Synthesis of Amphiphilic Acrylate Boron Fluorinated Polymers with

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Materials and Interfaces

Synthesis of Amphiphilic Acrylate Boron Fluorinated Polymers with Antifouling Behavior Yakun Li, Rongrong Chen, Yanhua Feng, Xun Sun, Liang Tang, Kazunobu Takahashi, Peili Liu, and Jun Wang Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b06337 • Publication Date (Web): 24 Apr 2019 Downloaded from http://pubs.acs.org on April 24, 2019

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Synthesis of Amphiphilic Acrylate Boron Fluorinated Polymers with Antifouling Behavior Yakun Li,a, b Rongrong Chen,*a, b, c YanHua Feng,d Xun Sun,a Liang Tang,a Kazunobu Takahashi,a, b Peili Liu,a, c and Jun Wang*a, b a Institute

of Advanced Marine Materials, College of Materials Science and Chemical

Engineering, Harbin Engineering University, Harbin 150001, China b

Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin 150001, China

c HIT

(Hainan) Military-Civilian Integration Innovation Research Institute Co., Ltd., Hainan 572427, China

d Qingdao

Advanced Marine Material Technology Co., Ltd., Qingdao 266100, China

* Corresponding authors: Rongrong Chen, E-mail: [email protected], Tel.: +86 451 8256 8276; Jun Wang, E-mail: [email protected], Tel.: +86 451 8253 3026

1


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Abstract

In the present study, we constructed two kinds of amphiphilic acrylate boron fluorinated polymers (ABFPs) with backbones comprising acrylate fluorinated polymers (AFPs) and side chains comprising hydrolyzable pyridine–phenyl borane functional groups. We determined the hydrolysis rates of the ABFPs by measuring their weight loss ratios. The ABFPs with shorter fluorinated side chains had higher rates of hydrolysis. We investigated and confirmed the amphiphilic and antifouling behavior of the ABFPs, using X-ray photoelectron spectroscopy (XPS) and surface wettability analyses. During immersion for 90 days in the Bohai Sea of China, the ABFP coatings exhibited good antifouling performance. We also assessed the environmental characteristics of the ABFP coatings by determining the chemical oxygen demand (COD) and growth rate of diatoms on their surfaces. The present study provides new insight into the development of environmentally friendly ABFPs with desirable antifouling properties. Keywords:

ABFPs;

Hydration;

Self-polishing

mechanism;

Environmental

friendliness; Antifouling paints

1. Introduction The adsorption of fouling organisms on the surfaces of equipment and structures used in marine industries can cause a series of problems.1 For example, unwanted adhesion has environmental and economic penalties, and can increase the sailing resistance of ships, accelerate the corrosion of metallic substrates, block the valves and pipes of seawater intake installations, and shorten the service life of marine equipment.2-4 Therefore, the development of antifouling methods is vitally important. However, 2



highly toxic antifouling coatings have caused serious environmental problems.5-9 The increased environmental risk associated with the use of harmful biocides and the anticipation of future prohibitions has prompted research into nontoxic approaches, such as the use of low surface energy fouling release coatings,10-12 zwitterionic polymers,13, 14 biodegradable copolymers,15, 16 and antibacterial polymeric materials.17, 18

Among the antifouling strategies mentioned above, fluorinated polymer films may provide a more environmentally friendly antifouling alternative.19 Owing to the low surface energy and elasticity modulus of fluorinated polymers, microorganisms find it difficult to spread secretions on the polymer surfaces, which inhibits effective surface adhesion and marine fouling. Although fluorinated polymers have excellent foulingrelease properties, they have only passable performance in practical antifouling applications. The main reason for this is that polymers with a purely hydrophobic nature have limited antifouling performance.20 For example, fluorinated polymers are ineffective against Navicula perminuta, which usually adheres more strongly to hydrophobic surfaces. Secondly, the durability of fluorinated polymers is poor. Although initially very good, their anti-adhesion performance gradually declines over time.21, 22 In addition to fluorinated polymers, non-copper self-polishing polymers provide an environmentally friendly antifouling strategy.23,

24

Alkylsilyl (meth)acrylate-based

polymers are non-copper self-polishing polymers with superior chemical stability and durability. Such polymers do not contain metal ions or other highly toxic functional groups, but the poor antifouling performance in static marine environments limit their widespread use.25 In a previous study, we synthesized a series of acrylate boron polymers and demonstrated their environmentally friendly resistance to macrofouling 3


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organisms.26 However, the polymers had poor antifouling performance with regard to slime and silt. Therefore, environmentally friendly polymers with amphiphilic properties may answer the pressing need for antifouling solutions. Owing to the poor antifouling performance of the acrylate boron polymers with regard to slime and silt, we synthesized a series of novel acrylate boron fluorinated polymers (ABFPs) with amphiphilic properties by adding fluorinated monomers. This improved their antifouling properties. We performed diatom anti-settling assays and real sea antifouling paint tests to determine the antifouling performance of the polymers. The chemical oxygen demand (COD) values and growth rates of diatoms were used to characterize the environmentally friendly properties of the polymers. Owing to the introduction of fluorinated side chains to the molecular main chain, the ABFPs had superior amphiphilic and antifouling properties compared with the acrylate boron polymers reported in our previous work. The present study will provide useful insight into amphiphilic fluorinated self-polishing polymers (Scheme 1).

2. Experimental 2.1 Materials We obtained xylene, toluene, propylene glycol methyl ether (PGME), absolute ethanol,

butyl

alcohol,

azobis-2-methylbutyronitrile

(AMBN),

and

azobisisobutyronitrile (AIBN) from the Tianjin Guangfu Fine Chemical Research Institute (Tianjin, China). Tetrahydrofuran (THF), ethyl acrylate (EA), methyl methacrylate (MMA), and acrylic acid (AA) were from Tianjin Zhiyuan Chemical Reagent Co., Ltd., China. Trifluoroethyl methacrylate (TFEMA) was purchased from Weihai New Era Chemical Co., Ltd., China. Hexafluorobutyl methacrylate (HFBMA) 4



was purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd. Pyridinetriphenylborane (PTPB) was obtained from Changzhou Kean Chemical Technology Co., Ltd. Benzoyl peroxide (BPO) were obtained from Shanghai Shanpu Chemical Co., Ltd. We purchased 2,4-diphenyl-4-methyl-1-pentene (MSD) from Adamas Reagent Co., Ltd. (Shanghai, China), and tralopyril from Xinyi Yonglong Chemical Co., Ltd. (Jiangsu, China). The artificial seawater (ASW) for the weight loss measurements was prepared using reef salt obtained from Seachem Laboratories (Madison, USA), whereas the ASW used for diatom cultivation and the relative tests was prepared in accordance with standard ASTM D1141-98. All reagents were used as received without further purification. 2.2 Synthesis of the acrylate boron fluorinated polymer We synthesized two kinds of ABFPs—acrylate boron tri-fluorinated polymers (ABTFPs) and acrylate boron hexa-fluorinated polymers (ABHFPs)—using acrylate fluorinated polymers (AFPs) and PTPB (Figure 1). The addition of TFEMA/HFBMA during the synthesis process distinguished them from acrylate boron polymers. 2.2.1 Synthesis of the AFPs Typically, the copolymerization of AFPs using AIBN, AMBN, and BPO as initiators was performed as follows. We placed 140 g of xylene, 70 g of PGME, and 10 g of EA in a round-bottom flask fitted with a magnetic stirrer and filled with nitrogen. The flask was placed in an oil bath at 95–100 °C. A monomer mixture comprising 10 g of MMA, 95 g of EA, 15–35 g of AA, and 50–70 g of TFEMA/HFBMA was added dropwise, and 2.0 g of AIBN and 8 g of AMBN dissolved in the monomer mixture initiated the polymerization. The polymerization was allowed to continue for 6 h, and then 20.0 g of xylene and 1 g of BPO were added dropwise to the mixture. After two hours, colorless transparent products were 5


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obtained. We then precipitated the products in a large excess of cold alcohol to remove the micromolecular impurities and unreacted monomers. Finally, we obtained the AFPs with a solid content of 40.52% after the addition of solvents.

CH3 H2C

CH3

C + H2C C

O

C + H2C C

CH +H2C C

O

O

O

O

O

CH3

CH2

CH2

H2 C

CH C

O

CH3

CH3 r

C C

H2 C

x

O

C

O

OH

C

y

r

C H2

O

O

r

H2 C

H C

z

C

O

O

H2C

CH3

H C

C

n

O

OH

CH2

R CH3

R

CH3 H2 C

r

C C

B :N

CH3

CH3 x

O

O

H2 C

C C

y

r

C H2

O

O

CH3

H2C

H C

r

H2 C

H C n

z

C

C

O

O

O

CH2

B N

O

:

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


R CH3 F R =

C F

F

or

F

F

F

C

C H

C

F

F

F

Figure 1. Synthetic route for acrylate boron fluorinated polymers (ABFPs)

Table 1. Polymer dispersity index and recipes for the synthesis of acrylate boron fluorinated polymers (ABFPs).

a

Sample

MMA/EA/AA/ TFEMA(HFBMA)/PTPBa

PDI

ABTFP-1

10.00/105.00/35.00/50.00/16.32

1.68

ABTFP-2

10.00/105.00/30.00/55.00/13.66

1.97

ABTFP-3

10.00/105.00/25.00/60.00/11.49

2.27

ABTFP-4

10.00/105.00/20.00/65.00/9.23

2.15

ABTFP-5

10.00/105.00/15.00/70.00/6.90

2.20

ABHFP-1

10.00/105.00/35.00/50.00/24.23

1.95

ABHFP-2

10.00/105.00/30.00/55.00/20.78

1.96

ABHFP-3

10.00/105.00/25.00/60.00/17.30

2.12

ABHFP-4

10.00/105.00/20.00/65.00/13.85

2.21

ABHFP-5 Feed weight ratio.

10.00/105.00/15.00/70.00/10.35

2.12

6



2.2.2 Synthesis of the ABFPs The second step in the synthesis was the reaction between the AFPs and PTPB. We charged a round-bottom ﬂask fitted with a mechanical stirring device with 6.9–24.2 g of PTPB (according to the measured acid value of the AFPs), 75 g of xylene, and 50 g of THF. The flask was placed in an oil bath at 95–100 °C, and then 150 g of the AFPs was added. The reaction mixture was stirred for 10 h and a light brown transparent solution was obtained. We then purified the product by removing the unreacted PTPB and other impurities using a vacuum filtration system. For the convenience of various applications, we concentrated the obtained polymers by rotary evaporation to adjust the non-volatile content to approximately 40%. The chemical structures of the ABFPs were characterized by Fourier-transform infrared (FTIR) spectroscopy (Figure S1) and proton nuclear magnetic resonance spectroscopy (1H NMR; Figure S2). Weight average molecular weight and viscosity of ABFPs were measured, as shown in Figure S3 and Figure S4 respectively.The recipes, polymer dispersity indices (PDIs), and the sample abbreviations of the various ABFPs are summarized in Table 1. We determined the degrees of polymerization of MMA, EA, AA, and TFEMA/HFBMA, and the PTPB grafting ratio; the results are listed in Table S1. Table S1 shows that most of the PTPB molecules grafted to the AAPs; the remaining PTPB and carboxy groups did not react owing to the steric effect, wherein the three benzene rings and one pyridine ring of PTPB hindered the reaction between PTPB and the carboxy groups.

7


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EPS Diatom

Protein and fouling organisms

:

N B

:

C

Hindering

Self-polishing

-

N B

Hydration shell

H2 C

CH3

CH3

H2 C

r

C C

film

x

O

C C

O

y

r

C H2

O

O H2C

CH3 F

C

F

CH

F

C

H C

r

H2 C

O

H2 C

n

z

C

Hydrolysis

H C C

O

C

H2 C

r

C x

O

O

O

H2C

B N

CH3

F

CH3

CH3

O

C C

y

r

C H2

O

O

C

F

CH

F

C

r

H2 C

H C

C

OH

F

C

F

CH

F

C

F

F

n

z

O

H2C F

H C

C

O

-

Polymer

O

F

Migration

:

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


O

OH

H2C F

CH3

CH3

F

F

F

F

Scheme 1. Antifouling process of acrylate boron fluorinated polymers (ABFPs) 2.3 Characterization The average molecular weights (Mw) and polymer dispersity indices (PDIs) of the AFPs and ABFPs were measured at 35 °C on a gel permeation chromatography (GPC) setup with a Waters 2414 refraction index detector. THF was used as the eluent at a flow rate of 1.0 mL/min, and monodisperse polystyrenes were used as the standards. The static contact angles (CAs) of water and perfluoropolyether lubricant oil were measured using a video optical contact angle system (OCA 20; DataPhysics, Germany) at 20-35 °C. The mean contact angle value of five measurements on different regions of the same sample was regarded as the corresponding apparent contact angle, and error bars represent the standard deviation. We examined the morphology of the ABFPs by scanning electron microscopy (SEM; JEOL JSM-6480A microscope) before and after immersion in seawater. The chemical states of the surfaces of the original ABFPs and hydrolyzed ABFPs were 8



examined to determine the hydrolysis mechanism by X-ray photoelectron analysis on a multi-functional X-ray photoelectron spectroscopy (XPS) instrument (PHI-5700; Perkin-Elmer, USA). We followed the same procedures outlined in our previous research for the weight loss measurements, diatom settlement assay, and growth inhibition assay.26 2.4 Thickness and roughness of ABFPs during antifouling test We spin-coated the ABFPs onto glass slides (SETCAS Electronics Co., Ltd., KW4B, China) at a rotation speed of 200 rpm for 40 s, then dried the samples at ambient temperature. A Phaeodactylum tricornutum Bohlin diatom suspension with a concentration of at least 1 × 105 algal cells per mL was placed in an aquarium. The dry samples were then placed on the bottom of the aquarium. Every 48 h, the samples were gently taken from the aquarium and washed with deionized water for 5 min to remove the unsettled diatoms. The substrates were placed in an oven at 100 °C for 6 h, and the thickness of the dry substrates was measured using a micrometer (Mitutoyu, 293-240-30, Japan). After measuring the thicknesses, the samples were placed in the diatom solution and the incubation process was allowed to continue. After immersion for 14 days, the ABFPs samples were taken out, washed with deionized water, lyophilized, and tested using a roughmeter (RT230; Beijing Shidai Jiaxiang Technology Co., Ltd.). We used the average of five roughness measurements. 2.5 Preparation of copper-free ABFP-based coatings and environmental tests We formulated various acrylate boron fluorinated coatings (ABFCs) with ABTFP1–5 and ABHFP-1–5 as binders. Typically, 70 g of ABFPs, 17.5 g of tralopyril, 47.24 g of pigments, 2.62 g of chlorinated paraffin, 3.5 g of anti-settling agent, and 27.49 g of solvent were mixed uniformly by mechanical stirring at 4000 rpm until the fineness of the paint was below 40 μm. The paints were then filtered and packaged for use. 9


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The fineness, viscosity, sagging properties, adhesive force, and toughness of the antifouling paints were tested using standards GB/T 6753-1986, GB/T 1723-1993, GB/T 9264-2012, GB/T 9286-1998, and GB/T 1731-1993, respectively. The relevant description can be seen in support information. The results are listed in Table 2.

Table 2. Basic properties of the various acrylate boron fluorinated polymer (ABFP)based coatings. Fineness

Viscosity

Sagging

Adhesive force

Toughness

(μm)

(KU)

properties (μm)

(level)

(mm)

ABTFC-1

20

67

450

0

1

ABTFC-2

10

70

450

0

1

ABTFC-3

20

65

450

0

1

ABTFC-4

20

72

500

1

1

ABTFC-5

40

70

450

0

1

ABHFC-1

15

71

500

0

1

ABHFC-2

30

68

450

0

1

ABHFC-3

30

73

550

1

1

ABHFC-4

20

70

500

0

1

ABHFC-5

30

71

500

0

1

Sample

We applied the ABFP paints to a fiberglass-reinforced resin panel (300 mm × 100 mm) to a total dry film thickness of 160 ± 5 μm, and placed the coated panels in ASW. The chemical oxygen demand (COD) of the seawater was measured and calculated according to standard ISO6060 at the time of immersion (0 days), and after 10 days to determine the environmental properties of the antifouling paints. 2.6 Real sea test We fixed the panels described above inside a stainless steel frame with insulated wire. A fiberglass-reinforced phenolic resin panel was chosen as the test plate instead 10



of a traditional steel plate because it made an anticorrosive paint unnecessary, and a lightweight panel is convenient for carrying out the whole test. We used a poly (dimethylsiloxane) fouling release coating, which was purchased from a domestic company, as a control in the test. The real sea test was conducted from a dock at Dachangshan Island, Dalian (12257′E, 3927′N) on May 16 2018. Visual examination of the coatings was carried out every month to record the attachment of fouling organisms.

3. Results and discussion 3.1 Static contact angles of ABFPs It is well known that antifouling properties are closely associated with the surface properties of antifouling films. To assess the surface wettability, we determined the water and oil contact angles (CAs) of the ABTFPs and ABHFPs before and after immersion for 200 h in ASW, as shown in Figure 2 (a). There was no difference between the original contact angles of the ABTFPs and ABHFPs, which indicated that the length of the fluorinated side chains had little influence on surface wettability. Furthermore, a larger content of fluorinated monomers TFEMA or HFBMA led to higher contact angles. However, after immersion in ASW for 200 h, the contact angles of the two polymers decreased (Figure 2 (b)). This was because the hydrophobic phenylpyridine side groups were hydrolyzed and fell off the backbone after the selfpolishing process. The attendant carboxylate ion moieties were more hydrophilic than the original phenylpyridine side groups. Therefore, the generated hydrophilic groups resulted in lower contact angles. It is worth noting that after immersion in ASW for 200 h, the contact angles of the ABTFPs decreased significantly compared with those of the ABHFPs. This may have arisen because the longer fluorinated side chains of 11


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the ABHFPs were not conducive to the hydrolyzation, indicating that ABFPs with longer fluorinated side chains have lower hydrolysis rates and weight loss ratios. Figure 2 (c) and (d) demonstrates that the ABTFPs and ABHFPs were lipophilic with regard to perfluoropolyether lubricant oil, and their lipophilicity increased with increasing fluorinated monomer content. However, unlike the water contact angle, the oil contact angle changed little after immersion in ASW for 200 h.

a

b 100

ABHFP ABTFP

60 40 20 0

c 70

60

40

20

50

55 60 65 TFEMA/HFBMA (wt%)

0

70

d

ABHFP ABTFP

80 70

Contact angle (degree)

60 50 40 30 20 10 0

ABHFP ABTFP

80

80



100


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


50


70


70

ABHFP ABTFP

60 50 40 30 20 10

50


0

70

50

Figure 2. Original water contact angle of acrylate boron tri-fluorinated polymers (ABTFPs) and acrylate boron hexa-fluorinated polymers (ABHFPs) (a), water contact angle after immersion in artificial seawater for 200 h (b), oil (perfluoropolyether lubricant oil) contact angle (c), oil (perfluoropolyether lubricant oil) contact angle after immersion in artificial seawater for 200 h (d). Error bars represent the standard error.

3.2 Weight loss ratio of ABFPs 12



To verify the hypothesis mentioned above and to inspect the hydrolysis rate, we carried out a weight loss ratio test. As seen in Figure 3, when the content of fluorinated monomers was higher than 65 wt% of the total monomers, the range of the weight loss ratio of the ABTFPs and ABHFPs became smaller. The reason for this phenomenon was that large hydrophobic fluorinated monomer content increased the hydrophobicity, which was not conducive to polymer hydrolysis. When the soak time was less than 96 h, the weight loss ratio of the ABHFP was negative, and the weight loss ratio of the ABHFPs was lower than that of the ABTFPs. This was because the longer fluorinated side chains of the ABHFPs reduced the hydrolysis rate to below that of water absorption. The weight loss ratios of most of the ABFPs were lower than those of acrylate boron polymers (ABPs), and the addition of fluorinated chains to the molecular structure may have contributed to these lower weight loss ratios. The results suggest that longer fluorinated side chains reduce hydrolysis, which corroborates the hypothesis mentioned above.

48 h ABHFP 96 h ABHFP 144 h ABHFP 48 h ABTFP 96 h ABTFP 144 h ABTFP

40 30 Weight loss ratio (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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20 10 0

-10 -20

50

55

60

65

70

HFBMA/TFEMA (%)

Figure 3. Weight loss ratios of acrylate boron tri-fluorinated polymers (ABTFPs) and acrylate boron hexa-fluorinated polymers (ABHFPs) during immersion in artificial 13


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seawater for 144 h. Error bars represent the standard deviation.

3.3 Surface topography and wettability change under seawater Both the composition and the surface topography can affect the antifouling performance of a material. To examine changes to the surface topography, we used SEM to assess the surfaces of ABTFP-5 and ABHFP-5 before and after immersion in ASW for 144 h, as shown in Figure 4. ABTFP-5 and ABHFP-5 were chosen for characterization because they had the most obvious surface topographies. We selected acrylate boron polymer (ABP) (without further details, when ABP is used in the following text it means ABP-1, which had the best antifouling performance) as a control in our investigations of the influence of fluorinated segments on the surface microstructure. The SEM images revealed numerous micron-sized holes on the surfaces of ABTFP-5 and ABHFP-5 after immersion in ASW for 144 h. However, the polymer surface of ABP was still relatively smooth after immersion in ASW for 144 h, and no migration of hydrophobic fluorinated segments contributed to the smooth surface. a

ABTFP-1 ABTFP-2 ABTFP-3 ABTFP-4 ABTFP-5

d 96 Contact angle (degree)

b

93

ABHFP-1 ABHFP-2 ABHFP-3 ABHFP-4 ABHFP-5

90 87 84 81

5 μm

5 μm

78 0

e

25

50

4.7μm

75 100 Time (s)

125

ABTFP-1 ABTFP-2 ABTFP-3 ABTFP-4 ABTFP-5

h 90

f


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


75

150

175

ABHFP-1 ABHFP-2 ABHFP-3 ABHFP-4 ABHFP-5

60 45 30 15

5 μm

5 μm

0 0

25

50

75 100 Time (s)

125

150

175

Figure 4. Scanning electron microscopy (SEM) images of thin films (a) ABTFP-5, (b) ABHFP-5, (c) ABP, (e) ABTFP-5 after immersion in artificial seawater (ASW) for 14



144 h, (f) ABHFP-5 after immersion in ASW for 144 h, and (g) ABP after immersion in ASW for 144 h. Water contact angle of original ABFPs (d) and ABFPs after immersion in ASW for 144 h (h).

When the ABFPs were immersed in the seawater, we assumed that the hydrophobic diphenyl borane pyridine side groups would fall off the molecular main chain, and the side chains would be hydrolyzed to hydrophilic carboxylate ions. After hydrolysis, the hydrophilic groups migrated to the surface forming a dispersion phase, and the hydrophobic segments and groups migrated to the interior of the polymer forming a continuous phase in the seawater. When the immersed polymers were removed from the water to examine their surfaces, the hydrophilic segments moved to the interior of the polymer, and the hydrophobic continuous phase migrated to the surface, which formed the porous surface microstructure. To verify the aforesaid conjecture, we examined the variation of the water contact angles with immersion time. As shown in Figure 4 (d), the contact angles of the polymers changed little over time. After immersion in ASW for 144 h, the hydrophobic diphenyl borane pyridine side groups hydrolyzed to hydrophilic carboxylate ions, and the polymer surface wettability changed, as depicted in Figure 4 (h). The initial contact angles ranged from 80 to 92 °, but after tens of seconds or several minutes, the contact angles decreased sharply, and those of ABTFP-4, ABHFP-4, and ABHFP-5 even decreased to 0 °. Because the test was carried out at the solid–gas interface, hydrophobic segments and groups gathered on the polymer surfaces. The initial contact angle of a drop of water on the surface of a hydrolysis polymer was almost the same as that of a drop on the original polymer owing to the presence of hydrophobic fluorinated side chains. After the water droplets contacted 15


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the polymer surfaces, the hydrophilic groups migrated to the surface, and the hydrophilic dispersion phase absorbed the water, leading to a critical decline in the contact angle. 3.4 XPS analysis of ABFPs The hydrolytic behavior of ABTFPs and ABHFPs has not been reported before, but is essential for an understanding of their hydrolysis mechanisms. The ABTFPs had higher hydrolysis rates than the ABHFPs, and ABTFP-1—having the greatest number of hydrolytic groups—was chosen for the XPS experiment. Figure 5 shows the XPS spectra of pristine ABTFP-1 and ABTFP-1 after immersion in ASW for 144 h, and the higher resolution spectra of O 1s.

5

4x10

b

C 1s 5

O 1s

3x10

5

4x10

C 1s

Intensity(Counts per second)


a

5

3x10

5

2x10

O 1s

5

2x10

F 1s 5

F 1s 5

1x10

1x10

Si 2p B 1s

Si 2p 0

0 0

200

400

600

800

Binding energy(ev)

1000

0

1200

c

200

400

600

800

Binding energy(ev)

1000

1200

d 4

3x10



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


B-O C-O

4

2x10

C=O 4

1x10

528

530

532

534

Binding energy(ev)

536

4

3x10

C=O 4

2x10

C-O

4

1x10

528

530

532

534

Binding energy(ev)

536

Figure 5. X-ray photoelectron spectroscopy (XPS) survey spectrum (a) and highresolution O 1s spectrum (c) of pristine ABTFP-1; XPS survey spectrum (b) and highresolution O 1s spectrum (d) of ABTFP-1 after immersion in ASW for 144 h. 16



The binding energies were referenced to the C 1s peak, which was assumed to have a binding energy of 284.8 eV. The presence of B 1s (193.1 eV) in the wide scan spectra of pristine ABTFP-1 confirmed that the PTPB had reacted successfully with the carboxyl groups (Figure 5 a).27 As shown in the Figure 5 b, there was no signal corresponding to B 1s after the polymer had been immersed in ASW for 144 h. Because the B 1s signal peak is associated with hydrolysable diphenyl borane pyridine side groups, the disappearance of the B 1s signal peak demonstrates that the hydrolysable diphenyl borane pyridine side groups separated themselves from the molecular main chain after the ABTFP-1 self-polished in the seawater. High resolution scanning of O 1s was used to reveal the change to elemental boron, and three signal peaks attributable to C=O, B-O, and C-O were observed at binding energies of 531.6 eV, 532.3 eV, and 532.7 eV, respectively (Figure 5 c).28, 29 After immersion of ABTFP-1 in ASW for 144 h, the signal peaks located at 532.7 eV and 531.6 eV were attributable to C-O and C=O species, respectively. The disappearance of the B-O species at 532.3 eV demonstrated that the hydrolysable boracic side groups had become detached from the molecular main chain. After the polymers had selfpolished, the generated carboxylate ions endowed the polymer with hydrophilic groups, in agreement with the hypothesis mentioned above. 3.5 Diatom settlement assay and growth rate inhibition testing of ABFPs We carried out a diatom settlement assay to investigate the antifouling properties and further examine the hydrolysis properties of the ABHFPs and ABTFPs. Generally speaking, antifouling and hydrolysis properties are proportional to the acid value (Figure S5). Polymers with higher acid values (160–180 mg KOH/g) have higher selfpolishing rates, and more diatoms fall off their surfaces owing to dynamic self17


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renewal. We examined the surface topographies of ABFP films immersed in a suspension of Phaeodactylum tricornutum Bohlin diatoms (Figure S6). After the samples had been exposed to the diatom suspension for 2 weeks, far fewer diatom cells had settled on the ABFPs film surfaces than on the blank surface. Apart from the the blank, the surfaces of ABTFP-3, ABTFP-4, and ABHFP-3 were infested with diatoms, and a small quantity of diatoms adhered to the surfaces of ABTFP-1, ABTFP-2, ABHFP-1, and ABHFP-2. It is very interesting that we only found a few diatoms on the porous texture surfaces of ABTFP-5, ABHFP-4, and ABHFP-5. The polymers with high acid values—that is, ABTFP-1, ABTFP-2, ABHFP-1, and ABHFP-2—had more labile esters, and higher rates of hydrolysis and surface selfrenewal. The high hydrolysis and self-renewal rates made the surfaces of ABTFP-1, ABTFP-2, ABHFP-1, and ABHFP-2 dynamic. Therefore, it was difficult for the diatom cells to settle on such unstable surfaces. The amphiphilic phase may explain the excellent antifouling properties of ABTFP-5, ABHFP-4, and ABHFP-5. There were numerous fluorinated chain segments in the molecular structures of ABTFP-5, ABHFP-4, and ABHFP-5. Such fluorinated chain segments formed the hydrophobic phase, and small numbers of hydrophilic groups generated after self-polishing process formed the hydrophilic phase. When the hydrolysed polymer immersed into water, the micro-structure appeared for the different wettability of hydrophobic phase and hydrophilic phase, and the amphiphilic phase and micro-structure were beneficial for the removal of fouling organisms. The porous surface structures were characterized by SEM and the hypothesis described above was verified. Compared with the diatom settlement results of the ABPs reported in our previous work, all the ABFP films had better diatom anti-settling properties than the ABPs, which demonstrated that the

18



introduction of fluorinated chain segments endowed the new polymers with better resistance to diatoms.

-1

5

3.0

b4

ABTFP-4 ABTFP-5 ABHFP-1 ABHFP-2 ABHFP-4 Control Blank

-3

3.5

Growth rate ( day )

a Cell (10 number/mL)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 29

2.5

48h 2.0

96h

144h

192h

240h

3

2

1

0

P-1 P-2 P-3 P-4 P-5 P-1 P-2 P-3 P-4 P-5 P-1 ank TF TF TF TF TF HF HF HF HF HF AB Bl AB AB AB AB AB AB AB AB AB AB

Time (h)

Polymer

Figure 6. Diatom density (a) and growth rate (b) in solutions containing acrylate boron hexa-fluorinated polymers (ABHFPs), acrylate boron tri-fluorinated polymers (ABTFPs), controls, and blanks. Error bars represent the 95% confidence intervals.

Environmentally friendly antifouling films have attracted more attention since the banning of TBT-based compounds. To investigate the environmentally friendly properties of ABHFPs and ABTFPs, we carried out a diatom inhibition test to determine whether the diatom anti-settling properties resulted from poisoning the diatom cells, and the results are shown in Figure 6. The control sample used in this test was ABP, which has a similar molecular structure to that of ABTFP-1/ABHFP-1 except for the fluorinated segment.26 The numbers of diatom cells in the suspensions containing ABTFP-4, ABTFP-5, ABHFP-1, ABHFP-2, ABHFP-4, and the blank were slightly greater than in the suspensions containing the other samples. However, there were no obvious differences in growth rates between the various diatom suspensions. The results demonstrated that the ABHFPs and ABTFPs had no detrimental effect on organisms when the polymers were immersed in seawater, and renewed their surfaces through self-polishing when the fouling organisms became 19


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attached to their surfaces. The tests indicate that ABHFPs and ABTFPs have environmentally friendly properties. 3.6 Surface roughness and film thickness of ABFPs During immersion in the diatom suspensions, the various ABFPs samples had different surface roughnesses and film thicknesses. As shown in Figure 7 (a), the roughness increased from ABFP-1 to ABFP-5. Figure S6 shows that the polymers with the most porous surfaces had the best antifouling performances. The main reason for this is that the amphiphilic phase made the polymer surfaces unsuitable for the adhesion of fouling organisms, and the micro-structure also inhibited the attachment of fouling organisms.30, 31 Figure 7 (b) shows that the film thicknesses decreased with time, and the films became thinner from ABFPs-1 to ABFPs-5 during the antifouling test. This was because ABFPs-1 had a higher acid value (Figure S5), and the polymers with higher acid values had more labile hydrolyzed esters during the antifouling test. Furthermore, the ABTFP coatings were thinner than the ABHFP coatings. The reason for this phenomenon was that the longer fluorinated side chains resisted hydrolysis, which was consistent with the results of the static contact angle tests and the weight loss ratio tests. However, unlike weight loss, the ABFPs had greater thickness loss owing to the presence of the diatoms, which can affect the hydrolysis rate of ABFPs.

20



a

0.8 0.7

b 140

ABTFP ABHFP

ABTFP-1

Thickness(μm)

0.5 0.4 0.3

ABHFP-2

120

ABTFP-3

ABHFP-3

ABTFP-4

ABHFP-4

100

ABTFP-5

ABHFP-5

80 60

0.2

40

0.1

20

0.0

0

ABFP-1

ABFP-2 ABFP-3 ABFP-4 Polymer categories

ABFP-5

ABHFP-1

ABTFP-2

0.6 Roughness (um)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 29

0

40

80

120 Time (h)

160

200

240

Figure 7. Roughness (a) and thickness (b) of the various acrylate boron fluorinated polymers (ABFPs).

3.7 Real sea test and environmental properties of the ABFCs We carried out an ocean raft test to verify the antifouling characteristics and practicability of the as-prepared ABFCs. Visual observation was used to assess the antifouling performance with regard to the adhesion of biomass including slime, and hard and soft fouling organisms. Figure 8 shows photographs of plates coated with ABP paints following immersion in seawater for 90 days to assess antifouling performance. As shown in the digital images, macroalgae was the main fouling organisms in the Bohai Sea. After immersion in seawater for 90 days (May–August), the blank panel was infested with macroalgae such as kelp and Ulva linza. We also found slime and silt on the surfaces of the control and ABP plates. In contrast to the blank, control, and ABP plates, there were no fouling organisms—not even slime—on the panels coated with ABTFC and ABHFC paints, and all the coatings had bright and clean surfaces. The reason for this phenomenon may be that continuous self-renewal of the coating surface, and the gradual releases of antifouling biocides deter fouling organisms. Another reason is that after the hydrolysis of hydrophobic diphenyl borane pyridine side groups, the hydrophilic groups moved to the surface and generated a 21


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hydration shell, which prevented fouling organisms from attaching to the surface. Therefore, the introduction of fluorinated side chains endows ABTFC and ABHFC paints with amphiphilic properties, which deter the settlement of macrofouling organisms, as well as slime and silt. The test results showed that ABFP coatings effectively prevent the adhesion of fouling organisms during the biological growth season, and have potential for use in maritime applications.

Figure 8. Photographs of the original panels coated with ABTFC and ABHFC paints, and blank, control, and ABP paints; and the corresponding panels following immersion in the Bohai Sea of China for 90 days.

We also evaluated the environmental properties of the ABFP antifouling paints according to COD.32 COD is a common parameter for evaluating the degree of contamination, water environmental release, and the impact of contaminants. COD1 and COD2 in Table 3 are the chemical oxygen demand values of the initial ASW and the ASW after immersion of the antifouling paints for 10 days, respectively. As shown in Table 3, COD2 was slightly higher than COD1, lower than the primary standard of GB8978-1996, which demonstrates that the antifouling paints had negligible impact on the environment. Compared to the static and closed laboratorial artificial seawater, dynamic and open nature seawater will show lower COD values 22



Page 24 of 29

when the test panels immersed in real sea. In conclusion, ABFP antifouling paints also have environmentally friendly properties.

Table 3. Chemical oxygen demand (COD) values of artificial seawater (ASW) following immersion of the various antifouling paints for 0 and 10 days. Sample

COD1(mg/L)

COD2(mg/L)

ABTFC-1

51.2

87

ABTFC-2

51.2

90

ABTFC-3

51.2

85

ABTFC-4

51.2

92

ABTFC-5

51.2

90

ABHFC-1

51.2

91

ABHFC-2

51.2

88

ABHFC-3

51.2

93

ABHFC-4

51.2

90

ABHFC-5

51.2

91

4. Conclusions In summary, we synthesized self-polishing amphiphilic acrylate boron fluorinated polymers to examine their antifouling performance and determine the antifouling mechanism, by which they function after the addition of fluorinated monomers. We determined contact angles, and conducted XPS and SEM analyses to elucidate the antifouling performance and mechanisms of the polymers. The results showed that self-polishing is accomplished by the peeling off of diphenyl borane pyridine side groups. Following self-polishing, the resulting hydrophilic carboxylate ions migrate to the polymer surface and absorb water to form a hydrophilic surface, which prevents the attachment of fouling organisms. We used a diatom anti-settling assay and a real sea test to evaluate the antifouling performance of the polymers. The ABFPs effectively prevented the adhesion of diatoms, and ABFP antifouling paints 23


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maintained bright and clean surfaces after immersion in the Bohai Sea of China for 90 days. Compared with ABP, amphiphilic ABFPs have better antifouling properties, especially in real sea conditions, which indicates that the introduction of fluorinated chain segments to the molecular structure effectively improves antifouling. We think that the hybrid polymers described in the present study are potential candidates for environmentally friendly antifouling materials.

Supporting information The Supporting Information is available free of charge on the ACS Publications website. The results of FTIR and 1H NMR characterization, the thermal stability, molecular weight, and viscosity values, the ABFP acid values, and the results of the diatom antisettling assays are available in the Supporting Information. Conflicts of interest There are no conflicts to declare.

Acknowledgments This work was supported by the National Natural Science Foundation of China (NSFC; number 51603053), the International S&T Cooperation Program of China (ISTCP; number 2015DFA50050), the Application Technology Research and Development Plan of Heilongjiang Province (number GX16A008), the Fundamental Research Funds of the Central University and the Application Technology Research and Development Projects of Harbin (number 2015 RAQXJ038), and the Defense Industrial Technology Development Program (number JCKY2016604C006).

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Synthesis of Amphiphilic Acrylate Boron Fluorinated Polymers with

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