JP5213415B2 - Triester vinyl ether and process for producing the same - Google Patents

Description

  The present invention relates to a novel vinyl ether and a production method and use thereof, and more specifically, for example, use of ink, paint, resist, color filter and the like, and raw materials for adhesives, plate making materials, sealants, image forming agents, and surfactants. The present invention relates to a triester vinyl ether that is useful as a raw material for a polymer composition having excellent curability, adhesion, transparency in the ultraviolet light region, and rigidity, or as a crosslinking agent and various synthetic reagents.

  The triester vinyl ether according to the present invention is a novel compound which is not described in a chemical abstract and is not found in other literatures as far as the present inventors know.

  An object of the present invention is to provide a triester vinyl ether and a production method and use thereof.

  According to the invention, the formula (I):

(In the formula, n represents an integer of 2 to 10)
The triester vinyl ether represented by these and its manufacturing method and use are provided.

  The triester vinyl ether (I) according to the present invention has a low odor, low volatility, low skin irritation, low toxicity, and excellent curability, adhesion, and transparency in the ultraviolet region. It is a useful compound as a raw material. The triester vinyl ether (I) of the present invention not only has three reactive vinyl ether groups, but also has a highly polar ester, a less polar cyclohexane ring and a skeleton of a moderately long alkyl group in the molecule. In addition, there is an advantage that the physical properties can be freely changed by appropriately selecting the raw material vinyl ether.

  Further, the compound of the present invention has a feature that it is liquid at room temperature within the range of n number defined by the formula (I), is easy to handle, and has high compatibility with various materials such as a polymerization catalyst. Furthermore, for example, the known formula (IV) described in “Macromolecular Symposia (2002), 187, 225-234” or “RadTech Report (1998), 12 (2), 37-48”:

Compared with the trimellitic acid derivative represented by the formula, the triester vinyl ether (I) of the present invention does not contain a benzene ring (a conjugated skeleton) in the molecule. There are features such as being able to ensure, and the disadvantages can be solved.

  The triester vinyl ether (I) according to the present invention can be produced by the reaction formula described below, and can be used with high selectivity by adopting appropriate raw materials in spite of using a two-step reaction. Can be prepared.

  Hereinafter, the present invention will be described in more detail. The triester vinyl ether (I) according to the present invention can be prepared according to the following reaction formula.

(In the formula, R ₁ , R ₂ and R ₃ represent OH, or R ₁ and R ₂ represent O, R ₃ represents OH, and n represents an integer of 2 to 10.)

Specific names of the compound (I) according to the present invention are as follows.
n = 2: 1,2,4-cyclohexanetricarboxylic acid triethyl ester trivinyl ether (also known as: 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) ethyl] ester)
n = 3: 1,2,4-cyclohexanetricarboxylic acid tripropyl ester trivinyl ether (also known as: 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) propyl] ester)
n = 4: 1,2,4-cyclohexanetricarboxylic acid tributyl ester trivinyl ether (also known as: 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) butyl] ester)
n = 5: 1,2,4-cyclohexanetricarboxylic acid tripentyl ester trivinyl ether (also known as: 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) pentyl] ester)
n = 6: 1,2,4-cyclohexanetricarboxylic acid trihexyl ester trivinyl ether (also known as 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) hexyl] ester)
n = 7: 1,2,4-cyclohexanetricarboxylic acid triheptyl ester trivinyl ether (also known as 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) heptyl] ester)
n = 8: 1,2,4-cyclohexanetricarboxylic acid trioctyl ester trivinyl ether (also known as: 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) octyl] ester)
n = 9: 1,2,4-cyclohexanetricarboxylic acid trinonyl ester trivinyl ether (also known as: 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) nonyl] ester)
n = 10: 1,2,4-cyclohexanetricarboxylic acid tridecyl ester trivinyl ether (also known as: 1,2,4-cyclohexanetricarboxylic acid tris [4- (ethynyloxy) decyl] ester)

Specific methods for synthesizing the compound (I) according to the present invention include, for example, the following methods.
For example, n-butyl alcohol and cyclohexanetricarboxylic acid ester or anhydride thereof are put in a glass reaction vessel, and concentrated sulfuric acid is added as a reaction catalyst. As addition amount of n-butyl alcohol, it is preferable to carry out by 10.0-20.0 mol with respect to 1.0 mol of cyclohexane tricarboxylic acid ester or its anhydride, and 14.0-16.0 mol is more preferable. The amount of concentrated sulfuric acid added is preferably 0.1 to 1.0 mol, more preferably 0.4 to 0.6 mol, relative to 1.0 mol of cyclohexanetricarboxylic acid ester or anhydride thereof. Next, the reaction mixture is heated to reflux and reacted while draining water to produce cyclohexanetricarboxylic acid tri-n-butyl ester as an intermediate. As reaction temperature, 110-125 degreeC is preferable, More preferably, it is 115-120 degreeC. The reaction time is preferably 10 to 20 hours, more preferably 15 to 17 hours.

  After completion of the reaction, the mixture is washed with a weak alkaline aqueous solution and separated for neutralization. Furthermore, in order to remove the remaining catalyst, unreacted raw materials, reaction intermediates and by-products, it is preferable to wash again with water, and then separate, dry and concentrate.

  Specific examples of weak alkalis for neutralization include sodium hydrogen carbonate and sodium carbonate. Sodium hydrogen carbonate is preferred from the standpoint of efficiency. As specific examples of desiccants for dehydration treatment, anhydrous inorganic salts such as magnesium sulfate, sodium sulfate, and calcium chloride and molecular sieves can be used. However, considering the efficiency of dehydration and low solubility in this extract From the viewpoint of quality, anhydrous inorganic salts are desirable, and anhydrous magnesium sulfate can be particularly preferably used.

  Next, for example, cyclohexanetricarboxylic acid tri-n-butyl ester is placed in a glass reaction vessel, and an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium butoxide is added as a reaction catalyst, Further vinyl ether is added. The addition amount of the alkali metal alkoxide is preferably 0.1 to 0.5 mol, more preferably 0.2 to 0.3 mol, relative to 1.0 mol of cyclohexanetricarboxylic acid tri-n-butyl ester. As addition amount of vinyl ether, it is preferable to carry out by 3.0-20.0 mol with respect to 1.0 mol of cyclohexane tricarboxylic acid tri-n-butyl ester, and 3.3-10.0 mol is more preferable. Next, when the reaction is carried out while raising the temperature while passing an inert gas such as nitrogen, cyclohexanetricarboxylic acid ester vinyl ether, which is a novel compound of the present invention, is produced. As reaction temperature, 90-140 degreeC is preferable, More preferably, it is 110-120 degreeC. The reaction time is preferably 2 to 10 hours, more preferably 3 to 5 hours.

Further, after the reaction, it is preferable to dilute with a solvent, wash with water to remove the remaining catalyst, unreacted raw materials, reaction intermediates and by-products, and then dry and concentrate. Specific examples of the solvent for dilution can include organic solvents such as hexane, benzene, toluene, xylene, methyl acetate, and ethyl acetate, but ethyl acetate is preferable from the viewpoint of efficiency.
On the other hand, as specific examples of desiccants for dehydration treatment, anhydrous inorganic salts such as magnesium sulfate, sodium sulfate, calcium chloride, etc. can be used, but quality considering the efficiency of dehydration and low solubility in this extract. From the upper surface, anhydrous magnesium sulfate can be particularly preferably used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.

Example 1
A 500 ml glass four-necked flask equipped with a stirrer, a condenser and a moisture meter is charged with 296 g of n-butyl alcohol and 39.7 g of cyclohexanetricarboxylic acid anhydride (purity 98.4%, 0.20 mol). 9.8 g of sulfuric acid (purity 98.0%, 0.10 mol) was added as a catalyst. Next, the temperature was raised until the internal temperature reached 116 ° C., and the reaction was carried out while draining water for 15 hours after the start of reflux. After completion of the reaction, the mixture was neutralized with a saturated sodium hydrogen carbonate solution and separated. Furthermore, it wash | cleaned with 200 ml of water, and after liquid separation, anhydrous magnesium sulfate was added as a desiccant and it filtered. Thereafter, the reaction solution was concentrated under reduced pressure to obtain 69.7 g of an ester. As a result of high performance liquid chromatography (HPLC) analysis, the purity of the ester was 97.5%. The yield of this product was 89.7% based on the raw material cyclohexanetricarboxylic anhydride.

Next, 38.4 g (purity 97.5%, 0.098 mol) of the above ester was charged into a 200 ml glass four-necked flask equipped with a stirrer, a cooler and a gas introduction tube, and sodium methoxide 1 as a catalyst. 0.5 g (purity 90.0%, 0.025 mol) was added. Then 61.0 g of hydroxybutyl vinyl ether (purity 99.0 g, 0.52 mol) was added. Next, the temperature was raised until the internal temperature reached 120 ° C., and the reaction was carried out for 3 hours after the reaction temperature reached 120 ° C. During this time, nitrogen gas was successively passed to extract the fraction. After completion of the reaction, the reaction mixture was dissolved in 150 ml of ethyl acetate, and after washing with water, anhydrous magnesium sulfate was added as a desiccant, followed by filtration. Thereafter, the reaction solution was concentrated under reduced pressure to obtain 35.4 g of ester vinyl ether.
As a result of high performance liquid chromatography (HPLC) analysis, the purity of the ester vinyl ether was 89.2%. The yield of this product was 63.3% based on the starting ester. Moreover, when 1.2% was refine | purified with the column chromatograph, 1.1 g of ester vinyl ether (1,2,4-cyclohexane tricarboxylic acid tributyl ester trivinyl ether) with a purity of 95.7% was obtained. The characteristic absorption value of ¹ H-NHR analysis of the obtained ester vinyl ether was as shown in Table I. Further, FIG. 1 shows an NMR chart of the obtained ester vinyl ether, and FIG. 2 shows an IR chart.

Example 2
Into a 200 ml glass four-necked flask equipped with a stirrer, a condenser and a gas introduction tube, was charged 19.2 g (purity 97.5%, 0.049 mol) of the ester obtained in the same manner as in Example 1. As a catalyst, 0.75 g of sodium methoxide (purity 90.0%, 0.012 mol) was added. Then 45.5 g of hydroxyethyl vinyl ether (purity 98.9%, 0.51 mol) was added. Next, the temperature was raised until the internal temperature reached 115 ° C., and the reaction was carried out for 5 hours after the reaction temperature reached 115 ° C. During this time, nitrogen gas was successively passed to extract the fraction.

After completion of the reaction, the reaction mixture was dissolved in 100 ml of ethyl acetate, and after washing with water, anhydrous magnesium sulfate was added as a desiccant, followed by filtration. Thereafter, the reaction solution was concentrated under reduced pressure to obtain 14.0 g of ester vinyl ether. As a result of high performance liquid chromatography (HPLC) analysis, the purity of the ester vinyl ether was 69.4%. The yield of this product was 46.8% based on the starting ester. Of these, 1.2 g was purified by column chromatography to obtain 0.5 g of ester vinyl ether (1,2,4-cyclohexanetricarboxylic acid triethyl ester trivinyl ether) having a purity of 99.2%. The characteristic absorption value of ¹ H-NMR analysis of the obtained ester vinyl ether was as shown in Table II. The NMR chart is shown in FIG. 3, and the IR chart is shown in FIG.

Example 3
In a 100 ml glass four-necked flask equipped with a stirrer, a cooler and a gas introduction tube, 19.2 g (purity 97.5%, 0.049 mol) of the above ester was charged, and 0.75 g of sodium methoxide as a catalyst ( 90.0% purity, 0.012 mol) was added. Then 26.0 g of hydroxyhexyl vinyl ether (purity 87.7%, 0.16 mol) was added. Next, the temperature was raised until the internal temperature reached 120 ° C., and the reaction was carried out for 5 hours after the reaction temperature reached 120 ° C. During this time, nitrogen gas was successively passed to extract the fraction.

After completion of the reaction, the reaction mixture was dissolved in 150 ml of ethyl acetate, and after washing with water, anhydrous magnesium sulfate was added as a desiccant, followed by filtration. Thereafter, the reaction solution was concentrated under reduced pressure to obtain 21.3 g of ester vinyl ether. As a result of high performance liquid chromatography (HPLC) analysis, the purity of the ester vinyl ether was 90.1%. The yield of this product was 66.3% based on the starting ester. Moreover, when 1.0 g was refine | purified in the column chromatograph, 0.2 g of ester vinyl ether (1,2,4-cyclohexanetricarboxylic acid trihexyl ester trivinyl ether) with a purity of 95.5% was obtained.
The characteristic absorption value of ¹ H-NMR analysis of the obtained ester vinyl ether was as shown in Table III. The NMR chart is shown in FIG. 5, and the IR chart is shown in FIG.

Example 4
A 200 ml glass four-necked flask equipped with a stirrer, a cooler, and a moisture determination receiver was charged with 96.2 g of n-butyl alcohol and 14.1 g of cyclohexanetricarboxylic acid (purity 96.2%, 0.063 mol). As a catalyst, 2.4 g of sulfuric acid (purity 98.0%, 0.024 mol) was added. Next, the temperature was raised until the internal temperature reached 116 ° C., and the reaction was carried out while draining water for 15 hours after the start of reflux. After completion of the reaction, the mixture was neutralized with a saturated sodium hydrogen carbonate solution and separated. Furthermore, it wash | cleaned with 50 ml of water, and after liquid separation, anhydrous magnesium sulfate was added as a desiccant and it filtered. Thereafter, the reaction solution was concentrated under reduced pressure to obtain 23.2 g of an ester. As a result of high performance liquid chromatography (HPLC) analysis, the purity of the ester was 98.3%. The yield of this product was 94.5% based on the raw material cyclohexanetricarboxylic acid anhydride.

  Next, 21.1 g (purity 98.3%, 0.054 mol) of the above ester was charged into a 100 ml glass four-necked flask equipped with a stirrer, a cooler, and a gas introduction tube, and sodium methoxide 0 as a catalyst. .83 g (purity 90.0%, 0.014 mol) was added. Subsequently, 33.5 g of hydroxybutyl vinyl ether (purity 99.0%, 0.29 mol) was added. Next, the temperature was raised until the internal temperature reached 120 ° C., and the reaction was carried out for 3 hours after the reaction temperature reached 120 ° C. During this time, nitrogen gas was successively passed to extract the fraction.

  After completion of the reaction, the reaction mixture was dissolved in 55 ml of ethyl acetate, and after washing with water, anhydrous magnesium sulfate was added as a desiccant, followed by filtration. Thereafter, the reaction solution was concentrated under reduced pressure to obtain 20.3 g of ester vinyl ether (1,2,4-cyclohexanetricarboxylic acid tributyl ester trivinyl ether). As a result of high performance liquid chromatography (HPLC) analysis, the purity of the ester vinyl ether was 89.4%. The yield of this product was 56.7% based on the starting ester.

  The novel compound triester vinyl ether (I) of the present invention has low odor, low volatility, low skin irritation, low toxicity, and excellent curability, adhesion, and transparency in the ultraviolet region. It can be expected to have useful properties as a polymerization composition raw material.

2 is an NMR chart of the triester vinyl ether of Example 1. 2 is an IR chart of the triester vinyl ether of Example 1. FIG. 2 is an NMR chart of the triester vinyl ether of Example 2. 2 is an IR chart of the triester vinyl ether of Example 2. FIG. 2 is an NMR chart of the triester vinyl ether of Example 3. 4 is an IR chart of the triester vinyl ether of Example 3. FIG.

Claims (4)

Formula (I):

(In the formula, n represents an integer of 2 to 10)
A compound represented by Formula (II):

The method for producing a compound according to claim 1, comprising reacting the compound represented by formula (I) with hydroxy vinyl ether in the presence of an alkali metal compound.   Use of the compound according to claim 1 as a raw material for electronic materials.   Use of the compound according to claim 1 as an ink raw material.

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