Method for producing low-chlorine epoxy resin and method for producing chlorine remover

Abstract

To relate to a technical field of an epoxy resin, specifically to a method for producing a low chlorine epoxy resin and a method for producing a chlorine removing agent.SOLUTION: A method for producing a low chlorine epoxy resin includes reacting a fluorine-containing tertiary amine-based chlorine removing agent with a chlorine-containing epoxy resin and producing a quaternary ammonium salt compound, then removing the quaternary ammonium salt compound, and obtaining a low chlorine epoxy resin, wherein a mass ratio of the epoxy resin to the fluorine-containing tertiary amine-based chlorine removing agent is 1,000:2 to 8, a structural formula of the fluorine-containing tertiary amine-based chlorine removing agent is represented by chemical formula 1, wherein R1, R2 and R3 are the same or different and represent an alkyl group, carbon chains of R1, R2 and R3 have 1 to 3 carbon atoms, R4 represents a perfluoroalkyl group and has a carbon chain having 4 to 5 carbon atoms, and Y1 represents a sulfonamide group, a sulfonimide group or a phenoxy group.SELECTED DRAWING: None

Description

Technical Field

[0001] This application relates to the technical field of epoxy resins, specifically to a method for producing a low-chlorine epoxy resin and a method for producing a chlorine remover.

Background Art

[0002] Epoxy resin is a polymer synthetic material with good adhesiveness, corrosion resistance, electrical insulation, and high strength. It is widely used in fields such as electronic component packaging materials for smart terminals, nonlinear optical materials, and electronic component packaging materials for new energy vehicles. In order to ensure the reliability of the insulation class and electrical properties of related electronic components, it is strongly required to increase the purity of epoxy resin and reduce the total chlorine content therein.

[0003] The total chlorine content is one of the main characteristic indicators representing the purity of epoxy resin. The total chlorine in epoxy resin includes easily hydrolyzable chlorine and hardly hydrolyzable chlorine. Chlorine in epoxy resin releases free chlorine ions under the action of high temperature, high humidity, and amine-based curing agents. These chlorine ions have a great impact on the performance of semiconductor components, thus affecting the safety and service life in the use of packaging materials. As the semiconductor industry develops, the line width of electronic components becomes increasingly narrow. Therefore, the impact of material corrosion on the stability of electronic components is increasing. Therefore, it is urgent to develop high-purity low-chlorine epoxy resin.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The object of this application is to provide a method for producing a low-chlorine epoxy resin and a method for producing a chlorine remover to address the drawback of high total chlorine content in epoxy resin. The embodiments of this application are realized as follows.

Means for Solving the Problems

[0005] A first embodiment of the present invention provides a method for producing a low-chlorine epoxy resin, the method being: The invention involves a fluorine-containing tertiary amine-based chlorine remover reacting with a chlorine-containing epoxy resin to produce a quaternary ammonium salt compound, and then removing the quaternary ammonium salt compound to obtain a low-chlorine epoxy resin. The mass ratio of the epoxy resin to the fluorine-containing tertiary amine-based chlorine remover is 1000:2 to 8. The structural formula of the aforementioned fluorine-containing tertiary amine-based chlorine remover is: [ka] And, In the formula, R1, R2, and R3 are the same or different and represent alkyl groups, with the carbon number of the carbon chains of R1, R2, and R3 being 1 to 3, R4 represents a perfluoroalkyl group and has the carbon number of the carbon chain being 4 to 5, and Y1 represents a sulfonamide group, a sulfonimide group, or a phenoxy group.

[0006] In some examples, the reaction equation for the reaction of a fluorine-containing tertiary amine-based chlorine remover with a chlorine-containing epoxy resin to produce a quaternary ammonium salt compound is: [ka] And, The aforementioned R5 is, [ka] or [ka] It represents.

[0007] In some examples, the reaction conditions for the fluorine-containing tertiary amine-based chlorine remover to react with the chlorine-containing epoxy resin are polishing in an aqueous phase for 2 to 6 hours, with a reaction temperature of 5 to 25°C.

[0008] In some embodiments, when the fluorine-containing tertiary amine-based chlorine remover reacts with the chlorine-containing epoxy resin, the reaction conditions are to grind in the aqueous phase for 4 hours, and the reaction temperature is 23 °C.

[0009] In some embodiments, removing the quaternary ammonium salt compound includes thoroughly washing and filtering with pure water multiple times.

[0010] In some embodiments, thoroughly washing with pure water multiple times includes washing with ultrapure water having an electrical resistivity greater than 15 MΩ·cm until the electrical resistivity of the eluate becomes greater than 10 MΩ·cm.

[0011] Further, a second aspect of the present application provides a method for producing a chlorine remover, the chlorine remover includes a fluorine-containing tertiary amine-based chlorine remover, and the production method includes

Chemical formula

[0012] In some embodiments, the molar ratio of the compound I to the compound II is 0.9 to 1.2:1, the reaction temperature is 10 to 25 °C, and the reaction time is 2 to 4 hours. <由

[0013] In some embodiments, the molar ratio of the compound I to the compound II is 1.1:1, the reaction temperature is 25 °C, and the reaction time is 2 hours.

[0014] In some embodiments, a carbonate is added as an acid binder when the compound I and the compound II react.

Advantages of the Invention

[0015] The beneficial effects of the present application are as follows. In the first aspect of the present application, a fluorine-containing tertiary amine-based chlorine remover reacts with a hydrophobic chlorine-containing epoxy resin to produce a water-soluble quaternary ammonium salt compound. Next, the quaternary ammonium salt compound is removed, and finally, it is dried to obtain a high-purity low-chlorine epoxy resin product. As measured, the total chlorine content of the epoxy resin produced by the method of the present application was reduced by 700 ppm to 1000 ppm.

[0016] In the second aspect of the present application, a fluorine-containing tertiary amine-based chlorine remover is produced by reacting a tertiary amine-based compound I having an active group X1 and a fluorine-containing segment compound II having an active group X2.

[0017] The fluorine-containing tertiary amine-based chlorine remover of the present application can react with a hydrophobic chlorine-containing epoxy resin to produce a water-soluble quaternary ammonium salt compound, so the purpose of removing easily hydrolyzable chlorine and hardly hydrolyzable chlorine is achieved. In addition, the fluorine-containing segment of the fluorine-containing tertiary amine-based chlorine remover can improve the reactivity of the tertiary amine group. Therefore, the fluorine-containing tertiary amine-based chlorine remover is more likely to react with the chlorine in the epoxy resin (here, "more likely to react" means compared with the reactivity of a tertiary amine without a fluorine segment). In addition, the fluorine-containing segment can reduce the surface tension and interfacial tension of the quaternary ammonium salt compound, and improve the water solubility of the quaternary ammonium salt compound. Therefore, when filtering, it can be separated and removed more efficiently.

[0018] The present invention's method for producing low-chlorine epoxy resin and chlorine remover is advantageous for scaling up production because it has a clear reaction mechanism, simple reaction conditions, and easy post-treatment. Furthermore, by adjusting the type and amount of fluorine-containing tertiary amine-based chlorine remover, it is possible to obtain epoxy resin products with different total chlorine content. [Modes for carrying out the invention]

[0019] The following provides general explanations and definitions of terms and expressions used in the specification and claims, so that those skilled in the art may understand the features and effects of the present invention. Unless otherwise specified, all technical and scientific terms used in this specification have the ordinary meanings known to those skilled in the art with respect to the present invention, and in case of any inconsistency, the definitions herein shall prevail.

[0020] The theories or mechanisms described and disclosed herein, whether true or false, do not limit the scope of the present invention in any way; in other words, the present invention can be implemented without being limited to any particular theory or mechanism.

[0021] In this specification, any characteristics defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, content, and concentrations, are done so for the sake of simplifying the description. From this perspective, when a numerical range or percentage range is described, it is considered to cover all possible secondary ranges and individual numerical values ​​(including integers and fractions) within the range, and to specifically disclose them.

[0022] For the sake of simplicity, this specification does not describe all possible combinations of each technical feature relating to each embodiment or example. Therefore, any combination of these technical features can be arbitrarily combined as long as there is no inconsistency, and all possible combinations are deemed to be included in the description herein.

[0023] The present invention will be further described below using specific examples. These examples are for illustrative purposes only and should not be used to limit the scope of the present invention. Furthermore, those skilled in the art will understand, upon reading the contents of this invention, that various changes or modifications can be made to the invention, and that these equivalent forms also fall within the scope of the claims of this application.

[0024] The following describes in more detail, with the use of specific examples, the chlorine remover provided by this application, the method for manufacturing the chlorine remover, and the method for manufacturing a low-chlorine epoxy resin using the chlorine remover.

[0025] In this application, a fluorine-containing tertiary amine chlorine remover is produced by the reaction of a tertiary amine compound I having an active group X1 and a fluorine-containing segment compound II having an active group X2, and the reaction formula is: [ka] And, Here, if X1 represents a primary amino group and X2 represents a sulfonyl fluoride group, then Y1 represents a sulfonamide group. If X1 represents a secondary amino group and X2 represents a sulfonyl fluoride group, then Y1 represents a sulfonimide group. If X1 represents a phenolic hydroxyl group and X2 represents an alkene, then Y1 represents a phenoxy group. R1, R2, and R3 are the same or different, represent alkyl groups, and the carbon number of the carbon chains of R1, R2, and R3 is 1 to 3. R4 represents a perfluoroalkyl group and has 4 to 5 carbon numbers in its carbon chain. Y1 represents a sulfonamide group, a sulfonimide group, or a phenoxy group.

[0026] Fluorine-containing tertiary amine-based chlorine removers can react with hydrophobic chlorine-containing epoxy resins to produce water-soluble quaternary ammonium salt compounds, thus achieving the objective of removing chlorine-containing epoxy resins. Furthermore, the fluorine-containing segment of the fluorine-containing tertiary amine-based chlorine remover can improve the reactivity of the tertiary amine group, making the fluorine-containing tertiary amine-based chlorine remover more readily reactive with chlorine in epoxy resins (here, "more readily reactive" refers to the reactivity compared to tertiary amines without the fluorine segment). In addition, the fluorine-containing segment can reduce the surface tension and interfacial tension of the quaternary ammonium salt compound, improving its water solubility, and thus allowing for more efficient separation and removal during filtration.

[0027] Example 1: Synthesis of fluorine-containing tertiary amine-based chlorine remover C-1 In a 2 L reaction vessel, N,N-dimethyl-1,3-propanediamine (10.7 g, 0.105 mol), perfluorobutanesulfonyl fluoride (30.2 g, 0.1 mol), and 50 mL of toluene as a solvent were added. Potassium carbonate was then added as an acid binder, and the mixture was reacted at 20°C for 6 hours (the reaction equation is shown below). Deionized water was then added, and the mixture was thoroughly stirred to make it homogeneous. Once homogeneous, the mixture was extracted, and the aqueous and organic phases were separated. The solvent was removed from the organic phase by rotary evaporation to obtain the fluorine-containing tertiary amine-based chlorine remover C-1. [ka]

[0028] Example 2: Synthesis of fluorine-containing tertiary amine-based chlorine remover C-2 In a 2 L reaction vessel, N-aminoethylpiperazine (14.1 g, 0.11 mol), perfluorobutanesulfonyl fluoride (30.2 g, 0.1 mol), and 50 mL of toluene as a solvent were added. Sodium carbonate was then added as an acid binder, and the mixture was reacted at 25°C for 2 hours. After that, deionized water was added and the mixture was thoroughly stirred to make it homogeneous. Once homogeneous, the mixture was extracted, and the aqueous and organic phases were separated. The solvent was removed from the organic phase by rotary evaporation to obtain the fluorine-containing tertiary amine-based chlorine remover C-2. [ka]

[0029] Example 3: Synthesis of fluorine-containing tertiary amine-based chlorine remover C-3 In a 2 L reaction vessel, 3-(dimethylamino)phenol (12.3 g, 0.09 mol), perfluoropropene [trimer] (15 g, 0.1 mol), and 50 mL of toluene as a solvent were added. Potassium carbonate was then added as an acid binder (the reaction equation is shown below), and the mixture was reacted at 23°C for 4 hours. After that, deionized water was added and the mixture was thoroughly stirred to make it homogeneous. Once homogeneous, the mixture was extracted, and the aqueous and organic phases were separated. The solvent was removed from the organic phase by rotary evaporation to obtain the fluorine-containing tertiary amine-based chlorine remover C-3. [ka]

[0030] Furthermore, chlorine-containing epoxy resins include easily hydrolyzable chlorine-containing epoxy resins. [ka] and poorly hydrolyzable chlorine-containing epoxy resins [ka] It includes, and in the formula, R5 is, [ka] or [ka] It represents. The fluorine-containing tertiary amine-based chlorine remover of this invention can react with both readily hydrolyzable and sparingly hydrolyzable chlorine in epoxy resins, and the reaction equation is shown below. [ka]

[0031] The following examples illustrate a process in which a fluorine-containing tertiary amine-based chlorine remover reacts with a biphenyldiphenol-type epoxy resin and a bisphenol F-type epoxy resin, respectively, to produce a low-chlorine epoxy resin. Furthermore, the fluorine-containing tertiary amine-based chlorine remover of this application has a similar chlorine reduction effect on other types of epoxy resins, such as bisphenol A type epoxy resins, phenol type epoxy resins, and aliphatic epoxy resins. Moreover, the manufacturing process can be estimated from the following examples, therefore, the process by which the fluorine-containing tertiary amine-based chlorine remover reacts with other types of epoxy resins to produce low-chlorine epoxy resins will not be explained here.

[0032] In this application, the method for measuring the total chlorine content is as specified in ISO 21627-3-2009, the method for measuring the easily hydrolyzable chlorine content is as specified in ISO 21627-2-2009, and the poorly hydrolyzable chlorine content is the difference between the total chlorine content and the easily hydrolyzable chlorine content.

[0033] Example 4: Production of low-chlorine epoxy resin LCE-1 The fluorine-containing tertiary amine-based chlorine remover C-1 (2g) and tetramethylbiphenyldiphenol-type epoxy resin (1000g, epoxy equivalent 187g / eq, total chlorine content 1351ppm, easily hydrolyzable chlorine content 164ppm, poorly hydrolyzable chlorine content 1187ppm) prepared in Example 1 were added to a polishing machine, and 500g of water was added. The mixture was polished at a reaction temperature of 20°C and reacted for 2 hours (the reaction equation is shown below). The solid product was then filtered and washed with ultrapure water with a resistivity greater than 15MΩ·cm until the resistivity of the eluate was greater than 10MΩ·cm. Finally, the solid product was dried under nitrogen heating to obtain high-purity tetramethylbiphenyldiphenol-type epoxy resin LCE-1, with a yield of 85%. Measurements revealed that the high-purity tetramethylbiphenyldiphenol type epoxy resin LCE-1 had an epoxy equivalent of 181 g / eq, a total chlorine content of 651 ppm, an easily hydrolyzable chlorine content of 92 ppm, and a poorly hydrolyzable chlorine content of 286 ppm. [ka] [ka]

[0034] In the formula, R5 is [ka] It represents.

[0035] Example 5: Production of low-chlorine epoxy resin LCE-2 In Example 1, the fluorine-containing tertiary amine-based chlorine remover C-1 (6 g) and tetramethylbiphenyldiphenol-type epoxy resin (1000 g, epoxy equivalent 187 g / eq, total chlorine content 1351 ppm, easily hydrolyzable chlorine content 164 ppm, poorly hydrolyzable chlorine content 1187 ppm) were added to a polishing machine. 500 g of water was then added, and the mixture was polished at a reaction temperature of 20°C for 2 hours. The solid product was then filtered and washed. The cake was then washed with ultrapure water with a resistivity greater than 15 MΩ·cm until the resistivity of the eluate was greater than 10 MΩ·cm. Finally, the product was dried under nitrogen heating to obtain a high-purity tetramethylbiphenyldiphenol-type epoxy resin with a yield of 80%. Measurements revealed that the high-purity tetramethylbiphenyldiphenol type epoxy resin LCE-2 had an epoxy equivalent of 180 g / eq, a total chlorine content of 251 ppm, a readily hydrolyzable chlorine content of 29 ppm, and a poorly hydrolyzable chlorine content of 222 ppm.

[0036] Example 6: Production of low-chlorine epoxy resin LCE-3 In Example 2, the fluorine-containing tertiary amine-based chlorine remover C-2 (8 g) and tetramethylbiphenyldiphenol-type epoxy resin (1000 g, epoxy equivalent 187 g / eq, total chlorine content 1351 ppm, easily hydrolyzable chlorine content 164 ppm, poorly hydrolyzable chlorine content 1187 ppm) were added to a polishing machine, and 500 g of water was added. After polishing at a reaction temperature of 20°C for 2 hours, the solid product was filtered and washed. When filtering and washing the solid product, ultrapure water with a resistivity greater than 15 MΩ·cm was used until the resistivity of the eluate was greater than 10 MΩ·cm. Finally, the product was dried under nitrogen heating, thereby obtaining a high-purity tetramethylbiphenyldiphenol-type epoxy resin with a yield of 86%. Measurements revealed that the high-purity tetramethylbiphenyldiphenol type epoxy resin LCE-2 had an epoxy equivalent of 181 g / eq, a total chlorine content of 421 ppm, a readily hydrolyzable chlorine content of 56 ppm, and a sparingly hydrolyzable chlorine content of 365 ppm.

[0037] Example 7: Production of low-chlorine epoxy resin LCE-4 In Example 2, the fluorine-containing tertiary amine-based chlorine remover C-2 (8 g) and tetramethylbisphenol F-type epoxy resin (1000 g, epoxy equivalent 195 g / eq, total chlorine content 1257 ppm, easily hydrolyzable chlorine content 186 ppm, poorly hydrolyzable chlorine content 1071 ppm) were added to a polishing machine, and 500 g of water was added. After polishing at a reaction temperature of 20°C for 2 hours, the solid product was filtered and washed. When filtering and washing the solid product, ultrapure water with a resistivity greater than 15 MΩ·cm was used until the resistivity of the eluate was greater than 10 MΩ·cm. Finally, the product was dried under nitrogen heating, thereby obtaining high-purity tetramethylbisphenol F-type epoxy resin. The yield was 89%. Measurements revealed that the high-purity tetramethylbisphenol F type epoxy resin LCE-4 had an epoxy equivalent of 186 g / eq, a total chlorine content of 327 ppm, a readily hydrolyzable chlorine content of 46 ppm, and a poorly hydrolyzable chlorine content of 281 ppm. [ka]

[0038] In the formula, R5 is [ka] It represents.

[0039] (Comparative example) In a 2 L reaction vessel, N-aminoethylpiperazine (0.12 mol, 15.4 g), benzenesulfonyl chloride (0.1 mol, 17.7 g), and 50 mL of toluene as a solvent were added. Potassium carbonate was then added as an acid binder, and the mixture was reacted at 25°C for 2 hours. After that, deionized water was added and the mixture was thoroughly stirred to make it homogeneous. Once homogeneous, the mixture was extracted, and the aqueous and organic phases were separated. The solvent was removed from the organic phase by rotary evaporation to obtain the tertiary amine-based chlorine remover C-4.

[0040] The prepared tertiary amine-based chlorine remover C-4 (8g) and tetramethylbisphenol F type epoxy resin (1000g, epoxy equivalent 195g / eq, total chlorine content 1257ppm, easily hydrolyzable chlorine content 186ppm, poorly hydrolyzable chlorine content 1071ppm) were added to a polishing machine, and 500g of water was added. After polishing at a reaction temperature of 20°C for 2 hours, the solid product was filtered and washed. When filtering and washing the solid product, ultrapure water with a resistivity greater than 15MΩ·cm was used until the resistivity of the eluate was greater than 10MΩ·cm. Finally, the product was dried under N2 temperature control, thereby obtaining high-purity tetramethylbisphenol F type epoxy resin. The yield was 95%. Measurements revealed that the high-purity tetramethylbisphenol F type epoxy resin LCE-5 had an epoxy equivalent of 194 g / eq, a total chlorine content of 1123 ppm, an easily hydrolyzable chlorine content of 156 ppm, and a poorly hydrolyzable chlorine content of 967 ppm.

[0041] As can be seen from Examples 4 to 7, the fluorine-containing tertiary amine-based chlorine remover of the present invention reacts with fluorine-containing epoxy resin to reduce the total amount of chlorine in the fluorine-containing epoxy resin, and the content of both easily hydrolyzable chlorine and poorly hydrolyzable chlorine is reduced. Furthermore, the objective of improving the chlorine removal effect can be achieved by increasing the amount of fluorine-containing tertiary amine-based chlorine remover used.

[0042] Although the present invention has been disclosed above in preferred embodiments, the present invention is not limited thereto. Those skilled in the art can make various changes and modifications as long as they do not deviate from the spirit and scope of the present invention; therefore, the scope of protection of the present invention shall be determined by the claims.

Claims

1. A method for producing low-chlorine epoxy resin, The invention involves a fluorine-containing tertiary amine-based chlorine remover reacting with a chlorine-containing epoxy resin to produce a quaternary ammonium salt compound, and then removing the quaternary ammonium salt compound to obtain a low-chlorine epoxy resin. The mass ratio of the epoxy resin to the fluorine-containing tertiary amine-based chlorine remover is 1000:2 to 8. The structural formula of the aforementioned fluorine-containing tertiary amine-based chlorine remover is: 【Chemistry 1】 And, In the formula, R １ and R ２ are the same or different, representing an alkyl group, and the R １ and R ２ The number of carbon atoms in the carbon chain is 1 to 3, R ３ represents an alkylene group, and the R ３ The number of carbon atoms in the carbon chain is 1 to 3, R ４ Y represents a perfluoroalkyl group and has 4 to 5 carbon atoms in its carbon chain. １ This is a method for producing a low-chlorine epoxy resin, characterized by representing a sulfonamide group.

2. The reaction equation for the reaction of a fluorine-containing tertiary amine-based chlorine remover with a chlorine-containing epoxy resin to produce a quaternary ammonium salt compound is: 【Chemistry 2】 And, The aforementioned R ５ is 【Chemistry 4】 A method for producing a low-chlorine epoxy resin according to claim 1, characterized by representing the above.

3. The method for producing a low-chlorine epoxy resin according to claim 1, characterized in that removing the quaternary ammonium salt compound includes thoroughly washing and filtering multiple times with pure water.

4. The method for producing a low-chlorine epoxy resin according to claim 3, characterized in that washing multiple times thoroughly with pure water includes washing with ultrapure water with a resistivity greater than 15 MΩ·cm until the resistivity of the eluate is greater than 10 MΩ·cm.

5. A method for manufacturing a chlorine remover, The chlorine remover includes a fluorine-containing tertiary amine-based chlorine remover. The aforementioned manufacturing method is 【Transformation 5】 Includes, Here, X １ This represents a primary amino group, X ２ If represents a sulfonyl fluoride group, Y １ This represents a sulfonamide group, R １ and R ２ are the same or different, representing an alkyl group, and the R １ and R ２ The number of carbon atoms in the carbon chain is 1 to 3, R ３ represents an alkylene group, and the R ３ The number of carbon atoms in the carbon chain is 1 to 3, R ４ A method for producing a chlorine remover, characterized in that it represents a perfluoroalkyl group and the number of carbon atoms in the carbon chain is 4 to 5.

6. The method for producing a chlorine remover according to claim 5, characterized in that the molar ratio of compound I to compound II is 0.9 to 1.2:1, the reaction temperature is 10 to 25°C, and the reaction time is 2 to 4 hours.

7. The method for producing a chlorine remover according to claim 6, characterized in that the molar ratio of compound I to compound II is 1.1:1, the reaction temperature is 25°C, and the reaction time is 2 hours.

8. A method for producing a chlorine remover according to claim 5, characterized in that a carbonate is added as an acid binder when compound I and compound II react.

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