CN109912412B - Non-volatile solubilizing diluent and preparation method and application thereof - Google Patents
Non-volatile solubilizing diluent and preparation method and application thereof Download PDFInfo
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- CN109912412B CN109912412B CN201910168443.4A CN201910168443A CN109912412B CN 109912412 B CN109912412 B CN 109912412B CN 201910168443 A CN201910168443 A CN 201910168443A CN 109912412 B CN109912412 B CN 109912412B
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Abstract
The solubilizing diluent is prepared through esterification reaction, has lipophilic ester group, can be mutually soluble with epoxy resin, contains hydrophilic hydroxyl, has low viscosity and high boiling point, is not easy to volatilize, can improve the compatibility of the epoxy resin and a curing agent, and reduces the viscosity of a system; the solubilizing diluent has no VOC emission in the using process and no pollution to the environment, has obvious effect by adding a small amount of solubilizing diluent, has low self viscosity and also has the function of a diluent. The diluent is applied to epoxy resin, can effectively reduce the viscosity of the epoxy resin, and can ensure that the traditional amine curing agent has better compatibility with the bulk E-type epoxy resin. The resin not only dispenses with the use of volatile solvent, but also becomes a part of a resin system, not only does not increase the cost of the resin, but also greatly improves the shock resistance and low-temperature performance of the cured resin.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of chemical synthesis, and particularly relates to a non-volatile solubilizing diluent as well as a preparation method and application thereof.
[ background of the invention ]
Because of its advantages of small shrinkage, good cohesiveness, high strength and mechanical properties, epoxy resin is widely used in high-performance paint, printing ink, adhesive and composite material. The excellent performances of the epoxy resin can be reflected only by the curing and crosslinking reaction of the epoxy resin and the curing agent. The properties of the cured product are greatly different depending on the curing agent. The commonly used room temperature curing agents are mainly amine curing agents. However, such curing agents as 651, 650, T31, etc. have poor compatibility with common E-type epoxy resins, cannot form a uniform system, and directly affect the cured performance. The conventional method is to add a large amount of volatile solvent such as ethanol, butanol, methyl cellosolve, etc. It has been used for many years because it has a function of lowering the viscosity of the system and a function of solubilization. However, with the increasing use of epoxy resins, serious environmental problems, safety problems and health problems are brought. The use of solvent-type resin systems is currently banned in the country on a comprehensive basis.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a non-volatile solubilizing diluent and a preparation method and application thereof; the solvent has lipophilic ester group, can be mutually dissolved with epoxy resin, and contains hydrophilic hydroxyl group, so that the compatibility of the epoxy resin and a curing agent can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a non-volatile solubilizing diluent having the chemical formula:
wherein n is a natural number of 1-12, and m and z are both natural numbers of 1-4; r is H or CH3。
A preparation method of the nonvolatile solubilizing diluent comprises the following steps: mixing phthalic anhydride and fatty alcohol with more than four carbon atoms, heating and uniformly stirring after mixing to form a mixture A; cooling the mixture A, and then adding toluene, dihydric alcohol and p-toluenesulfonic acid to obtain a mixture B; placing the mixture B in a water distribution device, heating and refluxing, monitoring the acid value in the reaction process, and ending the reaction when the acid value is less than 5 to obtain yellow liquid; distilling the yellow liquid under reduced pressure to remove toluene, and dissolving with dichloromethane to obtain a solution C; the solution C was washed to neutrality with sodium bicarbonate, washed with saturated brine, distilled under reduced pressure and the solvent removed to give a pale yellow product as a non-volatile solubilizing diluent.
The invention is further improved in that:
preferably, the mixing molar ratio of phthalic anhydride and four or more carbon aliphatic alcohols is 0.2: (0.2-0.3).
Preferably, the fatty alcohol having four or more carbon atoms is any one of n-butanol, n-octanol, or lauryl alcohol.
Preferably, phthalic anhydride and aliphatic alcohol having four or more carbon atoms are mixed, and then heated to 110 to 140 ℃.
Preferably, after cooling the mixture A, toluene is added, and the ratio of the glycol to the p-toluenesulfonic acid is (100-: (0.3-0.5) mol: (1.5-3) g; wherein the molar ratio of the dihydric alcohol to the phthalic anhydride is (3-5): 2.
preferably, the diol is any one of ethylene glycol, diethylene glycol, hexylene glycol, or propylene glycol.
Preferably, mixture B is heated and refluxed in a water-dividing device, and the temperature is 110 ℃.
Preferably, the solution C is washed to neutrality by sodium bicarbonate with a mass concentration of 5%.
Use of the above non-volatile solubilizing diluent in an epoxy resin system.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a non-volatile solubilizing diluent which is provided with lipophilic ester group, can be mutually soluble with epoxy resin, contains hydrophilic hydroxyl, has low viscosity and higher boiling point, is not easy to volatilize, can improve the compatibility of the epoxy resin and a curing agent, and reduces the viscosity of a system; the solubilizing diluent has no VOC emission in the using process and no pollution to the environment, has obvious effect by adding a small amount of solubilizing diluent, has low self viscosity and also has the function of a diluent.
The invention discloses a preparation method of a non-volatile solubilizing diluent, which is characterized in that the non-volatile solubilizing diluent is conveniently and rapidly synthesized through esterification reaction; the whole synthesis method has simplified steps and easily obtained raw materials.
The invention also discloses application of the non-volatile solubilizing diluent in epoxy resin, and the non-volatile solubilizing diluent is applied to the epoxy resin, can effectively reduce the viscosity of the epoxy resin and can ensure that the traditional amine curing agent has better compatibility with the bulk E-type epoxy resin. The resin not only dispenses with the use of volatile solvent, but also becomes a part of a resin system, not only does not increase the cost of the resin, but also greatly improves the shock resistance and low-temperature performance of the cured resin.
[ description of the drawings ]
FIG. 1 is an infrared spectrum of a solubilizing diluent obtained in example 1 of the present invention;
[ detailed description ] embodiments
The invention is described in further detail below with reference to the accompanying drawings:
the invention discloses a non-volatile solvent-increasing diluent for solvent-free epoxy resin, wherein the molecular formula of the solvent is as follows:
wherein n is a natural number of 1-12, and m and z are natural numbers of 1-4, respectively. R is H or CH3. The non-volatile compatibilization diluent for the epoxy resin is prepared by taking phthalic anhydride, butanol and diethylene glycol as examples, and the synthetic route is as follows:
the above synthetic routes are only a few examples.
The preparation process of the solubilizing diluent comprises the following steps:
drying the three-neck flask, the condenser tube and other instruments at 120 ℃ for 1.5h, taking out, placing in a dryer, cooling and installing. Adding 0.2mol of phthalic anhydride into a three-neck flask, and adding 0.2-0.3mol of fatty alcohol with more than four carbon atoms; the fatty alcohol with more than four carbon atoms is any one of n-butanol, n-octanol or lauryl alcohol, the heating temperature is 110-140 ℃, and the heating process is simultaneously stirred until the fatty alcohol is completely dissolved to form a mixture A. Cooling the mixture A to room temperature, adding 100-300mL of toluene, and measuring and recording the acid value; then adding 0.3-0.5mol of dihydric alcohol and 1.5-3g of p-toluenesulfonic acid to prepare a mixture B; the glycols included ethylene glycol, diethylene glycol, hexylene glycol, and propylene glycol, and the initial acid number of mixture B was measured and recorded. And placing the mixture B in a water separator, heating to 110 ℃ and refluxing, continuously separating generated water by using a water separator, monitoring the acid value of the whole reaction system in the reaction process until the acid value is lower than 5, finishing the reaction to obtain yellow liquid, distilling under reduced pressure to remove toluene, dissolving by using dichloromethane to obtain a solution C, washing the solution C to be neutral by using 5% sodium bicarbonate, washing twice by using saturated saline solution, and distilling under reduced pressure to remove the solvent to obtain a light yellow product which is a non-volatile solubilizing diluent.
The acid value test of the process is carried out according to GB/T1668-2008.
Example 1
Drying three-neck flask, condenser tube, etc. at 120 deg.C for 1.5h, taking out, cooling in drier, and installing; 0.2mol of phthalic anhydride is added into a three-neck flask, 0.22mol of n-butanol is added, the temperature is heated to 140 ℃, and the mixture is stirred until the phthalic anhydride is completely dissolved. Cooling to room temperature, adding 100mL of toluene, and measuring the acid value; then 0.3mol of diethylene glycol and 1.5g of p-toluenesulfonic acid are added to measure the initial acid value; adding a water separator, heating to 110 ℃ for reflux, continuously separating generated water by using a water separator, and monitoring the acid value in the reaction process. Stopping the reaction until the acid value is lower than 5; after the reaction was completed, a yellow liquid was obtained, toluene was removed by rotary evaporation, and then the solution was dissolved in methylene chloride, washed with 5% sodium hydrogencarbonate to be neutral, and washed twice with saturated brine to distill off the solvent to obtain a pale yellow solubilizing diluent.
The solubilizing diluent prepared in this example is used to prepare an epoxy resin system, and the specific epoxy resin system comprises the following components in parts by mass: 10 parts of epoxy E51 was mixed well with 2.6 parts of solubilizing diluent and the viscosity was tested to 584mpa.s at 25 ℃ which is lower than the prior solvent-based resin systems.
Example 2
Drying the three-neck flask, the condenser tube and other instruments at 120 ℃ for 1.5h, taking out, placing in a dryer, cooling and installing. 0.2mol of phthalic anhydride is added into a three-neck flask, 0.22mol of n-octanol is added, the temperature is heated to 110 ℃, and the mixture is stirred until the phthalic anhydride is completely dissolved. Cooling to room temperature, adding 200mL of toluene, and measuring the acid value; then, 0.3mol of ethylene glycol and 1.5g of p-toluenesulfonic acid were added to measure the initial acid value. Adding a water separator, heating to 110 ℃ for reflux, continuously separating generated water by using a water separator, and monitoring the acid value in the reaction process until the acid value is lower than 5. A yellow liquid was obtained, toluene was distilled off under reduced pressure, and then dissolved in methylene chloride, washed with 5% sodium hydrogencarbonate to neutrality, washed twice with saturated brine, and the solvent was distilled off to obtain a pale yellow solubilizing diluent.
The solubilizing diluent prepared in the embodiment is used for preparing an epoxy resin system, and the specific epoxy components comprise the following components in percentage by mass: 10 parts of epoxy E51 was mixed well with 3.5 parts of solubilizing diluent and the viscosity was tested to find a viscosity of 605mpa.s at 25 ℃ lower than the prior solvent-based resin systems.
Example 3
Drying the three-neck flask, the condenser tube and other instruments at 120 ℃ for 1.5h, taking out, placing in a dryer, cooling and installing. 0.2mol of phthalic anhydride is added into a three-neck flask, 0.22mol of n-butanol is added, the mixture is heated to 110 ℃, and the mixture is stirred until the phthalic anhydride is completely dissolved. After cooling to room temperature, 200mL of toluene, 0.3mol of hexanediol, and 1.5g of p-toluenesulfonic acid were added, and the initial acid value was measured. Adding a water separator, heating to reflux, continuously separating generated water by using a water separator, and monitoring the acid value in the reaction process. Until the reaction is finished when the acid value is lower than 5. A yellow liquid was obtained, toluene was distilled off under reduced pressure, and then dissolved in methylene chloride, washed with 5% sodium hydrogencarbonate to neutrality, washed twice with saturated brine, and the solvent was distilled off to obtain a pale yellow solubilizing diluent.
The solubilizing diluent prepared in the embodiment is used for preparing an epoxy resin system, and the specific epoxy components comprise the following components in percentage by mass: 10 parts of epoxy E51 was mixed well with 3 parts of solubilizing diluent and the viscosity was tested to find 624mpa.s at 25 ℃ lower than the prior solvent-based resin systems.
Example 4
Drying the three-neck flask, the condenser tube and other instruments at 120 ℃ for 1.5h, taking out, placing in a dryer, cooling and installing. 0.2mol of phthalic anhydride is added into a three-neck flask, 0.22mol of lauryl alcohol is added, the temperature is heated to 110 ℃, and the mixture is stirred until the phthalic anhydride is completely dissolved. After cooling to room temperature, 300mL of 150-200mL of toluene, 0.3mol of propylene glycol and 1.5g of p-toluenesulfonic acid were added to measure the initial acid value. Adding a water separator, heating to reflux, continuously separating generated water by using a water separator, and monitoring the acid value in the reaction process. Until the reaction is finished when the acid value is lower than 5. A yellow liquid was obtained, toluene was distilled off under reduced pressure, and then dissolved in methylene chloride, washed with 5% sodium hydrogencarbonate to neutrality, washed twice with saturated brine, and the solvent was distilled off to obtain a pale yellow solubilizing diluent.
The solubilizing diluent prepared in the embodiment is used for preparing an epoxy resin system, and the specific epoxy components comprise the following components in percentage by mass: 10 parts of epoxy E51 was mixed well with 4 parts of solubilizing diluent and tested for viscosity which was 594mpa.s at 25 ℃ lower than the current solvent-type resin system.
Example 5
Drying the three-neck flask, the condenser tube and other instruments at 120 ℃ for 1.5h, taking out, placing in a dryer, cooling and installing. 0.2mol of phthalic anhydride is added into a three-neck flask, 0.3mol of n-octanol is added, the temperature is heated to 130 ℃, and the mixture is stirred until the phthalic anhydride is completely dissolved. Cooling to room temperature, adding 150-200mL of toluene, and measuring the acid value; then, 0.5mol of propylene glycol and 3g of p-toluenesulfonic acid were added to measure the initial acid value. Adding a water separator, heating to 110 ℃ for reflux, continuously separating generated water by using a water separator, and monitoring the acid value in the reaction process until the acid value is lower than 5. A yellow liquid was obtained, toluene was distilled off under reduced pressure, and then dissolved in methylene chloride, washed with 5% sodium hydrogencarbonate to neutrality, washed twice with saturated brine, and the solvent was distilled off to obtain a pale yellow solubilizing diluent.
Example 6
Drying the three-neck flask, the condenser tube and other instruments at 120 ℃ for 1.5h, taking out, placing in a dryer, cooling and installing. 0.2mol of phthalic anhydride is added into a three-neck flask, 0.25mol of n-butanol is added, the mixture is heated to 140 ℃, and the mixture is stirred until the phthalic anhydride is completely dissolved. Cooling to room temperature, adding 300mL of toluene, and measuring the acid value; then, 0.4mol of ethylene glycol and 2g of p-toluenesulfonic acid were added to measure the initial acid value. Adding a water separator, heating to 110 ℃ for reflux, continuously separating generated water by using a water separator, and monitoring the acid value in the reaction process until the acid value is lower than 5. A yellow liquid was obtained, toluene was distilled off under reduced pressure, and then dissolved in methylene chloride, washed with 5% sodium hydrogencarbonate to neutrality, washed twice with saturated brine, and the solvent was distilled off to obtain a pale yellow solubilizing diluent.
Example 7
Drying the three-neck flask, the condenser tube and other instruments at 120 ℃ for 1.5h, taking out, placing in a dryer, cooling and installing. 0.2mol of phthalic anhydride is added into a three-neck flask, 0.27mol of lauryl alcohol is added, the temperature is heated to 120 ℃, and the mixture is stirred until the phthalic anhydride is completely dissolved. Cooling to room temperature, adding 120mL of toluene, and measuring the acid value; then, 0.4mol of hexanediol and 2.5g of p-toluenesulfonic acid were added to measure the initial acid value. Adding a water separator, heating to 110 ℃ for reflux, continuously separating generated water by using a water separator, and monitoring the acid value in the reaction process until the acid value is lower than 5. A yellow liquid was obtained, toluene was distilled off under reduced pressure, and then dissolved in methylene chloride, washed with 5% sodium hydrogencarbonate to neutrality, washed twice with saturated brine, and the solvent was distilled off to obtain a pale yellow solubilizing diluent.
Application example 1
Applying the solubilizing diluent prepared in the example 1 to a curing agent to prepare a curing component 1, wherein the mass ratio of the curing agent 651 to the mass ratio of 7 parts, and the mass ratio of the solubilizing diluent prepared in the example 1 to the mass ratio of 3 parts are uniformly mixed, and the viscosity of the mixture is 1237.5mpa.s at 25 ℃; 3.5 parts of the curing component 1 and 10 parts of the epoxy resin system prepared in the example 1 are uniformly mixed in parts by mass, and the mixture is kept stand at room temperature for 30min, so that the system is clear and transparent. The coating can be completely cured after 24 hours.
Application example 2
The solubilizing diluent prepared in the example 1 is applied to a curing agent to prepare a curing component 2, wherein the mass ratio of the curing agent 730 to 8 parts, and the mass ratio of the solubilizing diluent prepared in the example 1 to 2 parts are uniformly mixed, and the viscosity of the mixture is measured to be 610mpa.s at 25 ℃; by mass, 5 parts of the curing component 2 and 10 parts of the epoxy resin system prepared in the example 1 are uniformly mixed, and the mixture is kept stand at room temperature for 30min, so that the system is clear and transparent. Then coating the film and completely curing the film within 7 hours.
Referring to FIG. 1, the infrared spectrum of the solubilizing diluent prepared in example 1 of the present invention is shown in 3400-3518.3 cm-1Is the hydroxyl absorption peak; 1718.12cm-1Is the ester carbonyl absorption peak; 2958.41cm-1Is a methyl C-H stretching vibration absorption peak; 2873.02cm-1Is methylene C-H stretching vibration absorption peak; 1599.83cm-1、1448.71cm-1The absorption peak of the benzene ring skeleton can be 733.19cm-1Mutual evidence of the out-of-plane bending vibration absorption peaks of the ortho-position disubstituted benzene C-H; 1273.72cm-1Is a C-C stretching vibration absorption peak in the aromatic ester; 1117.91cm-1Is the C-O-C telescopic vibration absorption peak. According to absorption peak data of main groups shown by a spectrogram, the compound is relatively consistent with a compound to be synthesized in structure by combining experiments.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A non-volatile solubilizing diluent having the chemical formula:
2. a method of preparing the non-volatile solubilizing diluent of claim 1, wherein the preparation comprises the steps of: mixing phthalic anhydride and n-butyl alcohol, heating and uniformly stirring after mixing to form a mixture A; cooling the mixture A, and then adding toluene, diethylene glycol and p-toluenesulfonic acid to obtain a mixture B; placing the mixture B in a water distribution device, heating and refluxing, monitoring the acid value in the reaction process, and ending the reaction when the acid value is less than 5 to obtain yellow liquid; distilling the yellow liquid under reduced pressure to remove toluene, and dissolving with dichloromethane to obtain a solution C; the solution C was washed to neutrality with sodium bicarbonate, washed with saturated brine, distilled under reduced pressure and the solvent removed to give a pale yellow product as a non-volatile solubilizing diluent.
3. The method of preparing the non-volatile solubilizing diluent according to claim 2, wherein the mixing molar ratio of phthalic anhydride and n-butanol is 0.2: (0.2-0.3).
4. The method of claim 2, wherein phthalic anhydride and n-butanol are mixed, and the mixture is heated to 110-140 ℃.
5. The method of claim 2, wherein the mixture A is cooled and then toluene is added, and the ratio of diethylene glycol and p-toluenesulfonic acid is (100- & 300) mL: (0.3-0.5) mol: (1.5-3) g; wherein the molar ratio of the diethylene glycol to the phthalic anhydride is (3-5): 2.
6. the method of claim 2, wherein the mixture B is heated and refluxed at 110 ℃ in a water-dividing device.
7. The method of any one of claims 2-6, wherein solution C is washed to neutrality by sodium bicarbonate with a mass concentration of 5%.
8. Use of the non-volatile solubilizing diluent of claim 1 in an epoxy resin system.
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