A primer-free polyurea composition and its preparation method
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-02
- Publication Date
- 2026-08-14
AI Technical Summary
[0003]然而，聚脲喷涂技术在应用时面临两个核心挑战，第一，抢险现场常伴有高压泥浆涌水，特别是含膨润土等粘土矿物的泥浆，这些粘土矿物遇水形成带负电的胶体层，严重阻隔聚脲与基面的接触，导致粘结完全失败
[0034]与现有技术相比，本发明的有益效果是：涂层具有高强度和高韧性，能实现对泥浆基面的免底漆强力粘结，并且裂纹修复效率达到99%。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of polyurea preparation technology, specifically relating to a primer-free polyurea composition and its preparation method. Background Technology
[0002] In tunnel collapse emergency repair projects, polyurea spraying technology is highly favored due to its rapid curing and high strength.
[0003] However, polyurea spraying technology faces two core challenges in its application. First, emergency rescue sites often experience high-pressure mud and water inflows, especially mud containing clay minerals such as bentonite. These clay minerals form a negatively charged colloidal layer upon contact with water, severely hindering the contact between the polyurea and the substrate, leading to complete adhesion failure. Second, even if the polyurea successfully bonds, the repaired structure will still develop microcracks during long-term service due to factors such as geological subsidence, temperature stress, and vibration. These microcracks will gradually expand, becoming new leakage channels, causing the waterproofing system to fail and requiring secondary or even multiple repairs, which are costly and risky.
[0004] To address the challenges of application and durability in polyurea spraying technology, existing technologies propose integrating a debonding function into the polyurea to achieve primer-free application. However, existing primer-free polyurea still falls short in terms of rapid repair capabilities.
[0005] To address the existing problems, we propose a primer-free polyurea composition and its preparation method.
[0006] The information disclosed in this background section is only for understanding the background technology of the inventive concept, and therefore may include information that does not constitute prior art. Summary of the Invention
[0007] The purpose of this invention is to provide a primer-free polyurea composition to solve the problems mentioned in the background art.
[0008] On one hand, this disclosure provides an embodiment of a primer-free polyurea composition comprising:
[0009] Component A includes isocyanate prepolymer, modified polyether silicone oil, calixarene derivatives and catalyst. The modified polyether silicone oil includes quaternary ammonium salt cations and also includes hydroxyl or primary amino groups. The calixarene derivatives include coumarin groups and also include hydroxyl or primary amino groups.
[0010] Component B is a polyetheramine curing agent.
[0011] As an optional implementation, the raw material dosage of component A is 55%-80% isocyanate prepolymer, 2%-8% modified polyether silicone oil, 1%-5% calixarene derivative, and 0.1-1% catalyst.
[0012] As an optional implementation, the raw materials for preparing modified polyether silicone oil include a polyether segment introducer, a siloxane segment introducer, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and a catalyst, and also include a hydroxyl introducer or a primary amino introducer.
[0013] As an optional implementation, the raw materials for preparing calixarene derivatives include calixarene and coumarin acyl chloride derivatives, and also include hydroxyl introducers or primary amino introducers.
[0014] As an optional implementation method, the preparation steps of modified polyether silicone oil include:
[0015] 1) Add appropriate amounts of polyether segment introducer and siloxane segment introducer to the reactor, add appropriate amount of catalyst, react under the first process conditions, and obtain polyether silicone oil after the reaction is completed;
[0016] 2) Add the polyether silicone oil to the reaction vessel, then add an appropriate amount of 3-chloro-2-hydroxypropyltrimethylammonium chloride, then add a solvent to the reaction system, and then add a primary amino introducer or a hydroxyl introducer. After the reaction is completed under the second process conditions, the modified polyether silicone oil is obtained.
[0017] As an alternative implementation method, the first process conditions are a pH of 8.5-9.5 and a reaction at a temperature of 65-75°C for 4-5 hours.
[0018] As an alternative implementation method, the second process condition is to react at a temperature of 70-80°C for 3-4 hours.
[0019] As an optional implementation, the hydroxyl group introducer is one or more of propylene oxide, epichlorohydrin, and tetrahydrofuran.
[0020] As an alternative implementation, the primary amino initiator is one or more of ethylenediamine, hydroxylamine-O-sulfonic acid, and N,N-dimethylethylenediamine.
[0021] As an optional implementation method, the preparation steps of calixarene derivatives include:
[0022] 1) Dissolve calixarene and acid-binding agent in their solvent and add them to the reaction vessel. Add coumarin acyl chloride derivative to its solvent to prepare a solution. Then add the coumarin acyl chloride derivative solution dropwise into the calixarene and acid-binding agent solution and react under the third process conditions. After the reaction is completed, the first intermediate is obtained.
[0023] 2) Add an appropriate amount of the first intermediate to a solvent to prepare a first intermediate solution, then add the first intermediate solution to a reaction vessel, and add a hydroxyl introducer or a primary amino introducer to the reaction vessel. React under the fourth process conditions to obtain a calixarene derivative.
[0024] As an optional implementation, the third process condition is to maintain an ice bath at 0-5°C during the mixing of the two solutions, and after the coumarin acyl chloride derivative solution has been completely added, raise the temperature to 25-30°C and stir for 8-10 hours.
[0025] As an optional implementation, the fourth process condition is to use an inert gas for protection during the reaction and to stir at a temperature of 80-90°C for 4-6 hours.
[0026] On the other hand, this disclosure provides an embodiment in which a method for preparing a primer-free polyurea composition includes the following steps:
[0027] 1) Add appropriate amounts of polyether segment introducer and siloxane segment introducer to the reactor, add appropriate amount of catalyst, and react under the first process conditions. After the reaction is completed, polyether silicone oil is obtained.
[0028] 2) Add the polyether silicone oil to the reaction vessel, then add an appropriate amount of 3-chloro-2-hydroxypropyltrimethylammonium chloride, then add a solvent to the reaction system, and then add a primary amino introducer and a hydroxyl introducer. After the reaction is completed under the second process conditions, the modified polyether silicone oil is obtained.
[0029] 3) Dissolve calixarene and acid-binding agent in their solvent and add them to the reaction vessel. Add coumarin acyl chloride derivative to its solvent to prepare a solution. Then add the coumarin acyl chloride derivative solution dropwise into the calixarene and acid-binding agent solution and react under the third process conditions. After the reaction is completed, the first intermediate is obtained.
[0030] 4) Add an appropriate amount of the first intermediate to a solvent to prepare a first intermediate solution, then add the first intermediate solution to a reaction vessel, and add a hydroxyl introducer or a primary amino introducer to the reaction vessel. React under the fourth process conditions to obtain a calixarene derivative.
[0031] 5) Add a diluent to an appropriate amount of isocyanate prepolymer, and after a period of time, add an appropriate amount of modified polyether silicone oil and calixarene derivatives, and finally add an appropriate amount of catalyst. React under the fifth process conditions to obtain component A.
[0032] 6) Prepare appropriate amounts of component B and component A. Component B is a polyetheramine curing agent. Use a two-component polyurea spraying machine to spray components A and B onto the substrate under the process conditions of temperature 45-55℃, pressure 15-20MPa, and spray gun moving speed 0.5-1m / s.
[0033] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit this application.
[0034] Compared with the prior art, the beneficial effects of the present invention are: the coating has high strength and high toughness, can achieve strong adhesion to the mud base surface without primer, and the crack repair efficiency reaches 99%. Detailed Implementation
[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.
[0036] Example 1:
[0037] Preparation of modified polyether silicone oil:
[0038] 1) Add 100 parts of polyethylene glycol with a molecular weight of 2000 and 80 parts of octamethylcyclotetrasiloxane to a reaction vessel, add 0.1 parts of tetrabutylammonium hydroxide, and protect the reaction with an inert gas, such as nitrogen. Stir at 85°C for 5 hours to obtain polyether silicone oil.
[0039] 2) Add the polyether silicone oil to the reaction vessel, then add 15 parts of 15% 3-chloro-2-hydroxypropyltrimethylammonium chloride. The pH is 8.5 during the reaction. The reaction is carried out at 65°C for 4 hours. Then add ethyl acetate to the reaction system, followed by 5 parts of 10% propylene oxide. The reaction is carried out at 70°C for 3 hours. After the reaction is completed, the modified polyether silicone oil is obtained.
[0040] Preparation of calixarene derivatives:
[0041] 1) Dissolve 1,3-dimethoxy-4-tert-butylcalixarene and triethylamine in dichloromethane and add them to a reaction vessel. Add 20 parts of coumarin-3-formyl chloride to dichloromethane to prepare a solution. Then, add the coumarin acyl chloride derivative solution dropwise to the calixarene and acid-binding agent solution. Keep the two solutions in an ice bath at 0°C during the mixing process. After the solution is completely added, raise the temperature to 25°C and stir for 8 hours. After purification, the first intermediate is obtained.
[0042] 2) Add 10 parts of the first intermediate to ethyl acetate to prepare a solution of the first intermediate. Then add the first intermediate solution and 5 parts of 10% propylene oxide to the reaction vessel. The reaction is carried out under inert gas protection, such as nitrogen. Stir at 80°C for 4 hours. After the reaction is completed and purified, calixarene derivatives are obtained.
[0043] Preparation of primer-free polyurea compositions:
[0044] 1) Add propylene glycol methyl ether acetate to 55 parts of toluene diisocyanate and stir at 300 rpm for 10 min. Then add 2 parts of modified polyether silicone oil and 1 part of calixarene derivative. Then heat to 40°C and stir for 30 min. Then cool down to 25°C and finally add 0.1 parts of neodecanoate to obtain component A.
[0045] 2) Prepare component B (D-2000) and component A with a weight ratio of 100:40; use a two-component polyurea spraying machine to spray component A and component B onto the substrate under the process conditions of 45℃ temperature, 15MPa pressure and 0.5m / s spray gun moving speed.
[0046] Example 2:
[0047] Preparation of modified polyether silicone oil:
[0048] 1) Add 100 parts of polytetrahydrofuran with a molecular weight of 4000 and 100 parts of decamethylcyclopentasiloxane to a reaction vessel, add 3 parts of tetrabutylammonium hydroxide, and protect the reaction with an inert gas, such as nitrogen, and stir at 95°C for 6 hours to obtain polyether silicone oil.
[0049] 2) Add the polyether silicone oil to the reaction vessel, then add 20 parts of 20% 3-chloro-2-hydroxypropyltrimethylammonium chloride. During the reaction, the pH is 9.5, and the reaction is carried out at 75°C for 4-5 hours. Then add xylene to the reaction system, followed by 6 parts of 12% ethylenediamine. The reaction is carried out at 80°C for 4 hours. After the reaction is completed, the modified polyether silicone oil is obtained.
[0050] Preparation of calixarene derivatives:
[0051] 1) O(1),O(3)-bis(acetylated methyl)-p-tert-butylcalixarene and pyridine were dissolved in chloroform and added to a reaction vessel. 40 parts of coumarin-6-formyl chloride were added to chloroform to prepare a solution. Then, the coumarin-6-formyl chloride solution was added dropwise to the calixarene and pyridine solution. During the mixing of the two solutions, an ice bath of 5°C was maintained. After the solution was completely added, the temperature was raised to 30°C and stirred for 10 hours. After purification, the first intermediate was obtained.
[0052] 2) Add 10 parts of the first intermediate to xylene to prepare a first intermediate solution. Then add the first intermediate solution and 6 parts of 12% ethylenediamine to the reaction vessel. The reaction is carried out under inert gas protection, such as nitrogen. Stir at 90°C for 6 hours. After the reaction is completed and purified, calixarene derivatives are obtained.
[0053] Preparation of primer-free polyurea compositions:
[0054] 1) Add propylene glycol methyl ether to 80 parts of hexamethylene diisocyanate and stir at 500 rpm for 15 min. Then add 8 parts of modified polyether silicone oil and 5 parts of calixarane derivative. Then heat to 50°C and stir for 45 min. Then cool down to 30°C and finally add 1 part of bismuth isooctanoate to obtain component A.
[0055] 2) Prepare component B (T-5000) and component A with a weight ratio of 100:60; use a two-component polyurea spraying machine to spray component A and component B onto the substrate under the process conditions of 55℃ temperature, 20MPa pressure and 1m / s spray gun moving speed.
[0056] Example 3:
[0057] Preparation of modified polyether silicone oil:
[0058] 1) Add 100 parts of polyethylene glycol with a molecular weight of 3000 and 90 parts of dimethylcyclosiloxane to a reaction vessel, add 0.2 parts of tetrabutylammonium hydroxide, and protect the reaction with an inert gas, such as nitrogen. Stir at 90°C for 5.5 hours to obtain polyether silicone oil.
[0059] 2) The polyether silicone oil was added to the reactor, and then 17 parts of 18% 3-chloro-2-hydroxypropyltrimethylammonium chloride were added. The pH was 9 during the reaction, and the reaction was carried out at 70°C for 4.5 h. Toluene was then added to the reaction system, followed by 5 parts of 11% N,N-dimethylethylenediamine. The reaction was carried out at 75°C for 3.5 h. After the reaction was completed, the modified polyether silicone oil was obtained.
[0060] Preparation of calixarene derivatives:
[0061] 1) Dissolve p-tert-butylcalix[4] aromatics and N-methylmorpholine in dichloromethane and add them to the reaction vessel. Add 30 parts of coumarin-3-formyl chloride to dichloromethane to prepare a solution. Then add the coumarin acyl chloride derivative solution dropwise into the calix aromatics and acid-binding agent solution. Keep the two solutions in an ice bath at 3°C during the mixing process. After the solution is completely added, raise the temperature to 28°C and stir for 9 hours. After purification, the first intermediate is obtained.
[0062] 2) Add 10 parts of the first intermediate to ethyl acetate to prepare a first intermediate solution. Then add the first intermediate solution and 8 parts of epichlorohydrin with a concentration of 15% to the reaction vessel. The reaction is carried out under inert gas protection, such as nitrogen. Stir at 85°C for 5 hours. After the reaction is completed and purified, calixarene derivatives are obtained.
[0063] Preparation of primer-free polyurea compositions:
[0064] 1) Add propylene glycol methyl ether acetate to 70 parts of hexamethylene diisocyanate and stir at 400 rpm for 13 min. Then add 6 parts of modified polyether silicone oil and 3 parts of calixarene derivative. Then heat to 45°C and stir for 40 min. Then cool down to 28°C and finally add 0.8 parts of neodecanoate to obtain component A.
[0065] 2) Prepare component B (D-2000) and component A with a weight ratio of 100:50; use a two-component polyurea spraying machine to spray component A and component B onto the substrate under the process conditions of 50℃ temperature, 18MPa pressure and 0.8m / s spray gun moving speed.
[0066] Comparative Example 1:
[0067] Preparation of modified polyether silicone oil:
[0068] 1) Add 100 parts of polyethylene glycol with a molecular weight of 3000 and 90 parts of dimethylcyclosiloxane to a reaction vessel, add 0.2 parts of tetrabutylammonium hydroxide, and protect the reaction with an inert gas, such as nitrogen. Stir at 90°C for 5.5 hours to obtain polyether silicone oil.
[0069] The remaining preparation process is the same as in Example 3.
[0070] Comparative Example 2:
[0071] Preparation of modified polyether silicone oil: Same as in Example 3.
[0072] Preparation of primer-free polyurea compositions:
[0073] 1) Add propylene glycol methyl ether acetate to 700 parts of hexamethylene diisocyanate and stir at 400 rpm for 13 min. Then add 6 parts of modified polyether silicone oil and 3 parts of p-tert-butylcalix[4] aromatics. Then heat to 45°C and stir for 40 min. Then cool down to 28°C and finally add 0.8 parts of neodecanoate to obtain component A.
[0074] 2) Prepare component B (D-2000) and component A with a weight ratio of 100:50; use a two-component polyurea spraying machine to spray component A and component B onto the substrate under the process conditions of 50℃ temperature, 18MPa pressure and 0.8m / s spray gun moving speed.
[0075] Comparative Example 3:
[0076] Preparation of modified polyether silicone oil:
[0077] 1) Add 100 parts of polyethylene glycol with a molecular weight of 3000 and 90 parts of dimethylcyclosiloxane to a reaction vessel, add 0.2 parts of tetrabutylammonium hydroxide, and protect the reaction with an inert gas, such as nitrogen. Stir at 90°C for 5.5 hours to obtain polyether silicone oil.
[0078] 2) The polyether silicone oil was added to the reactor, and then 17 parts of 18% 3-chloro-2-hydroxypropyltrimethylammonium chloride were added. The pH was 9 during the reaction, and the reaction was carried out at 70°C for 4.5 hours. After the reaction was completed, the modified polyether silicone oil was obtained.
[0079] Preparation of calixarene derivatives: The preparation process is the same as in Example 3.
[0080] Preparation of primer-free polyurea compositions:
[0081] The modified polyether silicone oil prepared using this comparative example was prepared using the same process as the others.
[0082] The adhesion and self-healing properties of Examples 1-3 and Comparative Examples 1-3 were tested, and the specific test methods are as follows:
[0083] Adhesion performance test: Adhesion was tested according to the national standard GB / T 23446-2025.
[0084] Self-healing performance test: A 1 mm thick polyurea sample was prepared. The material was scratched with a clean blade, and after being placed under a polarizing microscope for a set time and temperature, the self-healing efficiency was calculated using the initial scratch width and the scratch width after repair. The self-healing efficiency was calculated using the following formula:
[0085] D% = (L2 - L1) / L2 × 100%;
[0086] L1—Repaired scratch width, mm; L2—Initial scratch width, mm.
[0087] Table 1 Test Results
[0088] The results show that the values of various indicators (adhesion, tensile strength, elongation at break, and tear strength) of Examples 1-3 are all high, indicating excellent mechanical properties.
[0089] All indicators of Comparative Examples 1-3 were significantly lower than those of Examples 1-3, and in particular, the data of Comparative Example 1 were much lower than those of Comparative Examples 2 and 3, indicating a lack of basic performance.
[0090] The data of Comparative Example 3 are between those of Examples 1-3 and Comparative Examples 1-2. Some indicators (such as tear strength of 71 MPa) are closer to the level of Examples 1-3 than those of Comparative Examples 1-2, but other indicators (adhesion, tensile strength, elongation at break) are still significantly different from those of Examples 1-3.
[0091] Table 2 Test Results
[0092] The results show that, in both Examples 1-3 and Comparative Examples 1-3, the self-healing efficiency increases significantly with increasing temperature.
[0093] Examples 1-3 achieved high efficiencies of 66%-93% within 0.5 hours. Especially at 60°C, the 0.5-hour efficiency of all examples exceeded 90%, indicating that Examples 1-3 responded extremely quickly in the initial heating stage. With prolonged time, the repair efficiency of all examples reached or approached 100% after 2 hours at 60°C.
[0094] The self-healing efficiency of Comparative Examples 1-3 at the same time point was significantly lower than that of Examples 1-3. At 0.5 h, the repair efficiency of Comparative Example 1 at 20°C was only 32%, less than half that of Examples 1-3. Although Comparative Example 3 performed better at low temperatures, the improvement in repair rate at high temperatures was less significant than that of Examples 1-3. However, at 20°C and 0.5 h, the repair efficiency of Comparative Example 3 was significantly better than that of Comparative Examples 1-2.
[0095] Although embodiments of the invention have been shown and described (see the detailed description above), it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A primer-free polyurea composition, characterized in that, The polyurea composition includes: Component A comprises isocyanate prepolymer, modified polyether silicone oil, calixarene derivative, and catalyst. The modified polyether silicone oil comprises quaternary ammonium salt cation and also includes hydroxyl or primary amino groups. The calixarene derivative comprises coumarin groups and also includes hydroxyl or primary amino groups. Component B is a polyetheramine curing agent.
2. The primer-free polyurea composition according to claim 1, characterized in that, The raw material usage of component A is 55%-80% isocyanate prepolymer, 2%-8% modified polyether silicone oil, 1%-5% calixarane derivative, and 0.1-1% catalyst.
3. The primer-free polyurea composition according to claim 1, characterized in that, The raw materials for preparing the modified polyether silicone oil include a polyether segment introducer, a siloxane segment introducer, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and a catalyst, and also include a hydroxyl introducer or a primary amino introducer.
4. The primer-free polyurea composition according to claim 1, characterized in that, The raw materials for preparing the calixarene derivatives include calixarene and coumarin acyl chloride derivatives, as well as hydroxyl introducers or primary amino introducers.
5. The primer-free polyurea composition according to claim 1, characterized in that, The preparation method of the modified polyether silicone oil includes the following steps: 1) Add appropriate amounts of polyether segment introducer and siloxane segment introducer to the reactor, add appropriate amount of catalyst, react under the first process conditions, and obtain polyether silicone oil after the reaction is completed; 2) Add the polyether silicone oil to the reaction vessel, then add an appropriate amount of 3-chloro-2-hydroxypropyltrimethylammonium chloride, then add a solvent to the reaction system, and then add a primary amino introducer or a hydroxyl introducer. After the reaction is completed under the second process conditions, the modified polyether silicone oil is obtained.
6. The primer-free polyurea composition according to claims 3-4, characterized in that, The hydroxyl group introducer is one or more of propylene oxide, epichlorohydrin, and tetrahydrofuran.
7. The primer-free polyurea composition according to claim 5, characterized in that, The primary amino introducing agent is one or more of ethylenediamine, hydroxylamine-O-sulfonic acid, and N,N-dimethylethylenediamine.
8. The primer-free polyurea composition according to claim 1, characterized in that, The preparation steps of the calixarene derivative include: 1) Dissolve calixarene and acid-binding agent in their solvent and add them to the reaction vessel. Add coumarin acyl chloride derivative to its solvent to prepare a solution. Then add the coumarin acyl chloride derivative solution dropwise to the calixarene and acid-binding agent solution and react under the third process conditions. After the reaction is completed, the first intermediate is obtained. 2) Add an appropriate amount of the first intermediate to a solvent to prepare a first intermediate solution, then add the first intermediate solution to a reaction vessel, and add a hydroxyl introducer or a primary amino introducer to the reaction vessel. React under the fourth process conditions to obtain a calixarene derivative.
9. A method for preparing a primer-free polyurea composition, characterized in that, The preparation method includes: 1) Add appropriate amounts of polyether segment introducer and siloxane segment introducer to the reactor, add appropriate amount of catalyst, react under the first process conditions, and obtain polyether silicone oil after the reaction is completed; 2) Add the polyether silicone oil to the reaction vessel, then add an appropriate amount of 3-chloro-2-hydroxypropyltrimethylammonium chloride, then add a solvent to the reaction system, and then add a primary amino introducing agent or a hydroxyl introducing agent. After the reaction is completed under the second process conditions, the modified polyether silicone oil is obtained. 3) Dissolve calixarene and acid-binding agent in their solvent and add them to the reaction vessel. Add coumarin acyl chloride derivative to its solvent to prepare a solution. Then add the coumarin acyl chloride derivative solution dropwise to the calixarene and acid-binding agent solution and react under the third process conditions. After the reaction is completed, the first intermediate is obtained. 4) Add an appropriate amount of the first intermediate to a solvent to prepare a first intermediate solution, then add the first intermediate solution to a reaction vessel, and add a hydroxyl introducer or a primary amino introducer to the reaction vessel. React under the fourth process conditions to obtain calixarene derivatives. 5) Add a diluent to an appropriate amount of isocyanate prepolymer, and after a period of time, add an appropriate amount of modified polyether silicone oil and calixarene derivative, and finally add an appropriate amount of catalyst. React under the fifth process conditions to obtain component A. 6) Prepare appropriate amounts of component B and component A. Component B is a polyetheramine curing agent. Use a two-component polyurea spraying machine to spray components A and B onto the substrate under the process conditions of temperature 45-55℃, pressure 15-20MPa, and spray gun moving speed 0.5-1m / s.