CN112673050B - Compound, preparation method, application and composition comprising compound - Google Patents
Compound, preparation method, application and composition comprising compound Download PDFInfo
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Abstract
A compound, a preparation method and application thereof and a composition containing the compound. The compound is
Or on the basis of the compound (I) as follows: each A can be replaced by
And all A's in said compound may be replaced by
The number of A contained in the compound is an integer between 2 and 32; a is
Rf is
Wherein n is an integer of 1-30; r 1 Is C 1 ‑C 5 An alkylene group. The compound solves the problems of poor friction resistance and poor practicability of the existing fingerprint resisting agent.
Description
Technical Field
The invention relates to the field of compounds, in particular to a compound, a preparation method, application and a composition of the compound.
Background
The anti-fingerprint agent is used as a special surface modifier, is widely applied to the surface of a touch screen, not only endows the surface of a substrate with excellent water and oil resistance, but also has a low friction coefficient, and is not easy to damage the surface of the substrate during wiping. At present, the main component of the anti-fingerprint agent is perfluoropolyether with siloxane groups, and the perfluoropolyether polymer has excellent thermal stability, chemical inertness, environmental protection, harmlessness and excellent water and oil resistance, so the anti-fingerprint agent is widely applied to various material protective agents, aviation lubricants and the like.
In the prior art, the anti-fingerprint agent is synthesized by adopting hydrosilylation reaction, and the anti-fingerprint agent with different structures is prepared by hydrosilylation of a perfluoropolyether compound and a functional silane coupling agent. The anti-fingerprint agent is dissolved in fluorine-containing solvent (such as HFE-7100, HFE-7200, etc.) before use. When the anti-fingerprint agent is used, silicon hydroxyl hydrolyzed from the terminal siloxane group is subjected to dehydration condensation with hydroxyl on the surface of a substrate at high temperature or under the action of a catalyst to form a firm chemical bond, so that the coating is endowed with excellent wear resistance.
For example, patent application CN101151269A adopts perfluoropolyether allyl ether compound and trichlorosilane to perform hydrosilylation reaction under the action of catalyst, and then obtains perfluoropolyether single-end siloxane anti-fingerprint agent through methoxylation; in patent application CN101189278A, perfluoropolyether allyl ether compound is sequentially added with tetramethyl disiloxane and vinyl disiloxane through hydrosilylation to obtain perfluoropolyether single-end siloxane anti-fingerprint agent, and the two anti-fingerprint agents have good water-proof and oil-proof effects, but the abrasion resistance of the agents is not tested.
Patent application CN106085227A points out that perfluoropolyether siloxane is taken as an anti-fingerprint agent, if only a single hydrolytic group exists at the tail end, the friction durability of the perfluoropolyether siloxane is problematic, so that the comb-shaped anti-fingerprint agent containing a plurality of siloxane groups is synthesized, the anti-fingerprint agent can resist BONSTAR0000# steel wool for 5000 times, but the anti-fingerprint agent adopts hydrogen-containing silicone oil as a carrier, the molecular weight of the anti-fingerprint agent is difficult to control, and the practicability is poor.
Patent application WO2017155787 adopts perfluoropolyether alcohol and glycidyl ether to react to prepare comb-shaped polyol, then allylation and hydrosilylation are carried out to obtain perfluoropolyether siloxane with a comb-shaped structure, and the abrasion resistance of the fingerprint resisting agent is lower than 5000 times of steel wool friction.
To sum up, current anti-fingerprint agent antifriction performance is poor, even partial anti-fingerprint agent antifriction is better, the practicality also can't satisfy the actual demand, very difficult industrialization is used, current anti-fingerprint agent uses fluorine-containing solvent to dissolve in addition, and the cost is higher.
Disclosure of Invention
The first purpose of the invention is to provide a compound, which comprises a perfluoropolyether unit and a siloxane unit, wherein the siloxane unit is distributed in a dendritic form and occupies a large proportion, so that the compound has good water-proof and oil-proof performance and wear resistance when being used as an anti-fingerprint agent, has good solubility, can be dissolved in a fluorine-containing solvent and a mixed solvent consisting of the fluorine-containing solvent and a conventional solvent, and greatly reduces the cost.
The second purpose of the invention is to provide a preparation method of the compound, and the method has the advantages of simple route, few byproducts, safe reagent, safe operation, easily available raw materials, low cost, high yield and the like, and is suitable for industrial popularization.
In order to achieve the above purpose, the invention provides the following technical scheme:
a compound which is:
each A can be replaced by
And all A's in said compound may be replaced by
The number of A contained in the compound is an integer between 2 and 32;
a is
Rf is
Wherein n is an integer of 1 to 30;
R 1 is C 1 -C 5 An alkylene group.
In the present invention, the "number of a contained in a compound" means the number of a unit group of a present in a compound, and may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 23, 26, 28, 30 or 32, and the number of a contained in the compound is preferably 2 m And m is 1,2, 3, 4 or 5.
In the invention, the substitution of A refers to the successive progressive substitution on the basis of the general formula (I), and the progressive frequency is 1,2, 3 or 4. Within the preferred range of the number of A contained in the compound, the more the number of substitution (or progression), the more the distribution of siloxane branches, 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 that: on one hand, the rubber has a plurality of ether bond structures, so that the flexibility of molecules is improved, the rubber is easier to stretch under the friction of external force, and the abrasion resistance is improved; on the other hand, a plurality of siloxane groups are introduced into the molecules and distributed in a dendritic form, so that the number of siloxane groups in the molecules is increased, the siloxane groups and hydroxyl on the surface of the base material are easier to react, the siloxane groups can be more firmly adsorbed on the surface of the base material, and the wear resistance is greatly improved.
In addition, when the substitution is carried out in a progressive way, all A or part A can be selected to be substituted by
Preferably all A's are replaced simultaneously
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 linear.
In the invention
Representing the location of the broken key.
Specifically, the compounds of the present invention may be of the formula:
wherein, Rf and R 1 And A has the meaning described in the present invention.
The compound of the invention is a compound shown in formula (I), formula (I-1a), formula (I-2a), formula (I-3a), formula (I-3b), formula (I-4a), formula (I-4b), formula (I-4c), formula (I-5) and other specific compounds which are not listed and fall into formula (I), n is independently an integer of 1-30, such as 1, 5, 10, 15, 20, 25, 30 and the like, and the preferable range is an integer of 5-30.
In another aspect, the present invention provides a composition comprising at least one compound of formula (I), formula (I-1a), formula (I-2a), formula (I-3a), formula (I-3b), formula (I-4a), formula (I-4b), formula (I-4c), or formula (I-5) of the present invention.
In some embodiments, the average degree of polymerization of all of the compounds in the composition is from 1 to 30.
Preferably, the average degree of polymerization of all of said compounds in said composition is between 5 and 30.
The compound of the invention contains perfluoropolyether units and siloxane units, has good water and oil resistance, and has firm adhesion on a base material decorated with hydroxyl, so the compound can be used in the fields of fingerprint resisting agents, lubricating agents, moisture proofing agents and the like. When it is used as an anti-fingerprint agent, it can exhibit more excellent abrasion resistance because siloxane units in the molecule are distributed in a dendritic form, and have a relatively large proportion.
The above compounds of the present invention can be prepared by a synthetic route which is conventional in the art, but preferably by the following method, comprising the following steps if the compound has a number of a of 2:
a, step a: carrying out ring-opening addition reaction on the compound (II) and glycidol to generate a compound (III);
step b: carrying out substitution reaction on the compound (III) and allyl bromide to generate a compound (IV);
step c: carrying out hydrosilylation reaction on the compound (IV) and trichlorosilane to generate a compound (V);
step d: carrying out Grignard reaction on the compound (V) and allyl magnesium bromide to generate a compound (VI);
step e: carrying out hydrosilylation reaction on the compound (VI) and trimethoxy silane to generate a compound (I);
if the number of A contained in the compound is 2 m And m is 2, 3, 4 or 5, comprising the steps of:
repeating the step a for m times by taking the step a as a repeating unit, wherein each repetition is to perform the addition reaction of the step a by taking a product obtained from the previous repetition as a raw material; then, the final product after the repetition is taken as a raw material, and the target objects (I-2), (I-3), (I-4) and (I-5) are respectively obtained by sequentially carrying out the steps b, c, d and e;
when the number of the A contained in the compound is 2-32, except for 2, 4, 8, 16 and 32, controlling the material ratio in the step a to ensure that the compound is not completely reacted (for example, after glycidol and the compound (II) are reacted at a molar ratio of 1: 1-1.1: 1 to obtain a compound (III), taking the compound (III) as a starting material, repeating the step a again to ensure that the molar ratio of the compound (III) and the glycidol is 1:1 to obtain trihydroxy perfluoropolyether glycerol), and then carrying out the steps b, c, d and e to obtain a target product;
as mentioned above, the present invention mainly relates to four types of chemical reactions (both step c and step e are hydrosilylation reactions), and the more complex the structure of the compound, the more complex the reaction type, and the more repeated the same reaction can obtain the compound with complex structure.
The method considers the factors of reaction activity, raw material cost, difficulty in material taking, efficiency, safety and the like, and has the advantages of simple route, few byproducts, safe reagent, safe operation, easily available raw materials, low cost, high yield and the like, so that the method is suitable for industrial popularization.
The compound (II) used in step a may be a commercially available or self-made product, and may be prepared by any one of the methods in example 1 to example 5 in CN 110857263A.
The invention also optimizes the reaction conditions from step a to step e, as follows.
Preferably, the grignard reaction process in step d is:
firstly, reacting the compound (V) with an allyl magnesium bromide solution for 2-4 h under an ice bath condition, then heating to 50-70 ℃ for reacting for 2-4 h, then quenching the reaction, and then separating out a product.
The quenching in step d can be selected from quenchers such as methanol and ammonium chloride, and preferably methanol. The concentration of the allyl magnesium bromide solution in this step is preferably 0.5 to 1.5mol/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 to 9:1, preferably 8: 1. The temperature of the temperature-raising reaction in the step can be selected from 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ and the like. The product can be separated by means of filtration, rotary evaporation, washing, distillation and the like.
Preferably, the process of the substitution reaction in step b is as follows:
and (3) reacting the compound (III) with allyl bromide in a fluorine-containing solvent at 50-70 ℃ by using strong base as a catalyst, and then separating out a product.
The strong base in step b may be sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium hydride (NaH), potassium carbonate or potassium tert-butoxide, and is preferably one of sodium hydride, sodium hydroxide and potassium hydroxide. The fluorine-containing solvent in this step is fluorine-containing organic solvent, and can be selected from 1,1, 2-trifluorotrichloroethane, HFE-7100 (methyl nonafluorobutyl ether), HFE-7200 (ethyl nonafluorobutyl ether), trifluorotrichloroethane, m-ditrifluorotoluene, perfluorohexane, etc., preferably methyl nonafluorobutyl ether. In this step, it is preferred to react the compound (III) with sodium hydride for a certain period of time, followed by addition of allyl bromide. The molar ratio of allyl bromide to the compound (III) in the reaction is preferably 2.1:1 to 4: 1. The product can be separated by neutralizing (with strong acid such as hydrochloric acid and sulfuric acid), and extracting, washing or distilling. The washing solvent can be one or more of dichloromethane, ethanol, acetone, and methanol.
Preferably, the process of the cycloaddition reaction in step a is as follows:
firstly, mixing a compound (II) and strong base in a fluorine-containing solvent (the optional sequence is that the compound (II) and the fluorine-containing solvent are added into a reaction vessel firstly, then the strong base is added, or the adding sequence is changed), dripping glycidol at 60-80 ℃, stirring and reacting for 10-20 h, and separating out a product after the reaction is finished.
In the reaction, the fluorine-containing solvent is preferably a mixed solution of methyl nonafluorobutyl ether and trifluorotrichloroethane, and the volume ratio of the methyl nonafluorobutyl ether to the trifluorotrichloroethane is preferably 1: 1.5-1.5: 1.
The molar ratio of the glycidol and the compound (II) in the reaction in the step is preferably 1:1 to 1.1: 1. The strong base may be potassium tert-butoxide, sodium hydroxide (NaOH), sodium hydride (NaH) or the like, and is preferably one of potassium tert-butoxide and NaH. The product can be separated by means of neutralization (using strong acid such as hydrochloric acid, sulfuric acid and the like) and then extraction, washing or distillation. The washing solvent is preferably ethanol.
Preferably, the hydrosilylation reaction process in step c is as follows:
the compound (IV) is reacted with trichlorosilane in a fluorine-containing solvent at 80 to 100 ℃ using Karstedt's catalyst, after which the product is isolated.
The fluorine-containing solvent in step c can be selected from m-ditrifluorotoluene, HFE-7100 (methyl nonafluorobutyl ether), HFE-7200 (ethyl nonafluorobutyl ether) and the like, and is preferably m-ditrifluorotoluene. In the step, a cocatalyst-methyl triacetoxysilane can be selected, and the addition amount is preferably 1-3% of the mass of the compound (IV). The Karstedt catalyst is preferably a dimethylbenzene solution of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum with the platinum content of 2 wt%, and the use amount of the Karstedt catalyst is such that the mass content of platinum in the reaction system reaches 60-100 ppm; specifically, Karstedt's catalyst is used in an amount such that the mass content of platinum in the reaction mixture is 60ppm, 64ppm, 65ppm, 70ppm, 74ppm, 80ppm, 84ppm, 85ppm, 90ppm, 95ppm or 100 ppm. The molar ratio of trichlorosilane to compound (IV) in this step is preferably 3:1 to 6: 1. The grignard reaction in 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 as follows:
reacting the compound (VI) with trimethoxy silane in a fluorine-containing solvent at 75-95 ℃ by adopting a Karstedt catalyst, and then separating out a product.
The fluorine-containing solvent in step c can be selected from m-ditrifluorotoluene, HFE-7100 (methyl nonafluorobutyl ether), HFE-7200 (ethyl nonafluorobutyl ether) and the like, and methyl nonafluorobutyl ether is preferred. In the step, a cocatalyst-methyl triacetoxysilane can be selected, and the addition amount is preferably 1-2% of the mass of the compound (VI). The Karstedt catalyst is preferably a dimethylbenzene solution of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum with the platinum content of 2 wt%, and the use amount of the Karstedt catalyst is such that the mass content of platinum in the reaction system reaches 60-100 ppm; specifically, Karstedt's catalyst is used in an amount such that the platinum content in the reaction system is 60ppm, 64ppm, 65ppm, 70ppm, 74ppm, 80ppm, 84ppm, 85ppm, 90ppm, 95ppm or 100 ppm. The molar ratio of the trimethoxy silane to the compound (VI) in this step is preferably 6.5:1 to 9: 1. The product can be separated by means of filtration, washing, distillation and the like.
In the synthesis of an alternative to compound (I), i.e. a compound containing more a units, step a is repeated using the same reaction conditions as above.
The compounds of the present invention described above may be used alone or may be used in combination. Whether used alone or as an ingredient of a composition, are useful for water and oil repellency, typically as an anti-fingerprint agent or lubricant.
When the compound is used as an anti-fingerprint agent, the compound can be dissolved by adopting a fluorine-containing solvent and a mixed solvent, wherein the mixed solvent is a mixture of the fluorine-containing solvent and a conventional organic solvent, the fluorine-containing solvent is one or more of methyl nonafluorobutyl ether (HFE-7100), methyl nonafluoroethyl ether (HFE-7200), m-ditrifluorotoluene (HFX) and the like, the conventional organic solvent is one of dichloromethane, acetone, ethyl acetate, cyclohexane and the like, and the volume ratio of the fluorine-containing solvent to the conventional organic solvent is 1: 5-5: 1.
In conclusion, compared with the prior art, the invention achieves the following technical effects:
(1) a dendritic perfluoropolyether siloxane is provided, which has a higher siloxane content and a higher number of siloxane branches, and has higher abrasion resistance when used as an anti-fingerprint agent;
(2) a route for synthesizing the dendritic perfluoropolyether siloxane is designed, and the route achieves the effects of few byproducts, safe reagents, safe operation, easily available raw materials, low cost, high yield and the like by using the steps as few as possible;
(3) the conditions of each step of reaction in the synthetic route are optimized to shorten the reaction time, improve the yield or purity, or reduce the cost and the like.
(4) Provides an anti-fingerprint agent molecule series with better solubility so as to reduce the usage amount of fluorine-containing solvent and reduce the cost of the solvent.
Drawings
Various additional advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings.
FIG. 1 is a nuclear magnetic spectrum of an anti-fingerprint agent prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of perfluoropolyether alcohols (weight average molecular weight 4500, average degree of polymerization 26.2);
FIG. 3 is a nuclear magnetic spectrum of the anti-fingerprint agent prepared in example 2 of the present invention;
FIG. 4 is a nuclear magnetic spectrum of an anti-fingerprint agent prepared in example 7 of the present invention;
FIG. 5 is a nuclear magnetic spectrum of the anti-fingerprint agent prepared in comparative example 1 of the present invention;
FIG. 6 is a nuclear magnetic spectrum of the anti-fingerprint agent prepared in comparative example 2 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) 100.0g (22.2mmol) of perfluoropolyether alcohol (weight average molecular weight 4500, average degree of polymerization 26.2), 50mL of a mixed solution of methyl nonafluorobutyl ether and trifluorotrichloroethane (volume ratio 1:1), 0.5g of potassium tert-butoxide (4.4mmol, 0.2equ) were added to a 250mL three-necked flask, a reflux condenser was placed, the mixture was mechanically stirred, 1.7g (22.9mmol, 1.03equ) of glycidol was slowly dropped at 70 ℃ to the mixture, the reaction was stopped after 12 hours of reaction, the reaction system was acidified with 1M hydrochloric acid, washed with water three times, washed with absolute ethanol three times, and distilled under reduced pressure at 80 ℃ to obtain 97.8g of perfluoropolyether glycerol ether, with a yield of 96.3%. The reaction formula is as follows:
(2)N 2 under protection, 97.8g (21.4mmol) of perfluoropolyether glycerol ether (weight average molecular weight 4574, average polymerization degree 26.2), 50mL of methyl nonafluorobutyl ether and 1.2g (48.7mmol) of sodium hydride were put into a 250mL three-necked flask, stirred at 60 ℃ for 2 hours, then 6.2g (51.3mmol, 2.4equ) of allyl bromide was added dropwise, the reaction was stopped after 6 hours of further reaction, the reaction system was acidified with 1M hydrochloric acid, washed with water three times, washed with absolute ethanol three times, and distilled under reduced pressure at 90 ℃ to obtain 91.6g of perfluoropolyether diallyl ether, with a yield of 92.1%. The reaction formula is as follows:
(3) 40.0g (8.6mmol) of perfluoropolyether diallyl ether (weight average molecular weight 4654, average degree of polymerization 26.2), 50g of m-ditrifluorotoluene, 0.5g of methyltriacetoxysilane, 0.3g of 1,3-Divinyl1, 1,3, 3-tetramethyldisiloxane platinum in xylene solution (platinum content in the reaction system: 64ppm) and 3.5g (25.8mmol, 3equ) of trichlorosilane were sequentially added to a 250mL pressure-resistant bottle, N 2 And (3) protecting, reacting at 90 ℃ for 9 hours, and distilling at 40 ℃ under reduced pressure to remove low-boiling-point substances to obtain a yellow reaction liquid containing 42.3g of perfluoropolyether-trichlorosilane. The reaction formula is as follows.
(4) The yellow reaction solution containing 42.3g (8.6mmol) of perfluoropolyether-trichlorosilane obtained in the step (3) is added into a 250mL three-necked bottle, and N 2 And (3) protection, dropwise adding 68.8mL (68.8mmol, 8equ) of 1M allyl magnesium bromide diethyl ether solution under ice bath, stirring for 3h, heating to 60 ℃, refluxing for 3h, adding methanol to quench the reaction, filtering, carrying out rotary evaporation on the filtrate, washing with acetone for three times, and carrying out reduced pressure distillation at 100 ℃ to obtain 38.1g of perfluoropolyether hexaallyl ether, wherein the yield is 89.3%. The reaction formula is as follows:
(5) 38.1g (7.7mmol) of perfluoropolyether hexaallyl ether (weight-average molecular weight 4958, average degree of polymerization 26.2), 50g of methyl nonafluorobutyl ether, 0.6g of methyl triacetoxysilane, and 0.4g of a xylene solution of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum having a platinum content of 2 wt% (platinum content 84ppm in the reaction system) were sequentially charged into a 250mL three-necked flask, and N was added 2 Protection, 6.6g (53.7mmol, 7equ) of trimethoxy silane is dripped at 80 ℃, stirred and reacted for 12 hours, filtered on a funnel paved with diatomite, filtrate is evaporated in a rotary manner, solvent is removed, the filtrate is washed three times by anhydrous acetone, reduced pressure distillation is carried out at 80 ℃ to obtain 35.8g of anti-fingerprint agent, and the yield is 82.0%. The reaction formula is as follows:
wherein A is
The nuclear magnetic spectrum of the anti-fingerprint agent obtained in example 1 is shown in fig. 1, wherein 0.00 is a peak of tetramethylsilicon, and fig. 2 is a nuclear magnetic spectrum of a raw material perfluoropolyether alcohol (weight average molecular weight 4500, average polymerization degree 26.2), wherein 1.36 and 2.1pm are impurity peaks introduced by trifluorotrichloroethane as a solvent.
Example 2
40.0g (8.7mmol) of perfluoropolyether glycerol ether (weight-average molecular weight 4574, average polymerization degree 26.2) was reacted in the same manner as in (1) to (5) in example 1 (the reaction conditions are the same, for example, the type concentration of the starting material and the temperature), to obtain 25.2g of the anti-fingerprint agent. The reaction procedure was as follows, and the overall yield of the following reaction formula was 41.2%.
Wherein A is
The nuclear magnetic spectrum of the anti-fingerprint agent prepared in example 2 is shown in fig. 3.
Example 3
50.0g of a perfluoropolyether alcohol (weight average molecular weight 2060, average degree of polymerization 11.5) was reacted in accordance with steps (1) to (5) in example 1 to obtain 47.5g of an anti-fingerprint agent in an overall yield of 60.2%.
Example 4
20.0g of a perfluoropolyether alcohol (weight average molecular weight 1500, average polymerization degree 8.1) was reacted in the steps (1) to (5) in example 1 to obtain 21.1g of an anti-fingerprint agent in an overall yield of 58.8%.
Example 5
Perfluoropolyether glycerin ether was synthesized in the same manner as in the step (1) in example 1 using 60.0g of perfluoropolyether alcohol (weight average molecular weight 2060, average polymerization degree 11.5) and then subjected to the reaction in example 2 to obtain 54.7g of anti-fingerprint agent in a total yield of 41.3% (referring to the yield of all reactions using perfluoropolyether alcohol as a starting material).
Example 6
Perfluoropolyether glycerin ether was synthesized in accordance with the procedure (1) in example 1 from 30.0g of perfluoropolyether alcohol (weight average molecular weight 1500, average polymerization degree 8.1) and then subjected to the reaction in example 2 to obtain 34.5g of anti-fingerprint agent in a total yield of 43.2% (referring to the yield of all reactions using perfluoropolyether alcohol as a starting material).
Example 7
Prepared by the same method as example 2
Using the above as a starting material, reactions were carried out in the steps (1) to (5) in example 1 to synthesize an anti-fingerprint agent:
wherein A is
The nuclear magnetic spectrum of the anti-fingerprint agent prepared in example 7 is shown in fig. 4.
Example 8
The anti-fingerprint agent was prepared by carrying out the reaction of the step (1) of example 1 and repeating the reaction 4 times, using perfluoropolyether glyceryl ether (weight average molecular weight 4574, average polymerization degree 26.2) as a starting material, and carrying out the reactions of the steps (2) to (5) of example 1:
wherein A is
Example 9
The anti-fingerprint agent was prepared by carrying out the reaction of the step (1) of example 1, using perfluoropolyether glyceryl ether (weight average molecular weight 4574, average polymerization degree 26.2) as a starting material, repeating the reaction 5 times, and carrying out the reactions of the steps (2) to (5) of example 1:
wherein A is
Comparative example 1
Synthesizing a single-end siloxane anti-fingerprint agent:
(1) 10.3g (5.0mmol) of perfluoropolyether alcohol (weight average molecular weight 2060, average polymerization degree 11.5) and 10mL of methyl nonafluorobutyl ether were added to a 100mL two-necked flask, followed by 0.9g (7.5mmol, 1.5equ) of allyl bromide and 0.4g of sodium hydroxide, and the mixture was placed in a reflux condenser, magnetically stirred, reacted at 60 ℃ for 12 hours, acidified with 1M hydrochloric acid, washed with water three times, washed with anhydrous ethanol three times, and distilled under reduced pressure at 80 ℃ to obtain 10.0g of perfluoropolyether allyl ether, with a yield of 96.0%. The reaction formula is as follows:
(2) 10.0g (4.8mmol) of perfluoropolyether allyl ether (average molecular weight of 2100, average degree of polymerization: 11.5) obtained in (1), 15.0g of methylnonafluorobutyl ether, 0.2g of methyltriacetoxysilane, and 0.1g of a xylene solution of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum having a platinum content of 2 wt% (platinum content in the reaction system: 74ppm) were successively charged into a 100mL two-necked flask, and N was 2 Protection, dripping 1.8g (14.4mmol, 3equ) of trimethoxy silane at 80 ℃, stirring for reaction for 12h, filtering on a funnel paved with diatomite, evaporating the filtrate to remove the solvent, washing with anhydrous acetone for three times, distilling at 80 ℃ under reduced pressure to obtain 9.1g of anti-fingerprint agent, wherein the yield is 86%, the characterization spectrogram 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 26.2) was reacted according to the procedure (1) of comparative example 1 to obtain perfluoropolyether allyl ether, and the reaction was carried out according to the procedures (3) to (5) of example 1 to obtain 23.6g of anti-fingerprint agent in an overall yield of 76.5% (referring to the yield of all reactions starting with perfluoropolyether alcohol), and the characterization spectrum is as follows, and the structural formula is as follows:
the dissolution properties of the anti-fingerprint agents prepared in the above examples and comparative examples are shown in table 1.
TABLE 1 dissolution Performance results for various anti-fingerprint agents
Note: the ratio of each solvent in the table is volume ratio
The method for testing the dissolution properties in table 1 is:
the anti-fingerprint agents of the examples or the comparative examples of the present invention were diluted with the solvents in table 1 to prepare anti-fingerprint agent dilutions having mass concentrations of 20%.
The results in table 1 show that the anti-fingerprint agent can be dissolved by a mixed solvent composed of a fluorine-containing solvent and a conventional organic solvent, wherein the volume ratio of the fluorine-containing solvent to the conventional organic solvent is 1: 5-5: 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 fingerprint resistant agents prepared in the above examples and comparative examples have properties as shown in Table 2.
TABLE 2 characterization results of various anti-fingerprint agents (average degree of polymerization in the table means degree of polymerization of perfluoropolyether alcohols)
Test methods for properties in table 2:
the anti-fingerprint agents of the examples or the comparative examples were diluted with a 3M mixed solvent of HFE-7100 and cyclohexane (the volume ratio of HFE-7100 to cyclohexane was 1: 3) to prepare a 0.5% diluted solution. The glass substrate is washed by piranha washing liquor in advance, and is washed by water and dried for later use. And soaking the pretreated glass slide in the diluted anti-fingerprint solution for 5min, taking out, drying in an oven at 150 ℃ for 30min, and directly carrying out subsequent performance detection on the glass cooled to room temperature.
(1) Contact angle test: the contact angles of water and n-hexadecane were measured using a contact angle tester. And (3) measuring at room temperature, paving and fixing the mobile phone touch screen glass sample to be measured on a horizontal platform of a contact angle tester, wherein the size of the liquid drop is 5 mu L.
(2) Stain resistance test for oil pen
A commercially available ink pen was used to draw blue lines on the cured film surface of the cell phone glass screen. The blue ink was evaluated for its resistance to staining according to its shrinkage. The criteria are as follows:
class C-no shrinkage, line formation,
stage B-shrinkage into a dashed line,
class a-shrinkage to point.
(3) Friction resistance test
And (3) carrying out a friction resistance test on a steel wool friction resistance tester by using #0000 steel wool with the load of 1kg, wherein the friction distance is 5cm, the reciprocating friction treatment is carried out for 3000-5000 times, the friction frequency is 55 times/min, and the contact angle test is carried out after the friction treatment.
As can be seen from the data of table 2, the anti-fingerprint agent of the present invention has excellent anti-friction properties. Within the preferred ranges of the anti-fingerprint agent compound of the present invention, the more siloxane groups are contained in the anti-fingerprint agent at the same degree of polymerization, the better the rub resistance. When the number of siloxane branches is the same, the polymerization degree of the perfluoropolyether is larger, the initial contact angle is larger, and the water and oil resistance is better.
The modification of glass by the compound of the present invention has been described above, but the present invention is not limited to the type of the substrate, and the present invention can also be applied to the surface modification of other materials such as ceramics and plastics.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (31)
1. A compound, characterized in that it is:
each A may be replaced by
And all A's in said compounds may be replaced by
The number of A contained in the compound is an integer between 2 and 32;
a is
Rf is
Wherein n is an integer of 1-30;
R 1 is C 1 -C 5 An alkylene group.
2. The compound of claim 1, wherein n is an integer from 5 to 30.
3. The compound of claim 1, wherein said compound contains an a number of 2 m And m is 1,2, 3, 4 or 5.
4. A compound according to claim 1 or 2, characterized in that it is:
5. a process for preparing a compound according to any one of claims 1 to 4, wherein if said compound contains an A number of 2, the process comprises the steps of:
step a: carrying out ring-opening addition reaction on the compound (II) and glycidol to generate a compound (III);
step b: carrying out substitution reaction on the compound (III) and allyl bromide to generate a compound (IV);
step c: carrying out hydrosilylation reaction on the compound (IV) and trichlorosilane to generate a compound (V);
step d: carrying out Grignard reaction on the compound (V) and allyl magnesium bromide to generate a compound (VI);
step e: carrying out hydrosilylation reaction on the compound (VI) and trimethoxy silane to generate a target compound (I);
if the number of A contained in the compound is 2 m M is 2, 3, 4 or5, the method comprises the following steps:
repeating the step a for m times by taking the step a as a repeating unit, and performing the ring-opening addition reaction of the step a again by taking the product obtained by the previous repetition as a raw material for each repetition; then, the final product after the repetition is taken as a raw material, and target compounds (I-2), (I-3), (I-4) and (I-5) are respectively obtained by sequentially carrying out the steps b, c, d and e;
when the number of the A contained compounds is 2-32, except for 2, 4, 8, 16 and 32, incomplete reaction is realized by controlling the material ratio in the step a, and then the target compound is obtained through the steps b, c, d and e;
6. the method for preparing the compound according to claim 5, wherein the Grignard reaction process in the step d is as follows:
firstly, reacting the compound (V) with an allyl magnesium bromide solution for 2-4 h under an ice bath condition, then heating to 50-70 ℃ for reacting for 2-4 h, then quenching the reaction, and then separating out a product.
7. The method of claim 6, wherein the quenching agent is methanol.
8. The method for preparing a compound according to claim 6, wherein the concentration of the allyl magnesium bromide solution is 0.5 to 1.5 mol/L.
9. The method according to claim 6, wherein the molar ratio of allyl magnesium bromide to the compound (V) is 6.5:1 to 9: 1.
10. The method for preparing the compound according to claim 5, wherein the substitution reaction in step b is performed by:
and (3) reacting the compound (III) with allyl bromide in a fluorine-containing solvent at 50-70 ℃ by using strong base as a catalyst, and then separating a product.
11. The method of claim 10, wherein the strong base is sodium hydride.
12. The method for preparing a compound according to claim 10, wherein the fluorine-containing solvent in the step b is methyl nonafluorobutyl ether.
13. The method according to claim 10, wherein the molar ratio of allyl bromide to the compound (III) is 2.1:1 to 4: 1.
14. The method of claim 5, wherein the cycloaddition reaction in step a is performed by:
firstly, mixing the compound (II) and strong base in a fluorine-containing solvent, then dripping glycidol at 60-80 ℃, reacting for 10-20 h, and then separating out a product.
15. The method for producing a compound according to claim 14, wherein the fluorine-containing solvent is a mixed solution of methyl nonafluorobutyl ether and trifluorotrichloroethane.
16. The method for preparing a compound according to claim 15, wherein the volume ratio of methyl nonafluorobutyl ether to trifluorotrichloroethane is 1:1.5 to 1.5: 1.
17. The method for preparing a compound according to claim 14, wherein the molar ratio of glycidol to compound (II) is 1:1 to 1.1: 1.
18. The method for preparing the compound according to claim 5, wherein the hydrosilylation reaction process in the step c is as follows:
and (3) reacting the compound (IV) with trichlorosilane in a fluorine-containing solvent at 80-100 ℃ by adopting a Karstedt catalyst, and then separating a product.
19. The method of claim 18, wherein the fluorine-containing solvent in step c is m-ditrifluorotoluene.
20. The method for producing a compound according to claim 18, wherein methyltriacetoxysilane is further added in an amount of 1 to 3% by mass based on the compound (IV) in the hydrosilylation reaction in the step c.
21. The method for preparing the compound according to claim 18, wherein in the step c, the Karstedt catalyst is preferably a xylene solution of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum with platinum content of 2 wt%, and the Karstedt catalyst is used in an amount such that the mass content of platinum in the reaction system is 60-100 ppm.
22. The method according to claim 18, wherein the molar ratio of trichlorosilane to compound (IV) is 3:1 to 6: 1.
23. The method for preparing the compound according to claim 5, wherein the hydrosilylation reaction process in the step e is as follows:
reacting the compound (VI) with trimethoxy silane in a fluorine-containing solvent at 75-95 ℃ by using a Karstedt catalyst, and then separating out a product.
24. The method of claim 23, wherein the fluorine-containing solvent in step e is methyl nonafluorobutyl ether.
25. The method of claim 23, wherein methyltriacetoxysilane is added in an amount of 1-2 wt% based on the compound (VI) in the hydrosilylation reaction of step e.
26. The method of claim 23, wherein in step e, the Karstedt catalyst is a xylene solution of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum with a platinum content of 2 wt%, and the Karstedt catalyst is used in an amount such that the mass content of platinum in the reaction system is 60-100 ppm.
27. The method of claim 23, wherein the molar ratio of trimethoxysilane to compound (VI) is 6.5:1 to 9: 1.
28. A composition for water and oil repellency comprising a compound according to any of claims 1 to 4.
29. The composition of claim 28, wherein the average degree of polymerization of all of said compounds in said composition is in the range of 1 to 30.
30. The composition of claim 28 or 29, wherein the average degree of polymerization of all of said compounds in said composition is from 5 to 30.
31. Use of a compound according to any one of claims 1 to 4 or a composition according to any one of claims 28 to 30 for an anti-fingerprint agent or lubricant.
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