A double-benzene ring urea bond composite modified polyether silicone oil and a preparation method thereof

Abstract

The application discloses a kind of double benzene ring urea bond composite modified polyether silicone oil and its preparation method and application.The polyether modified low hydrogen-containing silicone oil preparation method is: (1) by allyl alcohol polyoxyethylene polyoxypropylene ether and Boc-3-amino-4-phenyl butyric acid is reacted to prepare modified polyether;(2) by trifluoroacetic acid removal Boc protection group, obtain high-activity polyether intermediate containing free amino, benzene ring and end allyl;(3) by the free amino of high-activity polyether intermediate and phenyl isocyanate reaction preparation functionalized modified allyl polyether;(4) by functionalized modified allyl polyether and hydrogen-containing silicone oil is reacted to prepare modified silicone oil.The functionalized polyether modified silicone oil provided by the application has a variety of polyether structures, by introducing double benzene ring and rigid urea bond simultaneously, the characteristics of polyether hydrophilic wetting, organic silicon weather resistance and smoothness are considered, and the application range is wide.

Description

Technical Field

[0001] This invention relates to the field of silicone oil technology, specifically to a biphenyl ring urea bond composite modified polyether silicone oil and its preparation method. Background Technology

[0002] Silicone oil is a type of liquid substance with excellent safety, being non-toxic and harmless to the human body. It also possesses good physicochemical stability, with a pH value of approximately 7. The polysiloxane molecular structure of silicone oil endows it with excellent chemical stability. Furthermore, by controlling the degree of polymerization of polysiloxanes, changing the types of organic functional groups, or copolymerizing polysiloxanes with other organic monomers, various modified silicone oils can be prepared. These modified silicone oils are now widely used in multiple industries such as coatings, textiles, daily chemicals, and pesticides.

[0003] Polyether-modified silicone oil is currently the most widely produced and applied type of modified silicone oil. It is typically an oily polymer formed by chemically bonding the main chain or side chains of linear polydimethylsiloxane to polyether segments. Its molecule combines hydrophilic polyether segments with stable hydrophobic polysiloxane segments: the polyether segments contain polar ether bonds, which can form hydrogen bonds with water, making them water-soluble; the polysiloxane segments have high bond energy, are chemically stable, and are hydrophobic and non-lipophilic. These two components synergistically endow this type of material with excellent surface activity, significantly reducing the surface tension of aqueous solutions, and are widely used as nonionic surfactants.

[0004] However, existing polyether-modified silicone oils generally suffer from a single molecular structure and an imbalance in overall performance, limiting their application range and making it impossible to simultaneously achieve multiple functions, such as high-temperature resistance, compatibility, and interfacial adhesion. Therefore, developing a composite modified polyether silicone oil with innovative structure and comprehensive performance, along with its supporting preparation process, is a pressing technical problem to be solved in this field. Summary of the Invention

[0005] Purpose of the invention: In view of the deficiencies of the existing technology, the purpose of this invention is to provide a polyether silicone oil modified by a double benzene ring and a rigid urea bond composite structure. By introducing a double benzene ring and a rigid urea bond composite structure through molecular design, it can simultaneously take into account high temperature resistance, compatibility and interfacial adhesion performance.

[0006] Technical solution: The biphenyl ring urea bond composite modified polyether silicone oil provided by this invention has a molecular backbone composed of siloxane, propyl linker, EO / PO polyether segment, ester bond, benzene ring and urethane bond, as shown in Formula A below:

[0007] A Where m=100 180, n=12-20, a=10 16, b = 4-10, and m, n, a, b are positive integers; the polyether silicone oil molecular chain contains both a diphenyl ring structure and a urethane bond structure.

[0008] The polyether molecular structure provided by this invention has the following characteristics: (1) Two benzene ring structures are introduced into the molecular chain at the same time, which greatly improves the compatibility of the product with resin and organic solvent, and effectively inhibits molecular migration and precipitation; (2) The urethane bond is introduced, which has a significantly higher bond energy than ordinary ester bond and ether bond, which can improve the overall rigidity of the molecule, high temperature resistance and interfacial adhesion; (3) The EO / PO polyether chain segment is retained to ensure the product's excellent hydrophilicity, wetting and emulsification ability; (4) The siloxane main chain is connected by a highly stable C-Si bond, which gives the product the inherent properties of weather resistance, smoothness and anti-aging of organosilicon materials.

[0009] The preparation method of the above-mentioned bisphenyl ring urea bond composite modified polyether silicone oil includes the following steps: (1) Modified polyether was prepared by reacting allyl alcohol polyoxyethylene polyoxypropylene ether with Boc-3-amino-4-phenylbutyric acid. (2) The Boc protecting group was removed by trifluoroacetic acid to obtain a highly active polyether intermediate containing free amino groups, benzene rings and terminal allyl groups; (3) Functionalized modified allyl polyethers were prepared by reacting the free amino groups of highly active polyether intermediates with phenyl isocyanates; (4) Modified silicone oil is prepared by reacting functionalized allyl polyether with hydrogen-containing silicone oil.

[0010] Furthermore, the structure of the allyl alcohol polyoxyethylene polyoxypropylene ether is shown in Formula B, where x = 10. 16, y = 4 - 10;

[0011] B Further, the specific method of step (1) is as follows: in the reactor, allyl alcohol polyoxyethylene polyoxypropylene ether and anhydrous dichloromethane are added and stirred until completely dissolved, and then Boc-3-amino-4-phenylbutyric acid and catalyst are added in sequence. 1. Stir at room temperature until the solid is completely dissolved. Then, under continuous nitrogen protection, slowly add dicyclohexylcarbodiimide dichloromethane solution. The reaction temperature is 20-25℃. After reacting for 12-14 hours, filter the product, wash, and rotary evaporate to obtain the modified polyether.

[0012] The reaction process is as follows:

[0013] Further, the mass ratio of the allyl alcohol polyoxyethylene polyoxypropylene ether, Boc-3-amino-4-phenylbutyric acid, and dicyclohexylcarbodiimide is 10:(2.7). 3.2): (2.1-2.3); the catalyst 1 is 4-dimethylaminopyridine; where x=10 16, y = 4 - 10, and x and y are positive integers. Further, the specific method of step (2) is as follows: add the modified polyether obtained in step (1) dissolved in dichloromethane to the reactor, add trifluoroacetic acid, react at room temperature for 1.5-3h, remove trifluoroacetic acid and solvent, and obtain a highly active polyether intermediate containing free amino groups with the Boc protecting group removed.

[0014] The reaction process is as follows:

[0015] Further, in step (2), the volume ratio of trifluoroacetic acid to modified polyether dichloromethane solution is 1-1.1:1, and the reduced pressure rotary evaporation temperature is 30-35℃; where x=10 16, y = 4 - 10, and x and y are positive integers.

[0016] Further, the specific method of step (3) is as follows: add the active polyether intermediate obtained in step (2) and anhydrous toluene to the reactor, heat to 40~45℃, slowly add phenyl isocyanate, and react for 3~4 hours after the addition is completed to obtain functionalized modified allyl polyether with phenyl urea bond.

[0017] The reaction process is as follows:

[0018] Further, in step (3), the mass ratio of the highly reactive polyether intermediate to phenyl isocyanate is 10:1.1-1.3, and the time for adding phenyl isocyanate is controlled to be 0.5-1 h; where x=10 16, y = 4 - 10, and x and y are positive integers.

[0019] Further, the specific method of step (4) is as follows: add the functionalized modified allyl polyether and hydrogen-containing silicone oil obtained in step (3) to the reactor, heat to 85~100℃, add catalyst-2 and stir for 4-6 hours. After the reaction is completed, a yellow transparent liquid is obtained, which is the modified silicone oil.

[0020] The reaction process is as follows:

[0021] Further, in step (4), the mass ratio of functionalized modified allyl polyether to hydrogen-containing silicone oil is 1-1.1:1; the hydrogen content of the hydrogen-containing silicone oil is 0.10%-0.18%; the catalyst... 2 is a platinum catalyst; the catalyst The effective platinum content in component 2 is 1.0 × 10⁻⁶ of the total mass of the reactants. -5 -5.0×10 -6 m=100 180, n=12-20, a=10 16, b = 4 - 10, and m, n, a, and b are positive integers.

[0022] The purpose of this invention is to provide a polyether silicone oil modified with a bisphenyl ring urea bond composite structure. Through molecular design, a composite structure of a bisphenyl ring and a rigid urea bond is introduced, simultaneously achieving excellent high-temperature resistance, compatibility, and interfacial adhesion. The urea bond and the bisphenyl ring synergistically enhance molecular thermal stability, allowing the product to withstand short-term temperatures of 180-200℃, far superior to ordinary polyether silicone oils. It is also less prone to yellowing and degradation under high-temperature environments. The bisphenyl ring structure exhibits good compatibility with various polymer resins such as acrylic, polyurethane, and epoxy, with no precipitation observed after long-term use, and it does not affect the recoating performance of the paint film. The polar urea bond can form intermolecular hydrogen bonds, significantly improving adhesion to substrates such as metals, plastics, glass, and fabrics. Detailed Implementation

[0023] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0024] Example 1 Weigh 10.00 g APEG, 1.19 g 4-dimethylaminopyridine, and 2.78 g dicyclohexylcarbodiimide, add 70 mL anhydrous dichloromethane, and stir at room temperature under nitrogen protection. Slowly add 2.78 g Boc-3-amino-4-phenylbutyric acid, and react at room temperature for 13 h. Filter, wash the filtrate successively with dilute hydrochloric acid and saturated brine, dry with anhydrous sodium sulfate, and then rotary evaporate to obtain the modified polyether.

[0025] Add 20 mL of dichloromethane and 20 mL of trifluoroacetic acid to the above modified polyether, stir at room temperature for 2 h, and remove the solvent by rotary evaporation to obtain a highly active polyether intermediate containing free amino groups, benzene rings and terminal allyl groups.

[0026] Add 30 mL of anhydrous toluene to a highly active polyether intermediate, then slowly add 1.19 g of phenyl isocyanate dropwise over a period of 1 hour; heat to 42 °C and react for 3.5 hours, then remove toluene by rotary evaporation.

[0027] Add 5.88g of hydrogen-containing silicone oil with a hydrogen content of 0.18% and 0.05ml of platinum catalyst, react at 90℃ for 5h, cool, remove solvent, and filter to obtain a pale yellow transparent target product.

[0028] Example 2 All raw materials and solvents were prepared in the same proportions as in Example 1, scaled up 5 times; a 500mL four-necked reaction flask was used for the experiment. The final product's properties and performance were completely consistent with the 10g small-scale product.

[0029] Comparative Example 1 The process is basically the same as in Example 1, except that in step (3), 1.19g of phenyl isocyanate is replaced with 0.99g of n-butyl isocyanate, while the other process parameters remain unchanged, to obtain monophenyl cyclohexyl cyclourea modified polyether silicone oil.

[0030] Comparative Example 2 The process is basically the same as in Example 1, except that in step (3), 1.19g of phenyl isocyanate is replaced with 1.25g of cyclohexyl isocyanate, while the other process parameters remain unchanged, to obtain monophenylcycloalkyl urea modified polyether silicone oil.

[0031] Performance testing Waterborne acrylic coating system: Add 0.5wt% silicone oil, bake 30μm wet film at 80℃; Polyester textile finishing solution: 2wt% working solution for pad setting; Take the average of the three parallel groups.

[0032]

[0033] The quantitative comparison data above clearly shows that the present invention, through the modification of the composite molecular structure of the two benzene rings and rigid urea bonds, has significant advantages in core properties such as thermal stability, water washability, and interfacial adhesion, and can be adapted to the harsh application scenarios of high-end industrial additives.

[0034] The above implementation methods are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A bisphenyl cyclic urea bond composite modified polyether silicone oil, characterized in that, It has the structure shown in equation A below: A Where m=100 180, n=12-20, a=10 16, b = 4-10, and m, n, a, b are positive integers; the polyether silicone oil molecular chain contains both a diphenyl ring structure and a urethane bond structure.

2. A method for preparing the bisphenyl cyclic urea bond composite modified polyether silicone oil according to claim 1, characterized in that, Includes the following steps: (1) Modified polyether was prepared by reacting allyl alcohol polyoxyethylene polyoxypropylene ether with Boc-3-amino-4-phenylbutyric acid. (2) The Boc protecting group was removed by trifluoroacetic acid to obtain a highly active polyether intermediate containing free amino groups, benzene rings and terminal allyl groups; (3) Functionalized modified allyl polyethers were prepared by reacting the free amino groups of highly active polyether intermediates with phenyl isocyanates; (4) Modified silicone oil is prepared by reacting functionalized allyl polyether with hydrogen-containing silicone oil.

3. The preparation method according to claim 2, characterized in that, The specific method of step (1) is as follows: In the reactor, add allyl alcohol polyoxyethylene polyoxypropylene ether and anhydrous dichloromethane and stir until completely dissolved, then add Boc-3-amino-4-phenylbutyric acid and catalyst in sequence.

1. Stir at room temperature until the solid is completely dissolved. Then, under continuous nitrogen protection, slowly add dicyclohexylcarbodiimide dichloromethane solution. The reaction temperature is 20-25℃. After reacting for 12-14 hours, filter the product, wash, and rotary evaporate to obtain the modified polyether.

4. The preparation method according to claim 2, characterized in that, In step (1), the mass ratio of allyl alcohol polyoxyethylene polyoxypropylene ether, Boc-3-amino-4-phenylbutyric acid, and dicyclohexylcarbodiimide is 10:(2.7). 3.2): (2.1-2.3); the catalyst 1 is 4-dimethylaminopyridine.

5. The preparation method according to claim 2, characterized in that, The specific method of step (2) is as follows: add the modified polyether obtained in step (1) dissolved in dichloromethane to the reactor, add trifluoroacetic acid, react at room temperature for 1.5-3 hours, remove trifluoroacetic acid and solvent, and obtain a highly active polyether intermediate containing free amino groups with the Boc protecting group removed.

6. The preparation method according to claim 2, characterized in that, In step (2), the volume ratio of trifluoroacetic acid to modified polyether dichloromethane solution is 1-1.1:1, and the vacuum rotary evaporation temperature is 30-35℃.

7. The preparation method according to claim 2, characterized in that, The specific method of step (3) is as follows: add the active polyether intermediate obtained in step (2) and anhydrous toluene to the reactor, heat to 40~45℃, slowly add phenyl isocyanate, and react for 3~4 hours after the addition is completed to obtain functionalized modified allyl polyether with phenyl urea bond.

8. The preparation method according to claim 2, characterized in that, In step (3), the mass ratio of the highly active polyether intermediate to phenyl isocyanate is 10:1.1-1.3, and the time for adding phenyl isocyanate is controlled to be 0.5-1h.

9. The preparation method according to claim 2, characterized in that, The specific method of step (4) is as follows: add the functionalized modified allyl polyether and hydrogen-containing silicone oil obtained in step (3) to the reactor, heat to 85~100℃, add catalyst-2 and stir for 4-6 hours. After the reaction is completed, a yellow transparent liquid is obtained, which is the modified silicone oil.

10. The preparation method according to claim 2, characterized in that, In step (4), the mass ratio of functionalized modified allyl polyether to hydrogen-containing silicone oil is 1-1.1:1; the hydrogen content of the hydrogen-containing silicone oil is 0.10%-0.18%; the catalyst... 2 is a platinum catalyst; the catalyst The effective platinum content in component 2 is 1.0 × 10⁻⁶ of the total mass of the reactants. -5 -5.0×10 -6 .

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