A multi-arm polyether silicone oil and a preparation method thereof

Abstract

The present application relates to a kind of multi-arm polyether silicone oil and its preparation method, belong to the technical field of silicone oil.The multi-arm polyether silicone oil has unique multi-arm branched structure, its molecule includes a hydrophilic core formed by hydrophilic polyether segment and polyol ring opening, and at least three arms of hydrophobic polysiloxane segment end extend from the core, present "hydrophilic core-hydrophobic arm" structure.Its preparation method is first by rhodium catalyst catalysis allyl polyoxyethylene ether epoxy ether and single-end hydrogen-containing silicone oil is carried out low-temperature high selectivity silicon hydrogen addition, then the obtained intermediate is reacted with polyol to construct multi-arm structure.The product has low viscosity, high surface activity, excellent defoaming and antifoaming performance, good high-temperature shear stability, and in fabric finishing dual function of soft smooth and hydrophilic moisture absorption, comprehensive performance is significantly better than traditional linear or comb type polyether silicone oil.

Description

Technical Field

[0001] This invention belongs to the field of silicone oil technology, specifically, it relates to a multi-arm polyether silicone oil and its preparation method. Background Technology

[0002] Polyether-modified silicone oils are a class of "amphiphilic" surfactants that combine the hydrophobic, high / low temperature resistance, and low surface tension properties of polysiloxanes with the hydrophilic, emulsifying, and compatibility properties of polyether segments (usually ethylene oxide or propylene oxide copolymers). Their core mechanism of action lies in the directional alignment of hydrophobic silicone oil segments and hydrophilic polyether segments at gas-liquid, liquid-liquid, and liquid-solid interfaces, effectively reducing interfacial tension and thus exhibiting excellent wetting, emulsifying, dispersing, defoaming, and softening properties. Due to their excellent surface activity, physiological inertness, and environmental friendliness, these materials are widely used in numerous fields, including daily chemical products, textile printing and dyeing, coatings, oil extraction, and fermentation industries.

[0003] In the field of fabric finishing, polyether silicone oil, with its balance of soft, smooth feel and hydrophilicity and antistatic properties, has become a core component of high-end hydrophilic softeners. In the field of defoaming, its ability to spread rapidly and reduce local surface tension to puncture bubble films makes it a highly effective defoaming and foam-suppressing agent.

[0004] Currently, commercially available polyether-modified silicone oils can be mainly classified into the following three categories according to their molecular structure: Block / terminated linear polymers: These are typically polyethers and polysiloxanes linked by AB, ABA, or more complex linear sequences. While the synthesis of these structures is relatively straightforward, the molecular chains are prone to entanglement, leading to higher viscosity. Their interfacial alignment efficiency is limited, and there is room for improvement in reducing surface tension. Furthermore, they may undergo chain dissociation or degradation under high temperatures or high shear conditions.

[0005] Side-linked (comb-shaped) polymers: These polymers have polysiloxane as the main chain and polyether segments as side branches. This structure enhances hydrophilicity, but the main chain remains hydrophobic silicone oil. Its amphiphilic distribution is comb-like, and its ability to reconfigure at the interface is limited by the main chain conformation. It also suffers from high molecular weight and high viscosity, and under high shear, the grafting points may become mechanically weak points.

[0006] Branched / Multi-arm Polymers: To overcome the shortcomings of linear structures, researchers have begun to explore branched structures. For example, Chinese patent CN104650364B discloses a polyether-modified siloxane with a hyperbranched structure. This technology increases the functional group density and reduces viscosity to some extent by introducing a hyperbranched core. However, such branched structures are usually random or highly branched, with uneven distribution of molecular shape and branch length (high polydispersity index), resulting in low predictability and repeatability of their interfacial behavior. When applied to defoaming or fabric finishing, there is still room for optimization in the dispersibility of its hydrophobic core in aqueous media and its anchoring efficiency with hydrophobic interfaces (such as bubble films and fibers). Summary of the Invention

[0007] In order to solve the technical problems mentioned in the background art, the purpose of this invention is to provide a multi-arm polyether silicone oil and its preparation method.

[0008] The objective of this invention can be achieved through the following technical solutions: A multi-arm polyether silicone oil has a multi-arm branched structure comprising a hydrophilic core formed by ring-opening of a hydrophilic polyether segment and a polyol, and at least three branches extending outward from the core, each branch ending in a hydrophobic polysiloxane segment; the general structural formula of the multi-arm polyether silicone oil is as follows:

[0009] Specifically, the preparation method of multi-arm polyether silicone oil is as follows: Step S1: Under inert gas protection, add allyl polyoxyethylene ether epoxy ether, single-end hydrogen-containing silicone oil and anhydrous toluene to a dry reactor and stir until homogeneous. Then add a rhodium-based catalyst, heat and stir to carry out hydrosilylation reaction. After the reaction is completed, remove toluene by rotary evaporation under reduced pressure to obtain the intermediate. Step S2: Add the intermediate, polyol and dioxane to the drying reactor and stir to mix evenly. Add tetrabutylammonium bromide, heat and stir to carry out the ring-opening reaction. After the reaction is completed, filter and then remove the dioxane by rotary evaporation to obtain multi-arm polyether silicone oil.

[0010] Preferably, the average molecular weight of the allyl polyoxyethylene ether epoxy ether is 400-800. At this polyether chain length, the molecular weight of the silicone oil is moderate, providing a good hydrophilic balance.

[0011] Furthermore, the molar ratio of allyl to silane in allyl polyoxyethylene ether epoxy ether and single-ended hydrogen-containing silicone oil is 1:1.02-1.05.

[0012] Furthermore, the rhodium-based catalyst is a Wilkinson catalyst, with a concentration of 100-130 ppm in the reaction system and a hydrosilylation reaction temperature of 60-75℃. Its high selectivity catalysis allows for efficient reaction at lower temperatures while maintaining the structural stability of the intermediate.

[0013] Preferably, the polyol is one of triethanolamine and dipropylene glycol, which has good reactivity, maintains the hydrophilicity of the silicone oil molecular center, provides three-arm and four-arm structures, and has high compatibility in aqueous systems; furthermore, in the above general formula, X=3 or 4, correspondingly, R= or

[0014] Furthermore, the molar ratio of epoxy content to hydroxyl content of the intermediate is 1:1, and the proportion of tetrabutylammonium bromide in the reaction system is 0.12-0.16 wt%.

[0015] The beneficial effects of this invention are: The multi-arm polyether silicone oil prepared in this invention, with its "hydrophilic polyether core - hydrophobic silicone oil arms" multi-arm branched structure, achieves a paradigm shift over traditional linear and comb-type polyether silicone oils at the molecular engineering level, thus bringing a series of breakthrough advantages in basic physicochemical properties and application performance. Its core mechanism lies in the precise control of the arrangement of hydrophilic and hydrophobic segments in three-dimensional space: the highly hydrophilic core composed of polyol and polyether segments ensures excellent solubility and dispersion stability of the molecule in aqueous media, while the multiple hydrophobic silicone oil arms extending radially from this core act as multiple efficient "molecular anchors," capable of synergistically and firmly anchoring to various hydrophobic interfaces (such as bubble films, oil droplets, or fabric fiber surfaces). This unique "multi-anchor synergistic effect" fundamentally improves the interfacial adsorption efficiency and interaction strength of the molecule.

[0016] Specifically, this structure, while maintaining a suitable molecular weight, significantly reduces the hydrodynamic volume and interchain entanglement of the molecules, resulting in a product viscosity far lower than that of linear or comb-shaped polymers of similar molecular weight. This endows it with excellent fluidity and rapid penetration and diffusion capabilities in aqueous systems. This characteristic directly translates into outstanding surface activity, enabling it to significantly reduce the surface tension of solutions even at extremely low concentrations, laying the theoretical foundation for efficient defoaming and wetting. In defoaming applications, low viscosity ensures rapid arrival at the gas-liquid interface, while the simultaneous insertion of multiple silicone oil hydrophobic arms generates an efficient "multi-point puncture" and spreading effect on the bubble film, resulting in rapid defoaming (T... 1 / 2 Significantly shortens the foam length, and forms a more stable interfacial adsorption layer, effectively preventing foam regeneration and improving foam suppression performance (H). maxThe low Δγ level is particularly prominent. At the same time, the regular branched structure connects the chain segments through strong chemical bonds, which endows the product with excellent thermodynamic and mechanical stability, enabling it to maintain structural and performance stability (with minimal change in Δγ) even under harsh high-temperature and high-shear environments, overcoming the defects of traditional products that are prone to dissociation or degradation.

[0017] In the core application field of fabric finishing, the advantages of this invention are fully demonstrated. Its hydrophilic core ensures the long-term stability of the finishing agent in the processing bath, completely solving the problems of easy oil drift and incompatibility associated with traditional silicone oils. When treating fabrics, the radially distributed hydrophobic silicone oil arms can three-dimensionally bind the fibers, forming a uniform, smooth, and firmly firm soft film; simultaneously, the hydrophilic polyether core, encapsulated internally and partially exposed, cleverly endows the fabric with lasting hydrophilic and moisture-wicking properties, achieving a perfect unity of the seemingly contradictory hand feel characteristics of softness and smoothness versus dryness and hydrophilicity. Test data fully confirms that fabrics treated with this product achieve a superior soft hand feel while exhibiting hydrophilicity far exceeding that of traditional hydrophobic silicone oil products, and even surpassing some existing branched modified products. Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1: Preparation of polyether silicone oil with a three-arm structure. The specific implementation process is as follows: Step S1: Synthesis of intermediates for epoxy-terminated polyether modified silicone oil: Dry nitrogen gas is introduced into the reactor until a stable gas flow is observed. Under a dry nitrogen atmosphere, allyl polyoxyethylene ether epoxy ether, single-terminated hydrogen-containing silicone oil, and anhydrous toluene are added sequentially and stirred until homogeneous. Then, a rhodium catalyst is added and mixed. The reaction system is heated to 65°C and the reaction time is 3.5 h. The characteristic Si-H absorption peak almost disappears, indicating that hydrosilylation is essentially complete. In the above reaction, the allyl polyoxyethylene ether epoxy ether is... Using H-500 type raw material, RH-H222-10 type raw material for single-end hydrogen-containing silicone oil, and Wilkinson catalyst as rhodium catalyst, the raw material ratio is: allyl polyoxyethylene ether epoxy ether and single-end hydrogen-containing silicone oil, allyl to silane molar ratio is 1:1.02, anhydrous toluene is 1.2 times the total weight of the two, and the concentration of Wilkinson catalyst in the reaction system is 100 ppm; after the reaction is completed, the pressure is reduced and rotary evaporation is carried out at a temperature not exceeding 60°C until toluene is removed to obtain the intermediate.

[0020] Step S2, Synthesis of Multi-arm Polyether Silicone Oil: The reaction system was cleaned with dry nitrogen as described above. The intermediate, triethanolamine, and dioxane were added sequentially and mixed thoroughly. Then, tetrabutylammonium bromide was added and mixed. The temperature was controlled at 90°C, and the reaction time was 8 hours. The characteristic absorption peak of the epoxy group almost disappeared, indicating that the ring-opening reaction was essentially complete. In the above reaction, the molar ratio of epoxy content in the intermediate to hydroxyl content in the triethanolamine was 1:1, and the proportion of tetrabutylammonium bromide in the reaction system was 0.12 wt%. After the reaction was completed, the mixture was filtered, and then dioxane was removed by rotary evaporation to obtain the multi-arm polyether silicone oil.

[0021] Example 2: Preparation of polyether silicone oil with a three-arm structure. The specific implementation process is as follows: Step S1: Synthesis of intermediates for epoxy-terminated polyether modified silicone oil: Dry nitrogen gas is introduced into the reactor until a stable gas flow is observed. Under a dry nitrogen atmosphere, allyl polyoxyethylene ether epoxy ether, single-terminated hydrogen-containing silicone oil, and anhydrous toluene are added sequentially and stirred until homogeneous. Then, a rhodium catalyst is added and mixed. The reaction system is heated to 60°C and the reaction time is 4.2 h. The characteristic Si-H absorption peak almost disappears, indicating that hydrosilylation is essentially complete. In the above reaction, the allyl polyoxyethylene ether epoxy ether is... Using H-500 type raw material, RH-H222-10 type raw material for single-end hydrogen-containing silicone oil, and Wilkinson catalyst as rhodium catalyst, the raw material ratio is: allyl polyoxyethylene ether epoxy ether and single-end hydrogen-containing silicone oil, allyl to silane molar ratio is 1:1.02, anhydrous toluene is 1.2 times the total weight of the two, and the concentration of Wilkinson catalyst in the reaction system is 110 ppm; after the reaction is completed, the pressure is reduced and rotary evaporation is carried out at a temperature not exceeding 60°C until toluene is removed to obtain the intermediate.

[0022] Step S2, Synthesis of Multi-arm Polyether Silicone Oil: The reaction system was cleaned with dry nitrogen as described above. The intermediate, triethanolamine, and dioxane were added sequentially and stirred until homogeneous. Then, tetrabutylammonium bromide was added and mixed. The temperature was controlled at 90°C, and the reaction time was 7.5 h. The characteristic absorption peak of the epoxy group almost disappeared, indicating that the ring-opening reaction was essentially complete. In the above reaction, the molar ratio of the epoxy content of the intermediate to the hydroxyl content of the triethanolamine was 1:1, and the proportion of tetrabutylammonium bromide in the reaction system was 0.14 wt%. After the reaction was completed, the mixture was filtered, and then dioxane was removed by rotary evaporation to obtain the multi-arm polyether silicone oil.

[0023] Example 3: Preparation of polyether silicone oil with a four-arm structure. The specific implementation process is as follows: Step S1: Synthesis of intermediates for epoxy-terminated polyether modified silicone oil: Dry nitrogen gas is introduced into the reactor until a stable gas flow is observed. Under a dry nitrogen atmosphere, allyl polyoxyethylene ether epoxy ether, single-terminated hydrogen-containing silicone oil, and anhydrous toluene are added sequentially and stirred until homogeneous. Then, a rhodium catalyst is added and mixed. The reaction system is heated to 75°C and the reaction time is 4.5 h. The characteristic Si-H absorption peak almost disappears, indicating that hydrosilylation is essentially complete. In the above reaction, the allyl polyoxyethylene ether epoxy ether is... Using H-700 type raw material, RH-H222-10 type raw material for single-end hydrogen-containing silicone oil, and Wilkinson catalyst as rhodium catalyst, the raw material ratio is: allyl polyoxyethylene ether epoxy ether and the molar ratio of allyl to silane in single-end hydrogen-containing silicone oil is 1:1.05, anhydrous toluene is 1.4 times the total weight of the two, and the concentration of Wilkinson catalyst in the reaction system is 130 ppm; after the reaction is completed, the pressure is reduced and rotary evaporation is carried out at a temperature not exceeding 60°C until toluene is removed to obtain the intermediate.

[0024] Step S2, Synthesis of Multi-arm Polyether Silicone Oil: The reaction system was cleaned with dry nitrogen as described above. The intermediate, dipropylene glycol, and dioxane were added sequentially and mixed thoroughly. Then, tetrabutylammonium bromide was added and mixed. The temperature was controlled at 100℃, and the reaction time was 6 hours. The characteristic absorption peak of the epoxy group almost disappeared, indicating that the ring-opening reaction was essentially complete. In the above reaction, the molar ratio of the epoxy content of the intermediate to the hydroxyl content of the dipropylene glycol was 1:1, and the proportion of tetrabutylammonium bromide in the reaction system was 0.16 wt%. After the reaction was completed, the mixture was filtered, and then the dioxane was removed by rotary evaporation to obtain the multi-arm polyether silicone oil.

[0025] Example 4: Preparation of polyether silicone oil with a four-arm structure. The specific implementation process is as follows: Step S1: Synthesis of intermediates for epoxy-terminated polyether modified silicone oil: Dry nitrogen gas is introduced into the reactor until a stable gas flow is observed. Under a dry nitrogen atmosphere, allyl polyoxyethylene ether epoxy ether, single-terminated hydrogen-containing silicone oil, and anhydrous toluene are added sequentially and stirred until homogeneous. Then, a rhodium catalyst is added and mixed. The reaction system is heated to 70°C and the reaction time is 5 hours. The characteristic Si-H absorption peak almost disappears, indicating that hydrosilylation is essentially complete. In the above reaction, the allyl polyoxyethylene ether epoxy ether is... The raw material is H-700 type, the single-end hydrogen-containing silicone oil is RH-H222-10 type raw material, the rhodium catalyst is Wilkinson catalyst, the raw material ratio is: allyl polyoxyethylene ether epoxy ether and single-end hydrogen-containing silicone oil, the allyl to silane molar ratio is 1:1.04, the anhydrous toluene is 1.4 times the total weight of the two, and the concentration of Wilkinson catalyst in the reaction system is 130ppm; after the reaction is completed, the pressure is reduced and the rotary evaporation is carried out at a temperature not higher than 60℃ until the toluene is removed to obtain the intermediate.

[0026] Step S2, Synthesis of Multi-arm Polyether Silicone Oil: The reaction system was cleaned with dry nitrogen as described above. The intermediate, dipropylene glycol, and dioxane were added sequentially and stirred until homogeneous. Then, tetrabutylammonium bromide was added and mixed. The temperature was controlled at 95°C, and the reaction time was 6.5 h. The characteristic absorption peak of the epoxy group almost disappeared, indicating that the ring-opening reaction was essentially complete. In the above reaction, the molar ratio of the epoxy content of the intermediate to the hydroxyl content of the dipropylene glycol was 1:1, and the proportion of tetrabutylammonium bromide in the reaction system was 0.15 wt%. After the reaction was completed, the mixture was filtered, and then the dioxane was removed by rotary evaporation to obtain the multi-arm polyether silicone oil.

[0027] Comparative Example 1 was selected from commercially available side-chain polyether modified comb-type polyether silicone oil, model ZBH-207.

[0028] Comparative Example 2 was selected from commercially available hyperbranched polyether block-modified polyether silicone oil, model RH-NB-8520.

[0029] The relevant performance indicators were tested using Examples 2, 4, Comparative Example 1, and Comparative Example 2 as samples, as detailed below: 1. Basic physical and chemical properties: Viscosity: Measured using a rotational viscometer at 25°C and 60 rpm.

[0030] Surface tension: The equilibrium surface tension of a 0.1% aqueous solution at 25°C was measured using a surface tension meter via the platinum plate method.

[0031] 2. Defoaming performance: Defoaming rate: Referring to GB / T 26527-2024 standard, the sample was added to the standard foaming solution, and the time required for the foam to subside to half its volume was recorded (T). 1 / 2 ), which is characterized by the defoaming rate.

[0032] Defoaming performance: After defoaming, the maximum foam height (H) of the system under continuous aeration within 10 minutes was recorded. max This is characterized by its ability to suppress foam.

[0033] High-temperature shear stability: The sample was placed in a 5% aqueous dispersion and stirred at a constant temperature in an 80°C water bath (high-speed shear machine, 5000 rpm) for 20 min. The presence of layering, oil floating, or precipitation was observed and recorded. The sample was then cooled to 25°C and the surface tension of the dispersion was measured again. The deviation from the initial value (Δγ) was calculated.

[0034] 3. Fabric finishing performance: Stability of the finishing bath: Prepare the sample into a 30 g / L finishing working solution, let it stand for 24 h, and observe whether oil leaching occurs.

[0035] Softness and hydrophilicity: Pure cotton knitted fabric was used, and the finishing bath concentration was 30g / L, the liquor ratio was 1:20, and the fabric was immersed at 40℃ for 20 minutes. After drying and shaping, the hand feel was scored by 100 industry reviewers (1-5 points, the higher the score, the softer and smoother the fabric). The hydrophilicity test adopted the AATCC 79-2014 standard to determine the disappearance time of water droplets on the fabric surface.

[0036] The specific test results are shown in Table 1: Table 1

[0037] As can be seen from the test data in Table 1, the multi-arm polyether silicone oil prepared by this invention is significantly superior to the comparative example in several key performance indicators. Its ultra-low viscosity and surface tension prove the high interfacial efficiency of the "hydrophilic core-hydrophobic arm" structure; the excellent defoaming and foam suppression data and the stability after high-temperature shear confirm its multi-anchor synergistic effect and stable chemical structure; and the excellent compatibility, superior softness and rapid hydrophilicity exhibited in fabric finishing. In contrast, the comb-shaped structure of Comparative Example 1 has high viscosity, insufficient surface activity and poor hydrophilicity; although the hyperbranched structure of Comparative Example 2 has some improvement, it still has a significant gap with this invention in terms of overall performance improvement and structural regularity.

[0038] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0039] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A multi-arm polyether silicone oil, characterized in that, The chemical structure is shown in general formula (Ⅰ): Where X=3, corresponding to R= ; or X=4, corresponding to R= .

2. The method for preparing a multi-arm polyether silicone oil according to claim 1, characterized in that, The specific steps are as follows: Step S1: Under a dry inert gas atmosphere, allyl polyoxyethylene ether epoxy ether, single-ended hydrogen-containing silicone oil and anhydrous toluene are mixed, a rhodium-based catalyst is added, the temperature is raised and stirred to carry out a hydrosilylation reaction, and the intermediate is obtained after the reaction is completed. Step S2: Mix the intermediate, polyol and dioxane in a dry atmosphere, add tetrabutylammonium bromide, heat and stir to carry out the ring-opening reaction, and after the reaction is completed, process to obtain multi-arm polyether silicone oil.

3. The method for preparing a multi-arm polyether silicone oil according to claim 2, characterized in that, The average molecular weight of allyl polyoxyethylene ether epoxy ether is 400-800.

4. The method for preparing a multi-arm polyether silicone oil according to claim 3, characterized in that, The molar ratio of allyl to silane in allyl polyoxyethylene ether epoxy ether and single-ended hydrogen-containing silicone oil is 1:1.02-1.

05.

5. The method for preparing a multi-arm polyether silicone oil according to claim 4, characterized in that, The rhodium-based catalyst is a Wilkinson catalyst.

6. The method for preparing a multi-arm polyether silicone oil according to claim 5, characterized in that, Wilkinson catalyst, as a rhodium-based catalyst, has a concentration of 100-130 ppm in the reaction system and a hydrosilylation reaction temperature of 60-75℃.

7. The method for preparing a multi-arm polyether silicone oil according to claim 6, characterized in that, The molar ratio of epoxy content in the intermediate to hydroxyl content in the polyol is 1:1, and the proportion of tetrabutylammonium bromide in the reaction system is 0.12-0.16 wt%.

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