A perfluoropolyether siloxane compound containing a fluorescent labeling structure and its preparation method and application

Abstract

The present invention discloses a perfluoropolyether siloxane compound containing a fluorescent marker structure, a preparation method and an application thereof, and belongs to the technical field of anti-fingerprint film materials. By adding a fluorescent marker, the present invention can show a fluorescent effect under a specific light source such as ultraviolet light, thereby realizing a rapid detection of the integrity and uniformity of the coating. In addition, the coating can be applied to electronic equipment, household appliances, laboratory equipment, etc., meeting the requirements of aesthetics, antifouling, durability and anti-counterfeiting. The present invention can be widely used in the fields of high-end electronic products, luxury goods and special equipment, and provides an innovative solution for product quality control, anti-counterfeiting and brand protection.

Description

Technical Field

[0001] The invention belongs to the technical field of anti-fingerprint film materials, and specifically relates to a perfluoropolyether siloxane compound containing a fluorescent marking structure, and a preparation method and application thereof. Background Art

[0002] In modern society, electronic devices, home appliances, laboratory equipment, etc. are widely used in daily life and work, especially touch screen devices, smart phones, tablet computers and other frequently touched objects, whose surfaces are easily stained with fingerprints, oil and dust, resulting in a decline in the aesthetics and user experience of the products. In order to solve these problems, surface coating materials with anti-fingerprint properties have gradually appeared on the market. However, traditional anti-fingerprint coatings are limited to inhibiting fingerprint adhesion, and the requirements for coating durability, detectability, and deeper security identification have not been fully met.

[0003] In addition, in the production process of electronic manufacturing, medical devices and laboratory equipment, there are strict requirements for the integrity and uniformity of surface coatings. How to quickly detect the quality of coatings in the production process and ensure product performance is a technical challenge faced by manufacturers. Anti-fingerprint coatings with fluorescent marking function provide an effective way to solve this problem - by showing fluorescence under specific light sources such as ultraviolet light, the coverage effect and uniformity of the coating can be easily detected, improving the efficiency of quality control.

[0004] On the other hand, in order to prevent counterfeiting and protect brand rights, invisible labels with anti-counterfeiting functions are also needed on high-end electronic products, luxury goods and sensitive equipment. Anti-fingerprint coatings with fluorescent markings will only show specific fluorescent patterns or colors under specific light sources, thus serving as a covert anti-counterfeiting method to enhance product safety and brand recognition. This coating can also be used in special industries and security fields to identify key areas or important equipment through fluorescent markings, and perform encrypted identification when necessary.

[0005] Therefore, anti-fingerprint coating materials with fluorescent marking function came into being, combining multiple functions such as anti-fingerprint, anti-fouling, aesthetics, quality inspection and anti-counterfeiting, and becoming an emerging demand in modern high-end products and high-standard application scenarios. Summary of the invention

[0006] The first technical problem to be solved by the present invention is to provide a method for preparing a perfluoropolyether siloxane compound containing a fluorescent marking structure, the method has mild conditions, is easy to control, and is simple to operate; the second technical problem to be solved by the present invention is to provide a surface treatment agent based on a perfluoropolyether siloxane compound containing a fluorescent marking structure, the treatment agent has high slipperiness, high wear resistance, and also has fluorescent marking properties; the third technical problem to be solved by the present invention is to provide a film of the perfluoropolyether siloxane compound surface treatment agent, the film has a water contact angle of 110-115°.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0008] A perfluoropolyether siloxane compound containing a fluorescent labeling structure, the structural formula of which is: Ar-RX;

[0009] In the structural formula, Ar is a fluorinated aromatic ring, including hexafluorobenzene, octafluoronaphthalene, and perfluorobiphenyl;

[0010] R is -L-Rf-, L is a divalent organic group,

[0011] Rf is F(CF2) m -(OCF2) p -(OC2F4) q -(OC3F6) r -(OC4F8) s- OC(Z)F(CF2) n -, wherein p, q, r and s are independently and are integers of 0-50, the sum of p, q, r and s is not less than 1, the order and quantity of the repeating units with p, q, r and s enclosed in brackets are arbitrary in the formula, m and n are integers of 0-30, and Z is F or CF3;

[0012] X is -OCH2CH2CH2X1, wherein X1 is -SiR 1 3. R 1 It is a group that can be hydrolyzed to -OH.

[0013] Further, the L is -O-CH2-; R 1 For-OR 2 , R 2 It is a C1-C4 alkyl group.

[0014] Furthermore, in the molecular formula of Rf, the sum of p, q, r and s is an integer of 10-100, and m and n are independently integers of 1-3.

[0015] Furthermore, the preparation method of any of the above-mentioned perfluoropolyether siloxane compounds containing a fluorescent labeling structure comprises the following steps:

[0016] Step 1: Introduction of fluorinated aromatic rings: The perfluoropolyether alcohol is first dissolved with a fluorinated solvent and an organic solvent, and under alkaline conditions, a fluorinated solvent is added dropwise to dissolve the fluorinated aromatic ring compounds, and the single-ended perfluoropolyether alcohol compounds containing fluorinated aromatic rings are separated by a silica gel column;

[0017] Step 2: Preparation of Ar-Rf compound: The perfluoropolyether alcohol compound containing fluorinated aromatic ring is first dissolved in a fluorinated solvent and an organic solvent, 3-bromopropylene is added dropwise under alkaline conditions, and the solvent is removed by rotary evaporation to obtain the Ar-Rf compound;

[0018] Step 3: Preparation of Ar-Rf-Si compound: Dissolve the Ar-Rf compound obtained in the above step 2 in a fluorine-containing solvent, add alkoxysilane and an anti-translocation agent, add platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex under argon protection, extract and separate, and concentrate by rotary evaporation to obtain the Ar-Rf-Si compound.

[0019] Furthermore, the base in step 1 and step 2 is an inorganic base or an organic strong base, the inorganic base is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, sodium alcoholate, potassium alcoholate, and ammonia water; the organic strong base is one or more of triethylamine, diisopropylethylamine, and 4-dimethylaminopyridine; the organic solvent in step 1 is one or more of dimethylacetamide and dimethylformamide; the perfluoropolyether alcohol in step 1 The molar number is 1 equivalent, the amount of the base is 1.5-5 equivalents, the fluorinated aromatic ring compound is 0.5-2 equivalents, and the molecular weight of the perfluoropolyether group is 1000-10000; the organic solvent in the step 2 is one or more of tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, acetone, and methyl ethyl ketone; the fluorine-containing solvent in the steps 1 and 2 is one or more of nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, tridecafluorohexyl methyl ether, tridecafluorohexyl ethyl ether, and m-trifluorotoluene.

[0020] Furthermore, in the step three, the molar number of double bonds in the Ar-Rf compound is 1 equivalent, and the alkoxysilane is 1-3 equivalents; the alkoxysilane is a non-substituted alkoxysilane; the platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is chloroplatinic acid, di(1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane) platinum; the fluorine-containing solvent is one or more of m-ditrifluorotoluene, perfluorobutyl methyl (ethyl) ether, and perfluorohexyl methyl (ethyl) ether; the anti-transposition agent is methyltriacetoxysilane, the molar number of double bonds in the Ar-Rf compound is 1 equivalent, and the methyltriacetoxysilane is 0.01-1 equivalent.

[0021] Furthermore, the surface treatment agent for any of the above-mentioned perfluoropolyether siloxane compounds containing a fluorescent marker structure contains 0.1-30 wt% of the perfluoropolyether siloxane compound containing a fluorescent marker structure, and the remaining components are fluorine solvents; the fluorine solvent is one or more of nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, tridecafluorohexyl methyl ether, tridecafluorohexyl ethyl ether, and m-ditrifluorotoluene.

[0022] Furthermore, the film of the surface treatment agent of the perfluoropolyether siloxane compound containing the fluorescent labeling structure.

[0023] Furthermore, the method for preparing a film using the surface treatment agent of the perfluoropolyether siloxane compound containing a fluorescent marker structure is a wet coating method or a vapor deposition method; the wet coating method is to dilute the surface treatment agent of the perfluoropolyether siloxane compound containing a fluorescent marker structure with a fluorine solvent to a diluent with a concentration of 0.1-0.5 wt%, and then apply or spray it on a plasma-treated substrate, and then heat and cure it, and obtain the film after cooling, wherein the heating and curing temperature is 80-150 ° C, and the baking time is 10-60 min, wherein the fluorine solvent is one or more of perfluorobutyl methyl (ethyl) ether, perfluorohexyl methyl (ethyl) ether, m-ditrifluorotoluene, perfluorohexane, and perfluorooctane; the vapor deposition method is to prepare the surface treatment agent of the perfluoropolyether siloxane compound containing a fluorescent marker structure into pills, load it on a SiO2-deposited substrate through a vapor deposition machine, and cure it to form a uniform surface coating to obtain the film.

[0024] Furthermore, the substrates in the wet coating method or the vapor deposition method are all silicate glass, borosilicate glass, tempered glass, quartz glass or sapphire glass.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] (1) The compound with fluorescent marking function of the present invention has multiple functions such as anti-fingerprint, anti-fouling, aesthetics, quality inspection and anti-counterfeiting. After being applied to the surface of the substrate and cured into a film, it has a water contact angle of 110-115°, which can facilitate the quality inspection of the substrate coating.

[0027] (2) A perfluoropolyether siloxane compound containing a fluorescent labeling structure synthesized by the present invention is added in small amounts to a commercially available anti-fingerprint stock solution, and the resulting film has both high slipperiness and high wear resistance as well as fluorescent labeling properties.

[0028] (3) The perfluoropolyether siloxane compound containing a fluorescent labeling structure synthesized by the present invention has the advantages of simplified synthesis process steps and good economy. Its advantages are mainly manifested in that: the materials involved in the synthesis are all conventional products on the market and are easy to obtain; the preparation process uses some conventional chemical reactions and the reaction temperature is between 10-50 °C, and the conditions are mild and easy to control; the product synthesis requires fewer steps, the separation and purification steps are relatively simple, and the production cost is more advantageous. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The H of the perfluoropolyether single-end alcohol (A) with a fluorescent effect group prepared in Synthesis Example 1 1 -NMR spectrum;

[0030] Figure 2 is the H of the perfluoropolyether olefin Ar-Rf compound (B) prepared in Synthesis Example 1 1 -NMR spectrum;

[0031] Figure 3 is the H of the Ar-Rf-Si compound (C) prepared in Synthesis Example 1 1 -NMR spectrum. DETAILED DESCRIPTION

[0032] The present invention is further illustrated below in conjunction with specific examples. The examples are implemented based on the technical solutions of the present invention. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0033] The materials and reagents used in the following examples are as follows:

[0034] Perfluoropolyether di-terminal alcohol (average molecular weight 4000) was purchased from Solvay. 1, 3-Bis(trifluoromethyl)benzene (99.5%) was purchased from Zhengzhou Alpha Chemical Co., Ltd. 3-Propylene bromide, hexafluorobenzene, octafluoronaphthalene, perfluorobiphenyl, trimethoxysilane, potassium carbonate, N, N-dimethylformamide, N, N-diisopropylethylamine, methyltriacetoxysilane, and bis(1, 3-divinyl-1,1, 3, 3-tetramethyldisiloxane) platinum were purchased from Shanghai Titan Technology Co., Ltd. Nonafluorobutyl ethyl ether was purchased from Novec HFE-7200 manufactured by 3M. Chemically strengthened glass was purchased from Corning Gorilla Glass, with a thickness of 0.7 mm.

[0035] The materials and reagents used in the following comparative examples 1, 2 and 3 are as follows:

[0036] Commercially available anti-fingerprint stock solution: Optool UD509 (purchased from Daikin)

[0037] The control compound 1 is:

[0038] CF3(OCF2CF2) 22 (OCF2) 20 OCF2CH2OCH2CH2CH2Si(OCH3)3, this compound is synthesized with reference to the existing patent CN102666759B.

[0039] The control compound 2 is:

[0040] (CH3O)3SiCH2CH2CH2OCH2CF2(OCF2CF2) 22 (OCF2) 20 OCF2CH2OCH2CH2CH2Si(OCH3)3, the compound is synthesized with reference to the existing patent CN 102666759B

[0041] Synthesis example 1

[0042] Step 1: Preparation method of perfluoropolyether single-end alcohol (A) having fluorescent effect group

[0043] In a 500 mL round-bottom flask equipped with a magnetic stirrer, 100.0 g of perfluoropolyether alcohol was dissolved in 150 mL of m-ditrifluorotoluene and 100 mL of dimethylacetamide mixed solvent, and 15.3 g of potassium carbonate was added, and stirred in an oil bath at 70 °C. 20.7 g of hexafluorobenzene dissolved in 30 mL of m-ditrifluorotoluene was added dropwise using a constant pressure dropping funnel, and after the addition was completed, the reaction was carried out at 70 °C for 24 h. The following perfluoropolyether single-end alcohol (A) with a fluorescent effect group was obtained by extraction, vacuum concentration, and separation on a silica gel column. The NMR spectrum is shown in FIG. Figure 1 shown.

[0044] Perfluoropolyether single-end alcohol with fluorescent effect group (A):

[0045]

[0046] Step 2: Preparation method of perfluoropolyether olefin Ar-Rf compound (B)

[0047] In a 250 mL round-bottom flask equipped with a magnetic stirrer, 20.0 g of a perfluoropolyether single-end alcohol (A) with a fluorescent effect group was dissolved in a mixed solvent of 30 mL of m-ditrifluorotoluene and 10 mL of ethylene glycol dimethyl ether, and then 1.7 g of a 40 wt% aqueous solution prepared with potassium hydroxide was added, stirred at room temperature for 1 h, 2.5 g of 3-bromopropylene was added, and stirred at 50 ° C for 2 h. After extraction and vacuum concentration, a perfluoropolyether olefin Ar-Rf compound (B) was obtained. The NMR spectrum is shown in FIG. Figure 2 shown.

[0048] Perfluoropolyether olefin Ar-Rf compound (B):

[0049]

[0050] Step 3: Preparation of Ar-Rf-Si compound (C)

[0051] In a 250 mL round-bottom flask equipped with a magnetic stirrer, 10.0 g of Ar-Rf compound (B) was dissolved in 15 mL of m-ditrifluorotoluene solvent, 1.2 g of trimethoxysilane and 0.11 g of methyltriacetoxysilane were added, and 10 μL of platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex was added under argon protection at 50 °C, and the reaction was continued for 2 h. The TLC spot plate determined that the reaction was complete and the liquid was extracted and concentrated under reduced pressure to obtain Ar-Rf-Si compound (C). The NMR spectrum is shown in Figure 3 shown.

[0052] Ar-Rf-Si compound (C):

[0053]

[0054] Synthesis example 2

[0055] Step 1: Preparation method of perfluoropolyether single-end alcohol (D) with fluorescent effect group

[0056] In a 500 mL round-bottom flask equipped with a magnetic stirrer, 100.0 g of perfluoropolyether alcohol was dissolved in 150 mL of m-ditrifluorotoluene and 100 mL of dimethylacetamide mixed solvent, and 15.3 g of potassium carbonate was added, and stirred in an oil bath at 70 °C. 37.1 g of perfluorobiphenyl dissolved in 30 mL of m-ditrifluorotoluene was added dropwise using a constant pressure dropping funnel, and after the addition was completed, the reaction was carried out at 70 °C for 24 h. The following perfluoropolyether single-end alcohol (D) with a fluorescent effect group was obtained by extraction, vacuum concentration, and separation on a silica gel column.

[0057] Perfluoropolyether mono-end alcohol with fluorescent effect group (D):

[0058]

[0059] Step 2: Preparation method of perfluoropolyether olefin Ar-Rf compound (E)

[0060] In a 250 mL round-bottom flask equipped with a magnetic stirrer, 20.0 g of a perfluoropolyether single-end alcohol (D) having a fluorescent effect group was dissolved in a mixed solvent of 30 mL of m-ditrifluorotoluene and 10 mL of ethylene glycol dimethyl ether, and then 1.6 g of a 40 wt% aqueous solution prepared by potassium hydroxide was added. The mixture was stirred at room temperature for 1 h, and 2.3 g of 3-bromopropylene was added. The mixture was stirred and reacted at 50 °C for 2 h. The perfluoropolyether olefin Ar-Rf compound (E) was obtained by extraction and concentration under reduced pressure.

[0061] Perfluoropolyether olefin Ar-Rf compound (E):

[0062]

[0063] Step 3: Preparation of Ar-Rf-Si compound (F)

[0064] In a 250 mL round-bottom flask equipped with a magnetic stirrer, 10.0 g of Ar-Rf compound (E) was dissolved in 15 mL of m-ditrifluorotoluene solvent, 1.1 g of trimethoxysilane and 0.10 g of methyltriacetoxysilane were added, and 10 μL of platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex was added under argon protection at 50 °C, and the reaction was continued for 2 h. The TLC plate was used to judge that the reaction was complete and the liquid was extracted and concentrated under reduced pressure to obtain Ar-Rf-Si compound (F).

[0065] Ar-Rf-Si compound (F):

[0066]

[0067] Synthesis example 3

[0068] Step 1: Preparation method of perfluoropolyether single-end alcohol (G) with fluorescent effect group

[0069] In a 500 mL round-bottom flask equipped with a magnetic stirrer, 10.0 g of perfluoropolyether alcohol was dissolved in 15 mL of m-ditrifluorotoluene and 10 mL of dimethylacetamide mixed solvent, and 15.3 g of potassium carbonate was added, and stirred in an oil bath at 70 °C. 3.0 g of octafluoronaphthalene dissolved in 3 mL of m-ditrifluorotoluene was added dropwise using a constant pressure dropping funnel, and after the addition was completed, the reaction was carried out at 70 °C for 24 h. The following perfluoropolyether single-end alcohol (G) with a fluorescent effect group was obtained by extraction, vacuum concentration, and separation through a silica gel column.

[0070] Perfluoropolyether mono-end alcohol with fluorescent effect group (G):

[0071]

[0072] Step 2: Preparation method of perfluoropolyether olefin Ar-Rf compound (H)

[0073] In a 250 mL round-bottom flask equipped with a magnetic stirrer, 20.0 g of a perfluoropolyether single-end alcohol (G) having a fluorescent effect group was dissolved in a mixed solvent of 30 mL of m-ditrifluorotoluene and 10 mL of ethylene glycol dimethyl ether, and then 1.6 g of a 40 wt% aqueous solution prepared by potassium hydroxide was added, and the mixture was stirred at room temperature for 1 h. 2.4 g of 3-bromopropylene was added, and the mixture was stirred at 50 °C for 2 h. The mixture was extracted and concentrated under reduced pressure to obtain a perfluoropolyether olefin Ar-Rf compound (H).

[0074] Perfluoropolyether olefin Ar-Rf compound (H):

[0075]

[0076] Step 3: Preparation of Ar-Rf-Si compound (I)

[0077] In a 250 mL round-bottom flask equipped with a magnetic stirrer, 10.0 g of Ar-Rf compound (H) was dissolved in 15 mL of m-ditrifluorotoluene solvent, 1.1 g of trimethoxysilane and 0.10 g of methyltriacetoxysilane were added, and 10 μL of platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane complex was added under argon protection at 50 °C, and the reaction was continued for 2 h. The reaction was complete when the TLC plate was used to extract the separated liquid, and the liquid was concentrated under reduced pressure to obtain Ar-Rf-Si compound (I).

[0078] Ar-Rf-Si compound (I):

[0079]

[0080] Example 1

[0081] The Ar-Rf-Si compound (C) obtained in Synthesis Example 1 was dissolved in 3M™ Novec™ 7200 at a concentration of 20 wt %, thereby preparing a surface treatment agent 1.

[0082] The surface treatment agent 1 is deposited onto the chemically strengthened glass by vacuum deposition. -3 Pa, firstly, silicon dioxide was deposited on the chemically strengthened glass with a thickness of 10 nm by electron beam evaporation to form a silicon dioxide film, and then about 2 mg of the above-mentioned surface treatment agent, i.e., 0.4 mg of compound C, was deposited on each piece of chemically strengthened glass (55 mm×100 mm) by vacuum deposition. The chemically strengthened glass with the deposited film was then placed in an environment of 60% humidity and 70°C for 2 h for curing to form a thin film.

[0083] Example 2

[0084] The surface treatment agent 2 was prepared in the same manner as in Example 1, except that the Ar—Rf—Si compound (F) obtained in Synthesis Example 2 was used instead of the Ar—Rf—Si compound (C).

[0085] Example 3

[0086] The surface treatment agent 3 was prepared in the same manner as in Example 1, except that the Ar—Rf—Si compound (I) obtained in Synthesis Example 3 was used instead of the Ar—Rf—Si compound (C).

[0087] Embodiment 4-6

[0088] Surface treatment agents 4-6 were prepared by adding 5% by mass of surface treatment agents 1-3 to the commercially available Optool UD509 stock solution.

[0089] The method for preparing the surface treatment agents 4-6 into thin films is the same as that in Example 1.

[0090] Comparative Example 1

[0091] The commercially available Optool UD509 stock solution was prepared into a thin film in the same manner as in Example 1.

[0092] Comparative Example 2

[0093] The control compound 1 was dissolved in 3M™ Novec™ 7200 at a concentration of 20 wt % to prepare a surface treatment agent 7, and the surface treatment agent 7 was prepared into a film in the same manner as in Example 1.

[0094] Comparative Example 3

[0095] The control compound 2 was dissolved in 3M™ Novec™ 7200 at a concentration of 20 wt % to prepare a surface treatment agent 7, and the surface treatment agent 7 was prepared into a film in the same manner as in Example 1.

[0096] Next, the surface treatment layer formed on the surface of the substrate was evaluated by the following method. The results are shown in Table 1-2.

[0097] 1. Evaluation of hydrophobicity and oleophobicity

[0098] The surface of the glass substrate sample produced by the coating and baking treatment of the above-mentioned embodiment and comparative example samples was measured using a contact angle meter (SDC-100, manufactured by Dongguan Shengding Precision Instrument Co., Ltd.) to measure the contact angle of the surface treatment layer to water and the contact angle of n-hexadecane. The measurement uncertainty was ±1.3°.

[0099] 2. Determination of Slipperiness

[0100] The dynamic friction coefficient of the product relative to the public paper (Daboai) was tested using a friction coefficient tester (Jinan Nanguang Dynamic and Static Friction Tester, FPT-F1) under the following conditions.

[0101] Contact area: 20 mm × 20 mm;

[0102] Load: 200 g;

[0103] Line speed: 200 mm / min;

[0104] Stroke: 35 mm.

[0105] 3. Fluorescence effect evaluation

[0106] The light source module adopts a 254 nm wavelength ultraviolet LED and is equipped with an adjustable light intensity function. It can evenly illuminate the detection area and is suitable for coatings of various surface morphologies. It has a fluorescent effect (√) and does not have a fluorescent effect (×).

[0107] 4. Wear resistance evaluation

[0108] The water contact angle of the surface treatment layer after rubbing was evaluated using a friction tester (Dongguan Dazhong Instrument Co., Ltd., DZ-204-1) under the following conditions.

[0109] The water contact angle is measured every 3,000 times (the evaluation is terminated when the water contact angle is less than 100 degrees or the steel wool is rubbed for 20,000 times or is damaged).

[0110] Steel wool: BONSTAR#0000;

[0111] Load: 1 kg / cm 2 ;

[0112] Travel distance: 40 mm;

[0113] Moving speed: 60 rpm.

[0114] The test results of hydrophobicity, oleophobicity, slipperiness and fluorescence effect are shown in Table 1.

[0115] Table 1 Hydrophobicity, oleophobicity, slipperiness and fluorescence effect

[0116]

[0117] The steel wool wear resistance is shown in Table 2.

[0118] Table 2 Steel wool abrasion resistance

[0119]

[0120] It can be seen from the above examples that the surface treatment agent prepared by the perfluoropolyether siloxane compound of the present invention enables the glass substrate treated therewith to have excellent anti-fouling, anti-fingerprint, scratch resistance, wear resistance and fluorescent effect performance, and its comprehensive performance is better than that of commercially available products.

[0121] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A perfluoropolyether siloxane compound containing a fluorescent labeling structure, characterized in that: Its structural formula is: Ar-RX; In the structural formula, Ar is a fluorinated aromatic ring, including hexafluorobenzene, octafluoronaphthalene, and perfluorobiphenyl; R is -L-Rf-, L is a divalent organic group, Rf is F(CF2) m -(OCF2) p -(OC2F4) q -(OC3F6) r -(OC4F8) s- OC(Z)F(CF2) n -, wherein p, q, r and s are independently and are integers of 0-50, the sum of p, q, r and s is not less than 1, the order and quantity of the repeating units with p, q, r and s enclosed in brackets are arbitrary in the formula, m and n are integers of 0-30, and Z is F or CF3; X is -OCH2CH2CH2X1, wherein X1 is -SiR 1 3. R 1 It is a group that can be hydrolyzed to -OH.

2. The perfluoropolyether siloxane compound containing a fluorescent labeling structure according to claim 1, characterized in that: The L is -O-CH2-; R 1 For-OR 2 , R 2 It is a C1-C4 alkyl group.

3. The perfluoropolyether siloxane compound containing a fluorescent labeling structure according to claim 1, characterized in that: In the molecular formula of Rf, the sum of p, q, r and s is an integer of 10-100, and m and n are independently an integer of 1-3.

4. The method for preparing a perfluoropolyether siloxane compound containing a fluorescent labeling structure according to any one of claims 1 to 3, characterized in that: The preparation steps are as follows: Step 1: Introduction of fluorinated aromatic rings: The perfluoropolyether alcohol is first dissolved with a fluorinated solvent and an organic solvent, and under alkaline conditions, a fluorinated solvent is added dropwise to dissolve the fluorinated aromatic ring compounds, and the single-ended perfluoropolyether alcohol compounds containing fluorinated aromatic rings are separated by a silica gel column; Step 2: Preparation of Ar-Rf compound: The perfluoropolyether alcohol compound containing fluorinated aromatic ring is first dissolved in a fluorinated solvent and an organic solvent, 3-bromopropylene is added dropwise under alkaline conditions, and the solvent is removed by rotary evaporation to obtain the Ar-Rf compound; Step 3: Preparation of Ar-Rf-Si compound: Dissolve the Ar-Rf compound obtained in the above step 2 in a fluorine-containing solvent, add alkoxysilane and an anti-translocation agent, add platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane complex under argon protection, extract and separate, and concentrate by rotary evaporation to obtain the Ar-Rf-Si compound.

5. The method for preparing a perfluoropolyether siloxane compound containing a fluorescent labeling structure according to claim 4, characterized in that: The base in step 1 and step 2 is an inorganic base or an organic strong base, the inorganic base is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, sodium alcoholate, potassium alcoholate, and ammonia water; the organic strong base is one or more of triethylamine, diisopropylethylamine, and 4-dimethylaminopyridine; the organic solvent in step 1 is one or more of dimethylacetamide and dimethylformamide; the molar number of perfluoropolyether alcohol in step 1 is The amount of the base is 1.5-5 equivalents, the amount of the fluorinated aromatic ring compound is 0.5-2 equivalents, and the molecular weight of the perfluoropolyether group is 1000-10000; the organic solvent in the step 2 is one or more of tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, acetone, and methyl ethyl ketone; the fluorinated solvent in the steps 1 and 2 is one or more of nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, tridecafluorohexyl methyl ether, tridecafluorohexyl ethyl ether, and m-ditrifluorotoluene.

6. The method for preparing a perfluoropolyether siloxane compound containing a fluorescent labeling structure according to claim 4, characterized in that: In the step 3, the molar number of double bonds in the Ar-Rf compound is 1 equivalent, and the alkoxysilane is 1-3 equivalents; the alkoxysilane is a non-substituted alkoxysilane; the platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is chloroplatinic acid, di(1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane) platinum; the fluorine-containing solvent is one or more of m-ditrifluorotoluene, perfluorobutyl methyl (ethyl) ether, and perfluorohexyl methyl (ethyl) ether; the anti-transposition agent is methyltriacetoxysilane, the molar number of double bonds in the Ar-Rf compound is 1 equivalent, and the methyltriacetoxysilane is 0.01-1 equivalent.

7. A surface treatment agent comprising the perfluoropolyether siloxane compound containing a fluorescent labeling structure according to any one of claims 1 to 4, characterized in that: The surface treatment agent contains 0.1-30 wt% of the perfluoropolyether siloxane compound containing a fluorescent marker structure, and the remaining components are fluorine solvents; the fluorine solvents are one or more of nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, tridecafluorohexyl methyl ether, tridecafluorohexyl ethyl ether, and m-ditrifluorotoluene.

8. A film of a surface treatment agent of a perfluoropolyether siloxane compound containing a fluorescent labeling structure according to claim 7.

9. The method for preparing a film using a surface treatment agent of a perfluoropolyether siloxane compound containing a fluorescent labeling structure according to claim 8, characterized in that: The method is a wet coating method or a vapor deposition method; the wet coating method is to dilute the surface treatment agent of the perfluoropolyether siloxane compound containing a fluorescent marker structure with a fluorine solvent to a diluent with a concentration of 0.1-0.5 wt%, then coat or spray it on a substrate treated with plasma, and then heat and cure it, and obtain the film after cooling, wherein the heating and curing temperature is 80-150°C, and the baking time is 10-60 min, wherein the fluorine solvent is one or more of perfluorobutyl methyl (ethyl) ether, perfluorohexyl methyl (ethyl) ether, m-trifluorotoluene, perfluorohexane, and perfluorooctane; the vapor deposition method is to prepare the surface treatment agent of the perfluoropolyether siloxane compound containing a fluorescent marker structure into a pill, load it on a substrate deposited with SiO2 through a vapor deposition machine, and cure to form a uniform surface coating to obtain the film.

10. The method for preparing a film using a surface treatment agent of a perfluoropolyether siloxane compound containing a fluorescent labeling structure according to claim 9, characterized in that: The substrates in the wet coating method or the vapor deposition method are all silicate glass, borosilicate glass, tempered glass, quartz glass or sapphire glass.

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