A compound, a method for preparing the same, and a surfactant

Abstract

This invention provides a compound, its preparation method, and a surfactant, relating to the field of organic compound technology. The chemical formula of the compound is CF3(CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R; n=1~6, m=1~4, y=1~2, R is selected from saturated or unsaturated C1~C5 hydrocarbon groups or halogenated hydrocarbon groups. The compound of the present invention is an environmentally friendly and high-performance fluorinated surfactant. This type of surfactant molecule is decomposable and can decompose into fluorinated olefins under strong ultraviolet light or high temperature (above 200°C). The fluorinated olefins can further decompose into small molecule fluorides. It can also slowly oxidize and decompose under natural conditions. Moreover, the hydrophobicity and oleophobicity of this type of surfactant are not significantly different from those of perfluorinated surfactants. It has good compatibility with alcohols, phenols, and ester solvents, mild performance, and good detergency, foaming, emulsifying, and stabilizing chemical properties.

Description

Technical Field

[0001] This invention relates to the field of organic compound technology, and more particularly to a compound, its preparation method, and a surfactant. Background Technology

[0002] In recent years, research on environmentally friendly fluorinated surfactants has gradually become one of the most active research areas and development priorities among surfactants.

[0003] The hydrophobic group of ordinary surfactants is a long-chain alkane composed of hydrocarbon chains. Replacing the hydrogen atoms in the hydrocarbon chains of ordinary surfactant molecules with fluorine atoms creates fluorocarbon surfactants. Environmentally friendly fluorinated surfactants have the same hydrophilic group as ordinary surfactants, so they can be classified into various types, including anionic environmentally friendly fluorinated surfactants, cationic environmentally friendly fluorinated surfactants, nonionic environmentally friendly fluorinated surfactants, and amphoteric environmentally friendly fluorinated surfactants.

[0004] For a long time, perfluorinated surfactants have been widely used and received much attention in the market due to their irreplaceable role in industries such as fluorinated materials, fabric finishing agents, coatings, pigments, and additives. However, recent studies have found that PFAS (perfluorinated and polyfluoroalkyl substances, PFOA, PFOS, PFBS, PFHxS, PFBA, GenX) are difficult to degrade in the natural environment and have high bioaccumulation, easily accumulating in human and animal tissues and causing toxicity. As a result, they have been banned or restricted by countries around the world (including the EU, the US, and Canada). Therefore, developing new environmentally friendly fluorocarbon surfactants to replace PFAS is imperative. This trend is becoming increasingly severe in the context of modern green industry. Summary of the Invention

[0005] This invention provides a compound, its preparation method, and a surfactant to address the shortcomings of traditional perfluorinated and polyfluoroalkyl fluorinated surfactants, such as poor degradation and high bioaccumulation. It develops novel environmentally friendly fluorinated surfactants, enabling the efficient application of fluorinated surfactants that are easily degradable, safe, environmentally friendly, and have low biohazard, thus meeting the needs of various industries and the development of modern green industry.

[0006] In a first aspect, the present invention provides a compound having the chemical formula CF3(CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R; Where n = 1 to 6, for example, it can be 1, 2, 3, 4, 5, 6, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable. m = 1~4, for example, it can be 1, 2, 3, 4, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable. y = 1~2; R is selected from saturated or unsaturated C1-C5 hydrocarbon groups or haloalkyl groups.

[0007] The compound provided by this invention is an environmentally friendly and high-performance fluorinated surfactant. On the one hand, this type of surfactant molecule is decomposable, with the -CF2CH2CF2- or -CH2CF2CH2- segments embedded in the whole. It is precisely the introduction of H on the carbon atom adjacent to fluorine that allows it to decompose into fluorinated olefins under strong ultraviolet light or high temperature (above 200°C). The fluorinated olefins can further decompose into small molecule fluorides. Under natural conditions, it can slowly oxidize and decompose. On the other hand, this type of surfactant has similar hydrophobicity and oleophobicity to perfluorinated surfactants, and has good compatibility with alcohols, phenols, and ester solvents, expanding its application range. It has mild performance and good detergency, foaming, emulsification, and stable chemical properties, thus having broad application prospects and development potential in daily chemical industry, textile printing and dyeing, electroplating and corrosion protection.

[0008] Preferably, n = 3~5.

[0009] This scheme controls n=3~5 and controls the perfluorinated segments within an appropriate length range, resulting in a compound with highly efficient hydrophobic and oleophobic properties.

[0010] Preferably, m = 1~2.

[0011] This scheme controls m=1~2, which can ensure that the compound has good thermal stability, is not easily decomposed and ineffective under high temperature (250℃) conditions, and maintains stable physicochemical properties, making it suitable for high temperature preparation and application scenarios.

[0012] Preferably, R is selected from saturated or unsaturated C1-C3 hydrocarbon groups or halogenated hydrocarbon groups.

[0013] Preferably, R is selected from -CH3, -CH2Cl, -CF3, -CH2CH3, -CH=CH2 or -CH(CH3)=CH2, and more preferably -CH=CH2 or -CH(CH3)=CH2.

[0014] Preferably, the compound is selected from at least one of the following compounds: CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2, CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2, CF3CF2CF2CF2CH2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2, CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2, CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2, CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CH2O(C=O)CH=CH2, CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CF2CH2CH2O(C=O)CH=CH2.

[0015] A second aspect of the present invention provides a method for preparing the compound as described in the first aspect, comprising the following steps: S1. Transfer CF3 (CF2) n I reacts with vinylidene fluoride (mCH2=CF2) via an addition reaction to produce CF3(CF2). n (CH2CF2) m I; S2. Transfer CF3 (CF2) n (CH2CF2) m I reacts with ethylene (yCH2=CH2) via a free radical tuning polymerization reaction to produce CF3(CF2). n (CH2CF2) m (CH2CH2) y I; S3. Transfer CF3 (CF2) n (CH2CF2) m (CH2CH2) y I reacts with carboxylic acids and / or carboxylates via esterification to produce the CF3 (CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R.

[0016] Judging from the research and development technologies in recent years, most of the existing preparation technologies for various types of environmentally friendly fluorinated surfactants that meet the PFAS restriction requirements have problems such as low reaction selectivity, low yield, difficult purification, and environmentally unfriendly production process (the reaction process easily generates fluorinated olefin polymer byproducts PFAS). In addition, the products obtained are single-type surfactants, which limits their application scope in various fields.

[0017] The method for preparing the compound provided by this invention has the following beneficial effects: (1) The raw materials and products of the synthesis do not involve PFAS substances; (2) High yield and high conversion rate; (3) The R group in the molecule can be selected according to the customer’s requirements and the product has high adjustability.

[0018] Preferably, the reaction route of the addition reaction is as follows: .

[0019] Preferably, the catalyst used in the addition reaction is a metal fluoride salt, preferably one or more of cuprous fluoride, ferrous fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, and antimony trifluoride, more preferably one or more of cuprous fluoride, ferrous fluoride, and antimony trifluoride; More preferably, the temperature of the addition reaction is 80~160℃, for example, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, but not limited to the listed values; other unlisted values ​​within the range are also applicable; preferably, it is 110~140℃; the pressure of the addition reaction is 0.05~1.0 MPa, for example, 0.05 MPa, 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, but not limited to the listed values; other unlisted values ​​within the range are also applicable; preferably, it is 0.5~1.0 MPa.

[0020] Preferably, the catalyst is combined with the CF3 (CF2). n The molar ratio of I is (0.05~0.5):1, for example, it can be 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable; it is further preferred to be (0.25~0.5):1.

[0021] Preferably, the CF3 (CF2) n The molar ratio of I to the vinylidene fluoride is 1:(0.5~4).

[0022] Preferably, the reaction route of the free radical tuning reaction is as follows: .

[0023] Preferably, the initiator used in the free radical polymerization reaction is an organic peroxide, preferably one or more of peracetic anhydride, tert-butyl peroxyisopropyl carboxylate, tert-butyl peroxybenzoate, and dicumyl peroxide, more preferably tert-butyl peroxyisopropyl carboxylate. More preferably, the temperature of the free radical telomerization reaction is 60~160℃, for example, it can be 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable; preferably 80~140℃; the pressure of the free radical telomerization reaction is 0.05~1.5MPa, for example, it can be 0.05MPa, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable; preferably 0.3~1MPa.

[0024] Preferably, the mass of the initiator is equal to that of CF3 (CF2). n (CH2CF2) m The mass of I is 1% to 10%, more preferably 3% to 5%.

[0025] Preferably, the CF3 (CF2) n (CH2CF2) m The molar ratio of I to ethylene is 1:(1~2).

[0026] Preferably, the reaction route for the esterification reaction is as follows: M is selected from one or more of H, Na, K, Mg, and Li.

[0027] As a preferred option, when M is K, the byproduct potassium iodide can be purified into an industrial product with high value and wide application.

[0028] Preferably, the polymerization inhibitor used in the esterification reaction is selected from one or more of 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical (polymerization inhibitor 701), 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxo radical (polymerization inhibitor 702), p-hydroxyanisole, hydroquinone, tert-butylcatechol, and benzoquinone, and is more preferably one or more of p-hydroxyanisole, hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, and 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxo radical; More preferably, the temperature of the esterification reaction is 150~200℃, for example, it can be 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable; preferably it is 160~190℃.

[0029] The addition of a polymerization inhibitor during the esterification process in this scheme can prevent the polymerization of perfluorinated materials to produce PFAS-like substances.

[0030] Preferably, the solvent used in the esterification reaction is selected from one or more of tert-butanol, isopentylene glycol, ethanol, and methanol, and more preferably tert-butanol and / or ethanol.

[0031] The solvent used in the esterification reaction of this scheme is the solvent mentioned above. This type of solvent is low in toxicity, easy to separate, and can be recycled.

[0032] Preferably, the solvent used in the esterification reaction is the same as that used in the CF3 (CF2). n (CH2CF2) m (CH2CH2) y The mass ratio of I is (0.8~1.2):1, for example, it can be 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0033] Preferably, the mass of the polymerization inhibitor is equal to that of CF3 (CF2). n (CH2CF2) m (CH2CH2) y I is 0.1% to 0.5% of the mass, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0034] Preferably, the carboxylic acid and / or its carboxylate is combined with the CF3 (CF2). n (CH2CF2) m (CH2CH2) y The mass ratio of I is (0.25~0.45):1, for example, it can be 0.25:1, 0.30:1, 0.35:1, 0.40:1, 0.45:1, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable; it is further preferred to be (0.3~0.4):1.

[0035] Preferably, the esterification reaction time is 4 to 8 hours, for example, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0036] A third aspect of the invention provides a surfactant comprising the compounds described in the first aspect.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows: The compound provided by this invention, as a surfactant, is molecularly decomposable. It incorporates -CF2CH2CF2- or -CH2CF2CH2- segments, with H atoms introduced onto carbon atoms adjacent to fluorine. Under strong ultraviolet light or high temperature (above 200°C), it can decompose into fluorinated olefins, which can further decompose into small molecule fluorides. Under natural conditions, it can slowly oxidize and decompose. Furthermore, the hydrophobicity and oleophobicity of this compound are not significantly different from those of perfluorinated surfactants, and it has good compatibility with alcohols, phenols, and esters, thus expanding its application range.

[0038] The method for preparing the compound provided by this invention does not involve PFAS substances in the raw materials and products, and has a high yield of the target product and a high conversion rate of the raw materials. Attached Figure Description

[0039] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0040] Figure 1 The mass spectrum of CF3CF2CF2CF2CH2CF2CH2CH2CH2O(C=O)CH=CH2 provided in Example 1 is shown.

[0041] Figure 2 The NMR fluorine spectrum of CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2 provided in Example 1 is shown.

[0042] Figure 3 The mass spectrum of CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 provided in Example 2 is shown.

[0043] Figure 4 The mass spectrum of CF3CF2CF2CF2CH2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 provided in Example 2 is shown.

[0044] Figure 5The NMR fluorine spectra of CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 and CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 provided in Example 2 are shown.

[0045] Figure 6 The mass spectrum of CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2CH2O(C=O)C(CH3)=CH2 provided in Example 3 is shown.

[0046] Figure 7 The NMR fluorine spectrum of CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 provided in Example 3 is shown.

[0047] Figure 8 The mass spectrum of CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2CH2O(C=O)CH=CH2 provided in Example 3 is shown.

[0048] Figure 9 The NMR fluorine spectrum of CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2 provided in Example 3 is shown.

[0049] Figure 10 The mass spectrum of CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2 provided in Example 4.

[0050] Figure 11 It is provided in Example 4 Mass spectrum of CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CF2CH2CF2CF2CH2CH2CH2O(C=O)CH=CH2.

[0051] Figure 12 The NMR fluorine spectra of CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2 and CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CH2O(C=O)CH=CH2 provided in Example 4 are shown. Detailed Implementation

[0052] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0053] Unless otherwise specified in the embodiments of this invention, the techniques or conditions described in the literature in this field, or the product instructions, shall apply. Devices, instruments, reagents, etc., whose manufacturers are not specified, are all conventional products that can be purchased through legitimate channels. All raw materials used in this invention are readily available in the domestic market.

[0054] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0055] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0056] Unless otherwise specified, all contents in this invention are molar percentage contents.

[0057] Example 1 1. This embodiment provides a compound with the chemical formula CF3(CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R; Where n=3, m=1, y=1 R is -CH=CH2.

[0058] 2. The preparation method of the compound provided in this embodiment includes the following steps: S1. Preparation of intermediates 1-A and 1-B S11. Add 15.0g of cuprous fluoride and 17.0g of ferrous fluoride, totaling 0.362mol of catalyst, to a 2L stainless steel reactor; evacuate the 2L stainless steel reactor to a gauge pressure of -0.095MPa, add 500g (1.445mol) of perfluoroiodobutane (CF3CF2CF2CF2I, n=3), and then add 49.4g (0.772mol) of vinylidene fluoride (hereinafter referred to as: VDF) to a reactor pressure of 0.55MPa; raise the temperature to 130℃ for reaction, turn off the heating, turn on the cooling water, and maintain the reactor temperature at 120~130℃ until the reactor pressure drops below 0.05MPa to end the reaction, obtaining intermediate 1-A; take samples for testing, including: Perfluoroiodobutane was not detected. CF3CF2CF2CF2CH2CF2I (n=3, m=1) content 79.384%, The content of CF3CF2CF2CF2CH2CF2CH2CF2CF2I (n=3, m=2) was 14.163%. CF3CF2CF2CF2CH2CF2CH2CF2CH2CF2I (n=3, m=3) content 2.227%, Other contents: 4.226%; The conversion rate of perfluoroiodobutane was 100%, and the selectivity (n=3, m=1~3) was 95.774%.

[0059] S12. Add 16.6g of cuprous fluoride and 29g of antimony trifluoride, totaling 0.362mol of catalyst, to a 2L stainless steel reactor; evacuate the 2L stainless steel reactor to a gauge pressure of -0.095MPa, add 500g (1.445mol) of perfluoroiodobutane (CF3CF2CF2CF2I, n=3), and then add 47g (0.734mol) of vinylidene fluoride (VDF) to a reactor pressure of 0.43MPa; heat to 130℃ for reaction, turn off the heating, turn on the cooling water, and maintain the reactor temperature at 120~130℃ until the reactor pressure drops to 0.4MPa. Add VDF to bring the reactor pressure to 0.85MPa, repeating the addition of VDF until the total amount is 185g (2.89mol); after the reaction is complete, cool to room temperature to obtain intermediate 1-B. Take a sample for testing, in which: Perfluoroiodobutane was not detected; The content of CF3CF2CF2CF2CH2CF2I (n=3, m=1) was 14.514%; The content of CF3CF2CF2CF2CH2CF2CH2CF2CF2I (n=3, m=2) was 37.880%; CF3CF2CF2CF2CH2CF2CH2CF2CH2CF2I (n=3, m=3) content 26.408%; CF3CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CF2I (n=3, m=4) content 12.004%; Other contents: 9.194%; The conversion rate of perfluoroiodobutane was 100%, and the selectivity (n=3, m=1~4) was 90.806%.

[0060] S2. Preparation of intermediates 2-A and 2-B S2-1. The mixture of intermediates 1-A and 1-B (n=3, m=1~4) was subjected to vacuum distillation. 507.4g of the m=1 fraction (CF3CF2CF2CF2CH2CF2I component content 98.542%, 1.238mol) was added to a 2L stainless steel reactor purged with nitrogen. 25g of tert-butylperoxyisopropylcarbamate was added, and ethylene was introduced to 0.3MPa. The temperature was raised to 105℃, and cooling water was turned on to maintain the reactor temperature at 100~120℃ until the reactor pressure dropped to 0.05MPa. Ethylene was then added to bring the reactor pressure back to 0.3MPa, and this process was repeated until the total amount reached 42g (1.5mol). The cooling water was then turned off, and the temperature was raised to 155℃. After holding at this temperature for 1 hour, the temperature was lowered to room temperature to obtain intermediate 2-A. Samples were taken for testing, including: The content of CF3CF2CF2CF2CH2CF2CH2CH2I (n=3, m=1, y=1) was 91.055%; CF3CF2CF2CF2CH2CF2CH2CH2CH2CH2I (n=3, m=1, y=2) 3.004%; Other contents: 5.941%; CF3CF2CF2CF2CH2CF2I conversion rate: 100%; selectivity: 94.059%.

[0061] S2-2. The mixture of intermediates 1-A and 1-B (n=3, m=1~4) prepared by vacuum distillation was subjected to the following fraction: 509.4 g of the m=1~2 fraction (of which the content of CF3CF2CF2CF2CH2CF2I (m=1) was 45.876% and the molar content of CF3CF2CF2CF2CH2CF2CH2CF2I (m=2) was 50.325%, totaling 1.11 mol) was added to a 2L stainless steel reactor purged with nitrogen. 25 g of tert-butyl peroxyisopropylcarbamate was also added. Ethylene was introduced to 0.5 MPa, the temperature was raised to 110°C, the cooling water was turned on, and the reactor temperature was maintained at 100~120°C until the reactor pressure dropped to 0.05 MPa. Ethylene was added back to the reactor pressure until it reached 0.5 MPa. The addition of ethylene was repeated until the total amount was 42 g (1.5 mol). The cooling water was turned off, the temperature was raised to 155°C, and the temperature was maintained for 1 hour before being cooled to room temperature to obtain intermediate 2-B. Samples were taken for testing, and the content of CF3CF2CF2CF2CH2CF2CH2CH2I (n=3, m=1, y=1) was 37.862%. CF3CF2CF2CF2CH2CF2CH2CH2CH2CH2I (n=3, m=1, y=2) content 12.536%; CF3CF2CF2CF2CH2CF2CH2CF2CH2CH2I (n=3, m=2, y=1) content 42.723%; CF3CF2CF2CF2CH2CF2CH2CF2CH2CH2CH2CH2I (n=3, m=2, y=2) content 3.125%; Other contents: 3.754%; The combined conversion rates of CF3CF2CF2CF2CH2CF2I and CF3CF2CF2CF2CH2CF2CH2CF2I were 100%, and the combined selectivity was 96.246%.

[0062] S3. The prepared intermediates 2-A and 2-B (n=3, m=1~2, y=1~2) were subjected to vacuum distillation. 417g of the fraction with n=3, m=1, and y=1 was added to a 2L stainless steel reactor purged with nitrogen. Potassium acrylate (125g), ethanol solvent (417g), polymerization inhibitor p-hydroxyanisole (0.4g), and tert-butylcatechol (0.8g) were also added. The mixture was heated to 160℃ and held for 8 hours. Then, the temperature was lowered to 60℃. The solvent and other low-boiling-point substances were first distilled off, followed by vacuum distillation to obtain the target product. Samples were taken for analysis, including: CF3CF2CF2CF2CH2CF2CH2CH2CH2O(C=O)CH=CH2 (n=3, m=1, y=1) content 95.810%; Other contents: 4.190%; The conversion rate of CF3CF2CF2CF2CH2CF2CH2CH2I was 100%, and the selectivity was 95.810%.

[0063] Example 2 1. This embodiment provides a compound with the chemical formula CF3(CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R; Where n=3, m=1~2, y=1, R is -C(CH3)=CH2.

[0064] 2. The difference between the preparation method of the compound provided in this embodiment and that in Example 1 is: S3. The prepared intermediates 2-A and 2-B (n=3, m=1~2, y=1~2) were subjected to vacuum distillation. 313g of the fraction with n=3, m=1~2, and y=1 (where m=1 content was 49.750% and m=2 content was 44.444%) was added to a 2L stainless steel reactor purged with nitrogen. 125g of potassium methacrylate, 250g of tert-butanol solvent, 0.2g of the polymerization inhibitor p-hydroxyanisole, and 0.4g of hydroquinone were added. The mixture was heated to 180℃ and held for 6 hours. Then, the temperature was lowered to 60℃. The solvent and other low-boiling-point substances were first distilled off, and then the target product was distilled off under vacuum. Samples were taken for analysis, including: CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 (n=3, m=1, y=1) content 42.766%; CF3CF2CF2CF2CH2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 (n=3, m=2, y=1) content 46.450%; Other contents: 10.784%; The combined conversion rates of CF3CF2CF2CF2CH2CF2CH2CH2I and CF3CF2CF2CF2CH2CF2CH2CH2I were 100%, and the combined selectivity was 89.216%.

[0065] Example 3 1. This embodiment provides a compound with the chemical formula CF3(CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R; Where n=5, m=1, y=1, R is -C(CH3)=CH2.

[0066] 2. The preparation method of the compound provided in this embodiment includes the following steps: S1. 94.0 g of cuprous fluoride and 166.0 g of antimony trifluoride, totaling 2.067 mol of catalyst, were added to a 2L stainless steel reactor. The reactor was evacuated to a gauge pressure of -0.095 MPa. 2562.4 g (5.744 mol) of perfluorohexane (CF3CF2CF2CF2CF2CF2I, n=5) was added, followed by 49.4 g (0.772 mol) of vinylidene fluoride until the reactor pressure reached 0.55 MPa. The temperature was raised to 140℃, heating was stopped, and cooling water was turned on to maintain the reactor temperature at 130~140℃ until the reactor pressure dropped to 0.4 MPa. VDF was then added until the reactor pressure reached 1.0 MPa. This process of adding VDF was repeated until the total amount reached 498.4 g (7.788 mol). After the reaction was completed, the mixture was cooled to room temperature to obtain intermediate 1. Samples were taken for testing, including: Perfluorohexane 1.563%; The content of CF3CF2CF2CF2CF2CF2CH2CF2I (n=5, m=1) was 55.427%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2I (n=5, m=2) content 34.089%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2I (n=5, m=3) content 6.398%; Other contents: 2.523%; The conversion rate of perfluoroiodobutane was 98.437%, and the selectivity (n=5, m=1~3) was 97.435%.

[0067] S2. The prepared intermediate 1 (n=5, m=1~3) was subjected to vacuum distillation. 551.8g of the m=1 fraction (CF3CF2CF2CF2CF2CF2CH2CF2I component content 95.190%, 1.082mol) was added to a 2L stainless steel reactor purged with nitrogen. 17g of tert-butylperoxyisopropylcarbamate was added, and ethylene was introduced to 0.3MPa. The temperature was raised to 105℃, and cooling water was turned on to maintain the reactor temperature at 100~120℃ until the reactor pressure dropped to 0.05MPa. Ethylene was then added to bring the reactor pressure back to 0.3MPa, and this process was repeated until the total amount reached 30.8g (1.1mol). The cooling water was then turned off, and the temperature was raised to 155℃. After holding at this temperature for 1 hour, the temperature was lowered to room temperature to obtain intermediate 2. Samples were taken for testing, including: The content of CF3CF2CF2CF2CF2CF2CH2CF2I (n=5, m=1) was 6.597%. CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2I (n=5, m=1, y=1) content 83.679%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2CH2CH2I (n=5, m=1, y=2) content 7.961%; Other contents: 1.763%; The conversion rate of CF3CF2CF2CF2CF2CF2CH2CF2I was 93.403%, and the selectivity was 98.112%.

[0068] S3. The prepared intermediate 2 (n=5, m=1, y=1~2) was subjected to vacuum distillation. 845g of the y=1 fraction was added to a 2L stainless steel reactor purged with nitrogen, along with 225g of potassium methacrylate, 845g of tert-butanol solvent, 0.5g of polymerization inhibitor 701, and 2.0g of polymerization inhibitor 702. The mixture was heated to 185℃ and held for 6 hours, then cooled to 60℃. The solvent and other low-boiling-point substances were first distilled off, followed by vacuum distillation to obtain the target product. Samples were taken for analysis, including: CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 (n=5, m=1, y=1) content 96.130%; Other contents: 3.87%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2CH2I conversion rate: 100%, selectivity: 96.13%. In step S3 above, potassium methacrylate was replaced with potassium acrylate to synthesize CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2 (n=5, m=1, y=1) with a content of 98.513%.

[0069] Example 4 1. This embodiment provides a compound with the chemical formula CF3(CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R; Where n=5, m=3~4, y=1, R is -CH=CH2.

[0070] 2. The preparation method of the compound provided in this embodiment includes the following steps: S1. Add 49.5g of cuprous fluoride and 89.5g of antimony trifluoride, totaling 1.1mol of catalyst, to a 2L stainless steel reactor; evacuate the 2L stainless steel reactor to a gauge pressure of -0.095MPa, add 1338g (3.0mol) of perfluorohexane (CF3CF2CF2CF2CF2CF2I, n=5), and then add 49.4g (0.772mol) of vinylidene fluoride to a reactor pressure of 0.55MPa; heat to 140℃ for reaction, turn off the heating, turn on the cooling water, and maintain the reactor temperature at 135~145℃ for reaction until the reactor pressure drops to 0.4MPa. Add VDF to bring the reactor pressure to 1.0MPa, and repeat the addition of VDF until the total amount is 547.2g (8.55mol); after the reaction is completed, cool to room temperature to obtain intermediate 1; Sampling and testing, among which Perfluorohexane was not detected. The content of CF3CF2CF2CF2CF2CF2CH2CF2I (n=5, m=1) was 3.336%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2I (n=5, m=2) content 19.358%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2I (n=5, m=3) content 42.258%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CF2I (n=5, m=4) 26.452%; Other contents: 8.596%; The conversion rate of perfluoroiodobutane was 100%, and the selectivity (n=5, m=1~4) was 91.404%. S2. The prepared intermediate 1 (n=5, m=1~4) was subjected to vacuum distillation. 587.7g of the m=3~4 fraction (of which: n=5, m=3 component content 57.303%, n=5, m=4 component content 40.111%, 0.864mol) was added to a 2L stainless steel reactor purged with nitrogen. 12g of tert-butyl peroxyisopropylcarbamate was added, and ethylene was introduced to 0.3MPa. The temperature was raised to 130℃, and the cooling water was turned on to maintain the reactor temperature at 120~130℃ until the reactor pressure dropped to 0.05MPa. Ethylene was then added to bring the reactor pressure to 0.3MPa, and this process was repeated until the total amount used was 26.6g (0.95mol). The cooling water was then turned off, and the temperature was raised to 160℃. After holding at this temperature for 1 hour, the temperature was lowered to room temperature to obtain intermediate 2. Samples were taken for testing, including: Intermediate 1, not detected CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CH2I (n=5, m=3, y=1) content 53.011%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CH2CH2CH2I (n=5, m=3, y=2) content 0.531%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CF2CH2CH2I (n=5, m=4, y=1) content 35.695%; Other contents: 10.763%; The combined conversion rates of CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CF2CF2CF2I and CF3CF2CF2CF2CF2CF2CF2CH2CF2CF2CF2CF2CF2CF2CF2I are 100%; the combined selectivity is (n=5, m=3~4, y=1) 88.706%. S3. The prepared intermediate 2 (n=5, m=3~4, y=1~2) was subjected to vacuum distillation. 450g of the y=1 fraction was added to a 2L stainless steel reactor purged with nitrogen, along with 200g of potassium acrylate, 540g of tert-butanol solvent, 0.5g of polymerization inhibitor 701, and 1.0g of polymerization inhibitor 702. The mixture was heated to 185℃ and held at that temperature for 6 hours. Then, the temperature was lowered to 60℃. The solvent and other low-boiling-point substances were first distilled off, and then the target product was distilled off under vacuum. Sampled products were analyzed, including: CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CH2O(C=O)CH=CH2 (n=5, m=3, y=1) content 46.758%; CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CF2CH2CH2O(C=O)CH=CH2 (n=5, m=4, y=1) content 42.055% Other contents: 11.16%; The combined conversion rates of CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CH2I and CF3CF2CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CH2I were 100%, and the combined selectivity was 88.813%.

[0071] The mass spectra and nuclear magnetic resonance fluorine spectra of the target products obtained in the above embodiments are as follows: Figures 1-12 As shown, by Figures 1-12 It can be seen that the present invention has successfully prepared the above-mentioned target products.

[0072] Test Example 1 This test case examines compound CF3 (CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R thermal decomposition test.

[0073] Based on the fundamental characteristic that fluorine-containing compounds are more stable with a higher fluorine content, and considering factors such as the greater the number of -CH2CF2- blocks in the design structure of the compounds of this invention, the most difficult thermal decomposition test material is determined to be CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2 (n=5, m=1, y=1).

[0074] Test method: A 200g sample of CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2 (n=5, m=1, y=1) was placed in a 1L high-pressure reactor. The reactor was evacuated to -0.098 MPa, then filled with 0.1 MPa of nitrogen, and evacuated again to -0.098 MPa. The temperature was gradually increased, and after holding at 160℃ for 1 hour, the temperature was cooled to room temperature and the liquid phase was sampled and analyzed. Subsequently, the temperature was gradually increased at the following gradients: 180℃, 200℃, 220℃, 240℃, 260℃, 280℃, 300℃, and 320℃. After holding at each temperature for 1 hour, the temperature was cooled to room temperature and the liquid phase was analyzed. The test results are as follows: a small amount of decomposition occurred between 160 and 200℃, significant decomposition occurred between 220 and 260℃, and rapid and large-scale decomposition occurred above 300℃. The test results are shown in Table 1. In Table 1, the decomposition rate (%) = (initial substrate content - substrate content at the corresponding test temperature) / initial substrate content × 100%.

[0075] Table 1

[0076] Test Example 2 This test case verifies the compound CF3(CF2). n (CH2CF2) m (CH2CH2) y The effects of O(C=O)R as a fabric finishing agent were compared with those of perfluoroalkyl ethyl ester compounds.

[0077] Test method steps: Prepare the emulsified working solution by placing 45% of the compound of the present invention, 30% of octadecyl acrylate, 6% of N-(hydroxymethyl)acrylamide, 5% of dioctadecyl dimethyl ammonium chloride, 1% of dimethyl azobisisobutyrate, 5% of ethanol, 3% of acetone, and 5% of deionized water in a stirred reactor. Maintain the temperature at 70-80°C and the stirring speed at 150-200 rpm for 3 hours. Add acetic acid dropwise to adjust the pH value to 5.5-6.0. The emulsified working solution is now prepared.

[0078] Soak the dry fabric in the emulsified working solution for 30 minutes, then remove and apply at 2 kg / cm². 2 Press the fabric at 5 rpm, then hang it in an oven at 120~130℃ to dry. Then set the oven temperature to 150~170℃ and bake for 30 minutes. Take out the fabric and test its waterproof effect according to "Water Resistance: Spray Test" (AATCC 22-2014), and its oil resistance according to "Oil Repellency: Hydrocarbon Resistance Test" (AATCC118-2013).

[0079] (1) Take 200g of the product of this invention (in which CF3CF2CF2CF2CH2CF2CH2CH2O(C=O) CH=CH2, i.e., n=3, m=1, y=1 content 98.5%) to prepare an emulsion working solution and test the waterproof and oil-repellent effects on different fabrics as described above, and compare the effect with that of perfluorohexyl ethyl acrylate. The test results are as follows:

[0080] (2) Take 200g of the product of this invention (in which CF3CF2CF2CF2CH2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2 (n=3, m=2, y=1, content 97.8%) to prepare an emulsion working solution and test the waterproof and oil-repellent effects on different fabrics as described above, and compare the effect with that of perfluorohexyl ethyl acrylate. The test results are as follows:

[0081] (3) Take 200g of the product of this invention (in which CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O) CH=CH2, i.e., n=5, m=1, y=1, content 98.8%) to prepare an emulsion working solution and test the waterproof and oil-repellent effects on different fabrics as described above, and compare the effect with that of perfluorooctyl ethyl acrylate. The test results are as follows:

[0082] Test Examples 1 and 2 demonstrate that the compounds provided by this invention are comparable to perfluorinated surfactants in their effectiveness as surfactants and can be used as raw materials for fabric finishing. However, their biodegradability solves the problem of the inability to use perfluorinated surfactants, opening up new avenues for the application of fluorinated surfactants.

[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A compound, characterized in that, Its chemical formula is CF3(CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R; Where n = 1~6, m = 1~4, y = 1~2, R is selected from saturated or unsaturated C1-C5 hydrocarbon groups or haloalkyl groups.

2. The compound according to claim 1, characterized in that, The n=3~5, and / or the m=1~2.

3. The compound according to claim 1 or 2, characterized in that, The R is selected from saturated or unsaturated C1-C3 hydrocarbon groups or halogenated hydrocarbon groups.

4. The compound according to any one of claims 1 to 3, characterized in that, The R is selected from -CH3, -CH2Cl, -CF3, -CH2CH3, -CH=CH2 or -CH(CH3)=CH2.

5. The compound according to any one of claims 1 to 4, characterized in that, The compound is selected from at least one of the following compounds: CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2, CF3CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2, CF3CF2CF2CF2CH2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2, CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)C(CH3)=CH2, CF3CF2CF2CF2CF2CF2CH2CF2CH2CH2O(C=O)CH=CH2, CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CH2O(C=O)CH=CH2, CF3CF2CF2CF2CF2CF2CH2CF2CH2CF2CH2CF2CH2CF2CH2CH2O(C=O)CH=CH2.

6. A method for preparing the compound according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Transfer CF3 (CF2) n I reacts with vinylidene fluoride via an addition reaction to produce CF3 (CF2). n (CH2CF2) m I; S2. Transfer CF3 (CF2) n (CH2CF2) m I reacts with ethylene via a free radical tuning polymerization reaction to produce CF3 (CF2). n (CH2CF2) m (CH2CH2) y I; S3. Transfer CF3 (CF2) n (CH2CF2) m (CH2CH2) y I reacts with carboxylic acids and / or carboxylates via esterification to produce the CF3 (CF2). n (CH2CF2) m (CH2CH2) y O(C=O)R.

7. The method for preparing the compound according to claim 6, characterized in that, The catalyst used in the addition reaction is a metal fluoride salt, preferably one or more of cuprous fluoride, ferrous fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, and antimony trifluoride, more preferably one or more of cuprous fluoride, ferrous fluoride, and antimony trifluoride; The catalyst and the CF3(CF2) n The molar ratio of I is (0.05~0.5):1, preferably (0.25~0.5):1; More preferably, the temperature of the addition reaction is 80~160℃, more preferably 110~140℃; and the pressure of the addition reaction is 0.05~1.0 MPa, more preferably 0.5~1.0 MPa.

8. The method for preparing the compound according to claim 6 or 7, characterized in that, The initiator used in the free radical polymerization reaction is an organic peroxide, preferably one or more of peracetic anhydride, tert-butyl peroxyisopropyl carboxylate, tert-butyl peroxybenzoate, and dicumyl peroxide, more preferably tert-butyl peroxyisopropyl carboxylate. The mass of the initiator is the mass of CF3 (CF2). n (CH2CF2) m The mass of I is 1% to 10%, preferably 3% to 5%; More preferably, the temperature of the free radical polymerization reaction is 60~160℃, more preferably 80~140℃; and the pressure of the free radical polymerization reaction is 0.05~1.5 MPa, more preferably 0.3~1 MPa.

9. A method for preparing the compound according to any one of claims 6 to 8, characterized in that, The polymerization inhibitor used in the esterification reaction is selected from one or more of 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxo radical, p-hydroxyanisole, hydroquinone, tert-butylcatechol, and benzoquinone, preferably one or more of p-hydroxyanisole, hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, and 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxo radical; The mass of the polymerization inhibitor is the mass of CF3 (CF2). n (CH2CF2) m (CH2CH2) y 0.1% to 0.5% of the mass of I; More preferably, the temperature of the esterification reaction is 150~200℃, more preferably 160~190℃.

10. A surfactant, characterized in that, It is the compound as described in any one of claims 1 to 5.

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