阅读说明：本技术 制备单乙烯基醚的方法 (Process for preparing monovinyl ethers ) 是由 F·比内沃尔德 M·弗尔克特 R·平科斯 于 2019-08-19 设计创作，主要内容包括：本发明涉及一种制备其中R表示具有至少3个碳原子的有机基团的式(I)R-O-CH＝CH-2的单乙烯基醚的方法,所述方法包括：a)使其中R具有上述含义的式(II)R-OH的单羟基化合物在催化剂存在下与乙炔反应以得到包含单乙烯基醚、未转化的单羟基化合物和催化剂的产物混合物,b)向方法步骤a)中获得的产物混合物中加入包含至少一种其中X为包含比R少的碳原子数的烃基的式(III)X-O-2C-的酯基的酯,并使残余单羟基化合物R-OH与酯在催化剂的存在下反应以获得包含至少一种式(IV)R-O-2C-的酯基的酯交换产物和式(V)X-OH的醇,其中R和X具有上述含义,和c)由方法步骤b)之后获得的产物混合物分离单乙烯基醚,任选地随后通过蒸馏纯化单乙烯基醚。(The invention relates to a method for producing an organic radical of formula (I) R-O-CH (CH) wherein R represents an organic radical having at least 3 carbon atoms 2 The method of monovinyl ether of (a), the method comprising: a) reacting a monohydroxy compound of the formula (II) R-OH in which R has the abovementioned meaning with acetylene in the presence of a catalyst to give a product mixture comprising monovinylether, unconverted monohydroxy compound and catalyst, b) adding to the product mixture obtained in process step a) at least one compound selected from the group consisting ofX is a hydrocarbon group having a carbon number smaller than R and is represented by the formula (III) X-O 2 C-, and reacting the residual monohydroxy compound R-OH with the ester in the presence of a catalyst to obtain a catalyst comprising at least one R-O of the formula (IV) 2 C-and an alcohol of the formula (V) X-OH, where R and X have the abovementioned meanings, and C) separating the monovinyl ether from the product mixture obtained after process step b), optionally followed by purification of the monovinyl ether by distillation.)

1. A process for preparing a monovinyl ether of formula I:

R-O-CH＝CH₂，

wherein R represents an organic group having at least 3 carbon atoms,

the method comprises the following steps

a) Reacting a monohydroxy compound of formula II with acetylene in the presence of a catalyst to obtain a product mixture comprising monovinyl ether, unconverted monohydroxy compound, and catalyst:

R-OH

wherein R has the meaning given above,

b) adding to the product mixture obtained in process step a) an ester comprising at least one ester group of the formula III:

X-O₂C-，

wherein X is a hydrocarbon group containing a smaller number of carbon atoms than R,

and reacting the residual monohydroxy compound R-OH with an ester in the presence of a catalyst to obtain a transesterification product comprising at least one ester group of formula IV:

R-O₂C-

and alcohols of the formula V

X-OH

Wherein R and X have the abovementioned meanings, and

c) the monovinyl ether is isolated from the product mixture obtained after process step b), optionally followed by purification of the monovinyl ether by distillation.

2. The process according to claim 1, wherein R in formula I represents a non-aromatic hydrocarbon group having 3 to 10 carbon atoms.

3. The process according to claim 1 or 2, wherein R in formula I is cyclohexyl.

4. A process according to any one of claims 1 to 3 wherein the catalyst is an alkoxide of formula VI:

RO^-M⁺，

wherein R has the above-mentioned meaning, and M⁺Represents a metal cation.

5. The process according to any one of claims 1 to 4, wherein the catalyst is used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the monohydroxy compound.

6. The process according to any one of claims 1 to 5, wherein the product mixture obtained in step a) comprises, based on 100% by weight of the product mixture:

55 to 98.9% by weight of a monovinyl ether of the formula I,

1 to 35% by weight of a monohydroxy compound of the formula II, and

0.1-10 wt% of a catalyst.

7. A process according to any one of claims 1 to 6, wherein X in formula III represents methyl or ethyl.

8. The process according to any of claims 1 to 7, wherein the ester added in step b) comprises one or two ester groups of formula III.

9. The process according to any one of claims 1 to 8, wherein the ester added in step b) is an ester of formula VII:

X-O₂C-Z，

wherein X has the above-mentioned meaning and Z represents a hydrocarbon group having 6 to 20 carbon atoms, or

An ester of formula VIII:

X-O₂C-CO₂-X，

wherein X has the above-mentioned meaning.

10. The process as claimed in any of claims 1 to 8, wherein in step b) an amount of 200 parts by weight of ester per 100 parts by weight of monohydroxy compound of the formula II in the product mixture is added.

Examples

Cyclohexanol (CH) was vinylated with acetylene in the presence of KOH to give a crude product mixture containing 90 wt.% cyclohexyl vinyl ether (CHVE), 6 wt.% CH and 4 wt.% potassium salt of CH.

300g of biodiesel, which is a methyl ester of C16 to C18 fatty acids, were added to 800g of this crude product mixture over a period of 3 hours at 75 ℃ while continuously bubbling 20l/h of nitrogen through the solution to remove the methanol formed. After additional stirring and nitrogen stripping for 2 hours, 1025g of a product mixture containing 86 wt% CHVE, 1 wt% CH, and 13 wt% high boiling products including transesterification products (esters of CH and C16 to C18 fatty acids) was obtained.

The composition of the product mixture was determined by Gas Chromatography (GC) by measuring the area percentage of the corresponding peak.

887g of this product mixture were reacted at 2,5 mbar and 105-125 ℃ at 0,046m²Distillation in a thin film evaporator. 620g of pale yellow product were withdrawn from the top of the thin film evaporator as distillate. The distillate contained 98, 2% CHVE and 0, 3% CH. Also, the composition of the distillate was determined by GC as described above.

The high boilers are removed from the bottom of the thin-film evaporator.

The resulting mixture of CHVE and CH was thereafter fractionated in a 30cm packed column at 100 mbar and a bath temperature of 110 ℃ to give 575g of a colourless liquid containing 99.5% by weight CHVE and 0.4% by weight CH.