Para-ammonia type resin reactive diluent and synthesis method thereof

Abstract

The invention discloses a sec-ammonia type resin reactive diluent and a synthesis method thereof, monobasic primary amine or ether amine and diester maleate are reacted according to the mass ratio of (1-3): 1 under the solvent-free condition and in the inert gas atmosphere at the reaction temperature of 25-80 DEG C, and excessive amine is recovered after the reaction is completed, so that the sec-ammonia type resin reactive diluent is obtained. The secondary ammonia type resin reactive diluent provided by the invention can properly reduce the viscosity of the resin, and not only can solve the fluidity problem of a coating, but also can enable the coating to be convenient to use.

Description

Technical Field

[0001] The invention belongs to the technical field of resin active diluents, and in particular relates to a secondary amine type structured resin active diluent and a synthesis method thereof. Background Art

[0002] Polyaspartic acid ester polyurea material (abbreviated as "aspartic polyurea") is a new type of aliphatic, slow-reacting, high-performance coating material in the polyurea industry. It is called the third-generation polyurea. It has a wide range of performance parameters, a wide range of application scenarios, and is highly inclusive. It can meet the needs of various coating processes and is one of the best raw materials for making environmentally friendly coatings.

[0003] Asparagus polyurea materials have many advantages as follows: 1. High solid content and low viscosity. Very suitable for the development of high solid content or solvent-free coatings, good environmental protection; 2. Can be cured at low temperature, no catalyst is required, energy-saving and baking-free; 3. Simple construction method, not limited to two-component spraying equipment, can be conveniently used for air spraying, airless spraying, brushing, rolling and other construction methods, with wide applicability; 4. The urea bond energy generated by the reaction of asparagus polyurea resin and isocyanate curing agent is high, so it has excellent mechanical properties (high strength, high wear resistance, high impact resistance), weather resistance and chemical resistance.

[0004] Among them, "high solid and low viscosity", that is, high solid content and low viscosity, is its most outstanding advantage. Common asparagus polyurea resins generally have a viscosity between 200-2000mpa.s (25°C). These asparagus polyurea resins can meet the needs of some applications. However, for more functional needs, the application of these single polyurea resins is very limited. Therefore, many composite asparagus polyurea resins came into being. For example, epoxy-modified asparagus polyurea resins can meet the needs of marine concrete protection (Research on New Polyaspartic Acid Polyurea Coatings for Marine Concrete Protection [D]; Lu Ping; Ocean University of China) or in the field of marine heavy corrosion protection (Kong Zhenying; Lian Bingjie; Fang Jianjun; Coatings Technology and Abstracts [J]; 38.10, 2017, 24-30). In addition, fluorinated polyurea resin modified with fluorinated silicon can be used in hydropower dams to improve the water-facing surface and resist ice pull (Zhang Yuying; Liu Xiaonan; Li Bingqi; Qu Gaojian; Wang Chengpeng; China Coatings [J]; 37.09, 2022, 28-32). These modified polyurea resins or composite polyurea resins improve the performance of polyurea resins and increase their application scenarios.

[0005] Patent application 202210769873.3 discloses a polymer repair agent for cracks on concrete floors. The polymer repair agent components include: modified polyaspartic acid ester polyurea resin, ester diluent, glacial acetic acid and silane coupling agent; the preparation method of modified polyaspartic acid ester polyurea resin is: reacting γ-aminopropyl triethoxysilane with dialkyl maleate to obtain silane-modified maleate; reacting aliphatic diprimary amine with dialkyl maleate, and then transesterifying with methoxy polyethylene glycol to obtain methoxy polyethylene glycol-modified polyaspartic acid ester; adding methoxy polyethylene glycol-modified polyaspartic acid ester to diisocyanate for reaction; and then adding silane-modified maleate for end-capping to obtain the modified polyaspartic acid ester polyurea resin.

[0006] However, the modified polyaspartic acid ester polyurea resin reported in the above patent document adopts ethyl acetate and / or butyl acetate as ester diluents. Ethyl acetate and / or butyl acetate can partially solve the fluidity and ease of use of the coating, but at the same time increase VOC emissions.

[0007] These modified asparagus polyurea resins or composite asparagus polyurea resins have improved the performance of asparagus polyurea resins and expanded their application scenarios. At the same time, this modification will often increase the viscosity of the resin, and the viscosity will increase to several thousand or even tens of thousands of mPa.s (25°C). In addition, asparagus polyurea resins are often made into prepolymers in many applications, and the viscosity after being made into prepolymers will often be significantly improved. Finally, due to environmental protection requirements, many application engineers pursue high solid content when using asparagus polyurea resins. Inactive diluents often increase VOC emissions, which is not conducive to environmental protection. Therefore, an active diluent with appropriate viscosity control but no VOC emissions is very important. Summary of the invention

[0008] To solve the above problems, the primary purpose of the present invention is to provide a secondary amine resin active diluent and a synthesis method thereof. The present invention reduces the viscosity of the resin and solves the fluidity and ease of use of the coating through the design of the active diluent molecular structure.

[0009] Another object of the present invention is to provide a secondary amine resin active diluent and a synthesis method thereof, by designing an active diluent with excellent performance to reduce the viscosity of the resin and prepolymer, while avoiding the increase of VOC emissions, which can be used not only for polyurea resin, but also for polyurethane and epoxy curing agent.

[0010] To achieve the above objectives, the technical solution of the present invention is as follows.

[0011] A secondary amino resin active diluent, the structural formula of which is as follows:

[0012]

[0013] Among them, R' is a C1-C12 chain alkane or a cyclic alkane, and R is a C1-C6 chain alkane or a cyclic alkane.

[0014] The designed secondary amino resin active diluent of the present invention can not only increase the reaction activity through multi-functional groups, but also give the cured film a cross-linked structure, thereby obtaining a high cross-linked network and reducing the viscosity of the resin.

[0015] A method for synthesizing a secondary amino resin active diluent is as shown below:

[0016]

[0017] The monoprimary amine or ether amine represented by A and the maleic acid diester represented by B are reacted in a mass ratio of 1-3:1 under solvent-free conditions and an inert gas atmosphere at a reaction temperature of 25°C-80°C. The reaction completely recovers excess amine to obtain a secondary amine type resin active diluent.

[0018] Furthermore, the inert gas is any one of the following: nitrogen, argon.

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

[0020] The secondary amino resin active diluent realized by the present invention can not only increase the reaction activity through its multifunctional groups, but also give the cured film a cross-linked structure, obtain a high cross-linked network, reduce the viscosity of the resin, solve the fluidity of the coating, and make the coating convenient to use.

[0021] At the same time, the secondary amine type resin active diluent realized by the present invention is a diluent containing secondary amine, and there is an active hydrogen "-NH" on the secondary amine, which can react with isocyanate "-NCO" to form polyurea, and finally become a part of the polymer film. Instead of being discharged into the air in the form of VOC like ordinary diluents, it can reduce the viscosity of the resin and prepolymer while avoiding the increase of VOC emissions. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is the structural formula of the secondary amino resin active diluent realized by the present invention.

[0023] Figure 2 This is an example of the synthetic reaction formula of the secondary amino resin active diluent achieved by the present invention.

[0024] Figure 3 It is the nuclear magnetic hydrogen spectrum of the secondary amino type resin active diluent realized by the present invention.

[0025] Figure 4It is the nuclear magnetic carbon spectrum of the secondary amino resin active diluent realized by the present invention. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0027] like Figure 1 As shown, the structure of the secondary amino resin active diluent realized by the present invention is as follows:

[0028]

[0029] Among them, R' is a C1-C12 chain alkane or a cyclic alkane, and R is a C1-C6 chain alkane or a cyclic alkane.

[0030] The synthesis method of the secondary amino resin active diluent achieved by the present invention is as follows: Figure 2 As shown:

[0031]

[0032] The monoprimary amine or ether amine represented by A and the maleic acid diester represented by B are reacted in a mass ratio of 1-3:1 under solvent-free conditions and an inert gas atmosphere at a reaction temperature of 25°C-80°C. The reaction is monitored by TLC, and the excess amine is completely recovered in the reaction to obtain a secondary amine type resin active diluent.

[0033] The inert gas is any one of nitrogen and argon.

[0034] The implementation of the present invention is further described below in conjunction with specific embodiments.

[0035] Example 1.

[0036]

[0037] Into a three-necked flask with a condenser reflux tube and argon (any inert gas will do, argon here simply represents an inert gas) protection, add 17.2 g of diethyl maleate, slowly introduce 12 g of isopropylamine at 40°C, continue the reaction at 40°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess isopropylamine to obtain about 22.98 g of M1 as a light yellow liquid, with a yield of 99.4%.

[0038] Example 2.

[0039]

[0040] Into a three-necked flask equipped with a condenser reflux tube and argon protection, 144 g of dimethyl maleate was added, and 150 g of tert-butylamine was slowly introduced at 60°C. The reaction was continued at 60°C and the progress of the reaction was monitored by TLC. When the reaction was complete, the excess tert-butylamine was recovered to obtain about 216 g of M2 as a light yellow liquid with a yield of 99.5%.

[0041] Example 3.

[0042]

[0043] 172 g of diethyl maleate was added into a three-necked flask with a condenser reflux tube and argon protection, and 100 g of cyclohexylamine was slowly added at 60°C. The reaction was continued at 60°C and the progress of the reaction was monitored by TLC. When the reaction was complete, the excess cyclohexylamine was recovered to obtain about 269 g of M3 light yellow liquid with a yield of 99.3%.

[0044] Example 4.

[0045]

[0046] 228 g of di-n-butyl maleate was added into a three-necked flask with a condenser reflux tube and argon protection, and 200 g of 2-methylcyclohexylamine was slowly added at 80°C. The reaction was continued at 80°C and the reaction progress was monitored by TLC. When the reaction was complete, the excess 2-methylcyclohexylamine was recovered to obtain about 338 g of M4 as a light yellow liquid with a yield of 99.1%.

[0047] Example 5.

[0048]

[0049] 144 g of dimethyl maleate was added into a three-necked flask with a condenser reflux tube and argon protection, and 200 g of cyclopentylamine was slowly added at 25°C. The reaction was continued at 80°C and the progress of the reaction was monitored by TLC. When the reaction was complete, the excess cyclopentylamine was recovered to obtain about 228 g of M5 light yellow liquid with a yield of 99.6%.

[0050] Example 6.

[0051]

[0052] 200 g of diisopropyl maleate was added into a three-necked flask with a condenser reflux tube and argon protection, and 250 g of 2-isopropylcyclopentylamine was slowly added at 75°C. The reaction was continued at 75°C and the progress of the reaction was monitored by TLC. When the reaction was complete, the excess 2-isopropylcyclopentylamine was recovered to obtain about 325 g of M6 light yellow liquid with a yield of 99.4%.

[0053] Example 7.

[0054]

[0055] Into a three-necked flask with a condenser reflux tube and argon protection, 452 g of dilauryl maleate was added, and 90 g of methylamine was slowly introduced at 25°C. The reaction was continued at 25°C and the progress of the reaction was monitored by TLC. When the reaction was complete, the excess methylamine was recovered to obtain about 477 g of M7 as a light yellow oily liquid with a yield of 99.2%.

[0056] Example 8.

[0057]

[0058] 172 g of diethyl maleate was added into a three-necked flask with a condenser reflux tube and argon protection, and 200 g of 2,6-dimethylcyclohexylamine was slowly added at 60°C. The reaction was continued at 60°C and the progress of the reaction was monitored by TLC. When the reaction was complete, the excess 2,6-dimethylcyclohexylamine was recovered to obtain about 297 g of M8 light yellow liquid with a yield of 99.3%.

[0059] The physical properties of resin reactive diluents are shown in the following table.

[0060] Table 1. Viscosity and density of each active diluent

[0061]

[0062] Among them, the nuclear magnetic hydrogen spectrum of M1 is as follows Figure 3 As shown, the M1 NMR carbon spectrum is as follows Figure 4 The properties of other M2-M7 are similar, and only M1 is used as an example for explanation.

[0063] Take M1, M3 and M4 as examples to conduct combined experiments with resins, the results are as follows:

[0064] Table 2: Viscosity changes of each resin before and after adding diluent

[0065]

[0066] *The test temperature is 25℃, unit is mPa·s.

[0067] In Table 2, LR-1420 and LR-2925 are asparagine polyurea resin products produced by our company, Incozol 4 is a bisoxazolidine latent resin produced by Incorez Limited, and HDPOL-7710 is an MPO / AA polyester polyol produced by Huide Technology.

[0068] As can be seen from the table, this type of secondary amine resin diluent can reduce the viscosity of asparagine polyurea resins such as LR-1420 and LR2925, latent polyurea resins such as Incozol 4, and polyurethane resins such as HDPOL-7710. Moreover, the viscosity decreases as the amount of diluent added increases.

[0069] It can be seen from this that the secondary amine resin active diluent implemented in the present invention can appropriately reduce the viscosity of the resin, and there is no VOC emission, which can not only solve the fluidity of the coating, but also make the coating convenient to use.

[0070] Moreover, the resin reactive diluent implemented by the present invention can be used not only for polyurea resin, but also for polyurethane and epoxy curing agent.

[0071] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A secondary amino resin active diluent, characterized in that The secondary amino resin active diluent has a structure as shown in Formula M: Among them, R' is a C1-C12 chain alkane or a cyclic alkane, and R is a C1-C6 chain alkane or a cyclic alkane.

2. A method for synthesizing a secondary amino resin active diluent as claimed in claim 1, characterized in that The synthesis method is as follows: The monoprimary amine or ether amine represented by A and the maleic acid diester represented by B are reacted in a mass ratio of 1-3:1 under solvent-free conditions and an inert gas atmosphere at a reaction temperature of 25°C-80°C. The reaction completely recovers excess amine to obtain a secondary amine type resin active diluent.

3. The synthetic method of the secondary amino resin reactive diluent as claimed in claim 2, characterized in that Add diethyl maleate into a container with a condenser reflux tube and inert gas protection, slowly introduce isopropylamine at 40°C, continue the reaction at 40°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess isopropylamine to obtain a light yellow liquid, which is a secondary amine resin active diluent.

4. The synthetic method of the secondary amino resin reactive diluent as claimed in claim 2, characterized in that Add dimethyl maleate into a container with a condenser reflux tube and inert gas protection, slowly introduce tert-butylamine at 60°C, continue the reaction at 60°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess tert-butylamine to obtain a light yellow liquid, which is a secondary amine type resin active diluent.

5. The synthetic method of the secondary amino resin reactive diluent as claimed in claim 2, characterized in that Add diethyl maleate into a container with a condenser reflux tube and inert gas protection, slowly add cyclohexylamine at 60°C, continue the reaction at 60°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess cyclohexylamine to obtain a light yellow liquid, which is a secondary amino resin active diluent.

6. The synthetic method of the secondary amino resin reactive diluent as claimed in claim 2, characterized in that Add di-n-butyl maleate into a container with a condenser reflux tube and inert gas protection, slowly add 2-methylcyclohexylamine at 80°C, continue the reaction at 80°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess 2-methylcyclohexylamine to obtain a light yellow liquid, which is a secondary amino resin active diluent.

7. The synthetic method of the secondary amino resin reactive diluent as claimed in claim 2, characterized in that Add dimethyl maleate into a container with a condenser reflux tube and an inert gas, slowly add cyclopentylamine at 25°C, continue the reaction at 80°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess cyclopentylamine to obtain a light yellow liquid, which is a secondary amino resin active diluent.

8. The synthetic method of the secondary amino resin reactive diluent as claimed in claim 2, characterized in that Add diisopropyl maleate into a container with a condenser reflux tube and inert gas protection, slowly add 2-isopropylcyclopentylamine at 75°C, continue the reaction at 75°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess 2-isopropylcyclopentylamine to obtain a light yellow liquid, which is a secondary amino resin active diluent.

9. The synthetic method of the secondary amino resin reactive diluent as claimed in claim 2, characterized in that Add dilauryl maleate into a container with a condenser reflux tube and inert gas protection, slowly introduce methylamine at 25°C, continue the reaction at 25°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess methylamine to obtain M7 light yellow oily liquid, which is a secondary amino resin active diluent.

10. The method for synthesizing the secondary amino resin reactive diluent as claimed in claim 2, characterized in that Add diethyl maleate into a container with a condenser reflux tube and inert gas protection, slowly add 2,6-dimethylcyclohexylamine at 60°C, continue the reaction at 60°C, monitor the reaction progress by TLC, and when the reaction is complete, recover the excess 2,6-dimethylcyclohexylamine to obtain a light yellow liquid, which is a secondary amino resin active diluent.

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