Epoxy resin and preparation method thereof

Abstract

The invention provides epoxy resin and a preparation method thereof, and the method comprises the following steps: 1, in the presence of a catalyst and a promoter, carrying out an etherification reaction on a triphenol compound and halogenated alkylene oxide to generate an intermediate product; and 2, mixing the intermediate product with an organic solvent and solid alkali, and carrying out a cyclization reaction to prepare the epoxy resin. By designing the preparation method, the halogen impurity content in the epoxy resin product can be obviously reduced in a simple and low-cost manner, and the epoxy resin product has excellent performance.

Description

Technical Field

[0001] This application relates to the field of polymers, and more specifically to a special epoxy resin with low halogen content and its preparation method. Background Technology

[0002] Epoxy resins are widely used in adhesives and composite materials due to their excellent mechanical properties, adhesive properties, chemical stability, and electrical insulation. However, in high-end electronic fields such as integrated circuit packaging, copper-clad laminates, electronic component packaging, and semiconductor packaging materials, higher quality requirements are placed on epoxy resins, forcing epoxy resin suppliers to innovate their processes and upgrade the quality of their existing epoxy resins.

[0003] For example, the synthesis of epoxy resins inevitably results in residual halogen elements (especially chlorine), which are unacceptable in some demanding fields. The presence of chlorine in epoxy resins can negatively impact electronic components. On one hand, in humid and hot environments, organic chlorine compounds form chloride ions due to trace hydrolysis of the epoxy resin, causing electrochemical corrosion of metal conductors, leading to circuit breaks or signal transmission failures. On the other hand, chloride ions can cause resin degradation during high-temperature curing or long-term service, reducing the dielectric strength and thermal stability of the encapsulation material.

[0004] In the existing technology, relevant research institutions and manufacturers have invested a great deal of effort in trying to develop technologies to remove halogen impurities from epoxy resins, but have been unable to make effective progress. Specifically, inorganic chloride ion impurities in epoxy resins can be relatively easily removed by washing with water, but the removal of organic chlorides is extremely difficult. Even with process improvements and complex purification steps, it is difficult to reduce the organic chloride content to the required low level. Moreover, these operations inevitably increase the complexity of epoxy resin processing and production costs, seriously reducing its commercial competitiveness.

[0005] Furthermore, compared to traditional bisphenol A resins, triphenol-based epoxy resins exhibit higher high-temperature resistance and greater hardness in the cured product; however, they often contain higher halogen content (e.g., chlorine content), posing a greater challenge to halogen removal. Therefore, there is an urgent need for a technology capable of preparing epoxy resins with low halogen content (especially low chlorine content). Summary of the Invention

[0006] To address the aforementioned problems, the inventors of this application conducted extensive and in-depth research and developed an epoxy resin and its preparation method. This method effectively achieves the preparation of epoxy resin with low halogen content (especially low chlorine content) through simple and low-cost process steps. Furthermore, the epoxy resin obtained thereby exhibits excellent properties, thus successfully solving the problems faced by the prior art.

[0007] The first aspect of this application provides a method for preparing epoxy resin, the method comprising the following steps:

[0008] Step 1: In the presence of a catalyst and a co-catalyst, the triphenol compound undergoes an etherification reaction with a halo-epoxyalkane to generate an intermediate product;

[0009] Step 2: Mix the intermediate product with an organic solvent and a solid alkali to induce a cyclization reaction, thereby obtaining the epoxy resin.

[0010] According to an embodiment of the first aspect of this application, the triphenol compound has the structure shown in Formula I:

[0011]

[0012] In formula I, R is a trivalent group selected from trivalent C1-C1 groups. 12 Alkyl, trivalent C2-C 12 alkenyl, trivalent C2-C 12 Aldehyde group, trivalent C1-C 12 Alkoxy, trivalent C3-C 12 cycloalkyl, trivalent C3-C 12 Cycloalkoxy, trivalent C6-C 16 Aryl, trivalent C6-C 16 aryloxy;

[0013] R1-R 15 Each is independently selected from: hydrogen, hydroxyl, C1-C 12 Alkyl, C2-C 12 alkenyl, C1-C 12 Alkoxy, C3-C 12 cycloalkyl, C3-C 12 Cycloalkoxy, C6-C 16 Aryl, C6-C 16 aryloxy;

[0014] And at least one of R1-R5 is a hydroxyl group, R6-R 10 At least one of them is a hydroxyl group, R 11 -R 15 At least one of them is a hydroxyl group.

[0015] According to another embodiment of the first aspect of this application, the halo-epoxyalkane has the structure shown in Formula II:

[0016]

[0017] R 16 R 17 R 18 R19 R 20 R 21 Each is independently selected from H, C1-C 12 Alkyl, C2-C 12 alkenyl, C1-C 12 Alkoxy, C3-C 12 cycloalkyl, C3-C 12 Cycloalkoxy, C6-C 16 Aryl, C6-C 16 Aryloxy, halogen, hydroxyl, nitro, amino, ester group, provided that R 19 R 20 and R 21 At least one of them is a halogen, which is selected from at least one of the following: fluorine, chlorine, bromine, and iodine.

[0018] According to another embodiment of the first aspect of this application, in step one, the catalyst is a quaternary ammonium salt selected from one or more of the following: benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, and tetrabutylammonium chloride.

[0019] According to another embodiment of the first aspect of this application, in step one, the co-catalyst is selected from one or more of the following: methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, and ethylene glycol.

[0020] According to another embodiment of the first aspect of this application, the molar ratio of the catalyst to the triphenol compound is 0.01:1 to 0.1:1.

[0021] According to another embodiment of the first aspect of this application, the molar ratio of the co-catalyst to the triphenol compound is 0.5:1 to 8:1.

[0022] According to another embodiment of the first aspect of this application, the molar ratio of the triphenol compound to the halo-epoxyalkane is 1:3 to 1:25.

[0023] According to another embodiment of the first aspect of this application, in step one, the etherification reaction is carried out at a temperature of 50-110°C for 3-8 hours.

[0024] According to another embodiment of the first aspect of this application, in step two, the organic solvent is selected from one or more of the following: toluene, methyl isobutyl ketone, butanone, and ethylbenzene.

[0025] According to another embodiment of the first aspect of this application, in step two, the molar ratio of the organic solvent to the triphenol compound used in step one is 2:1 to 30:1.

[0026] According to another embodiment of the first aspect of this application, in step two, the solid alkali is selected from one or more of the following: sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0027] According to another embodiment of the first aspect of this application, in step two, the molar ratio of the solid alkali to the triphenol compound used in step one is 3:1 to 8:1.

[0028] According to another embodiment of the first aspect of this application, in step two, the cyclization reaction is carried out at a temperature of 20-80°C for 1-5 hours.

[0029] According to another embodiment of the first aspect of this application, after the etherification reaction in step one is completed, unreacted raw materials are removed from the reaction product mixture before the cyclization reaction in step two is carried out.

[0030] According to another embodiment of the first aspect of this application, after the cyclization reaction in step two, washing and solvent removal operations are performed.

[0031] According to another embodiment of the first aspect of this application, after the etherification reaction in step one is completed, unreacted raw materials are removed from the reaction product mixture by distillation at a temperature of 60 to 150°C for 1 to 4 hours under reduced pressure of -0.06 to -0.1 MPa, and then the cyclization reaction in step two is carried out.

[0032] According to another embodiment of the first aspect of this application, after the cyclization reaction in step two, the product is washed until neutral, and then distilled for 1-4 hours at a temperature of 60-150°C and a pressure of -0.06--0.1 MPa to remove the solvent.

[0033] The second aspect of this application provides an epoxy resin prepared by the method described in the first aspect of this application.

[0034] According to one embodiment of the second aspect of this application, the total halogen content of the epoxy resin is less than 2000 ppm based on the total mass of the epoxy resin. Attached Figure Description

[0035] In the following detailed embodiments, exemplary technical solutions of this application will be explained and described in conjunction with the accompanying drawings. It should be understood that the scope of protection of this invention is not limited thereto, but is defined by the claims.

[0036] Figure 1 A schematic diagram of the reaction mechanism according to an exemplary embodiment of this application is shown;

[0037] Figure 2The H of the product obtained according to one embodiment of this application is shown. 1 NMR spectrum. Detailed Implementation

[0038] The “range” disclosed in this document takes the form of a lower limit and an upper limit. It can be one or more lower limits and one or more upper limits, respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this way are inclusive and composable; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is also expected that ranges of 60-110 and 80-120 are also included. Furthermore, if the minimum range values ​​are listed as 1 and 2, and if the maximum range values ​​are listed as 3, 4, and 5, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0039] In this application, unless otherwise stated, the numerical range "ab" is a shortened representation of any combination of real numbers from a to b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in this document, and "0-5" is simply a shortened representation of these numerical combinations.

[0040] Unless otherwise specified in this application, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0041] Unless otherwise specified, all technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0042] In this application, unless otherwise specified, the term "comprising" as used herein can be either open-ended or closed-ended. For example, "comprising" may mean that it may also include other components not listed, or it may only include the listed components.

[0043] The method for preparing epoxy resin in this application includes the following steps:

[0044] Step 1: In the presence of a catalyst and a co-catalyst, the triphenol compound undergoes an etherification reaction with a halo-epoxyalkane to generate an intermediate product;

[0045] Step 2: Mix the intermediate product with an organic solvent and a solid alkali to induce a cyclization reaction, thereby obtaining the epoxy resin.

[0046] According to one embodiment of this application, the triphenol compound has the structure shown in Formula I:

[0047]

[0048] In formula I, R is a trivalent group selected from trivalent C1-C1 groups. 12 Alkyl, trivalent C2-C 12 alkenyl, trivalent C2-C 12 Aldehyde group, trivalent C1-C 12 Alkoxy, trivalent C3-C 12 cycloalkyl, trivalent C3-C 12 Cycloalkoxy, trivalent C6-C 16 Aryl, trivalent C6-C 16 Aryloxy groups; for example, R is selected from trivalent C1-C8 alkyl, trivalent C2-C8 alkenyl, trivalent C2-C8 aldehyde, trivalent C1-C8 alkoxy, trivalent C3-C 10 cycloalkyl, trivalent C3-C 10 Cycloalkoxy, trivalent C6-C 12 Aryl, trivalent C6-C 12 aryloxy group; or R is selected from trivalent C1-C6 alkyl, trivalent C2-C6 alkenyl, trivalent C2-C6 aldehyde, trivalent C1-C6 alkoxy, trivalent C3-C8 cycloalkyl, trivalent C3-C8 cycloalkoxy, trivalent C6-C 10 Aryl, trivalent C6-C 10 Aryloxy group; or R is selected from trivalent C1-C4 alkyl, trivalent C2-C4 alkenyl, trivalent C2-C4 aldehyde, trivalent C1-C4 alkoxy, trivalent C3-C6 cycloalkyl, trivalent C3-C6 cycloalkoxy, trivalent C6-C8 aryl, trivalent C6-C8 aryl; preferably R is trivalent methyl (methoxy) or trivalent ethyl (methoxy).

[0049] Additionally, in equation I, R1-R 15 Each is independently selected from: hydrogen, hydroxyl, C1-C 12 Alkyl, C2-C 12 alkenyl, C1-C 12 Alkoxy, C3-C 12 cycloalkyl, C3-C 12 Cycloalkoxy, C6-C 16 Aryl, C6-C 16 Aryloxy groups; for example, R1-R 15 Each is independently selected from: hydrogen, hydroxyl, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 alkoxy, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-C 12 Aryl, C6-C 12 Aryloxy group; and at least one of R1-R5 is a hydroxyl group, R6-R 10 At least one of them is a hydroxyl group, R 11 -R 15At least one of them is a hydroxyl group. That is to say, all three benzene rings shown in Formula I are phenolic or polyphenolic groups, and may optionally be substituted by one or more other substituents as described above.

[0050] In this application, "trivalent group" means that the group represented by R is connected to the three aromatic rings (phenolic rings or substituted phenolic rings) shown in Formula I by three covalent bonds.

[0051] According to an exemplary embodiment of this application, the triphenol compound represented by Formula I is 4,4,4-methylenetriphenol or 1,1,1-tris(4-hydroxyphenyl)ethane.

[0052] According to another embodiment of the first aspect of this application, the halo-epoxyalkane has the structure shown in Formula II:

[0053]

[0054] R 16 R 17 R 18 R 19 R 20 R 21 Each is independently selected from H, C1-C 12 Alkyl, C2-C 12 alkenyl, C1-C 12 Alkoxy, C3-C 12 cycloalkyl, C3-C 12 Cycloalkoxy, C6-C 16 Aryl, C6-C 16 Aryloxy, halogen, hydroxyl, nitro, amino, ester group; or R 16 R 17 R 18 R 19 R 20 R 21 Each is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 alkoxy, C3-C 10 cycloalkyl, C3-C 10 Cycloalkoxy, C6-C 12 Aryl, C6-C 12 Aryloxy, halogen, hydroxyl, nitro, amino, ester group; or R 16 R 17 R 18 R 19 R 20 R 21 Each is independently selected from H, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C6-C 10 Aryl, C6-C10 Aryloxy, halogen, hydroxyl, nitro, amino, ester group. The prerequisite is R. 19 R 20 and R 21 At least one of them is a halogen, which is selected from at least one of the following: fluorine, chlorine, bromine, iodine; preferably, the halogen is chlorine.

[0055] According to an exemplary embodiment of this application, the haloalkylene oxide represented by Formula II is epichlorohydrin.

[0056] According to one embodiment of this application, in step one, the haloepoxide represented by Formula II is chemically equivalent or chemically excess of the triphenol compound represented by Formula I. Specifically, the molar ratio of the triphenol compound represented by Formula I to the haloepoxide represented by Formula II is 1:3 to 1:25, for example 1:5 to 1:25, or 1:10 to 1:25, or 1:15 to 1:25, or 1:17 to 1:24.

[0057] According to one embodiment of this application, the catalyst used in step one is a quaternary ammonium salt, such as a salt formed by a halide anion and a quaternary ammonium cation. For example, the catalyst is selected from one or more of the following: benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, and tetrabutylammonium chloride; preferably benzyltriethylammonium chloride or tetraethylammonium chloride.

[0058] According to one embodiment of this application, in step one, the molar ratio of the catalyst to the triphenol compound represented by Formula I is 0.01:1 to 0.1:1, for example 0.02:1 to 0.08:1, or 0.03:1 to 0.07:1, or 0.04:1 to 0.06:1, or within a range obtained by combining any two of the above end values.

[0059] According to another embodiment of this application, the co-catalyst used in step one is selected from one or more of the following: methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol; preferably ethanol, isopropanol or n-butanol.

[0060] According to another embodiment of this application, in step one, the molar ratio of the co-catalyst to the triphenol compound is 0.5:1 to 8:1, for example 1:1 to 6:1, or 2:1 to 5:1, or 3:1 to 4:1, or within a range obtained by combining any two of the above end values.

[0061] According to another embodiment of this application, in step one, the etherification reaction is carried out at a temperature of 50-110°C for 3-8 hours; for example, the temperature of the etherification reaction can be 70-110°C or 90-110°C.

[0062] According to another embodiment of this application, the etherification reaction mixture generated from the etherification reaction contains the target intermediate product, as well as a large amount of unreacted starting material. Since the haloepoxides of this invention are chemically equivalent or chemically excess, the etherification reaction mixture contains a large amount of unreacted haloepoxides. It is necessary to remove the unreacted starting material from the etherification reaction product mixture before subjecting the intermediate product to the cyclization reaction in step two.

[0063] According to another embodiment of the first aspect of this application, after the etherification reaction in step one is completed, unreacted raw materials (halogenated epoxides) are removed from the etherification reaction product mixture by distillation at a temperature of 60 to 150°C for 1 to 4 hours under reduced pressure of -0.06 to -0.1 MPa. The remaining material (intermediate product) is then sent to carry out the cyclization reaction in step two.

[0064] Figure 1 This diagram illustrates a reaction flow according to an exemplary embodiment of the present application, wherein the triphenol compound is 4,4,4-methylenetriphenol, and the haloepoxide is epichlorohydrin. The two undergo an etherification reaction in the presence of a catalyst and a co-catalyst to produce… Figure 1 The chlorine-containing intermediate product is shown. This mixture of etherification reaction products, after distillation to remove excess epichlorohydrin, is further fed into a cyclization reaction to produce… Figure 1 The target product shown is epoxy resin.

[0065] According to one embodiment of this application, the organic solvent used in step two is selected from one or more of the following: toluene, methyl isobutyl ketone, butanone, ethylbenzene; preferably toluene or methyl isobutyl ketone.

[0066] According to another embodiment of this application, in step two, the molar ratio of the organic solvent to the triphenol compound used in step one is 2:1 to 30:1, for example, 5:1 to 25:1, or 10:1 to 20:1, or 12:1 to 15:1, or within a range obtained by combining any two of the above end values.

[0067] According to one embodiment of this application, the solid alkali used in step two is selected from one or more of the following: sodium hydroxide, potassium hydroxide, and lithium hydroxide; preferably sodium hydroxide.

[0068] According to another embodiment of the first aspect of this application, in step two, the molar ratio of the solid alkali to the triphenol compound used in step one is 3:1 to 8:1, for example, 4:1 to 7:1, or 5:1 to 6:1, or within a range obtained by combining any two of the above end values.

[0069] According to another embodiment of this application, the cyclization reaction in step two is carried out at a temperature of 20-80°C for 1-5 hours, for example, the reaction temperature can be 50-70°C and the reaction time can be 2-4 hours.

[0070] According to another embodiment of this application, water is not added to the reaction system during the cyclization reaction.

[0071] According to another embodiment of this application, the cyclization reaction product mixture formed by the cyclization reaction contains organic solvents in addition to the target product, requiring a third step: washing and solvent removal.

[0072] Specifically, in step three, the cyclization reaction product mixture is first washed with water until neutral, and then distilled for 1-4 hours at a temperature of 60-150°C and a pressure of -0.06--0.1 MPa to remove the solvent.

[0073] Based on the method of the present invention described above, particularly the use of an anhydrous system in the cyclization reaction process, epoxy resin products are prepared using a simple and cost-effective process. The halogen content is significantly reduced; for example, based on the total mass of the epoxy resin, the total halogen content is less than 2000 ppm, or less than 1950 ppm, preferably less than 1800 ppm, more preferably less than 1600 ppm, and even more preferably less than 1500 ppm. The applicant has also found that the epoxy resin obtained by the present invention possesses extremely superior properties, such as epoxy value and viscosity at the target operating temperature. The combination of the aforementioned extremely low halogen content and other excellent properties makes the epoxy resin of the present invention highly suitable for high-standard advanced electronic and electrical applications.

[0074] The present application is described below by way of specific embodiments, the purpose of which is to provide a better understanding of the content of the present application. It should be understood that these embodiments are merely illustrative and not restrictive. The reagents used in the embodiments, unless otherwise stated, are commercially available. The methods and conditions used in the embodiments, unless otherwise specified, are conventional methods and conditions.

[0075] Example

[0076] Preferred embodiments of the present invention are specifically illustrated in the following examples; however, it should be understood that the scope of protection of this application is not limited thereto. All equivalent transformations or modifications made in accordance with the essence of this application should be covered within the scope of protection of this application.

[0077] In the following examples, the epoxy value of the epoxy resin was measured according to the national standard method GB-T1677-2008.

[0078] The viscosity of epoxy resin was measured according to the national standard method GBT 22314-2008.

[0079] The total chlorine content of epoxy resin was measured according to ISO 21627-3:2009.

[0080] Example 1

[0081] Add 630 g of epichlorohydrin, 98 g of 4,4,4-methylenetriphenol, 1.5 g of benzyltriethylammonium chloride, and 50 g of ethanol to a 2000 ml four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Start stirring and heat the mixture in the flask to 90°C, maintaining this temperature for 4 hours. After the reaction is complete, distill the mixture in the flask at -0.09 MPa and 85°C for 2 hours to remove unreacted epichlorohydrin. After distillation, lower the temperature of the reaction system to 50°C, add 300 g of toluene, then add 49 g of solid sodium hydroxide. Maintain the temperature of the mixture in the flask at 50°C and continue the reaction under these conditions for 3 hours, then stop heating.

[0082] The materials in the reactor were separated into layers. The oil phase was recovered by liquid-liquid separation, washed with deionized water until neutral, and then distilled for 2 hours at -0.09 MPa and 120°C to remove toluene. The obtained product was characterized by NMR. 1 NMR spectrum as follows Figure 2 As shown, this embodiment demonstrates that epoxy resin was successfully prepared.

[0083] Characterized using the above-mentioned detection techniques, its yield was found to be 95%, epoxy value was 0.61 mol / 100 g, and viscosity was 2300 mPa•s@70. o C, the total chlorine content is 1760 ppm.

[0084] Example 2

[0085] Add 630 g of epichlorohydrin, 98 g of 4,4,4-methylenetriphenol, 1.5 g of benzyltriethylammonium chloride, and 57 g of isopropanol to a 2000 ml four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Start stirring and heat the mixture to 80°C, maintaining this temperature for 8 hours. After the reaction, distill the mixture at 90°C under a pressure of -0.08 MPa for 1 hour to remove unreacted epichlorohydrin. After distillation, lower the temperature of the reaction system to 50°C, add 300 g of toluene, then add 50 g of solid sodium hydroxide. Maintain the temperature of the mixture at 50°C and continue the reaction under these conditions for 3 hours, then stop heating.

[0086] The material in the reactor was separated into layers. The oil phase was recovered by liquid separation and washed with deionized water until neutral. Toluene was removed by distillation at a pressure of -0.09 MPa and a temperature of 120°C for 3 hours. The obtained product was characterized by nuclear magnetic resonance, which proved that epoxy resin was prepared in this example.

[0087] Characterized using the above-mentioned detection techniques, its yield was found to be 92%, epoxy value was 0.60 mol / 100 g, and viscosity was 2780 mPa•s@70. o C, the total chlorine content is 1540 ppm.

[0088] Example 3

[0089] Add 630 g of epichlorohydrin, 100 g of 1,1,1-tris(4-hydroxyphenyl)ethane, 2.5 g of benzyltriethylammonium chloride, and 85 g of isopropanol to a 2000 ml four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Start stirring and heat the mixture in the flask to 100°C, maintaining this temperature for 3 hours. After the reaction is complete, distill the mixture in the flask at -0.09 MPa and 80°C for 2 hours to remove unreacted epichlorohydrin. After distillation, lower the temperature of the reaction system to 50°C, add 250 g of toluene, then add 60 g of solid sodium hydroxide. Maintain the temperature of the mixture in the flask at 50°C and continue the reaction under these conditions for 4 hours, then stop heating.

[0090] The materials in the reactor were separated into layers. The oil phase was recovered by liquid separation and washed with deionized water until neutral. Toluene was removed by distillation at a pressure of -0.09 MPa and a temperature of 120°C for 2 hours. The obtained product was characterized by nuclear magnetic resonance, which proved that epoxy resin was prepared in this example.

[0091] Characterized using the above-mentioned detection techniques, its yield was found to be 93%, epoxy value was 0.60 mol / 100 g, and viscosity was 3720 mPa•s@70. o C, the total chlorine content is 1920 ppm.

[0092] Example 4

[0093] Add 540 g of epichlorohydrin, 100 g of 1,1,1-tris(4-hydroxyphenyl)ethane, 2.5 g of benzyltriethylammonium chloride, and 50 g of ethanol to a 2000 ml four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Start stirring and heat the mixture in the flask to 90°C, maintaining this temperature for 4 hours. After the reaction is complete, distill the mixture in the flask at -0.09 MPa and 120°C for 2 hours to remove unreacted epichlorohydrin. After distillation, lower the temperature of the reaction system to 60°C, add 400 g of methyl isobutyl ketone, and then add 60 g of solid potassium hydroxide. Maintain the temperature of the mixture in the flask at 60°C and continue the reaction under these conditions for 2 hours, then stop heating.

[0094] The materials in the reactor were separated into layers. The oil phase was recovered by liquid separation and washed with deionized water until neutral. Methyl isobutyl ketone was removed by distillation at a pressure of -0.08 MPa and a temperature of 150°C for 2 hours. The obtained product was characterized by nuclear magnetic resonance, which proved that epoxy resin was prepared in this example.

[0095] Characterized using the above-mentioned detection techniques, its yield was found to be 90%, epoxy value was 0.58 mol / 100 g, and viscosity was 4260 mPa•s@70. o C, the total chlorine content is 1770 ppm.

[0096] Example 5

[0097] Add 750 g of epichlorohydrin, 98 g of 4,4,4-methylenetriphenol, 2.0 g of tetraethylammonium chloride, and 50 g of ethanol to a 2000 ml four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Start stirring and heat the mixture in the flask to 95°C, maintaining this temperature for 5 hours. After the reaction, distill the mixture in the flask at -0.09 MPa and 130°C for 1 hour to remove unreacted epichlorohydrin. After distillation, lower the temperature of the reaction system to 50°C, add 300 g of methyl isobutyl ketone, and then add 50 g of solid sodium hydroxide. Maintain the temperature of the mixture in the flask at 50°C and continue the reaction under these conditions for 3 hours, then stop heating.

[0098] The materials in the reactor were separated into layers. The oil phase was recovered by liquid separation and washed with deionized water until neutral. Methyl isobutyl ketone was removed by distillation at a pressure of -0.08 MPa and a temperature of 140°C for 2 hours. The obtained product was characterized by nuclear magnetic resonance, which proved that epoxy resin was prepared in this example.

[0099] Characterized using the above-mentioned detection techniques, its yield was found to be 95%, epoxy value was 0.62 mol / 100 g, and viscosity was 1850 mPa•s@70. o C, the total chlorine content is 1450 ppm.

[0100] Example 6

[0101] Add 540 g of epichlorohydrin, 98 g of 4,4,4-methylenetriphenol, 2.0 g of tetraethylammonium chloride, and 80 g of n-butanol to a 2000 ml four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Start stirring and heat the mixture in the flask to 110°C, maintaining this temperature for 4 hours. After the reaction, distill the mixture in the flask at -0.09 MPa and 140°C for 2 hours to remove unreacted epichlorohydrin. After distillation, lower the temperature of the reaction system to 70°C, add 400 g of methyl isobutyl ketone, and then add 50 g of solid sodium hydroxide. Maintain the temperature of the mixture in the flask at 70°C and continue the reaction under these conditions for 2 hours, then stop heating.

[0102] The materials in the reactor were separated into layers. The oil phase was recovered by liquid separation and washed with deionized water until neutral. Methyl isobutyl ketone was removed by distillation at a pressure of -0.08 MPa and a temperature of 140°C for 2 hours. The obtained product was characterized by nuclear magnetic resonance, which proved that epoxy resin was prepared in this example.

[0103] Characterized using the above-mentioned detection techniques, its yield was found to be 89%, epoxy value was 0.57 mol / 100 g, and viscosity was 3100 mPa•s@70. o C, the total chlorine content is 1870 ppm.

[0104] To further demonstrate the superior technical advancements achieved by the method of this invention, the following comparative examples are provided. These comparative examples employ synthesis processes that do not fall within the scope of protection of this invention.

[0105] Comparative Example 1

[0106] Add 630 g of epichlorohydrin, 98 g of 4,4,4-methylenetriphenol, 1.5 g of benzyltriethylammonium chloride, and 50 g of ethanol to a 2000 ml four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Start stirring and heat the contents of the flask to 90°C, maintaining the reaction at this temperature for 4 hours. Then, lower the temperature of the reaction system to 50°C and add 98 g of a 50% sodium hydroxide aqueous solution. Maintain the temperature of the contents of the flask at 50°C and continue the reaction under these conditions for 3 hours, after which heating is stopped.

[0107] The materials in the reactor were separated into layers. The oil phase was recovered through liquid-liquid separation and washed with deionized water until neutral. Unreacted epichlorohydrin and ethanol were removed by distillation for 2 hours at -0.09 MPa and 120°C to obtain the epoxy resin product. Characterization using the above-mentioned detection techniques revealed a yield of 85%, an epoxy value of 0.60 mol / 100 g, and a viscosity of 2690 mPa•s@70. o C, the total chlorine content is 7420 ppm.

[0108] Comparative Example 2

[0109] Add 540 g of epichlorohydrin, 100 g of 1,1,1-tris(4-hydroxyphenyl)ethane, 2.5 g of benzyltriethylammonium chloride, and 50 g of ethanol to a 2000 ml four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Start stirring and heat the contents of the flask to 90°C, maintaining the reaction at this temperature for 4 hours. Then, lower the temperature of the reaction system to 60°C and add 120 g of a 50% potassium hydroxide aqueous solution. Maintain the temperature of the contents of the flask at 60°C and continue the reaction under these conditions for 2 hours, after which heating is stopped.

[0110] The materials in the reactor were separated into layers. The oil phase was recovered by liquid-liquid separation and washed with deionized water until neutral. Unreacted epichlorohydrin and ethanol were removed by distillation for 2 hours at -0.08 MPa and 150°C to obtain the epoxy resin product. Characterization using the above-mentioned detection techniques revealed a yield of 84%, an epoxy value of 0.59 mol / 100 g, and a viscosity of 3890 mPa•s@70. o C, the total chlorine content is 6850 ppm.

Claims

1. A method for preparing epoxy resin, the method comprising the following steps: Step 1: In the presence of a catalyst and a co-catalyst, the triphenol compound undergoes an etherification reaction with a halo-epoxyalkane to generate an intermediate product; Step 2: Mix the intermediate product with an organic solvent and a solid alkali to induce a cyclization reaction, thereby obtaining the epoxy resin.

2. The method as described in claim 1, characterized in that, The triphenol compound has the structure shown in Formula I: In formula I, R is a trivalent group selected from trivalent C1-C1 groups. 12 Alkyl, trivalent C2-C 12 alkenyl, trivalent C2-C 12 Aldehyde group, trivalent C1-C 12 Alkoxy, trivalent C3-C 12 cycloalkyl, trivalent C3-C 12 Cycloalkoxy, trivalent C6-C 16 Aryl, trivalent C6-C 16 aryloxy; R1-R 15 Each is independently selected from: hydrogen, hydroxyl, C1-C 12 Alkyl, C2-C 12 alkenyl, C1-C 12 Alkoxy, C3-C 12 cycloalkyl, C3-C 12 Cycloalkoxy, C6-C 16 Aryl, C6-C 16 aryloxy; And at least one of R1-R5 is a hydroxyl group, R6-R 10 At least one of them is a hydroxyl group, R 11 -R 15 At least one of them is a hydroxyl group.

3. The method as described in claim 1, characterized in that, The halo-oxidized alkane has the structure shown in Formula II: R 16 R 17 R 18 R 19 R 20 R 21 Each is independently selected from H, C1-C 12 Alkyl, C2-C 12 alkenyl, C1-C 12 Alkoxy, C3-C 12 cycloalkyl, C3-C 12 Cycloalkoxy, C6-C 16 Aryl, C6-C 16 Aryloxy, halogen, hydroxyl, nitro, amino, ester group, provided that R 19 R 20 and R 21 At least one of them is a halogen, which is selected from at least one of the following: fluorine, chlorine, bromine, and iodine.

4. The method as described in claim 1, characterized in that, In step one, The catalyst is a quaternary ammonium salt, selected from one or more of the following: benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, and tetrabutylammonium chloride; The co-catalyst is selected from one or more of the following: methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, and ethylene glycol; The molar ratio of the catalyst to the triphenol compound is from 0.01:1 to 0.1:1; The molar ratio of the co-catalyst to the triphenol compound is 0.5:1 to 8:1; The molar ratio of the triphenol compound to the halo-oxidized alkane is 1:3 to 1:

25.

5. The method as described in claim 1, characterized in that, In step one, the etherification reaction is carried out at a temperature of 50-110°C for 3-8 hours.

6. The method as described in claim 1, characterized in that, In step two, The organic solvent is selected from one or more of the following: toluene, methyl isobutyl ketone, methyl ethyl ketone, and ethylbenzene; The molar ratio of the organic solvent to the triphenol compound used in step one is 2:1 to 30:1; The solid alkali is selected from one or more of the following: sodium hydroxide, potassium hydroxide, and lithium hydroxide; The molar ratio of the solid alkali to the triphenol compound used in step one is 3:1 to 8:1; and In step two, the cyclization reaction is carried out at a temperature of 20-80°C for 1-5 hours.

7. The method as described in claim 1, characterized in that, After the etherification reaction in step one is completed, the unreacted raw materials are removed from the reaction product mixture, and then the cyclization reaction in step two is carried out. After the cyclization reaction in step two, washing and solvent removal are performed.

8. The method as described in claim 7, characterized in that, After the etherification reaction in step one is completed, the unreacted raw materials are removed from the reaction product mixture by distillation at a temperature of 60 to 150°C for 1 to 4 hours under reduced pressure of -0.06 to -0.1 MPa, and then the cyclization reaction in step two is carried out. After the cyclization reaction in step two, the product is washed until neutral, and then distilled for 1-4 hours at a temperature of 60-150°C and a pressure of -0.06--0.1 MPa to remove the solvent.

9. An epoxy resin prepared by any one of claims 1-8.

10. The epoxy resin as described in claim 9, characterized in that, Based on the total mass of the epoxy resin, the total halogen content of the epoxy resin is less than 2000 ppm.

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