Open Access Article
Xiaolong Qiaoa,
Hailong Luc,
Hui Caid,
Shuzhen Ni*b and
Xiaofan Zhou
*a
aJiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Jiangsu Provincial Key Lab of Pulp and Paper Science and Technology, College of Light Industry and Food, Nanjing Forestry University, Nanjing, 210037, China. E-mail: zhounjfuacademic@163.com
bState Key Laboratory of Biobased Material and Green Papermaking, Qilu University of Technology, Shandong Academy of Sciences, Jinan, 250353, China. E-mail: nishuzhen@qlu.edu.cn
cInstitute of Chemical Industry of Forest Products, Chinese Academy of Forestry, National Engineering Lab for Biomass Chemical Utilization, Key Lab of Biomass Energy and Material of Jiangsu Province, Nanjing, 210042, China
dSinolight Paper Inspection & Certification CO.,Ltd, Beijing, 100102, China
First published on 18th February 2021
In this study, we prepared chemical staple fibers (CSFs) by plasticizing bleached coniferous pulps (BCPs) with 1-allyl-3-methylimidazolium chloride (AMIMCl) under high temperature and pressure. It became a transparent paper after hot-pressing when the mass ratio of AMIMCl to BCPs was 4
:
5. Interestingly, it could be hot-pressed into a new transparent paper after the transparent paper prepared above was torn into pieces. The morphologies of fibers showed that BCPs could be plasticized with AMIMCl. The glass transition temperature (Tg) occurred in CSFs when the mass ratio of AMIMCl to BCPs was 4
:
5 and the corresponding temperature was 149 °C, which was lower than the initial decomposition temperature, therefore, CSFs could achieve workability to a certain extent. The plasticizing effect of AMIMCl on BCPs was further verified by testing the properties of the paper. The plasticizing effects of 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-ethyl-3-methylimidazolium acetate (EMIMAc) on BCPs showed the universality of the method for preparing CSFs with AMIMCl.
Among the most promising biopolymers, cellulose which consists of β-(1→4)-linked glucose repeating units4 is the most abundant natural polymer and has numerous applications in papermaking, film manufacturing, pharmaceuticals, textile and food industries.5–7 Due to the numerous inter- and intramolecular hydrogen bonds and amphiphilicity of repeat units,8 cellulose can neither dissolve in common solvents nor melt at elevated temperature even above the decomposition temperature, which makes this fantastic material difficult to process.9,10
So far, several solvents have been used for cellulose dissolution and film preparation, including ionic liquids (ILs), N-methylmorpholine-N-oxide, urea/NaOH, and ZnCl2. Among these solvents, ILs were essentially the most promising green solvent because of their negligible vapor pressure, low toxicity, easy recyclability, non-flammability, high chemical and thermal stability.11–14 Known as powerful solvents for cellulose and wood, ILs have been extensively studied for the plasticization of wood cell walls.15,16 Bulk wood samples treated with a small amount of ILs could achieve large deformations under low pressure without cell wall fracture.16 As early as in 2003, Mark P. Scott has regarded ILs as replacements for traditional plasticizers, with the potential to achieve materials that had better thermal stability, and a wider temperature range of flexible plastic behavior.17 As one of the ILs, 1-allyl-3-methylimidazolium chloride (AMIMCl) is a powerful non-derivatizing solvent for cellulose, and a solution containing 14.5 wt% cellulose can be prepared at 80 °Cwithout any pretreatment.18 It was first synthesized in Zhang's group in 2003.19
Cellulose content in cotton is nearly to 100%,20 which is the purest natural cellulose21 and widely used in the textile industry. We plasticized it and prepared chemical fibers successfully in our previous work,22 but it was rarely used in pulp and paper industry due to the price of cotton was higher than bleached coniferous pulps (BCPs). In terms of fiber length, BCPs are shorter than cotton. BCPs which main components are cellulose and a small amount of hemicellulose with the lignin removed in the process of bleaching are widely used in pulp and paper industry.23,24 It has superior quality of brightness, softness and cleanliness in comparison to unbleached pulps.25
In this study, we prepared chemical staple fibers (CSFs) by plasticizing BCPs with AMIMCl in a similar way to plasticize cotton under high temperature and pressure. The purpose of plasticizing was to reduce its melting point before it decomposed and achieved workability to a certain extent. There was no waste liquid in the process as the liquid ratio was small and the mass of AMIMCl was less than BCPs. Application of CSFs prepared by AMIMCl in papermaking was also discussed. Finally, in order to know whether the method of preparing CSFs with AMIMCl was universal, we chose 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-ethyl-3-methylimidazolium acetate (EMIMAc) for a simple experiment.
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5, 2
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5, 3
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5, 4
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5 at room temperature, respectively. Then, the mixture was hot pressed for 1 minute at 160 °C, 2 MPa. It would be a piece of paper after hot-pressing when the mass ratios of AMIMCl to BCPs were 1
:
5, 2
:
5, 3
:
5. This process could only be hot pressed once and couldn't be repeated. However, it would be a piece of transparent paper after hot-pressing when the mass ratio of AMIMCl to BCPs was 4
:
5. Interestingly, it could be hot pressed into a new piece of transparent paper after the piece of transparent paper prepared above was torn to pieces and this process could be repeated several times.
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5 due to the fact that BCPs were plasticized with the addition of AMIMCl gradually under high temperature and pressure.
:
5, 2
:
5, 3
:
5, 4
:
5, respectively. It was evident that the crystalline indices of the CSFs were higher than BCPs. The increase in crystallinity was attributed to the amorphous regions were dissolved by AMIMCl under high temperature and pressure. The more AMIMCl was added, the higher crystallinity was.
C in the molecular structure of AMIMCl. That at 1370 cm−1 showed C–H asymmetric deformations.26 Additionally, absorption peaks caused by C–O were observed near 1100 cm−1, 1050 cm−1 and 990 cm−1, these were typical absorption bands of cellulose.28 The results of FT-IR analysis indicated that no new chemical structures occurred, only initial characteristics were observed in the CSFs, and proved that there was no chemical reaction between AMIMCl and BCPs.
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5, 2
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5, 3
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5, 4
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5.
Fig. 6 presented the derivative thermogravimetric (DTG) curves of the samples. The temperatures corresponding to the maximum decomposition rates of BCPs were 360.17 °C and CSFs were 273.70 °C (AMIMCl to BCPs was 1
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5, w/w), 273.21 °C (2
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5), 273.71 °C (3
:
5), 267.45 °C (4
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5), respectively; although thermal stability of CSFs was lower than BCPs, the temperatures corresponding to the maximum decomposition rates of CSFs were almost the same with the addition of AMIMCl.
In brief, AMIMCl had large effect on the thermal stability of BCPs in the beginning, then, the CSFs were very stable with the addition of AMIMCl.
DSC curves of CSFs were shown in Fig. 7. There were no exothermic peak of BCPs and CSFs when the mass ratios of AMIMCl to BCPs were 1
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5, 2
:
5, 3
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5. However, the exothermic peak occurred when the mass ratio of AMIMCl to BCPs was 4
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5 and the corresponding temperature was 149 °C, which was lower than the initial decomposition temperatures of CSFs in Fig. 5, therefore, CSFs could achieve workability to a certain extent. It was the same to the phenomenon in Fig. 1.
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5, 2
:
5, 3
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5. It would be a new piece of transparent paper after hot-pressing when the mass ratio of AMIMCl to paper was 4
:
5. This was the same as the phenomenon in Fig. 1 and 7, confirming that the paper was indeed plasticized by AMIMCl. For better comparison, unplasticized paper made from BCPs was also hot pressed under the same conditions.
The physical properties of paper and plasticized paper could be seen in Table 1. The grammage of all dried paper was 100 g m−2 and the density was about 0.67 g cm−3. The tensile index increased with the increase of the mass proportion of AMIMCl. The burst index increased continuously from sample 1 to sample 3 and then tended to be stable. The reason for this phenomenon was that the fibers of BCPs were initially bonded by hydrogen bonds. The bonding between fibers was enhanced due to the interaction between the melt formed by melting after BCPs were plasticized into CSFs. AMIMCl had little effect on the tear index, but great effect on the folding strength. The folding strength increased with the increase of the mass proportion of AMIMCl, especially for sample 5, which increased significantly, further indicating the plasticizing effect of AMIMCl on BCPs.
| Sample | AMIMCl : paper (w/w) |
Grammage of dried paper [g m−2] | Density [g cm−3] | Tensile index [N m g−1] | Burst index [kPa·m2 g−1] | Tear index [mN·m2 g−1] | Folding strength |
|---|---|---|---|---|---|---|---|
| 1 | 0 | 100 | 0.63 | 9.044 | 0.40 | 0.22 | 5 |
| 2 | 1 : 5 |
100 | 0.65 | 9.629 | 0.75 | 0.30 | 8 |
| 3 | 2 : 5 |
100 | 0.67 | 12.66 | 1.20 | 0.23 | 29 |
| 4 | 3 : 5 |
100 | 0.71 | 14.25 | 1.20 | 0.25 | 33 |
| 5 | 4 : 5 |
100 | 0.67 | 16.06 | 1.18 | 0.25 | 60 |
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5, which was the best plasticizing mass ratio for AMIMCl. BMIMCl (melting point was 70 °C) was solid at room temperature, so we adopted the method shown in Fig. 9. Both BMIMCl and EMIMAc plasticized BCPs could be hot pressed into a piece of paper and then hot pressed for a second time, which was similar to the effect in Fig. 1. DSC curves of CSFs prepared by BMIMCl and EMIMAc were shown in Fig. 11. Tg was 169 °C and 143 °C respectively with the appearance of exothermic peaks, which was lower than the initial decomposition temperatures in Fig. 10 and directly confirmed that BCPs were plasticized by two ILs. In short, the above results indicated that the preparation method of CSFs was applicable not only to AMIMCl but also to other ILs.
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5 and the corresponding temperature was 149 °C, which was lower than the initial decomposition temperature, therefore, CSFs could achieve workability to a certain extent. The plasticizing effect of AMIMCl on BCPs was further verified by testing the properties of paper. The plasticizing effects of BMIMCl and EMIMAc on BCPs showed the universality of the method of preparing CSFs with AMIMCl.
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