A non-pfas fluoropolymers and methods of making and using the same

Abstract

The application discloses a non-PFAS fluorine-containing polymer and a preparation method and application thereof, and the preparation method comprises the following steps: performing an ester exchange reaction on a fluorinated malonic acid ester compound and a polyol in the presence of a catalyst, and the fluorinated malonic acid ester compound is selected from the following structural formula: wherein R1 is selected from C 1~10 The polymer can not only avoid environmental safety risks, but also has a comparable effect to the PFAS fluorine-containing polymer when being used as a wetting and leveling agent in a coating.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a non-PFAS fluoropolymer, its preparation method, and its application. Background Technology

[0002] According to the 2018 OECD definition, perfluorinated and polyfluoroalkyl compounds (PFAS) are fluorides containing at least one perfluorinated methyl or methylene carbon atom (without any H / Cl / Br / I atoms) (see Formula A). PFAS is a large family, encompassing more than 4,700 man-made chemicals. Currently known PFAS are numerous, with common categories including perfluoroalkyl acids (PFAA), perfluoroalkyl ether acids (PFEA), perfluoroalkyl sulfonyl fluorides (PASF), and perfluoroalkyl sulfonamides (FASA). Although their properties differ, they all possess extremely strong and stable C-F bonds (approximately 485 kJ / mol). Since their introduction in the late 1940s, PFAS have been used in an increasingly wide range of consumer and industrial applications, from food packaging and clothing to electronics, aerospace, fire-fighting foams, cosmetics, fluoropolymers, industrial additives, and coatings, thanks to their outstanding surface activity and thermal stability. They possess oil and water repellency, as well as high stability and high-temperature resistance due to their carbon-fluorine bonds. Due to the extremely high stability of the C-F bond, PFAS hardly degrades in the natural environment, resulting in their exceptional persistence; hence, they are known as "permanent chemicals." However, with increasing global calls for environmental protection and growing demands for human health safeguards, recent studies have confirmed that some PFAS compounds exhibit high environmental persistence, with some exhibiting bioaccumulation and toxicity, potentially having profound impacts on aquatic environments, soil, and even human health. Therefore, the application of PFAS has gradually come under regulatory restrictions in recent years.

[0003] ; In the coatings industry, currently commercially available fluoropolymers (such as resins and additives) all belong to the PFAS type. However, based on the aforementioned safety and environmental risks, it is necessary to develop a method for preparing polymers that do not belong to the PFAS type but still have considerable effects. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the first aspect of the present invention proposes a method for preparing non-PFAS fluoropolymers, which can prepare non-PFAS polymers and have the same effects as PFAS polymers.

[0005] A second aspect of the present invention also provides a non-PFAS polymer.

[0006] A third aspect of the present invention also provides a wetting and leveling agent.

[0007] A fourth aspect of the present invention provides an application of a non-PFAS polymer.

[0008] A method for preparing a non-PFAS fluoropolymer according to a first aspect of the present invention includes the following steps: The fluoromalonate compound and the polyol are subjected to transesterification in the presence of a catalyst to obtain the product. The fluoromalonate compounds are selected from the following structural formulas: ; Among them, R1 is selected from C 1~10 Alkyl groups.

[0009] According to a preferred embodiment of the present invention, the polyol includes at least one selected from ethylene glycol, diethylene glycol, 1,6-hexanediol, trimethylolpropane, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, pentaerythritol, polyether polyol, polyester polyol, and polycarbonate polyol.

[0010] According to a preferred embodiment of the present invention, R1 is selected from C. 1~6 Alkyl groups.

[0011] According to a preferred embodiment of the present invention, the molar ratio of the fluoromalonate compound to the polyol is 1:(0.49~1.95).

[0012] According to a preferred embodiment of the present invention, the temperature of the transesterification reaction is 110~230°C.

[0013] According to a preferred embodiment of the present invention, the raw materials used in the preparation method further include diethyl malonate.

[0014] According to a preferred embodiment of the present invention, when the fluoromalonate compound is selected from the following structural formula, In the presence of a catalyst, fluoromalonate compounds and polyols undergo transesterification to obtain intermediate products. Then the intermediate product and A second transesterification reaction was carried out to obtain a fluoropolymer.

[0015] According to a preferred embodiment of the present invention, the preparation method further includes mixing the product obtained from the transesterification reaction, compound 1, and base catalyst I to carry out a Michael addition reaction, thereby obtaining the product; The structural formula of compound 1 is as follows: R2 is selected from H and C.1~20 Alkyl, polyether segments, , hydroxyl, phenyl, C containing oxygen atoms 3~8 At least one C-substituted heterocyclic alkyl group or dimethylamino group 1~10 Alkyl groups; The monomers of the polyether segment include ethylene oxide and / or propylene oxide; Where m is selected from integers from 0 to 30, and q is selected from integers from 1 to 3.

[0016] According to a preferred embodiment of the present invention, the catalyst comprises a base catalyst II and / or an organotin catalyst.

[0017] According to a preferred embodiment of the present invention, the polyether segment has the following structural formula: n is an integer selected from 1 to 20.

[0018] According to a preferred embodiment of the present invention, the alkaline catalyst I is selected from at least one of Allnex's blocked alkaline catalyst Acure 500, tetrabutylammonium hydroxide, DBU, or DMAP.

[0019] According to a preferred embodiment of the present invention, the base catalyst II is selected from at least one of Allnex's blocked base catalyst Acure 500, tetrabutylammonium hydroxide, DBU or DMAP.

[0020] According to a preferred embodiment of the present invention, compound 1 is selected from the following structural formulas: .

[0021] According to a preferred embodiment of the present invention, the reaction temperature of the Michael addition is 40~120°C.

[0022] The preparation method according to embodiments of the present invention has at least the following beneficial effects: This invention obtains non-PFAS fluoropolymers by transesterification of fluoromalonate compounds and polyols. These polymers can avoid environmental and safety risks and have comparable effects as wetting and leveling agents in coatings as PFAS fluoropolymers.

[0023] According to a second aspect of the present invention, a non-PFAS fluoropolymer is provided, which is prepared by the preparation method described in the first aspect of the present invention.

[0024] A third aspect of the present invention provides a wetting and leveling agent comprising a non-PFAS fluoropolymer prepared by the preparation method described in the first aspect of the present invention, or a non-PFAS fluoropolymer described in the second aspect of the present invention.

[0025] The fourth aspect of the present invention provides the application of the non-PFAS fluoropolymer described in the second aspect of the present invention, or the wetting and leveling agent described in the third aspect of the present invention, in coatings and inks.

[0026] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Attached Figure Description

[0027] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 This is the 1H NMR spectrum of the fluoropolymer P1 in Example 1 of the present invention; Figure 2 This is the 1H NMR spectrum of the fluoropolymer P2 in Example 2 of the present invention; Figure 3 This is the 1H NMR spectrum of the fluoropolymer P3 in Example 3 of the present invention; Figure 4 This is the 1H NMR spectrum of the fluoropolymer P4 in Example 4 of this invention; Figure 5 This is the 1H NMR spectrum of the fluoropolymer P5 in Example 5 of the present invention; Figure 6 This is the 1H NMR spectrum of the fluoropolymer P6 in Example 6 of the present invention; Figure 7 This is the 1H NMR spectrum of the fluoropolymer P7-1 from Example 7 of this invention. Detailed Implementation

[0028] The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0029] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0030] In some embodiments of the present invention, a method for preparing a non-PFAS fluoropolymer is provided, comprising the following steps: The fluoromalonate compound and the polyol are subjected to transesterification in the presence of a catalyst to obtain the product. The fluoromalonate compounds are selected from the following structural formulas: ; Among them, R1 is selected from C 1~10 Alkyl groups.

[0031] It is understood that the present invention can obtain non-PFAS fluoropolymers by transesterification of fluoromalonate compounds and polyols. These polymers can avoid environmental and safety risks and have comparable effects to PFAS fluoropolymers as wetting and leveling agents in coatings.

[0032] In some embodiments of the present invention, the polyol includes at least one of ethylene glycol, diethylene glycol, 1,6-hexanediol, trimethylolpropane, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, pentaerythritol, polyether polyol, polyester polyol, and polycarbonate polyol.

[0033] In some embodiments of the present invention, R1 is selected from C. 1~6 Alkyl groups.

[0034] In some embodiments of the present invention, the molar ratio of the fluoromalonate compound to the polyol is 1:(0.49~1.95).

[0035] In some embodiments of the present invention, the temperature of the transesterification reaction is 110~230°C.

[0036] In some embodiments of the present invention, the raw materials used in the preparation method further include diethyl malonate.

[0037] In some embodiments of the present invention, when the fluoromalonate compound is selected from the following structural formulas, In the presence of a catalyst, fluoromalonate compounds and polyols undergo transesterification to obtain intermediate products. Then the intermediate product and A second transesterification reaction was carried out to obtain a fluoropolymer.

[0038] In this invention, the definition of R1 is the same as the definition of R1 in the first aspect of this invention.

[0039] In some embodiments of the present invention, the preparation method further includes mixing the product obtained from the transesterification reaction, compound 1, and base catalyst I to carry out a Michael addition reaction, thereby obtaining the product; The structural formula of compound 1 is as follows: R2 is selected from H and C. 1~20 Alkyl, polyether segments, , hydroxyl, phenyl, C containing oxygen atoms 3~8 At least one C-substituted heterocyclic alkyl group or dimethylamino group 1~10 Alkyl groups; The monomers of the polyether segment include ethylene oxide and / or propylene oxide; Where m is selected from integers from 0 to 30, and q is selected from integers from 1 to 3.

[0040] In some embodiments of the present invention, R2 is selected from H and C. 1~18 Alkyl, polyether segments, , hydroxyl, phenyl, C containing oxygen atoms 3~6 At least one C-substituted heterocyclic alkyl group or dimethylamino group 1~10 Alkyl groups.

[0041] In some embodiments of the present invention, m is selected from an integer from 1 to 20; in some embodiments, m is selected from an integer from 1 to 10; for example, m is selected from 0, 1, 2, 3, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30 or any two of the above values ​​forming a subrange.

[0042] In some embodiments of the present invention, the catalyst includes base catalyst II and / or organotin catalyst.

[0043] In some embodiments of the present invention, the structural formula of the polyether segment is as follows: n is an integer selected from 1 to 20.

[0044] In some embodiments of the present invention, the alkaline catalyst I is selected from at least one of Allnex's blocked alkaline catalyst Acure500, tetrabutylammonium hydroxide, DBU, or DMAP.

[0045] In some embodiments of the present invention, the base catalyst II is selected from at least one of Allnex's blocked base catalyst Acure 500, tetrabutylammonium hydroxide, DBU, or DMAP.

[0046] In some embodiments of the present invention, compound 1 is selected from the following structural formulas: .

[0047] In some embodiments of the present invention, the reaction temperature of the Michael addition is 40~120°C.

[0048] In some embodiments of the present invention, a non-PFAS fluoropolymer is provided, which is prepared by the preparation method described in the first aspect of the present invention.

[0049] In some embodiments of the present invention, a wetting and leveling agent is provided, comprising a non-PFAS fluoropolymer prepared by the preparation method described in the first aspect of the present invention, or a non-PFAS fluoropolymer described in the second aspect of the present invention.

[0050] Therefore, when the wetting and leveling agent of the present invention is applied to varnish, it has good compatibility and leveling properties, does not reduce the adhesion of recoating, and the resulting dry film has a smooth appearance.

[0051] In some embodiments of the present invention, the application of the non-PFAS fluoropolymer described in the second aspect of the present invention, or the wetting and leveling agent described in the third aspect of the present invention, in coatings and inks is provided.

[0052] Definitions and General Terms “C 1~20 "alkyl" refers to an alkyl group with a total number of carbon atoms of 1-20, including C14 and C24. 1-20 straight-chain alkyl, C 1-20 Branched alkyl groups and C 3-20 The cycloalkyl group can be, for example, a straight-chain alkyl group with a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, or 20; a branched-chain alkyl group with a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, or 20; or a cycloalkyl group with a total number of carbon atoms of 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, or 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, etc. "C 1~10 Alkyl group, C 1~6 "alkyl" has a similar interpretation, except that the number of carbon atoms is different.

[0053] "C containing oxygen atoms" 3~8 "Heterocyclic alkyl" refers to a heterocyclic group with a total number of carbon atoms of 3-6, wherein the cyclic atoms in the heterocycle contain at least one oxygen atom.

[0054] Example 1 This example provides a non-PFAS fluoropolymer, and the reaction equation and preparation method are as follows:

[0055] At room temperature, 178.16 g (1.00 mol) of diethyl fluoromalonate, 94.63 g (1.05 mol) of 2-methyl-1,3-propanediol, and 0.27 g of FASCAT 4100 (butylstannic acid) were added to a 500 mL four-necked flask equipped with a distillation apparatus. N2 was then introduced, stirring was started, and slow heating was initiated. The reaction temperature was controlled between 110 and 230 °C, ensuring the distillation temperature did not exceed 78 °C during this period. When the temperature of the materials in the reactor reached 230 °C, the temperature was maintained until the distillation temperature dropped to 55 °C, at which point heating was stopped. Afterward, the temperature was lowered and maintained at 60 °C, and vacuum distillation was initiated for 0.5 hours to remove residual ethanol from the reactor. When the non-volatile content exceeds 98% (after drying in an oven at 150°C for 0.5 hours, the same applies below), stop vacuum distillation and prepare to cool the reaction system to 40°C to obtain a deep yellow viscous liquid, which is a non-PFAS fluoropolymer. This polymer contains hydroxyl groups at both ends, denoted as P1. The weight-average molecular weight Mw measured by GPC is 3612.92.

[0056] The 1H NMR spectrum of the prepared non-PFAS fluoropolymer is shown below. Figure 1 As shown, the polymer of the present invention has been synthesized.

[0057] Example 2 This example provides a non-PFAS fluoropolymer prepared using the same method and dosage as in Example 1, except that 2-methyl-1,3-propanediol in Example 1 is replaced with an equimolar amount of 1,6-hexanediol (1.05 mol, 124.08 g). A deep yellow viscous liquid is obtained, and this polymer, denoted as polymer P2, contains hydroxyl groups at both ends. GPC analysis shows a weight-average molecular weight (Mw) of 4201.97.

[0058]

[0059] The 1H NMR spectrum of the prepared non-PFAS fluoropolymer is shown below. Figure 2 As shown, the polymer of the present invention has been synthesized.

[0060] Example 3 This example provides a non-PFAS fluoropolymer prepared using the same method and dosage as in Example 1, except that 0.5 mol of diethyl fluoromalonate was replaced with 0.5 mol (80.09 g) of diethyl malonate in Example 1. A yellow, viscous liquid was obtained. This polymer, denoted as polymer P3, contains hydroxyl groups at both ends. GPC analysis showed a weight-average molecular weight (Mw) of 3433.02.

[0061]

[0062] The 1H NMR spectrum of the prepared non-PFAS fluoropolymer is shown below. Figure 3As shown, the polymer of the present invention has been synthesized.

[0063] Example 4 This example provides a non-PFAS fluoropolymer prepared using the same method and dosage as in Example 1, except that the amount of 2-methyl-1,3-propanediol in Example 1 was reduced to 90.12 g (1.0 mol), and the amount of diethyl fluoromalonate was increased to 187.07 g (1.05 mol), while all other conditions remained unchanged. A deep yellow viscous liquid was obtained. This polymer, which does not contain hydroxyl groups at either end, is designated as polymer P4. GPC analysis showed a weight-average molecular weight (Mw) of 3700.96.

[0064]

[0065] The 1H NMR spectrum of the prepared non-PFAS fluoropolymer is shown below. Figure 4 As shown, the polymer of the present invention has been synthesized.

[0066] Example 5 This example provides a non-PFAS fluoropolymer, prepared in the same way and in the same amount as in Example 4, except that the 0.525 mol of diethyl fluoromalonate in Example 4 is replaced with diethyl malonate (0.525 mol, 84.09).

[0067]

[0068] The 1H NMR spectrum of the prepared non-PFAS fluoropolymer is shown below. Figure 5 As shown, the polymer of the present invention has been synthesized.

[0069] Example 6 This example provides a non-PFAS fluoropolymer. P1 prepared in Example 1 was cooled to below 100°C, and then 0.1 mol (16.61 g) of ethyl 4,4-difluoroacetoacetate and 0.02 g of FASCAT 4100 catalyst were added to the reaction system. N2 was then introduced, stirring was started, and slow heating began. The reaction temperature was controlled between 110 and 230°C, ensuring the distillation temperature did not exceed 78°C during this period. When the material temperature in the reactor reached 230°C, the temperature was maintained until the distillation temperature dropped to 55°C, at which point heating was stopped. The temperature was then lowered and maintained at 60°C, and vacuum distillation was initiated for 0.5 hours to remove residual ethanol from the reactor. When the non-volatile content exceeded 98% (after drying in an oven at 150°C for 0.5 hours, the same applies below), vacuum distillation was stopped, and the reaction system was cooled to 40°C to obtain a deep yellow viscous liquid, which is the non-PFAS fluoropolymer, denoted as P6. GPC determined the weight-average molecular weight (Mw) to be 3853.02.

[0070]

[0071] The 1H NMR spectrum of the prepared non-PFAS fluoropolymer is shown below. Figure 6 As shown, the polymer of the present invention has been synthesized.

[0072] Example 7 This example provides a non-PFAS fluoropolymer, prepared by the following method: At room temperature, 178.16 g (1.00 mol) of diethyl fluoromalonate, 96.69 g (1.05 mol) of glycerol, and 0.27 g of FASCAT 4100 (butylstannic acid) were added to a 500 mL four-necked flask equipped with a distillation apparatus. N2 was then introduced, stirring was started, and slow heating was initiated. The reaction temperature was controlled between 110 and 230 °C, ensuring the distillation temperature did not exceed 78 °C during this period. When the temperature of the materials in the reactor reached 230 °C, the temperature was maintained until the distillation temperature dropped to 55 °C, at which point heating was stopped. Afterward, the temperature was lowered and maintained at 60 °C, and vacuum distillation was initiated for 0.5 hours to remove residual ethanol from the reactor. When the non-volatile content exceeds 98% (after drying in an oven at 150°C for 0.5 hours, the same applies below), stop vacuum distillation and prepare to cool the reaction system to 40°C to obtain a deep yellow viscous liquid, which is a non-PFAS fluorinated polymer. This polymer is branched and has hydroxyl groups at the molecular ends, denoted as P7. The weight-average molecular weight Mw measured by GPC is 3654.29.

[0073] After cooling the above reaction to below 100°C, 1.15 mol (191.04 g) of ethyl 4,4-difluoroacetoacetate and 0.2 g of FASCAT 4100 catalyst were added to the reaction system. N2 was then introduced, stirring was started, and slow heating began. The reaction temperature was controlled between 110 and 230°C, ensuring the distillation temperature did not exceed 78°C during this period. When the material temperature in the reactor reached 230°C, the temperature was maintained until the distillation temperature dropped to 55°C, at which point heating was stopped. The temperature was then lowered and maintained at 60°C, and vacuum distillation was initiated for 0.5 hours to remove residual ethanol from the reactor. When the non-volatile content exceeded 98% (after drying in an oven at 150°C for 0.5 hours, the same applies below), vacuum distillation was stopped, and the reaction system was cooled to 40°C to obtain a deep yellow viscous liquid, which is the non-PFAS fluoropolymer, denoted as P7-1. GPC determined the weight-average molecular weight (Mw) to be 6415.44.

[0074] The reaction equation for this step is as follows:

[0075] The 1H NMR spectrum of the prepared non-PFAS fluoropolymer is shown below. Figure 7 As shown, the polymer of the present invention has been synthesized.

[0076] Comparative Example 1 This example provides a PFAS-type fluoropolymer: the preparation method is as follows: At room temperature, 79.3 g of butyl acetate was added to a 500 mL four-necked flask, preparing to heat to 90 °C. During the heating process, 1.24 mol of butyl acrylate (158.79 g) and 1.24 mol of acrylic acid were added to a beaker. 2 Hydroxyethyl ester (228.31 g), 0.09 mol tridecyl fluorooctyl acrylate (37.00 g), and 0.051 mol n-dodecyl mercaptan (10.39 g) were stirred until homogeneous and then used as a mixed monomer for later use. In a smaller beaker, 0.035 mol azobisisobutyronitrile (5.93 g) and 26.98 g butyl acetate were added and stirred until homogeneous, serving as the initiator component. Once the temperature in the reaction flask reached a constant 90°C, the mixed monomer component and the initiator component were simultaneously added dropwise using two peristaltic pumps, completing the addition over approximately 3 hours. After the addition was complete, the mixture was kept at 90°C for another hour. After the incubation period, the mixture was further distilled under reduced pressure at 90°C for 30 minutes, ultimately yielding a colorless, transparent, viscous liquid leveling agent. GPC analysis determined the weight-average molecular weight (Mw) to be 9715.46.

[0077] Performance Evaluation 1. Compatibility test In solvent-based two-component polyurethane varnish formulations (see Table 1), 0.5% of the non-PFAS fluoropolymers of Examples 1-7 and the PFAS fluoropolymer of Comparative Example 1 were added, respectively. The mixture was dispersed at 500 rpm for 5 min, allowed to stand until all foam was eliminated in the container, and the transparency was observed to determine the compatibility between the leveling agent and the varnish system (by visual inspection, grade 0 being the worst and grade 5 the best; specific grades are shown in Table 2). Specific experimental results are shown in Table 3. Table 1

[0078] Table 2

[0079] Table 3

[0080] As can be seen from Table 3 above, in the varnish coating formulation, similar to the PFAS leveling agent prepared by the traditional free radical polymerization method in Comparative Example 1, Examples P1~P6 and P7-1 all have good compatibility with varnish. However, P7 shows poor compatibility with varnish because the branched molecule contains more hydroxyl groups on its periphery, resulting in a large difference in polarity.

[0081] 2. Paint film test In solvent-based two-component polyurethane clear varnish formulations (formulations shown in Table 1), 0.5% of the non-PFAS fluoropolymers of Examples 1-7 and the PFAS fluoropolymer of Comparative Example 1 were added, respectively. The mixture was dispersed at 500 rpm for 5 min, allowed to stand until all foam was eliminated in the can, and then film was formed on the same dark-colored substrate. The transparency and leveling of the film were observed visually (visual inspection grade is shown in Table 4). The appearance of the dry film and recoating adhesion were tested according to industry standard HG / T 2454-2014. Specific results are shown in Table 5.

[0082] Table 4

[0083] Table 5

[0084] As can be seen from Table 5, Example P7 exhibits poor compatibility, poor leveling properties, significant haziness in the paint film transparency, and failure to pass recoating adhesion tests. The leveling properties of P1 to P3 are slightly better than those of P4 to P7. The leveling properties of P7-1 are the best due to its high fluorine content, and it achieves the same effect as the traditional PFAS leveling agent in Comparative Example 1.

[0085] The present invention has been described in detail above with reference to the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A method for preparing a non-PFAS fluoropolymer, characterized in that, Includes the following steps: The fluoromalonate compound and the polyol are subjected to transesterification in the presence of a catalyst to obtain the product. The fluoromalonate compounds are selected from the following structural formulas: ； Among them, R1 is selected from C 1~10 Alkyl groups.

2. The preparation method according to claim 1, characterized in that, The polyol includes at least one of ethylene glycol, diethylene glycol, 1,6-hexanediol, trimethylolpropane, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, pentaerythritol, polyether polyol, polyester polyol, and polycarbonate polyol.

3. The preparation method according to claim 1, characterized in that, The molar ratio of the fluoromalonate compound to the polyol is 1:(0.49~1.95).

4. The preparation method according to claim 1, characterized in that, The catalyst includes base catalyst II and / or organotin catalyst.

5. The preparation method according to claim 1, characterized in that, The raw materials used in the preparation method also include diethyl malonate.

6. The preparation method according to claim 1, characterized in that, When the fluoromalonate compound is selected from the following structural formulas... In the presence of a catalyst, fluoromalonate compounds and polyols undergo transesterification to obtain intermediate products. Then the intermediate product and A second transesterification reaction was carried out to obtain a fluoropolymer.

7. The preparation method according to claim 1, characterized in that, The preparation method further includes mixing the product obtained from the transesterification reaction, compound 1, and base catalyst I to carry out a Michael addition reaction, thereby obtaining the product; The structural formula of compound 1 is as follows: R2 is selected from H and C. 1~20 alkyl, F-substituted C 2~10 Alkyl, polyether segments, , hydroxyl, phenyl, C containing oxygen atoms 3~8 At least one C-substituted heterocyclic alkyl group or dimethylamino group 1~10 Alkyl groups; The monomers of the polyether segment include ethylene oxide and / or propylene oxide; Where m is selected from integers from 0 to 30, and q is selected from integers from 1 to 3.

8. A non-PFAS fluoropolymer, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 7.

9. A wetting and leveling agent, characterized in that, This includes non-PFAS fluoropolymers prepared by the preparation method according to any one of claims 1 to 7, or non-PFAS fluoropolymers according to claim 8.

10. The application of the non-PFAS fluoropolymer of claim 8, or the wetting and leveling agent of claim 9, in coatings and inks.

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