Preparation method of brominated epoxy resin with ultraviolet light shielding property

Abstract

The invention discloses a preparation method of brominated epoxy resin with ultraviolet light shielding property, which comprises the following steps: reacting basic liquid epoxy resin E-51 with tetrabromobisphenol A and phenolic resin to synthesize brominated epoxy resin, and adding a solvent to adjust the viscosity of the system, thereby finally obtaining the brominated epoxy resin with ultraviolet light shielding property. The prepared brominated epoxy resin is novel epoxy resin, the resin system structure contains bromine, the brominated epoxy resin not only has excellent electrical insulativity and adhesion of common epoxy resin, but also has excellent self-flame retardance and ultraviolet shielding effect, provides more excellent performance operation space for use of downstream customers, and has wide application prospects. The flame retardant is mainly used as various flame-retardant composite materials, structural materials, adhesives and coatings, and is widely applied to the industries of buildings, aviation, ships and electronics.

Description

Technical Field

[0001] The invention relates to a method for preparing brominated epoxy resin with ultraviolet light shielding property, belonging to the technical field of polymer materials. Background Art

[0002] Brominated epoxy resin has good self-extinguishing and heat resistance, low toxicity, and is a new type of epoxy resin developed in recent years. Brominated epoxy resin contains bromine in its molecular structure. It not only has the excellent electrical insulation and adhesion of general epoxy resins, but also has excellent self-flaming retardancy. It is mainly used as various flame-retardant composite materials, structural materials, adhesives, and coatings. It is widely used in construction, aviation, shipbuilding, and electronic and electrical industries. At present, no preparation method of brominated epoxy resin with ultraviolet light shielding has been retrieved, so the present invention provides a preparation method of brominated epoxy resin with ultraviolet light shielding. This brominated epoxy resin is used to improve the ability of electronic laminates to block ultraviolet rays. By using this resin, the function of blocking ultraviolet rays can be achieved by reducing or even eliminating the need to use high-cost additives. The resin can be used to prepare the product required for copper-clad laminates using conventional bifunctional epoxy resins, can be applied to existing industrial formulas, and can be molded with a common hot glue machine in combination with a curing agent. Summary of the invention

[0003] Purpose of the invention: Currently, no method for preparing brominated epoxy resin with ultraviolet light shielding properties has been found. Therefore, the present invention provides a method for preparing brominated epoxy resin with ultraviolet light shielding properties, which has better performance than ordinary brominated epoxy resins, has mild production conditions, and is suitable for industrial production.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is:

[0005] A method for preparing a brominated epoxy resin having ultraviolet light shielding properties comprises the following steps:

[0006] (1) One-stage chain extension reaction: Add basic liquid epoxy resin E-51, tetrabromobisphenol A and a certain amount of phenolic resin into the reactor, heat and dissolve and stir evenly, add catalyst, continue to heat and maintain at 140-150°C for a period of time;

[0007] (2) Second stage solvent dilution: After the reaction is completed, a certain amount of acetone solvent is added to adjust the viscosity of the resin system to obtain a brominated epoxy resin with ultraviolet light shielding properties.

[0008] As a preferred embodiment, the method for preparing the brominated epoxy resin having ultraviolet light shielding properties described above comprises the following steps:

[0009] (1) One-stage chain extension reaction: basic liquid epoxy resin E-51 (epoxy equivalent 186 g / eq), tetrabromobisphenol A and a certain amount of phenolic resin are added to the reactor, heated and dissolved and stirred evenly, a catalyst is added, and the temperature is continued to be raised and maintained at 140-150° C. for a period of time. The designed epoxy equivalent of the chain extension reaction is 420-460 g / eq;

[0010] (2) Second stage solvent dilution: After the reaction is completed, a certain amount of acetone solvent is added to adjust the viscosity of the resin system to obtain a brominated epoxy resin with ultraviolet light shielding properties.

[0011] As a preferred embodiment, the above-mentioned method for preparing the brominated epoxy resin having ultraviolet light shielding properties is as follows:

[0012] It is characterized in that

[0013] In step (1), the amount of phenolic resin in the first-stage chain extension reaction is 1%-3% of the mass of the basic liquid epoxy resin E-51, and the mass ratio of the basic liquid epoxy resin E-51 to tetrabromobisphenol A in the first-stage chain extension reaction is 10:4.6-10:5.1; the catalyst is butyltriphenylphosphine bromide, and the amount of the catalyst is 0.5-1‰ of the mass of tetrabromobisphenol A.

[0014] As a more preferred embodiment, in the above-mentioned method for preparing brominated epoxy resin with UV shielding properties, in step (1), the amount of phenolic resin TPN used in the chain extension reaction is 1%, 2%, or 3% of the mass of the basic liquid epoxy resin E-51.

[0015] As a more preferred embodiment, the above-mentioned method for preparing the brominated epoxy resin having ultraviolet light shielding properties is as follows:

[0016] In step (1), the mass ratios of the base liquid epoxy resin E-51 and tetrabromobisphenol A in the first-stage chain extension reaction are 10:4.6, 10:4.8, 10:5.0, and 10:5.1.

[0017] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0018] Compared with common brominated epoxy resins, the brominated epoxy resin with ultraviolet light shielding property prepared by the present invention creatively adds phenolic resin TPN for chain extension reaction (common brominated epoxy resins are synthesized by adding brominated bisphenol A to epoxy resins, while the present invention adds phenolic resin to introduce multifunctional phenolic, which is then synthesized with basic epoxy resin to form multifunctional epoxy, thereby improving the heat resistance and weather resistance of the resin cured product; the prepared brominated epoxy resin with ultraviolet light shielding property has improved hardness and ultraviolet light shielding property after being mixed with other resins and accelerators and cured, and has excellent ultraviolet light shielding property. When used in the downstream laminate industry, the produced board has excellent aging resistance.

[0019] The brominated epoxy resin prepared by the present invention is a new type of epoxy resin, which contains bromine in the resin system structure. It not only has the excellent electrical insulation and adhesion of general epoxy resins, but also has excellent self-flaming retardancy and ultraviolet light shielding effects, providing more excellent performance operating space for downstream customers. It is mainly used as various flame-retardant composite materials, structural materials, adhesives, and coatings, and is widely used in construction, aviation, shipbuilding, and electronic and electrical industries. DETAILED DESCRIPTION

[0020] The phenolic resin used in the following examples is phenolic resin TPN1 produced by Nanya Electronic Materials (Kunshan) Co., Ltd.

[0021] Example 1

[0022] A method for preparing a brominated epoxy resin having ultraviolet light shielding property comprises the following steps:

[0023] Add 500g of epoxy resin E-51, 240g of tetrabromobisphenol A, 15g of phenolic resin TPN into a four-necked flask, and then add 0.24g of catalyst butyl triphenylphosphonium bromide (methanol solution), and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 186.25g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. Theoretical equivalent (converted to solid content) is 422.2g / eq, and the measured equivalent (converted to solid content) is 424.1g / eq.

[0024] Example 2

[0025] A method for preparing a brominated epoxy resin having ultraviolet light shielding property comprises the following steps:

[0026] Add 500g of epoxy resin E-51, 255g of tetrabromobisphenol A, 15g of phenolic resin TPN into a four-necked flask, and then add 0.255g of catalyst butyl triphenylphosphonium bromide (dissolved in methanol), and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 190g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. Theoretical equivalent (converted to solid content) is 444.6g / eq, and the measured equivalent (converted to solid content) is 447.2g / eq.

[0027] Example 3

[0028] A method for preparing a brominated epoxy resin having ultraviolet light shielding property comprises the following steps:

[0029] Add 500g of epoxy resin E-51, 230g of tetrabromobisphenol A, 110g of phenolic resin TPN into a four-necked flask, and then add 0.23g of catalyst butyl triphenylphosphonium bromide (methanol solution), and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 185g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. Theoretical equivalent (converted to solid content) is 420.5g / eq, and the measured equivalent (converted to solid content) is 422.1g / eq.

[0030] Example 4

[0031] A method for preparing a brominated epoxy resin having ultraviolet light shielding property comprises the following steps:

[0032] Add 500g of epoxy resin E-51, 240g of tetrabromobisphenol A, 110g of phenolic resin TPN into a four-necked flask, and then add 0.24g of catalyst butyl triphenylphosphonium bromide (methanol solution), and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 187.5g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. Theoretical equivalent (converted to solid content) is 435.2g / eq, and the measured equivalent (converted to solid content) is 436.3g / eq.

[0033] Example 5

[0034] A method for preparing a brominated epoxy resin having ultraviolet light shielding property comprises the following steps:

[0035] Add 500g of epoxy resin E-51, 250g of tetrabromobisphenol A, 110g of phenolic resin TPN into a four-necked flask, and then add 0.25g of catalyst butyl triphenylphosphonium bromide (dissolved in methanol), and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 190g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. Theoretical equivalent (converted to solid content) is 450.6g / eq, and the measured equivalent (converted to solid content) is 452.9g / eq.

[0036] Example 6

[0037] A method for preparing a brominated epoxy resin having ultraviolet light shielding property comprises the following steps:

[0038] Add 500g of epoxy resin E-51, 255g of tetrabromobisphenol A, 110g of phenolic resin TPN into a four-necked flask, and then add 0.255g of catalyst butyl triphenylphosphonium bromide (methanol solution), and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 191.25g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. Theoretical equivalent (converted to solid content) is 458.6g / eq, and the measured equivalent (converted to solid content) is 461.5g / eq.

[0039] Example 7

[0040] A method for preparing a brominated epoxy resin having ultraviolet light shielding property comprises the following steps:

[0041] Add 500g of epoxy resin E-51, 230g of tetrabromobisphenol A, 115g of phenolic resin TPN into a four-necked flask, and then add 0.23g of catalyst butyl triphenylphosphonium bromide (methanol solution), and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 186.25g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. Theoretical equivalent (converted to solid content) is 433.4g / eq, and the measured equivalent (converted to solid content) is 435.1g / eq.

[0042] Example 8

[0043] A method for preparing a brominated epoxy resin having ultraviolet light shielding property comprises the following steps:

[0044] Add 500g of epoxy resin E-51, 250g of tetrabromobisphenol A, 115g of phenolic resin TPN into a 2000ml four-necked flask, and then add 0.25g of catalyst butyl triphenylphosphonium bromide (methanol solution), and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 191.25g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. The theoretical equivalent (converted to solid content) is 458.9g / eq, and the measured equivalent (converted to solid content) is 459.8g / eq.

[0045] Comparative Example 1

[0046] A method for preparing a brominated epoxy resin without adding phenolic resin TPN comprises the following steps:

[0047] Add 500g of epoxy resin E-51, 257.5g of tetrabromobisphenol A, and 0.258g of catalyst butyl triphenylphosphonium bromide (methanol solution) into a four-necked flask, and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 189.4g of acetone solvent to dissolve the system resin, and continue stirring for 0.5 hours after the addition. Theoretical equivalent (converted to solid content) 435g / eq, measured equivalent (converted to solid content) 437.6g / eq. Example 8 A comparative experiment of a brominated epoxy resin with ultraviolet light shielding and a brominated epoxy resin without phenolic resin TPN:

[0048] Comparison of basic indicators:

[0049] Table 1

[0050]

[0051] The preparation of the comparative resin sample glue is shown in Table 2:

[0052] Table 2

[0053]

[0054]

[0055] Small samples of the above four components were scraped on the surface of a transparent heat-resistant glass slide. The thickness of the scraped paint film was about 50um. The paint film was cured in an oven at 170 degrees Celsius for 5 minutes. Finally, the performance of the paint film was tested. The test comparison results of the four samples are shown in Table 3.

[0056] Table 3

[0057] Test items Sample 1 Sample 2 Sample 3 Sample 4 Film hardness 2-3H 2-3H 3-4H 1-2H Flame retardant grade of cured resin B2 B2 B2 B2 Paint film UV absorption rate % 85 89 92 18 .

[0058] The manual method tests the hardness of epoxy cured paint films using a Chinese pencil, which has different hardnesses from 9H to 6B, with 9H being the hardest and 6B being the softest.

[0059] A1, A2, B1, B2 are the flame retardant grade determination methods in the German standard DIN4102. A1 has the highest flame retardant grade and B2 has the lowest flame retardant grade. Low-bromine epoxy resin only has a lower flame retardant grade.

[0060] The UV absorbance of the paint film was tested using a Linshang LS117 optical densitometer in the wavelength range of 100-280 nanometers.

[0061] Compared with common brominated epoxy resins, the brominated epoxy resin with ultraviolet light shielding property prepared by the invention has greatly improved hardness and ultraviolet light shielding property after being mixed with other resins and accelerators and cured.

[0062] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a brominated epoxy resin having ultraviolet light shielding properties, characterized in that: The following steps are involved: (1) One-stage chain extension reaction: Add basic liquid epoxy resin E-51, tetrabromobisphenol A and a certain amount of phenolic resin into the reactor, heat up and dissolve and stir evenly, add catalyst, continue to heat up and maintain at 130-160°C for a period of time; (2) Second stage solvent dilution: After the reaction is completed, a certain amount of acetone solvent is added to adjust the viscosity of the resin system to obtain a brominated epoxy resin with ultraviolet light shielding properties.

2. The method for preparing a brominated epoxy resin having ultraviolet light shielding properties according to claim 1, characterized in that: The following steps are involved: (1) One-stage chain extension reaction: basic liquid epoxy resin E-51 (epoxy equivalent 186 g / eq), tetrabromobisphenol A and a certain amount of phenolic resin are added to the reactor, heated and dissolved and stirred evenly, a catalyst is added, and the temperature is continued to be raised and maintained at 140-150° C. for a period of time. The designed epoxy equivalent of the chain extension reaction is 420-460 g / eq; (2) Second stage solvent dilution: After the reaction is completed, a certain amount of acetone solvent is added to adjust the viscosity of the resin system to obtain a brominated epoxy resin with ultraviolet light shielding properties.

3. The method for preparing a brominated epoxy resin having ultraviolet light shielding properties according to claim 2, characterized in that: In step (1), the amount of phenolic resin in the first-stage chain extension reaction is 1%-3% of the mass of the basic liquid epoxy resin E-51, and the mass ratio of the basic liquid epoxy resin E-51 to tetrabromobisphenol A in the first-stage chain extension reaction is 10:4.6-10:5.1; the catalyst is butyltriphenylphosphine bromide or triphenylphosphine, and the amount of the catalyst is 0.5-1‰ of the mass of tetrabromobisphenol A.

4. The method for preparing a brominated epoxy resin having ultraviolet light shielding properties according to claim 3, characterized in that: In step (1), the amount of phenolic resin TPN used in the first-stage chain extension reaction is 1%, 2%, or 3% of the mass of the basic liquid epoxy resin E-51.

5. The method for preparing the brominated epoxy resin having ultraviolet light shielding property according to claim 3, characterized in that: In step (1), the mass ratios of the base liquid epoxy resin E-51 and tetrabromobisphenol A in the first-stage chain extension reaction are 10:4.6, 10:4.8, 10:5.0, and 10:5.

1.

6. A method for preparing a brominated epoxy resin having ultraviolet light shielding properties, characterized in that: It includes the following steps: Add 500g of epoxy resin E-51, 240g of tetrabromobisphenol A, 10g of phenolic resin, and then add 0.24g of catalyst butyl triphenylphosphonium bromide into a four-necked flask, and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 187.5g of acetone solvent to dissolve the system resin. After the addition, continue stirring for 0.5 hour to obtain the product.

7. A method for preparing a brominated epoxy resin having ultraviolet light shielding properties, characterized in that: It includes the following steps: Add 500g of epoxy resin E-51, 230g of tetrabromobisphenol A, 15g of phenolic resin, and 0.23g of catalyst butyl triphenylphosphonium bromide into a four-necked flask, and maintain the temperature at 140-150°C for 4 hours; then cool to 60°C and add 186.25g of acetone solvent to dissolve the system resin. Continue stirring for 0.5 hour after the addition.

Images