molecules

Review
Fluoropolymer: A Review on Its Emulsion Preparation and
Wettability to Solid-Liquid Interface
Lei Liang *, Tao Wen, Jun Xin, Chao Su, Ke Song, Wei Zhao, Hongwu Liu and Gui Su

Geological Exploration and Development Research Institute, CNPC Chuanqing Drilling Engineering
Company Limited (CCDC), Chengdu 610051, China
* Correspondence: [email protected]

Abstract: In the preparation of a superamphiphobic surface, the most basic method is to reduce
the surface free energy of the interface. The C—F bond has a very low surface free energy, which
can significantly change the wettability of the solid–liquid interface and make it a hydrophobic or
oleophobic, or even superamphiphobic surface. Based on the analysis of a large number of research
articles, the preparation and application progress in fluoropolymer emulsion were summarized. After
that, some corresponding thoughts were put forward combined with our professional characteristics.
According to recent research, the status of the fluoropolymer emulsion preparation system was
analyzed. In addition, all related aspects of fluoropolymer emulsion were systematically classified
in varying degrees. Furthermore, the interaction between fluoropolymer structure and properties,
especially the interaction with nanomaterials, was also explored. The aim of this review is to try to
attract more scholars’ attention to fluorocarbon interfacial materials. It is expected that it will make
a certain theoretical and practical significance in the preparation and application of fluoropolymer.

Keywords: fluoropolymer; emulsion polymerization; wettability; solid–liquid interface; nanomaterials;

enhancing oil recovery

1. Introduction
Citation: Liang, L.; Wen, T.; Xin, J.;
In order to adapt to the natural environment, organisms have evolved waterproof
Su, C.; Song, K.; Zhao, W.; Liu, H.; Su,
ability in some tissues and organs, such as the flowers and leaves of lotus [1], the feet
G. Fluoropolymer: A Review on Its
of water striders [2], and the feathers of kingfishers [3]. With this inspiration, people
Emulsion Preparation and Wettability
began to explore the production mechanism of the superhydrophobic phenomenon. In
to Solid-Liquid Interface. Molecules
the preparation of a superhydrophobic surface, reducing its surface free energy is the
2023, 28, 905. https://doi.org/
core problem when changing its wettability [4]. Changing the roughness of the interface
10.3390/molecules28020905
and coating the interface with low surface free energy materials are the most common
Academic Editor: Andrea Dorigato methods [5]. The C—F bond has a very low surface free energy. The wettability of the
Received: 3 November 2022
solid–liquid interface can be significantly changed by using fluorinated compounds, which
Revised: 13 December 2022
can achieve a hydrophobic or super-amphiphobic effect [6,7]. However, the dispersion
Accepted: 14 December 2022 of fluorocarbons in the preparation process has become a difficult problem due to the
Published: 16 January 2023 low free energy of fluorocarbons. Especially in polymerization, the type and cost of
materials hindered the development in the fields [8,9]. In recent years, the development of
the fluorine industry has promoted the process of fluoropolymer. Abundant fluorinated
monomers have made corresponding breakthroughs in the research of fluoropolymers. In
Copyright: © 2023 by the authors. the preparation of fluoropolymer, fluorinated acrylic monomers are widely used [10,11].
Licensee MDPI, Basel, Switzerland. In the meantime, the diversification of emulsifiers and emulsion polymerization has also
This article is an open access article effectively solved the dispersion problem of fluoropolymer in the system [12].
distributed under the terms and Fluoropolymer emulsion is a kind of polymer obtained by emulsion polymeriza-
conditions of the Creative Commons
tion. Under the action of an emulsifier, the polymer particles can be dispersed evenly to
Attribution (CC BY) license (https://
form a stable emulsion. According to the dispersing medium, it can be divided into the
creativecommons.org/licenses/by/
water-based emulsion and oil-based emulsion [13,14]. Fluoropolymer has good thermal
4.0/).

Molecules 2023, 28, 905. https://doi.org/10.3390/molecules28020905 https://www.mdpi.com/journal/molecules

Molecules 2023, 28, 905 2 of 15

stability [15], good flame retarding [16], anti-oxidation [17], and anti-aging effect [18]. It has
good chemical inertness and strong adaptability to the environment. Therefore, it is widely
used in aerospace [19], optical electronics [20], textile coatings [21], and other fields. At the
same time, fluoropolymers also have significant defects, such as poor solubility in organic
solvents, and synthesized fluoropolymers generally have high crystallinity [22,23]. This
makes the synthesis and processing more difficult. To overcome these difficulties, emulsion
polymerization has been used to increase the dispersity of the synthesized fluoropolymer
in the reaction system [24]. In recent years, resource shortage, environmental pollution,
and other issues have gradually received the attention of society. To meet the growing
and gradually diversified social needs, the research and development of environmentally
friendly fluoropolymer [25,26], especially the synthesis and application of fluoropolymer
emulsion, is an inevitable trend in the development of organic fluorine materials [27]. The
harm of water-based emulsion to the environment is far less than that of oil-based. With
the enhancement of people’s environmental awareness, the development and utilization
of waterborne fluoropolymer emulsion has attracted more and more attention [28–30].
Fluoropolymer emulsion with water basis has great advantages. On the one hand, it can
avoid environmental pollution caused by the volatilization of organic solvents. On the
other hand, it also can reduce the production and cost of products, and greatly reduces the
harm of organic solvents.
After the problems were solved, scholars synthesized many fluoropolymer emulsions
with different structures and properties. Fluoropolymer emulsion has been widely used
in coating materials [31], the textile industry [32], building materials [33], the petroleum
industry [34], medical materials [35,36], and especially in the combination of nanomaterials
and applications [37]. It has become the research focus of many scholars. In addition, the
development direction of various fields in the international community is towards the
sustainable development of energy conservation and environmental protection. In addition
to the consideration of some new structures and new methods, the safety of materials
becomes more important than the superiority of the performance [38,39]. Researchers
have made headway in nano-coating materials by using nanomaterials such as preparing
nano-polymer emulsion, grafting modification, or by enhancing the efficiency of materials.
Fluoropolymers with different structures and their combination with different nanomateri-
als can significantly improve the wettability of a solid–liquid interface [40]. In the process
of oil and gas development, the wettability of hydrophilic and oleophilic reservoirs can
be reversed and transformed into hydrophobic, even amphiphobic ones. Therefore, this
can reduce migration resistance, increase the flowback efficiency, and enhance oil and
gas recovery.
Through the analysis of the preparation and application of a large number of flu-
oropolymer emulsions, this article summarized and analyzed the present situation of
fluoropolymer emulsion preparation systems, including the polymerization monomers,
polymerization methods, emulsification systems, and initiating systems. Combined with
our professional characteristics, the research in this field was summarized and the corre-
sponding thinking was put forward. The structure and properties of fluoropolymers were
also explored, especially the interaction between fluoropolymers and nanomaterials. The
aim is to attract more scholars’ attention to fluorocarbon interfacial materials. It is expected
that this will play a certain theoretical and practical part in the preparation and application
of fluoropolymer emulsions.

2. Fluorinated Monomers
The most commonly used reactions in polymerization are free radical copolymer-
ization and condensation polymerization. The reaction requires at least two functional
groups [41]. Therefore, the monomer in the preparation is mostly a fluorinated group
on one side, and the other side has a reactive functional group. The chemical structure
and composition of segments determines the performance of fluorinated polymers, while
the type and number of active functional groups in monomers control the direction of
Molecules 2023, 28, 905 3 of 15

polymerization [42]. Therefore, it is very important to select suitable monomers for emul-
sion polymerization in many fluorinated monomers [43]. According to the different active
functional groups in the monomers, the commonly used fluorinated monomers can be
divided into several types (Figure 1).

Figure 1. Structural diagram of several types fluorinated monomers. (a): Alkene (Alkyne) fluorinated
monomers, (b): Acrylic acid (ester) fluorinated monomers, (c): Fluorinated aromatic (heterocyclic)
monomers, (d): Others. (R for alkyl group. RF for fluoroalkyl. R1 , R2 for halogen atom, hydroxyl
group, amino group, etc.).

2.1. Alkene (Alkyne) Fluorinated Monomers

Fluorinated monomers containing double or triple bonds are mainly fluorinated
alkenes (alkynes) and nitriles (Figure 1a). The fluorinated monomers commonly used are
mainly fluoroalkenes containing C2~C4 chains, such as vinyl fluoride (VF), vinylidene
fluoride (VDF), trifluoro ethylene chloride (CTFE), tetrafluoroethylene (TFE), hexafluo-
ropropylene (HFP), etc. [44,45]. However, in this kind of structure, the reaction activity
of the fluorinated group connected with a double (triple) bond is lower than that of the
nonfluorine monomer due to its strong induction effect [46].

2.2. Acrylic Acid (Ester) Fluorinated Monomers

Similar to the alkenes (alkynes) fluorinated monomers, fluorinated acrylic acid (ester)
monomers are free radical copolymerizations of double bonds (Figure 1b). The difference is
that the introduction of carboxyl and ester groups enhances the reactivity and dispersion of
the monomers in the system to different degrees, which can improve the adhesion on the
substrate, and enhance the curing ability and crosslinking ability of the materials [47]. The
most widely studied is the use of fluorinated acrylate monomers. The fluorinated groups
in the side chain of fluorinated acrylate polymers play a shielding role in the main chain
and internal structure, and still have stable physicochemical properties at a low fluorine
content. The fluorinated acrylate polymers after chemical modification can not only inherit
the excellent properties of acrylate itself, but also have the advantages of high stability
specific surface physical properties and photochemical properties [48,49].
Molecules 2023, 28, 905 4 of 15

2.3. Fluorinated Aromatic (Heterocyclic) Monomers

The electron density of aromatic (hetero) ring compounds is high, which has
a greater impact on the surrounding chemical environment (Figure 1c). They have stronger
adsorption than ordinary monomers. They can change their solubility in polymers and
greatly reduce the crystallization performance of final polymers [50]. These monomers are
commonly used as intermediates in fluoropolymers, such as the reaction core of core–shell
emulsion polymerization, the branching chain for graft copolymerization, etc. [51].

2.4. Others
The above types of fluorinated monomers are polymerized as the center of the addition
reaction. Moreover, the elimination of small molecule polycondensation is more accurate
in fluoropolymer emulsion (Figure 1d). Unlike addition polymerization, polycondensation
mainly relies on the elimination of the end groups in monomers [52]. Generally, a monomer
has two or more easily eliminated functional groups, such as hydroxyl, amino, halogen
atoms, etc. The advantage of this kind of monomer is that the reaction selectivity is
very strong, which is conducive to the design of the specific molecular structure. The
disadvantage is that the fluorinated monomer with multiple substituent groups is generally
very expensive. In the reaction process, a lot of heat is released, and a lot of energy is
consumed to neutralize the energy released from the reaction [53,54].
In addition to the above types of fluorinated monomers, there are also fluorinated
monomers such as fluorinated phosphates, fluorinated olefin sulfonates, fluorinated chlorosi-
lanes, etc. [55]. These monomers act as emulsifiers while polymerizing, which can reduce
or remove the emulsifiers. The disadvantages are that they are difficult to prepare and
retain, and the use cost is high. However, they have great advantages in structural design
and reaction stability.

3. Fluoropolymer and Emulsion Polymerization

For emulsion polymerization, we generally divide according to the reaction characteris-
tics or the interaction in the reaction process. From the reaction mechanism, polymerization
can be divided into free radical polymerization, ion polymerization, and step-by-step poly-
merization [56]. Additionally, it can be divided into homogeneous polymerization and
heterogeneous polymerization according to the compatibility of the reaction system.
The preparation methods can be divided into conventional and unconventional emul-
sion polymerization. Based on conventional emulsion polymerization, the development
and applications of unconventional emulsion polymerization are very extensive. The syn-
thesized emulsion has a stable performance and can meet different application conditions.
Next, we compare several different aggregation methods combined with their applica-
tion examples, and analyze the application scenarios and their respective advantages
and disadvantages.

3.1. Conventional Emulsion Polymerization

The conventional emulsion polymerization is included with polymerize monomer, wa-
ter/oil phase, initiator, and emulsifier in the reaction system. This method is easy to operate
and with low cost, but the emulsifying performance of the system is not stable [57]. Most
of the reactions were polymerized with fluorinated acrylate monomers, and fluoropolymer
emulsions with different properties were obtained in different emulsifying systems and
initiating systems.
Chen et al. [58] used cationic and non-ionic composite emulsifying systems, and the
self-crosslinking copolymer emulsion containing fluorinated acrylate/acrylic eighteen alkyl
ester had good crosslinking properties at very low concentrations. Lineman et al. [59] ob-
tained an average size of 191 nm fluoropolymer emulsion using a solid initiator, twelve alkyl
three methyl ammonium bromide, as an emulsifier. Under the same structure, nanoemul-
sion has a better performance. Deng et al. [60] synthesized two block fluoropolymer emul-
sions with perfluoroacrylate and twelve alcohol acrylate as raw materials. Cheng et al. [61]
Molecules 2023, 28, 905 5 of 15

prepared three fluorocarbon copolymer emulsions with acrylic perfluoroalkyl ester, methyl
methacrylate, and butyl acrylate as raw materials. Compared with copolymer emulsion,
terpolymer emulsion had a lower concentration. It can achieve a better hydrophobic effect
under low temperatures. Zhou et al. [62] used emulsion polymerization to synthesize
a fluoropolymer emulsion. After treatment, the contact angle between the fabric and water
can reach 142◦ , which has a good hydrophobic effect.
It is obvious that fluoropolymer is mainly used for its strong hydrophobic ability.
Therefore, in conventional emulsion polymerization, besides the variability of initiator
and emulsifier, the choice of monomer is also diverse. With graft copolymerization, the
characteristics of various monomers can be integrated into one, and fluoropolymers with
superior properties can be obtained.

3.2. Fine/Mini Emulsion Polymerization

Fine/mini emulsion polymerization shows great advantages over conventional emul-
sion polymerization. Unlike conventional emulsion polymerization, the nucleation mecha-
nism of micelle in fine/mini emulsion polymerization is monomer droplet nucleation. The
nucleated monomer droplet can be regarded as an independent microreactor, in which
the monomer is directly polymerized and transformed into nanoparticles [63]. In this way,
the premature migration and diffusion of monomers to the aqueous phase can be avoided
resulting in the hydrolysis of oligomer and termination of polymerization.
Fine and mini emulsion polymerization is not very different from the reaction mecha-
nism. However, their nucleation size distribution is different. Fine emulsion polymerization
is a thermodynamically unstable system than mini emulsion polymerization. Fine emulsion
polymerization usually uses C12~C14 alcohols or alkanes as a stabilizer [64]. The reaction
requires external strength (high agitate or ultrasonic) to homogenize them. However,
mini-emulsion polymerization usually uses C5~C6 emulsifier [65]. Fine and mini emulsion
polymerization are all mixed nucleation, which can form emulsion automatically [66]. In
any case, the ratio of each component and polymerization can be generated. There are also
some differences in particle size.
The process of pre-emulsification in fine/mini emulsion polymerization is very critical.
Usually, a stable monomer droplet is formed under the combined action of emulsifier and
assistant emulsion [67], then polymerized in a submicron monomer droplet formed by
high agitate or ultrasonic pre-emulsification [68]. The formation of sub-micron monomer
droplets can play an electrostatic and spatial stabilizing role, thereby preventing small
droplets from aggregating into large droplets. This helps reduce the content of emulsifiers
to ensure the stability of the emulsion.
An emulsion of three fluoroethyl methacrylate and butyl acrylate copolymers (PF3-co-BA)
was prepared by fine emulsion polymerization at Wuhan University of Technology, China [69].
The influence of reaction conditions on the nucleation size was discussed. The conversion of
fluorinated monomer in polymer emulsion prepared by fine emulsion polymerization was
much higher than that of conventional emulsion polymerization when the raw material ratio
was the same. A kind of fluorinated acrylate copolymer (FPA) emulsion was prepared to utilize
fine emulsion polymerization from the Shaanxi University of Science and Technology [70].
The latex particles in FPA emulsion are regular spheres with an average particle size of about
200 nm (Figure 2a). Chen used mini-emulsion polymerization to obtain a polymethacrylate
mini-emulsion. The particle size of the emulsion was less than 100 nm. However, the large
amount of emulsifier used led to its poor hydrophobicity. It can be seen that the polymer
emulsion prepared by mini emulsion polymerization is usually smaller and more stable than
fine emulsion polymerization. The drawback is that a large number of emulsifiers and stabilizers
are needed to increase the reaction cost while the application of the emulsion is also limited.

3.3. Core–Shell Emulsion Polymerization

The core–shell model was first proposed in 1970 [71]. It is a multi-stage emulsion poly-
merization method. It takes polymerized dispersed prepolymer as the reaction core to fur-
Molecules 2023, 28, 905 6 of 15

ther polymerize and finally forms a two-layer structure of core and shell. According to the
way of adding monomer, it can be divided into the batch method, pre-swelling method, and
semi-continuous method. Polymer emulsion with microphase separation structure [72].

Figure 2. Fluoropolymer and emulsion polymerization (a): TEM of FPA emulsion, (b): TEM of
F0 emulsion, (c): Structure diagram of P(CTFE-IBVE-SUA).

Tang used a semi-continuous method to produce a core–shell fluorinated acrylate

emulsion. The emulsion was based on butyl acrylate and methyl methacrylate copolymer
as the core, and butyl acrylate, methyl methacrylate, and trifluoro ethyl methacrylate
copolymer as the shell. The formation of the core–shell structure was confirmed by testing
and analyzing the monomer conversion rate and the growth and distribution of latex
particles in the emulsion polymerization. Qu et al. [73] prepared a core–shell emulsion
that used silica as the core and fluorinated acrylate polymer as the shell. The effect of
dodecafluoroheptyl dodecyl methacrylate and methacryloxypropyl triisoxysilane on the
emulsion core–shell structure was studied. The stable core–shell emulsion can be used to
prepare high-performance water-proofing materials [74]. The paint used tridecafluorooctyl
methacrylate as fluorinated monomers. Two kinds of emulsions were prepared by con-
ventional emulsion polymerization and core–shell emulsion polymerization, respectively.
It was found that the hydrophobicity of the emulsions was good after coating. However,
the core–shell emulsion polymerized at the same monomer concentration had better hy-
drophobicity. A polyurethane/fluorinated acrylate hybrid emulsion (F0) was synthesized
(Figure 2b). The polymer particles in the emulsion show a regular spherical shape and have
an obvious core–shell structure [75].

3.4. Non-Soap Emulsion Polymerization

An emulsifier is needed in conventional and fine/mini emulsion polymerization.
Non-soap emulsion polymerization means that the purpose of emulsification is without
an emulsifier, and uses the polarity of the reaction monomer or initiator in the system [76,77].
Molecules 2023, 28, 905 7 of 15

It is also possible to graft the polar group onto the polymer to give it a surface-active
emulsion polymerization. Non-soap emulsion polymerization generally uses a reactive
emulsifier, which enters the main chain of polymerization at the same time as emulsifica-
tion, while ensuring the stability of the emulsion and avoiding the effect of other small
molecule residual compounds on the properties of the emulsion [78]. It can also be achieved
by adding cosolvent or inorganic powder. The cosolvent acts as an emulsifier and can
be separated better than the conventional emulsifier. The addition of inorganic powder
indicates that the particles of the emulsion are polymerized at the water/oil interface
as the reaction site [79]. Non-soap emulsion polymerization is used to prepare reactive
fluorinated emulsifiers and fluorinated monomers. The content of surfactant in polymer
emulsion obtained by this method is very low, which can greatly enhance the surface
properties of emulsion and has an unparalleled advantage in other aspects, such as optical
and electrical properties.
Meng et al. [80] synthesized a dodecafluoroheptyl methacrylate fluoropolymer with
fluorinated alkenes sulfonate (PSVNa) as the monomer. The results showed that 95 wt.%
of the fluorinated monomer had been grafted in the main chain of the polymer, and the
conversion, stability, and hydrophobicity of the emulsion were better than that polymer-
ized by emulsifier. The pre-polymer prepared in an organic solvent can also be added
to the water to disperse stable small molecule polymer emulsion, and then continue to
initiate a reaction to obtain non-soap fluoropolymer emulsion. Liu et al. [81] prepared
a chlorotrifluoroethylene-vinyl isobutyl ether-sodium undecanoate fluoropolymer emul-
sion (P(CTFE-IBVE-SUA)) by non-soap emulsion polymerization (Figure 2c). After investi-
gating the effect of monomer ratio on polymerization, the effect of emulsified monomer
SUA on emulsion and polymer performance was studied. The results showed that the
polymer emulsion had strong stability and good hydrophobic ability as a coating material.
The particle size distribution of the emulsion is uniform and has a core–shell structure.
It can be seen from the above methods that conventional emulsion polymerization is
easy to operate and the most widely applied. Fine/mini emulsion polymerization can make
the reaction easier and improve the stability of the emulsion [82–86]. Core–shell emulsion
polymerization can show better performance under the same concentration of fluorinated
monomer, and the design of the polymer molecule is easier to achieve [87,88]. Non-soap
emulsion polymerization either does not use emulsifiers or uses them in a slightly superior
way to emulsifier systems. The disadvantage is that fluorinated monomers with polar
functional groups are usually expensive [89–91].

3.5. Structures of Fluoropolymer

In the main synthesis methods of general polymers, the synthesized polymers can
be divided into homopolymers, block copolymers, and graft copolymers according to the
different distributions of the monomers involved in the polymerization. They can also be
divided into amorphous polymers and crystalline polymers according to the structural
characteristics of the polymers [92]. Fluorinated polymers can be divided into linear,
umbrella, branch, and dumbbell polymers according to their topological structure.
Different polymer structures give the prepared emulsions distinct application proper-
ties. The linear structure usually has a long fluorocarbon branched chain (Figure 3a) [93].
The main chain is the alkyl or ester group. It is used in paint as a hydrophobic anti-fouling
coating material.
Compared with linear fluoropolymers, fluoropolymers with more branched chains
have better performance. Figure 3b) is a fluoropolymer with an umbrella structure. In con-
trast experiments with linear fluorinated polymers containing the same fluorine content, it
is found that the hydrophobicity of the umbrella structure emulsion is obviously improved,
the contact angle between the coating interface and water is increased by 6.2◦ , and the
water absorption of the material is also 11.1% lower than that of linear type [94].
On the basis of linear and umbrella structures, a fluoropolymer with a dendritic
structure was synthesized by the Chengdu Institute of organic chemistry, Chinese Academy
Molecules 2023, 28, 905 8 of 15

of Sciences [95]. The specific process of synthesis is shown in Figure 3c. The results
show that the contact angle between water and dendrimer (111.3◦ ) is higher than that
of the umbrella (104.8◦ ) and linear (98.7◦ ) when the fluorine content is at 60%, and the
fluorine content of dendrimer is 12.77% and 6.20% higher than that of linear and umbrella
structure, respectively.

Figure 3. Fluoropolymers with different configurations (a): a linear fluoropolymer, (b): a dendrimer fluoropoly-
mer, (c): an umbrella fluoropolymer, (d): a dendrimer fluoropolymer, (e): some amorphous fluoropolymers.

In addition to the above common configurations, other regular configurations of fluo-

ropolymers can be used in specific environments and processes. In Figure 3d, Zhang et al. [96]
prepared dumbbell-shaped fluoro-graft polymers (FMCDs) with polyglycidyl ether-PEG (PBG)
as the reaction core, and then polymerized with fluorinated monomers after activation. The
polyether structure in the main chain made it highly water-soluble. The fluoromethyl group at
the end of the chain showed extremely strong hydrophobicity, with good performance in the
emulsification and demulsification process. The design and development of such structures can
provide new research ideas for the research and application of fluoropolymers.
The above-fluorinated polymers are symmetrical and regular in structure, all of which
show the related properties of the crystal. In addition, there are amorphous fluorinated
polymers. This can be seen from the fluorinated polymers with the amorphous structure
shown in Figure 3e [97]. The fluorinated functional groups on the surface are more inter-
laced with each other than the previous fluorinated polymers. Due to the special structure
of raw materials, the research cost is high, the reaction controllability is poor, and the
related application examples are also limited. It could certainly be applied in the fields of
super bispecific materials and multiphase separation [98].
Combining the above examples of fluoropolymer with different topological struc-
tures, the fluoropolymer emulsion is used as the interface material. Its hydrophobic-
ity/oleophobicity performance mainly comes from the fluorocarbon chain of the fluo-
ropolymer. The closer the interface arrangement is, the longer the fluorine chain is, and the
higher the fluorine content of the surface is, the better the hydrophobicity/oleophobicity
performance is.
Molecules 2023, 28, 905 9 of 15

4. Wettability Application
4.1. Interaction with Nanomaterials
As the frontier science of materials research, nanomaterials can significantly improve
the performance of materials with their unique properties of nano size. Fluoropolymer
materials can be combined with nanomaterials to prepare nano fluoropolymer materials,
so as to enhance or improve the properties of materials and make the interface achieve
the excellent performance of hydrophobicity or super-amphiphilicity [99]. The nano-grade
fluoropolymer emulsion can be directly synthesized through polymerization, and can also
be prepared by grafting modification with nanomaterials. At present, the preparation
method is more economical and the fluorinated material is used to modify the surface of
nano silica. The nanomaterials obtained by this method are stable in performance, uniform
in particle size, easy to operate and prepare, and extensive in raw materials.
Figure 4a briefly describes a method of preparing fluorinated nanomaterials from
fluorinated polymer and nano-SiO2 [100]. This method takes nano-SiO2 prepared by
tetraethoxysilane (TEOS) as the core and modifies fluorinated ethoxy silane to obtain
a fluorinated nanomaterial. It has super liquid rejection performance. The contact angle
with various liquids is more than 140◦ after being prepared into a film (water: 167.5◦ ,
diesel: 140.4◦ , soybean oil: 146.6◦ , xylene: 140.5◦ , diiodomethane: 158.6◦ , decalin: 142.5◦ ).
Jiang et al. [101] synthesized a fluorinated block copolymer and attached it to the surface
of nano-SiO2 (Figure 4b). The obtained fluorinated polymer nanoparticles have a raspberry
structure and also show good amphiphilic properties in terms of properties. The contact
angle between the prepared interface and water and oil exceeds 150 ◦ C. Figure 4c is the
scanning electron microscope results of nanomaterials with different fluorine content
prepared by changing the concentration of fluorinated monomers and nanoparticles [102].
The results show that the larger the fluorine content of the system is, the smaller the particle
size of the prepared nanoparticles is, and the better the performance is. The contact angle
with water and n-dodecane is about 180◦ and 109◦ , respectively.

Figure 4. Application of fluoropolymer in coating nanomaterials (a): Preparation method of nano-

silica particles of a fluoropolymer, (b): Molecular structure of a fluoropolymer and the SEM of its
raspberry nanomaterials, (c): SEM of the surface of the nanomaterial with different fluorine content,
(d): Apparent contact angle of oil and water droplets as a function of acetone cosolvent concentration.
Molecules 2023, 28, 905 10 of 15

In addition to the nano-SiO2 system, other nanomaterials such as graphene, nano-

cellulose, nano-coal ash, and some inorganic nano-oxides can be used to interact with
fluoropolymers. Adam mixed fluoropolymer emulsion and nano-ZnO particles to prepare
a composite nano spray material. In Figure 4d, the change of the contact angle of the
nanomaterial prepared by the mixture of acetone and water in the mixing agent was
studied [103]. The results show that the prepared nanomaterials have good hydrophobicity
at different cosolvent ratios, and the contact angle with water (oil) droplets can reach 160◦
at a certain cosolvent ratio.

4.2. Application on EOR

With the change in national energy strategy, especially in the progress of enhancing oil
recovery (EOR), the exploration and exploitation of oil and gas play an important strategic
role. The ability of fluoropolymer emulsion to improve and transform the wettability of the
interface can be applied to the transformation of reservoir wettability, the development of
condensate gas reservoirs, and the injection and reflow process.
Feng et al. [104] obtained a fluorinated two-affinity block polymer emulsion using
polyethylene glycol monomethyl ether (MPEG) and dodecafluoroheptyl methacrylate as
the main raw materials. Figure 5a shows the wettability of the core surface on different
droplets before and after treatment with fluoropolymer emulsion. By measuring the contact
angle, the wettability of the core surface is changed from parent to gas wetting, indicating
that the polymer emulsion can be used as a wetting reversal agent to change the wettability
of the reservoir.

Figure 5. Application of fluoropolymer in reservoir wettability reversion (a): Contact angle of

different droplets with the cores, (b): SEM of the cores with gas-wetted nano-SiO2 , (c): Polarizing
micrographs and apparent morphology of PFG4 emulsion.
Molecules 2023, 28, 905 11 of 15

Similarly, a fluoropolymer emulsion prepared by Jin et al. [105] was used as a wetting
reversal agent to treat the core. At the concentration of 0.1 wt.%, the contact angle between
the core with water and n-hexadecane increased from 23◦ and 0◦ before treatment to 61◦ and
70◦ after treatment. When the concentration was at 0.3 wt.%, the contact angles increased
to 152◦ and 127◦ , respectively. It can be seen from Figure 5b that the fluorinated polymer
modified by nano-SiO2 on the core surface has a stronger wettability reversal ability after
adhesion. It can be used to improve the wettability of the core. The wettability of the core
changes from liquid wetting to strong gas wetting.
Our team has also researched fluoropolymer emulsion as a wetting reversal agent.
Figure 5c is a polymer microemulsion wetting reversal agent (PFG4) [106]. The emulsion
has strong stability, dispersibility, and very low surface free energy. After injection, it can
effectively change the wettability of the formation and increase the permeability of the
formation to achieve the effect of enhancing oil recovery and flow back rate and reducing
the resistance of oil and gas production. In summary, the application of fluoropolymer
emulsion is mainly used in the presence of a solid–liquid interface. As a coating material or
nano adsorbent material, it can act on the solid surface and change the wettability of the
solid surface by reducing the interfacial tension and achieving the effect of hydrophobicity
or super-amphiphobicity.

5. Conclusions and Outlook

With the continuous in-depth study of fluoropolymer emulsion, not only have new
methods of preparing such functional materials been put forward, but also the practical
application and mechanism of action in various fields have been further explored and
expanded. At present, the research focus of fluoropolymer emulsion is to enhance the per-
formance of fluoropolymer and reduce the cost of synthesis and harm to the environment.
Therefore, the research of fluoropolymer emulsion has a good application prospect.
Fluorinated acrylate polymers, as the main research objects of fluoropolymer emulsion,
have shown excellent interfacial properties for a long time. The conditions of synthesis and
source of raw materials have been relatively stable and mature. However, a large number
of non-emulsifiers exist widely in these emulsions. Non-soap emulsion polymerization
can avoid adverse effects caused by emulsifiers. The monomer synthesis required for the
reaction is difficult, expensive, and difficult to preserve. Therefore, improving the synthesis
methods of such monomers to reduce the cost of preparation, improving the emulsifying
system, and introducing a system are other directions of fluoropolymer emulsion.
In application, fluoropolymer emulsion is mainly used as coating material, synthesis of
nanoparticles, or modification with nanomaterials to improve the hydrophobicity ability of
solid surfaces. It can also be used as a polymer surfactant with appropriate concentration. It
may also be extended to take into account experiments and computational models showing
that the interfacial properties of polymers can be adjusted by varying the composition
of polymer mixtures with two different polymer topologies [107–110]. However, in the
application process, the circulation of fluorine and its harm to the environment is only
slightly mentioned. There is no detailed quantitative analysis and research, which can be
used as a new research direction.

Author Contributions: Conceptualization, L.L., and T.W.; writing—original draft preparation, L.L.
and J.X.; writing—review and editing, L.L. and C.S.; supervision, K.S. and W.Z.; search strategy, H.L.
and G.S. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Molecules 2023, 28, 905 12 of 15

Conflicts of Interest: The authors declare no conflict of interest.

Sample Availability: Samples of the compounds are available from the authors.

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