Non-ionic active epoxy emulsifier as well as preparation method and application thereof

Abstract

The invention relates to the technical field of C08G81 / 00, in particular to a nonionic active epoxy emulsifier and a preparation method and application thereof.The nonionic active epoxy emulsifier is prepared from, by weight, 500-1500 parts of polyhydric alcohol, 150-300 parts of epoxy resin, 50-150 parts of ether compounds, 100-300 parts of modified polyhydric alcohol and 1-5 parts of a catalyst, and the nonionic active epoxy emulsifier can be grafted to an oily epoxy curing agent as an active emulsifier. Compared with a water-based curing agent prepared by a method of adding an emulsifier, the self-emulsifying water-based epoxy curing agent shows better stability, is easy to store and transport, and has a longer shelf life.

Description

Technical Field

[0001] The invention relates to the technical field of C08G81 / 00, in particular to a nonionic active epoxy emulsifier and a preparation method and application thereof. Background Art

[0002] The preparation of existing water-based epoxy curing agents is mainly achieved through the following three methods. The first is to make the curing agent water-based by adding various inactive epoxy emulsifiers, but a large number of experiments are required to find a suitable emulsifier, which consumes manpower and material resources, and most of this water-based can only form a dispersion, and the high viscosity limits its application; in addition, the storage stability is poor, it is easy to stratify, and it is difficult to control the degree of water-basedness of the product during the production process, resulting in poor reproducibility of product indicators. For example, a Chinese patent (publication number CN 103249777A) discloses an improved method for epoxy resin aqueous dispersions and surfactants used in amine polymer compositions, which are prepared by reacting an amide amine composition with an epoxy composition, but the dispersion particle size is large (800-950nm), which makes the dispersion stability poor, and the heat storage at 50°C is less than 10 days, which affects the storage stability of the product. The second is to carry out chain extension-addition-end-capping procedures on some basic amines, introduce hydrophilic segments and hydrophobic segments on the basic amines to achieve water-based products. This method is easy to prepare water-soluble or semi-water-soluble water-based products, but most of these products can only be based on water-based modification of simple basic amines (such as diethylenetriamine, triethylenetetramine, etc.), and the basic amines are too simple in structure, resulting in many defects in the performance of the cured paint film, such as poor acid resistance, water resistance, and salt spray resistance. Moreover, this method can only be grafted based on a single amine curing agent, which is completely non-versatile, resulting in a long development cycle and time-consuming and labor-intensive. The third is to achieve the water-based process by introducing some special raw materials, such as organosilicon compounds, titanates, isocyanates, etc., but the reactions involved in these compounds have relatively high requirements for process and control, and are not easy to operate; and these compounds are generally expensive, resulting in high product prices and little market promotion prospects. For example, a Chinese patent (publication number CN108164151A) discloses a method for preparing micron-level surface-modified glass powder for integrated circuit substrates. After alkali-free glass sheets and alkali-free glass sand are ground and classified, they are added to a high-speed mixer and stirred at high speed to increase the temperature. At the same time, a silane coupling agent is added, and then stirred at high speed, kept warm and discharged. Finally, the powder is passed through a high-speed disperser and transported to a high-speed classifier through airflow to cut large particles. The powder is sieved to obtain modified glass powder. However, it is difficult to achieve uniform coverage of the surface of the glass powder, and the stability and consistency of the modification effect cannot be guaranteed. Summary of the invention

[0003] In order to solve the above problems, the present invention provides a nonionic active epoxy emulsifier, which can be grafted onto an oily epoxy curing agent as an active emulsifier to form a self-emulsifying water-based epoxy curing agent. Compared with the water-based curing agent prepared by adding an emulsifier, the self-emulsifying water-based epoxy curing agent exhibits better stability, is easy to store and transport, and has a longer shelf life.

[0004] On one hand, the present invention provides a nonionic active epoxy emulsifier, wherein the raw materials for preparing the nonionic active epoxy emulsifier include at least 500-1500 parts of polyol, 150-300 parts of epoxy resin, 50-150 parts of ether compound, 100-300 parts of modified polyol and 1-5 parts of catalyst in parts by weight.

[0005] As a preferred technical solution, the epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin. Preferably, the epoxy resin is bisphenol A epoxy resin, and the molecular weight of the bisphenol A epoxy resin is not limited, preferably E51.

[0006] The present invention develops a reactive emulsifier with a novel structure, which can be connected with an amine curing agent by means of chemical grafting to become a self-emulsifying waterborne epoxy curing agent. On the one hand, the previous method of using a curing agent as a starting material and gradually grafting and deriving is changed, thereby improving the screening efficiency of the curing agent and shortening the development cycle of the waterborne curing agent. On the other hand, the reactive emulsifier can react with any type of amine epoxy curing agent to realize the water-based curing agent, which is not only suitable for simple basic amine modification, but also suitable for the development of water-based products of amine curing agents with more complex structures such as phenolic amine, polyamide, and addition amine, thereby avoiding the step of gradually deriving from the basic amine through complicated steps to obtain a water-based product.

[0007] Specifically, the present invention optimizes the main chain segment in the emulsifier structure to be epoxy resin, especially bisphenol A epoxy resin, to improve the lipophilicity of the emulsification, and adjusts the water-oil ratio of the product by adjusting the molecular weight of the bisphenol A epoxy resin. At the same time, the bisphenol A epoxy resin as a rigid group can improve the hardness of the product and other physical properties of the paint film.

[0008] As a preferred technical solution, the polyol is at least one of ethylene glycol, polyethylene glycol, and polypropylene glycol, preferably polyethylene glycol.

[0009] As a preferred technical solution, the number average molecular weight of the polyethylene glycol is 200-6000, preferably 600-2000, and is selected from one of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyethylene glycol 1200, polyethylene glycol 1500, polyethylene glycol 2000, polyethylene glycol 4000, and polyethylene glycol 6000. Preferably, the relative molecular mass of the polyethylene glycol is 600-2000 g / mol, and is selected from one of polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyethylene glycol 1200, polyethylene glycol 1500, and polyethylene glycol 2000.

[0010] Furthermore, by inserting polyethylene glycol segments into the main chain segments of bisphenol A epoxy resin, the polyether structure in the polyethylene glycol can improve the hydrophilicity of the emulsifier, and the HLB value of the molecule can be adjusted by adjusting the molecular weight of the polyethylene glycol (i.e., the number of polyether segments) to maintain the solubility and thermal stability of the final product in water.

[0011] As a preferred technical solution, the ether compound is selected from at least one of ethylene glycol-1,2-diglycidyl ether, propylene glycol-1,2-diglycidyl ether, propylene glycol-1,3-diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, diethylene glycol diglycidyl ether and dipropylene glycol diglycidyl ether, preferably neopentyl glycol diglycidyl ether.

[0012] As a preferred technical solution, the catalyst is selected from one of triphenylphosphine, triphenylphosphine, and boron trifluoride ethyl ether, preferably boron trifluoride ethyl ether.

[0013] As a preferred technical solution, the raw materials for preparing the modified polyol include at least 400-600 parts of polyethylene glycol, 100-200 parts of glycidyl ether compounds, and 1-5 parts of acidic catalysts, calculated by weight.

[0014] As a preferred technical solution, the glycidyl ether compound is selected from at least one of trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, and pentaerythritol glycidyl ether.

[0015] As a preferred technical solution, the preparation method of the modified polyol is: adding polyethylene glycol into a reaction vessel, heating to 50-80°C, 2Under protective conditions, add an acidic catalyst, stir and react at 50-70°C for 20-40 minutes; then add a glycidyl ether compound, stir at 50-70°C for 20-40 minutes, then heat to 80-100°C, keep warm for 60-90 minutes, then raise the temperature to 120-130°C for 60-90 minutes, and keep warm for at least 2 hours to obtain a modified polyol.

[0016] As a preferred technical solution, the acidic catalyst is selected from one of triphenylphosphine, triphenylphosphine, and boron trifluoride ethyl ether, preferably boron trifluoride ethyl ether.

[0017] Furthermore, neopentyl glycol diglycidyl ether chain segments and trimethylolpropane triglycidyl ether are introduced into the structure. On the one hand, the presence of the side chains can greatly reduce the viscosity of the emulsifier, which is convenient for operation in actual production; on the other hand, the hydrophilic segments in the active emulsifier can be further improved to achieve the water-based nature of a type of oily epoxy curing agent with strong hydrophobicity; it can also assist in adjusting the HLB value of the product to make it easier to dissolve in water and avoid forming a dispersion-type water-based epoxy curing agent, thereby further improving the thermal stability of the product and its adaptability to a variety of water-based epoxy resins.

[0018] Another aspect of the present invention provides a method for preparing a nonionic reactive epoxy emulsifier, comprising at least the following steps:

[0019] (1) Add polyol into a reaction vessel and heat to 50-80°C under N 2 Under protective conditions, add a catalyst and stir the reaction at 50-70°C for 20-40 minutes;

[0020] (2) adding epoxy resin, stirring at 50-70°C for 20-40 minutes, then heating to 80-100°C, keeping warm for 60-90 minutes, then heating to 120-130°C for 60-90 minutes, and keeping warm for at least 2 hours;

[0021] (3) Then, the temperature is lowered to 80-100° C., a mixture of an ether compound and a modified polyol is added, and the mixture is kept at 80-100° C. for 60-90 minutes, and then the temperature is raised to 130-140° C. for 60-90 minutes, and the mixture is kept at this temperature for at least 5 hours to obtain a nonionic active epoxy emulsifier.

[0022] The emulsifier provided by the present invention contains epoxy groups, which can react with active amino groups in oily epoxy curing agents for prepolymerization, and smoothly introduce hydrophilic units into amine epoxy curing agents by means of chemical grafting, thereby preparing an amine epoxy curing agent with a hydrophilic segment. The amine curing agent with a hydrophilic segment has good compatibility with water, thereby ensuring good thermal stability in water. In addition, the novel water-based polyamide curing agent containing a self-emulsifying segment can effectively emulsify water-based or oily epoxy resins without the need for an external emulsifier, thereby forming a paint film with excellent performance.

[0023] The third aspect of the present invention provides an application of a nonionic active epoxy emulsifier for water-based treatment of oily curing agents.

[0024] As a preferred technical solution, the oily curing agent is an oily amine curing agent, including but not limited to one of diethylenetriamine, triethylenetetramine, phenolic amine, polyamide, and addition amine.

[0025] As a preferred technical solution, the water-based treatment of the oily curing agent includes at least the following steps: adding a nonionic active epoxy emulsifier and an oily curing agent into a reaction container, heating to 80-90°C, stirring for reaction for 1-3h, then cooling to 60-70°C, adding deionized water and stirring for 1-3h, cooling and discharging to obtain a water-based curing agent.

[0026] The mass ratio of the nonionic active epoxy emulsifier to the oily curing agent is 1:(2-3), and the amount of deionized water added is determined based on the solid content of the water-based curing agent.

[0027] The reactive emulsifier provided by the present invention can quickly screen different oily curing agents and convert them into water-based curing agents in batches, thereby expanding the application range of water-based curing agents, shortening the research and development cycle, and having stronger versatility.

[0028] In addition, the solid content of commercially available water-based curing agents is mostly around 50-70wt%. The water-based epoxy curing agent obtained based on the emulsifier provided by the present invention can obtain a stable water-based epoxy curing agent without high-speed dispersion, so a high-solid content product can be prepared. The construction unit can add water as needed at the construction site, which provides convenience for water-based epoxy construction.

[0029] The present invention records that the emulsifier is applied to some commercially available oily epoxy curing agents, and good results are achieved, which proves the versatility of the emulsifier of the present invention. The polyethylene glycol segment and the bisphenol A segment in the structure can be adjusted as needed to adapt to more types and models of oily curing agents, thereby achieving the purpose of water-based curing agents.

[0030] Beneficial Effects

[0031] 1. The present invention provides a nonionic active epoxy emulsifier, which can be grafted onto an oily epoxy curing agent as an active emulsifier to form a self-emulsifying water-based epoxy curing agent. Compared with the water-based curing agent prepared by adding an external emulsifier, it exhibits better stability, is easy to store and transport, and has a longer shelf life.

[0032] 2. The present invention develops a reactive emulsifier with a novel structure, which can be connected with an amine curing agent by means of chemical grafting to become a self-emulsifying water-based epoxy curing agent. On the one hand, it changes the previous method of using the curing agent as the starting material and gradually grafting and deriving, thereby improving the screening efficiency of the curing agent and shortening the development cycle of the water-based curing agent; on the other hand, the reactive emulsifier can react with any type of amine epoxy curing agent to achieve the water-based curing agent, which is not only suitable for simple basic amine modification, but also for the development of water-based products of amine curing agents with more complex structures such as phenolic amines, polyamides, and addition amines, thereby avoiding the step of gradually deriving from the basic amines through complicated steps to obtain water-based products.

[0033] 3. The present invention optimizes the main chain segment in the emulsifier structure to be epoxy resin, especially bisphenol A epoxy resin, to improve the lipophilicity of the emulsification, and adjusts the water-oil ratio of the product by adjusting the molecular weight of the bisphenol A epoxy resin. At the same time, the bisphenol A epoxy resin as a rigid group can improve the hardness of the product and other physical properties of the paint film.

[0034] 4. The present invention can improve the hydrophilicity of the emulsifier by inserting polyethylene glycol segments into the main chain segments of bisphenol A epoxy resin. The polyether structure in the polyethylene glycol can also adjust the molecular weight of the polyethylene glycol (i.e., the number of polyether segments) to adjust the HLB value of the molecule to maintain the solubility and thermal stability of the final product in water.

[0035] 5. The present invention introduces neopentyl glycol diglycidyl ether chain segments and trimethylolpropane triglycidyl ether into the structure. On the one hand, the presence of the side chain can greatly reduce the viscosity of the emulsifier, which is convenient for operation in actual production; on the other hand, it can further increase the hydrophilic segment in the active emulsifier to achieve water-based treatment of a type of oily epoxy curing agent with strong hydrophobicity; it can also assist in adjusting the HLB value of the product to make it easier to dissolve in water and avoid forming a dispersion-type water-based epoxy curing agent, thereby further improving the thermal stability of the product and its compatibility with a variety of water-based epoxy resins. DETAILED DESCRIPTION

[0036] Example 1

[0037] On the one hand, Example 1 of the present invention provides a nonionic active epoxy emulsifier, and its preparation raw materials include 1000 parts of polyol, 180 parts of epoxy resin, 80 parts of ether compound, 200 parts of modified polyol, and 3 parts of catalyst, by weight.

[0038] The epoxy resin is bisphenol A epoxy resin E51.

[0039] The polyol is polyethylene glycol 1000.

[0040] The ether compound is neopentyl glycol diglycidyl ether.

[0041] The catalyst is boron trifluoride etherate.

[0042] By weight, the raw materials for preparing the modified polyol include 500 parts of polyethylene glycol, 151 parts of glycidyl ether compounds, and 3 parts of acidic catalysts.

[0043] The glycidyl ether compound is trimethylolpropane triglycidyl ether.

[0044] The preparation method of the modified polyol is as follows: adding polyethylene glycol into a reaction container, heating to 80° C., and 2 Under protective conditions, an acidic catalyst was added, and the reaction was stirred at 60°C for 30 minutes; then a glycidyl ether compound was added, stirred at 60°C for 30 minutes, and then heated to 90°C, kept warm for 609 minutes, and then heated to 125°C for 609 minutes, and kept warm for 3 hours to obtain a modified polyol.

[0045] The acidic catalyst is boron trifluoride etherate.

[0046] The polyethylene glycol is polyethylene glycol 1000.

[0047] Embodiment 1 of the present invention provides a method for preparing a nonionic reactive epoxy emulsifier, comprising the following steps:

[0048] (1) Add polyol into a reaction vessel and heat to 80°C under N 2 Under protection conditions, the catalyst was added and the reaction was stirred at 60°C for 30 min;

[0049] (2) Then, epoxy resin was added, stirred at 60°C for 30 min, then heated to 90°C, kept at this temperature for 609 min, then heated to 125°C for 609 min, and kept at this temperature for 3 h;

[0050] (3) Then, the temperature is lowered to 90°C, and a mixture of ether compounds and modified polyols is added. After the mixture is kept at 90°C for 60 minutes, the temperature is raised to 135°C for 60 minutes, and the mixture is kept at this temperature for 6 hours to obtain a nonionic active epoxy emulsifier.

[0051] The third aspect of Example 1 of the present invention provides an application of a nonionic active epoxy emulsifier for water-based treatment of an oily curing agent.

[0052] The oily curing agent is the commercially available Cardolite NX-2009 addition amine type oily top coating curing agent.

[0053] The mass ratio of the nonionic active epoxy emulsifier to the oily curing agent is 1:3.

[0054] The water-based treatment of the oily curing agent comprises the following steps: adding a nonionic active epoxy emulsifier and an oily curing agent into a reaction container, heating to 85° C., stirring for reaction for 2 hours, then cooling to 70° C., adding deionized water and stirring for 2 hours, cooling and discharging to obtain a water-based curing agent with a solid content of 80 wt%.

[0055] Example 2

[0056] Example 2 of the present invention provides a nonionic active epoxy emulsifier and a preparation method and application thereof. The specific implementation method is the same as that of Example 1, except that the oily curing agent is a commercially available Hensamide-5650S polyamide oily mid-prime curing agent, and the solid content of the water-based curing agent is 70wt%.

[0057] Example 3

[0058] Example 3 of the present invention provides a nonionic active epoxy emulsifier and a preparation method and application thereof. Its specific implementation method is the same as that of Example 1, except that the oily curing agent is the commercially available Wansheng WSCM-1102 phenolic amine type oily mid-primer curing agent, and the solid content of the water-based curing agent is 55wt%.

[0059] Example 4

[0060] Embodiment 4 of the present invention provides a nonionic active epoxy emulsifier and its preparation method and application. Its specific implementation is the same as that of Embodiment 1, except that, by weight, its preparation raw materials include 600 parts of polyol, 180 parts of epoxy resin, 80 parts of ether compound, 200 parts of modified polyol, and 3 parts of catalyst. By weight, the preparation raw materials of the modified polyol include 300 parts of polyethylene glycol, 151 parts of glycidyl ether compound, and 3 parts of acidic catalyst. The polyethylene glycol 1000 is replaced by polyethylene glycol 600, and the solid content of the water-based curing agent is 70wt%.

[0061] Example 5

[0062] Example 5 of the present invention provides a nonionic active epoxy emulsifier, a preparation method and application thereof, and its specific implementation method is the same as that of Example 1, except that the mass ratio of the nonionic active epoxy emulsifier to the oily curing agent is 1:2, and the solid content of the water-based curing agent is 70wt%.

[0063] Performance Testing

[0064] The water-based curing agent provided in the embodiment was subjected to various performance tests in Table 1. The test standards and results are shown in Table 1.

[0065] Table 1

[0066]

[0067]

Claims

1. A nonionic reactive epoxy emulsifier, characterized in that: The raw materials for its preparation include at least 500-1500 parts of polyol, 150-300 parts of epoxy resin, 50-150 parts of ether compound, 100-300 parts of modified polyol and 1-5 parts of catalyst in parts by weight.

2. The nonionic reactive epoxy emulsifier according to claim 1, characterized in that: The epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin.

3. The nonionic reactive epoxy emulsifier according to claim 1, characterized in that: The polyol is at least one of ethylene glycol, polyethylene glycol and polypropylene glycol.

4. The nonionic reactive epoxy emulsifier according to claim 3, characterized in that: The number average molecular weight of the polyethylene glycol is 200-6000, preferably 600-2000.

5. The nonionic reactive epoxy emulsifier according to claim 4, characterized in that: The ether compound is selected from at least one of ethylene glycol-1,2-diglycidyl ether, propylene glycol-1,2-diglycidyl ether, propylene glycol-1,3-diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, diethylene glycol diglycidyl ether and dipropylene glycol diglycidyl ether.

6. The nonionic reactive epoxy emulsifier according to claim 5, characterized in that: The catalyst is selected from one of triphenylphosphine, triphenylphosphine and boron trifluoride etherate.

7. The nonionic reactive epoxy emulsifier according to claim 6, characterized in that: In parts by weight, the raw materials for preparing the modified polyol include at least 400-600 parts of polyethylene glycol, 100-200 parts of glycidyl ether compounds, and 1-5 parts of acidic catalysts.

8. The nonionic reactive epoxy emulsifier according to claim 7, characterized in that: The glycidyl ether compound is selected from at least one of trimethylolpropane triglycidyl ether, glycerol triglycidyl ether and pentaerythritol glycidyl ether.

9. A method for preparing the nonionic reactive epoxy emulsifier according to any one of claims 1 to 8, characterized in that: At least the following steps are included: (1) Add polyol into a reaction vessel, heat to 50-80°C, add catalyst under N2 protection, and stir the reaction at 50-70°C for 20-40 minutes; (2) adding epoxy resin, stirring at 50-70°C for 20-40 minutes, then heating to 80-100°C, keeping warm for 60-90 minutes, then heating to 120-130°C for 60-90 minutes, and keeping warm for at least 2 hours; (3) Then, the temperature is lowered to 80-100° C., a mixture of an ether compound and a modified polyol is added, and the mixture is kept at 80-100° C. for 60-90 minutes, and then the temperature is raised to 130-140° C. for 60-90 minutes, and the mixture is kept at this temperature for at least 5 hours to obtain a nonionic active epoxy emulsifier.

10. Use of the nonionic reactive epoxy emulsifier according to any one of claims 1 to 8, characterized in that: The invention is applied to the water-based treatment of oily curing agent, and the water-based treatment of the oily curing agent comprises at least the following steps: adding a nonionic active epoxy emulsifier and an oily curing agent into a reaction container, heating to 80-90°C, stirring for reaction for 1-3h, then cooling to 60-70°C, adding deionized water and stirring for 1-3h, cooling and discharging to obtain a water-based curing agent; the mass ratio of the nonionic active epoxy emulsifier to the oily curing agent is 1:(2-3).

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