Polyether modified fluorine-containing polysiloxane as well as preparation method and application thereof
By preparing polyether-modified fluorinated polysiloxane as a slip agent, the problems of poor recoating performance and easy wear of coatings were solved, and the lubricity and wear resistance of the coatings were improved, as well as the leveling effect and recoating performance of the coatings.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHAMBROAD CHEM IND RES INST CO LTD
- Filing Date
- 2024-10-29
- Publication Date
- 2026-05-01
AI Technical Summary
Existing coatings have problems such as poor recoating performance, easy wear of the coating, inability to effectively protect the surface of metal equipment and buildings, and excessive stability of coating foam leading to reduced recoating performance.
Using polyether-modified fluorinated polysiloxane as a lubricant, silicone oil with long-chain fluorinated side groups was prepared through ring-opening polymerization and addition polymerization. This reduced the surface tension of the coating and improved its lubricity and wear resistance.
It improves the lubricity and wear resistance of the coating, reduces the surface friction coefficient, improves the leveling effect and recoating performance of the coating, and solves the problems of coating foam stability and recoating performance.
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Figure CN121949797A_ABST
Abstract
Description
A polyether-modified fluorinated polysiloxane, its preparation method and application Technical Field
[0001] This invention belongs to the field of coating additives technology, and particularly relates to a polyether-modified fluorinated polysiloxane, its preparation method and application. Background Technology
[0002] Slip agents are surface conditioners for paint films, typically added to coatings. After drying and curing, slip agent molecules float on the coating, reducing the surface tension and surface resistance, thereby reducing the friction between the coating and another surface, increasing the coating's wear resistance, and thus improving the workability of continuous industrial coating. Therefore, they are widely used in coatings for household appliances, automobiles, furniture, adhesive boards, coil coatings, and cans. Commonly used slip agents include: (1) aliphatic hydrocarbons such as liquid paraffin, low molecular weight polyethylene, polypropylene, and polytetrafluoroethylene; (2) fatty acid amides such as some unsaturated fatty amides; (3) organosilicones such as polydimethylsiloxane, polyphenylmethylsiloxane, and polyether-modified polydimethylsiloxane.
[0003] Although wood coatings, appliance coatings, plastic coatings, and architectural coatings differ in appearance and protective properties, the ultimate goal is to achieve a smoother surface and a better feel, meeting the end-customer's performance requirements. During actual coating application, localized damage may necessitate repair and recoating. If the coating's recoating performance is poor, the applied film is prone to wear, thus failing to effectively protect metal equipment and building surfaces.
[0004] Common silicone oils are dimethyl polysiloxanes. Replacing (or partially replacing) the methyl group in dimethyl polysiloxane with ethyl, propyl, or other multi-carbon alkyl groups, or vinyl, phenyl, or hydrogen groups, yields silicone oils with different properties. Introducing chlorophenyl or trifluoropropyl groups into the main chain of silicone oil molecules can significantly improve their lubrication performance. Because fluorine and hydrogen atoms have similar atomic radii, fluorine atoms replacing methyl hydrogen atoms in fluorosilicone oils exhibit a unique "pseudo-effect." Trifluoromethyl and methyl groups have the same steric hindrance, and the highly electronegative fluorine atoms are strongly bonded to carbon atoms. The chemically stable fluorinated side groups act as a "shielding" effect on the Si-O main chain of the fluorosilicone oil molecule, improving its chemical resistance. Furthermore, silicone oils with long-chain fluorinated side groups have very low surface activity due to the very low surface energy of fluorine atoms, giving fluorosilicone oils unique properties and a very broad application prospect as surface treatment materials.
[0005] This invention aims to provide a modified fluorinated polysiloxane that can improve the recoating performance of coatings. Summary of the Invention
[0006] In view of this, the technical problem to be solved by the present invention is to provide a polyether-modified fluorinated polysiloxane, its preparation method and application. The polyether-modified fluorinated polysiloxane can be used as a slip agent to improve the lubricity and wear resistance of the paint film and slightly reduce the surface tension, so as to solve the problems of excessive foaming stability and reduced recoating performance of the coating.
[0007] This invention provides a polyether-modified fluorinated polysiloxane, comprising the structure shown in formula (I):
[0008]
[0009] Where x is an integer from 10 to 100, y and z are each an integer from 1 to 10, m is an integer from 10 to 50, and n is an integer from 5 to 25;
[0010] R′ is selected from C1 to C10 fluoroalkyl groups;
[0011] R is selected from H, substituted or unsubstituted C1 to C10 alkyl groups, and substituted or unsubstituted epoxy groups;
[0012] The substituents in the substituted C1-C10 alkyl group and the substituted epoxy group are each independently selected from one or more of halogens, C1-C10 alkyl groups and epoxy groups.
[0013] Preferably, it includes the structure shown in formula (II):
[0014]
[0015] Where x is an integer from 10 to 100, y and z are each an integer from 1 to 10, m is an integer from 10 to 50, and n is an integer from 5 to 25;
[0016] R is selected from H, C1 to C10 alkyl or epoxy groups.
[0017] This invention also provides a method for preparing polyether-modified fluorinated polysiloxane, comprising the following steps:
[0018] S1) Hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane shown in formula (III) are mixed evenly, and an acidic catalyst is added to undergo a ring-opening polymerization reaction to obtain the side-chain fluorinated silicone oil shown in formula (IV); the molar ratio of hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane shown in formula (III) is 1:x / 4:z / 4:y / 3;
[0019] S2) The side-chain fluorinated silicone oil of formula (IV) is reacted with the allyl polyether of formula (V) to obtain the polyether-modified fluorinated polysiloxane of formula (I);
[0020]
[0021] Where x is an integer from 10 to 100, y and z are each an integer from 1 to 10, m is an integer from 10 to 50, and n is an integer from 5 to 25;
[0022] R′ is selected from C1 to C10 fluoroalkyl groups;
[0023] R is selected from H, substituted or unsubstituted C1 to C10 alkyl groups, and substituted or unsubstituted epoxy groups;
[0024] The substituents in the substituted C1-C10 alkyl group and the substituted epoxy group are each independently selected from one or more of halogens, C1-C10 alkyl groups and epoxy groups.
[0025] Preferably, the acidic catalyst is selected from acidic resins;
[0026] And / or, the mass of the acidic catalyst is 1% to 10% of the total mass of hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane as shown in formula (III).
[0027] Preferably, the reaction in step S2) is carried out in the presence of a catalyst; the catalyst is selected from nickel-based catalysts and / or platinum-based catalysts.
[0028] Preferably, the total mass ratio of the fluorinated silicone oil with side chain shown in formula (IV) to the allyl polyether shown in formula (V) to the active metal element in the catalyst is 1g:1-80μg.
[0029] Preferably, the temperature of the ring-opening polymerization reaction in step S1) is 50–90°C; and the temperature of the reaction in step S2) is 70–100°C.
[0030] This invention also provides the application of the above-mentioned polyether-modified fluorinated polysiloxane as an organosilicon lubricant.
[0031] The present invention also provides a coating comprising the above-described polyether-modified fluorinated polysiloxane.
[0032] Preferably, the coating comprises a coating base and a polyether-modified fluorinated polysiloxane; the mass of the polyether-modified fluorinated polysiloxane is 0.1% to 0.5% of the mass of the coating base.
[0033] This invention provides a polyether-modified fluorinated polysiloxane, comprising the structure shown in formula (I). Compared with the prior art, this invention uses a polyether-modified fluorinated polysiloxane prepared from a fluorinated polysiloxane as an organosilicon lubricant. As a coating additive, it can float on the surface of the paint film. Due to the very low surface energy of fluorine atoms in the long-chain fluorinated side groups of the silicone oil, it has very low surface activity, thus achieving the effect of reducing the surface tension of the coating. At the same time, the introduction of trifluoropropyl groups can greatly improve the lubrication performance of the silicone oil and reduce the coefficient of friction between the coating film and a second surface, preventing scratches on the paint film and thus improving the workability of continuous chemical coating. Detailed Implementation
[0034] 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.
[0035] This invention provides a polyether-modified fluorinated polysiloxane, comprising the structure shown in formula (I):
[0036]
[0037] Wherein, x is an integer from 10 to 100, preferably an integer from 20 to 100, even more preferably an integer from 30 to 100, even more preferably an integer from 40 to 100, even more preferably an integer from 40 to 90, even more preferably an integer from 40 to 80; in some embodiments provided by the present invention, x is 40, 60, 70 or 80.
[0038] y is an integer from 1 to 10, preferably an integer from 2 to 10, more preferably an integer from 2 to 9, and even more preferably an integer from 3 to 9; in some embodiments provided by the present invention, y is 5, 9, 3 or 8.
[0039] z is an integer from 1 to 10, preferably an integer from 2 to 10, more preferably an integer from 2 to 9, even more preferably an integer from 3 to 8, and most preferably an integer from 4 to 6; in some embodiments provided by the present invention, z is 5, 4 or 6.
[0040] m is an integer from 10 to 50, more preferably an integer from 10 to 40, even more preferably an integer from 10 to 35, even more preferably an integer from 10 to 30, even more preferably an integer from 10 to 25, and most preferably an integer from 12 to 20; in some embodiments provided by the present invention, m is specifically 15, 12 or 20.
[0041] n is an integer from 5 to 25, more preferably an integer from 2 to 20, even more preferably an integer from 5 to 15, and most preferably an integer from 5 to 10; in some embodiments provided by the present invention, n is specifically 5, 8 or 10.
[0042] R′ is a C1 to C10 fluoroalkyl group, preferably a C1 to C8 fluoroalkyl group, more preferably a C1 to C6 fluoroalkyl group, even more preferably a C2 to C5 fluoroalkyl group, even more preferably a C2 to C4 fluoroalkyl group, and most preferably trifluoropropyl.
[0043] R is H, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted epoxy group, preferably H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted epoxy group, more preferably H, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted epoxy group, even more preferably H, a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted epoxy group, and most preferably H, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted epoxy group.
[0044] The substituents in the substituted C1-C10 alkyl groups and the substituted epoxy groups are each independently one or more of halogens, C1-C10 alkyl groups and epoxy groups, preferably one or more of halogens, C1-C6 alkyl groups and epoxy groups, more preferably one or more of halogens, C1-C5 alkyl groups and epoxy groups, even more preferably one or more of halogens, C1-C3 alkyl groups and epoxy groups, and most preferably one or more of halogens, methyl, ethyl and epoxy groups; the halogen can be any halogen known to those skilled in the art and there are no special limitations, but fluorine is preferred in this invention.
[0045] According to the present invention, specifically, the polyether-modified fluorinated polysiloxane includes the structure shown in formula (II):
[0046]
[0047] Wherein, x is an integer from 10 to 100, preferably an integer from 20 to 100, even more preferably an integer from 30 to 100, even more preferably an integer from 40 to 100, even more preferably an integer from 40 to 90, even more preferably an integer from 40 to 80; in some embodiments provided by the present invention, x is 40, 60, 70 or 80.
[0048] y is an integer from 1 to 10, preferably an integer from 2 to 10, more preferably an integer from 2 to 9, and even more preferably an integer from 3 to 9; in some embodiments provided by the present invention, y is 5, 9, 3 or 8.
[0049] z is an integer from 1 to 10, preferably an integer from 2 to 10, more preferably an integer from 2 to 9, even more preferably an integer from 3 to 8, and most preferably an integer from 4 to 6; in some embodiments provided by the present invention, z is 5, 4 or 6.
[0050] m is an integer from 10 to 50, more preferably an integer from 10 to 40, even more preferably an integer from 10 to 35, even more preferably an integer from 10 to 30, even more preferably an integer from 10 to 25, and most preferably an integer from 12 to 20; in some embodiments provided by the present invention, m is specifically 15, 12 or 20.
[0051] n is an integer from 5 to 25, more preferably an integer from 2 to 20, even more preferably an integer from 5 to 15, and most preferably an integer from 5 to 10; in some embodiments provided by the present invention, n is specifically 5, 8 or 10.
[0052] R is H, an alkyl or epoxy group of C1 to C10, preferably H, an alkyl or epoxy group of C1 to C6, more preferably H, an alkyl or epoxy group of C1 to C5, even more preferably H, an alkyl or epoxy group of C1 to C3, and most preferably H, methyl, ethyl or epoxy group.
[0053] This invention utilizes polyether-modified fluorinated polysiloxanes prepared from fluorinated polysiloxanes as organosilicon lubricants. As a coating additive, it floats on the paint film surface. Due to the very low surface energy and low surface activity of fluorine atoms in the long-chain fluorinated side groups of the silicone oil, it can reduce the surface tension of the coating. Simultaneously, the introduction of trifluoropropyl groups significantly improves the lubrication performance of the silicone oil and reduces the coefficient of friction between the coating film and a second surface, preventing scratches on the paint film and thus improving the workability of continuous chemical coating processes.
[0054] The present invention also provides a method for preparing polyether-modified fluorinated polysiloxane, comprising the following steps: S1) mixing hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane shown in formula (III) uniformly, adding an acidic catalyst, and undergoing a ring-opening polymerization reaction to obtain the side-chain fluorinated silicone oil shown in formula (IV); the molar ratio of hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane shown in formula (III) is 1:x / 4:z / 4:y / 3; S2) reacting the side-chain fluorinated silicone oil shown in formula (IV) with the allyl polyether shown in formula (V) to obtain the polyether-modified fluorinated polysiloxane shown in formula (I);
[0055]
[0056] Wherein, x is an integer from 10 to 100, y and z are each independently an integer from 1 to 10, m is an integer from 10 to 50, and n is an integer from 5 to 25; R′ is a C1 to C10 fluoroalkyl group; R is H, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted epoxy group; the substituents in the substituted C1 to C10 alkyl group and the substituted epoxy group are each independently one or more of halogen, C1 to C10 alkyl group and epoxy group.
[0057] This invention does not impose any special restrictions on the source of any raw materials; they can be commercially available. The x, y, z, m, n, R′ and R mentioned above are the same as those mentioned above and will not be repeated here.
[0058] Hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane, and perfluoroalkylmethylcyclotrisiloxane of formula (III) are mixed uniformly, and an acidic catalyst is added to undergo a ring-opening polymerization reaction. In this invention, the hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane, and perfluoroalkylmethylcyclotrisiloxane of formula (III) are preferably mixed uniformly in a protective atmosphere. The protective atmosphere can be any atmosphere known to those skilled in the art and is not particularly limited; nitrogen is preferred in this invention. The acidic catalyst is preferably a solid acid catalyst, more preferably an acidic resin. In the embodiments provided by this invention, The following description uses Rohm and Haas UP150 acidic resin as an example. The mass of the acidic catalyst is preferably 1% to 10% of the total mass of hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane shown in formula (III), more preferably 2% to 8%, even more preferably 2% to 6%, even more preferably 2% to 4%, and most preferably 3%. The temperature of the ring-opening polymerization reaction is preferably 50 to 90°C, more preferably 60 to 80°C, and even more preferably 60 to 70°C. The time of the ring-opening polymerization reaction is preferably 4 to 10 hours, more preferably 4 to 8 hours, even more preferably 5 to 7 hours, and most preferably 6 hours.
[0059] After the ring-opening polymerization reaction, the low-boiling substances are preferably removed under negative pressure and heating conditions to obtain the side-chain fluorinated silicone oil shown in formula (IV); the pressure of the negative pressure is preferably -0.05 to -0.1 MPa, more preferably -0.08 to -0.1 MPa, even more preferably -0.09 to -0.1 MPa, and most preferably -0.094 to -0.099 MPa; the heating temperature is preferably 60℃ to 90℃, more preferably 70℃ to 90℃, and even more preferably 80℃; the heating time is 30 to 90 min, more preferably 40 to 80 min, even more preferably 50 to 70 min, and most preferably 60 min.
[0060] The fluorinated silicone oil with side chains of formula (IV) is reacted with the allyl polyether of formula (V) to obtain the polyether-modified fluorinated polysiloxane of formula (I); the reaction is preferably carried out in the presence of a catalyst; the catalyst is preferably a nickel-based catalyst and / or a platinum-based catalyst, more preferably one or more of metallic platinum, chloroplatinic acid and platinum chelates; the mass ratio of the total mass of the fluorinated silicone oil with side chains of formula (IV) and the allyl polyether of formula (V) to the mass of the active metal element in the catalyst is preferably 1 g: 1-80 μg; the reaction is preferably carried out in an organic solvent; the organic solvent is selected from one or more of benzene, toluene, ethanol, ethylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether and isopropanol; the reaction is preferably carried out in a protective atmosphere; the protective atmosphere can be any protective atmosphere known to those skilled in the art, and there are no special limitations, but nitrogen is preferred in this invention; the reaction temperature is preferably 70-100°C, more preferably... The preferred temperature is 80–90°C. In this invention, this step specifically involves: in a protective atmosphere, mixing and heating the side-chain fluorinated silicone oil of formula (IV) with a portion of the allyl polyether of formula (V), and heating the mixture until the temperature reaches 40–60°C, preferably 45–55°C, more preferably 50°C, adding a catalyst, and continuing to heat the mixture until the reaction temperature is reached. Then, adding the remaining allyl polyether of formula (V) to react and obtain the polyether-modified fluorinated polysiloxane of formula (I). The portion of the allyl polyether of formula (V) is 50%–70% of the total amount of allyl polyether of formula (V), i.e., the portion of the allyl polyether of formula (V) and the remaining allyl polyether of formula (V), more preferably 55%–65%, and even more preferably 60%. The reaction time is preferably 2–5 h, more preferably 3–4 h, and even more preferably 3 h. After the reaction is completed, the polyether-modified fluorinated polysiloxane of formula (I) is obtained.
[0061] In one specific embodiment of the present invention, the polyether-modified fluorinated polysiloxane is prepared according to the following reaction formula:
[0062]
[0063] The preparation method of polyether-modified fluorinated polysiloxane provided by this invention is simple, easy to control, and has a short preparation cycle, making it suitable for industrial production.
[0064] The present invention also provides an application of the above-mentioned polyether-modified fluorinated polysiloxane as an organosilicon lubricant.
[0065] The present invention also provides a coating comprising the above-mentioned polyether-modified fluorinated polysiloxane; the coating comprising a coating base and the polyether-modified fluorinated polysiloxane; the mass of the polyether-modified fluorinated polysiloxane is preferably 0.1% to 0.5% of the mass of the coating base, more preferably 0.2% to 0.4%, even more preferably 0.2% to 0.3%, and most preferably 0.25%.
[0066] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a polyether-modified fluorinated polysiloxane provided by the present invention, its preparation method and application.
[0067] All reagents used in the following examples are commercially available.
[0068] Example 1
[0069] 1. Preparation of fluorinated silicone oil:
[0070] After thoroughly drying a 500ml four-necked flask, purge it with nitrogen for 10 minutes. Then, add 168g of octamethylcyclotetrasiloxane, 39g of trifluoropropylmethylcyclotrisiloxane, 8.1g of hexamethyldisiloxane, and 15g of hydrogen-containing tetramethylcyclotetrasiloxane (D4). H The product was placed in a four-necked flask equipped with a thermometer and a stirrer. Then, 6.9 g of acidic resin (Rohm and Haas UP150) was added as a catalyst. The temperature was raised to 60°C, and the reaction was carried out for 6 hours to obtain a transparent product. Then, under negative pressure (vacuum gauge pressure -0.094 to -0.099 MPa), low-boiling substances were removed at 80°C for 60 minutes to obtain an intermediate product M1 with a molecular weight of 6306.
[0071]
[0072] 2. Preparation of polyether-modified fluorinated organosilicon:
[0073] 120 g of fluorinated polysiloxane (M1) and 19.34 g of allyl polyether were added to a reaction flask equipped with an N2 conduit, thermometer, and distillation apparatus. The mixture was slowly heated by passing N2 through it. When the temperature reached 50 °C, 6.97 mg of chloroplatinic acid catalyst was added, and stirring continued. After adding the catalyst, when the temperature stabilized at 80–90 °C, 12.89 g of allyl polyether was added dropwise. The temperature was maintained at 80–90 °C, and the addition polymerization reaction was carried out for 3 hours to obtain polyether-modified organosilicon N1.
[0074]
[0075] Example 2
[0076] 1. Preparation of fluorinated silicone oil:
[0077] After thoroughly drying a 500ml four-necked flask, purge it with nitrogen for 10 minutes. Then, add 118.4g of octamethylcyclotetrasiloxane, 93.6g of trifluoropropylmethylcyclotrisiloxane, 32.4g of hexamethyldisiloxane, and 40g of hydrogen-containing tetramethylcyclotetrasiloxane (D4). H The product was placed in a four-necked flask equipped with a thermometer and a stirrer, and then 8.9 g of acidic resin (Rohm and Haas UP150) was added as a catalyst. The temperature was raised to 60 °C, and the reaction was carried out for 6 hours to obtain a transparent product. Then, under negative pressure conditions (vacuum gauge pressure of -0.094 to -0.099 MPa), the low-boiling substances were removed at 80 °C for 60 minutes to obtain an intermediate product M2 with a molecular weight of 6790.
[0078]
[0079] 2. Preparation of polyether-modified organosilicon:
[0080] 120 g of fluorinated polysiloxane (M1) and 14.34 g of allyl polyether were added to a reaction flask equipped with an N2 inlet, thermometer, and rectifier. The mixture was slowly heated by passing N2 through it. When the temperature reached approximately 50 °C, 6.72 mg of chloroplatinic acid catalyst was added, and stirring continued. After adding the catalyst, when the temperature stabilized at 80–90 °C, 9.56 g of allyl polyether was added dropwise. The temperature was maintained at 80–90 °C, and the addition polymerization reaction was carried out for 3 hours to obtain polyether-modified fluorinated organosilicon N2.
[0081]
[0082] Example 3
[0083] 1. Preparation of fluorinated silicone oil:
[0084] After thoroughly drying a 500ml four-necked flask, purge it with nitrogen for 10 minutes. Then, add 177.6g of octamethylcyclotetrasiloxane, 62.4g of trifluoropropylmethylcyclotrisiloxane, 32.4g of hexamethyldisiloxane, and 36g of hydrogen-containing tetramethylcyclotetrasiloxane (D4). H The product was placed in a four-necked flask equipped with a thermometer and a stirrer, and then 9.3 g of acidic resin (Rohm and Haas UP150) was added as a catalyst. The temperature was raised to 60 °C, and the reaction was carried out for 6 hours to obtain a transparent product. Then, under negative pressure conditions (vacuum gauge pressure of -0.094 to -0.099 MPa), the low-boiling substances were removed at 80 °C for 60 minutes to obtain an intermediate product M3 with a molecular weight of 6950.
[0085]
[0086] 2. Preparation of polyether-modified fluorinated organosilicon:
[0087] 120 g of fluorinated polysiloxane (M3) and 15.72 g of allyl polyether were added to a reaction flask equipped with an N2 inlet, thermometer, and rectifier. The mixture was slowly heated by passing N2 through it. When the temperature reached approximately 50 °C, 6.79 mg of chloroplatinic acid catalyst was added, and stirring continued. After adding the catalyst, when the temperature stabilized at 80–90 °C, 10.48 g of allyl polyether was added dropwise. The temperature was maintained at 80–90 °C, and the addition polymerization reaction was carried out for 3 hours to obtain polyether-modified fluorinated organosilicon N3.
[0088]
[0089] Performance testing
[0090] Experimental Example 1: Surface Tension Test
[0091] Surface tension was measured using the platinum plate method, and the results are shown in Table 1.
[0092] Table 1 Surface tension test results
[0093] Surface tension (mN / m): Example 1: 22.56; Example 2: 21.42; Example 3: 23.18 surface
[0094] Test Example 2 Antifogging Stability
[0095] The purchased paint (Nippon Cloud Clean Anti-Formaldehyde Odorless 5-in-1) was mixed with those used in Examples 1-3, and shaken for 60 minutes in a shaker. The mixture was then compared with a control group (plain paint) to evaluate the foam-stabilizing effect of the silicone additive based on the amount of foam produced. The evaluation criteria were graded from 1 to 7, where grade 1 indicates no foam and grade 7 indicates a large amount of foam.
[0096] Table 2 Foam formation results
[0097] 0.25% Blank Group Example 1 Example 2 Example 30min 777710min 666620min 555530min 443440min 422350min212260min1111 surface
[0098] Test Example 3: Coefficient of Friction
[0099] Coating preparation: After all the foam disappeared, a 70 μm coating was prepared on the tinplate sheet. The coating was blown clean for 10 min and then baked in a vacuum drying oven at 130℃ for 30 min. The dynamic friction at ten different points was measured simultaneously, and the average friction coefficient was calculated. The results are shown in Table 3.
[0100] Table 3. Friction coefficient test results
[0101] Average coefficient of friction: Blank group, Example 1, Example 2, Example 3, 0.25% (added 0.61, 0.33, 0.39, 0.33) surface
[0102] Experiment 4: Leveling performance test and recoating performance test
[0103] Take a piece of steel and remove oil, scale, rust, and old coatings from its surface by shot blasting (achieving Swedish rust removal standard SA2.5). Then, add the silicone lubricant described in this application to the coating (Nippon Cloud Clean Anti-Formaldehyde Odorless 5-in-1) at a certain ratio (0.25%) and apply it to the steel surface for 2-3 mm. Bake and cure at 50-60℃ for 15 minutes, then brush it for another 2-3 mm. During each brushing process, evaluate the leveling effect of the silicone additive based on the speed of leveling and the smoothness of the coating surface. At the same time, when applying the second coat, observe the adhesion and bonding force of the coating on the first coating surface. Evaluate the recoating effect of the coating based on the presence of a clear interface between the two coatings and the strength of the adhesion between the coatings. The results are shown in Table 4. The evaluation standard is 1-4 levels, where level 1 is the worst in leveling effect and recoating performance, and level 4 is the best in leveling effect and recoating performance.
[0104] Table 4 Results of leveling performance and recoating performance tests
[0105] Examples: Leveling effect, Recoating performance, Blank group 44, Examples 112, Examples 222, Examples 323 surface
[0106] In summary, the slip agent of this invention exhibits a low coefficient of friction and surface tension, excellent leveling effect, and lubrication performance. When added to coatings in a certain proportion, it can solve problems such as excessive foaming and reduced recoating performance, providing customers with coating products that have a good surface feel.
[0107] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A polyether-modified fluorinated polysiloxane, characterized in that, Including the structure shown in equation (I): Wherein, x is an integer from 10 to 100, y and z are each independently an integer from 1 to 10, m is an integer from 10 to 50, and n is an integer from 5 to 25; R′ is selected from C1 to C10 fluoroalkyl groups; R is selected from H, substituted or unsubstituted C1 to C10 alkyl groups, and substituted or unsubstituted epoxy groups; the substituents in the substituted C1 to C10 alkyl groups and the substituted epoxy groups are each independently selected from one or more of halogens, C1 to C10 alkyl groups, and epoxy groups.
2. The polyether-modified fluorinated polysiloxane according to claim 1, characterized in that, Including the structure shown in equation (II): Where x is an integer from 10 to 100, y and z are each an integer from 1 to 10, m is an integer from 10 to 50, and n is an integer from 5 to 25; R is selected from H, C1 to C10 alkyl or epoxy groups.
3. A method for preparing polyether-modified fluorinated polysiloxane, characterized in that, Includes the following steps: S1) Hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane of formula (III) are mixed evenly, and an acidic catalyst is added to undergo a ring-opening polymerization reaction to obtain the side-chain fluorinated silicone oil of formula (IV); the molar ratio of hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane of formula (III) is 1:x / 4:z / 4:y / 3; S2) The side-chain fluorinated silicone oil of formula (IV) is reacted with the allyl polyether of formula (V) to obtain the polyether-modified fluorinated polysiloxane of formula (I); Wherein, x is an integer from 10 to 100, y and z are each independently an integer from 1 to 10, m is an integer from 10 to 50, and n is an integer from 5 to 25; R′ is selected from C1 to C10 fluoroalkyl groups; R is selected from H, substituted or unsubstituted C1 to C10 alkyl groups, and substituted or unsubstituted epoxy groups; the substituents in the substituted C1 to C10 alkyl groups and the substituted epoxy groups are each independently selected from one or more of halogens, C1 to C10 alkyl groups, and epoxy groups.
4. The preparation method according to claim 3, characterized in that, The acidic catalyst is selected from acidic resins; and / or, the mass of the acidic catalyst is 1% to 10% of the total mass of hexamethyldisiloxane, octamethylcyclotetrasiloxane, D4Hcyclotetrasiloxane and perfluoroalkylmethylcyclotrisiloxane shown in formula (III).
5. The preparation method according to claim 3, characterized in that, The reaction in step S2) is carried out in the presence of a catalyst; the catalyst is selected from nickel-based catalysts and / or platinum-based catalysts.
6. The preparation method according to claim 5, characterized in that, The total mass ratio of the fluorinated silicone oil with side chain shown in formula (IV) to the allyl polyether shown in formula (V) to the active metal element in the catalyst is 1 g: 1-80 μg.
7. The preparation method according to claim 3, characterized in that, The temperature of the ring-opening polymerization reaction in step S1) is 50–90°C; the temperature of the reaction in step S2) is 70–100°C.
8. The application of the polyether-modified fluorinated polysiloxane according to claim 1 or 2, or the polyether-modified fluorinated polysiloxane prepared by any one of claims 3 to 7, as an organosilicon lubricant.
9. A coating, characterized in that, Includes the polyether-modified fluorinated polysiloxane as described in claim 1 or 2, or the polyether-modified fluorinated polysiloxane prepared by any one of the preparation methods of claims 3 to 7.
10. The coating according to claim 9, characterized in that, The coating comprises a coating base and a polyether-modified fluorinated polysiloxane; the mass of the polyether-modified fluorinated polysiloxane is 0.1% to 0.5% of the mass of the coating base.