WO2021004286A1

WO2021004286A1 - Compound, preparation method therefor, use thereof, and composition composed of same

Info

Publication number: WO2021004286A1
Application number: PCT/CN2020/098080
Authority: WO
Inventors: 李义涛; 曾永昌; 刘群方; 侯琴卿; 王建; 卢灿江
Original assignee: 东莞东阳光科研发有限公司
Priority date: 2019-07-09
Filing date: 2020-06-24
Publication date: 2021-01-14
Also published as: CN112673050B; CN112673050A

Abstract

Disclosed are a compound, a preparation method therefor, the use thereof, and a composition containing the compound. The compound has formula (I), or the following replacements are made on the basis of compound (I): each A can be replaced with formula (aa), and all As in the compound can be replaced with formula (aa), wherein the number of A contained in the compound is an integer between 2 and 32, and A has formula (bb); Rf has formula (cc), wherein n is an integer of 1-30; and R₁ is a C₁-C₅ alkylene group. The compound solves the problem of existing fingerprint-resistant agents having poor wear resistance and poor practicality.

Description

A compound and its preparation method, use and composition

Technical field

The present invention relates to the field of compounds, in particular to a compound and its preparation method, use and composition.

Background technique

As a special surface modifier, the anti-fingerprint agent is widely used on the surface of touch screens. It not only gives the surface of the substrate excellent water and oil resistance, but also the coating has a low coefficient of friction. It is not easy to cause damage to the surface of the substrate when wiping. . At present, the main component of anti-fingerprint agent is perfluoropolyether with siloxane group. The perfluoropolyether polymer has excellent thermal stability, chemical inertness, environmental protection and harmlessness, and its water and oil resistance performance is excellent, so It is widely used in various material protection agents and aviation lubricants.

The synthesis of anti-fingerprint agents in the prior art usually adopts hydrosilylation reaction, and anti-fingerprint agents with different structures are prepared through hydrosilylation of perfluoropolyether compounds and functional silane coupling agents. Use fluorine-containing solvents (such as HFE-7100, HFE-7200, etc.) to dissolve the anti-fingerprint agent before use. When the anti-fingerprint agent is used, the silanol group hydrolyzed from the terminal siloxane group is dehydrated and condensed with the hydroxyl group on the surface of the substrate under high temperature or under a catalyst to form a strong chemical bond, thereby giving the coating excellent wear resistance.

For example, patent application CN101151269A uses perfluoropolyether allyl ether compound and trichlorosilane to undergo hydrosilylation reaction under the action of a catalyst, and then through methoxylation to obtain a perfluoropolyether single-ended siloxane anti-fingerprint agent ; Patent application CN101189278 A adopts perfluoropolyether allyl ether compound in sequence with tetramethyldisiloxane and vinyldisiloxane to obtain perfluoropolyether single-end siloxane anti-fingerprint agent. The two anti-fingerprint agents have good water and oil repellent effects, but their abrasion resistance has not been tested.

Patent application CN106085227A pointed out that perfluoropolyether siloxane as an anti-fingerprint agent, if there is only a single hydrolyzable group at the end, its friction durability is problematic. For this reason, the patent has synthesized a comb containing multiple siloxane groups. The anti-fingerprint agent can withstand 5000 times of BONSTAR0000# steel wool grinding, but the anti-fingerprint agent molecule uses hydrogen-containing silicone oil as the carrier, its molecular weight is difficult to control, and its practicality is poor.

Patent application WO2017155787 uses perfluoropolyether alcohol to react with glycidyl ether to prepare comb polyol, and then allylation and hydrosilylation to obtain comb structure perfluoropolyether siloxane. The anti-fingerprint agent is resistant to Abrasiveness is less than 5000 times of steel wool rubbing.

In summary, the existing anti-fingerprint agents have poor friction resistance. Even though some anti-fingerprint agents have good friction resistance, their practicability cannot meet actual needs and are difficult to be industrially applied. In addition, the existing anti-fingerprint agents are dissolved in fluorine-containing solvents. higher cost.

Summary of the invention

The first object of the present invention is to provide a compound, which contains perfluoropolyether units and siloxane units, and the siloxane units are distributed in a dendritic manner and occupy a relatively large proportion. Therefore, it is not only good for anti-fingerprint agents, It has water and oil resistance and abrasion resistance, and has good solubility. It can be dissolved in both fluorine-containing solvents and mixed solvents composed of fluorine-containing solvents and conventional solvents, which greatly reduces the cost.

The second object of the present invention is to provide a method for preparing the above compound, which has the advantages of simple route, few by-products, safe reagents, safe operation, easy availability of raw materials, low cost, high yield, etc., and is suitable for industrial promotion.

In order to achieve the above objectives, the present invention provides the following technical solutions:

A compound which is:

Or make the following substitutions based on compound (I):

Each A can be replaced by

And all A in the compound can be replaced with

The number of A in the compound is an integer between 2 and 32;

A is

Rf is

Wherein n is an integer from 1 to 30;

R ₁ is a C ₁ -C ₅ alkylene group.

In the present invention, "the number of compounds containing A" refers to the number of A unit groups in the compound, which can be 2, 3, 4, 5, 6, 7, 8, 9. 1, 10, 12, 14, 16, 18, 20, 22, 23, 26, 28, 30 or 32, etc. The number of the compound containing A is preferably 2 ^m , m=1, 2, 3, 4 or 5.

In the present invention, the replacement of A refers to a continuous and progressive replacement based on the general formula (I), and the number of progression is 1, 2, 3, or 4. Within the preferred range of the number of A in the compound, the more the number of replacements (or the number of advancements), the more the distribution of siloxane branches and the better the abrasion resistance exhibited when used as an anti-fingerprint agent. The reason why the compound of the present invention has good abrasion resistance is: on the one hand, it contains multiple ether bond structures, which improves the flexibility of the molecule, and is easier to stretch under external friction, which is beneficial to improve the abrasion resistance; On the one hand, the introduction of multiple siloxane groups into the molecule, which is distributed in a dendritic shape, increases the number of siloxane groups in the molecule, making it easier to react with the hydroxyl groups on the surface of the substrate, thereby enabling stronger adsorption On the surface of the substrate, the wear resistance is greatly improved.

In addition, when replacing progressively, you can choose to replace all A or part of A with

It is preferable to replace all A with

In the present invention, R ₁ can be -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -or -CH _2- CH ₂ -CH ₂ -CH ₂ -CH ₂ -, or isomers of the above groups, preferably straight chain. In the present invention

Represents the location of the broken key.

Specifically, the compound of the present invention may have the following molecular formula:

Wherein, Rf, R ₁ and A have the meanings according to the present invention.

Formula (I), Formula (I-1a), Formula (I-2), Formula (I-2a), Formula (I-3), Formula (I-3a), Formula (I-3b), Formula (I-4), formula (I-4a), formula (I-4b), formula (I-4c), formula (I-5) and compounds not listed herein but fall into general formula (I) In other specific compounds, n each independently is optionally an integer of 1-30, such as 1, 5, 10, 15, 20, 25, 30, etc., and a preferred range is an integer of 5-30.

On the other hand, the present invention provides a composition comprising formula (I), formula (I-1a), formula (I-2), formula (I-2a), formula (I-3 ), formula (I-3a), formula (I-3b), formula (I-4), formula (I-4a), formula (I-4b), formula (I-4c) or formula (I-5) At least one compound shown.

In some embodiments, the average degree of polymerization of all the compounds in the composition is 1-30.

Preferably, the average degree of polymerization of all the compounds in the composition is 5-30.

The above-mentioned compound of the present invention contains perfluoropolyether units and siloxane units, has good water and oil repellency, and has strong adhesion on substrates modified with hydroxyl groups, so it can be used as anti-fingerprint agents, lubricants, and moisture-proof Agents and other fields. When it is used as an anti-fingerprint agent, since the siloxane units in the molecule are distributed in a dendritic shape, it accounts for a relatively large proportion, and can exhibit more excellent wear resistance.

The above-mentioned compounds of the present invention can be prepared by conventional synthetic routes in the art, but the following method is preferably used. If the number of A in the compound is 2, the following steps are included:

Step a: Compound (II) undergoes a ring-opening addition reaction with glycidol to produce compound (III);

Step b: Compound (III) undergoes substitution reaction with allyl bromide to produce compound (IV);

Step c: Compound (IV) undergoes a hydrosilylation reaction with trichlorosilane to produce compound (V);

Step d: Compound (V) undergoes a Grignard reaction with allyl magnesium bromide to form compound (VI);

Step e: Compound (VI) undergoes a hydrosilylation reaction with trimethoxysilane to generate compound (I);

If the number of A in the compound is 2 ^m and m = 2, 3, 4 or 5, the following steps are included:

Using the step a as a repeating unit, repeat m times, and each repetition is the product obtained from the previous repetition as the raw material for the addition reaction of step a; then, the final product after the repetition is used as the raw material, and then the Steps b, c, d, e to obtain the targets (I-2), (I-3), (I-4) and (I-5) respectively;

When the number of the compound containing A is between 2 and 32 other than 2, 4, 8, 16, and 32, the material ratio in step a is controlled to make it incompletely reacted (for example, glycidol After reacting with compound (II) in a molar ratio of 1:1 to 1.1:1 to obtain compound (III), compound (III) is used as the starting material to repeat step a again, so that the molar ratio of compound (III) to glycidol is 1:1, react to obtain trihydroxyperfluoropolyether glycerol), and then step b, c, d, e to obtain the target;

As mentioned above, the present invention mainly involves four types of chemical reactions (step c and step e are both hydrosilylation reactions). There is no problem that the more complex the structure of the compound, the more complex the reaction type, and the same reaction can be obtained by repeating the same reaction. Complex structure compounds.

The method takes into account factors such as reactivity, raw material cost, difficulty in obtaining materials, efficiency, safety, etc., and has the advantages of simple route, few by-products, safe reagents, safe operation, easy availability of raw materials, low cost, high yield, etc., so it is suitable for industrialization Promotion.

The compound (II) used in the step a can be a commercially available or self-made product, and the compound (II) can be prepared by referring to any one of the methods in Example 1 to Example 5 in CN110857263A.

The present invention also optimizes the reaction conditions of step a to step e, which are specifically as follows.

Preferably, the Grignard reaction process in step d is:

First, the compound (V) is reacted with the allyl magnesium bromide solution under ice bath conditions for 2 to 4 hours, and then the temperature is raised to 50 to 70° C. for 2 to 4 hours, then the reaction is quenched, and then the product is separated.

The quenching in step d can select quenching agents such as methanol and ammonium chloride, preferably methanol. The concentration of the allyl magnesium bromide solution in this step is preferably 0.5 to 1.5 mol/L, such as 0.5M, 0.7M, 0.8M, 1.0M, 1.2M, 1.5M, and the like. The molar ratio of the allyl magnesium bromide to the compound (V) in this step is preferably 6.5:1-9:1, preferably 8:1. The temperature of the heating reaction in this step can be 50°C, 55°C, 60°C, 65°C, 70°C, etc. This step can choose filtration, rotary steaming, washing, distillation and other means to separate the products.

Preferably, the substitution reaction process in step b is:

Using a strong base as a catalyst, the compound (III) is reacted with allyl bromide in a fluorine-containing solvent at 50-70°C, and then the product is separated.

The strong base in step b can be sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium hydride (NaH), potassium carbonate or potassium tert-butoxide, etc., preferably sodium hydride, sodium hydroxide, potassium hydroxide One of them. The fluorine-containing solvent in this step refers to a fluorine-containing organic solvent, and 1,1,2-trifluorotrichloroethane, HFE-7100 (methyl nonafluorobutyl ether) and HFE-7200 (ethyl nonafluorobutyl ether) can be selected , Trifluorotrichloroethane, m-ditrifluorotoluene, perfluorohexane, etc., preferably methyl nonafluorobutyl ether. In this step, it is preferable to react compound (III) with sodium hydride for a period of time, and then add allyl bromide to react. The molar ratio of allyl bromide to compound (III) in the reaction is preferably 2.1:1 to 4:1. In this step, neutralization (using strong acids such as hydrochloric acid and sulfuric acid) can be used first, and then the products can be separated by means of extraction, washing or distillation. The washing solvent can be selected from one or a mixture of dichloromethane, ethanol, acetone, and methanol.

Preferably, the process of the ring-opening addition reaction in step a is:

First mix the compound (II) and the strong base in the fluorine-containing solvent (the optional order is to first add the compound (II) and the fluorine-containing solvent to the reaction vessel, then add the strong base, or change the order of addition), Add glycidol dropwise at 60-80°C, stir and react for 10-20h, and separate the product after the reaction.

In this step of the reaction, the fluorine-containing solvent is preferably a mixed solution of methyl nonafluorobutyl ether and trifluorotrichloroethane, and the volume ratio of the two is preferably 1:1.5 to 1.5:1.

The molar ratio of glycidol to compound (II) in this step is preferably 1:1 to 1.1:1. The strong base may be potassium tert-butoxide, sodium hydroxide (NaOH), sodium hydride (NaH), etc., preferably one of potassium tert-butoxide and NaH. The product can be neutralized first (using strong acids such as hydrochloric acid and sulfuric acid), and then separated by means such as extraction, washing or distillation. The washing solvent is preferably ethanol.

Preferably, the hydrosilylation reaction process in step c is:

Using Karstedt catalyst, the compound (IV) and trichlorosilane are reacted in a fluorine-containing solvent at 80-100° C., and then the product is separated.

The fluorine-containing solvent in step c can be m-ditrifluorotoluene, HFE-7100 (methyl nonafluorobutyl ether) and HFE-7200 (ethyl nonafluorobutyl ether), etc., preferably m-ditrifluorotoluene. In this step, a co-catalyst-methyltriacetoxysilane can also be selected, and the added amount is preferably 1% to 3% of the mass of compound (IV). The Karstedt catalyst is preferably a xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum with a platinum content of 2wt%. The amount of Karstedt catalyst used should be such that the platinum in the reaction system The mass content of the Karstedt catalyst reaches 60-100 ppm; specifically, the usage amount of Karstedt catalyst makes the mass content of platinum in the reactant be 60 ppm, 64 ppm, 65 ppm, 70 ppm, 74 ppm, 80 ppm, 84 ppm, 85 ppm, 90 ppm, 95 ppm or 100 ppm. The molar ratio of trichlorosilane to compound (IV) in this step is preferably 3:1 to 6:1. In this step, the Grignard reaction of step d can be directly carried out after the excess trichlorosilane is removed by distillation under reduced pressure.

Preferably, the hydrosilylation reaction process in step e is:

Using Karstedt catalyst, the compound (VI) is reacted with trimethoxysilane in a fluorine-containing solvent at 75-95°C, and then the product is separated.

The fluorine-containing solvent in step c can choose m-ditrifluorotoluene, HFE-7100 (methyl nonafluorobutyl ether), HFE-7200 (ethyl nonafluorobutyl ether), etc., preferably methyl nonafluorobutyl ether. In this step, a co-catalyst-methyl triacetoxysilane can also be selected, and the added amount is preferably 1% to 2% of the mass of compound (VI). The Karstedt catalyst is preferably a xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum with a platinum content of 2wt%. The amount of Karstedt catalyst used should be such that the platinum in the reaction system The mass content of the Karstedt catalyst reaches 60-100 ppm; specifically, the amount of Karstedt catalyst used should make the platinum content in the reaction system 60 ppm, 64 ppm, 65 ppm, 70 ppm, 74 ppm, 80 ppm, 84 ppm, 85 ppm, 90 ppm, 95 ppm or 100 ppm. The molar ratio of trimethoxysilane to compound (VI) in this step is preferably 6.5:1-9:1. In this step, filtration, washing, distillation and other means can be selected to separate the products.

When synthesizing an alternative to compound (I), that is, when the compound contains more A units, step a needs to be repeated, and the reaction conditions used during the repetition are the same as above.

The above-mentioned compounds of the present invention can be used alone or in a composition. Whether used alone or as a component of the composition, it can be used for water and oil repellency, and is typically used as an anti-fingerprint agent or lubricant.

When the above-mentioned compound of the present invention is used as an anti-fingerprint agent, it can not only be dissolved in a fluorine-containing solvent, but also can be dissolved in a mixed solvent. The mixed solvent is a mixture of a fluorine-containing solvent and a conventional organic solvent. The fluorine-containing solvent is a mixture of one or more of methyl nonafluorobutyl ether (HFE-7100), methyl nonafluoroethyl ether (HFE-7200), m-ditrifluorotoluene (HFX), etc. The conventional organic solvent is One of dichloromethane, acetone, ethyl acetate, cyclohexane, etc., and the volume ratio of the fluorine-containing solvent to the conventional organic solvent is 1:5 to 5:1.

In summary, compared with the prior art, the present invention achieves the following technical effects:

(1) A dendritic perfluoropolyether siloxane is provided, which has higher siloxane content and more siloxane branches, and is used as an anti-fingerprint agent with higher abrasion resistance ；

(2) A route for synthesizing dendritic perfluoropolyether siloxane was designed, which achieved fewer by-products, safe reagents, safe operation, easy availability of raw materials, low cost, and high yield with as few steps as possible. effect;

(3) Optimize the reaction conditions of each step in the synthetic route to shorten the reaction time, increase the yield or purity, or reduce the cost.

(4) Provides a molecular series of anti-fingerprint agents with better solubility to reduce the use of fluorine-containing solvents and reduce solvent costs.

Description of the drawings

By reading the detailed description of the preferred embodiments below, various other advantages and benefits will become clear to those of ordinary skill in the art. The drawings are only used for the purpose of illustrating the preferred embodiments, and are not considered as a limitation to the present invention. Also, throughout the drawings, the same reference symbols are used to denote the same components.

Figure 1 is the nuclear magnetic spectrum of the anti-fingerprint agent prepared in Example 1 of the present invention;

Figure 2 is the nuclear magnetic spectrum of perfluoropolyether alcohol (weight average molecular weight 4500, average polymerization degree 26.2);

Figure 3 is a nuclear magnetic spectrogram of the anti-fingerprint agent prepared in Example 2 of the present invention;

4 is a nuclear magnetic spectrum of the anti-fingerprint agent prepared in Example 7 of the present invention;

Figure 5 is a nuclear magnetic spectrum of the anti-fingerprint agent prepared in Comparative Example 1 of the present invention;

Figure 6 is a nuclear magnetic spectrum of the anti-fingerprint agent prepared in Comparative Example 2 of the present invention.

Detailed ways

The embodiments of the present invention will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. If specific conditions are not indicated in the examples, it shall be carried out in accordance with the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used without the manufacturer's indication are all conventional products that can be purchased commercially.

Example 1

(1) 100.0g (22.2mmol) of perfluoropolyether alcohol (weight average molecular weight 4500, average degree of polymerization of 26.2), 50mL methyl nonafluorobutyl ether and trifluorotrichloroethane mixed solution (volume ratio 1:1), 0.5g of potassium tert-butoxide (4.4mmol, 0.2equ) was added to a 250mL three-necked flask, equipped with a condenser reflux tube, mechanically stirred, slowly drop 1.7g (22.9mmol, 1.03equ) at 70℃ After 12 hours of reaction, the reaction was stopped, the reaction system was acidified with 1M hydrochloric acid, washed three times with water, three times with absolute ethanol, and distilled under reduced pressure at 80°C to obtain 97.8 g of perfluoropolyether glycerol ether with a yield of 96.3%. The reaction formula is:

(2) Under the protection of N ₂ , 97.8g (21.4mmol) of perfluoropolyether glycerol ether (weight average molecular weight 4574, average degree of polymerization of 26.2), 50mL methyl nonafluorobutyl ether and 1.2g (48.7mmol) Sodium hydride was added to a 250mL three-necked flask, stirred at 60°C for 2h, then 6.2g (51.3mmol, 2.4equ) of allyl bromide was added dropwise, the reaction was continued for 6h, then the reaction was stopped, and the reaction system was acidified with 1M hydrochloric acid. It was washed three times with water, three times with absolute ethanol, and distilled under reduced pressure at 90°C to obtain 91.6 g of perfluoropolyether diallyl ether with a yield of 92.1%. The reaction formula is:

(3) 40.0g (8.6mmol) of perfluoropolyether diallyl ether (weight average molecular weight 4654, average degree of polymerization of 26.2), 50g m-difluorotoluene, 0.5g methyl triacetoxy Silane, 0.3g of a xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum with a platinum content of 2wt% (the platinum content in the reaction system is 64ppm) and 3.5g (25.8mmol, 3equ) of trichlorosilane were added to a pressure bottle of 250mL, N ₂ protection, 90 deg.] C reaction 9h, 40 ℃ low boiling material removed by distillation under reduced pressure, to give 42.3g containing perfluoropolyether - tris Yellow reaction liquid of chlorosilane. The reaction formula is as follows.

(4) the (3) step comprising 42.3g (8.6mmol) perfluoropolyether - trichlorosilane yellow reaction solution was added to 250mL three-necked flask, a solution of 68.8mL (68.8mmol under N _2, the ice bath was , 8equ) 1M allyl magnesium bromide diethyl ether solution, stirred for 3h, heated to 60℃, refluxed for 3h, added methanol to quench the reaction, filtered, the filtrate was rotary evaporated and washed with acetone three times, and then distilled at 100℃ under reduced pressure. 38.1g of perfluoropolyether hexaallyl ether, yield 89.3%. The reaction formula is:

(5) 38.1g (7.7mmol) of perfluoropolyether hexaallyl ether (weight average molecular weight 4958, average degree of polymerization of 26.2), 50g methyl nonafluorobutyl ether, 0.6g methyl triacetoxy Silane and 0.4g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum with a platinum content of 2wt% in xylene solution (the platinum content in the reaction system is 84ppm) are added sequentially Put 6.6g (53.7mmol, 7equ) of trimethoxysilane in a 250mL three-necked flask under N ₂ protection, add 6.6g (53.7mmol, 7equ) of trimethoxysilane dropwise at 80℃, stir and react for 12h, filter on a funnel spread with diatomaceous earth, and remove the filtrate by rotary evaporation. The solvent was washed three times with anhydrous acetone and distilled under reduced pressure at 80°C to obtain 35.8 g of anti-fingerprint agent with a yield of 82.0%. The reaction formula is:

Where A is

The NMR spectrum of the anti-fingerprint agent obtained in Example 1 is shown in Figure 1, where 0.00 is the base peak of tetramethyl silicon, and Figure 2 is the raw material perfluoropolyether alcohol (weight average molecular weight 4500, average degree of polymerization is 26.2 ) NMR spectrum, where 1.36 and 2.1pm are the impurity peaks introduced by the solvent trifluorotrichloroethane.

Example 2

40.0 g (8.7 mmol) of perfluoropolyether glyceryl ether (weight average molecular weight 4574, average degree of polymerization of 26.2) was reacted according to steps (1) to (5) in Example 1 (referring to the same reaction conditions, for example Concentration of raw material type, temperature, etc.), to obtain 25.2 g of anti-fingerprint agent. The reaction process is as follows, and the total yield of the following reaction formula is 41.2%.

Where A is

The nuclear magnetic spectrum of the anti-fingerprint agent prepared in Example 2 is shown in FIG. 3.

Example 3

50.0 g of perfluoropolyether alcohol (weight average molecular weight 2060, average polymerization degree 11.5) was reacted according to steps (1) to (5) in Example 1 to obtain 47.5 g of anti-fingerprint agent, with a total yield of 60.2 %.

Example 4

20.0g of perfluoropolyether alcohol (weight average molecular weight 1500, average polymerization degree of 8.1) was reacted according to steps (1) to (5) in Example 1, to obtain 21.1g of anti-fingerprint agent, with a total yield of 58.8 %.

Example 5

60.0g of perfluoropolyether alcohol (weight average molecular weight 2060, average degree of polymerization is 11.5) was synthesized according to step (1) in Example 1, and then according to the reaction process in Example 2. 54.7 g of anti-fingerprint agent was obtained, with a total yield of 41.3% (referring to the yield of all reactions with perfluoropolyether alcohol as the starting reactant).

Example 6

30.0 g of perfluoropolyether alcohol (weight average molecular weight 1500, average degree of polymerization is 8.1) was synthesized according to step (1) in Example 1, and then according to the reaction process in Example 2. 34.5 g of anti-fingerprint agent was obtained, with a total yield of 43.2% (referring to the yield of all reactions with perfluoropolyether alcohol as the starting reactant).

Example 7

Prepared using the same method as in Example 2

Using this as a raw material, follow the steps (1) to (5) in Example 1 to react to synthesize an anti-fingerprint agent:

Where A is

The nuclear magnetic spectrum of the anti-fingerprint agent prepared in Example 7 is shown in FIG. 4.

Example 8

Using perfluoropolyether glycerol ether (weight average molecular weight 4574, average degree of polymerization of 26.2) as the raw material, the reaction was carried out according to the step (1) of Example 1, and repeated 4 times, and then the step (2) of Example 1 was repeated to The reaction of step (5) is carried out to prepare an anti-fingerprint agent:

Where A is

Example 9

Using perfluoropolyether glycerol ether (weight average molecular weight 4574, average degree of polymerization of 26.2) as the raw material, the reaction was carried out according to the step (1) of Example 1, and repeated 5 times, and then the step (2) of Example 1 was repeated to The reaction of step (5) is carried out to prepare an anti-fingerprint agent:

Where A is

Comparative example 1

Synthetic single-ended siloxane anti-fingerprint agent:

(1) Add 10.3 g (5.0 mmol) of perfluoropolyether alcohol (weight average molecular weight 2060, average degree of polymerization of 11.5), 10 mL of methyl nonafluorobutyl ether into a 100 mL two-necked flask, and then add 0.9 g (7.5mmol, 1.5equ) of allyl bromide and 0.4g of sodium hydroxide, install the condenser reflux tube, magnetically stir, react at 60℃ for 12h, acidify the reaction system with 1M hydrochloric acid, wash three times with water, and wash with absolute ethanol Three times, under reduced pressure distillation at 80°C, 10.0 g of perfluoropolyether allyl ether was obtained with a yield of 96.0%. The reaction formula is:

(2) 10.0 g (4.8 mmol) of perfluoropolyether allyl ether (weight average molecular weight 2100, average degree of polymerization of 11.5) obtained in (1), 15.0 g methyl nonafluorobutyl ether, 0.2 g Methyltriacetoxysilane and 0.1g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum with a platinum content of 2wt% in xylene (the platinum in the reaction system 74ppm) was added to a 100mL two-necked flask, N ₂ protection, and 1.8g (14.4mmol, 3equ) of trimethoxysilane was added dropwise at 80°C, stirred and reacted for 12h, on a funnel paved with diatomaceous earth After filtering, the filtrate was rotary evaporated to remove the solvent, washed with anhydrous acetone three times, and distilled under reduced pressure at 80°C to obtain 9.1 g of anti-fingerprint agent with a yield of 86%. The characteristic spectrum is shown in Figure 5, and the structural formula is as follows:

Comparative example 2

30.0g (4.4mmol) of perfluoropolyether alcohol (weight average molecular weight 4500, average degree of polymerization of 26.2), according to the step (1) of Comparative Example 1, to prepare perfluoropolyether allyl ether, and then according to the implementation Steps (3) to (5) in Example 1 were reacted to obtain 23.6 g of anti-fingerprint agent, with a total yield of 76.5% (referring to the yield of all reactions with perfluoropolyether alcohol as the starting reactant). The spectrum is as 6, and the structural formula is as follows:

The solubility properties of the anti-fingerprint agents prepared in the above examples and comparative examples are shown in Table 1.

Table 1 Solubility results of various anti-fingerprint agents

Note: The ratio of each solvent in the table is volume ratio

The test method of dissolution performance in Table 1 is:

The anti-fingerprint agent of the embodiment of the present invention or the comparative example is diluted with the solvent in Table 1 to prepare an anti-fingerprint agent diluent with a mass concentration of 20%.

The results in Table 1 show that the anti-fingerprint agent of the present invention can be dissolved in a mixed solvent composed of a fluorine-containing solvent and a conventional organic solvent, wherein the volume ratio of the fluorine-containing solvent and the conventional organic solvent is 1:5 to 5:1; preferably, The fluorine-containing solvent is any one of methyl nonafluorobutyl ether (HFE-7100), methyl nonafluoroethyl ether (HFE-7200), and m-ditrifluorotoluene (HFX); the conventional organic solvent is Any one of dichloromethane, acetone, ethyl acetate, and cyclohexane.

The performance of the anti-fingerprint agent prepared in the above examples and comparative examples is shown in Table 2.

Table 2 Performance characterization results of various anti-fingerprint agents (the average degree of polymerization in the table refers to the degree of polymerization of perfluoropolyether alcohol)

Test method of performance in Table 2:

The anti-fingerprint agent of the embodiment or the comparative example was diluted with a mixed solvent of 3M HFE-7100 and cyclohexane (the volume ratio of HFE-7100 to cyclohexane is 1:3) to prepare a mass concentration of 0.5% Diluent. The glass substrate is cleaned in advance with piranha lotion, washed and air-dried for later use. The pretreated glass slide was immersed in the diluted anti-fingerprint solution, soaked for 5 minutes, and then taken out, dried in an oven at 150°C for 30 minutes, and the glass cooled to room temperature was directly subjected to subsequent performance testing.

(1) Contact angle test: Use a contact angle tester to measure the contact angle of water and n-hexadecane. The measurement is carried out at room temperature, and the touch screen glass sample of the mobile phone to be tested is laid flat on the horizontal platform of the contact angle meter and fixed, and the droplet size is 5 μL.

(2) Oil pen stain resistance test

Use a commercially available ink pen to draw a blue line on the surface of the cured film of the glass screen of the mobile phone. According to the shrinkage of the blue ink, evaluate its stain resistance. The evaluation criteria are as follows:

Class C-no shrinkage, line,

Class B-Shrink to a dotted line,

Class A-Shrink to a point.

(3) Friction resistance test

Use #0000 steel wool to carry out friction resistance test with a load of 1kg on a steel wool friction tester, a friction distance of 5cm, a reciprocating friction treatment of 3000 to 5000 times, a friction frequency of 55 times/min, and a contact angle test after the friction treatment .

It can be seen from the data in Table 2 that the anti-fingerprint agent of the present invention has excellent anti-friction properties. In the preferred range of the anti-fingerprint agent compound of the present invention, the more siloxane groups contained in the anti-fingerprint agent under the same degree of polymerization, the better the friction resistance performance. When the number of siloxane branches is the same, the greater the degree of polymerization of the perfluoropolyether, the greater the initial contact angle, and the better the water and oil resistance.

The above only lists the modification of glass by the compound of the present invention, but the present invention does not limit the type of substrate. The present invention can also be used for surface modification of other materials such as ceramics and plastics.

The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or changes within the technical scope disclosed by the present invention. All replacements shall be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

A compound characterized in that it is:

Or make the following substitutions based on compound (I):

Each A can be replaced by
And all A in the compound can be replaced with

The number of A in the compound is an integer between 2 and 32;

A is

Rf is
Wherein n is an integer from 1 to 30;

R 1 is a C 1 -C 5 alkylene group.
The compound of claim 1, wherein n is an integer from 5 to 30;

Preferably, the number of A in the compound is 2 m , and m=1, 2, 3, 4 or 5.
The compound of claim 1 or 2, wherein it is:

or
The preparation method of the compound according to any one of claims 1 to 3, characterized in that, if the number of A in the compound is 2, it comprises the following steps:

Step a: Compound (II) undergoes a ring-opening addition reaction with glycidol to produce compound (III);

Step b: Compound (III) undergoes substitution reaction with allyl bromide to produce compound (IV);

Step c: Compound (IV) undergoes a hydrosilylation reaction with trichlorosilane to produce compound (V);

Step d: Compound (V) undergoes a Grignard reaction with allyl magnesium bromide to form compound (VI);

Step e: Compound (VI) undergoes a hydrosilylation reaction with trimethoxysilane to generate target compound (I);

If the number of A in the compound is 2 m and m = 2, 3, 4 or 5, the following steps are included:

Taking the step a as a repeating unit, repeat m times, and each repetition is to perform the ring-opening addition reaction of step a again with the product obtained from the previous repetition as the raw material; then, the final product after the repetition is used as the raw material, in sequence After the steps b, c, d, and e, the target compounds (I-2), (I-3), (I-4), (I-5) are respectively obtained;

When the number of the compound containing A is between 2 and 32 other than 2, 4, 8, 16, and 32, the material ratio in step a is controlled to make it incompletely reacted, and then the step b, c, d, e to obtain the target compound;
The method for preparing the compound according to claim 4, wherein the Grignard reaction process in step d is:

Firstly, the compound (V) is reacted with the allyl magnesium bromide solution in an ice bath for 2 to 4 hours, and then the temperature is increased to 50 to 70°C for 2 to 4 hours, then the reaction is quenched, and then the product is separated;

Preferably, the quencher used for quenching is methanol;

Preferably, the concentration of the allyl magnesium bromide solution is 0.5 to 1.5 mol/L;

Preferably, the molar ratio of the allyl magnesium bromide to the compound (V) is 6.5:1-9:1.
The method for preparing the compound according to claim 4, wherein the process of the substitution reaction in step b is:

Using a strong base as a catalyst, the compound (III) is reacted with allyl bromide in a fluorine-containing solvent at 50-70°C, and then the product is separated; wherein, the strong base is preferably sodium hydride; in step b The fluorine-containing solvent is preferably methyl nonafluorobutyl ether; the molar ratio of allyl bromide to compound (III) is preferably 2.1:1 to 4:1.
The method for preparing the compound according to claim 4, wherein the process of the ring-opening addition reaction in step a is:

First, the compound (II) and the strong base are mixed in a fluorine-containing solvent, then glycidol is added dropwise at 60-80°C, and the reaction is for 10-20 hours, and then the product is isolated; the fluorine-containing solvent is preferably methyl nonafluorobutyl The volume ratio of the mixed solution of ether and trifluorotrichloroethane is preferably 1:1.5 to 1.5:1; the molar ratio of the glycidol to compound (II) is preferably 1:1 to 1.1:1.
The method for preparing the compound according to claim 4, wherein the process of the hydrosilylation reaction in step c is:

Using Karstedt catalyst to react compound (IV) with trichlorosilane in a fluorine-containing solvent at 80-100°C, and then separate the product;

Preferably, the fluorine-containing solvent in step c is m-ditrifluorotoluene;

Preferably, methyltriacetoxysilane is also added in the hydrosilylation reaction of step c, and the added amount is preferably 1% to 3% of the mass of compound (IV);

In the step c, the Karstedt catalyst is preferably a xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum with a platinum content of 2wt%, and the amount of Karstedt catalyst used The mass content of platinum in the reaction system should reach 60-100 ppm; the molar ratio of trichlorosilane to compound (IV) is preferably 3:1-6:1.
The method for preparing the compound according to claim 4, wherein the process of the hydrosilylation reaction in step e is:

Using Karstedt catalyst, the compound (VI) is reacted with trimethoxysilane in a fluorine-containing solvent at 75-95°C, and then the product is separated;

Preferably, the fluorine-containing solvent in step e is methyl nonafluorobutyl ether;

Preferably, methyltriacetoxysilane is also added in the hydrosilylation reaction in step e, and the added amount is preferably 1% to 2% of the mass of compound (VI);

In the step e, the Karstedt catalyst is preferably a xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum with a platinum content of 2wt%, and the usage amount of the Karstedt catalyst The mass content of platinum in the reaction system should reach 60-100 ppm; the molar ratio of trimethoxysilane to compound (VI) is preferably 6.5:1-9:1.
A composition comprising the compound of any one of claims 1-3.
The composition according to claim 10, wherein the average degree of polymerization of all the compounds in the composition is 1-30.
The composition according to claim 10 or 11, wherein the average degree of polymerization of all the compounds in the composition is 5-30.
The use of the compound of any one of claims 1-3 or the composition of any one of claims 10-12 for water and oil repellency, preferably as an anti-fingerprint agent or lubricant.