Epoxy resin with low hydrolytic chlorine content and preparation method thereof

Abstract

The invention provides epoxy resin with low hydrolytic chlorine content and a preparation method thereof. The content of hydrolytic chlorine in the epoxy resin is less than or equal to 50ppm. The content of hydrolyzed chlorine in the epoxy resin provided by the invention can be lower than the content of hydrolyzed chlorine in the existing commercially available epoxy resin product by one order of magnitude. The epoxy resin with low hydrolytic chlorine content provided by the invention can meet the requirements of high-end fields such as IC (Integrated Circuit) packaging and the like.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin technology, and more specifically, to an epoxy resin with low hydrolytic chlorine content and its preparation method. Background Technology

[0002] Epoxy resins possess abundant reactive groups, including epoxy groups, hydroxyl groups, ether bonds, and other active and polar groups. They can be combined with various curing agents to form curing systems and cured products with excellent performance and diverse characteristics, meeting the requirements of different applications and processing conditions. Therefore, they are widely used in coatings, electronics, composite materials, building materials, aerospace materials, and new energy vehicles.

[0003] Epoxy resins are generally manufactured from phenols, amines, carboxylic acids, alcohols, and epichlorohydrin, using caustic soda as a catalyst. During the reaction process, incomplete reactions and side reactions result in the presence of impurities such as hydrolyzable chlorine and non-hydrolyzable chlorine, as well as residual inorganic chloride ions in the finished product. Inorganic chloride ions can be removed to below 1 ppm through repeated water washing. Non-hydrolyzable chlorine has a relatively small impact on resin properties, while hydrolyzable chlorine significantly affects the curing reactivity of epoxy resins and the properties of the cured product. Particularly in the electronics and electrical appliance industry, the presence of hydrolyzable chlorine can corrode electronic components. Therefore, epoxy resins with low hydrolyzable chlorine content are in high-end applications. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides an epoxy resin with low hydrolyzable chlorine content and its preparation method. The hydrolyzable chlorine content in the epoxy resin provided by this invention is significantly lower than that in commercially available epoxy resin products, potentially by an order of magnitude. The low hydrolyzable chlorine content epoxy resin provided by this invention can meet the needs of high-end applications such as IC packaging.

[0005] Firstly, one of the objectives of this invention is to provide an epoxy resin with low hydrolyzable chlorine content.

[0006] Specifically, the hydrolyzed chlorine content in the epoxy resin provided by the present invention can be as low as less than or equal to 50 ppm; more preferably, the hydrolyzed chlorine content in the epoxy resin can be as low as between 5 and 30 ppm. The hydrolyzed chlorine content in the epoxy resin provided by the present invention is reduced by at least one order of magnitude compared with the hydrolyzed chlorine content in existing commercially available epoxy resin products.

[0007] Furthermore, the epoxy resin molecule mentioned above includes at least two epoxy groups; preferably, the epoxy resin can be any one of glycidyl ether group, glycidyl ester group, or glycidyl amine group epoxy resin.

[0008] Secondly, another objective of the present invention is to provide a method for preparing epoxy resin with low hydrolytic chlorine content, which is one of the objectives of the present invention.

[0009] Specifically, the preparation method includes the following steps: adding components including a polyhydroxy compound and an alkaline catalyst into an epoxy resin solution for reaction, and washing with water to obtain an epoxy resin with low hydrolytic chlorine content.

[0010] More specifically, the preparation method includes the following steps: adding a polyhydroxy compound to hot water and adding an alkaline catalyst to form a stable mixture, then adding it to an epoxy resin solution for reaction, and washing with water after the reaction to obtain an epoxy resin with low hydrolytic chlorine content.

[0011] It is worth noting that the hydrolyzed chlorine content in epoxy resins prepared by existing methods or commercially available products is often relatively high, typically around 800-1000 ppm. However, some high-end applications require a lower hydrolyzed chlorine content in epoxy resins; for example, electronic-grade epoxy resins require a hydrolyzed chlorine content of less than 300 ppm. Typically, the hydrolyzed chlorine in epoxy resins is mainly composed of unclosed chloropropanol compounds. This invention involves adding a polyhydroxy compound to the epoxy resin. The polyhydroxy compound reacts with the hydrolyzed chlorine to effectively convert organic chlorine into inorganic chlorine. Water washing then almost completely removes the inorganic chlorine from the epoxy resin, effectively eliminating the hydrolyzed chlorine. Furthermore, the polyhydroxy compound used in this invention can be completely removed by multiple water washes, and its participation has almost no impact on the epoxy resin before and after the reaction.

[0012] Furthermore, the temperature of the hot water is 80–100°C; the reaction temperature is 70–100°C, preferably 80–100°C; and the reaction time is 1–8 hours, preferably 2–6 hours.

[0013] Furthermore, the mixture obtained after the reaction is cooled, preferably to 10–35°C, more preferably to room temperature.

[0014] Furthermore, the washing method is as follows: deionized water is used, and the amount of deionized water is 3 to 10 times the mass of epoxy resin; the water temperature is 50 to 80°C; and the washing is repeated 3 to 5 times.

[0015] It is worth mentioning that the epoxy resin containing hydrolyzed chlorine used in this case contains two or more epoxy groups in its molecules; it can be a commercially available epoxy resin with a hydrolyzed chlorine content greater than 300 ppm.

[0016] Furthermore, the polyhydroxy compound is selected from at least one of polyvinyl alcohol, D-sorbitol, corn starch, and chitosan; wherein the amount of the polyhydroxy compound is 0.1% to 1% of the mass of the epoxy resin.

[0017] Further, the alkaline catalyst is selected from alkali metal hydroxides and / or alkali metal carbonates; preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate; wherein, the amount of alkaline catalyst used is 0.1 to 1% of the mass of epoxy resin.

[0018] Furthermore, the solvent in the epoxy resin solution is an organic solvent insoluble in water. Preferably, the organic solvent is selected from at least one of toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone. This invention uses the aforementioned solvent to both fully dissolve the epoxy resin and to effectively separate the inorganic chlorine produced in the reaction. Furthermore, the solvent is immiscible with water, which is more conducive to the removal of inorganic chlorine and polyhydroxy compounds by water washing after the reaction.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] 1. The raw materials used in this invention are widely available, low in cost, and highly efficient in processing.

[0021] 2. The process method provided by this invention is simple, mild, has a short processing time, and is highly efficient. It is suitable for industrial production to remove hydrolyzed chlorine from epoxy resin.

[0022] 3. This invention utilizes the nucleophilic substitution reaction between the hydroxyl groups in the polyhydroxy compound and the chlorine-containing compound in the epoxy resin to convert organic chlorine into inorganic chlorine. The inorganic chlorine is then removed by water washing, which effectively removes the chlorine-containing compound from the epoxy resin and reduces the hydrolyzed chlorine content in the epoxy resin, meeting the needs of epoxy resin in high-end fields such as IC packaging. Detailed Implementation

[0023] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0024] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.

[0025] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0026] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0027] Unless otherwise specified, the raw materials used in the examples and comparative examples are all publicly available in the prior art, such as those that can be directly purchased or prepared according to publicly available methods. The specific sources of some of these raw materials are as follows:

[0028] Bisphenol A type epoxy resin is derived from Baling Petrochemical CYD-128 epoxy;

[0029] Bisphenol F type epoxy resin is derived from OLin DER351;

[0030] 4,4'-Diaminodiphenylmethane epoxy resin is derived from Shanghai Huayi Resin AG-80;

[0031] All other raw materials are from commercially available products.

[0032] In the following examples and comparative examples, the test method for hydrolyzed chlorine adopts GB / T 4618.2-2008, Determination of chlorine content in plastics and epoxy resins, Part 2, Saponifiable chlorine.

[0033] The specific embodiments and comparative examples provided by this invention are as follows:

[0034] Example 1

[0035] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0036] Step 1: Dissolve 100g of bisphenol A type epoxy resin (measured hydrolytic chlorine content 531ppm) in 200g of toluene;

[0037] Step 2: Dissolve 0.5g of polyvinyl alcohol completely in 10g of hot water at 90℃, then add 0.5g of sodium hydroxide to dissolve, forming a stable aqueous solution;

[0038] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 30ppm.

[0039] Example 2

[0040] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0041] Step 1: Dissolve 100g of bisphenol F epoxy resin (measured hydrolytic chlorine content 815ppm) in 200g of toluene;

[0042] Step 2: Dissolve 0.8g of polyvinyl alcohol completely in 10g of hot water at 90℃, then add 0.5g of sodium hydroxide to dissolve, forming a stable aqueous solution;

[0043] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 26ppm.

[0044] Example 3

[0045] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0046] Step 1: Dissolve 100g of bisphenol A type epoxy resin (hydrolyzed chlorine content 531ppm) in 200g of xylene;

[0047] Step 2: Dissolve 0.5g of polyvinyl alcohol completely in 10g of hot water at 90℃, then add 0.5g of sodium hydroxide to dissolve, forming a stable aqueous solution;

[0048] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 41ppm.

[0049] Example 4

[0050] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0051] Step 1: Dissolve 100g of bisphenol A type epoxy resin (measured hydrolytic chlorine content 531ppm) in 200g of toluene;

[0052] Step 2: Dissolve 0.5g of polyvinyl alcohol completely in 10g of hot water at 90℃, then add 0.5g of potassium hydroxide to dissolve, forming a stable aqueous solution;

[0053] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 18ppm.

[0054] Example 5

[0055] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0056] Step 1: Dissolve 100g of bisphenol A type epoxy resin (measured hydrolytic chlorine content 531ppm) in 200g of toluene;

[0057] Step 2: Dissolve 0.5g of polyvinyl alcohol completely in 10g of hot water at 90℃, then add 0.5g of sodium hydroxide to dissolve, forming a stable aqueous solution;

[0058] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 100℃, and the reaction time is 5 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 16ppm.

[0059] Example 6

[0060] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0061] Step 1: Dissolve 100g of bisphenol A type epoxy resin (measured hydrolytic chlorine content 531ppm) in 200g of toluene;

[0062] Step 2: Dissolve 0.5g of polyvinyl alcohol completely in 10g of hot water at 90℃, then add 0.5g of sodium hydroxide to dissolve, forming a stable aqueous solution;

[0063] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 300g of deionized water at 60℃ and wash three times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 42ppm.

[0064] Example 7

[0065] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0066] Step 1: Dissolve 100g of diglycidyl phthalate (measured hydrolyzed chlorine content 872ppm) in 200g of toluene;

[0067] Step 2: Dissolve 0.8g of D-sorbitol completely in 10g of hot water at 90℃, then add 0.5g of sodium hydroxide to dissolve it, forming a stable aqueous solution;

[0068] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 35ppm.

[0069] Example 8

[0070] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0071] Step 1: Dissolve 100g of 4,4'-diaminodiphenylmethane epoxy resin (measured hydrolytic chlorine content 625ppm) in 200g of toluene;

[0072] Step 2: Add 0.8g of corn starch to 10g of hot water at 90℃, then add 0.5g of sodium hydroxide to dissolve it, forming a stable aqueous solution;

[0073] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 32ppm.

[0074] Example 9

[0075] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0076] Step 1: Dissolve 100g of bisphenol A type epoxy resin (measured hydrolytic chlorine content 531ppm) in 200g of toluene;

[0077] Step 2: Add 0.5g of chitosan to 10g of hot water at 90℃, then add 0.5g of sodium hydroxide to dissolve it, forming a stable aqueous solution;

[0078] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 45ppm.

[0079] Example 10

[0080] This embodiment illustrates the preparation of epoxy resin, and the specific process is as follows:

[0081] Step 1: Dissolve 100g of bisphenol A type epoxy resin (measured hydrolytic chlorine content 531ppm) in 200g of toluene;

[0082] Step 2: Dissolve 0.5g of polyvinyl alcohol completely in 10g of hot water at 90℃, then add 0.5g of potassium carbonate to dissolve, forming a stable aqueous solution;

[0083] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 36ppm.

[0084] Comparative Example 1

[0085] This comparative example illustrates the preparation of epoxy resin, and the specific process is as follows:

[0086] Step 1: Dissolve 100g of bisphenol A type epoxy resin (measured hydrolytic chlorine content 531ppm) in 200g of toluene;

[0087] Step 2: Dissolve 0.5g of polyvinyl alcohol completely in 10g of hot water at 90℃ to form a stable aqueous solution;

[0088] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After that, cool to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 475ppm.

[0089] Comparative Example 2

[0090] This comparative example illustrates the preparation of epoxy resin, and the specific process is as follows:

[0091] Step 1: Dissolve 100g of bisphenol A type epoxy resin (measured hydrolytic chlorine content 531ppm) in 200g of toluene;

[0092] Step 2: Dissolve 0.5g of sodium hydroxide completely in 10g of water to form a stable aqueous solution;

[0093] Step 3: Add the aqueous solution from Step 2 to Step 1, and stir the reaction in a flask equipped with a reflux condenser. The reaction temperature is 80℃, and the reaction time is 3 hours. After cooling to 30℃, add 500g of deionized water at 60℃ and wash 5 times to separate the organic phase. Remove the solvent by vacuum distillation at 100℃ to obtain epoxy resin with low hydrolytic chlorine content. The hydrolytic chlorine content test result is 168ppm.

[0094] Finally, it should be noted that while the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. The above embodiments are merely illustrative of the technical solutions of the present invention and are not intended to limit it. Those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and all fall within the protection scope of the present invention.

Claims

1. An epoxy resin with low hydrolyzable chlorine content, wherein the hydrolyzable chlorine content in the epoxy resin is less than or equal to 50 ppm.

2. The epoxy resin with low hydrolyzable chlorine content according to claim 1, characterized in that, The epoxy resin contains less than or equal to 5 to 30 ppm of hydrolyzed chlorine.

3. The epoxy resin with low hydrolyzable chlorine content according to claim 1, characterized in that, The epoxy resin molecule includes at least two epoxy groups.

4. The epoxy resin with low hydrolyzable chlorine content according to claim 3, characterized in that, The epoxy resin is selected from at least one of glycidyl ether-based, glycidyl ester-based, and glycidyl amine-based epoxy resins.

5. A method for preparing an epoxy resin with low hydrolyzable chlorine content according to any one of claims 1 to 4, the method comprising: Components including polyhydroxy compounds and alkaline catalysts are added to an epoxy resin solution for reaction, and then washed with water to obtain an epoxy resin with low hydrolytic chlorine content.

6. The preparation method according to claim 5, characterized in that, The process includes the following steps: adding a polyhydroxy compound to hot water and adding an alkaline catalyst to form a stable mixture, then adding it to an epoxy resin solution to react, and washing with water after the reaction to obtain the epoxy resin with low hydrolytic chlorine content.

7. The preparation method according to claim 5, characterized in that, The hydrolyzed chlorine-containing epoxy resin contains two or more epoxy groups in its molecules; and / or, The epoxy resin contains more than 300 ppm of hydrolyzed chlorine.

8. The preparation method according to claim 5, characterized in that, The polyhydroxy compound is selected from at least one of polyvinyl alcohol, D-sorbitol, corn starch, and chitosan; and / or, The amount of the polyhydroxy compound used is 0.1% to 1% of the mass of the epoxy resin.

9. The preparation method according to claim 5, characterized in that, The alkaline catalyst is selected from alkali metal hydroxides and / or alkali metal carbonates; preferably at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate; and / or, The amount of alkaline catalyst used is 0.1% to 1% of the mass of epoxy resin.

10. The method for preparing the epoxy resin with low hydrolyzable chlorine content according to claim 6, characterized in that, The solvent in the epoxy resin solution is selected from water-insoluble organic solvents, preferably at least one of toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone.

11. The method for preparing the epoxy resin with low hydrolyzable chlorine content according to claim 6, characterized in that, The temperature of the hot water is 80–100°C; and / or, The reaction temperature is 70–100°C, preferably 80–100°C; and / or, The reaction time is 1–8 hours, preferably 2–6 hours; and / or, The mixture obtained from the reaction was cooled before washing with water.

12. The method for preparing the epoxy resin with low hydrolyzable chlorine content according to claim 6, characterized in that, The water washing method is as follows: the amount of water used is 3 to 10 times the mass of the epoxy resin; the water temperature is 50 to 80°C; washing is performed 3 to 5 times; deionized water is used.