WO2024116206A1

WO2024116206A1 - A process of polymerization of fluoromonomers

Info

Publication number: WO2024116206A1
Application number: PCT/IN2023/051114
Authority: WO
Inventors: Rajeev Chauhan; Bhupender Singh Rawat; Vadde SRISHYALAM; Suresh Babu KANCHARLA; Ranjeet Singh; Gaurav Kumar; Shriraj Modi
Original assignee: Gujarat Fluorochemicals Limited
Priority date: 2022-11-30
Filing date: 2023-11-29
Publication date: 2024-06-06

Abstract

The present invention discloses a process for polymerizing a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers in an aqueous dispersion medium containing a non-fluorinated imino acid type hydrocarbon surfactant to form a fluoropolymer. The process comprises the steps of: (a) pressurizing a polymerization reactor containing an aqueous medium with a fluoromonomer or a mixture of fluoromonomers and/or non- fluorinated monomers; (b) initiating a polymerization reaction of the fluoromonomer or the mixture of fluoromonomers and/or non-fluorinated monomers to form a fluoropolymer by adding an initiator; (c) propagating said polymerization reaction; and (d) terminating the polymerization reaction after consumption of a desired quantity of the fluoromonomer or the mixture of fluoromonomers and/or non- fluorinated monomers, wherein the hydrocarbon surfactant is represented by Formula I.

Description

GFL-202211069190 1 TITLE OF THE INVENTION A PROCESS OF POLYMERIZATION OF FLUOROMONOMERS FIELD OF THE INVENTION [001] The present invention pertains to a process of polymerization of a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers in an aqueous dispersion medium. Particularly, the present invention pertains to a process of polymerization of a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers in presence of non-fluorinated surfactants, more particularly a non-fluorinated imino acid type hydrocarbon containing surfactant. BACKGROUND OF THE INVENTION [002] Fluoropolymers represent a class of materials exhibiting extreme chemical resistance and favorable dielectric properties. Fluoropolymer is a fluorocarbon-based polymer with multiple carbon–fluorine bonds. These fluoropolymers are stable due to the multiple carbon–fluorine bonds present in a chemical compound. Consequently, there is an ever-increasing demand for these materials from industries engaged in manufacturing coatings, tapes and tubing, architectural fabrics, non-stick and industrial coatings, fluoroelastomer hoses for auto industry, sealing gaskets and liners for chemical industry, insulation for wires and cables, lubricants and so forth. This increasing demand in turn is driving a renewed interest in developing environment-friendly and more efficient routes for manufacturing fluoropolymers. Fluoropolymers are typically synthesized from alkenes in which one or more hydrogen atoms have been replaced by fluorine atom(s). These fluorinated monomers include tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), poly(propyl vinyl ether) (PPVE), poly(methyl vinyl ether) (PMVE), vinylidene fluoride (VDF), vinylfluoride (VF), etc. Polymerization of the aforesaid monomers affords the corresponding polymers, viz., polytetrafluoroethylene (PTFE), perfluoro alkoxy ether GFL-202211069190 2 (PFA) polymer, fluorinated ethylene propylene (FEP) polymer, polyethylenetetrafluoroethylene (ETFE), polychlorotrifluoroethylene (PCTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), Perfluorinated fluroelastomers or Perfluoroelastomer (FFPM/FFKM), Perfluorosulfonic acid (PFSA) and their modified grades etc. The best-known fluoropolymer is polytetrafluoroethylene (PTFE). [003] Fluoropolymers are primarily manufactured via heterogeneous polymerization reactions including aqueous systems. Generally, the reaction requires monomers and a radical initiator in a suitable aqueous reaction medium. Aqueous dispersion polymerization of fluorine containing monomers typically requires a surfactant capable of emulsifying both the reactants and the reaction products for the duration of the polymerization reaction. As discussed below, the surfactant of choice in the synthesis of fluoropolymers is generally a perfluorinated surfactant or a partially fluorinated surfactant. The most frequently used perfluorinated surfactant in the production of fluoropolymers and fluoroelastomers is a Perfluorooctanoic acid (PFOA) salt. [004] Although perfluorosurfactants are better in lowering the surface tension of water than comparable hydrocarbon surfactants, they have high stability, and good resistance to chemical degradation. However, fluorinated surfactants persist in the environment for a longer duration of time and have been detected in humans and wildlife. Perfluorosurfactants are a group of chemicals used to make fluoropolymer coatings and products that resist heat, oil, stains, grease and water. Perfluorosurfactants may be accumulated in living bodies by consumption through contaminated water or food. Perfluorosurfactants such as PFOA are considered to have several health effects affecting growth and development, reproduction, thyroid function, immune system and the like. Annexure-XVII to REACH, Entry 68, by the European Chemicals Agency, had placed restrictions on the manufacture, placing on the market and use of certain dangerous substances, mixtures and articles containing Perfluorooctanoic acid (PFOA) and its salts. Restrictions were also placed on any related substance (including its salts and polymers) having a linear or branched GFL-202211069190 3 perfluoroheptyl group with the formula C7F15- directly attached to another carbon atom or a linear or branched perfluorooctyl group with the formula C⁸F¹⁷, as one of the structural elements. However, on December 16, 2020, said Annexure XVII was revised to delete entry 68 pertaining to PFOA and its salts as these are now regulated under Regulation (EU) 2019/1021 on persistent organic pollutants (POP Recast Regulation) that lays down more severe restrictions for such substances. Hence, in view of the more stringent restrictions imposed by the European Chemicals Agency, there is a need for a process for polymerization of fluoromonomers, which does not involve the use of fluorinated surfactants. US9255164 discloses a process for the polymerization of fluoromonomer to form a dispersion of fluoropolymer particles in an aqueous medium in a polymerization reactor, by (a) providing the aqueous medium in the reactor, (b) adding the fluoromonomer to the reactor, (c) adding initiator to the aqueous medium, the combination of steps (b) and (c) being carried out essentially free of hydrocarbon-containing surfactant and resulting in the kick-off of the polymerization of the fluoromonomer, and (d) metering hydrocarbon-containing surfactant into the aqueous medium after the kick-off of polymerization, e.g., after the concentration of the fluoropolymer in the aqueous medium is at least 0.6 wt %, the metering being at a rate reducing the telogenic activity of said surfactant while maintaining surface activity. [005] Similarly, WO2019172382 discloses a method for producing a fluoropolymer, which is capable of reducing the content of impurities, which is characterized by comprising a polymerization step wherein a fluoropolymer is obtained by carrying out polymerization of a fluoromonomer in an aqueous medium in the presence of a surfactant, and which is also characterized in that the surfactant is a carboxylic acid type hydrocarbon-containing surfactant. [006] A process for the polymerization of fluoromonomers and fluoroelastomers using a non- fluorinated surfactant would solve the aforesaid issues of persistence in the eco-system, bioaccumulation of fluorosurfactants. New polymerization processes are needed that utilize non- fluorinated surfactants or reduced amounts of perfluoroalkyl surfactants. In order to address this GFL-202211069190 4 issue, several different approaches have been attempted to reduce or eliminate the use of perfluoroalkyl surfactants in the polymerization of halogen-containing monomers. [007] The conventionally prepared fluoropolymer has several drawbacks and limitations such as increased or higher thermal instability and degradation during extended periods of heating at elevated temperatures. Further, the significant limitation of the conventionally prepared fluoropolymer is the tendency of polymer materials to generate higher pores when subjected to tensile strain. [008] Therefore, there is a strong requirement to employ further non-fluorinated surfactants in fluoropolymerisation processes. In addition, there is a requirement for a simplified and economical process for the preparation of fluoropolymers using non-fluorinated surfactants, which is devoid of passivating the surfactant. There is a need for simplified process for the preparation of fluoropolymers that yield a stable emulsion. SUMMARY OF THE INVENTION [009] In one aspect, the present invention relates to a process for preparing fluoropolymers and/or a mixture of fluoromonomers and/or non- fluorinated monomers in an aqueous dispersion medium to form a fluoropolymer comprising the steps of: a) pressurizing a polymerization reactor containing an aqueous medium with a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers; b) initiating a polymerization reaction of the fluoromonomer or the mixture of fluoromonomers and/or non-fluorinated monomers to form a fluoropolymer by adding an initiator; c) propagating said polymerization reaction; and d) terminating the polymerization reaction after consumption of a desired quantity of the fluoromonomer or the mixture of fluoromonomers and/or non-fluorinated monomers; GFL-202211069190 5 wherein the process comprises adding a non-fluorinated imino acid type hydrocarbon surfactant represented by formula I:

Formula I Wherein, R is a hydrocarbon, linear or branched alkyl group with 8 to 22 carbon atoms; R1 = H, -CH2COO-M+. M is a univalent cation selected from H+, NH4+, Na+ and K+. BRIEF DESCRIPTION OF THE DRAWINGS [010] Reference will be made to embodiments of the invention, examples of which may be illustrated in accompanying figures. These figures are intended to be illustrative, not limiting. Although the invention is generally described in context of these embodiments, it should be understood that it is not intended to limit the scope of the invention to these particular embodiments. Figure 1 illustrates a graph between LIDA surfactant concentration and viscosity. Figure 2 illustrates a graph between LIDA surfactant concentration and dispersion stability. DETAILED DESCRIPTION OF THE INVENTION [011] Discussed below are some representative embodiments of the present invention. The invention in its broader aspects is not limited to the specific details and representative methods. An illustrative example is described in this section in connection with the embodiments and methods provided. It is to be noted that, as used in the specification, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a GFL-202211069190 6 composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise. [012] The expression of various quantities in terms of “%” or “% w/w” means the percentage by weight of the total solution or composition unless otherwise specified. [013] The term “ppm” refers to “parts per million”. The concentrations of various components in ppm are based on the weight of the aqueous medium. The present invention, in all its aspects, is described in detail as follows: [014] Described herein is a process that eliminates the use of perfluorinated or partially fluorinated surfactants in the polymerization of fluoromonomers, without adding complex reaction steps. The present invention provides a simplified process for the preparation of fluoropolymers that yield a stable emulsion. The novel process for preparing fluoropolymers using only non- fluorinated imino acid type hydrocarbon surfactants comprise the steps of pressurizing a polymerization reactor containing an aqueous medium with a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers followed by initiating the reaction by adding an initiator followed by the propagation step. Once the desired quantity of the fluoromonomer or the mixture of fluoromonomers and/or non- fluorinated monomers is consumed, the polymerization reaction is terminated. [015] In accordance with an embodiment of the invention, the process involves polymerization of fluoromonomers or a mixture of fluoromonomers and/or non-fluorinated monomers in an aqueous dispersion medium in presence of non-fluorinated imino acid type hydrocarbon surfactant which can act as CTA (chain transfer agent) and/or dispersion/ latex stabilizer. [016] One embodiment of the present invention relates to a process for polymerizing a fluoromonomer or a mixture of fluoromonomers and/or non- fluorinated monomers in an aqueous dispersion medium to form a fluoropolymer comprising: GFL-202211069190 7 a) pressurizing a polymerization reactor containing an aqueous medium with a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers; b) initiating a polymerization reaction of the fluoromonomer or the mixture of fluoromonomers and/or non-fluorinated monomers to form a fluoropolymer by adding an initiator; c) propagating said polymerization reaction; and d) terminating the polymerization reaction after consumption of a desired quantity of the fluoromonomer or the mixture of fluoromonomers and/or non-fluorinated monomers; wherein the process comprises adding a non-fluorinated imino acid type hydrocarbon surfactant represented by formula I:

Formula I Wherein, R is a hydrocarbon, linear or branched alkyl group with 8 to 22 carbon atoms; R1 = H, -CH2COO-M+; and M is a univalent cation selected from H+, NH4+, Na+ and K+. [017] In accordance with an embodiment of the invention, a novel process for polymerization of fluoromonomers or a mixture of fluoromonomers and/or non-fluorinated monomers in an aqueous dispersion medium in presence of non-fluorinated imino acid type hydrocarbon surfactant which can act as CTA (chain transfer agent) and dispersion/ latex stabilizer is disclosed. [018] In accordance with an embodiment of the invention, the non-fluorinated imino acid type hydrocarbon surfactant is added to the polymerization reactor prior to adding the initiator, in one shot or as metered addition. The polymerization reaction of the fluoromonomer or the mixture of fluoromonomers and/or non-fluorinated monomers is then initiated by adding an initiator after the GFL-202211069190 8 addition of the non-fluorinated imino acid type hydrocarbon surfactant. Preferably, no degradation agent is added into the polymerization reactor. In particular, the aqueous medium is free of the hydrocarbon-containing oleophilic nucleation sites before kicking off the polymerization reactor, in particular, since no degradation agent is added. Preferably, no surfactant, in particular non- fluorinated imino- acid type hydrocarbon surfactant, is added into the polymerization reactor during the propagation phase. [019] Alternatively, in accordance with another embodiment of the invention, the non- fluorinated imino acid type hydrocarbon surfactant is added after the initiator has been added to the polymerization reactor and/or during propagation of the polymerization reaction and no hydrocarbon surfactant is added into the polymerization reactor before the initiation of the polymerization reaction. Preferably, the non-fluorinated imino acid type hydrocarbon surfactant is added in one shot into the polymerization reactor, in particular after initialization and/or during propagation of the polymerization reaction. Preferably, the surfactant is added after the concentration of the fluoropolymer particles in the aqueous medium is greater than or equal to 2 wt% based on the aqueous medium. Generally, no more than 3000 ppm of the surfactant is added into the polymerization reactor during the propagation phase. [020] Preferably, prior to pressurizing the polymerization reactor with a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers, oxygen is removed from the polymerization reactor until a concentration of oxygen less than or equal to 20 ppm is reached. [021] The aqueous reaction mixture formed in the present invention comprises surfactants, fluoromonomers, non-fluorinated monomers and initiators. Chain transfer agents and paraffin wax. Degradation agent is not added into the polymerization reaction during the course of the reaction. [022] In accordance with yet another embodiment, the non-fluorinated imino acid type hydrocarbon surfactant may be added in either or both the phases-during the initiation phases and the propagation phase. GFL-202211069190 9 Surfactant [023] The term “surfactant” means a type of molecule which has both hydrophobic and hydrophilic portions, which allows it to stabilize and disperse hydrophobic molecules and aggregates of hydrophobic molecules in aqueous systems. A preferred group of surfactants for fluoropolymer synthesis according to the embodiments of the present invention include non- fluorinated, hydrocarbon containing surfactant. The hydrocarbon containing surfactant here refers to non-fluorinated imino-acid type hydrocarbon surfactant. [024] In an embodiment, the hydrocarbon containing surfactant used in the present invention is represented by formula I:

Formula I Wherein, R is a hydrocarbon, linear or branched alkyl group with 8 to 22 carbon atoms; R1 = H, -CH2COO-M+; and M^{is a univalent cation selected from H+, NH4+, Na+ and K+.} [025] The non-fluorinated imino-acid type hydrocarbon surfactant is specifically chosen from lauryl-imino-di-acetic acid (LIDA) and lauryl-imino-monoacetic acid (LIMA). Preferably, the surfactant useful for the present invention is lauryl-imino-di-acetic acid (LIDA). Apart from reducing surface tension, LIDA also acts as an efficient latex stabilizer by inhibiting degradation of the polymer latex. Further, it also acts as a molecular weight regulator by controlling the chain length of the polymer, thereby eliminating the need to add any chain transfer agent to the polymerization reaction. The structure of LIDA is as follows: GFL-202211069190 10

The ammonium, sodium or potassium salt of LIDA may be used. [026] The amount of surfactant added into the polymerization reactor ranges from 20 to 7000 ppm, in particular 30 to 4000 ppm, in particular 50 to 3000 ppm. If the hydrocarbon surfactant is added prior to initializing the polymerization reaction, an amount of more than or equal to 100 ppm surfactant is preferred. If the hydrocarbon surfactant is added after initialization of the polymerization reaction and/or during propagation of the polymerization reaction, in particular after the concentration of the fluoropolymer particles in the aqueous medium is greater than or equal to 2 wt% based on the aqueous medium, an amount of less than 3000 ppm is preferred. [027] No fluorosurfactant is added into the polymerization reactor during the course of the reaction. Only non-fluorinated imino acid type hydrocarbon surfactants are used in the present invention. Preferably, the hydrocarbon surfactant is not passivated. [028] The hydrocarbon surfactant may be added either in ‘one shot’ into the polymerization reactor or may be metered at a pre-defined rate. By ‘one shot’ addition, it means that the surfactant is not added at any pre-defined rate into the polymerization reactor and that the dosing of the surfactant may be carried out at any rate. Fluoromonomers [029] The term “fluoromonomer” or the expression “fluorinated monomer” means a polymerizable alkene which contains at least one fluorine atom, fluoroalkyl group or fluoroalkoxy GFL-202211069190 11 group attached to the double bond of the alkene that undergoes polymerization. The term “fluoropolymer” and fluoroelastomers means a polymer or elastomer formed by the polymerization of at least one fluoromonomer and it is inclusive of homopolymers, copolymers, terpolymers and higher polymers. Examples of fluoromonomers that can be used in the present invention include but are not limited to vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), vinyl fluoride (VF), hexafluoroisobutylene, perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-tri fluoro-1- propene, 2-trifluoromethyl-3,3,3-trifluoropropene, perfluoropropylvinyl ether (PPVE), perfluoro methyl vinyl ether (PMVE), fluorinated allyl ethers, fluorinated dioxoles, 1,2,3,3,3- pentafluoropropene, and 3,3,3,4,4-pentafluoro-1-butene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoro-n-propyl vinyl ether, perfluoro-2-propoxypropyl vinyl ether, perfluoro(1,3-dioxole) and perfluoro(2,2-dimethyl-1,3-dioxole), partly fluorinated allylic monomers, fluorinated allylic monomers, and so forth, each of which can be used individually or in combination. Preferably, the fluoromonomer is tetrafluoroethylene (TFE) and the fluoropolymer is polytetrafluoroethylene (PTFE), however the process described herein can be applied to the polymerization of any fluoromonomer. Non-fluorinated monomers [030] The term “non-fluorinated monomer” refers to a polymerizable molecule which does not contain fluorine atom. Non-fluorinated monomers, useful for the present invention are selected from unsaturated dibasic acid monoester selected from the group consisting of maleic acid monoesters and citraconic acid monoesters, styrene, ethylene, propene, 2-hydroxyethyl allyl ether, 3- allyloxypropanediol, hydrophilic (meth)acrylic monomers such as acrylic acid, methacrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate, or hydroxyethylhexyl(meth)acrylates, phosphonic acid or vinyl phosphonate. The aqueous emulsion further comprises an initiator for initiating the polymerization process. Initiators GFL-202211069190 12 [031] The term “initiator” and the expressions “radical initiator” and “free radical initiator” refer to a chemical that is capable of providing a source of free radicals, either induced spontaneously, or by exposure to heat or light. Examples of suitable initiators include peroxides, peroxy bicarbonates and azo compounds. Initiators may also include reduction-oxidation systems which provide a source of free radicals. The term “radical” and the expression “free radical” refers to a chemical species that contains at least one unpaired electron. The radical initiator is added to the reaction mixture in an amount sufficient to initiate and maintain the polymerization reaction rate. The radical initiator may comprise a persulfate salt, such as sodium persulfate, potassium persulfate or ammonium persulfate. Alternatively, the radical initiator may comprise a redox system. “Redox system” is understood by a person skilled in the art to mean a system comprising an oxidizing agent, a reducing agent and optionally, a promoter as an electron transfer medium. In a preferred embodiment, the radical initiator is selected from the group consisting of Disuccinic Acid Peroxide (DSAP), Ammonium Persulfate (APS), Potassium Persulfate (KPS), Sodium Persulfate (NaPS), Potassium permanganate (KMnO4), Oxalic acid, Sodium sulfite, Sodium bisulfite, Sodium acetate, peroxides, peroxy bicarbonates or azo compounds and combinations thereof. These radical initiators may also function as oxidizing agents and may form redox systems with reducing agents such as sodium sulfite and sodium bisulfite. [032] The initiator is added in one shot into the polymerization reactor initially. Alternatively, the initiator can be metered into the polymerization reactor. Preferably, prior to adding the initiator into the polymerization reactor, it is dissolved in a suitable solvent such as water. [033] The amount of initiator added ranges from 150 to 650 ppm based on the weight of the total primary monomer and/or co-monomer to be polymerized. Chain-transfer agents [034] Chain transfer agents, also referred to as modifiers or regulators, comprise of at least one chemically weak bond. A chain-transfer agent reacts with the free-radical site of a growing polymer chain and halts an increase in chain length. Chain transfer agents are often added during GFL-202211069190 13 emulsion polymerization to regulate chain length of a polymer to achieve the desired properties in the polymer. Examples of chain transfer agents that can be used in the present invention include, but are not limited to, halogen compounds, acetates, hydrocarbons in general, aromatic hydrocarbons, aliphatic hydrocarbons, thiols (mercaptans), alcohols, esters and so forth; each of which can be used individually or in combination. [035] In a preferred embodiment the chain transfer agent is ethyl acetate. The amount of chain- transfer agents added to the polymerization reaction is preferably from about 0.0023 to about 0.230 wt %, more preferably from about 0.001 to about 0.075 wt % based on the total weight of primary monomer and/or co-monomer consumed in the polymerization reaction. Polymerization conditions [036] The temperature for the polymerization reaction may vary, for example, from 15 to 135 °C, depending on the initiator system chosen and the reactivity of the monomer/fluoromonomer(s) selected. In a preferred embodiment, polymerization is carried out at a temperature in the range of 65 to 100 °C. The pressure of the polymerization reactor may vary from 2-200 bar, depending on the reaction equipment, the initiator system, and the monomer selection. In a preferred embodiment, the reaction is carried out at a pressure in the range of 10 to 60 bar. [037] Polymerization occurs under stirring or agitation. The stirring may be constant or may be varied to optimize process conditions during the course of the polymerization. In one embodiment, both multiple stirring speeds and multiple temperatures are used for controlling the reaction. [038] According to one embodiment of the process of the invention, a pressurized polymerization reactor equipped with a stirrer and heat control means is charged with water, preferably deionized water., non-fluorinated hydrocarbon-containing imino-acid type surfactant in accordance with the invention, chain transfer agents, initiators, at least one fluoromonomer and non-fluorinated monomer likewise. GFL-202211069190 14 [039] The aqueous emulsion of the present invention may optionally comprise stabilizing agents such as Paraffin wax. [040] Prior to the introduction of the non-fluorinated imino acid type hydrocarbon surfactant, and a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomer into the reaction vessel and commencement of the reaction, air is preferably removed from the reactor in order to obtain an oxygen-free environment for the polymerization reaction. Preferably, the oxygen is removed from the reaction vessel until its concentration is less than 20 ppm. The reactor may also be purged with a neutral gas such as, for example, nitrogen or argon. Preferably, the concentration of O2 in the reactor is reduced to less than 20 ppm by applying nitrogen-vacuum cycles. [041] The reactor containing the aqueous medium is then pressurized with at least one fluoromonomer or a mixture of a fluoromonomer and/or a non-fluorinated monomer. The imino acetic acid surfactant is then added in one shot into the polymerization reactor, in particular in an amount greater than or equal to 100 ppm. Afterwards, the initiator is added. Subsequently, the start of the reaction or the kick-off the reaction is indicated by a drop in the reactor pressure. After initiation of the polymerization reaction, further initiator is added in one shot or continuously metered into the reaction at a rate of 0.01-0.1 g/L-h. The polymerization reaction is then allowed to propagate. No surfactant is added into the polymerization reactor during the propagation phase. Preferably, no degradation agent is added into the reactor during the course of the reaction. Upon conversion of the desired quantity of the fluoromonomer, pressure of the reactor is reduced. The addition of the monomer and initiator dosing are stopped once pressure reached 25 to 30 bar. The batch is then terminated by stopping the agitator. The aqueous reaction medium containing the fluoropolymer is then recovered from the reaction vessel. Preferably, the solid content ranges from 15 to 35 %, more preferably from 20 to 30 %. The particle size of the fluoropolymer particles ranges from 150 to 500 nm, in particular 150 to 350 nm and in particular 200 to 350nm. GFL-202211069190 15 [042] Alternatively, instead of an addition prior to kick-off of the polymerization reaction, the imino acetic acid surfactant may be added into the polymerization reactor after initiation of the polymerization reaction, with no surfactant being added into the reactor prior to initiation. [043] In accordance with another embodiment, the imino acetic acid surfactant, which is preferably LIDA may be added into the polymerization reactor both before initiation of the polymerization reaction as well as after the initiation, i.e., during the propagation phase. The non- fluorinated imino acid type hydrocarbon surfactant may be either added in one shot or metered into the polymerization reactor. [044] In an embodiment, a process for polymerizing a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers in an aqueous dispersion medium to form a fluoropolymer is disclosed comprising the steps of: a) adding water to a polymerization reactor; b) adding a non-fluorinated surfactant along with polymerization initiator; c) pressurizing the polymerization reactor with a fluoromonomer or a mixture of fluoromonomers and or non-fluorinated monomers; d) initiating a polymerization reaction of the fluoromonomer or the mixture of fluoromonomers and or non-fluorinated monomers to form a fluoropolymer by adding an initiator; e) propagating said polymerization reaction; and f) terminating the polymerization reaction after consumption of a desired quantity of the fluoromonomer or the mixture of fluoromonomers. [045] In another embodiment, a process for polymerizing a fluoromonomer or a mixture of fluoromonomers and or non-fluorinated monomers in an aqueous dispersion medium to form a fluoropolymer is disclosed comprising the steps of: a) adding water to a polymerization reactor; GFL-202211069190 16 b) pressurizing the polymerization reactor with a fluoromonomer or a mixture of fluoromonomers and or non-fluorinated monomers; c) initiating a polymerization reaction of the fluoromonomer or the mixture of fluoromonomers and or non-fluorinated monomers to form a fluoropolymer by adding an initiator; d) adding a non-fluorinated surfactant in one shot or metered through the reaction either from start of reaction or at a delayed stage in to the reaction; e) propagating said polymerization reaction; and f) terminating the polymerization reaction after consumption of a desired quantity of the fluoromonomer or the mixture of fluoromonomers. [046] In another embodiment, a process for polymerizing a fluoromonomer or a mixture of fluoromonomers and/ or non-fluorinated monomers in an aqueous dispersion medium to form a fluoropolymer is disclosed comprising the steps of: a) adding water to a polymerization reactor; b) adding a non-fluorinated surfactant; c) pressurizing the polymerization reactor with a fluoromonomer or a mixture of fluoromonomers and or non-fluorinated monomers; d) initiating a polymerization reaction of the fluoromonomer or the mixture of fluoromonomers and or non-fluorinated monomers to form a fluoropolymer by adding an initiator; e) adding a non-fluorinated surfactant in one shot or metered through the reaction either from start of reaction or at a delayed stage in to the reaction; f) propagating said polymerization reaction; and g) terminating the polymerization reaction after consumption of a desired quantity of the fluoromonomer or the mixture of fluoromonomers. GFL-202211069190 17 Examples: [047] The present invention is more particularly described in the following examples that are intended as illustration only, since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art. Unless otherwise noted, all parts, percentages and ratios reported in the following examples are on a weight basis, and all reagents used in the examples were obtained or are available from the chemical suppliers. The following examples illustrate the basic methodology and versatility of the present invention. Example 1: [048] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 20 ppm. The speed of the agitator is maintained at 21 rpm. [049] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 116.4 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant and 29.1 ppm of Potassium persulfate (KPS). The pressure and the temperature of the reactor increased to 44.5 bar and 83°C, respectively. [050] The polymerization reaction is then initiated by addition of 26.51 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.053 g/L*h is dosed into the reactor. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. [051] After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 2: GFL-202211069190 18 [052] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O² content to < 20 ppm. The speed of the agitator is maintained at 21 rpm. [053] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 174.5 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant and 29.1 ppm of Potassium persulfate (KPS). The pressure and the temperature of the reactor are increased to 44.5 bar and 83 °C, respectively. [054] The polymerization reaction is then initiated by addition of 26.51 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.04 g/L*h is dosed into the reactor. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 3: [055] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 20 ppm. The speed of the agitator is maintained at 21 rpm. [056] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 232.72 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant and 29.1 ppm of Potassium persulfate (KPS). The pressure and the temperature of the reactor are increased to 44.5 bar and 83 °C, respectively. [057] The polymerization reaction is then initiated by addition of 26.51 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.07g/L*h is dosed into the reactor. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. GFL-202211069190 19 [058] After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 4: [059] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 20 ppm. The speed of the agitator is maintained at 21 rpm. [060] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 174.5 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant and 29.1 ppm of Potassium persulfate (KPS). The pressure and the temperature of the reactor are increased to 44.5 bar and 83 respectively. [061] The polymerization reaction is then initiated by addition of 26.51 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.025g/L*h is dosed into the reactor. Ethyl acetate is added during the propagation of 90.9 ppm. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. [062] After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 5: [063] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O² content to < 20 ppm. The speed of the agitator is maintained at 21 rpm. [064] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 58.18 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant. The pressure and the temperature of the reactor increased to 44.5 bar and 83°C, respectively. GFL-202211069190 20 [065] The polymerization reaction is then initiated by addition of 11.36 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.013 g/L-h is dosed into the reactor. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. [066] After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 6: [067] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 20 ppm. The speed of the agitator is maintained at 21 rpm. [068] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 36.97 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant. The pressure and the temperature of the reactor are increased to 44.5 bar and 83.68 °C, respectively. [069] The polymerization reaction is then initiated by addition of 11.36 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.013 g/L-h is dosed into the reactor. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. [070] After consumption of 35 kg of VDF, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 7: [071] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 20 ppm. The speed of the agitator is maintained at 21 rpm. [072] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor. GFL-202211069190 21 [073] The pressure and the temperature of the reactor increased to 44.5 bar and 83.67 °C, respectively. [074] The polymerization reaction is then initiated by addition of 26.51 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.025g/L*h is dosed into the reactor.174.5 ppm LIDA is added to the polymerization reactor during the propagation phase at rate of 0.016 to 0.027 g/L*h after 2.5 kg monomer consumption. [075] After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 8: [076] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 20 ppm. The speed of the agitator is maintained at 21 rpm. Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 116.4 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant and 44 ppm of Potassium persulfate (KPS). The pressure and the temperature of the reactor increased to 44.5 bar and 88.46 °C, respectively. [077] The polymerization reaction is then initiated by addition of 26.51 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.08 g/L*h is dosed into the reactor. Acrylic acid is dosed during propagation phase at rate of 0.15 g/L*h and dosed 730.3 ppm into polymerization reaction. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. GFL-202211069190 22 [078] After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 9: [079] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 20 ppm. The speed of the agitator is maintained at 30 rpm. [080] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 145.5 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant and 30.6 ppm of Potassium persulfate (KPS). The pressure and the temperature of the reactor are increased to 44.5 bar and 90.76 °C, respectively. [081] The polymerization reaction is then initiated by addition of 31.5 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.052 g/L*h is dosed into the reactor. Monomethylester maleic anhydride is dosed during propagation phase at rate of 0.128 g/L-h and dosed 856.1 ppm into polymerization reaction. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. [082] After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 10: [083] 132 L of de-ionized water is charged into a polymerization reactor. Thereafter, 56 g of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 20 ppm. The speed of the agitator is maintained at 30 rpm. [084] Vinylidene fluoride (VDF) is charged into the reactor under pressure through a compressor followed by addition of 174.5 ppm of Lauryl-imino-di-acetic acid (LIDA) surfactant and 30.3 ppm GFL-202211069190 23 of Potassium persulfate (KPS). The pressure and the temperature of the reactor increased to 44.5 bar and 90.9 °C, respectively. [085] The polymerization reaction is then initiated by addition of 30.3 ppm of KPS. Commencement of the reaction is indicated by a drop in the pressure of the reactor. Once the reaction starts, a continuous dose of KPS at a rate of 0.055 g/L*h is dosed into the reactor. Monomethylester maleic anhydride is dosed during propagation phase at rate of 0.11 g/L*h and dosed 762.4 ppm into polymerization reaction. No further LIDA surfactant is added to the polymerization reactor during the propagation phase. [086] After consumption of 35 kg of VDF, the pressure of the reactor is reduced to 30 bar, addition of VDF and initiator dosing are stopped. The agitator is then stopped to terminate the batch reaction. Example 11: [087] 83 L of de-ionized water is charged into a polymerization reactor. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 10 ppm. Afterwards 5927.71 ppm PPVE, 1566.26 ppm CCl4, 126.4 ppm Lauryl-imino-di-acetic acid (LIDA) and 12.1 ppm Ethane are added into reactor. The speed of the agitator is maintained at 60 rpm. [088] Tetrafluoroethylene (TFE) is charged into the reactor. The pressure and the temperature of the reactor are increased to 24 bar and 82.1 °C, respectively. [089] The polymerization reaction is then initiated by addition of 240.96 ppm of Potassium Persulfate (KPS). Commencement of the reaction is indicated by a drop in the pressure of the reactor.5150 ppm Lauryl-imino-di-acetic acid (LIDA) is dosed in one-shot into reactor at 1.5 kg TFE consumption. After surfactant dosing is completed, a KPS and PPVE are continuously added at a rate of 0.04 g/L*h and 6.16 g/L*h into the reactor respectively. Initiator dosing is stopped after 28 kg of TFE and 3.264 kg PPVE consumption. The agitator is then stopped to terminate the batch reaction. Example 12: GFL-202211069190 24 [090] 83 L of de-ionized water is charged into a polymerization reactor. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 10 ppm. Afterwards, 5927.71 ppm PPVE, 1566.26 ppm CCl4, 154 ppm Lauryl-imino-di-acetic acid (LIDA) and 12.1 ppm Ethane are added into reactor. The speed of the agitator is maintained at 60 rpm. Tetrafluoroethylene (TFE) is charged into the reactor. The pressure and the temperature of the reactor increased to 24 bar and 83.5°C, respectively. [091] The polymerization reaction is then initiated by addition of 240.96 ppm of Potassium Persulfate (KPS). Commencement of the reaction is indicated by a drop in the pressure of the reactor.2156 ppm Lauryl-imino-di-acetic acid (LIDA) is added into the reactor in one-shot after consumption of 1.5 kg TFE. Just after surfactant dosing is completed, a continuous dose of KPS and PPVE at a rate of 0.025 g/L-h and 8.26 g/L-h are dosed into the reactor respectively. Initiator dosing is stopped after 28 kg of TFE and 3.264 kg PPVE consumption. The agitator is then stopped to terminate the batch reaction. Example 13: [092] 70 L of de-ionized water is charged into a polymerization reactor. Thereafter, 3 kg of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 10 ppm. Afterwards, 807.86 ppm DSAP initiator is added into reactor. The speed of the agitator is maintained at 50 rpm. Tetrafluoroethylene (TFE) is charged into the reactor. The pressure and the temperature of the reactor are increased to 21 bar and 80.25 °C, respectively. [093] After consumption of 2.34 kg TFE, 857.15 ppm Lauryl-imino-di-acetic acid (LIDA) is added into reactor in one-shot. After consumption of 24 kg of TFE the agitator is stopped to terminate the batch reaction. Example 14: GFL-202211069190 25 [094] 70 L of de-ionized water is charged into a polymerization reactor. Thereafter, 3 kg of wax is added. Nitrogen-vacuum cycles are applied to the reactor to bring O2 content to < 10 ppm. After oxygen qualification of reactor added 3000 ppm DSAP initiator into reactor. The speed of the agitator is maintained at 50 rpm. [095] Tetrafluoroethylene (TFE) is charged into the reactor. The pressure and the temperature of the reactor are increased to 21 bar and 82.5°C, respectively. Delayed addition that is at 2.34 kg TFE consumption added 6142.86 ppm Lauryl-imino-di-acetic acid (LIDA) is dosed in one-shot into reactor. After consumption of 24 kg of TFE the agitator is stopped to terminate the batch reaction. 1. Latex particle size/Primary particle size: [096] Latex particle size may be measured to measure the particle size of dispersed systems from sub- nanometer to several micrometers in diameter. The latex particle size may be measured by using the technique of Dynamic Light Scattering (DLS). The instrument used to determine the particle size of Fluoropolymer dispersions reported in the embodiments was HORIBA SZ 100 manufactured by HORIBA Scientific or Malver Zetasizer manufactured by Malvern Panalytical. Particle size analysis was performed by dynamic light scattering (DLS). To perform analysis, a first polystyrene cuvette was flushed with water used to dilute the dispersion sample with the help of a syringe. 0.8 g dispersion sample was taken in the cuvette and diluted to 100 ml by adding water. The cuvette having diluted sample was placed in the instrument chamber for determination of median particle size DV (50). 2. Determination of Fluoropolymer Content/Solid Content: [097] The solid content of fluoropolymer in dispersion is calculated by using following equation: Fluoropolymer Content (%) = (WD-WA) x 100 (WB-WA) Wherein, WA: Weight of Aluminium Petri dish GFL-202211069190 26 WB: Weight of Aluminium Petri dish + Fluoropolymer dispersion WC: Weight of fluoropolymer after drying at 105± 5 ^oC WD: Weight of fluoropolymer after drying the sample at 380 ± 5 ^oC. 3. pH: [098] pH may be measured by using pH-meter. The pH of the dispersion may be determined by ASTM E70 standard using SPECTRA LAB ACCUPH-3 instrument. 4. Standard specific gravity (SSG): [099] Standard specific gravity (SSG) is the property usually used to measure the relative molecular mass of the polymers used in the PTFE industry. SSG shall be determined in accordance with the procedure described in ASTM D4895. To perform the test, a sample is allowed to go through sintering and cooling cycle in accordance with the appropriate sintering schedule as described in ASTM D4895. The SSG of unmodified PTFE is inversely related to its molecular mass. 5. Extrusion pressure (PEX): [100] The extrusion pressure indicates the extent of fibrillation in fine powder PTFE. PEX reported in the embodiments have been measured by Jennings vertical paste extruder tested as per ASTM D4895. 6. Melting point and Enthalpy: [101] Melting point and enthalpy reported in the embodiments have been measured by DSC (Differential scanning calorimetry) in accordance with ASTM D4591 which defines Standard Test Method for Determining Temperatures and Heats of Transitions of Fluoropolymers by Differential GFL-202211069190 27 Scanning Calorimetry. All measurements have been performed on TA Instruments DSC Q200 differential scanning calorimeter. 7. Tensile strength and Elongation: [102] Tensile strength indicates the amount of stress the material can withstand under tensile load. Elongation at break is the percentage increase in length that a material will achieve before breaking. Tensile strength and elongation are measured in accordance with ASTM D638. 8. Solution Viscosity: [103] Solution viscosity is directly proportional to molecular weight of the polymer. In embodiments mentioned in the disclosure, solution viscosity is used to indicate differences in molecular weight of PVDF homopolymers and copolymers. Solution viscosity measurements have been performed on Anton Paar RheolabQC rotational rheometer equipped with CC27 concentric cylinder measuring system. 7% PVDF solution by weight in N-Methyl-2-pyrrolidone (NMP) is used for the measurement. PVDF powder is dissolved in NMP at 60 °C for 8 hours under constant stirring. The solution is allowed to cool to 25 °C in a water bath for 3 hours prior to measurement. Solution viscosity measurement is performed under constant shear rate ramp from 5 s-1 to 150 s- 1 shear rate at 25 °C. Viscosity values are recorded for every 5-unit increment in shear rate to obtain a viscosity Vs shear rate curve. Solution viscosity values reported in the embodiments are viscosity values in centipoise (cP) for 100 s-1 shear rate. 9. Melt Flow Rate: [104] The melt flow rate (MFR) or melt flow index (MFI) is a measure of the ease of flow of the melt of a thermoplastic polymer. It is defined as the weight of polymer in grams flowing in 10 min through a die of specific diameter and length by a pressure applied by a specific weight at a given temperature. MFR measurements also indicate differences in molecular weight of thermoplastic GFL-202211069190 28 polymers where MFR is inversely proportional to molecular weight of the polymer. MFR measurements reported in the embodiments have been performed in accordance to ASTM D1238 on a Zwick Roell Mflow extrusion plastometer MFR tester. MFR values for fluoroplastic resins in examples 11 & 12 have been measured at a temperature of 372±1 ˚C under 5 kg load. 10. PPVE Content: [105] PPVE content reported in the embodiments refer to the actual % of comonomer incorporated in the fluoroplastic resin. PPVE content is measured through Fourier-transform infrared spectroscopy on a Perkin Elmer Spectrum Two FT-IR Spectrometer. IR is passed through a thin film sample under absorbance. Two peaks are obtained at wavelength range of 994 (Peak- 1) & 2365 (Peak-2) cm ¹. PPVE content is obtained by taking ratio of height of peak-1 & peak-2 and multiplying the same with a factor 0.95. 11. Latex Stability: [106] Latex stability is measured by a high-speed stirring machine at 1000 rpm. Agitation renders the surface of dispersion “turbulent” or “wavy. Agitation is stopped when the surface of agitation dispersion no longer showed visible turbulence. Latex stability is reported as the time from the start of agitation until the surface of the dispersion is no longer turbulent due to coagulation of polymeric particles under high shear condition. [107] The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive. [108] The drawings and the forgoing description give examples of embodiments. Those skilled in the art will appreciate that one or more of the described elements may well be combined into a single functional element. Alternatively, certain elements may be split into multiple functional elements. Elements from one embodiment may be added to another embodiment. [109] For example, orders of processes described herein may be changed and are not limited to the manner described herein. GFL-202211069190 29 [110] Moreover, the actions of any flow diagram need not be implemented in the order shown; nor do all the acts necessarily need to be performed. Also, those acts that are not dependent on other acts may be performed in parallel with the other acts. The scope of embodiments is by no means limited by these specific examples. Numerous variations, whether explicitly given in the specification or not, such as differences in structure, dimension, and use of material are possible. The scope of embodiments is at least as broad as given by the following claims. [111] Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any component(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature or component of any or all the claims. Table 1:

GFL-202211069190 30

Table 2:

GFL-202211069190 31

Table 3:

GFL-202211069190 32 Table 4:

GFL-202211069190 33 Detailed analysis of examples (1-14) Example-1-7 (for homopolymer of VDF monomer) [112] LIDA surfactant has dual properties in emulsion polymerization. It has evidently shown the properties as a chain transfer agent (CTA) as well dispersion stabilizer. LIDA surfactant controls, alters and regulates the solution viscosity of polymer. In examples (1,2,3,5 and 6), surfactant amount variation is depicted vs solution viscosity. As per graph as higher the surfactant quantity, lower will be the solution viscosity of polymer. Table 5:

[113] As the LIDA surfactant quantity increases, stability increases accordingly. [114] Figures 1 and 2 show a relationship between Surfactant quantity, Latex stability and Viscosity. As surfactant quantity increases, the dispersion stability increases as shown in figure 2. Example-2 and 4 which are without and with CTA (ethyl acetate) in combination with LIDA surfactant. [115] As per data, LIDA surfactant alone gives much CTA effect as with combination with LIDA surfactant and ethyl acetate-CTA. As per viscosity data provided, without CTA LIDA experiment viscosity is approximately same as with CTA-LIDA surfactant experiment. GFL-202211069190 34 [116] Example-7, it is delayed addition and continuous dosing of LIDA surfactant. There is only effect observed i.e., high coagulum formation as compared to one-shot dosing and initial phase addition experiments (refer Example- 2 and 7 for comparison). Example-8-10: [117] Example-8, 9 and 10 copolymers of VDF with other comonomer. [118] Example-8 is copolymer of VDF and Acrylic acid. Properties are found better here. [119] Example- 9 and 10 are the copolymer of VDF and Monomethyl ester maleic anhydride. In these examples surfactant amount is varied and impact on the viscosity and stability of Latex. [120] As surfactant quantity increases, Solution viscosity decreases. However, as surfactant quantity increases, latex stability also increases. [121] Surfactant quantity ∝ Latex stability ∝ 1/ Solution Viscosity. Table 6:

Note: Example-1 to 10, compare the Viscosity data and remove the MFI column from Table-1 and 2. Example-11-12: [122] Example-11 and 12 are the copolymer of Tetrafluoroethylene and Perfluoropropylvinyl Ether (PPVE). [123] In these examples as surfactant quantity increases, the molecular weight decreases of polymer and latex stability increases. For this polymer Molecular weight is correlated with MFI and Melting point. [124] (Molecular weight inversely proportional to MFI and directly proportional to Melting point). GFL-202211069190 35 • MOLECULAR WEIGHT ^^ 1/MFI ^^ MP [125] Note: This polymer is different from (Example-1 to 10) and it is not soluble in NMP solvent. So, there is no solution viscosity data available. Table 7:

Example-13-14 [126] Example-13 and 14 are the homopolymer of tetrafluoroethylene (TFE). [127] In these examples, as the surfactant quantity increases, here it is found molecular weight to be decreasing due to CTA effect and increased latex stability of polymer. [128] For this polymer, molecular wight is correlated as i.e., it is inversely proportional to SSG and directly proportional to Melting point. • MOLECULAR WEIGHT ^^ 1/SSG ^^ MP [129] Note: TFE homopolymer is a non-melt processable polymer. So, MFI and solution viscosity data are not available. Table 8:

[130] C08 IDA, C12 IDA and C18 IDA are imino-di-acetic acid with 8, 12 and 18 carbons, respectively (In below table 9). GFL-202211069190 36 Table 9:

GFL-202211069190 37

GFL-202211069190 38

GFL-202211069190 39

[131] C12 IDA is prepared with the process as disclosed in US3009892 with TFE as a monomer. This surfactant worked well in both continuous and one-shot dosing. primary particle size is good and within the range of better processability of polymer. Latex stability is better than C8 and C18. [132] For C08 IDA surfactant, coagulum formation is high when the same amount of surfactant is used. The high amount of surfactant has been used for better latex stability. The primary particle size is high and latex stability is low with C08 IDA surfactant. With higher TII values, the required surfactant quantity and the reaction time remains high. [133] C18 IDA surfactant is good as C12 IDA, however it’s mechanical properties are not good as compared to C12 and C08. [134] C18 IDA surfactant is good as C12 IDA, however it’s mechanical properties are not good as compared to C12 and C08. GFL-202211069190 40 [135] Branched C08-IDA is imino-di-acetic acid with 8 carbons having following structure:

[136] Tables 10 and 11 show a preparation of composition comprising branched C08-IDA and study results. Table 10:

GFL-202211069190 41

Table 11:

GFL-202211069190 42

GFL-202211069190 43

GFL-202211069190 44

GFL-202211069190 45

[137] The foregoing description of the invention has been set merely to illustrate the invention and is not intended to be limiting. Since the modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to the person skilled in the art, the invention should be construed to include everything within the scope of the disclosure.

Claims

GFL-202211069190 46 Claims 1. A process for polymerizing a fluoromonomer or a mixture of fluoromonomers and/or non- fluorinated monomers in an aqueous dispersion medium to form a fluoropolymer comprising: a) pressurizing a polymerization reactor containing an aqueous medium with a fluoromonomer or a mixture of fluoromonomers and/or non-fluorinated monomers; b) initiating a polymerization reaction of the fluoromonomer or the mixture of fluoromonomers and/or non-fluorinated monomers to form a fluoropolymer by adding an initiator; c) propagating said polymerization reaction; and d) terminating the polymerization reaction after consumption of a desired quantity of the fluoromonomer or the mixture of fluoromonomers and/or non-fluorinated monomers, wherein the process comprises adding a non-fluorinated imino acid type hydrocarbon surfactant represented by formula I:

Formula I Wherein, R is a hydrocarbon, linear or branched alkyl group with 8 to 22 carbon atoms; R1 = H, -CH2COO-M+. M is a univalent cation selected from H+, NH4+, Na+ and K+. 2. The process as claimed in claim 1, wherein the non-fluorinated imino acid type hydrocarbon surfactant is added to the polymerization reactor prior to adding the initiator in step (b). 3. The process as claimed in claim 2, wherein no hydrocarbon surfactant is added into the polymerization reactor during propagating the polymerization reaction in step (c). GFL-202211069190 47 4. The process as claimed in claim 1, wherein the non-fluorinated imino acid type hydrocarbon surfactant is added into the polymerization reactor after the initiator has been added in step (b) and wherein no hydrocarbon surfactant is added into the polymerization reactor before the initiation of the polymerization reaction. 5. The process as claimed in claim 1, wherein the non-fluorinated imino acid type hydrocarbon surfactant is added into the polymerization reactor prior to adding the initiator in step (b) and after adding the initiator (step b). 6. The process as claimed in claim 4, wherein the non-fluorinated imino acid type hydrocarbon surfactant is added after the concentration of the fluoropolymer particles in the aqueous medium is greater than or equal to 2 wt% based on the aqueous medium. 7. The process as claimed in any of the preceding claims, wherein the non-fluorinated imino acid type hydrocarbon surfactant is lauryl-imino-di-acetic acid (LIDA) or its salts. 8. The process as claimed in any of the preceding claims, wherein the non-fluorinated imino acid type hydrocarbon surfactant is added in an amount of 20 to 7000 ppm, in particular 30 to 4000 ppm, in particular 50 to 3000 ppm, based on the weight of the aqueous medium. 9. The process as claimed in claim 4, wherein the non-fluorinated imino acid type hydrocarbon surfactant is added in an amount less than 3000 ppm. 10. The process as claimed in claim 2, wherein the non-fluorinated imino acid type hydrocarbon surfactant is added to the polymerization reactor in an amount of more than or equal to 100 ppm. 11. The process as claimed in any of the preceding claims, wherein the non-fluorinated imino acid type hydrocarbon surfactant is added in one shot into the polymerization reactor. 12. The process as claimed in any of the preceding claims, wherein the non-fluorinated imino acid type hydrocarbon surfactant is metered into the polymerization reactor. 13. The process as claimed in any of the preceding claims, wherein the non-fluorinated imino acid type hydrocarbon surfactant is not passivated. GFL-202211069190 48 14. The process as claimed in any of the preceding claims, wherein no degradation agent is added to the polymerization reactor. 15. The process as claimed in claim 2, wherein the aqueous medium is free of hydrocarbon- containing oleophilic nucleation sites before kicking off the polymerization reactor. 16. The process as claimed in any of the preceding claims, wherein the initiator is added in one shot into the polymerization reactor. 17. The process as claimed in any of claims 1 to 14, wherein the initiator is metered into the polymerization reactor. 18. The process as claimed in any of the preceding claims, wherein the initiator is added in an amount ranging from 150 to 650 ppm. 19. The process as claimed in any of the preceding claims, comprising addition of chain transfer agents selected from halogen compounds, aliphatic hydrocarbons, aromatic hydrocarbons, thiols (mercaptans), alcohols, and esters; wherein the chain transfer agent is ethyl acetate. 20. The process as claimed in any of the preceding claims, wherein the fluoromonomers are selected from the group consisting of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), trifluoroethylene, chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), vinyl fluoride, hexafluoroisobutylene, perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3-tri fluoro-1- propene, 2-trifluoromethyl-3,3,3-trifluoropropene, perfluoropropylvinyl ether (PPVE), perfluoro methyl vinyl ether (PMVE), fluorinated allyl ethers, fluorinated dioxoles, 1,2,3,3,3- pentafluoropropene, and 3,3,3,4,4-pentafluoro-1-butene. 21. The process as claimed in any of the preceding claims, wherein the non-fluorinated monomers are selected from unsaturated dibasic acid monoester selected from the group consisting of maleic acid monoesters and citraconic acid monoesters, styrene, ethylene, propene, 2-hydroxyethyl allyl ether, 3-allyloxypropanediol, hydrophilic (meth)acrylic monomers such as acrylic acid, methacrylic acid, hydroxyethyl (meth)acrylate, GFL-202211069190 49 hydroxypropyl(meth)acrylate or hydroxyethylhexyl(meth)acrylates, phosphonic acid or vinyl phosphonate. 22. The process as claimed in any of the preceding claims, wherein the solid content of the fluoropolymer formed after termination of the reaction ranges from 15 to 35%. 23. The process as claimed in any of the preceding claims, wherein the size of the fluoropolymer particles ranges from 150 to 500 nm, in particular 150 to 350 nm, in particular 200 to 350nm. 24. The process as claimed in any of the preceding claims, wherein no fluorinated surfactant is added. 25. The process as claimed in any of preceding claims, wherein the non-fluorinated imino acid type hydrocarbon surfactant is acting as CTA (chain transfer agent). 26. The process as claimed in any of preceding claims, wherein the non-fluorinated imino acid type hydrocarbon surfactant is acting as dispersion/ latex stabilizer.