High-molecular-weight bisphenol structure type epoxy resin, water-based high-molecular-weight bisphenol structure type epoxy resin emulsion and preparation method of water-based high-molecular-weight bisphenol structure type epoxy resin emulsion

Abstract

The invention discloses a high-molecular-weight bisphenol structure type epoxy resin, a water-based high-molecular-weight bisphenol structure type epoxy resin emulsion and a preparation method of the water-based high-molecular-weight bisphenol structure type epoxy resin emulsion. The high-molecular-weight bisphenol structural type epoxy resin comprises at least one of a bisphenol F structural unit, a bisphenol A structural unit and a hydrogenated bisphenol A structural unit, and the mass ratio of the bisphenol A structural unit in all the bisphenol structural units is not more than 60%. The high-molecular-weight epoxy resin is low in softening temperature and easy to hydrate, and the water-based high-molecular-weight bisphenol structure type epoxy resin emulsion prepared from the high-molecular-weight epoxy resin is high in stability and low in cosolvent content. The preparation method is simple, low in cost and suitable for industrial production.

Description

Technical Field

[0001] This invention relates to an epoxy resin, specifically a high molecular weight bisphenol structured epoxy resin, and also to an aqueous high molecular weight bisphenol structured epoxy resin emulsion and its preparation method, belonging to the field of aqueous epoxy resins. Background Technology

[0002] Currently, most bisphenol A type waterborne epoxy resins on the market are low molecular weight bisphenol A type waterborne epoxy resins and medium molecular weight bisphenol A type waterborne epoxy resins, such as E-51, E-44, E-20 and other waterborne epoxy resins. No high molecular weight bisphenol A type epoxy resins such as E-03 waterborne epoxy resin have been found.

[0003] E-03 is a high molecular weight solid bisphenol A epoxy resin. Due to its high molecular weight (4800-8000 g / mol) and high softening point (130-150℃), it brings many inconveniences to production and application. Therefore, the production and application of high molecular weight bisphenol A epoxy resin E-03 are limited, especially in terms of waterborne application, which is very difficult. Even with the addition of a large amount of organic co-solvent, it is not easy to emulsify.

[0004] Therefore, it is of great significance to develop a high molecular weight epoxy resin that is an E-03 analog and easily water-soluble. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the first objective of this invention is to provide a high molecular weight bisphenol-structured epoxy resin. This epoxy resin has a similar molecular weight and structure to the E-03 product and is easily water-based.

[0006] The second objective of this invention is to provide a method for preparing a high molecular weight bisphenol-structured epoxy resin. This method is simple, low-cost, and suitable for industrial production.

[0007] A third objective of this invention is to provide an aqueous high molecular weight bisphenol-structured epoxy resin emulsion. This aqueous epoxy resin emulsion exhibits uniform particle size distribution and high stability.

[0008] The fourth objective of this invention is to provide a method for preparing an aqueous high molecular weight bisphenol-structured epoxy resin emulsion. This method is simple, easy to operate, and inexpensive.

[0009] To achieve the above-mentioned technical objectives, the present invention provides a high molecular weight bisphenol-structured epoxy resin, which comprises at least one of bisphenol F structural units, bisphenol A structural units, and hydrogenated bisphenol A structural units, with the specific structural expression as follows:

[0010]

[0011] Where x, y, and z are all between 0 and 25, and x + y + z > 0.

[0012] R1, R2, and R3 are all

[0013] One of them, where R is R1, R2, or R3;

[0014] The bisphenol A structural unit accounts for no more than 60% of the total mass of all bisphenol structural units.

[0015] The high molecular weight bisphenol structured epoxy resin of this invention has a similar structure to the E-03 product and a comparable molecular weight, and has excellent hydration properties.

[0016] As a preferred embodiment, the high molecular weight bisphenol-structured epoxy resin has a molecular weight of 5000–7000 g / mol.

[0017] As a preferred embodiment, the softening point of the high molecular weight bisphenol-structured epoxy resin is 15–95°C.

[0018] The present invention also provides a method for preparing a high molecular weight bisphenol-structured epoxy resin, wherein a bisphenol epoxy resin with a molecular weight not exceeding 600 is polymerized with a bisphenol-structured substance under the action of a catalyst to obtain the epoxy resin.

[0019] This invention synthesizes a high molecular weight bisphenol-structured epoxy resin by chain extension modification of a low molecular weight bisphenol-structured epoxy resin using a bisphenol-containing structural substance. Compared with E-03 resin, the modified high molecular weight bisphenol-structured epoxy resin obtained by this invention has a significantly lower softening point and improved hydration properties.

[0020] As a preferred embodiment, the bisphenol epoxy resin with a molecular weight not exceeding 600 includes at least one of hydrogenated bisphenol A epoxy resin with a molecular weight not exceeding 500, bisphenol A epoxy resin with a molecular weight not exceeding 600, and bisphenol F epoxy resin with a molecular weight not exceeding 400. The low molecular weight bisphenol epoxy resin used in this invention is beneficial for controlling the molecular weight and softening point of the modified epoxy resin.

[0021] As a preferred embodiment, the hydrogenated bisphenol A epoxy resin with a molecular weight not exceeding 500 has an epoxy equivalent of 0.40–0.45 eq / 100g and a viscosity of 1000–4000 mPa·s (25°C).

[0022] As a preferred embodiment, the bisphenol A epoxy resin with a molecular weight not exceeding 600 has an epoxy equivalent of 0.35–0.45 eq / 100g and a viscosity of 6000–50000 mPa·s (25°C).

[0023] As a preferred embodiment, the bisphenol F epoxy resin with a molecular weight not exceeding 400 has an epoxy equivalent of 160–180 eq / g and a viscosity of 2000–5000 mPa·s (25°C).

[0024] As a preferred embodiment, the bisphenol-containing substance includes at least one of bisphenol A, bisphenol F, and hydrogenated bisphenol A.

[0025] As a preferred embodiment, the mass ratio of the bisphenol-based epoxy resin with a molecular weight not exceeding 600 to the bisphenol-containing structural material is 100:40-65. This invention improves the performance of epoxy resin by controlling the content of bisphenol A structural units within a suitable range.

[0026] As a preferred embodiment, the catalyst comprises at least one of triphenylphosphine, quaternary ammonium salt, and boron trifluoride complex.

[0027] As a preferred embodiment, the amount of catalyst added is 0.05 to 0.5 wt% of the bisphenol-containing structural substance.

[0028] As a preferred embodiment, the polymerization reaction conditions are: temperature of 100–200°C and time of 2–5 hours.

[0029] The present invention also provides a method for preparing an aqueous high molecular weight bisphenol structured epoxy resin emulsion, wherein the method comprises mixing the above-mentioned high molecular weight bisphenol structured epoxy resin with raw materials containing a reactive emulsifier and water to carry out an emulsification reaction, thereby obtaining the emulsion.

[0030] As a preferred embodiment, the reactive emulsifier is an epoxy-containing emulsifier. Epoxy-containing emulsifiers include JEFFADD CE-301, NSF-1802B, EP-100, etc.

[0031] As a preferred embodiment, the mass ratio of the high molecular weight bisphenol structured epoxy resin, reactive emulsifier, and water is 40-45:5-10:40-50.

[0032] As a preferred embodiment, the raw material also includes a co-solvent.

[0033] As a preferred embodiment, the co-solvent comprises an alcohol ether solvent.

[0034] As a preferred embodiment, the amount of the co-solvent added does not exceed 1 / 9 of the total mass of the high molecular weight bisphenol structured epoxy resin, reactive emulsifier, and deionized water.

[0035] As a preferred embodiment, the raw materials for the waterborne high molecular weight bisphenol structured epoxy resin emulsion are configured according to the following mass content:

[0036] High molecular weight bisphenol structured epoxy resin 40-45%;

[0037] 5-10% reactive emulsifier;

[0038] 40-50% deionized water;

[0039] Cosolvent: 0-10%.

[0040] This invention also provides an aqueous high molecular weight bisphenol-structured epoxy resin emulsion, which is prepared by the above method. This aqueous high molecular weight bisphenol-structured epoxy resin emulsion exhibits high stability.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) The modified high molecular weight bisphenol structure epoxy resin has a similar structure and comparable molecular weight to solid bisphenol A type high molecular weight epoxy resin E-03, but its softening temperature (softening point) is significantly lower and it is easy to hydrate, thus overcoming the disadvantage that E-03 epoxy resin is difficult to water-based.

[0043] (2) The prepared waterborne high molecular weight bisphenol structured epoxy resin emulsion has low co-solvent content, excellent environmental performance, and a uniform and stable system.

[0044] (3) The preparation method is simple and the cost is low, making it suitable for industrial applications. Attached Figure Description

[0045] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0046] Figure 1 This is a schematic diagram of the GPC process for the high molecular weight epoxy resin prepared in Example 1.

[0047] Figure 2 This is a schematic diagram of the GPC process for the high molecular weight epoxy resin prepared in Example 2.

[0048] Figure 3 This is a schematic diagram of the GPC process for the high molecular weight epoxy resin prepared in Example 3. Detailed Implementation

[0049] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0050] The hydrogenated bisphenol A epoxy resin used in this invention is CYD-3000H, a product of Hunan Petrochemical Company, and the bisphenol F epoxy resin is CYD-175, a product of Hunan Petrochemical Company.

[0051] Example 1

[0052] (1) Preparation of high molecular weight epoxy resin

[0053] 200 g of hydrogenated bisphenol A epoxy resin and 92.5 g of hydrogenated bisphenol A were added to a four-necked flask and heated to 120 °C to dissolve. 0.10 g of tetrabutylammonium bisulfate was then added, and the mixture was slowly heated to 180 °C. The reaction was maintained for 5 hours to obtain a high molecular weight epoxy resin. The resin had a molecular weight of 6100 g / mol and a softening point of 20 °C.

[0054] (2) Preparation of waterborne epoxy resin

[0055] 280 g of the high molecular weight epoxy resin prepared in (1) and 50 g of Heinzmann's JEFFADD CE-301 were added to an emulsification kettle and heated to dissolve. High-speed stirring was then started, and 330 g of deionized water was slowly added dropwise using the principle of phase inversion to obtain an aqueous epoxy resin emulsion with a solid content of 50%. The particle size D50 of this aqueous epoxy resin emulsion was 0.42 μm, and it did not separate or settle after centrifugation at 3000 rpm / 30 min.

[0056] Example 2

[0057] (1) Preparation of high molecular weight epoxy resin

[0058] 200 g of bisphenol A epoxy resin with an epoxy equivalent of 190 g / eq and 94 g of hydrogenated bisphenol A were added to a four-necked flask and heated to 100 °C to dissolve. 0.15 g of triphenylphosphine was added, and the mixture was slowly heated to 190 °C and maintained for 3 hours to obtain a high molecular weight epoxy resin. The resin had a molecular weight of 6800 g / mol and a softening point of 88 °C.

[0059] (2) Preparation of waterborne epoxy resin

[0060] 280 g of the high molecular weight epoxy resin prepared in (1), 45 g of Foshan Norton Chemical Technology Co., Ltd.'s EP-100, and 40 g of propylene glycol methyl ether were added to an emulsification kettle. After heating and dissolving, high-speed stirring was started, and 285 g of deionized water was slowly added dropwise using the principle of phase inversion to obtain an aqueous epoxy resin emulsion with a solid content of 50%. The particle size D50 of this aqueous epoxy resin emulsion was 1.05 μm, and it did not separate or settle after centrifugation at 3000 rpm / 30 min.

[0061] Example 3

[0062] (1) Preparation of high molecular weight epoxy resin

[0063] 100 g of hydrogenated bisphenol A epoxy resin, 100 g of bisphenol F epoxy resin, 42 g of bisphenol A, and 64 g of hydrogenated bisphenol A were added to separate four-necked flasks. The mixture was heated to 120 °C to dissolve the resin. 0.1 g of triphenylphosphine bromide was then added, and the mixture was slowly heated to 155 °C and maintained for 3 hours to obtain a high molecular weight epoxy resin. The resin had a molecular weight of 5600 g / mol and a softening point of 30 °C.

[0064] (2) Preparation of waterborne epoxy resin

[0065] 280 g of the high molecular weight epoxy resin prepared in (1), 34 g of NSF-1802B from Changshu Naisu Biomaterials Technology Co., Ltd., and 15 g of diethylene glycol butyl ether were added to an emulsification kettle. After heating and dissolving, high-speed stirring was started, and 299 g of deionized water was slowly added dropwise using the principle of phase inversion to obtain an aqueous epoxy resin emulsion with a solid content of 50%. The particle size D50 of this aqueous epoxy resin emulsion was 0.65 μm, and it did not separate or settle after centrifugation at 3000 rpm / 30 min.

[0066] Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A high molecular weight bisphenol-structured epoxy resin, characterized in that: It contains at least one of the following structural units: bisphenol F, bisphenol A, and hydrogenated bisphenol A. The specific structural expression is as follows: Where x, y, and z are all between 0 and 25, and x + y + z > 0; R1, R2, and R3 are all One of them, where R is R1, R2, or R3; The bisphenol A structural unit accounts for no more than 60% of the total mass of all bisphenol structural units.

2. The high molecular weight bisphenol-structured epoxy resin according to claim 1, characterized in that: The high molecular weight bisphenol-structured epoxy resin has a molecular weight of 5000–7000 g / mol.

3. A high molecular weight bisphenol-structured epoxy resin according to claim 1 or 2, characterized in that: The softening point of the high molecular weight bisphenol structured epoxy resin is 15–95°C.

4. A method for preparing a high molecular weight bisphenol-structured epoxy resin according to any one of claims 1 to 3, characterized in that: The product is obtained by polymerizing bisphenol-based epoxy resins with a molecular weight not exceeding 600 with bisphenol-containing structural substances under the action of a catalyst.

5. The method for preparing a high molecular weight bisphenol-structured epoxy resin according to claim 4, characterized in that: The bisphenol epoxy resin with a molecular weight not exceeding 600 includes at least one of hydrogenated bisphenol A epoxy resin with a molecular weight not exceeding 500, bisphenol A epoxy resin with a molecular weight not exceeding 600, and bisphenol F epoxy resin with a molecular weight not exceeding 400.

6. The method for preparing a high molecular weight bisphenol-structured epoxy resin according to claim 5, characterized in that: The hydrogenated bisphenol A epoxy resin with a molecular weight not exceeding 500 has an epoxy equivalent of 0.40 to 0.45 eq / 100g and a viscosity of 1000 to 4000 mPa·s. The bisphenol A epoxy resin with a molecular weight not exceeding 600 has an epoxy equivalent of 0.35 to 0.45 eq / 100g and a viscosity of 6000 to 50000 mPa·s.

7. The method for preparing a high molecular weight bisphenol-structured epoxy resin according to claim 5, characterized in that: The bisphenol F epoxy resin with a molecular weight not exceeding 400 has an epoxy equivalent of 160–180 eq / g and a viscosity of 2000–5000 mPa·s.

8. The method for preparing a high molecular weight bisphenol-structured epoxy resin according to claim 4, characterized in that: The bisphenol-containing substance includes at least one of bisphenol A, bisphenol F, and hydrogenated bisphenol A.

9. A method for preparing a high molecular weight bisphenol-structured epoxy resin according to any one of claims 4 to 8, characterized in that: The mass ratio of the bisphenol epoxy resin with a molecular weight not exceeding 600 to the bisphenol-containing structural substance is 100:40-65.

10. The method for preparing a high molecular weight bisphenol-structured epoxy resin according to claim 4, characterized in that: The catalyst includes at least one of triphenylphosphine, quaternary ammonium salt, and boron trifluoride complex.

11. A method for preparing a high molecular weight bisphenol-structured epoxy resin according to claim 4 or 10, characterized in that: The catalyst is added at an amount of 0.05 to 0.5 wt% of the bisphenol-containing structural substance.

12. The method for preparing a high molecular weight bisphenol-structured epoxy resin according to claim 4, characterized in that: The polymerization reaction conditions are: temperature of 100-200℃ and time of 2-5h.

13. A method for preparing an aqueous high molecular weight bisphenol-structured epoxy resin emulsion, characterized in that: The high molecular weight bisphenol structured epoxy resin according to any one of claims 1 to 3 is mixed with raw materials containing reactive emulsifier and water and subjected to an emulsification reaction to obtain the product.

14. The method for preparing an aqueous high molecular weight bisphenol-structured epoxy resin emulsion according to claim 13, characterized in that: The reactive emulsifier is an emulsifier containing epoxy groups.

15. A method for preparing an aqueous high molecular weight bisphenol-structured epoxy resin emulsion according to claim 13 or 14, characterized in that: The mass ratio of the high molecular weight bisphenol structured epoxy resin, reactive emulsifier, and water is 40-45:5-10:40-50.

16. The method for preparing an aqueous high molecular weight bisphenol-structured epoxy resin emulsion according to claim 13, characterized in that: The raw materials also include a cosolvent.

17. The method for preparing an aqueous high molecular weight bisphenol-structured epoxy resin emulsion according to claim 16, characterized in that: The co-solvent is an alcohol ether solvent.

18. A method for preparing an aqueous high molecular weight bisphenol-structured epoxy resin emulsion according to claim 16 or 17, characterized in that: The amount of the co-solvent added shall not exceed 1 / 9 of the total mass of the high molecular weight bisphenol structured epoxy resin, reactive emulsifier and deionized water.

19. A water-based high molecular weight bisphenol-structured epoxy resin emulsion, characterized in that: Prepared by the method described in any one of claims 13 to 18.

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