entrainer and said second Brønsted acid. The vinyl derivative of forming an azeotrope having a higher boiling point, or said entrainer and said second The aforementioned vinyl derivatives of Brønsted acids form a heterogeneous azeotrope, which phase separation of said vinyl derivative of said entrainer and said second Brønsted acid. occurs in the condensation of the azeotrope after distillation, or said entrainer is present in said second azeotrope. before said vinyl derivative of Brønsted acid and said first Brønsted acid. A mixture of the above derivatives is converted into a transvinyl derivative by forming an azeotrope with the above vinyl derivative. 8. The method of claim 7, wherein the method is separated and recovered from the reaction mixture. 9. After the transvinylation reaction and before the addition of the entrainer, the transvinylation reaction The mixture is fed to a separation zone to combine the catalyst and the second Brønsted acid in the transvinylation reaction. 8. The method of claim 7, comprising separating from other components of the reaction mixture. 10. produced by the transvinylation reaction and of the second Brønsted acid. The vinyl derivative of the first Brønsted acid remaining after azeotropic distillation of the vinyl derivative 8. The method of claim 7, wherein the conjugate acid of the conductor is recovered. 11. said vinyl derivative of said first Bronsted acid has 1 to about 12 carbon atoms; a vinyl derivative of a carboxylic acid having a child, and the second Brønsted 8. The method of claim 7, wherein the acid is a carboxylic acid having from 1 to about 7 carbon atoms. 12. said vinyl derivative of said first Bronsted acid is vinyl acetate; , the second Brønsted acid is propionic acid, acrylic acid, methacrylic acid , butyric acid, isobutyric acid, 2-methylbutyric acid, valeric acid, benzoic acid, cyclohexanoic acid, an acid selected from the group consisting of clohexenoic acid, pivalic acid and crotonic acid; The method according to claim 11. 13. 8. The method of claim 7, wherein the entrainer is water. 14. Transvinyl esters of carboxylic acids having from 1 to about 12 carbon atoms a first carbon having from 1 to about 12 carbon atoms; Presence of a catalyst capable of catalyzing the transvinylation reaction of vinyl derivatives of acids said second carboxylic acid having from 1 to about 7 carbon atoms. While forming the vinyl derivative of the bonic acid and distilling the said reaction product, water is A vinyl derivative of at least the second carboxylic acid is added to the vinylation reaction mixture. added to the transvinylation reaction mixture in sufficient quantity to form an azeotrope with Then, the vinyl derivative of the second carboxylic acid is trans-vibrated by azeotropic distillation. The above-mentioned production method, which comprises recovering as a product of the nylation reaction. 15. said 1 to about 7 carbon atoms produced by said transvinylation reaction; said vinyl derivative of a carboxylic acid having 15. The method of claim 14, wherein the second carboxylic acid is pivalic acid. 16. said vinyl derivative of said first carboxylic acid is vinyl acetate; the catalyst is a ruthenium-based catalyst, and the second carboxylic acid is a propylene-based catalyst; Hydronic acid, acrylic acid, methacrylic acid, butyric acid, isobutyric acid, 2-methylbutyric acid, valeric acid , benzoic acid, cyclohexanoic acid, cyclohexenoic acid, pivalic acid and crotonic acid 15. The method according to claim 14, wherein the carboxylic acid is selected from the group consisting of: 17. After the transvinylation reaction and before the addition of the entrainer, the transvinylation reaction The reaction mixture is fed to a separation zone to transvinylate the catalyst and the second Brønsted acid. 15. The method of claim 14, comprising separating from other components of the reaction mixture. 18. Claims 7 and 14, wherein the vinyl-forming derivative is a compound of the formula: How to install: R-CR2=CR0R1 (wherein R is carboxy, amide, alloxy, and alkoxy, R0, R 1 and R2 are each independently hydrogen, alkyl of 1 to about 12 carbon atoms, cycloa one of alkyl, aryl and alkyl ether). 19. The above vinyl-forming derivatives include vinyl pivalate, vinyl methacrylate, vinyl Nyl acrylate, vinyl benzoate, vinyl propionate and vinyl chloride 18. The compound selected from the group consisting of tonate and mixtures thereof. The method described in.