Multicomponent-Reaction-Ready Biomass-Sourced Organic Hybrids

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Multicomponent-Reaction-Ready BiomassSourced Organic Hybrids Fabricated via the Surface Immobilization of Polymers with Lignin-Based Compounds Takashi Hamada, Shuhei Yamashita, Masaaki Omichi, Kimio Yoshimura, Yuji Ueki, Noriaki Seko, and Ryohei Kakuchi ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b06812 • Publication Date (Web): 21 Feb 2019 Downloaded from http://pubs.acs.org on February 21, 2019

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ACS Sustainable Chemistry & Engineering

Multicomponent-Reaction-Ready Biomass-Sourced Organic

Hybrids

Fabricated

via

the

Surface

Immobilization of Polymers with Lignin-Based Compounds Takashi Hamada1,*, Shuhei Yamashita2, Masaaki Omichi1, Kimio Yoshimura1, Yuji Ueki1, Noriaki Seko1, and Ryohei Kakuchi2,*

1Department

of Advanced Functional Materials Research, Takasaki Advanced

Radiation Research Institute, Quantum Beam Science Research Directorate, National Institutes for Quantum and Radiological Science and Technology (QST)

1233 Watanuki-machi, Takasaki 370-1292, Gunma, Japan

2Division

of Molecular Science, Graduate School of Science and Technology, Gunma

University

ACS Paragon Plus Environment

1

ACS Sustainable Chemistry & Engineering 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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1-5-1 Tenjin-cho, Kiryu 376-8515, Gunma, Japan

E-mail: [email protected] and [email protected].


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ABSTRACT: Compounds derived from two major biomass components, cellulose and lignin, were artificially re-combined via the radiation-induced graft polymerization of vinyl monomers, which could be potentially sourced from lignin, onto cellulose fabric. This process yielded organic hybrids featuring a cellulose substrate and surface aldehyde groups from lignin-obtained vanillin. Then, the surface Kabachnik-Fields threecomponent reaction (KF-3CR) of poly(methacrylated vanillin) (PMV) sourced aldehydes was carried out with amines and phosphites. Overall, the surface KF-3CR on the cellulose fabric grafted with PMV represents a facile preparation of multi-functional molecules on cellulose surfaces along with α-amino phosphonate ester integrations.

Keywords; multi-component reactions, cellulose, lignin-sourced, organic hybrids, amino phosphonates Introduction Modern chemical processes require a transition from petroleum-dependent chemistry to the utilization of biomass-based compounds.1 Among a number of bio-resources, wood biomass has increasingly attracted attention since it does not compete with


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human food supplies. Though it is known that wood biomass, i.e., lignocellulose, is composed of polysaccharides (cellulose and hemicellulose) and an aromatic polymer (lignin), the use of the latter is largely behind that of the polysaccharides.2, 3 Hence, the utilization of lignin-derived chemicals remains as one of the most important milestones to be achieved. In this context, polymer synthesis from lignin-based chemicals (e.g., vanillin) is designed to meet sustainability requirements, indicating that lignin-based compounds are an excellent alternative for conventional monomers.4-10 Additionally, new synthetic approaches in polymer chemistry based on vanillin from lignin have been proposed, having the green advantage of the reactivity of aromatic aldehydes such as vanillin.10 Particularly, polymers featuring vanillin are reported to be highly compatible with multicomponent reaction (MCR) based polymer modifications.10 Since MCRs have very recently been integrated into polymer science and thus blooming10-22, the report by Kakuchi et al. has illustrated the use of vanillin in polymer science from a greenchemistry perspective and as reactive polymers in general.23-26 Regarding the structure, lignocellulosic biomass is composed of cellulose and hemicellulose polysaccharides and lignin. These biomass-derived polysaccharides,


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especially cellulose, are usually subject to decomposition reactions that yield platform chemicals, or to polymer analogous reactions to produce cellulose-based plastics such as acetates.

27, 28

In addition to providing starting materials, cellulose itself is an

indispensable a substrate material.29 Historically, cellulose fiber has been employed as in a wide range of applications. In addition, cellulose nano-fibers play an indispensable role in modern material sciences.30,

31

Considering cellulose as a substrate material,

surface immobilization of the vanillin polymers could lead to unique organic hybrid materials with the polymers featuring lignin-derived compounds as surface modifiers. This could achieve the merging of biomass components, cellulose and lignin, to essentially re-build novel substrate structures, thus fulfilling the fabrication of functional materials from biomass-derived chemicals. To accomplish this, the radiation-induced graft polymerization may be a useful technique, as the solid-state polymerization of a vinyl monomer on a wide range of substrates could proceed under rather mild reaction conditions. Exposure of the substrates to radiation is known to induce the generation of radicals on the material surface, from which the polymerization of common vinyl monomers is initiated. Unlike


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other surface initiated polymerizations, such as the surface initiated atom transfer radical polymerization, the radiation-induced graft polymerization does not need chemical modification of substrate surfaces to install polymerization initiators. This allows for easy surface modification of substrate materials with functional polymers without harming the surface structures. If the material substrate allows for radical generation, any combination of substrate and vinyl monomers would be adequate, regardless of their miscibility. In fact, radiation-induced graft polymerization accepts a wide range of materials as a modifiable substrate, including polyethylene (PE),32-34 polypropylene,35,

36

polytetrafluoroethylene,37 poly(ethylene-co-tetrafluoroethylene),38

poly(vinylidene fluoride),39 poly(ether ether ketone),40,

41

and even cellulose,42-44 to

mention a few. Moreover, cellulose was reported to be an appropriate matrix for the graft polymerization of vinyl monomers such as glycidylmethacrylate, yielding cellulosebased functional fabrics.44 In this context, the fabrication of biomass-derived reactive organic hybrids may be feasible: cellulose would be the substrate and polymers with vanillin would act as MCR-ready bio-based surface modifiers.


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In this work, we investigated the radiation-induced graft polymerization of monomers featuring lignin-model compounds onto PE surfaces and the subsequent KabachnikFields reaction (KF-3CR) on the obtained PE surfaces. Then, we prepared biomassderived organic hybrids comprised of cellulose and polymers featuring lignin-model compounds as the grafted reactive polymer (Scheme 1). OMe O O

50 kGy

H

fabrics fabrics: PE or cellulose

H

Ar NH2

O P OR

1.

OMe

O H O

fabrics

OR

Representation

n O

1,4-dioxane for PE MeOH for cellulose

n O

OMe

O

1,4-dioxane

Scheme

fabrics

O

of

the

O OR P OR NH Ar

radiation-induced

graft

polymerization

of

Methacrylated vanillin (MV) and the solid-state KF-3CR with amine and phosphite.

Experimental


7


Page 8 of 46

Materials Non-woven fabric composed of polyethylene coated polypropylene fiber (PE fabric) was provided by Kurashiki Textile Manufacturing Co., Ltd. Cellulose fabric was obtained from Marusan Sangyo Co., Ltd. Methacrylated vanillin (MV) was synthesized according to reported procedures.7, 10 1,4-Dioxane (super dehydrated) and tetrahydrofuran (THF, super dehydrated, stabilizer free) were purchased from FUJIFILM Wako Pure Chemical Co., Ltd. and used as received. p-Anisidine, 4-chloroaniline, 4-iodoaniline, hexylamine, diisopropyl phosphite, dimethyl phosphite, and dibutyl phosphite were purchased from Tokyo Chemical Industry Co., Ltd. and also used as received. Characterization Fourier transform infrared (FT-IR) spectra were recorded on a Perkin-Elmer FTIR spectrometer equipped with an attenuated total reflectance (ATR) unit in the range from 4000 to 400 cm−1. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) was performed with the spectrometer attached to a HITACHI SU3500 microscope. The sample was attached to the holder with carbon tape and coated with Au. Solid-state

31P

nuclear magnetic resonance (NMR) spectrum was recorded on a


8

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Bruker AVANCE 300 spectrometer. For the measurement of solid-state NMR, the fabric was freeze-crushed under liquid nitrogen using a ball mill and then packed with KBr in a ZrO2 rotor with a 4 mm diameter. Thermogravimetric analysis (TGA) was carried out using a Thermal Plus/TG-DTA 8120 (Rigaku, Japan) at a heating rate of 10 °C/min under nitrogen flow (50 mL/min). Graft polymerization of MV A PE fabric (roughly 3 × 2 cm, 36 mg) was placed in a glass tube and dried under vacuum for 30 min to remove air. Then, the glass tube was filled with nitrogen gas, and the PE fabric was irradiated with

60Co

-rays to a total dose of 10–50 kGy. Nitrogen was

bubbled for 10 min into a solution of MV/1,4-dioxane (0.5 g/5 mL), which was then added to the glass tube and the mixture was heated to 60 °C for a pre-determined period. The grafted-fabric was removed and washed three times with 1,4-dioxane, and then with THF. Finally, the obtained poly(methacrylated vanilline)-grafted PE (PE-PMV) was dried under vacuum at 80 °C for 5 h. The grafting degree (GD) was calculated as follows:


9


𝐺𝐷 (%) =

𝑊𝑔 ― 𝑊0 𝑊0

× 100

Page 10 of 46

(1)

where W0 and Wg are the weight before and after graft polymerization, respectively. The graft polymerization of MV into the cellulose fabric was conducted using the same procedure except methanol was used as solvent instead of 1,4-dioxane. The surface KF-3CR of PMV-grafted fabrics A typical KF-3CR in the solid state proceeded as follows: p-anisidine (0.82 g, 6.6 mmol) and diisopropyl phosphite (2.2 mL, 13.3 mmol) were dissolved in 1.5 mL of 1,4dioxane. A piece of about 3×2 cm2 (70 mg) of PE-PMV was immersed in the solution

and heated at 80 °C for 24 h. The obtained fabric was washed several times with 1,4dioxane and THF, and then dried under vacuum at 80 °C for 5 h to obtain the -amino phosphonate-grafted PE (PE-PAP). The recovery ratio was calculated from:


10

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Recovery ratio (%) =

(𝑊𝑘 ― 𝑊𝑔) 𝑀𝑊 𝑜𝑓 1 𝑢𝑛𝑖𝑡 𝑜𝑓 𝑃𝐴𝑃 (𝑊𝑔 ― 𝑊0) 𝑀𝑊 𝑜𝑓 𝑀𝑉

× 100

(2)

where Wk is the weight of the fabric after the KF-3CR process.

The surface wettability measurement Cellulose fabrics before and after KF-3CR were immersed in the water and then wiped with Kimwipes. The water uptakes were calculated using the following equation.

Water uptake (%) =

𝑊𝑤𝑒𝑡 ― 𝑊𝑑𝑟𝑦 𝑊𝑑𝑟𝑦

× 100

(3)

Where Wwet is the weight of fabric after immersion in water and Wdry is the weight of dried fabric.

Results and discussion Radiation-induced graft polymerization of MV


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As discussed in the introduction, the aim of this manuscript was to fabricate biomassderived organic hybrids featuring MCR-ready reactivity with cellulose as the substrate and polymers bearing lignin-based compounds as surface modifiers. To achieve this, the first step is the surface immobilization of the polymers via graft polymerization. To verify whether the monomers with lignin-derived compounds are compatible with the graft polymerization technique, model reactions were designed and carried out with PE as substrate, which was expected not to induce undesirable side reactions that hamper a facile surface characterization. Therefore, PE was selected as the model substrate material and MV as the model biomass-derived vinyl monomer. For this, the PE fabric was placed in a glass tube and pre-irradiated with a dose of 50 kGy, then the graft polymerization of MV was conducted in 1,4-dioxane at 60 °C for 5 h. The weight and thickness of the PE fabric increased after this reaction, and the GD calculated from equation (1) was 136%. Figure 1 shows the relationship between GDs, pre-irradiation (10, 20, or 50 kGy), and polymerization time. Radiation-induced graft polymerizations are known to be initiated from surface radicals that are generated by radiation. Accordingly, increasing the pre-irradiation period and dose led to higher GDs, which


12

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reached 160% at 60 °C for 7 h for the 50 kGy pre-irradiated PE fabric (Figure 1). Next, to elucidate the chemical structure of the MV-grafted PE fabric, ATR-FTIR measurements were conducted. Figure 2 shows the ATR-FTIR spectra before and after the graft polymerization. For the MV-grafted PE with a GD of 136%, clear ester and aldehyde absorptions at 1753 and 1695 cm−1 appeared along with the peaks at 1461 and 731 cm−1 that correspond to the PE fabric. This spectrum of the PE fabric demonstrates

that

MV

was

successfully

grafted

after

the

radiation-induced

polymerization. The structure of the obtained PE fabric was also characterized by SEM because the graft polymerization could have a significant impact on the substrate surface. Figure 3 shows the SEM images of the starting PE fabric and the grafted PEPMV. The former features a fiber structure, with an average fiber diameter of 19±1 m. After the graft polymerization, PE fibers became dense and the average diameter increased to 26±3 m, suggesting that the fiber surfaces were chemically modified with the polymers. In addition, the grafted PE fabric essentially maintained the PE network structure even after the graft polymerization. These results clearly indicate that PMV grafting proceeded in the material surfaces and that the fiber structure was rather intact,


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Page 14 of 46

yielding PE fabrics with poly(methacrylated vanillin) on the surface (PE-PMV). Overall, the experimental data shows that the biomass-sourced MV could be compatible with the radiation-induced graft polymerization conditions.

Figure 1. Effect of polymerization time and the pre-irradiation dose on the GD for the graft polymerization of MV into pre-irradiated PE fabric (lines are inserted for guidance).


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phosphonate ester unit

ester C=O

Absorbance

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


PE-PAP

PE-PMV aldehyde C=O

PE

2400

2000

1600

1200

800 -1

Wavenumbers (cm )

Figure 2. ATR-FTIR spectra of the PE fabric and PE-PMVs with a GD = 136% before and after KFR with p-anisidine and diisopropyl phosphite.

Figure 3. SEM micrographs of (a) the starting PE fabric and (b) PE-PMV with GD = 136%

Model surface KF-3CR on the PMV functionalized PE fabrics


15


Page 16 of 46

Next, MCR was conducted on the surface of the PE-PMV. For this, the KF-3CR was selected because PMV has been reported to be highly compatible with this reaction, essentially enabling quantitative aldehyde conversion to afford the corresponding polymeric

α-amino

phosphonates.10

Therefore,

for

the

multi-component

post-

polymerization modification on the solid state, KF-3CR was performed using PE-PMV,

p-anisidine, and diisopropyl phosphite as follows. The PE-PMV with a GD of 136% was immersed in a 1,4-dioxane solution of p-anisidine and diisopropyl phosphite, the reaction progress was monitored by ATR-FTIR (Figure 4). As expected from the KF3CR mechanism, the peaks at around 1695 cm−1 owing to PMV aldehyde groups disappeared shortly after the reaction initiated, and a new band at 1623 cm−1 developed. This shows that the PMV aldehyde groups were converted to the corresponding imine moieties via condensation reactions with p-anisidine agreeing with previous studies on the PMV reactivity. Then, the peaks at 1623 cm−1 of the generated polymeric imines gradually decreased with increasing reaction time, while a new absorption at 978 cm−1, corresponding to phosphonate, increased. After 18 h, the imine absorption practically disappeared, indicating that the imine formation was a fast


16

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process and their reaction with diisopropyl phosphite in the solid state slowly proceeded (Scheme 2), similarly to the reported reaction in solution. The phosphorous immobilization via surface KF-3CR on the PE-PMV was evidenced by solid-state

31P

NMR. In the spectrum shown in Figure 5, a peak attributed to phosphonate was observed at 19.0 ppm, which agrees with the peak at 20.4 ppm observed for the corresponding polymeric phosphonates measured in solution. To further prove that the surface reaction proceeds via the KF-3CR pathway, SEM-EDX measurements of the obtained PE-PAP were carried out to directly detect the elements derived from each of the KF-3CR reactants. Since nitrogen detection via SEM-EDX would be rather difficult because of a severe overlapping with oxygen and carbon bands, p-chloro-aniline was employed instead of p-anisidine. In the SEM-EDX of the p-chloro-aniline tethered PEPAP (PE-PAP4, details are described in the Table 2), the chlorine peak of the amine reactant was detected at around 2.63 eV, Figure 6. In addition, a new phosphorus atom peak was observed at 2.0 eV after the KF-3CR and a small nitrogen peak due to the amine reactant was detected at around 0.4 eV. Thus, the SEM-EDX profile also shows that the phosphite and amine components were successfully integrated through the KF-


17


3CR process. These experimental results demonstrate that the surface KF-3CR proceeded smoothly on the PMV segments to prepare functional materials surfaces.

Absorbance (normalized at 1754 cm-1)

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 18 of 46

phosphonate ester unit

imine C=N aldehyde CHO

18 h

ester C=O

12 h 7h 5h 3h 1h 0h

1800

1600

1400

1200

1000

-1

Wavenumbers (cm ) Figure 4. FTIR spectra of the kinetic experiments for PE-PMV (GD = 136%) with panisidine and diisopropyl phosphite.


18

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MeO PE

n O

OMe

NH2

O

H

O P OiPr

PE

OiPr

n O

1,4-dioxane

O

H O

OMe O i O Pr P i O Pr NH

MeO MeO

PE NH2

n O

OMe H

O

Very fast

O P OiPr OiPr Slow

N MeO

Scheme 2. Representation of the solid-state KF-3CR mechanism.

80

60

40

20

0

-20

-40

Chemical shift (ppm)

Figure 5. Solid-state

31P

NMR spectrum of PE-PAP with a GD = 136% and recovery

ratio of 92%.


19


PE-PAP

P Cl

Intensity

PE-PAP

Intensity

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 46

PE-PMV

PE-PMV

PE PE

0

1

2

3

4

5

6

7

8

1.5

Energy (keV)

2

2.5

3

Energy (keV)

Figure 6. SEM-EDX spectra of the PE fabric, PE-PMV (GD = 136%), and the corresponding p-chloro-aniline tethered PE-PAP after KF-3CR with p-chloro-aniline and diisopropyl phosphite in the solid state (left). Magnified 1.5-3 keV region (right).

Influence of the GD on the solid-state KF-3CR Although the KF-3CR of PE-PMV smoothly proceeded on the PE surface, the aim of this work is to fabricate functional fabrics. Along with the KF-3CR reactivity, the physical structure of the fabric is an important factor. The SEM image of the PE-PAP with a GD = 136% showed obvious cracks in the PE fiber structure with an average diameter of 34±4 m. Since the grafted PAP segment features bulky α-amino phosphonate


20

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monomeric units, and thus a larger volume than the starting PMV polymer, the PE-PAP fabric could not maintain the network structure. Since such cracks in fabrics were assumed to be induced by the increased volume of the graft polymer, tuning the amount of graft polymers (the GD) was expected to suppress them. Therefore, the surface KF3CR was carried out using PE-PMV with different GDs as follows. p-Anisidine, diisopropyl phosphite and PE-PMV were mixed in 1,4-dioxane at 80 °C for 24 h. The PE-PMV GDs ranged from 30 to 160%, as summarized in Table 1. Regardless of the GD values, the gravimetrically determined recovery ratios were very high (>90%, Table 1). Furthermore, the ATR-FTIR shows that the aldehyde conversions were practically quantitative (>95%). SEM measurements demonstrate that the structure of the PE-PAP fabric with a GD = 90% maintained the surface network, whereas the PE-PAP with a GD = 136% showed obvious cracks in the structure (Figure 7). These results clearly indicate that fine-tuning of the GDs provides functional fabrics without physical defects such as cracking of the fibrous structures.


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Page 22 of 46

Table 1. KF-3CR of PE-PMV with different of GDs using p-anisidine and diisopropyl phosphite

Recovery Entry

GD (%)

Amine

Phosphite ratio (%)a

(%)b

1

30

quantitative

>95

2

46

98

>95

3

57

96

>95

97

>95

MeO

4

a

Conversion

78

NH2

H

O P OiPr i

O Pr

5

90

97

>95

6

136

92

>95

7

160

94

>95

Determined by gravimetry according to equation (2).

b

Determined from the

consumption of aldehyde and imine by ATR-FTIR.


22

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Figure 7. SEM micrographs of PE-PAP 1 (a) GD = 136% and (b) GD = 90% synthesized via surface KF-3CR with p-anisidine and diisopropyl phosphite.

Generality of the KF-3CR in the solid state As the surface KF-3CR of PE-PMV smoothly proceeded in the solid state, a library synthesis of functional PE fabrics was conducted with a range of amines and phosphites. Table 2 summarizes the generality of the reaction. The surface KF-3CR of PE-PMV with a range of aromatic amines and phosphites afforded high recovery ratios (>85%) and practically perfect aldehyde consumption regardless of the reactant structures. Contrastingly, the KF-3CR of PE-PMV with hexylamine and diisopropyl phosphite yielded a low recovery ratio of 51% (PE-PAP 7). The ATR-FTIR spectrum of PE-PAP 7 showed that the CHO group was almost consumed; however, the generated


23


Page 24 of 46

imine groups remained even after 24 h. This is an agreement with a previous report, in which the KF-3CR of poly(4-vinyl benzaldehyde) with 1-hexylamine and diisopropyl phosphite resulted in a moderate conversion (~ 60%). Nevertheless, the surface KF3CR of PE-PMV proved to be an efficient surface modification procedure with a green advantage due to the vanillin-based PMV.

Table 2. Library synthesis of PE-PAP from PE-PMV via KF-3CR

GD Amine

Phosphite

136

NH2

MeO

94

H

H NH2

O P OiPr i

Conv.

Td

Wt800 °C

ratio (%)a

(%)b

(°C)

(%)

Product

(%) MeO

Recovery

PE-PAP1

92

>95

196

23.0

PE-PAP2

94

>95

202

18.6

O Pr O P OMe OMe


24

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MeO

102

NH2

H

Cl

102

NH2

H

I

101

NH2

H

F3CO

117

102

a

NH2

H

NH2

H

O P OBu

PE-PAP3

82

>95

186

16.0

PE-PAP4

95

>95

214

16.5

PE-PAP5

94

>95

219

17.2

PE-PAP6

94

>95

214

15.5

PE-PAP7

51

70c

188

11.1

OBu O P OiPr i

O Pr O P OiPr OiPr

O P OiPr i

O Pr

O P OiPr i

O Pr



c

b

Determined from the

The aldehyde was perfectly

consumed and the conversion was roughly estimated by the remaining imine group in the ATR-FTIR spectra.

Since PE fabrics featuring polymeric α-amino phosphonate esters were expected to show unique thermal properties due to heteroatom integrations, the TG/DTA properties of PE-PAP were analyzed (Figure 8) and are summarized in Table 2. As expected from previous investigations on PMV thermal properties, the residual amount of PE-PAPs at


25


800 °C (Wt800

°C)

was higher than that of the starting PE-PMV, whereas all PE-PAPs

showed fairly low decomposition initiation temperatures likely due to the P-O bonding cleavage.45 This increase in Wt800

°C

shows that the phosphorus and nitrogen atoms

enhanced the thermal resistant abilities of the PE-PAPs. Therefore, the experimental data demonstrates that the combination of the radiation-induced graft polymerization of MV and the surface KF-3CR would be an advantageous synthetic method that allows surface decoration with otherwise synthetically difficult α-amino phosphonate esters.

100 80

Weight (%)

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 26 of 46

60 40

PE PE-PMV PE-PAP1 PE-PAP2 PE-PAP3 PE-PAP4 PE-PAP5 PE-PAP6 PE-PAP7

20 0

100 200 300 400 500 600 700 800

Temperature (°C)


26

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Figure 8. TGA curves for the starting PE fabric, PE-PMV with GD=136%, and PE-PAPs 1-7 (numbers correspond to those in Table 2) measured at a heating rate of 10 °C/min under nitrogen.

Proof-of-concept fabrication of biomass-derived MCR-ready organic hybrids The main objective of this study is to fabricate biomass-sourced organic hybrids featuring MCR-ready reactivity with cellulose as the substrate and polymers bearing lignin-model compounds as surface modifiers. For this, it was successfully demonstrated that a bio-derived monomer of MV is compatible with the graft polymerization technique. Moreover, the PMV-decorated PE was allowed to react with amines and phosphites under KF-3CR conditions. Finally, the PE substrate was exchanged with cellulose fabric to experimentally demonstrate the feasibility of the proposed materials. Using graft polymerization conditions similar to those of the PE fabric, the graft polymerization of MV onto cellulose fabric was first carried out in 1,4-dioxane. However, there was no MV conversion. After optimizing the conditions, the graft polymerization


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with pre-irradiated cellulose fabric (20 and 50 kGy), proceeded at 60 °C for 5 h in methanol, yielding poly(methacrylated vanillin)-grafted cellulose (Cell-PMV) with GDs of 57% and 71%, respectively (Table 3). Since cellulose fabrics feature hydrophilic surfaces, this solvent dependency might be owing to enhanced monomer diffusion in a polar solvent of MeOH as compared to the non-polar solvent of 1,4-dioxane. The progress of the radiation-induced graft polymerization of MV onto cellulose was also confirmed by ATR-FTIR similarly to the PE fabric. The characteristic ester and CHO adsorptions of the PMV were observed at 1753 and 1692 cm−1, respectively, in the spectrum of the Cell-PMV with a GD of 57% (Figure 9). Next, KF-3CR was conducted for Cell-PMV (GD = 57%) with p-anisidine and diisopropyl phosphite in a manner similar to PE-PMV. The CHO adsorption at 1692 cm−1 completely disappeared while the ester band remained intact after the reaction (Figure 9). Although the peaks of phosphonate esters largely overlap with that of cellulose, the strong phosphonate ester peak appeared at around 979 cm−1. These results indicate that the KF-3CR of Cell-PMV with

p-anisidine and diisopropyl phosphite underwent practically quantitatively even in the solid state. Furthermore, solid-state

31P

NMR spectrum of the Cell-PAP showed the


28

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peak attributed to α-amino phosphonate unit at 19 ppm. However, unlike the PE fabrics, a penetration of the remaining phosphite residues was preliminarily implied by a peak at around 5 ppm (Figure S1). This might be owing to the high polarity and hydrophilicity of the cellulose surface due to the presence of numerous hydroxyl groups, which could result in a compatibility with polar phosphonate esters. Nevertheless, solid-state

31P

NMR of the Cell-PAP further supported that the KF-3CR of Cell-PMV with p-anisidine and diisopropyl phosphite underwent in an essentially similar to that on the PE-PMV. Along with the

31P

NMR measurement, a new phosphorus atom peak was observed at

2.0 eV in the SEM-EDX spectrum of Cell-PAP after the KF-3CR with Cell-PMV with a GD of 57%, p-anisidine and diisopropyl phosphite in the same manner to the case for PE fabrics (Figure S2). In addition to the successful surface KF-3CR on Cell-PMV, the fabric structure is also an important factor. Therefore, the SEM images of the cellulose fabric and Cell-PMV before and after the surface modifications were obtained. The starting cellulose fabric featured a fiber structure with an average diameter of 9±2 m (Figure 10). After the graft polymerization of MV, the obtained Cell-PMV fabric maintained a fairly intact fiber structure with an increased average fiber diameter of


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14±3 m. Finally, after the KF-3CR process, the fiber structure was still intact and the average fiber diameter increased to 20±4 m with no detectable damages to the cellulose fabric (Figure 10). Along with the analytical data for the KF-3CR on cellulose fabrics, the TG/DTA property of Cell-PAP was analyzed. As expected from the thermal property of PE-PAP, the residual amount of Cell-PAP at 800 °C (Wt800

°C)

was higher

than that of the starting Cell-PMV with a GD of 57% and cellulose (Figure S3). Last but not least, the surface property of Cell-PAP was characterized by the wettability measurements. As a result, cellulose fabric showed the water uptake of 111% and thus the hydrophilic material surfaces. In a contrast, the water uptake of Cell-PAP significantly decreased to 14% even with the low GD of 14%. In a combination of the results obtained in the Table 2, the obtained result should lead to a fine-tuning of the material properties via potential diversity oriented polymer synthesis based on the KF3CR, which indeed takes advantage of the nature of KF-3CR as a MCR. Overall, it was demonstrated that biomass-derived and MCR-ready organic hybrids can be successfully prepared by radiation-induced graft polymerization of potentially ligninsourced MV.


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phosphonate ester unit ester C=O

Absorbance

Page 31 of 46

Cell-PAP

Cell-PMV aldehyde C=O

Cell

2400

2000

1600

1200

800 -1

Wavenumbers (cm )

Figure 9. ATR-FTIR spectra of the cellulose fabric, Cell-PMV with a GD = 57%, and the corresponding Cell-PAP after KF-3CR with p-anisidine and diisopropyl phosphite.


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Table 3. Radiation-induced graft polymerization of MV from cellulose fabric and solidstate KF-3CRa,b

Dose

GD

Recovery

Entry

a

Amine

Conv.

Phosphite

(kGy)

(%)

ratio (%)c

(%)d

1

5

14

92

>95

2

10

33

83

>95

72

>95

70

>95

3

20

57

4

50

71

MeO

H

NH2

Graft polymerization was conducted for 5 h.

b

O P OiPr OiPr

The KF-3CR was performed for 24 h.


d

c

Determined from the



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Figure 10. SEM micrographs of (a) cellulose fabric, (b) Cell-PMV with a GD = 57%, and (c) the corresponding Cell-PAP after solid-state KF-3CR with p-anisidine and diisopropyl phosphite.

Conclusions In this study, a bio-sourced vinyl monomer (MV) was found to be compatible with the radiation-induced graft polymerization technique to immobilize PMV segments on fabric materials, such as PE and cellulose, without damaging the fabrics structure. In addition, PMV-grafted fabrics, PE-PMV, and Cell-PMV, were successfully subjected to KF-3CR with aromatic amines and phosphites, affording the corresponding polymeric α-amino phosphonate esters integrated fabric materials. Through this process, wood biomasssourced cellulose and lignin could be artificially re-combined to produce MCR-ready cellulose fabrics that allow the insertion of multiple functional units. The results lay the basis for the preparation of functional fabric materials sourced from wood biomass compounds.


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Supporting Information Supporting Information is available free of charge on the ACS Publications website. Solid-state

31P

NMR, SEM-EDX and TG/DTA results for the Cell-PAP were

depicted in the supporting information.

Corresponding Author *T. Hamada. E-mail: [email protected]

*R. Kakuchi. E-mail: [email protected].

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Funding Sources


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R.K. gratefully acknowledges the Leading Initiative for Excellent Young Researchers (LEADER) for financial support.

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TOC

Sweet reunion of the wood biomass sourced two components of cellulose and lignin.


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Multicomponent-Reaction-Ready Biomass-Sourced Organic Hybrids

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