A dual-end z-type perfluoropolyether siloxane, and a preparation method and application thereof

Abstract

The application provides a kind of double-end Z type perfluoropolyether siloxane and its preparation method and application, it is related to substrate surface treatment technical field.The double-end Z type perfluoropolyether siloxane with the structure shown in formula I provided by the application is terminated by siloxane at both ends of perfluoropolyether siloxane, with excellent low surface energy and wear resistance, can form a strong antifouling coating on the surface of glass, ceramic, silicon wafer and plastic substrate, can effectively improve the antifouling ability of substrate surface, as coating material has good application prospect.Moreover, in the preparation method provided by the application, when amine is used as catalyst, double-end Z type perfluoropolyether alcohol reacts with chlorosiloxane to obtain product;when sodium alcoholate is used as catalyst, double-end Z type perfluoropolyether alcohol reacts with sodium alcoholate, and then reacts with chlorosiloxane to obtain product.The preparation method provided by the application is simple in process, simple in operation, low in energy consumption, low in production difficulty, low in production cost, friendly to environment, suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of substrate surface treatment, in particular to a double-end Z-type perfluoropolyether siloxane and a preparation method and application thereof. BACKGROUND

[0002] With the increasing use of touch screen electronic devices, organic glass, mirror surface material polyester and ceramics in daily life, their surfaces will inevitably be eroded by water and oil stains during long-term use. The demand for water and oil resistance and wear resistance of the surfaces of these hard materials is increasing. Coating the above-mentioned materials with a material having good water and oil resistance and wear resistance can effectively solve the above-mentioned problems.

[0003] Perfluoropolyether (PFPE) is a polymer composed of different repeating units such as CF2O, CF2CF2O, CF2CF(CF3)O and CF2CF2CF2CF2O, and has high thermal stability, chemical inertness, low volatility, low surface energy, wide liquid temperature range, excellent viscosity-temperature performance, high toughness, non-bioaccumulation and toxicity. Therefore, perfluoropolyether is widely used as a coating material.

[0004] At present, the commonly used perfluoropolyether mainly includes perfluoropolyether type siloxane. The perfluoropolyether type siloxane is mainly obtained by allylation reaction of perfluoropolyether alcohol with allyl bromide, and then siloxane alkylation reaction of the allylated perfluoropolyether with trimethoxysilane in the presence of a noble metal catalyst. However, the perfluoropolyether type siloxane has relatively few anchor points on the material surface and relatively weak anchoring ability, resulting in poor wear resistance on the material surface. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a double-end Z-type perfluoropolyether siloxane and a preparation method and application thereof. The double-end Z-type perfluoropolyether siloxane provided by the present application has excellent wear resistance and stain resistance.

[0006] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0007] The present application provides a double-end Z-type perfluoropolyether siloxane having the structure shown in formula I:

[0008]

[0009] In formula I, R is an alkyl group; p+q=10-110.

[0010] Preferably, the value ratio of p and q in formula I is 1:2-3; R is a C1-C3 alkyl group.

[0011] The application provides a preparation method of the double-end Z-type perfluoropolyether siloxane, and the preparation method comprises Method I or Method II.

[0012] The Method I comprises the following steps:

[0013] The double-end Z-type perfluoropolyether alcohol, chlorosiloxane, tertiary amine and a first heteroatom-fluorine mixed solvent are mixed to perform a first condensation reaction, so that the double-end Z-type perfluoropolyether siloxane is obtained.

[0014] The Method II comprises the following steps:

[0015] The double-end Z-type perfluoropolyether alcohol, sodium alcoholate and alcohol are mixed to perform a substitution reaction, so that the double-end Z-type perfluoropolyether sodium alcoholate is obtained.

[0016] The double-end Z-type perfluoropolyether sodium alcoholate, chlorosiloxane and a second heteroatom-fluorine mixed solvent are mixed to perform a second condensation reaction, so that the double-end Z-type perfluoropolyether siloxane is obtained.

[0017] The chemical formula of the double-end Z-type perfluoropolyether alcohol is shown in formula II.

[0018] HOCH2-(CF2CF2O) p (CF2O) q -CH2OH formula II.

[0019] The value ranges of p and q in formula II are the same as those of p and q in formula I.

[0020] The chemical formula of the chlorosiloxane is ROSiCl, and R in the ROSiCl is the same as R in formula I.

[0021] Preferably, in the Method I, the molar ratio of the double-end Z-type perfluoropolyether alcohol to the tertiary amine is 1:1-2.

[0022] The tertiary amine comprises one or more of triethylamine, tripropylamine, tributylamine, trihexylamine, trisbenzylamine, dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine and hexadecyl dimethyl tertiary amine.

[0023] Preferably, in the Method I and the Method II, the molar ratio of the double-end Z-type perfluoropolyether alcohol to the chlorosiloxane is independently 1:2-4.

[0024] Preferably, in the Method II, the molar ratio of the double-end Z-type perfluoropolyether alcohol to the sodium alcoholate is 1:2-2.5.

[0025] The sodium alcoholate comprises one or more of sodium methoxide, sodium ethoxide and sodium tert-butoxide.

[0026] The alcohol comprises one or more of methanol, ethanol and tert-butanol.

[0027] Preferably, in the method two, the temperature of the substitution reaction is 20-40℃, and the time is 8-16h.

[0028] Preferably, the first heteroatom-fluorine mixed solvent and the second heteroatom-fluorine mixed solvent both comprise a heteroatom-containing organic solvent and a fluorine-containing organic solvent.

[0029] The heteroatom-containing organic solvent independently comprises one or more of acetonitrile, butanone, tetrahydrofuran, 1,4-dioxane and N-methyl pyrrolidone.

[0030] The fluorine-containing organic solvent independently comprises one or more of perfluorocycloether, perfluorohexane, trifluorotrichloroethane and dichlorodifluoroethane.

[0031] In the first heteroatom-fluorine mixed solvent and the second heteroatom-fluorine mixed solvent, the volume ratio of the heteroatom-containing organic solvent to the fluorine-containing organic solvent is independently 1:0.25-0.5.

[0032] Preferably, the temperature of the first condensation reaction and the second condensation reaction is independently 25-35℃, and the time is independently 5-24h.

[0033] The application also provides the use of the double-end Z-type perfluoropolyether siloxane described in the above technical solution or prepared by the preparation method described in the above technical solution as a coating material.

[0034] The double-end Z-type perfluoropolyether siloxane provided by the application has the structure shown in formula I, both ends of the perfluoropolyether siloxane are capped by siloxane, and the double-end group is anchored to the surface of a material, thereby increasing the coverage area of the perfluoropolyether on the surface of the material, having excellent low surface energy and wear resistance, and being capable of forming a firm antifouling coating on the surface of a substrate such as glass, ceramic, silicon wafer and plastic, thereby having a long service life and being capable of effectively improving the antifouling ability of the surface of the substrate, and having a good application prospect as a coating material.

[0035] The application provides a preparation method of the double-end Z-type perfluoropolyether siloxane described in the above technical solution. In the preparation method provided by the application, when a tertiary amine is used as a catalyst, the double-end Z-type perfluoropolyether alcohol and chlorosiloxane can be reacted to prepare the double-end Z-type perfluoropolyether siloxane in one step; when sodium alcoholate is used as a catalyst, the double-end Z-type perfluoropolyether alcohol reacts with sodium alcoholate to generate double-end Z-type perfluoropolyether sodium alcoholate, and then the double-end Z-type perfluoropolyether sodium alcoholate reacts with chlorosiloxane to prepare the double-end Z-type perfluoropolyether siloxane. The preparation method provided by the application has the advantages of simple process, simple operation, low energy consumption, low production difficulty, low production cost, environmental friendliness and suitability for industrialized production. DETAILED DESCRIPTION

[0036] The application provides a double-end Z-shaped perfluoropolyether siloxane with the structure shown in formula I.

[0037]

[0038] In the formula I, R is an alkyl group; p+q=10-110.

[0039] In the application, the R is an alkyl group, preferably a C1-C3 alkyl group, more preferably including a methyl group, an ethyl group or a propyl group.

[0040] In the application, the p+q is an integer of 10-110, preferably an integer of 30-110, more preferably an integer of 50-110. In the application, the value ratio of p and q in the formula I is preferably 1:2-3, more preferably 1:2-2.5.

[0041] The application provides a preparation method of the double-end Z-shaped perfluoropolyether siloxane.

[0042] Unless otherwise specified, the raw materials used in the application are all commercially available.

[0043] In the application, the method one includes the following steps:

[0044] The double-end Z-shaped perfluoropolyether alcohol, chlorosiloxane, tertiary amine and first heteroatom-fluorine mixed solvent are mixed to perform a first condensation reaction, so that the double-end Z-shaped perfluoropolyether siloxane is obtained.

[0045] The chemical formula of the double-end Z-shaped perfluoropolyether alcohol is shown in formula II.

[0046] HOCH2-(CF2CF2O) p (CF2O) q -CH2OH formula II.

[0047] The value range of p and q in the formula II is the same as that of p and q in the formula I.

[0048] The chemical formula of the chlorosiloxane is ROSiCl, and the R in the ROSiCl is the same as that in the formula I.

[0049] In the present application, the molecular weight of the double-end Z-type perfluoropolyether alcohol is preferably 2000-20000 g / mol, more preferably 5000-20000 g / mol, and further preferably 10000-20000 g / mol. In the present application, the chlorosiloxane includes trimethoxysilane, triethoxysilane or tripropoxysilane. In the present application, the molar ratio of the double-end Z-type perfluoropolyether alcohol to chlorosiloxane is preferably 1:2-4, more preferably 1:2.5-3.5, and further preferably 1:3.

[0050] In the present application, the amine preferably includes one or more of triethylamine, tripropylamine, tributylamine, trihexylamine, tris-benzylamine, dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine and hexadecyl dimethyl tertiary amine, and more preferably includes triethylamine, tripropylamine, tributylamine, trihexylamine, tris-benzylamine, dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine or hexadecyl dimethyl tertiary amine. In the present application, the molar ratio of the double-end Z-type perfluoropolyether alcohol to amine is preferably 1:1-2, more preferably 1:1-1.8, and further preferably 1:1.2-1.5.

[0051] The mixing method in the present application is not particularly limited, and any mixing method known to those skilled in the art can be used, as long as the raw materials can be uniformly mixed, for example, by stirring.

[0052] In the present application, the first heteroatom-fluorine mixed solvent preferably includes a heteroatom-containing organic solvent and a fluorine-containing organic solvent; the heteroatom-containing organic solvent preferably includes one or more of acetonitrile, butanone, tetrahydrofuran, 1,4-dioxane and N-methyl pyrrolidone, and more preferably includes acetonitrile, butanone, tetrahydrofuran, 1,4-dioxane or N-methyl pyrrolidone; the fluorine-containing organic solvent preferably includes one or more of perfluorocycloether, perfluorohexane, trifluorotrichloroethane and dichlorodifluoroethane, and more preferably includes perfluorocycloether, perfluorohexane, trifluorotrichloroethane or dichlorodifluoroethane; and the volume ratio of the heteroatom-containing organic solvent to the fluorine-containing organic solvent is preferably 1:0.25-0.5, and more preferably 1:0.3-0.5.

[0053] In the present application, the temperature of the first condensation reaction is preferably 25-35°C, more preferably 28-32°C, and further preferably 30°C; and the time of the first condensation reaction is preferably 5-24h, more preferably 10-24h, and further preferably 15-24h. In the present application, taking tris-benzylamine as an example, the reaction occurring in the first condensation reaction is shown in formula (1):

[0054]

[0055] After the first condensation reaction, the present application preferably further comprises post-treatment, which preferably comprises: sequentially subjecting the obtained crude product liquid to solid-liquid separation, alcohol washing and drying to obtain the double-end Z-type perfluoropolyether siloxane. The present application is not particularly limited for the solid-liquid separation, and any solid-liquid separation method known to those skilled in the art can be used, such as vacuum rotary evaporation or centrifugal separation; the purpose of the concentration is to remove the solvent and unreacted chlorosiloxane in the crude product liquid. In the present application, the alcohol used in the alcohol washing preferably comprises one or more of methanol, ethanol and propanol. In the present application, the drying temperature is preferably 40-60°C, more preferably 45-50°C, and the present application is not particularly limited for the drying time, which can be dried to constant weight.

[0056] In the present application, the method two comprises the following steps:

[0057] mixing the double-end Z-type perfluoropolyether alcohol, sodium alcoholate and alcohol to perform a substitution reaction to obtain double-end Z-type perfluoropolyether sodium alcoholate;

[0058] mixing the double-end Z-type perfluoropolyether sodium alcoholate with chlorosiloxane and a second mixed solvent of heteroatom-fluorine to perform a second condensation reaction to obtain the double-end Z-type perfluoropolyether siloxane;

[0059] The chemical formula of the double-end Z-type perfluoropolyether alcohol is shown in formula II:

[0060] HOCH2-(CF2CF2O) p (CF2O) q -CH2OH Formula II;

[0061] The value ranges of p and q in formula II are the same as those of p and q in formula I;

[0062] The chemical formula of the chlorosiloxane is ROSiCl, and R in ROSiCl is the same as R in formula I.

[0063] The present application mixes the double-end Z-type perfluoropolyether alcohol, sodium alcoholate and alcohol to perform a substitution reaction to obtain double-end Z-type perfluoropolyether sodium alcoholate.

[0064] In the present application, the sodium alcoholate preferably comprises one or more of sodium methoxide, sodium ethoxide and sodium tert-butoxide, more preferably comprises sodium methoxide, sodium ethoxide or sodium tert-butoxide. In the present application, the molar ratio of the double-end Z-type perfluoropolyether alcohol to sodium alcoholate is preferably 1:2-2.5, more preferably 1:2.1-2.4, and further preferably 1:2.2-2.3.

[0065] In the present application, the alcohol preferably comprises one or more of methanol, ethanol and tert-butanol, more preferably comprises methanol, ethanol and or tert-butanol. In the present application, the mass to volume ratio of the double-end Z-type perfluoropolyether alcohol to alcohol is preferably 1g:5-20mL, more preferably 1g:10-15mL.

[0066] The present application does not have special limitation on the mixing, and any mixing method known to those skilled in the art can be used, and the raw materials can be mixed uniformly, for example, by stirring.

[0067] In the present application, the temperature of the substitution reaction is preferably 20-40℃, more preferably room temperature (25℃), and the time of the substitution reaction is preferably 0.5-2h, more preferably 1-1.5h.

[0068] After the substitution reaction is completed, the present application preferably further comprises removing the solvent from the obtained substitution reaction solution, and the present application does not have special limitation on the removal method of the solvent, and any removal method known to those skilled in the art can be used, for example, vacuum rotary evaporation.

[0069] After obtaining the double-end Z-type perfluoropolyether alcohol sodium, the present application mixes the double-end Z-type perfluoropolyether alcohol sodium with chlorosiloxane and a second heteroatom-fluorine mixed solvent to perform a second condensation reaction, thereby obtaining the double-end Z-type perfluoropolyethersiloxane.

[0070] In the present application, the molar ratio of the double-end Z-type perfluoropolyether alcohol to chlorosiloxane, the optional type of the second heteroatom-fluorine mixed solvent, the conditions of the second condensation reaction and the post-treatment after the completion of the second condensation reaction are preferably the same as those of the method, and will not be described here.

[0071] The preparation method provided by the present application overcomes the shortcomings of complex process, harsh conditions and expensive catalyst in the preparation process of traditional perfluoropolyether chlorosiloxane, and a series of double-end Z-type perfluoropolyethersiloxanes can be prepared by adding perfluoropolyethers with different molecular weights, and the method has the characteristics of low production cost, simple process, mild reaction conditions and low energy consumption.

[0072] The present application also provides the application of the double-end Z-type perfluoropolyethersiloxane provided by the above technical solution or the double-end Z-type perfluoropolyethersiloxane prepared by the preparation method provided by the above technical solution as a coating material. In the present application, the application preferably refers to the application of the double-end Z-type perfluoropolyethersiloxane as an antifouling film of glass, ceramic, silicon wafer or plastic. The perfluoropolyethersiloxane provided by the present application has excellent low surface energy and wear resistance, has a long service life as a coating material, can form a strong antifouling coating on the surface of a substrate such as glass, ceramic, silicon wafer and plastic, can effectively improve the antifouling ability of the surface of the substrate, and has a good application prospect as a coating material.

[0073] The technical solutions in the present application will be clearly and completely described below in combination with the embodiments in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0074] Example 1

[0075] 2 g of Z-type perfluoropolyether alcohol (p+q=110, Mw=20000 g / mol) was placed in a 50 mL round-bottom flask, 10 mL of acetonitrile, 5 mL of perfluoro cyclic ether, 1 mL of triethylamine and 30.14 mg of trimethoxy chlorosilane were sequentially added, and the mixture was stirred and mixed uniformly, and then reacted at room temperature under stirring for 24 h. After the reaction was completed, the obtained crude product liquid was vacuum rotary evaporated to remove the solvent and unreacted trimethoxy chlorosilane, washed with methanol, and dried at 45°C until the weight was constant, to obtain Z-type perfluoropolyether siloxane (colorless and transparent, with a yield of 95%).

[0076] The infrared spectrum (KBr) of the Z-type perfluoropolyether siloxane was: 2954, 2925, 2854, 1463, 1401, 1151, 1099, 1057, 836, 814, 720, 688, 557, 536 cm -1 .

[0077] Example 2

[0078] 2 g of Z-type perfluoropolyether alcohol (p+q=55, Mw=10000 g / mol) was placed in a 50 mL round-bottom flask, 10 mL of acetonitrile, 5 mL of perfluoro cyclic ether, 1 mL of triethylamine and 37.68 mg of trimethoxy chlorosilane were sequentially added, and the mixture was stirred and mixed uniformly, and then reacted at room temperature under stirring for 24 h. After the reaction was completed, the obtained crude product liquid was vacuum rotary evaporated to remove the solvent and unreacted trimethoxy chlorosilane, washed with methanol, and dried at 45°C until the weight was constant, to obtain Z-type perfluoropolyether siloxane (colorless and transparent, with a yield of 96%).

[0079] The infrared spectrum (KBr) of the Z-type perfluoropolyether siloxane was: 2955, 2926, 2856, 1463, 1402, 1150, 1098, 1062, 836, 815, 728, 687, 559, 534 cm -1 .

[0080] Example 3

[0081] 2 g of double-ended Z-type perfluoropolyether alcohol (p+q=10, Mw=2000 g / mol) was placed in a 50 mL round-bottom flask, and 10 mL of acetonitrile, 5 mL of perfluorocyclic ether, 2 mL of triethylamine and 325.93 mg of trimethoxychlorosilane were added in sequence and stirred to mix evenly. The mixture was reacted at room temperature with stirring for 24 h. After the reaction, the crude product liquid was vacuum evaporated to remove the solvent and unreacted trimethoxychlorosilane, washed with methanol, and dried at 45 ° C to constant weight to obtain double-ended Z-type perfluoropolyether siloxane (colorless and transparent, yield 95%).

[0082] Infrared spectrum of double-terminated Z-type perfluoropolyether siloxane (KBr): 2954, 2925, 2855, 1462, 1401, 1152, 1097, 1056, 836, 814, 721, 688, 557, 536 cm -1 .

[0083] Example 4

[0084] 2 g of double-terminal Z-type perfluoropolyether alcohol (p+q=55, Mw=10000 g / mol) was placed in a 50 mL round-bottom flask, and 10 mL of acetonitrile, 5 mL of perfluorocyclic ether, 1 mL of triethylamine and 95.39 mg of triethoxychlorosilane were added in sequence and stirred to mix evenly. The mixture was reacted at room temperature with stirring for 24 h. After the reaction, the crude product liquid was vacuum evaporated to remove the solvent and unreacted triethoxychlorosilane, washed with methanol, and dried at 45 ° C to constant weight to obtain double-terminal Z-type perfluoropolyether siloxane (colorless and transparent, with a yield of 94%).

[0085] Infrared spectrum of double-terminated Z-type perfluoropolyether siloxane (KBr): 2955, 2927, 2854, 1463, 1402, 1153, 1100, 1057, 837, 814, 719, 688, 556, 535 cm -1 .

[0086] Example 5

[0087] A 50 mL round bottom flask was charged with 2 g of Z-type perfluoropolyether diol (p+q=110, Mw=20000 g / mol), 10 mL of ethanol and 14.97 mg of sodium ethoxide, and the mixture was stirred at room temperature for 1 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation to obtain sodium Z-type perfluoropolyether diol (white viscous liquid). A 50 mL round bottom flask containing the sodium Z-type perfluoropolyether diol was charged with 10 mL of acetonitrile, 5 mL of perfluoro cyclic ether, and 30.14 mg of chlorotrimethylsilane, and the mixture was stirred at room temperature for 24 h. After the reaction was completed, the crude product liquid was subjected to vacuum rotary evaporation to remove the solvent and unreacted chlorotrimethylsilane. The solid product was separated by centrifugation, washed with methanol, and dried at 45°C until the weight was constant to obtain Z-type perfluoropolyether siloxane (colorless and transparent, yield 92%).

[0088] The infrared spectrum (KBr) of the Z-type perfluoropolyether siloxane was 2954, 2925, 2856, 1463, 1403, 1151, 1098, 1058, 836, 815, 720, 689, 557, 537 cm -1 .

[0089] Example 6

[0090] A 50 mL round bottom flask was charged with 2 g of Z-type perfluoropolyether diol (p+q=110, Mw=20000 g / mol), 10 mL of ethanol and 14.97 mg of sodium ethoxide, and the mixture was stirred at room temperature for 1 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation to obtain sodium Z-type perfluoropolyether diol (white viscous liquid). A 50 mL round bottom flask containing the sodium Z-type perfluoropolyether diol was charged with 10 mL of acetonitrile, 5 mL of perfluoro cyclic ether, and 30.14 mg of chlorotrimethylsilane, and the mixture was stirred at room temperature for 24 h. After the reaction was completed, the crude product liquid was subjected to vacuum rotary evaporation to remove the solvent and unreacted chlorotrimethylsilane. The solid product was separated by centrifugation, washed with methanol, and dried at 45°C until the weight was constant to obtain Z-type perfluoropolyether siloxane (colorless and transparent, yield 92%).

[0091] The infrared spectrum (KBr) of the Z-type perfluoropolyether siloxane was 2954, 2925, 2856, 1463, 1403, 1151, 1098, 1058, 836, 815, 720, 689, 557, 537 cm -1 .

[0092] Example 7

[0093] Into a 50 mL round bottom flask, 2 g of Z-type perfluoropolyether diol (p+q=10, Mw=2000 g / mol) was placed, followed by the addition of 10 mL of ethanol and 149.97 mg of sodium ethoxide, and the reaction was stirred at room temperature for 1 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation to obtain sodium Z-type perfluoropolyether diol (white viscous liquid). Into the 50 mL round bottom flask containing the sodium Z-type perfluoropolyether diol, 10 mL of acetonitrile, 3 mL of perfluoro cyclic ether, and 325.93 mg of chlorotrimethylsilane were sequentially added, and the reaction was stirred at room temperature for 24 h. After the reaction was completed, the obtained crude product liquid was subjected to vacuum rotary evaporation to remove the solvent and unreacted chlorotrimethylsilane. The obtained solid product was centrifuged, washed with methanol, and dried at 45°C until the weight was constant to obtain Z-type perfluoropolyether siloxane (colorless and transparent, yield 95%).

[0094] The infrared spectrum (KBr) of the Z-type perfluoropolyether siloxane was 2953, 2926, 2853, 1462, 1400, 1152, 1099, 1057, 835, 815, 721, 689, 557, 537 cm -1 .

[0095] Example 8

[0096] Into a 50 mL round bottom flask, 2 g of Z-type perfluoropolyether diol (p+q=55, Mw=10000 g / mol) was placed, followed by the addition of 10 mL of ethanol and 29.94 mg of sodium ethoxide, and the reaction was stirred at room temperature for 1 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation to obtain sodium Z-type perfluoropolyether diol (white viscous liquid). Into the 50 mL round bottom flask containing the sodium Z-type perfluoropolyether diol, 10 mL of acetonitrile, 3 mL of perfluoro cyclic ether, and 96.36 mg of chlorotrimethylsilane were sequentially added, and the reaction was stirred at room temperature for 24 h. After the reaction was completed, the obtained crude product liquid was subjected to vacuum rotary evaporation to remove the solvent and unreacted chlorotrimethylsilane. The obtained solid product was centrifuged, washed with methanol, and dried at 45°C until the weight was constant to obtain Z-type perfluoropolyether siloxane (colorless and transparent, yield 93%).

[0097] The infrared spectrum (KBr) of the Z-type perfluoropolyether siloxane was 2954, 2925, 2854, 1464, 1401, 1151, 1099, 1055, 836, 814, 720, 689, 557, 536 cm -1 .

[0098] Test Example

[0099] The Z-type perfluoropolyether silicone films prepared in Examples 1-8 were respectively loaded on the surface of a silicon wafer to form Z-type perfluoropolyether silicone films with a thickness of 10-100 μm, and the contact angle and wear resistance of the Z-type perfluoropolyether silicone films were tested.

[0100] (1) Contact angle test

[0101] The contact angle was tested by a contact angle measuring instrument, and water and diiodomethane were respectively dropped on the surface of the Z-type perfluoropolyether silicone film sample, with a volume of 5 μL for each drop, and the testing temperature was 25°C. The surface tension test method was the Owens two-liquid method.

[0102] The contact angle test results are shown in Table 1.

[0103] Table 1 Water and diiodomethane contact angles and surface tension of the silicon wafer and the Z-type perfluoropolyether silicone films of Examples 1-8

[0104] Example Water contact angle Diiodomethane contact angle Surface tension Silicon wafer 87° 53° 44.41 mN / m Example 1 102° 100° 11.86 mN / m Example 2 119° 99° 8.88 mN / m Example 3 119° 99° 8.94 mN / m Example 4 117° 99° 9.21 mN / m Example 5 95° 100° 12.40 nM / m Example 6 114° 99° 9.42 mN / m Example 7 117° 100° 8.78 mN / m Example 8 116° 100° 8.84 mN / m

[0105] As can be seen from Table 1, the water contact angle of the Z-type perfluoropolyether silicone prepared in the application is above 95°, the diiodomethane contact angle is above 99°, and the surface tension is below 13 mN / m, indicating that the Z-type perfluoropolyether silicone prepared in the application can effectively reduce the surface tension of the silicon wafer and has excellent antifouling performance.

[0106] (2) Wear resistance test

[0107] The Z-type perfluoropolyether silicone films were tested for friction by using an MS-9000 friction tester, with 0000# rhinoceros steel wool as the friction medium, a friction stroke of 2 mm, a frequency of 2 Hz, a load of 2 N, and reciprocating friction. The water contact angle was tested after friction for 3000 times, 5000 times and 10000 times, respectively.

[0108] The water contact angle test method was the same as the above contact angle test method.

[0109] The wear resistance test results are shown in Table 2.

[0110] Table 2 Water contact angles of the silicon wafer and the Z-type perfluoropolyether silicone films of Examples 1-8 after steel wool abrasion test

[0111] Example Rubbed 3000 times Rubbed 5000 times Rubbed 10000 times Silicon wafer 83° 83° 83° Example 1 86° 87° 87° Example 2 96° 93° 93° Example 3 95° 94° 90° Example 4 94° 87° 85° Example 5 87° 85° 87° Example 6 95° 90° 87° Example 7 96° 94° 90° Example 8 94° 91° 89°

[0112] As can be seen from Table 2, the water contact angle of the Z-type perfluoropolyether silicone film prepared in the application is still above 85° after 10000 times of steel wool friction, indicating that the Z-type perfluoropolyether silicone prepared in the application has excellent wear resistance.

[0113] The above merely describes the preferred embodiments of the present application, and it should be pointed out that, for those skilled in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as falling within the protection scope of the present application.

Claims

1. A double-end Z-type perfluoropolyether siloxane, having a structure shown in Formula I: wherein R is a C1-C3 alkyl group; and p+q=10-55. In the Formula I, the ratio of the values of p and q is 1:2-3. 2.A method for preparing the double-end Z-type perfluoropolyether siloxane according to claim 1, comprising Method I or Method II. The Method I comprises the following steps: mixing a double-end Z-type perfluoropolyether alcohol, chlorosiloxane, a tertiary amine, and a first heteroatom-fluorine mixed solvent to perform a first condensation reaction, thereby obtaining the double-end Z-type perfluoropolyether siloxane; The Method II comprises the following steps: mixing a double-end Z-type perfluoropolyether alcohol, sodium alcoholate, and alcohol to perform a substitution reaction, thereby obtaining a double-end Z-type perfluoropolyether sodium alcoholate; mixing the double-end Z-type perfluoropolyether sodium alcoholate with chlorosiloxane and a second heteroatom-fluorine mixed solvent to perform a second condensation reaction, thereby obtaining the double-end Z-type perfluoropolyether siloxane; The double-end Z-type perfluoropolyether alcohol has a chemical formula shown in Formula II: wherein p and q have the same value range as p and q in the Formula I. The double-end Z-type perfluoropolyether alcohol has a weight average molecular weight of 2000-10000 g / mol. HOCH2-(CF2CF2O) p (CF2O) q -CH2OH Formula II; The chlorosiloxane has a chemical formula of ROSiCl, wherein R is the same as R in the Formula I. In the Method I, the molar ratio of the double-end Z-type perfluoropolyether alcohol to the tertiary amine is 1:1-2. The tertiary amine comprises one or more of triethylamine, tripropylamine, tributylamine, trihexylamine, tris(benzyl)amine, dodecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, and hexadecyl dimethyl tertiary amine.

3. The preparation method according to claim 2, characterized in that In the Method I and the Method II, the molar ratio of the double-end Z-type perfluoropolyether alcohol to the chlorosiloxane is independently 1:2-4. In the Method II, the molar ratio of the double-end Z-type perfluoropolyether alcohol to the sodium alcoholate is 1:2-2.

5.

4. The preparation method according to claim 2, characterized in that The sodium alcoholate comprises one or more of sodium methoxide, sodium ethoxide, and sodium tert-butoxide.

5. The preparation method according to claim 2, characterized in that The alcohol comprises one or more of methanol, ethanol, and tert-butanol. In the Method II, the substitution reaction is performed at a temperature of 20-40℃ for 8-16 hours. The first heteroatom-fluorine mixed solvent and the second heteroatom-fluorine mixed solvent each comprise a heteroatom-containing organic solvent and a fluorine-containing organic solvent.

6. The production method according to claim 2, 4 or 5, characterized by, The heteroatom-containing organic solvent independently comprises one or more of acetonitrile, butanone, tetrahydrofuran, 1,4-dioxane, and N-methyl pyrrolidone.

7. The preparation method according to claim 2, characterized in that The fluorine-containing organic solvent independently comprises one or more of perfluorocyclic ether, perfluorohexane, trifluorotrichloroethane, and dichlorodifluoroethane. In the first heteroatom-fluorine mixed solvent and the second heteroatom-fluorine mixed solvent, the volume ratio of the heteroatom-containing organic solvent to the fluorine-containing organic solvent is independently 1:0.25-0.

5. The temperature of the first condensation reaction and the second condensation reaction is independently 25-35℃, and the time is independently 5-24 hours. 9.The double-end Z-type perfluoropolyether siloxane according to claim 1, or the double-end Z-type perfluoropolyether siloxane prepared by the method according to any one of claims 2-8, as a coating material.

8. The production method according to claim 2, 3, 4, 5 or 7, characterized by, ​ ​

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