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2, 5-Furandicarboxylic acid and Itaconic acid Derived Fully Biobased Unsaturated Polyesters and their Cross-linked Networks Jinyue Dai, Songqi Ma, Na Teng, Xinyan Dai, Xiaobin Shen, Sheng Wang, Xiaoqing Liu, and Jin Zhu Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b00049 • Publication Date (Web): 22 Feb 2017 Downloaded from http://pubs.acs.org on February 26, 2017

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Industrial & Engineering Chemistry Research

2, 5-Furandicarboxylic acid and Itaconic acid Derived Fully Biobased Unsaturated Polyesters and their Cross-linked Networks

†‡

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Jinyue Dai, , Songqi Ma,*, Na Teng, Xinyan Dai, Xiaobin Shen, , Sheng Wang, , Xiaoqing †

Liu, *, Jin Zhu

†

†

Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, P.R.China ‡

University of Chinese Academy of Sciences, Beijing 100049, China

*Corresponding

author：E-mail: [email protected] (Songqi Ma); [email protected] (Xiaoqing Liu)

ABSTRACT: A range of fully bio-based unsaturated polyesters (bio-UPs) derived from 2, 5-furandicarboxylic (FDCA), itaconic acid (IA), succinic acid (SA), and 1, 3propanediol (PD) were obtained via the direct polycondensation. The chemical structures of the bio-UPs were identified by FT-IR and 1H-NMR before they were cured together with a bio-based, non-volatile reactive diluent-guaiacol methacrylate (GM). The thermal and mechanical characterizations of the cured bio-UPs were evaluated using thermogravimetric analysis (TGA), 3-point bending tests, and dynamic mechanical analysis (DMA). Results showed that the thermal properties, flexural strength and modulus of the cured bio-UPs were greatly improved after introducing FDCA. The temperature of 5% thermal weight loss (Td5%) reached up to 330 °C, and the flexural strength and modulus reached up to 122.8 MPa and 3521 MPa, respectively. These results indicate that the bio-UPs have potential to replace the petroleum-based UPs.

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1. INTRODUCTION Over the past few years, along with the increasing concern about environmental protection and continuous consumption of fossil oil reserves, exploring and utilizing the renewable resource has received much attention by both academia and industry around the world.

1-5

As the majorities of polymeric materials are derived from fossil

resources accounting for about 7% of crude oil and natural gas annual consumption in the world, using bio-based resources to synthesize novel polymers is important both from ecological and sustainability considerations. 6 Unsaturated polyester (UP) has wide applications in transportation, construction, aerospace, marine, and auto industries because of excellent thermal, mechanical, and corrosion resistant performances, and has a growing global market forecast to reach USD 10.48 billion in 2019. 7 Commercially available UPs are currently obtained from petroleum-based monomers (e.g. phthalic acids, phthalic fumaric acid and maleic anhydrides, and glycols). In recent years, increasing attention has been captured to explore various bio-based monomers for developing bio-based UPs.

8-11

Plant oils

primarily consisting of unsaturated triglycerides are potential alternatives due to their similar structures to UPs. Acrylated epoxidized soybean oil (AESO) is one of the most common used and commercially available plant oil-based UP analogs. However, their thermal and mechanical properties were not satisfactory because of the flexible long aliphatic chains of AESO, as a result, over 50 % non-renewable rigid monomers, like styrene, 12-13 acrylate, 14 and divinylbenzene, 15-16 were often used together with AESO. In recent years, a great deal of bio-based compounds from sucrose,


17

betulin,

18

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isosorbide, 19 tannic acid, 20 and myrcene 21 and galic acid, 22 etc. have also been utilized to enhance performance of AESO-based polymers. At the same time, for the purpose of preparing higher performance bio-UPs, growing bio-based dicarboxylic acids and dialcohols 23-27 have been exploited directly to be as the substitutes for the petroleumbased monomers for synthesizing bio-based UPs in recent decades. As an example, Sadler et al.

23

reported several bio-based UPs synthesized from isosorbide, maleic

anhydride and other diacids, and the polymers exhibited good thermodynamic properties with Tg of 53～107 °C and storage modulus of 430-1650 MPa. Rorrer et al. 27

prepared bio-based UPs from muconic acid, succinic acid and 1, 4-butanediol via

bulk polycondensation, and bio-based fiberglass panel with excellent properties was achieved after loading woven fiber glass mat followed by chemical cross-linking. Itaconic acid is one of the top 12 value added bio-based platform chemicals reported by the U.S. Department of Energy, 28 and it has similar structure (two carboxyl groups and one exo-double bond) to maleic acid and maleic anhydride. Thus, as a probable substitute for maleic acid or maleic anhydride, itaconic acid has been employed to prepare bio-based UPs.

29-33

In our previous works,

34-36

a range of fully

bio-based UPs were synthesized successfully based on itaconic acid and other bio-based diols, and the resulting polymers showed high performance due to the compact chemical structure of itaconic acid. However, compared with the commonly used UPs, the thermodynamic properties of previous reported bio-UPs still need to be improved further due to the lack of rigid structure. 2, 5-Furandicarboxylic acid (FDCA), which can be derived from sugars or polysaccharides via oxidizing hydroxymethylfurfural



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(HMF), 37-38 is a potential platform chemical in the synthesis of bio-based polyesters with excellent properties. For example, poly (ethylene 2, 5-furandicarboxylate) (PEF) exhibited better barrier properties to carbon dioxide and oxygen permeability in addition to the comparable or even better thermomechanical properties relative to poly (ethylene terephthalate) (PET).

39-41

Although FDCA-based UPs have been seldom

studied so far, previous work has demonstrated that FDCA-based UPs could achieve comparable thermal and mechanical performances with petroleum-based ones. 26 In this work, a range of fully bio-based UPs were prepared based on itaconic acid, 2, 5-furandicarboxylic acid, succinic acid and 1, 3-propanediol via melt polycondensation for the first time. As far as we know, almost all the UPs have extremely high viscosities that reactive diluent-styrene-which is identified as volatile organic compounds (VOCs) and hazardous air pollutants (HAPs)

42

is utilized together to achieve indispensable

processability. Thus, in this paper, guaiacol methacrylate (GM) from softwood lignin 43-44

as the green and non-volatile reactive diluent was cured together with the

synthesized bio-UPs. The relationships between chemical structures and mechanical, thermo-mechanical and thermal properties were investigated. The aim of this work is to develop a potential cured-UP with superior performance and high bio-based content via a facile and eco-friendly approach.

2. EXPERIMENTAL SECTION 2.1. Materials. 2, 5-Furandicarboxylic acid (FDCA) was bought from Sichuan Dagaote Technology Co., Ltd, China. Itaconic acid (IA) was supplied by Zhejiang Guoguang Biochemistry Co., Ltd, China. 1, 3-Propandiol (PD), succinic acid (SA),


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dichloromethane (DCM), guaiacol, methacryloyl chloride, dibutyltin dilaurate (DBTDL),

triethylamine,

4-methoxyphenol

(MEHQ),

p-toluenesulfonic

acid

monohydrate and tert-Butyl peroxybenzoate (TBPT) were purchased from Aladdin Reagent, China. All of the chemicals were used as received. Guaiacol methacrylate (GM) (Scheme 1) was synthesized from methacrylic anhydride esterified guaiacol as reported previously. 43-44

Scheme 1. The chemical structure of guaiacol methacrylate (GM) 2.2 Characterization. The 1H-NMR characterization was conducted on a 400MHz AVANCE III Bruker NMR spectrometer (Bruker, Switzerland) using chloroform-d as a solvent. The FT-IR spectra determination was carried out on a NICOLET 6700 FT-IR (NICOLET, America). Gel contents of the cured bio-UPs were measured by extracting the samples in acetone (the polymer could swell in acetone). 0.5 g of specimens were cut from the cured bio-UPs and extracted with acetone for 48 h by a Soxhlet extractor, then they were dried at 60 °C in a vacuum oven for 24 hours. According to the weight difference of the samples before and after extraction, gel contents were calculated. To achieve high accuracy, the data of all the gel contents in this work were obtained by averaging three repeated samples. Gel permeation chromatography (GPC, HLC-8320, Tosoh Corporation, Japan) was applied to measure the number-average molecular



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weight and polydispersity index of the bio-UPs. Monodisperse polystyrene was used as the standard sample, and THF was used as the mobile phase at a flow rate of 1 mL/min. Mettler-Toledo MET DSC (METTLER TOLEDO, Switzerland) was utilized to monitor the non-isothermal curing reaction under nitrogen atmosphere at a heating rate of 10 °C/min. Flexural properties were conducted on a Instron 5569A Universal Mechanical Testing Machine with a three-point bending mode at a speed of 1 mm/min, and each data was calculated by averaging the results of the five repeated samples. Dynamic mechanical analysis (DMA) was conducted on a Mettler-Toledo DMA/SDTA861e coupled under a tension mode. All the specimens with sizes of 70 mm ×10 mm ×3 mm were measured from 0 °C to 200 °C at a heating rate of 3 °C/min and a frequency of 1 Hz. Thermogravimetric analysis (TGA) was conducted on a Mettler-Toledo TGA/DSC1 Thermogravimetric Analyzer (METTLER TOLEDO, Switzerland) was used to determine the thermal stability of the cured bio-UPs with highly pure nitrogen or air as purge gas at a scanning rate of 20 °C/min from 50 °C to 600 °C. 5～10 mg of each sample was utilized. 2.3. Preparation of the fully bio-UPs. Table 1 presents the specific formulations of bio-UPs. Herein, p-toluenesulfonic acid monohydrate (0.5 mol% relative to diacid) and MEHQ (0.5 wt.% relative to the total weight of mixtures) were used as the prepolymerization catalyst and the free radical polymerization inhibitor, respectively. The mixtures of IA, PD, SA, FDCA, catalyst and inhibitor were placed in a four-necked flask with a reflux condenser, a thermometer, a mechanical stirrer, and a nitrogen inlet. After pre-polymerizing at 140 °C for 2 h, DBTDL (0.5 wt.% relative to the total weight


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of reactants) as the polycondensation catalyst was introduced. The reaction proceeded at 160 °C under the vacuum of 0.09-0.095 MPa for 5 h, and then the systems were cooled down and discharged prior to storing at a dry environment. The bio-UPs at room temperature were light yellow and viscous liquids. Scheme 2 presents the synthetic route. Table 1. Feed compositions, synthetic conditions and Mn of the bio-UPs

a

Bio-UPs

IA/FDCA / PD/ SA (molar ratio)

Prepoly.

Polycondensation

Mna (g/mol)

PPI PPIF5 PPIF10 PPIF15 PPIF20 PPIF25 PPIF15S20 PPIF15S40 PPIF15S60

1/0/1.2/0 0.95/0.05/1.2/0 0.9/0.1/1.2/0 0.85/0.15/1.2/0 0.8/0.2/1.2/0 0.75/0.25/1.2/0 0.65/0.15/1.2/0.2 0.45/0.15/1.2/0.4 0.25/0.15/1.2/0.6

2 2 2 2 2 2 2 2 2

5 5 5 5 5 5 5 5 5

1.1 ×103 0.9 ×103 1.1 ×103 1.0 ×103 1.1 ×103 1.0 ×103 1.1×103 1.2×103 1.1×103

Reaction time (h)

Number-average molecular weight

Scheme 2. Synthesis of the fully bio-based UPs (bio-UPs)



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2.4. Preparation of the cured bio-UPs. A predetermined content of bio-UPs, GM (shown in Table 2) and TBPT (2 wt.% of the total weight of bio-UPs and GM) were placed in a 100 mL bottle. After being stirred and degassed under vacuum, the mixtures were poured into a preheated stainless mold coated with mold release agent. The curing reaction was carried out at 80 °C for 2 h, 120 °C for 2 h, and 160 °C for 3 h based on the previously demonstrated conditions for curing itaconic acid-based UPs.

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Cured

samples were carefully taken out from the mold after being cooled down.

Table 2. Feed compositions, bio-based content and gel content for different cured bio-UPs Weight ratio (%) sample cured-PPI cured-PPIF5 cured-PPIF10 cured-PPIF15 cured-PPIF20 cured-PPIF25 cured-PPIF15S20 cured-PPIF15S40 cured-PPIF15S60

UP

GM

Bio-based content (wt.%)

60 60 60 60 60 60 60 60 60

40 40 40 40 40 40 40 40 40

85.6 85.6 85.6 85.6 85.6 85.6 85.6 85.6 85.6

Bio-UP PPI PPIF5 PPIF10 PPIF15 PPIF20 PPIF25 PPIF15S20 PPIF15S40 PPIF15S60

Gel content (wt.%) 99.7 99.7 99.0 98.3 98.0 97.9 98.5 95.9 93.1

3. RESULTS AND DISCUSSION 3.1. Preparation and characterization of the bio-UPs. In the present work, the bio-UPs were synthesized from diacids and diols via the direct melt polycondensation with negligible VOC emission. Meanwhile, it should be pointed out that all monomers in this study came from renewable resources.

10

So far, some international standards

have been established for determining the bio-based content in order to standardize the


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development of bio-based polymeric materials. The concept of bio-based content is referred to as “the amount of bio-based carbon in the material or product as a percent of the weight (mass) of the total organic carbon in the product” by United States Department of Agriculture (USDA).

45

The bio-based content of the synthesized bio-

UPs in our study reached 100% because all of the monomers used can be from biomass. The bio-based content of the cured bio-UPs was also calculated and summarized in Table 2. All the cured bio-UPs exhibited a high bio-based content of 85.6%. Therefore, the synthesis procedure of UPs and final cured-UPs kept in line with the rules of Green Chemistry. The chemical compositions and structures of the bio-UPs were confirmed by FT-IR and 1H-NMR. The FT-IR spectra of the bio-UPs (PPI/ PPIF5/PPIF15S20) shown in Figure 1 are quite similar to each other. The broad adsorption peak at around 3540 cm1

corresponds to the -OH stretching. The peak at 1732 and the peaks at 817 and 1639

cm-1 are attributed to the C=O stretching of ester units and the C=CH2 stretching vibration of itaconic acid unit, respectively. The spectra of the bio-UPs (except PPI) also display characteristic C-H stretching (3122 cm-1) and C=C skeletal-in-plane vibration (1582 cm-1and 767 cm-1) peaks of furan unit. 46 The spectra of the others bioUPs are shown in supporting information (Figure S1). The structures of bio-UPs could be confirmed preliminary from the aforementioned FT-IR results. 1H NMR spectra are given to further confirm the chemical structures as shown in Figure 2. As shown, all of the peaks match well the protons of bio-UPs. The compositions of the bio-UPs were calculated from the integral area of different protons in the bio-UPs’ 1H NMR spectra.



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The results summarized in Table 3 showed that the final molar ratios of different monomer segments of all the bio-UPs were consistent with the molar ratios of the feed monomers. All the results demonstrate that the target compounds were successfully synthesized. As can be seen Table 1, all the synthesized bio-UPs presents similar number-average molecular weight (Mn) ranged from 0.9 × 103 to 1.2 × 103 g/mol.

Figure 1. FT-IR spectra of PPI, PPIF5, PPIF15S20


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Figure 2. NMR spectra of the bio-UPs

Table 3. The relative molar ratios of the monomers in the feed and in the bio-UPs, characterized by 1H NMR sample

IA/FDCA / PD/ SA Molar ratiofeed(%)

IA/FDCA / PD/ SA Molar ratioNMR(%)

PPI PPIF5 PPIF10 PPIF15 PPIF20 PPIF25 PPIF15S20 PPIF15S40 PPIF15S60

45.5/0/54.5/0 43.2/2.3/54.5/0 40.9/4.6/54.5/0 38.7/6.8/54.5/0 36.4/9.1/54.5/0 34.1/11.4/54.5/0 29.6/6.8/54.5/9.1 20.5/6.8/54.5/18.2 11.4/6.8/54.5/27.3

44.2/0/55.8/0 44.1/2.5/53.4/0 41.9/4.6/53.5/0 37.2/6.9/55.9/0 34.6/7.8/57.6/0 33.9/11.4/54.7/0 26.8/6.0/53.6/13.6 20.4/6.6/54.1/18.9 10.8/6.5/55.0/27.7



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3.2. The gel content of the cured bio-UPs. The gel content is one of the critical indicators for evaluating the performance of the cured bio-UPs. As seen in Table 2, all of the cured bio-UPs presented high gel content ranged from 93.1 wt.% to 99.7 wt.%, which suggests that a high degree of cross-linking has occurred. The cured bio-UPs showed decreased gel content with the increase of furan content, which was owing to the decreased cross-link density of the cured bio-UPs after introducing furan unit. 3.3. The flexural properties of the cured bio-UPs. The flexural stress-strain curves of the cured bio-UPs are illustrated in Figure 3 and their corresponding data are included in Table 4. Obviously in Figure 3a, the stress of the cured bio-UPs (from cured-PPI to cured-PPIF25) virtually increased linearly with strain to the peak value without yield, implying the nature of brittle fracture. 47 Moreover, in the Figure 3b, the increasing content of succinic acid (SA) in the UPs significantly altered fracture behavior of the cured bio-UPs. The stress increased linearly first, then yielded and presented a peak value. Afterwards, the stress began to decrease with the strain, and broke in the end. This is a remarkable feature of toughness fracture.

47

As shown in

Table 4, the flexural strength of the cured bio-UPs (from cured-PPI to cured-PPIF25) reveal a slightly increasing tendency from 116.8 MPa to 122.8 MPa with the increase of FDCA content up to 15 mol%, thereafter the flexural strength demonstrate a reducing trend as FDCA content increased. Meanwhile, the flexural strength of the other cured bio-UPs (from cured-PPIF15 to cured-PPIF15S60) exist decreasing trend from 122.8 MPa to 41.9 MPa along with the increase of the SA content.


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Especially, the cured-PPIF15S60 was not suitable for flexural strength test as it was too soft to be tested. These results demonstrate that materials with varied performance could be easily obtained by adjusting the molar ratio of monomers (FDCA or SA).

Figure 3. Flexural stress-strain curves of the cured bio-UPs

Table 4 Flexural and thermal properties of the cured bio-UPs

Cured-URs cured-PPI cured-PPIF5 cured-PPIF10 cured-PPIF15 cured-PPIF20 cured-PPIF25 cured-PPIF15S20 cured-PPIF15S40 cured-PPIF15S60 a

Flexural strength,

b

σa (MPa)

Eb (MPa)

εc (%)

Tgd (oC)

E’e (MP a)

116.8±7.1 122.3±3.7 122.7±5.2 122.8±2.0 114.7±9.3 116.8±3.1 103.1±9.8 41.9±0.8 /

2714±18 2765±32 2825±21 2935±19 3365±34 3521±15 2460±9 955±10 /

5.5±0.7 4.8±0.3 6.1±0.8 4.9±0.1 4.1±0.6 3.8+0.1 5.9±0.3 24.3±3.1 /

141.7 125.8 119.0 127.6 125.4 121.1 117.1 83.9 73.5

1850 2213 2239 2391 2685 2841 1452 527 175

Flexural modulus,

d

νef/103 (mol m−3)

5.84 4.95 4.91 4.24 2.83 2.65 2.82 0.89 0.11

Td5% (oC)

R600 (%)

299 310 319 330 323 318 311 305 299

5.0 5.7 6.4 8.6 8.1 9.0 6.3 6.1 4.0

Glass transition temperature by DMA, cStrain at break

(%), e Storage modulus at 25 °C, f Cross-link density.

3.4. Dynamic mechanical analysis of the cured bio-UPs. Figure 4 presents the DMA curves of the changes of storage modulus and tan δ with temperature for the cured bio-UPs, the values of modulus at 25 °C and glass transition temperature (Tg) are listed



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in Table 4. The Tgs of the cured bio-UPs were determined from the peak temperatures of the temperature dependent curves of tan δ shown in Figure 4a and Figure 4b. The Tg of cross-linked polymer is mainly dependent on its chain segment’s chemical structure and cross-link density.48 It can be seen that all the cured bio-UPs displayed Tgs ranging from 73.5 oC to 141.7 oC, covering most applications’ requirement. The cured-PPI exhibited the highest Tg (147.1 oC) because of the higher cross-link density (Table 3) induced by higher functionality of C=C bond than other cured bio-UPs. Meanwhile, it’s quite clear that Tg declined after the introduction of FCDA in bio-UPs. This is because the introduction of FDCA decreased the number of C=C bonds of the bio-UPs, resulting in the decreased cross-link density for the cured bio-UPs. More interestingly, the Tg of the cured bio-UPs (from cured-PPIF5 to cured-PPIF25) did not further decrease with the FDCA content increasing. This is due to the fact that furan ring of FDCA made great contribution to the rigidity and intermolecular force of molecular chains, and then decreased the mobility of chain segment of the cured bio-UPs. 49 In other cured bio-UPs

(from

cured-PPIF15

to

cured-PPIF15S60),

the

Tg

reduced linearly with increasing the SA content. As shown in Figure 4c and Figure 4d, it is quite clear that the storage modulus (25 o

C) of the cured bio-UPs (from cured-PPI to cured-PPIF25) increased as the FDCA

content increased, which is due to the increased stiffness of the cured bio-UPs after introducing FCDA. And, in other cured bio-UPs (from cured-PPIF15 to curedPPIF15S60), the storage modulus (25 oC) reduced sharply with the increase of SA content. This is due to the reason that the introduction of SA decreased the number of


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C=C bonds of the bio-UPs, resulting in the decreased cross-link density for the cured bio-UPs. The following equation is employed to calculate the cross-link density (νe) of the cured bio-UPs: 35 ve 

E' 3RT

(1)

where E’ is the elastic modulus of the cured bio-UPs in its rubbery plateau region (E’ at the temperature of Tg+40 K at which all the cured bio-UPs were in a rubbery state was selected in this work), T is the absolute temperature and R is the universal gas constant. The calculated cross-link density for the cured bio-UPs is summarized in Table 4. As shown, the cross-link density of the cured bio-UPs (from cured-PPI to cured-PPIF25) was decreased with the addition of FDCA. Meanwhile, for the other cured bio-UPs (from cured-PPIF15S20 to cured-PPIF15S60), the increasing SA content also led to the further reduced cross-link density. The cause of this phenomenon was that FDCA or SA introduction decreased the number of C=C bonds of the bio-UPs, generating the cured bio-UPs with decreased cross-linking density.



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Figure 4. DMA curves of the cured bio-UPs 3.4. Thermal properties of the cured bio-UPs. TGA was carried out for measuring thermal stability and degradation behaviors of the cured bio-UPs under N2 atmosphere. Figure 5 and Table 4 show the non-isothermal TGA curves and the data of the cured bio-UPs The degradation temperature for 5% weight loss (Td5%) and the residue at 600 ºC (R600) were regarded as the indicators to appraise the thermal stabilities of the cured bio-UPs. All the samples showed high thermal stability with Td5% of above 299 ºC. It can be also seen that the cured bio-UPs (from cured-PPIF5 to cured-PPIF15S40 ) containing furan unit are more thermally stable in comparison with the cured-PPI (without furan unit), confirming that the introduction of FDCA well strengthened the thermal stability of these cured bio-UPs, which is in agreement with the previously reported work. 50


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Figure 5. TGA curves of the cured bio-UPs under N2 atmosphere

4. CONCLUSIONS A series of fully bio-based UPs (bio-UPs) were successfully synthesized from renewable monomers (itaconic acid, 2, 5-furandicarboxylic, succinic acid and 1, 3propanediol) via direct polycondensation. Together with a bio-based, non-volatile reactive diluent GM, the cured bio-UPs with high bio-based content were achieved. Meanwhile, the cured bio-UPs exhibited high and varied thermal and mechanical properties. They are thermally stable up to 330 °C, and have Tg of 73.5-141.7 °C and flexural strength of 41.9-116.8 MPa. These properties are comparable or even better than those of petroleum-based UPs. 51-54 Thus, these bio-UPs showed great potential to be as green alternatives to the fossil-derived UPs.

NOTES The authors declare no competing financial interest. *Corresponding authors: [email protected] (Songqi Ma); [email protected] (Xiaoqing Liu)



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ACKNOWLEDGMENTS The authors are grateful for the financial support from National Natural Science Foundation of China (Grant No. 51473180, 51373194), National Key Technology Support Program (2015BAD15B08) and Youth Innovation Promotion Association of the Chinese Academy of Sciences (Grant No. 2012229). ASSOCIATED CONTENT Supporting Information FT-IR spectra of bio-based UPs (PPIF10, PPIF15, PPIF20, PPIF25, PPIF15S40, PPIF15S60). REFERENCES (1) Corma, A.; Iborra, S.; Velty, A., Chemical routes for the transformation of biomass into chemicals. Chem. Rev. 2007, 107, 2411-2502. (2) Takami, S.; Okuda, K.; Man, X.; Umetsu, M.; Ohara, S.; Adschiri, T., Kinetic Study on the Selective Production of 2-(Hydroxybenzyl)-4-methylphenol from Organosolv Lignin in a Mixture of Supercritical Water and p-Cresol. Ind. Eng. Chem. Res. 2012, 51, 4804-4808. (3) Kupiainen, L.; Ahola, J.; Tanskanen, J., Comparison of formic and sulfuric acids as a glucose decomposition catalyst. Ind. Eng. Chem. Res. 2010, 49, 8444-8449. (4) Williams, C. K.; Hillmyer, M. A., Polymers from renewable resources: a perspective for a special issue of polymer reviews. Polym. Rev. 2008, 48, 1-10.


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