Acrylate containing perfluoropolyether and synthesis method thereof

Abstract

The invention relates to the technical field of organic matter synthesis, and particularly discloses acrylic ester containing perfluoropolyether and a synthesis method of the acrylic ester, the structural general formula of the acrylic ester is Rf (CH2) mOC (O) CR1 = CH2, Rf is a perfluoropolyether fragment, and R1 is H, Me, CF3 or a halogen atom; m > = 1. Acrylic ester is obtained by taking perfluoropolyether alcohol and acrylic anhydride as raw materials and adding a solvent, a catalyst and alkali for reaction, acyl chloride with low flash point and high toxicity is not used as a raw material, and acrylic anhydride with low flash point and no toxicity is used as a raw material and reacts with perfluoropolyether alcohol, so that the acrylic ester is obtained. The perfluoropolyether-containing acrylate with excellent performance can be prepared, the reaction conditions are mild, the raw materials have the advantages of no toxicity and high flash point, a reaction system does not need to be waterless and oxygen-free, no obvious heat release exists in the reaction process, the reaction process is safe, no HCl gas is generated in the reaction process, and large-scale production is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to an acrylate containing perfluoropolyether and a synthesis method thereof. Background Art

[0002] Fluorine-containing polymers mainly refer to compounds formed by partial or complete replacement of hydrogen atoms in the main chain or side chain of organic polymers by fluorine atoms. On the one hand, fluorine atoms have strong electronegativity, small radius, low polarizability, and the CF bond formed is quite stable; on the other hand, the negative charge density on fluorine atoms is large, and fluorine atoms are larger than hydrogen atoms, so that the fluorine atoms linked to adjacent carbon atoms repel each other, resulting in a smaller bond angle of carbon-carbon bonds, so that the fluorine atoms linked to adjacent carbon atoms cannot be in the same plane. Fluorine atoms are therefore distributed in a spiral along the carbon chain and surrounded by the carbon chain. Fluorine atoms play a good shielding role on carbon-carbon bonds. Therefore, the surface energy of fluorine-containing polymers is significantly reduced, showing excellent hydrophobicity and oleophobicity, chemical inertness, good heat resistance and flame retardant properties. Due to their unique excellent properties, fluorine-containing polymers have been widely used as important polymer materials, especially coating materials. However, long-chain fluorocarbon compounds have the disadvantages of being difficult to degrade, having high bioaccumulative toxicity and great environmental hazards, and their scope of use has been gradually restricted. In this context, perfluoropolyether, another important member of fluorocarbons, is an ideal material to replace traditional fluorocarbons because of its natural advantages of biodegradability and low cumulative toxicity.

[0003] Fluorinated acrylate monomers can be obtained by partially or completely replacing the carbon-hydrogen bonds of acrylate with fluorine atoms. Self-polymerization or copolymerization of fluorinated acrylate monomers has become an important method for preparing fluorinated polymers. Since the reaction enthalpy and Qe value of fluorinated alkyl acrylate monomers (fluorinated acrylate monomers) are basically the same as those of ordinary acrylate monomers, fluorinated alkyl acrylate monomers can easily undergo free radical homopolymerization or free radical copolymerization with non-fluorinated monomers to prepare fluorinated polymers.

[0004] At present, fluorinated acrylate monomers are mainly obtained by the reaction of fluorinated aliphatic alcohols with (meth)acryloyl chloride. (Meth)acryloyl chloride has the advantages of high reactivity and relatively mild reaction conditions. However, the reaction will produce HCl gas, so an acid-binding agent needs to be added to neutralize it. Common acid-binding agents include tertiary amines such as TEA, DBU, and DMAP. Moreover, when (meth)acryloyl chloride is used as a raw material, the reaction is carried out under water-free and oxygen-free conditions, and the acyl chloride has high toxicity and a low flash point, which is not conducive to industrial production. Summary of the invention

[0005] The object of the present invention is to provide an acrylate containing perfluoropolyether and a synthesis method thereof. The raw materials used to synthesize the acrylate have the advantages of being non-toxic or low-toxic and having a high flash point, and the synthesis method is simple and easy, has a high reaction rate, and is mild under mild conditions, which is conducive to large-scale production.

[0006] The present invention is achieved through the following technical solutions:

[0007] A perfluoropolyether-containing acrylate, the general structural formula of the acrylate is Rf(CH 2 ) m OC(O)CR 1 =CH 2 , wherein Rf is a perfluoropolyether fragment, R 1 H, Me, CF 3 Or a halogen atom; m≥1.

[0008] The acrylate of the invention is obtained by reacting perfluoropolyether alcohol and acid anhydride as raw materials, adding a solvent, a catalyst and a base. The invention does not use low-flash-point and highly toxic acyl chloride as the raw material, but uses non-toxic and high-flash-point acid anhydride as the raw material to react with the perfluoropolyether alcohol. The acrylate containing perfluoropolyether can not only prepare excellent performance, but also has the advantages of mild reaction conditions, non-toxic raw materials and high flash points, the reaction system does not need to be anhydrous and oxygen-free, and there is no obvious heat release during the reaction. The invention is safe, and no HCl gas is generated during the reaction, which is conducive to large-scale production.

[0009] A method for synthesizing acrylate containing perfluoropolyether comprises the following steps:

[0010] The catalyst is added into a reaction container, and then a solvent, a base and anhydride are added, stirred, and then perfluoropolyether alcohol is added for reaction. After the reaction is completed, the reaction is allowed to stand for stratification, and the lower layer of liquid is collected and spin-dried to obtain the target product; the solvent is immiscible with the perfluoropolyether alcohol, and the catalyst, base and acrylic anhydride are soluble in the solvent.

[0011] The acrylic anhydride used in the synthesis method of the present invention has the advantages of being non-toxic and having a high flash point.

[0012] The present invention adopts a heterogeneous reaction: the solvent and the perfluoropolyether alcohol are immiscible, while the catalyst, the base and acrylic anhydride are soluble in the solvent. After the reaction is completed, the excess acrylic anhydride, the catalyst and the base are in the solvent layer, while the product is in the lower layer. After the reaction is completed, the lower layer liquid is collected, and a small amount of solvent in it is dried by spin drying to obtain the product. No complicated post-processing is required, and the target product can be obtained with high yield and high purity.

[0013] In a preferred embodiment, the molar ratio of perfluoropolyether alcohol: anhydride: catalyst: base is 1: 1-2: 0.05-0.3: 0.5-1.5.

[0014] In a preferred embodiment, the perfluoropolyether alcohol includes Y-type, Z-type or K-type, and its molecular weight ranges from 500 to 8000.

[0015] In a preferred embodiment, the acid anhydride includes at least one of methacrylic anhydride and acrylic anhydride.

[0016] In a preferred embodiment, the solvent includes at least one of dichloromethane, acetonitrile, tetrahydrofuran, toluene, N,N-dimethylformamide and diethyl ether.

[0017] In a preferred embodiment, the catalyst includes at least one of N,N-dimethylpyridine and pyridine. N,N-dimethylpyridine is preferably used, which has obvious advantages over pyridine as a catalyst: for example, pyridine is included in the list of Class 2B carcinogens, and the acylation reaction rate catalyzed by N,N-dimethylpyridine is 103-105 times faster than that of pyridine.

[0018] In a preferred embodiment, the base is at least one of triethylamine, DBU, DBN and DIPEA.

[0019] In a preferred embodiment, the temperature of the reaction system is 25°C-80°C; and the reaction time is 6h-24h.

[0020] In a preferred embodiment, the mixture is stirred for 0.5 h to 2 h before adding the perfluoropolyether alcohol.

[0021] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0022] The raw materials used to synthesize the acrylic ester of the present invention have the advantages of being non-toxic or low-toxic and having a high flash point, and the reaction system does not need to be anhydrous and oxygen-free, and there is no obvious heat release during the reaction, which is safe; the synthesis method is simple and easy, the reaction rate is high, and the conditions are mild, and the board invention adopts a heterogeneous reaction, does not require complex post-processing, and is conducive to large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings described herein are used to provide a further understanding of the embodiments of the present invention, constitute a part of this application, and do not constitute a limitation of the embodiments of the present invention. In the drawings:

[0024] Figure 1 This is the NMR image of the acrylate prepared in Example 1 of the present invention;

[0025] Figure 2 This is an infrared image of the acrylate prepared in Example 1 of the present invention;

[0026] Figure 3 This is the NMR image of the acrylate prepared in Example 2 of the present invention;

[0027] Figure 4This is the NMR image of the acrylate prepared in Example 3 of the present invention;

[0028] Figure 5 This is the NMR image of the acrylate prepared in Example 4 of the present invention;

[0029] Figure 6 This is the NMR image of the acrylate prepared in Example 6 of the present invention;

[0030] Figure 7 This is the NMR image of the acrylate prepared in Example 10 of the present invention;

[0031] Figure 8 This is the NMR image of the acrylate prepared in Example 11 of the present invention;

[0032] Fig. 9 This is the NMR image of the acrylate prepared in Example 12 of the present invention;

[0033] Fig.10 This is the NMR image of the acrylate prepared in Example 13 of the present invention. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. The schematic implementation mode of the present invention and its description are only used to explain the present invention and are not intended to limit the present invention. The embodiments described below are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0035] In the following description, a large number of specific details are set forth in order to provide a thorough understanding of the present invention. However, it is apparent to those of ordinary skill in the art that these specific details do not have to be employed to practice the present invention. In other embodiments, in order to avoid confusing the present invention, known structures, materials or methods are not specifically described. The materials, instruments and reagents used in the following examples, unless otherwise specified, can be obtained from commercial sources. The technical means used in the examples, unless otherwise specified, are conventional means well known to those skilled in the art.

[0036] In order to solve the problem that the existing fluorinated acrylate monomer is mainly obtained by the reaction of fluorinated aliphatic alcohol and (meth) acryloyl chloride, the reaction will produce HCl gas, so it is necessary to add an acid binding agent to neutralize it. Common acid binding agents include tertiary amine substances such as TEA, DBU, and DMAP; and the use of (meth) acryloyl chloride as a raw material is carried out under anhydrous and oxygen-free conditions, and the acyl chloride has a high toxicity and a low flash point, which is not conducive to industrial production. This embodiment provides a perfluoropolyether-containing acrylate, the general structural formula of which is Rf(CH 2 ) m OC(O)CR 1 =CH 2 , wherein Rf is a perfluoropolyether fragment, R 1 H, Me, CF 3 Or a halogen atom; m≥1.

[0037] The acrylic ester of the present embodiment is obtained by reacting perfluoropolyether alcohol and acid anhydride as raw materials, adding solvent, catalyst and base. The present invention does not use low flash point and highly toxic acyl chloride as raw material, but uses non-toxic and high flash point acrylic anhydride as raw material to react with perfluoropolyether alcohol. Not only can the acrylic ester containing perfluoropolyether with excellent performance be prepared, but the reaction conditions are mild, the raw materials have the advantages of non-toxicity and high flash point, the reaction system does not need to be anhydrous and oxygen-free, there is no obvious heat release during the reaction, it is safe, and no HCl gas is generated during the reaction, which is conducive to large-scale production.

[0038] The specific synthesis method comprises the following steps:

[0039] The catalyst is added into a reaction container, and then a solvent, a base and acrylic anhydride are added, stirred, and then perfluoropolyether alcohol is added for reaction. After the reaction is completed, the reaction is allowed to stand for stratification, and the lower layer of liquid is collected and spin-dried to obtain the target product; the solvent is immiscible with the perfluoropolyether alcohol, and the catalyst, the base and acrylic anhydride are soluble in the solvent.

[0040] This embodiment adopts a heterogeneous reaction: the solvent and the perfluoropolyether alcohol are immiscible, while the catalyst, the base and acrylic anhydride are soluble in the solvent. After the reaction is completed, the excess acrylic anhydride, the catalyst and the base are in the solvent layer, while the product is in the lower layer. After the reaction is completed, the lower layer liquid is collected, and a small amount of solvent in it is dried by spin drying to obtain the product. No complicated post-processing is required, and the target product can be obtained with high yield and high purity.

[0041] The perfluoropolyether alcohol includes Y type, Z type or K type, and its molecular weight ranges from 500 to 8000; the acid anhydride includes at least one of methacrylic anhydride and acrylic anhydride.

[0042] The solvent includes at least one of dichloromethane, acetonitrile, tetrahydrofuran, toluene, N,N-dimethylformamide and diethyl ether; the catalyst includes at least one of N,N-dimethylpyridine and pyridine; and the base includes at least one of triethylamine, DBU, DBN and DIPEA.

[0043] The temperature of the reaction system is 25°C-80°C; the reaction time is 6h-24h; and the mixture is stirred for 0.5h-2h before adding the perfluoropolyether alcohol.

[0044] Preferably, the volume ratio of perfluoropolyether alcohol: acrylic anhydride: catalyst: base is 1: 1-2: 0.05-0.3: 0.5-1.5. After the specific selection of the catalyst and the base is determined, the mass ratio of perfluoropolyether alcohol, acrylic anhydride, catalyst and base has a great influence on the yield of the product. Therefore, it is necessary to reasonably control the mass ratio of perfluoropolyether alcohol, acrylic anhydride, catalyst and base.

[0045] Embodiment 1:

[0046] The catalyst of this embodiment is N,N-dimethylpyridine, the acid anhydride is methacrylic anhydride, the solvent is dichloromethane, and the base is triethylamine. The acrylate of this embodiment is obtained by reacting K-type perfluoropolyether alcohol and methacrylic anhydride with dichloromethane, N,N-dimethylpyridine and triethylamine, and the general structural formula is Rf(CH 2 )OC(O)C(CH 3 )=CH 2 , wherein Rf is a perfluoropolyether fragment, that is, in this embodiment, R 1 Me, m = 1; the specific structural formula is as follows:

[0047]

[0048] The method for synthesizing the acrylic acid ester of the present embodiment comprises the following steps:

[0049] A 250 mL single-mouth bottle was used as the reaction vessel, and the reaction device was equipped with a magnetic stirrer. N, N-dimethylpyridine (0.16 g), dichloromethane (100 mL), triethylamine (0.88 g), and methacrylic anhydride (1.62 g) were added at room temperature and pressure, stirred for half an hour, and then perfluoropolyether alcohol (10 g, molecular weight: 1000) was added and stirred for 24 hours. Feed ratio (molar ratio): perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.2:0.1:1. After the reaction was completed, the reaction was allowed to stand for stratification, and the lower layer of liquid was collected and dried to obtain a colorless transparent liquid. The yield was 67%.

[0050] The synthetic route of the present embodiment is as follows:

[0051]

[0052] The NMR of the acrylate prepared in this example is as follows Figure 1 As shown, the infrared spectrum is as Figure 2 As shown, from Figure 1 , Figure 2 It was found that a small amount of perfluoropolyether alcohol remained unreacted.

[0053] Embodiment 2:

[0054] This embodiment is based on embodiment 1, and the difference from embodiment 1 is that the amount of methacrylic anhydride is increased. Specifically:

[0055] A 250 mL single-mouth bottle was used as the reaction vessel. The reaction device was equipped with a magnetic stirrer. N, N-dimethylpyridine (0.16 g), dichloromethane (100 mL), triethylamine (0.88 g), and methacrylic anhydride (1.75 g) were added at room temperature and pressure, stirred for half an hour, and then perfluoropolyether alcohol (10 g, molecular weight: 1000) was added, and stirring was continued for 24 hours. Feed ratio: perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.3:0.1:1. After the reaction was completed, the layers were allowed to stand and the lower layer of liquid was collected and dried to obtain a colorless transparent liquid. The yield was 92%.

[0056] The NMR of the acrylate prepared in this example is as follows Figure 3 As shown, from Figure 3 It can be seen that a small amount of perfluoropolyether alcohol remains unreacted.

[0057] From the comparison between Example 2 and Example 1, it can be seen that:

[0058] When the amounts of perfluoropolyether alcohol, N,N-dimethylpyridine and triethylamine remain unchanged, increasing the amount of methacrylic anhydride can improve the product yield, but a small amount of perfluoropolyether alcohol will still remain unreacted.

[0059] Embodiment 3:

[0060] This embodiment is based on embodiment 1, and the difference from embodiment 1 is that the amount of methacrylic anhydride and N,N-dimethylpyridine is increased. Specifically:

[0061] A 250 mL single-mouth bottle was used as the reaction vessel. The reaction device was equipped with a magnetic stirrer. N, N-dimethylpyridine (0.21 g), dichloromethane (100 mL), triethylamine (0.88 g), and methacrylic anhydride (2.02 g) were added at room temperature and pressure, stirred for half an hour, and then perfluoropolyether alcohol (10 g, molecular weight: 1000) was added, and stirring was continued for 24 hours. Feed ratio: perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1: 1.5: 0.2: 1. After the reaction was completed, the layers were allowed to stand and the lower layer of liquid was collected and dried to obtain a colorless transparent liquid. The yield was 96%.

[0062] The NMR of the acrylate prepared in this example is as follows Figure 4 As shown, from Figure 4 It can be seen that the perfluoropolyether alcohol reacts completely.

[0063] From the comparison of Example 1 to Example 3, it can be seen that:

[0064] The feed ratio of fluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine will affect the product yield. When the ratio of fluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine is 1:1.5:0.2:1, the perfluoropolyether alcohol reacts completely and the yield reaches 96%.

[0065] This embodiment not only has a higher yield, but also adopts a heterogeneous reaction, and does not require complicated post-treatment. Dichloromethane and perfluoropolyether alcohol are not miscible (high molecular weight perfluoropolyether alcohol is almost insoluble in dichloromethane), while N, N-dimethylpyridine, triethylamine, and methacrylic anhydride are soluble in dichloromethane. After the reaction is completed, excess methacrylic anhydride, triethylamine, and N, N-dimethylpyridine will be in the dichloromethane layer, and the product will be in the lower layer. After the reaction is completed, the lower layer liquid is collected, and a small amount of solvent in it is dried by spin drying to obtain the product.

[0066] Embodiment 4:

[0067] The catalyst of this embodiment is N,N-dimethylpyridine, the acid anhydride is methacrylic anhydride, the solvent is acetonitrile, and the base is triethylamine. The method for synthesizing acrylate of this embodiment comprises the following steps:

[0068] A 250 mL single-mouth bottle was used as the reaction vessel. The reaction device was equipped with a magnetic stirrer. N, N-dimethylpyridine (0.21 g), acetonitrile (100 mL), triethylamine (0.88 g), and methacrylic anhydride (2.02 g) were added at room temperature and pressure, stirred for half an hour, and then perfluoropolyether alcohol (10 g, molecular weight: 1000) was added, and stirring was continued for 24 hours. Feed ratio: perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1: 1.5: 0.2: 1. After the reaction was completed, the layers were allowed to stand and the lower layer of liquid was collected and dried to obtain a colorless transparent liquid. The yield was 97%.

[0069] The NMR of the acrylate prepared in this example is as follows Figure 5 As shown, from Figure 5 It can be seen that the perfluoropolyether alcohol reacts completely.

[0070] Embodiment 5:

[0071] The catalyst of this embodiment is N,N-dimethylpyridine, the acid anhydride is methacrylic anhydride, the solvent is tetrahydrofuran, and the base is triethylamine. The method for synthesizing acrylate of this embodiment comprises the following steps:

[0072] A 250 mL single-mouth bottle was used as the reaction vessel, and the reaction device was equipped with a magnetic stirrer. N, N-dimethylpyridine (0.21 g), tetrahydrofuran (100 mL), triethylamine (0.88 g), and methacrylic anhydride (2.02 g) were added at room temperature and pressure, stirred for half an hour, and then perfluoropolyether alcohol (10 g, molecular weight: 1000) was added to react for 24 hours. Feed ratio: perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.5:0.2:1. After the reaction was completed, the layers were allowed to stand and the lower layer of liquid was collected and spin-dried to obtain a colorless transparent liquid. The yield was 95%. The perfluoropolyether alcohol in this embodiment reacted completely.

[0073] Embodiment 6:

[0074] This embodiment is based on Example 1, and the difference from Example 1 is that: the amount of methacrylic anhydride and N, N-dimethylpyridine is increased, and the reaction time is shortened. Specifically:

[0075] A 250 mL single-mouth bottle was used as the reaction vessel. The reaction device was equipped with a magnetic stirrer. N, N-dimethylpyridine (0.21 g), dichloromethane (100 mL), triethylamine (0.88 g), and methacrylic anhydride (2.02 g) were added at room temperature and pressure, stirred for half an hour, and then perfluoropolyether alcohol (10 g, molecular weight: 1000) was added to react for 6 hours. The feed ratio was perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.5:0.2:1. After the reaction was completed, the mixture was allowed to stand for stratification, and the lower layer of liquid was collected and dried to obtain a colorless transparent liquid. The yield was 96%.

[0076] The NMR of the acrylate prepared in this example is as follows Figure 6 As shown, from Figure 6 It can be seen that the perfluoropolyether alcohol reacts completely.

[0077] From the comparison between Example 1 and Example 6, it can be seen that:

[0078] When the dosage of methacrylic anhydride and N, N-dimethylpyridine is increased, even if the reaction time is shortened, the perfluoropolyether alcohol can be completely reacted to ensure the product yield.

[0079] Embodiment 7:

[0080] The difference between this embodiment and embodiment 6 is that the catalyst used is pyridine, and the reaction time is 24 hours. Specifically:

[0081] A 250 mL single-mouth bottle was used as the reaction vessel, and the reaction device was equipped with a magnetic stirrer. Pyridine (0.27 g), DCM (100 mL), triethylamine (0.88 g), and methacrylic anhydride (2.02 g) were added at room temperature and pressure, stirred for half an hour, and then perfluoropolyether alcohol (10 g, molecular weight: 1000) was added for 24 hours. The feed ratio was perfluoropolyether alcohol: methacrylic anhydride: pyridine: triethylamine = 1: 1.5: 0.2: 1. After the reaction was completed, the mixture was allowed to stand for stratification, and the lower layer of liquid was collected and dried to obtain a colorless transparent liquid. The yield was 84.5%.

[0082] Compared with Example 6, it can be seen that when the catalyst is replaced with pyridine, the reaction time is longer and the yield is reduced.

[0083] Embodiment 8:

[0084] The difference between this embodiment and embodiment 6 is that the acid anhydride used is acrylic anhydride, specifically:

[0085] A 250 mL single-mouth bottle was used as the reaction vessel, and the reaction device was equipped with a magnetic stirrer. N, N-dimethylpyridine (0.21 g), dichloromethane (100 mL), triethylamine (0.88 g), and acrylic anhydride (1.65 g) were added at room temperature and pressure, stirred for half an hour, and then perfluoropolyether alcohol (10 g, molecular weight: 1000) was added to react for 6 hours. The feed ratio was: perfluoropolyether alcohol: acrylic anhydride: N, N-dimethylpyridine: triethylamine = 1: 1.5: 0.2: 1. After the reaction was completed, the reaction was allowed to stand for stratification, and the lower layer of liquid was collected and spun dry to obtain a colorless transparent liquid with a yield of 92%.

[0086] Compared with Example 6, it can be seen that when the raw material is replaced with acrylic anhydride, the corresponding product can also be obtained, but the yield is reduced, and there are trace impurities in the product, and the purity of the product is slightly lower than that of methacrylic anhydride.

[0087] Embodiment 9:

[0088] This embodiment is based on embodiment 6, and the difference from embodiment 6 is that the amount of materials used is enlarged as a whole. Specifically:

[0089] Use a 20L reactor as a container, add N, N-dimethylpyridine (22.46g), dichloromethane (10L), triethylamine (93g), methacrylic anhydride (212.6g) at room temperature and pressure, stir for half an hour, then add perfluoropolyether alcohol (1006g, molecular weight: 1000) and react for 6h. Feed ratio: perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.5:0.2:1. After the reaction is completed, stand and separate, collect the lower layer of liquid and spin dry to obtain a colorless transparent liquid. The yield is 97%. The perfluoropolyether alcohol reacts completely.

[0090] Embodiment 10:

[0091] This embodiment is based on embodiment 6, and the difference from embodiment 6 is that the amount of materials used is enlarged as a whole. Specifically:

[0092] Use a 20L reactor as a container, add N, N-dimethylpyridine (35.91g), dichloromethane (10L), triethylamine (148.73g), methacrylic anhydride (339.89g) at room temperature and pressure, stir for half an hour, then add perfluoropolyether alcohol (1.6kg, molecular weight: 1000) and react for 6h. Feed ratio, perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.5:0.2:1. After the reaction is completed, stand and separate, collect the lower layer of liquid and spin dry to obtain a colorless transparent liquid. The yield is 96%.

[0093] The NMR of the acrylate prepared in this example is as follows Figure 7 As shown, from Figure 7 It can be seen that the perfluoropolyether alcohol reacts completely.

[0094] Embodiment 11:

[0095] This embodiment is based on the embodiment 6, and the difference from the embodiment 6 is that the amount of materials used is enlarged as a whole. Specifically:

[0096] Use a 20L reactor as a container, add N, N-dimethylpyridine (27g), dichloromethane (10L), triethylamine (113g), methacrylic anhydride (258g) at room temperature and pressure, stir for half an hour, then add perfluoropolyether alcohol (1018g, molecular weight: 900) and react for 6h. Feed ratio, perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.5:0.2:1. After the reaction is completed, stand and separate, collect the lower layer of liquid and spin dry to obtain a colorless transparent liquid. The yield is 98%.

[0097] The NMR of the acrylate prepared in this example is as follows Figure 8 As shown, from Figure 8 It can be seen that the perfluoropolyether alcohol reacts completely.

[0098] Embodiment 12:

[0099] This embodiment is based on embodiment 6, and the difference from embodiment 6 is that the amount of materials used is enlarged as a whole. Specifically:

[0100] Use a 20L reactor as a container, add N, N-dimethylpyridine (47g), dichloromethane (10L), triethylamine (195g), methacrylic anhydride (447g) at room temperature and pressure, stir for half an hour, then add hexafluoropropylene oxide trimer perfluoropolyether alcohol (1002g) and react for 6h. Feed ratio, perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.5:0.2:1. After the reaction is completed, stand and separate, collect the lower layer of liquid and spin dry to obtain a colorless transparent liquid. The yield is 97%.

[0101] The NMR of the acrylate prepared in this example is as follows Fig. 9 As shown, from Fig. 9 It can be seen that the perfluoropolyether alcohol reacts completely.

[0102] Embodiment 13:

[0103] This embodiment is based on embodiment 6, and the difference from embodiment 6 is that the amount of materials used is enlarged as a whole. Specifically:

[0104] Use a 20L reactor as a container, add N, N-dimethylpyridine (1.45g), dichloromethane (10L), triethylamine (6.02g), methacrylic anhydride (13.77g) at room temperature and pressure, stir for half an hour, then add Y-type perfluoropolyether alcohol (30g) and react for 6h. Feed ratio, perfluoropolyether alcohol: methacrylic anhydride: N, N-dimethylpyridine: triethylamine = 1:1.5:0.2:1. After the reaction is completed, stand and separate, collect the lower layer of liquid and spin dry to obtain a colorless transparent liquid. The yield is 98%.

[0105] The NMR of the acrylate prepared in this example is as follows Fig.10 As shown, from Fig.10 It can be seen that the perfluoropolyether alcohol reacts completely.

[0106] From the comparison of Example 1 to Example 13, it can be seen that:

[0107] The feed ratio of perfluoropolyether alcohol: acrylic anhydride: catalyst: base has a great influence on the yield rate. The specific selection of catalyst and acid anhydride has an influence on the yield and purity of the product. When N, N-dimethylpyridine is used as the catalyst and methacrylic anhydride is used as the acid anhydride, the yield rate is the best and the purity is the highest, while the specific selection of solvent and base has little effect on the product yield.

[0108] In summary, the present application screened out the best combination of raw materials, solvents, catalysts and bases through a large number of experiments, and determined the best parameters corresponding to the best combination, among which perfluoropolyether alcohol and methacrylic anhydride are the best raw materials. When the raw materials are a combination of perfluoropolyether alcohol and methacrylic anhydride, N, N-dimethylpyridine is used as a catalyst, triethylamine is used as a base, dichloromethane, acetonitrile, tetrahydrofuran, etc. are used as solvents, and the molar ratio and reaction time between the materials are reasonably designed, so that the yield can be greater than 95%; and the purity is high and almost no impurities are contained.

[0109] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An acrylate containing perfluoropolyether, characterized in that: The general structural formula of the acrylate is Rf(CH2) m OC(O)CR1=CH2, wherein Rf is a perfluoropolyether fragment, R1 is H, Me, CF3 or a halogen atom; m≥1.

2. The method for synthesizing acrylate according to claim 1, wherein: The steps include: The catalyst is added into a reaction container, and then a solvent, a base and an acid anhydride are added, stirred, and then perfluoropolyether alcohol is added for reaction. After the reaction is completed, the reaction is allowed to stand for stratification, and the lower layer of liquid is collected and spin-dried to obtain the target product; the solvent is immiscible with the perfluoropolyether alcohol, and the catalyst, the base and the acid anhydride are soluble in the solvent.

3. The synthesis method according to claim 2, characterized in that The molar ratio of the perfluoropolyether alcohol: the acid anhydride: the catalyst: the base is 1:1-2:0.05-0.3:0.5-1.

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4. The synthesis method according to claim 2, characterized in that The perfluoropolyether alcohol includes Y type, Z type or K type, and its molecular weight ranges from 500 to 8000.

5. The synthesis method according to claim 2, characterized in that The acid anhydride includes at least one of methacrylic anhydride and acrylic anhydride.

6. The synthesis method according to claim 2, characterized in that The solvent includes at least one of dichloromethane, acetonitrile, tetrahydrofuran, toluene, N,N-dimethylformamide and ether.

7. The synthesis method according to claim 2, characterized in that The catalyst includes at least one of N,N-dimethylpyridine and pyridine.

8. The synthesis method according to claim 2, characterized in that The base is at least one of triethylamine, DBU, DBN and DIPEA.

9. The synthesis method according to claim 2, characterized in that: The temperature of the reaction system is 25°C-80°C; the reaction time is 6h-24h.

10. The synthesis method according to claim 2, characterized in that: Before adding the perfluoropolyether alcohol, stir for 0.5 h to 2 h.

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