Synthetic method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate

Abstract

The invention discloses a synthetic method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate, ethoxylated tetrahydrofurfuryl alcohol and acrylic acid are subjected to esterification reaction in the presence of a solvent and a catalyst to obtain ethoxylated tetrahydrofurfuryl alcohol acrylate, the content of tetrahydrofurfuryl alcohol acrylate in the ethoxylated tetrahydrofurfuryl alcohol acrylate is lower than 0.1%, and the content of tetrahydrofurfuryl alcohol acrylate in the ethoxylated tetrahydrofurfuryl alcohol acrylate is lower than 0.1%. And the number of ethoxy is 1-4. In the modified ethoxylated tetrahydrofurfuryl alcohol acrylate, the content of tetrahydrofurfuryl alcohol acrylate is lower than 0.1%, so that the toxicity and irritation are effectively reduced, the EO number is controlled to be 1-4, and the dissolving property of a monomer is also effectively maintained.

Description

Technical Field

[0001] The invention relates to a method for synthesizing tetrahydrofurfuryl alcohol acrylate derivatives, in particular to a method for synthesizing modified ethoxylated tetrahydrofurfuryl alcohol acrylate. Background Art

[0002] Tetrahydrofurfuryl alcohol acrylate (THFA), CAS No.: 2399-48-6, can be used as a monomer diluent in ultraviolet (UV) curing products. Its special cyclic ether structure makes it have better adhesion to most substrates than other monofunctional monomers. It also has low shrinkage, strong weather resistance, strong wear resistance and strong water resistance. Therefore, it is widely used in light-cured adhesives, coatings, inks and other fields. However, its homopolymer Tg is -20℃, and due to its low molecular weight, it is easy to volatilize, has a slightly unpleasant odor, and is also quite irritating. Summary of the invention

[0003] The invention provides a method for synthesizing modified ethoxylated tetrahydrofurfuryl alcohol acrylate. The modified ethoxylated tetrahydrofurfuryl alcohol acrylate is synthesized by reacting ethoxylated tetrahydrofurfuryl alcohol with acrylic acid, thereby reducing the irritating odor of the product.

[0004] Specifically, the synthesis method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate comprises the following steps: esterifying ethoxylated tetrahydrofurfuryl alcohol with acrylic acid in the presence of a solvent and a catalyst to obtain ethoxylated tetrahydrofurfuryl alcohol acrylate (THFEOA).

[0005] Furthermore, the content of tetrahydrofurfuryl alcohol acrylate in the target product is controlled to be less than 0.1%, which effectively reduces toxicity and irritation. At the same time, the EO number is controlled to be 1-4, which also effectively maintains the solubility of the monomer.

[0006] The synthesis route is as follows:

[0007]

[0008] Among them, R=H or CH3, n=1,2,3,4.

[0009] The solvent is one or more of cyclohexane, toluene, heptane and petroleum ether.

[0010] The molar ratio of acrylic acid to ethoxylated tetrahydrofurfuryl alcohol is 1.05-1.3:1, preferably 1.1-1.2:1.

[0011] The catalyst is preferably sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid or the like.

[0012] In one embodiment of the present invention, ethoxylated tetrahydrofurfuryl alcohol is shown in the following formula:

[0013]

[0014] The preparation of ethoxylated tetrahydrofurfuryl alcohol is as follows: tetrahydrofurfuryl alcohol and ethylene oxide are used as main raw materials, reacted in a nitrogen atmosphere and in the presence of a catalyst until the pressure in the reactor remains constant, and the reaction materials are separated by distillation in a distillation tower to obtain synthetic ethoxylated tetrahydrofurfuryl alcohol.

[0015] Wherein, the reaction temperature is 80-150°C, preferably 100-140°C.

[0016] The molar number of ethylene oxide is 1-10 times that of tetrahydrofurfuryl alcohol, preferably 1-5 times. Finally, ethoxylated tetrahydrofurfuryl alcohol with a molar number of 1-4 is obtained. When the molar number is too low, the conversion rate of residual tetrahydrofurfuryl alcohol is low. When the molar number is large, too much ethoxylation will reduce the solubility of the later acrylate product and affect the performance of the monomer.

[0017] The catalyst is lithium hydroxide, strong calcium oxide, sodium hydroxide, or potassium hydroxide.

[0018] In the distillation separation of the distillation tower, the raw material tetrahydrofurfuryl alcohol and the ethoxylated tetrahydrofurfuryl alcohol with the molar number of 1, 2, 3, and 4 are distilled out in sequence, and the ethoxylated tetrahydrofurfuryl alcohol with the large molar number of the heavy component at the bottom of the kettle cannot be distilled out. The tetrahydrofurfuryl alcohol distilled out first and the ethoxylated tetrahydrofurfuryl alcohol with the large molar number of the bottom of the kettle can be returned to the front ethoxylation reactor as raw materials for rearrangement reaction.

[0019] Advantages of the present invention:

[0020] 1. The present invention synthesizes ethoxylated tetrahydrofurfuryl alcohol with a molar number of 1-4, which is used to synthesize ethoxylated tetrahydrofurfuryl alcohol acrylate with acrylic acid, thereby effectively maintaining the solubility of the monomer.

[0021] 2. The high residual tetrahydrofurfuryl alcohol will lead to a high content of tetrahydrofurfuryl alcohol acrylate in the subsequent acrylate, which is highly irritating and cannot achieve the purpose of reducing toxicity and modification. The ethoxylated tetrahydrofurfuryl alcohol synthesized by the present invention controls the residual tetrahydrofurfuryl alcohol to be less than 0.1%.

[0022] 3. The present invention can obtain ethoxylated tetrahydrofurfuryl alcohol with a molar number of 1-4 and a yield of 85%.

[0023] 4. Since the residual amount of tetrahydrofurfuryl alcohol in the ethoxylated tetrahydrofurfuryl alcohol synthesized by the present invention is less than 0.1%, the content of tetrahydrofurfuryl alcohol acrylate in the target product ethoxylated tetrahydrofurfuryl alcohol acrylate synthesized subsequently is less than 0.1%, which effectively reduces the toxicity and irritation. At the same time, since the EO number is in the range of 1-4, the solubility of the monomer is also effectively maintained. Specific embodiments

[0024] Example 1 Preparation of ethoxylated tetrahydrofurfuryl alcohol with a mole of 1

[0025]

[0026] With tetrahydrofurfuryl alcohol and ethylene oxide as main raw materials, ethoxylation reaction is firstly carried out to obtain ethoxylated tetrahydrofurfuryl alcohol intermediate.

[0027] Synthesis steps:

[0028] 1) First replace the air in the kettle with nitrogen.

[0029] 2) Then, tetrahydrofurfuryl alcohol was added into the autoclave, and lithium hydroxide as a catalyst was added in an amount of 0.2%.

[0030] 3) Turn on the bottom pump of the kettle to heat the tetrahydrofurfuryl alcohol externally to 130-135°C.

[0031] 4) Add ethylene oxide in an amount twice the molar number of tetrahydrofurfuryl alcohol into the reactor.

[0032] 5) React until the pressure in the reactor remains constant, remove the residual ethylene oxide by negative pressure, cool down, add acid to neutralize the catalyst, filter, and obtain a filtrate.

[0033] 6) The filtrate enters a distillation tower for distillation and separation, and the raw material tetrahydrofurfuryl alcohol and ethoxylated tetrahydrofurfuryl alcohol with a mole number of 1 are distilled out in turn, and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number of heavy components at the bottom of the kettle cannot be distilled out. The residual amount of tetrahydrofurfuryl alcohol in the ethoxylated tetrahydrofurfuryl alcohol with a mole number of 1 is less than 0.1%.

[0034] Distillation separation conditions:

[0035] The fraction with a pressure of -95KPA and a gas phase temperature below 120°C is used as the raw material of unreacted tetrahydrofurfuryl alcohol; this fraction accounts for 22%.

[0036] The fraction with a pressure of -95KPA and a gas phase temperature of 120°C-180°C is the target product, ethoxylated tetrahydrofurfuryl alcohol, which is the raw material for the esterification reaction; this fraction accounts for 65%.

[0037] When the gas phase temperature is higher than 180°C, the distillation can be stopped and the bottoms can be returned to the ethoxylation reactor as raw materials; this distillate accounts for 13%.

[0038] The tetrahydrofurfuryl alcohol distilled out first and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number in the bottom of the kettle can be returned to the front ethoxylation reactor as raw materials for rearrangement reaction.

[0039] Example 2 Preparation of ethoxylated tetrahydrofurfuryl alcohol with a molar number of 2

[0040] 1) First replace the air in the kettle with nitrogen.

[0041] 2) Then, tetrahydrofurfuryl alcohol was added into the autoclave, and potassium hydroxide as a catalyst was added in an amount of 0.2%.

[0042] 3) Turn on the bottom pump of the kettle to heat the tetrahydrofurfuryl alcohol externally to 130-135°C.

[0043] 4) Add ethylene oxide in an amount twice the molar number of tetrahydrofurfuryl alcohol into the reactor.

[0044] 5) reacting until the pressure in the reactor remains constant, removing the residual ethylene oxide by negative pressure, cooling, adding acid to neutralize the catalyst, filtering, and obtaining ethoxylated tetrahydrofurfuryl alcohol with a molar number of 2.

[0045] 6) The filtrate enters a distillation tower for distillation and separation, and the raw material tetrahydrofurfuryl alcohol and ethoxylated tetrahydrofurfuryl alcohol with a mole number of 2 are distilled out in turn, and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number of heavy components at the bottom of the kettle cannot be distilled out. The residual amount of tetrahydrofurfuryl alcohol in the ethoxylated tetrahydrofurfuryl alcohol with a mole number of 2 is less than 0.1%.

[0046] Distillation separation conditions:

[0047] The fraction with a pressure of -95KPA and a gas phase temperature below 120°C is used as the raw material of unreacted tetrahydrofurfuryl alcohol; this fraction accounts for 14%.

[0048] The fraction with a pressure of -95KPA and a gas phase temperature of 120°C-180°C is used as the raw material for our target product, ethoxylated tetrahydrofurfuryl alcohol, i.e., the raw material for the esterification reaction; this fraction accounts for 78%.

[0049] When the gas phase temperature is higher than 180°C, the distillation can be stopped and the bottoms can be returned to the ethoxylation reactor as raw materials; this fraction accounts for 8%.

[0050] The tetrahydrofurfuryl alcohol distilled out first and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number in the bottom of the kettle can be returned to the front ethoxylation reactor as raw materials for rearrangement reaction.

[0051] Example 3 Preparation of 3 moles of ethoxylated tetrahydrofurfuryl alcohol

[0052] 1) First replace the air in the kettle with nitrogen.

[0053] 2) Then, tetrahydrofurfuryl alcohol was added into the autoclave, and calcium hydroxide as a catalyst was added in an amount of 0.2%.

[0054] 3) Turn on the bottom pump to heat tetrahydrofurfuryl alcohol externally to 130-135°C

[0055] 4) Add ethylene oxide in an amount twice the molar number of tetrahydrofurfuryl alcohol into the reactor.

[0056] 5) reacting until the pressure in the reactor remains constant, removing the residual ethylene oxide by negative pressure, cooling, adding acid to neutralize the catalyst, filtering, and obtaining 3 moles of ethoxylated tetrahydrofurfuryl alcohol.

[0057] 6) The filtrate enters a distillation tower for distillation and separation, and the raw material tetrahydrofurfuryl alcohol and ethoxylated tetrahydrofurfuryl alcohol with a mole number of 3 are distilled out in turn, and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number of heavy components at the bottom of the kettle cannot be distilled out. The residual amount of tetrahydrofurfuryl alcohol in the ethoxylated tetrahydrofurfuryl alcohol with a mole number of 3 is less than 0.1%.

[0058] Distillation separation conditions:

[0059] The fraction with a pressure of -95KPA and a gas phase temperature below 120°C is used as the raw material of unreacted tetrahydrofurfuryl alcohol; this fraction accounts for 33%.

[0060] The fraction with a pressure of -95KPA and a gas phase temperature of 120°C-180°C is used as the raw material for our target product, ethoxylated tetrahydrofurfuryl alcohol, i.e., the raw material for the esterification reaction; this fraction accounts for 62%.

[0061] When the gas phase temperature is higher than 180°C, the distillation can be stopped and the bottoms can be returned to the ethoxylation reactor as raw materials; this fraction accounts for 5%.

[0062] The tetrahydrofurfuryl alcohol distilled out first and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number in the bottom of the kettle can be returned to the front ethoxylation reactor as raw materials for rearrangement reaction.

[0063] Example 4 Preparation of 4 moles of ethoxylated tetrahydrofurfuryl alcohol

[0064] 1) First replace the air in the kettle with nitrogen.

[0065] 2) Then, tetrahydrofurfuryl alcohol was added into the autoclave, and sodium hydroxide as a catalyst was added in an amount of 0.2%.

[0066] 3) Turn on the bottom pump of the kettle to heat the tetrahydrofurfuryl alcohol externally to 130-135°C.

[0067] 4) Add ethylene oxide in an amount twice the molar number of tetrahydrofurfuryl alcohol into the reactor.

[0068] 5) reacting until the pressure in the reactor remains constant, removing the residual ethylene oxide by negative pressure, cooling, adding acid to neutralize the catalyst, filtering, and obtaining ethoxylated tetrahydrofurfuryl alcohol with a molar number of 4.

[0069] 6) The filtrate enters a distillation tower for distillation and separation, and the raw material tetrahydrofurfuryl alcohol and ethoxylated tetrahydrofurfuryl alcohol with a mole number of 1 are distilled out in turn, and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number of heavy components at the bottom of the kettle cannot be distilled out. The residual amount of tetrahydrofurfuryl alcohol in the ethoxylated tetrahydrofurfuryl alcohol with a mole number of 4 is less than 0.1%.

[0070] Distillation separation conditions:

[0071] The fraction with a pressure of -95KPA and a gas phase temperature below 120°C is used as the raw material of unreacted tetrahydrofurfuryl alcohol; this fraction accounts for 42%.

[0072] The fraction with a pressure of -95KPA and a gas phase temperature of 120°C-180°C is used as the raw material for our target product, ethoxylated tetrahydrofurfuryl alcohol, i.e., the raw material for the esterification reaction; this fraction accounts for 56.5%.

[0073] When the gas phase temperature is higher than 180°C, the distillation can be stopped and the bottoms can be returned to the ethoxylation reactor as raw materials; this fraction accounts for 1.5%.

[0074] The tetrahydrofurfuryl alcohol distilled out first and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number in the bottom of the kettle can be returned to the front ethoxylation reactor as raw materials for rearrangement reaction.

[0075] Embodiment 5

[0076] The ethoxylated tetrahydrofurfuryl alcohol obtained in Example 1 was used as a raw material, and cyclohexane, acrylic acid and sulfuric acid as a catalyst were added in sequence to carry out an esterification reaction. After the reaction was completed, the solvent cyclohexane was removed by neutralization and separation to obtain low color number clear ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA.

[0077] The molar ratio of acrylic acid to ethoxylated tetrahydrofurfuryl alcohol is 1.05:1.

[0078] In ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA, the content of tetrahydrofurfuryl alcohol acrylate is less than 0.1%, and the EO number is 1. Different catalysts will not affect the EO number in esterification. It mainly affects the chromaticity, reaction time, yield, etc.; the EO number has been fixed in the first step of ethoxylation reaction distillation;

[0079] Embodiment 6

[0080] The ethoxylated tetrahydrofurfuryl alcohol obtained in Example 2 was used as a raw material, and cyclohexane, acrylic acid and a catalyst methanesulfonic acid were added in sequence to carry out an esterification reaction. After the reaction was completed, the solvent cyclohexane was removed by neutralization and separation to obtain low color number clear ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA.

[0081] The molar ratio of acrylic acid to ethoxylated tetrahydrofurfuryl alcohol is 1.05:1.

[0082] In the ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA, the content of tetrahydrofurfuryl alcohol acrylate is less than 0.1%, and the EO number is 2.

[0083] Embodiment 7

[0084] The ethoxylated tetrahydrofurfuryl alcohol obtained in Example 3 was used as a raw material, and cyclohexane, acrylic acid and a catalyst were added in sequence to carry out an esterification reaction. After the reaction was completed, the solvent cyclohexane was removed by neutralization and separation to obtain low color number clear ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA.

[0085] The molar ratio of acrylic acid to ethoxylated tetrahydrofurfuryl alcohol is 1.05:1.

[0086] In the ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA, the content of tetrahydrofurfuryl alcohol acrylate is less than 0.1%, and the EO number is 3.

[0087] Embodiment 8

[0088] The ethoxylated tetrahydrofurfuryl alcohol obtained in Example 4 was used as a raw material, and cyclohexane, acrylic acid and a catalyst p-toluenesulfonic acid were added in sequence to carry out an esterification reaction. After the reaction was completed, the solvent cyclohexane was removed by neutralization and separation to obtain low color number clear ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA.

[0089] The molar ratio of acrylic acid to ethoxylated tetrahydrofurfuryl alcohol is 1.05:1.

[0090] In the ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA, the content of tetrahydrofurfuryl alcohol acrylate is less than 0.1%, and the molar number of EO is 4.

[0091] Comparative Example 1

[0092] Take the large mole number of ethoxylated tetrahydrofurfuryl alcohol in Example 1 as a raw material, add cyclohexane, acrylic acid and catalyst sulfuric acid in sequence, carry out esterification reaction, and after the reaction is completed, remove the solvent cyclohexane by neutralization and separation to obtain low color number clear ethoxylated tetrahydrofurfuryl alcohol acrylate THFEOA.

[0093] Implementations five to eight mainly reflect different product colors and yields, and their performance characteristics are the same.

[0094] The performance characterization of the ethoxylated tetrahydrofurfuryl alcohol acrylate of Examples 5 to 8 and Comparative Example 1:

[0095]

[0096]

[0097] By ethoxylating tetrahydrofurfuryl alcohol acrylate, the THFEOA obtained has greatly reduced odor and irritation, and the viscosity of the monomer does not increase much, which does not affect the solubility of the formula. In addition, the curing rate is not affected and the shrinkage rate of curing is effectively reduced, improving the performance.

Claims

1. A method for synthesizing modified ethoxylated tetrahydrofurfuryl alcohol acrylate, characterized in that: Ethoxylated tetrahydrofurfuryl alcohol and acrylic acid are subjected to an esterification reaction in the presence of a solvent and a catalyst to obtain ethoxylated tetrahydrofurfuryl alcohol acrylate, wherein the content of tetrahydrofurfuryl alcohol acrylate in the ethoxylated tetrahydrofurfuryl alcohol acrylate is less than 0.1%, and the number of ethoxy groups is 1-4; Among them, R=H or CH3, n=1,2,3,4.

2. The synthetic method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 1, characterized in that: The solvent is one or more of cyclohexane, toluene, heptane and petroleum ether.

3. The synthetic method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 1, characterized in that: The molar ratio of acrylic acid to ethoxylated tetrahydrofurfuryl alcohol is 1.05-1.3:

1.

4. The synthetic method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 1, characterized in that: The molar ratio of acrylic acid to ethoxylated tetrahydrofurfuryl alcohol is 1.1-1.2:

1.

5. The synthetic method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 1, characterized in that: The catalyst is preferably sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid or methanesulfonic acid.

6. The synthetic method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 1, characterized in that: The ethoxylated tetrahydrofurfuryl alcohol is shown in the following formula: The preparation method is as follows: tetrahydrofurfuryl alcohol and ethylene oxide are used as main raw materials, react in a nitrogen atmosphere and in the presence of a catalyst until the pressure in the reactor remains constant, and the reaction materials are separated by distillation in a distillation tower to obtain synthetic ethoxylated tetrahydrofurfuryl alcohol.

7. The method for synthesizing modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 6, characterized in that: The reaction temperature is 80-150°C.

8. The method for synthesizing modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 6, characterized in that: The mole number of the ethylene oxide is 1-10 times that of tetrahydrofurfuryl alcohol.

9. The synthetic method of modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 6, characterized in that: The catalyst is lithium hydroxide, strong calcium oxide, sodium hydroxide, or potassium hydroxide.

10. The method for synthesizing modified ethoxylated tetrahydrofurfuryl alcohol acrylate according to claim 6, characterized in that: In the distillation separation of the distillation tower, the raw material tetrahydrofurfuryl alcohol and the ethoxylated tetrahydrofurfuryl alcohol with a mole number of 1-4 are distilled out in sequence, and the heavy component at the bottom of the kettle is the ethoxylated tetrahydrofurfuryl alcohol with a large mole number; the tetrahydrofurfuryl alcohol distilled out first and the ethoxylated tetrahydrofurfuryl alcohol with a large mole number at the bottom of the kettle are returned to the front ethoxylation reactor as raw materials for rearrangement reaction.

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