Non-ionic reactive emulsifier as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of fine chemical engineering, and discloses a nonionic reactive emulsifier as well as a preparation method and application thereof, the molecular structural formula of the nonionic reactive emulsifier is # imgabs0 #, R1 is selected from C5-C20 aliphatic groups or C8-C12 alkylphenol groups; the atom B is selected from oxygen or nitrogen; r2 and R3 are selected from hydrogen or a C2-C18 hydrocarbyl group comprising at least one double bond, and when R2 or R3 is hydrogen, the other must be a C2-C18 hydrocarbyl group comprising at least one double bond; when R2 and R3 are both not hydrogen, both R2 and R3 are C2-C18 alkyl containing at least one double bond, and n = 3-14. The emulsifier disclosed by the invention can be used for preparing addition type water-based organic silicon emulsion. In the film forming process of the organic silicon emulsion, unsaturated double bonds in the emulsifier can fully react with the curing agent and stably exist in a cured product, so that the application performance of the addition type water-based organic silicon emulsion is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of fine chemical engineering, and specifically relates to a nonionic reactive emulsifier, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous strengthening of global environmental regulations, the production and application of solvent-based polymer products are gradually shifting towards water-based polymer and solvent-free polymer products to reduce the emission of volatile organic solvents (VOCs) and lower the potential risks to the environment and human health. Water-based polymer products also have the advantages of safe production and construction, non-flammability, less odor, and easy cleaning of equipment. The market that traditional solvent-based polymer products have long occupied is gradually being replaced by newly developed water-based polymer products. Most water-based polymer products exist in the form of latex or emulsion. In the manufacturing process of these products, surfactants must be used, and the selection of surfactants is crucial for the performance of the final product. Products prepared using traditional surfactants are usually unstable. During the film-forming process, the surfactants remaining in the aqueous phase will hinder the mutual approach of latex particles, slow down the film-forming speed, resulting in slow drying of the latex and weak initial adhesion. The surfactants remaining in the film are prone to migrate to the film surface, forming a surfactant layer. When the film comes into contact with water or is in a humid environment, it will cause defects such as frosting, whitening, and decreased gloss. In addition, the surfactants are also prone to migrate to the interface between the coating film and the substrate, thereby reducing the adhesion of the latex to the substrate when in contact with water.

[0003] The phase inversion method is the most commonly used method for preparing water-based silicone resin materials. The water-based silicone resin prepared by the phase inversion method not only has small particle size and good stability, but also has low cost, and is a relatively common and suitable method for industrialization. For the water-based silicone resin emulsion prepared by the phase inversion method, since the traditional externally added emulsifier uses small molecule substances, the prepared water emulsion is prone to demulsification and is unstable, and the free small molecules cause a decline in the performance of the coating film, mainly the corrosion resistance performance is greatly affected, resulting in the existence of the emulsifier having a certain impact on the water resistance of the coating film.

[0004] Chinese Patent CN 114672029 A discloses a non-ionic organosilicon surfactant. The aqueous organosilicon resin emulsion prepared therefrom has good compatibility with silicone oil and can significantly reduce the interfacial tension between water and silicone oil. However, it cannot participate in the film-forming curing reaction and form a cross-linked network with latex particles, and is likely to cause a decrease in mechanical properties and migrate to the film surface when free in the cross-linked network. Chinese Patents CN 111019119 A and CN 107474236A respectively disclose a reactive emulsifier, which is beneficial to the copolymerization with monomers, thereby anchoring the emulsifier molecules on the particle surface. During the film-forming process of the polymer emulsion, physical desorption and aggregation are not likely to occur, and the water resistance of the coating film can be significantly improved. The non-ionic emulsifier has a wide pH adaptability, is not easily demulsified due to the presence of an acid-base environment or electrolyte, and can be used in synergy with ionic and amphoteric emulsifiers to adjust the HLB value to meet the requirements of different oil phases, and the prepared aqueous organosilicon emulsion has good stability. Therefore, in order to overcome the shortcomings of traditional surfactants, it is of great significance to develop a new non-ionic surfactant that can participate in the film-forming reaction. Summary of the Invention

[0005] In order to solve the deficiencies of the above-mentioned existing technologies, the object of the present invention is to provide a non-ionic reactive emulsifier. The active double bond in the molecular structure of this emulsifier reacts with hydrogen-containing silicone oil to form a firm cross-linked network with the addition-type organosilicon polymer through chemical bonds, and has good surface activity, which can effectively reduce the interfacial tension.

[0006] Another object of the present invention is to provide a preparation method of the above non-ionic reactive emulsifier. This method uses a mono-hydroxy-terminated polyether compound, N,N'-carbonyldiimidazole, and an unsaturated alcohol or unsaturated amine.

[0007] Another object of the present invention is to provide the application of the above non-ionic reactive emulsifier.

[0008] The object of the present invention is achieved by the following technical solutions:

[0009] A non-ionic reactive emulsifier contains a compound shown in formula (I):

[0010]

[0011] Wherein, R1 is selected from a C5-C 20 aliphatic hydrocarbon group or a C8-C 12 alkylphenol group; atom B is selected from oxygen or nitrogen; R2 and R3 are selected from hydrogen or an unsaturated C2-C 18 hydrocarbon group containing at least one double bond, and when R2 or R3 is hydrogen, the other must be an unsaturated C2-C 18Hydrocarbyl; when neither R2 nor R3 is hydrogen, both are unsaturated C2-C hydrocarbyls containing at least one double bond 18 hydrocarbyl, and n = 3-14.

[0012] The method for preparing the nonionic reactive emulsifier includes the following steps:

[0013] S1. React N,N'-carbonyldiimidazole and the monohydroxy-terminated polyether compound (a) at 30-80 °C for hydroxyl activation reaction to obtain the active intermediate (b);

[0014]

[0015] S2. React the active intermediate (b) with an unsaturated alcohol or an unsaturated amine at 30-80 °C. After the reaction is completed, dialyze the product in a dialysis bag in distilled water to remove the residual unreacted compounds and the by-product imidazole, and finally obtain the nonionic reactive emulsifier by freeze-drying.

[0016] Preferably, the molar ratio of the monohydroxy-terminated polyether compound to N,N'-carbonyldiimidazole in step S1 is 1:(1-2).

[0017] Preferably, the monohydroxy-terminated polyether compound in step S1 is one or more of fatty alcohol polyoxyethylene, alkylphenol polyoxyethylene ether, or fatty acid polyoxyethylene ether.

[0018] Preferably, the molar ratio of the unsaturated alcohol or unsaturated amine to the active intermediate in step S2 is (1-2):1.

[0019] Preferably, the unsaturated alcohol in step S2 is one or more of 3-methyl-3-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol, 3-methyl-2-buten-1-ol; the unsaturated amine is diallylamine or / and allylethylamine.

[0020] Preferably, the reaction time in step S2 is 4-6 h; the dialysis time is 24-48 h.

[0021] The application of the nonionic reactive emulsifier in the preparation of an aqueous silicone emulsion.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The present invention activates the hydroxyl group of a mono-hydroxyl terminated polyether compound through N,N'-carbonyldiimidazole to obtain a reactive intermediate, and then reacts with an unsaturated alcohol or unsaturated amine to obtain a nonionic reactive emulsifier. This emulsifier has active double bonds, which can react with the curing agent of the hydrogen-containing silicone oil of the addition-type silicone polymer, and form a strong crosslinked network with the addition-type silicone polymer through chemical bonds. It has good surface activity, can effectively reduce the interfacial tension, and at the same time ensures the preparation of a stable addition-type aqueous silicone emulsion, thereby enhancing the durability and stability of the cured film of the silicone emulsion and being applicable to a wider range of application fields.

[0024] 2. The raw materials of the present invention are easily available and the preparation is simple. By changing the length of the polyether chain, the hydrophilic-lipophilic balance of the emulsifier can be adjusted, providing key auxiliary support for the development of clean and environmentally friendly aqueous silicone emulsions.

[0025] 3. The nonionic reactive emulsifier prepared by the present invention can be used to prepare an addition-type aqueous silicone emulsion. During the curing film formation process of the silicone emulsion, the double bond in the emulsifier structure can fully react with the hydrogen-containing silicone oil curing agent. This emulsifier stably exists in the cured film, rather than being free in the system like a small molecule emulsifier, solving the performance defects of the coating film caused by the presence of the emulsifier in ordinary silicone emulsions and the migration of the emulsifier during film formation, and improving the application performance of the addition-type aqueous silicone emulsion products. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is the infrared spectrum of the nonionic reactive emulsifier (V) in Example 1.

[0027] Figure 2 It is for the nonionic reactive emulsifier (V) in Example 1 1 1H-NMR spectrum (the deuterated reagent is deuterated DMSO).

[0028] Figure 3 It is the infrared spectra of isodecyl polyoxyethylene ether, diallylamine, and nonionic reactive emulsifier (VI) in Example 2.

[0029] Figure 4 It is for the nonionic reactive emulsifier (VI) in Example 2 1 1H-NMR spectrum (the deuterated reagent is deuterated DMSO).

[0030] Figure 5 It is the particle size analysis and optical photos of the aqueous silicone emulsions prepared in Application Example 1, Application Example 2, and Comparative Example 1 respectively. DETAILED DESCRIPTION OF THE INVENTION

[0031] The present invention will be further described in detail below in conjunction with embodiments, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field.

[0032] Example 1

[0033] 1. Add 19.87 g of N,N'-carbonyldiimidazole and 100 ml of anhydrous toluene into a reaction kettle, and heat with stirring in an oil bath to 60 °C; drop 50 g of isomeric decyl alcohol polyoxyethylene ether (hydroxyl value of 125 mg KOH / g) into the reaction kettle within 30 min, and continue to keep the temperature at 60 °C for reaction for 4 h to obtain an active intermediate.

[0034] 2. Drop 4.22 g of 3-methyl-3-buten-1-ol into the active intermediate and stir, heat up to 60 °C and keep the temperature for reaction for 4 h. After the reaction is completed, remove toluene under reduced pressure. Use a dialysis bag with a molecular weight cut-off (MWCO) of 500 Da and dialyze in distilled water for 48 h to completely remove the remaining small molecule reactants and small molecule products. Finally, freeze-dry at -60 °C for 48 h to obtain a pale yellow nonionic reactive emulsifier (V), and its structural formula is:

[0035]

[0036] Figure 1 are the infrared spectra of isomeric decyl alcohol polyoxyethylene ether, 3-methyl-3-buten-1-ol and nonionic reactive emulsifier (V) in Example 1. From Figure 1 it can be seen that the hydroxyl infrared absorption peak of isomeric decyl alcohol polyoxyethylene ether at 3464 cm -1- disappears in the nonionic reactive emulsifier (V), and the hydroxyl infrared absorption peak of 3-methyl-3-buten-1-ol at 3316 cm -1 disappears; a characteristic absorption peak of carbonyl appears at 1748 cm -1 , a characteristic infrared absorption peak of C-H of carbon-carbon double bond appears at 3077 cm -1 , and a characteristic infrared absorption peak of carbon-carbon double bond appears at 1649 cm -1 , indicating that the nonionic reactive emulsifier (V) has been successfully prepared. Figure 2 is the 1 H-NMR spectrum of nonionic reactive emulsifier (V) in Example 1 (the deuterated reagent is deuterated DMSO). From Figure 2It can be known that the chemical shift δ = 0.7 - 1.5 ppm is the chemical shift of CH3 and CH2 in the isomeric decanol alkyl chain; δ = 1.67 ppm is the chemical shift of CH3 connected to the double bond; δ = 4.6 - 4.8 ppm is the chemical shift of the double bond CH2; δ = 3.4 - 3.6 ppm is the chemical shift of the alkoxy CH2; among which δ = 2.46 ppm is the solvent peak of deuterated DMSO, and δ = 3.30 ppm is the water peak of deuterated DMSO.

[0037] Example 2

[0038] 1. Add 19.87 g of N,N'-carbonyldiimidazole and 100 mL of anhydrous toluene into a reaction kettle, stir and heat up to 60 °C in an oil bath; drop 50 g of isomeric decanol polyoxyethylene ether (hydroxyl value is 125 mg KOH / g) into the reaction kettle within 30 min, and continue to keep the temperature at 60 °C for reaction for 4 h to obtain an active intermediate.

[0039] 2. Add 12.40 g of diallylamine to the active intermediate and stir, heat up to 60 °C and keep the temperature for reaction for 4 h, remove toluene under reduced pressure, use a dialysis bag with a cut-off molecular weight (MWCO) of 500 Da, dialyze in distilled water for 48 h to completely remove the residual small molecule reactants and small molecule products, and finally freeze-dry at -60 °C for 48 h to obtain a light yellow non-ionic reactive emulsifier (VI), and its structural formula is:

[0040]

[0041] Figure 3 is the infrared spectrum of isomeric decanol polyoxyethylene ether, diallylamine, and non-ionic reactive emulsifier (VI) in Example 2. From Figure 3 It can be known that the hydroxyl infrared absorption peak of isomeric decanol polyoxyethylene ether at 3464 cm -1 disappears in the non-ionic reactive emulsifier VI; a characteristic absorption peak of carbonyl appears at 1747 cm -1 , a characteristic infrared absorption peak of C-H of carbon-carbon double bond appears at 3080 cm -1 , and a characteristic infrared absorption peak of carbon-carbon double bond appears at 1648 cm -1 , indicating that the non-ionic reactive emulsifier (VI) has been successfully prepared. Figure 4 is the 1 1H-NMR spectrum of the non-ionic reactive emulsifier (VI) in Example 2 (the deuterated reagent is deuterated DMSO). From Figure 4It can be known that δ = 0.7 - 1.5 ppm is the chemical shift of CH3 and CH2 in the isomeric decanol alkyl chain; δ = 5.0 - 5.1 ppm is the chemical shift of the double bond CH2; δ = 5.6 - 5.7 ppm is the chemical shift of CH connected to the double bond; δ = 3.4 - 3.6 ppm is the chemical shift of the alkoxy CH2; among which δ = 2.46 ppm is the solvent peak of deuterated DMSO, and δ = 3.29 ppm is the water peak of deuterated DMSO.

[0042] Application Example 1

[0043] 1. Weigh 64.71 wt% of vinyl-terminated silicone oil (vinyl content is 0.2 mmol / g), 20 wt% of vinyl MQ resin (vinyl content is 1 mmol / g), 15.25 wt% of hydrogen-containing silicone oil curing agent (hydrogen content is 1.8 mmol / g), 0.03 wt% of Karstedt catalyst (3000 ppm) and 0.01 wt% of 1-ethynyl-1-cyclohexanol, and mix and stir evenly to obtain an addition-curable silicone polymer.

[0044] 2. Mix the nonionic reactive emulsifier (V) prepared in Example 1 and the anionic emulsifier sodium dodecyl sulfate (SDS) with a mass ratio of 4:1 to obtain a composite emulsifier;

[0045] 3. Add 0.8 g of the composite emulsifier to 10 g of the addition-curable silicone polymer and stir for 20 min to mix evenly. Increase the speed of the homogenizer to 10000 r, and slowly drop by drop add deionized water. The viscosity of the rubber compound gradually increases and turns into a viscous paste. Continue to add deionized water. When the viscosity drops sharply, it means the phase inversion is completed. Then add the remaining deionized water at one time. The total mass of the above deionized water is 10 g. Increase the speed to 15000 r and continue to homogenize for 30 min to obtain an addition-curable aqueous silicone emulsion, and the sample is labeled as 1#.

[0046] Application Example 2

[0047] 1. Weigh 64.71 wt% of vinyl-terminated silicone oil (vinyl content is 0.2 mmol / g), 20 wt% of vinyl MQ resin (vinyl content is 1 mmol / g), 15.25 wt% of hydrogen-containing silicone oil curing agent (hydrogen content is 1.8 mmol / g), 0.03 wt% of Karstedt catalyst (3000 ppm) and 0.01 wt% of 1-ethynyl-1-cyclohexanol, and mix and stir evenly to obtain an addition-curable silicone polymer.

[0048] 2. Mix the nonionic reactive emulsifier (VI) prepared in Example 2 and the anionic emulsifier sodium dodecyl sulfate (SDS) with a mass ratio of 4:1 to obtain a composite emulsifier;

[0049] 3. Add 0.8 g of compound emulsifier to 10 g of addition-type silicone polymer and stir for 20 min to mix evenly. Increase the rotation speed of the homogenizer to 10,000 r, and slowly drop deionized water drop by drop. The viscosity of the rubber compound gradually increases and turns into a viscous paste. Continue to drop deionized water. When the viscosity drops sharply, it means that the phase inversion is completed. Then add the remaining deionized water at one time. The total mass of the above deionized water is 10 g. Increase the rotation speed to 15,000 r and continue to homogenize for 30 min to obtain an addition-type aqueous silicone emulsion, and the sample is marked as 2#.

[0050] Comparative Example 1

[0051] 1. Weigh 64.71 wt% of vinyl-terminated silicone oil (vinyl content is 0.2 mmol / g), 20 wt% of vinyl MQ resin (vinyl content is 1 mmol / g), 15.25 wt% of hydrogen-containing silicone oil curing agent (hydrogen content 1.8 mmol / g), 0.03 wt% of Karstedt catalyst (3000 ppm) and 0.01 wt% of 1-ethynyl-1-cyclohexanol, and mix and stir evenly to obtain an addition-type silicone polymer.

[0052] 2. Mix isomeric decanol polyoxyethylene ether and anionic emulsifier sodium dodecyl sulfate (SDS) with a mass ratio of 4:1 to obtain a compound emulsifier;

[0053] 3. Add 0.8 g of compound emulsifier to 10 g of addition-type silicone polymer and stir for 20 min to mix evenly. Increase the rotation speed of the homogenizer to 10,000 r, and slowly drop deionized water drop by drop. The viscosity of the rubber compound gradually increases and turns into a viscous paste. Continue to drop deionized water. When the viscosity drops sharply, it means that the phase inversion is completed. Then add the remaining deionized water at one time. The total mass of the above deionized water is 10 g. Increase the rotation speed to 15,000 r and continue to homogenize for 30 min to obtain an addition-type aqueous silicone emulsion, and the sample is marked as 3#.

[0054] Figure 5 Particle size analysis and optical photos of the aqueous silicone emulsions prepared for Application Example 1, Application Example 2 and Comparative Example 1 respectively. From Figure 5 It can be seen that the particle sizes of the emulsions prepared in Application Examples 1-2 are small and concentrated, and the appearance is delicate, milky white with a blue light. While the appearance of the emulsion prepared in Comparative Example 1 is milky white with a blue light, and the particle size is slightly larger than that of the aqueous silicone emulsions prepared in Application Examples 1-2.

[0055] The performance of the aqueous silicone emulsions prepared with the nonionic reactive emulsifiers in Examples 1-2 and Comparative Example 1 was tested. For the thermal stability test of the aqueous silicone emulsion, the emulsion was filled into a thumb bottle and stored in an oven at 50 °C for 7 days to observe whether stratification occurred. For the freeze-thaw stability test of the aqueous silicone emulsion, the emulsion was placed at -5 °C for 24 h and then returned to room temperature, and this cycle was repeated 3 times to observe any abnormal phenomena such as stratification and flocculation of the sample. For the centrifugal stability test, the aqueous silicone emulsion was filled into a centrifuge tube and centrifuged at 4000 r for 10 min to observe whether stratification occurred in the aqueous silicone emulsion. For the water whitening resistance test of the film formed from the aqueous silicone emulsion, the aqueous silicone emulsion was coated on a glass slide using a wet film applicator and then cured at 80 °C for 3 h. The glass slide was immersed in deionized water at 25 °C to observe whether whitening occurred on the surface of the glass slide, and the time when whitening occurred was recorded. The performance test results are shown in Table 1:

[0056] Table 1 Performance of the silicone emulsions prepared with the nonionic reactive emulsifiers in Examples 1-2 and Comparative Example 1

[0057] Sample Appearance of emulsion Thermal storage stability Freeze-thaw stability Centrifugal stability Water-white time 1# Slightly blue and milky white No delamination No delamination and flocculation No delamination >24h 2# Slightly blue and milky white No delamination No delamination and flocculation No delamination >24h 3# Slightly blue and milky white No delamination No delamination and flocculation No delamination 6h

[0058] Table 1 shows the performance of the silicone emulsions prepared with the nonionic reactive emulsifiers in Examples 1-2 and Comparative Example 1. As can be seen from Table 1, compared with the aqueous silicone emulsion 3# prepared with isomeric decanol polyoxyethylene ether, the aqueous silicone emulsions 1# and 2# prepared with the nonionic reactive emulsifier of the present invention have better thermal storage stability, centrifugal stability and freeze-thaw stability. Since the unsaturated double bonds in the nonionic reactive emulsifier react with the hydrogen-containing silicone oil curing agent, the emulsifier is stably present in the cured film, improving the water whitening resistance of the films formed from the aqueous silicone emulsions 1# and 2#.

[0059] The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A non-ionic reactive emulsifier, characterized in that, The nonionic reactive emulsifier comprises a compound having the structure shown in formula (I): Among them, R1 is selected from C5-C 20 aliphatic hydrocarbon group or C8-C 12 alkylphenol group; atom B is selected from oxygen or nitrogen; R2 and R3 are selected from hydrogen or C2-C 18 hydrocarbon group containing at least one double bond, and when R2 or R3 is hydrogen, the other must be C2-C 18 hydrocarbon group containing at least one double bond; when neither R2 nor R3 is hydrogen, both are C2-C 18 hydrocarbon group containing at least one double bond, and n = 3-14.

2. The preparation method of the nonionic reactive emulsifier according to claim 1, characterized in that, The method comprises the following steps: S1. Reacting N,N'-carbonyldiimidazole with a monohydroxy-terminated polyether compound at 30-80 °C to carry out hydroxy activation reaction to obtain an active intermediate; S2. Reacting the active intermediate with an unsaturated alcohol or an unsaturated amine at 30-80 °C. After the reaction is completed, dialyze the product in distilled water with a dialysis bag to remove residual unreacted compounds and by-product imidazole, and finally obtain the nonionic reactive emulsifier by freeze-drying.

3. The preparation method of the nonionic reactive emulsifier according to claim 2, characterized in that, In step S1, the molar ratio of the monohydroxy-terminated polyether compound to N,N'-carbonyldiimidazole is 1:(1-2).

4. The preparation method of the non-ionic reactive emulsifier according to claim 2, characterized in that, In step S1, the monohydroxy-terminated polyether compound is one or more of fatty alcohol polyoxyethylene, alkylphenol polyoxyethylene ether or fatty acid polyoxyethylene ether.

5. The preparation method of the nonionic reactive emulsifier according to claim 2, wherein, In step S2, the molar ratio of the unsaturated alcohol or unsaturated amine to the active intermediate is (1-2):

1.

6. The preparation method of the nonionic reactive emulsifier according to claim 2, characterized in that, In step S2, the unsaturated alcohol is one or more of 3-methyl-3-buten-1-ol, 3-buten-2-ol, 3-buten-1-ol, 3-methyl-2-buten-1-ol; the unsaturated amine is diallylamine or / and allylethylamine.

7. The preparation method of the nonionic reactive emulsifier according to claim 2, characterized in that, In step S2, the reaction time is 4-6 h; the dialysis time is 24-48 h.

8. Use of the nonionic reactive emulsifier according to claim 1 in the preparation of an aqueous silicone emulsion.

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