Modified block silicone oil as well as preparation method and application thereof

Abstract

The invention provides modified block silicone oil as well as a preparation method and application thereof, and relates to the technical field of high polymer materials. The modified block silicone oil is prepared by carrying out ring-opening addition reaction on amino-terminated silicone oil and isopentenol polyoxyethylene ether glycidyl ether in the presence of a basic catalyst. A plurality of isopentenol polyoxyethylene ether chain segments are covalently grafted to a silicone oil main chain through ether bonds by utilizing a reaction of an epoxy group and a primary amine group to generate a novel organic silicon macromolecule with a block structure, and the macromolecule simultaneously retains a free radical polymerization double bond at the tail end of isopentenol, so that the organic silicon macromolecule has a high molecular weight. The copolymer can be used as a macromonomer to participate in subsequent emulsion polymerization; the molecular structure has the hydrophilicity of a polyether chain segment and the hydrophobicity of an organic silicon chain segment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a modified block silicone oil and a preparation method and application thereof. BACKGROUND

[0002] Waterborne acrylate emulsion has become one of the most widely used coating binders in the fields of construction, industry, wood, etc. due to its environmental protection, non-toxicity, easy construction and other advantages. However, its inherent technical bottleneck is also brought by the characteristic of using water as the dispersion medium: the acrylate resin itself has a relatively high polarity, resulting in a high surface energy of the paint film prepared therefrom, which is easy to be wetted and attached by water, oil and other pollutants, thereby showing poor performance in terms of stain resistance, anti-blocking and water resistance.

[0003] The core to endow the waterborne acrylate coating with excellent stain resistance is to significantly reduce the surface energy of the paint film. At present, the mainstream technical path to achieve this goal is to carry out modification with organosilicon or organofluorine. Among them, although organofluorine compounds can provide extremely low surface energy, they have problems such as high cost, potential environmental accumulation risk and poor compatibility with emulsion systems. Therefore, the development of non-fluorine high-performance stain-resistant coatings has become an important development direction of the industry.

[0004] Organosilicon, especially polydimethylsiloxane, is considered as an ideal substitute for fluorine compounds due to its extremely low surface tension, good flexibility and hydrophobicity. Existing organosilicon modified acrylate technologies mostly use physical blending or simple silicone-acrylate emulsion copolymerization. However, the silicone oil blended physically is easy to migrate to the surface during film formation, causing paint film defects and not lasting; and the conventional copolymerization technology often uses vinyl silicone oil, the reactivity and distribution in the polymer chain of which with acrylate monomers are difficult to accurately control, resulting in low modification efficiency, and excessive addition easily causing emulsion stability problems. More importantly, a single hydrophobic structure is difficult to resist the invasion of oily stains, and cannot achieve the effect of truly hydrophobic and oleophobic "dual hydrophobicity".

[0005] Therefore, there is an urgent need in the art for an acrylate emulsion with durable and excellent paint film and dual-hydrophobic stain-resistant function. SUMMARY

[0006] The first object of the present application is to provide a modified block silicone oil, which has both hydrophilic polyether chain segments and hydrophobic organosilicon chain segments, and has a free radical polymerizable double bond at the end.

[0007] The second object of the present application is to provide a preparation method of the modified block silicone oil, which covalently grafts multiple isopentenol polyoxyethylene ether segments to the silicone oil main chain through ether bonds to generate a new type of organic silicone macromolecule with a block structure, and the macromolecule retains a radical polymerizable double bond at the isopentenol end, so that it can be used as a macromolecular monomer to participate in subsequent emulsion polymerization.

[0008] The third object of the present application is to provide an application of the modified block silicone oil in preparing a water-based acrylate emulsion, which stably embeds silicone segments with surface migration tendency in the polymer molecular chain, and in the film forming process, the silicone segments can spontaneously accumulate on the surface of the paint film to form a low surface energy layer, thereby giving the paint film long-lasting and excellent hydrophobicity and oleophobicity, and achieving high-efficiency antifouling.

[0009] In order to achieve the above objects of the present application, the present application provides the following technical solutions. In a first aspect, the present application provides a modified block silicone oil having the following general formula (I): [CH2=C(CH3)-CH2-CH2-O-(CH2CH2O)m-O-CH2-CH(OH)-CH2-]2N-R-N[CH2-CH(OH)-CH2-O-(CH2CH2O)m-O-CH2-CH2-C(CH3)=CH2]2 (I); In formula (I), m is a natural number between 3 and 7, and R is a polydimethylsiloxane main chain.

[0010] In a second aspect, the present application provides a preparation method of the modified block silicone oil, comprising the following steps: Step S10: preparing isopentenol polyoxyethylene ether glycidyl ether; Step S20: performing ring-opening addition reaction on the amino-terminated silicone oil and the isopentenol polyoxyethylene ether glycidyl ether in the presence of an alkaline catalyst to obtain the modified block silicone oil.

[0011] Optionally, in step S20, the molar ratio of the amino-terminated silicone oil to the isopentenol polyoxyethylene ether glycidyl ether is 1:4.

[0012] Optionally, the molecular weight of the amino-terminated silicone oil is 4000-10000.

[0013] Optionally, the molecular weight of the amino-terminated silicone oil is 8000.

[0014] Optionally, the alkaline catalyst is triethylamine, and the amount of the alkaline catalyst is 0.1%-0.3% of the total mass of the reactants.

[0015] Optionally, the amount of the alkaline catalyst is 0.2% of the total mass of the reactants.

[0016] Optionally, the reaction temperature in step S20 is 75-85℃.

[0017] Optionally, the reaction temperature in step S20 is 80℃.

[0018] Optionally, the specific operation of step S10 is as follows: Step S11: reacting isoprenol polyoxyethylene ether with epichlorohydrin in the presence of a Lewis acid catalyst at 40-70℃; Step S12: adding sodium hydroxide solution to the product obtained in step S11 to perform ring closing reaction, and the reaction temperature is controlled at 30-50℃; Step S13: purifying, dehydrating and filtering the product obtained in step S12 to obtain the isoprenol polyoxyethylene ether glycidyl ether.

[0019] Optionally, the Lewis acid catalyst is boron trifluoride etherate complex, and the amount of the Lewis acid catalyst is 0.2%-0.3% of the mass of isoprenol polyoxyethylene ether.

[0020] Optionally, the amount of the Lewis acid catalyst is 0.25% of the mass of isoprenol polyoxyethylene ether.

[0021] Optionally, the molar ratio of isoprenol polyoxyethylene ether to epichlorohydrin is 1:1.05-1.1.

[0022] Optionally, the molar ratio of isoprenol polyoxyethylene ether to epichlorohydrin is 1:1.05.

[0023] Optionally, the mass concentration of the sodium hydroxide solution in step S12 is 40%, and the molar ratio of sodium hydroxide to isoprenol polyoxyethylene ether is 1.15:1.

[0024] Optionally, the reaction temperature in step S11 is 50℃.

[0025] In a third aspect, the application provides a use of a modified block silicone oil in preparing a water-based acrylate emulsion, wherein the water-based acrylate emulsion is prepared by emulsion polymerization of reaction monomers and functional monomers, the functional monomers are the modified block silicone oil, and the mass of the functional monomers accounts for 15%-25% of the mass of the reaction monomers.

[0026] In summary, the present application at least has the following beneficial effects: 1. The present application utilizes the reaction of epoxy groups and primary amine groups to covalently graft multiple isopentenyl alcohol polyoxyethylene ether chain segments to the silicone oil main chain through ether bonds to generate a new type of organic silicone macromolecule with a block structure, which retains the radical-polymerizable double bond at the isopentenyl alcohol end, enabling it to act as a macromonomer in subsequent emulsion polymerization; its molecular structure combines the hydrophilicity of polyether segments and the hydrophobicity of silicone segments.

[0027] 2. The present application provides a fluorine-free double-repellent antifouling silicone-modified acrylate emulsion with a clear synthesis route and low cost, and its polymer molecular chain stably embeds silicone segments with surface migration tendency. During film formation, these silicone segments can spontaneously accumulate on the surface of the paint film to form a low surface energy layer, thereby imparting the paint film with long-lasting and excellent hydrophobicity and oleophobicity, achieving efficient antifouling. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is the paint film contact angle state diagram of Example 1 of the present application, where a corresponds to the water contact angle and b corresponds to the oil contact angle; Figure 2 is the paint film contact angle state diagram of Example 2 of the present application, where a corresponds to the water contact angle and b corresponds to the oil contact angle; Figure 3 is the paint film contact angle state diagram of Example 3 of the present application, where a corresponds to the water contact angle and b corresponds to the oil contact angle; Figure 4 is the paint film contact angle state diagram of Example 4 of the present application, where a corresponds to the water contact angle and b corresponds to the oil contact angle; Figure 5 is the paint film contact angle state diagram of Comparative Example 1 of the present application, where a corresponds to the water contact angle and b corresponds to the oil contact angle. DETAILED DESCRIPTION

[0029] The technical solutions of the present application will be described below in conjunction with the examples, obviously, the described examples are part of the examples of the present application, rather than all the examples. Based on the examples in the present application, all other examples obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0030] Based on the defects of the paint film stability, poor controllability and inability to achieve double-repellent effect of the silicone-modified acrylate technology proposed in the foregoing background art, the inventors propose an innovative molecular design, which introduces silicone segments into silicone macromonomer in a stable and controllable manner, and then efficiently introduces them into the acrylate polymer network, thereby significantly reducing the surface energy of the paint film and simultaneously imparting the paint film with resistance to both water-based and oil-based contaminants, achieving excellent hydrophobicity and oleophobicity.

[0031] Therefore, the embodiment of the present application provides a modified block silicone oil which has a special block structure after modification and retains a polymerizable double bond at the end, so as to be able to be chemically bonded with an acrylate matrix.

[0032] Next, the preparation method of the modified block silicone oil is described in detail, which mainly includes two steps. The first step is to prepare a modifier, i.e. iso-pentenyl alcohol polyoxyethylene ether glycidyl ether. The second step is to prepare the modified block silicone oil by using iso-pentenyl alcohol polyoxyethylene ether glycidyl ether and amino-terminated silicone oil as raw materials.

[0033] Firstly, regarding the preparation of iso-pentenyl alcohol polyoxyethylene ether glycidyl ether, iso-pentenyl alcohol polyoxyethylene ether is used as raw material, and the system is capped by epoxy chloropropane to synthesize a bifunctional reactive monomer with a polymerizable double bond and an epoxy group, i.e. iso-pentenyl alcohol polyoxyethylene ether glycidyl ether. The specific steps are as follows: Step S11: 1 eq of iso-pentenyl alcohol polyoxyethylene ether is added to the reactor, and 0.25% of its mass of boron trifluoride etherate complex is added as a catalyst. Under the protection of nitrogen atmosphere, the system is warmed to 50℃. Then, 1.05 eq of epoxy chloropropane is slowly added at this temperature range, and the temperature and rate are strictly controlled to ensure the smooth reaction. After the addition is completed, the system is kept at temperature until the epoxy value reaches the theoretical requirement.

[0034] Step S12: After the reaction of step S11 is completed, 40wt.% sodium hydroxide aqueous solution containing 1.15 eq of sodium hydroxide is added to the system for ring closure reaction. The reaction temperature is strictly controlled between 30~50℃.

[0035] Step S13: After the reaction of step S12 is completed, the system is allowed to stand and separate. The upper organic phase is taken and diatomite and white clay are added for adsorption purification and stirring. Finally, the system is dehydrated at 120℃ under vacuum for 2 hours, and then filtered to obtain the final product, iso-pentenyl alcohol polyoxyethylene ether glycidyl ether, which is clear and viscous. The product has an allyl ether structure at the end which can be free radical polymerized and an active epoxy group in the side chain.

[0036] In some embodiments of the present application, the structure general formula of iso-pentenyl alcohol polyoxyethylene ether glycidyl ether is R', wherein the complete structure of R' is CH2=C(CH3)-CH2-CH2-O-(CH2CH2O)m-O-CH2-CH(O)-CH2-} (m is the number of repeating units of the polyoxyethylene segment, which can be a natural number between 3~7); the R' molecule contains 1 epoxy ring, which is the only reaction site for reaction with silicone oil, and the ring opening reaction occurs after the reaction with amino active hydrogen.

[0037] It should be noted that R' is obtained by epoxy termination of isopentenyl polyoxyethylene ether with epichlorohydrin, and thus the value of m in the structure of R' depends on the number of repeating units of polyoxyethylene in the raw material isopentenyl polyoxyethylene ether. In a more preferred embodiment, m = 7, so the raw material isopentenyl polyoxyethylene ether contains 7 polyoxyethylene groups, and thus the obtained isopentenyl polyoxyethylene ether glycidyl ether contains 7 repeating units of polyoxyethylene segments.

[0038] Secondly, isopentenyl polyoxyethylene ether glycidyl ether is used as a modifier to react with amino-terminated silicone oil to synthesize a macromolecular reactive block silicone monomer. The specific steps are as follows: In terms of molar ratio, 4 eq of isopentenyl polyoxyethylene ether glycidyl ether is reacted with 1 eq of amino-terminated silicone oil. First, the amino-terminated silicone oil is added to the reactor, and 0.2% of triethylamine based on the total mass of the reactants is added as a catalyst. Under the condition of 80°C and stirring, the isopentenyl polyoxyethylene ether glycidyl ether is slowly added dropwise into the silicone oil. After the dropwise addition is completed, the reaction is continued at this temperature until the epoxy value of the system decreases to zero, indicating that the reaction is complete.

[0039] This step utilizes the reaction between epoxy groups and primary amine groups to covalently graft multiple isopentenyl polyoxyethylene ether segments to the silicone main chain through ether bonds to generate a new type of organic silicone macromolecule with a block structure. The macromolecule retains the radical-polymerizable double bond at the isopentenyl alcohol end, allowing it to participate in subsequent emulsion polymerization as a macromolecular monomer; its molecular structure has both the hydrophilicity of the polyether segment and the hydrophobicity of the silicone segment.

[0040] In some embodiments of the present application, the amino-terminated silicone oil can be specifically a bis-amino-terminated polydimethylsiloxane, and its general structure is H2N-R-NH2, wherein R represents a polydimethylsiloxane main chain, which can be -(Si(CH3)2-O)n- (n is the number of repeating units of polydimethylsiloxane segments), and the -NH2 at both ends is a primary amino group, and there are a total of 4 active hydrogens. n -Si(CH3)2-(n is the number of repeating units of polydimethylsiloxane segments), and the -NH2 at both ends is a primary amino group, and there are a total of 4 active hydrogens.

[0041] In some embodiments of the present application, the molecular weight of the amino-terminated silicone oil can be 4000-10000, and the silicone oil in this molecular weight range can ensure that the paint film has very low surface energy. In a more preferred embodiment, the molecular weight of the amino-terminated silicone oil can be 8000.

[0042] In the above ring-opening addition reaction, 1 mol of H2N-R-NH2 contains 4 active hydrogens, which can completely react with 4 mol of R' epoxy ring. First, the primary amino group -NH2 at both ends of H2N-R-NH2 releases 1 active hydrogen respectively to attack the epoxy ring of R'; the C-O bond of the epoxy ring is broken, and the oxygen atom combines with hydrogen to form a hydroxyl group -OH, generating an intermediate containing a secondary amino group -NH-: R'-NH-R-NH-R'. The secondary amino group -NH- at both ends of the intermediate releases the remaining 2 active hydrogens respectively to attack the epoxy ring of another 2 molecules of R'; the epoxy ring is opened again and a hydroxyl group -OH is formed, and finally a product completely grafted with 4 R' is generated, which is the modified block silicone oil.

[0043] The complete structure of the modified block silicone oil obtained by the above reaction is as follows: [CH2=C(CH3)-CH2-CH2-O-(CH2CH2O)m-O-CH2-CH(OH)-CH2-]2N-R-N[CH2-CH(OH)-CH2-O-(CH2CH2O)m-O-CH2-CH2-C(CH3)=CH2]2. It can be seen from the structural formula that the modified block silicone oil is centered on the polydimethylsiloxane backbone R, and the left and right ends are completely symmetrical; the tertiary amino group at each end is connected to 2 R' residues, and each R' residue retains the hydroxyl group generated by the ring-opening of the epoxy group, while retaining the original isopentenyl group of R', without loss of functional groups.

[0044] The modified block silicone oil obtained by the above reaction can be used as a functional monomer to perform emulsion copolymerization with an acrylate hard monomer (such as styrene, methyl methacrylate) and an acrylate soft monomer (such as butyl acrylate), to prepare a silicone-modified acrylate emulsion with dual-repellent function. Specifically, the functional monomer is mixed with the acrylate monomer to form an oil phase for polymerization. Subsequently, a conventional emulsion polymerization process (pre-emulsification method or semi-continuous dropwise addition method) is used to perform the copolymerization reaction.

[0045] In some embodiments of the present application, the raw materials for preparing the silicone-modified acrylate emulsion include reaction monomers, styrene, an emulsifier, an initiator, water, and the modified block silicone oil, wherein the mass of the modified block silicone oil accounts for 10% to 35% of the total mass of all monomers, and more preferably, the mass of the modified block silicone oil accounts for 15% to 25% of the total mass of all monomers.

[0046] The silicone-modified acrylate emulsion prepared by this scheme has silicone chain segments with surface migration tendency stably embedded in the polymer molecular chain. During film formation, these silicone chain segments can spontaneously accumulate on the surface of the paint film to form a low surface energy layer, thereby imparting the paint film with long-lasting and excellent hydrophobicity and oleophobicity, achieving high-efficiency stain resistance.

[0047] The technical solutions of the present application will be further described below with reference to the embodiments. Example

[0048] Example 1 provides a silicone-modified acrylate emulsion prepared by the following method.

[0049] A. Preparation of isopentenyl alcohol polyoxyethylene ether glycidyl ether.

[0050] 1 eq of isopentenyl alcohol polyoxyethylene ether was added to the reactor, and 0.25% of its mass of boron trifluoride etherate complex was added as a catalyst. The system was warmed to 50°C under the protection of a nitrogen atmosphere. Then, 1.05 eq of epichlorohydrin was slowly added at this temperature range, and the temperature and rate were strictly controlled during the addition to ensure smooth reaction. After the addition was completed, the reaction was maintained until the epoxy value of the system reached the theoretical requirement.

[0051] After the reaction was completed, 1.15 eq of sodium hydroxide was added to the system in the form of a 40 wt.% sodium hydroxide aqueous solution to perform the ring closure reaction, and the reaction temperature was strictly controlled between 30-50°C during this stage.

[0052] After the reaction was completed, the system was allowed to stand and separate, and the upper organic phase was taken and stirred with diatomite and white clay for adsorption purification. Finally, the system was dehydrated at 120°C under vacuum for 2 hours, and then filtered to obtain the final product, isopentenyl alcohol polyoxyethylene ether glycidyl ether, which was clear and viscous.

[0053] B. Preparation of modified block silicone oil.

[0054] 4 eq of isopentenyl alcohol polyoxyethylene ether glycidyl ether was reacted with 1 eq of amino-terminated silicone oil in a molar ratio. The amino-terminated silicone oil was first added to the reactor, and 0.2% of its total mass of triethylamine was added as a catalyst. The isopentenyl alcohol polyoxyethylene ether glycidyl ether was slowly added to the silicone oil at 80°C under stirring. After the addition was completed, the reaction was continued at this temperature until the epoxy value of the system dropped to zero, indicating that the reaction was complete.

[0055] C. Preparation of silicone-modified acrylate emulsion.

[0056] The reaction monomers, modified block silicone oil, emulsifier, initiator, initiator, coupling agent, and water were mixed to form the polymerization raw materials, and then a copolymerization reaction was performed through a conventional emulsion polymerization process (pre-emulsification method).

[0057] The reaction monomers include methyl methacrylate, styrene, butyl acrylate, and acrylic acid. The mass of the modified block silicone oil is 10% of the mass of the reaction monomers. Specifically, the mass of each reaction raw material is as follows: 32 parts by mass of methyl methacrylate, 41 parts by mass of styrene, 35 parts by mass of butyl acrylate, 3 parts by mass of acrylic acid, 11.1 parts by mass of modified block silicone oil, 1.5 parts by mass of non-ionic emulsifier (NP-40), 2.5 parts by mass of anionic emulsifier (Co436), 0.6 parts by mass of initiator (potassium persulfate), 1 part by mass of coupling agent (A171), and 100 parts by mass of water. Example

[0058] Example 2 is basically the same as Example 1, except that in Example 2, the mass of the modified block silicone oil is 15% of the mass of the reaction monomers when preparing the silicone-modified acrylate emulsion. Example

[0059] Example 3 is basically the same as Example 1, except that in Example 3, the mass of the modified block silicone oil is 25% of the mass of the reaction monomers when preparing the silicone-modified acrylate emulsion. Example

[0060] Example 4 is basically the same as Example 1, except that in Example 4, the mass of the modified block silicone oil is 35% of the mass of the reaction monomers when preparing the silicone-modified acrylate emulsion.

[0061] Comparative Example 1 is basically the same as Example 1, except that in Comparative Example 1, no modified block silicone oil is added when preparing the silicone-modified acrylate emulsion.

[0062] The silicone-modified acrylate emulsions prepared in Examples 1-4 and Comparative Example 1 are subjected to performance testing. The silicone-modified acrylate emulsion is allowed to form a film at room temperature for 24 hours, and then dried at 80°C for 12 hours. The film of each example and comparative example is then subjected to performance testing.

[0063] The film hardness is tested according to the standard GB / T 6739-2006 “Pigments and Varnishes - Determination of Film Hardness by Pencil Method”. The film adhesion is tested according to the standard GB / T 9286-2021 “Pigments and Varnishes - Crosshatch Test”. The contact angle is tested using a detection instrument, OSA-100CMC, from Ningbo Xianbianjia. The contact angles of the above-mentioned films with water and oil (silicone oil) are tested using the detection instrument. The water resistance is tested according to the standard GB / T 1733-1993 “Determination of Water Resistance of Paint Film”. The test results are shown in Table 1.

[0064] Table 1 Test results of Examples 1-4 and Comparative Example 1 From Table 1 and Figures 1-5It can be seen from the comparison that with the gradual increase of the amount of the modified block silicone oil, the hardness of the paint film and the hydrophobic and oleophobic properties and water resistance are improved to different degrees. Compared with Comparative Example 1, although 10% of the modified block silicone oil is added in Example 1, the hydrophobicity is only slightly improved. The reason is that the distribution of the hydrophobic groups on the surface of the paint film is sparse, so that a continuous hydrophobic layer cannot be formed. However, with the increase of the amount of the modified block silicone oil, the enrichment of the silicone oil molecules on the surface of the paint film reaches a threshold value, forming a continuous low-surface-energy hydrophobic layer, which significantly reduces the wettability of water. The oleophobicity is similar to the hydrophobicity. With the increase of the amount of the modified block silicone oil, the density of the oleophobic groups on the surface increases, and when the amount of the modified block silicone oil reaches 25%, a perfect oleophobic layer is formed on the surface of the paint film. When the amount of the modified block silicone oil is 35%, the oleophobicity is only slightly optimized, so the oleophobicity tends to be stable.

[0065] For the adhesion of the paint film, the low amount of the modified block silicone oil does not affect the adhesion of the paint film, but the high amount of the modified block silicone oil weakens the interfacial bonding force between the paint film and the substrate, resulting in a decrease in the adhesion.

[0066] Therefore, the application limits the amount of the modified block silicone oil to 15% to 25%, so that the quality of the paint film formed thereby is less affected, the hardness is larger, the adhesion is good, and the paint film also has excellent hydrophobic and oleophobic properties and improved water resistance.

[0067] The above are preferred embodiments of the application, and do not limit the protection scope of the application. Therefore, any equivalent changes made on the basis of the structure, shape and principle of the application should be covered within the protection scope of the application.

Claims

1. A modified block silicone oil characterized in that, has the structure shown in the following general formula (I): [CH2=C(CH3)-CH2-CH2-O-(CH2CH2O)m-O-CH2-CH(OH)-CH2-]2N-R-N[CH2-CH(OH)-CH2-O-(CH2CH2O)m-O-CH2-CH2-C(CH3)=CH2]2 (I); In formula (I), m is a natural number between 3 and 7, and R is a polydimethylsiloxane main chain.

2. A process for preparing the modified block silicone oil according to claim 1, characterized by, The method comprises the following steps: The method comprises the following steps: S10: preparing isopentenyl alcohol polyoxyethylene ether glycidyl ether; S20: performing ring-opening addition reaction on the terminal amino silicone oil and the isopentenyl alcohol polyoxyethylene ether glycidyl ether in the presence of an alkaline catalyst to obtain the modified block silicone oil.

3. The method for producing a modified block silicone oil according to claim 2, characterized by, In step S20, the molar ratio of the terminal amino silicone oil to the isopentenyl alcohol polyoxyethylene ether glycidyl ether is 1:

4.

4. The method for producing a modified block silicone oil according to claim 2, characterized by, The molecular weight of the terminal amino silicone oil is 4000-10000.

5. The method of preparing a modified block silicone oil according to claim 2, characterized by, The alkaline catalyst is triethylamine, and the amount of the alkaline catalyst is 0.1%-0.3% of the total mass of the reactants.

6. The method of preparing a modified block silicone oil according to claim 2, characterized by, The reaction temperature in step S20 is 75-85°C.

7. The method of preparing a modified block silicone oil according to claim 2, characterized by, The specific operation of step S10 is as follows: S11: performing reaction on isopentenyl alcohol polyoxyethylene ether and epichlorohydrin in the presence of a Lewis acid catalyst at 40-70°C; S12: adding sodium hydroxide solution to the product obtained in step S11 to perform ring closure reaction, and the reaction temperature is controlled at 30-50°C; S13: performing purification, dehydration and filtration on the product obtained in step S12 to obtain the isopentenyl alcohol polyoxyethylene ether glycidyl ether.

8. The method of preparing a modified block silicone oil according to claim 7, characterized in that, The Lewis acid catalyst is boron trifluoride etherate complex, and the amount of the Lewis acid catalyst is 0.2%-0.3% of the mass of isopentenyl alcohol polyoxyethylene ether.

9. The method for preparing the modified block silicone oil according to claim 7, characterized in that, The molar ratio of the isopentenyl alcohol polyoxyethylene ether to the epichlorohydrin is 1:1.05-1.

1.

10. Use of the modified block silicone oil according to claim 1 in the preparation of an aqueous acrylate emulsion, characterized in that, The aqueous acrylate emulsion is prepared by emulsion polymerization of reaction monomers and functional monomers, wherein the functional monomers are the modified block silicone oil according to any one of claims 1-9, and the mass of the functional monomers accounts for 15%-25% of the mass of the reaction monomers.

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