Modification of Pulp Cellulose of Belangke Bamboo (Gigantochloa

pruriens) using [2-(Acryloyloxy)Ethyl] Trimethyl Ammonium

Chloride and Maleic Anhydride

Rina Ridara

, Diana Adnanda Nasution

and Basuki Wirjosentono

Postgraduate Chemistry Study Program, Faculty of Mathematics and Natural Sciences, Universitas Sumatera Utara,

Jl. Bioteknologi No. 1 Kampus USU, Medan, Indonesia

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Sumatera Utara, Jl. Bioteknologi

No. 1, Medan 20155, Indonesia

Keywords: Cellulose, Belangke Bamboo, Modification, Antimicrobial Compound.

Abstract: In this work, pulp cellulose (Cell) was prepared from Belangke bamboo (gigantochloa pruriens) by Craft

delignification process. The AETAC/MA-modified Cellulose (AETAC/MA-g-Cell) was characterised using

infrared spectroscopy (FTIR) for chemical structure, differential scanning calorimetry (DSC) for thermal

properties and scanning electron microscopy (SEM) for morphological images. Results of FTIR spectra of

the AETAC/MA-g-Cell after exhaustive Sokhlet extraction in n-hexane still showed stable absorption peak

of AETAC/MA carbonyl group (>C=O) at 1705 cm

-1

and disappearance of double bond absorption peak af

acryloyl group (>C=C<) at 1630 cm

-1

. These evidences indicated that the AETAC/MA modifiers have

successfully bound into the cellulose, in which hydroxyl groups of the cellulose have esterified with maleic

anhydride and bound with acryloyl groups of AETAC. Further data of DSC analysis of the modified

cellulose showed slightly lower decomposition temperature of 300

C when compared to that of fresh

cellulose of 270-400

C. Whereas SEM images of the modified cellulose also indicated rougher surface

when compared to that of fresh cellulose fibres. The AETAC/MA-modified cellulose then may be utilised

as antimicrobial materials for various cellulose products.

1 INTRODUCTION

Indonesia is a tropical country rich in non-timber

crops that can be used as an alternative raw material

for the pulp and paper industry. One type of non-

timber plant is bamboo. Bamboo is a general term

for members of the wooden grass, the Bambusoideae

subfamily and the Andropogoneae / Poacea family.

Bamboo has several advantages compared to woody

plants that grow fast and can be harvested after 3-5

years of planting, much shorter than needle wood

which takes 10-20 years. In addition, bamboo has

high productivity and can grow in arid soils (My &

Le, 2015). As a non woody plant, bamboo is known

for its long fiber with an average fiber length of

1.90-3.24 (Tian, 2013).

Bamboo is grass, cylindrical in shape which is

mostly hollow (though some species are solid

cylindrical). Bamboo usually has a height of 20-25

meters. Biomass production in the planting season is

around 3-5 months. Bamboo consists of 26-43%

cellulose, 21-31% lignin, and 15-26% hemicellulose.

In theory, the mechanical properties of bamboo

mainly depend on (1) species, (2) age, (3) moisture

content, (4) position along the stem (top or bottom),

and (5) node and segment position. Belangke

bamboo (Gigantochloa pruriens) which is 125

species of bamboo in Indonesia can grow to 10

meters in length with a diameter of 5 cm and a

length of 35 cm. This type of bamboo has been used

by the community for various household, equipment,

construction and handicraft industries. Textile fibers

made from bamboo are still not popular, and even

more than 1500 species of bamboo in the world,

only a few types are processed into textile materials

(Waite, 2009).

However, given its availability, especially in

Indonesia which is abundant, the prospect of

bamboo fiber as a textile material for clothing is

quite promising compared to other natural fibers.

Nowadays, the use of antimicrobial textile materials

has been growing, due to the people's perception of

Ridara, R., Adnanda Nasution, D. and Wirjosentono, B.

Modiﬁcation of Pulp Cellulose of Belangke Bamboo (Gigantochloa pruriens) using [2-(Acryloyloxy)Ethyl] Trimethyl Ammonium Chloride and Maleic Anhydride.

DOI: 10.5220/0008932303050311

In Proceedings of the 1st International Conference on Chemical Science and Technology Innovation (ICOCSTI 2019), pages 305-311

ISBN: 978-989-758-415-2

305

using hygienic and clean textile materials which is

increasing. Textile materials, especially for

underwear, are indeed susceptible to exposure, and

can even be a living medium for microbes, which

cause these textile materials: easy to smell, have

spots, and damage (Kumar, 2011).

Cellulose is one of the most widely dispersed,

renewable, and biodegradable polymers. Cellulose is

a natural polymer that does not dissolve in water due

to long chains and high molecular weight (more than

500,000 Da) (Fathanah, Lubis, Othman, Handayani,

& Karlina, 2017).

Cellulose is the main element of all plant material,

forming about half to one third of all plant tissue and

is constantly formed from photosynthesis (Sun, Sun,

Zhao, & Sun, 2004). This is the main structural

component that provides strength and stability to plant

cell walls which are arranged in microfibrils in cell

walls, interrupted by hemicellulose and surrounded by

a lignin matrix. Depending on the type of plant, most

plant material consists of about 40 - 55% cellulose, 15

- 35% lignin and 25 - 40% hemicellulose. On the cell

wall of natural plants, cellulose crystals are covered

with these substances which makes it difficult to get

pure cellulose. Chemically, cellulose is a naturally

occurring linear polymer of anhydroglucose unit

connected to one and four carbon atoms by β-

glycosidic bonds. It is proven by the presence of three

hydroxyl (OH) groups with different acidity /

reactivity, where secondary OH is located in the C-2,

and C-3 positions, and the primary OH is located in

the C-6 position. This is also verified by the formation

of various strong hydrogen bonds between molecules

and intramolecules (Penjumras, Abdul, Talib, &

Abdan, 2014). In recent years, interest in cellulose-

based materials has increased due to the demand for

renewable resources (Mohanty et al., 2005).

MA grafting into various polymers has been

popular for the past 20 years. Grafted copolymers

can be used as the main component. Various

polymers have been used as backbones for grafting

maleic anhydride. Other types of thermoplastics (PS,

EVA, PES), as well as elastomers (EPDM, EPR,

NR), can also be used as polymers for MA grafting

(Krump, Alexy, & Luyt, 2005).

As is known, 2-acryloyloxyethyl trimethyl

ammonium chloride (AETAC) consists of

quaternary ammonium salt groups and unsaturated

vinyl groups. Vinyl groups can be polymerized and

can react with a variety of vinyl monomers, which in

2016 Shen et al conducted research on poly [(2-

acryloyloxyethyl trimethyl ammonium chloride) -co-

(acrylic acid)] branches onto starch for cotton warp

sizing (Shen, Zhu, & Liu, 2016).

Wool fiber antimicrobial textile material has

been developed using a coating technique with a

bioactive polymer material, [2- (acryloiloxy) ethyl]

trimethylammonium chloride (AETAC).

Antimicrobial properties of wool fiber coated with

bioactive polymers were tested against Gram-

positive and Gram-negative bacteria,

Staphylococcus aureus and Klebsiella pneumoniae.

Furthermore, the surface morphology characteristics

of the fibers were tested using reflected infrared

spectroscopy (ATR-FTIR), electron microscopy

(SEM), tensile strength and contact angle to water

drops. the result is that Q-chitosan-based

antibacterial properties against wool can be

improved by grafting wool fabric with polystyrene

sulphonate (pSS), which shows very good

antibacterial activity against Staphylococcus aureus

and Klebsiella but less good against the fungus

Aspergillus fumigatus. Transplanting a wool fabric

with pSS not only increases the tensile strength of

the fabric but also increases the durability of the

treatment of several washings. pSS-g-wool, Q-

chitosan evenly covers the surface of the treated

fiber and after 5x the washing is still intact.

Therefore this grafting process is commercially

viable for wool fabrics (Hassan, 2015).

The two most common methods used to analyze

thermal properties are thermogravimetric analysis

(TGA) and (DSC). The TGA technique measures the

weight loss and mass change of a substance as a

function of temperature. However, there are several

reactions that can occur without mass loss. In this

case, DSC is able to detect these reactions

(Zakikhani, 2016).

In this research, the surface modification of

cellulose fiber from Belangke bamboo will be

modified with antimicrobial compound (AETAC),

with the help of maleic anhydride (AM) and

ammonium persulfate as comonomer and initiator.

Furthermore, the surface morphology characteristics

of the fibers were tested using reflected infrared

spectroscopy (ATR-FTIR), electron microscopy

(SEM), Thermal Analysis Differential Scanning

Calorimetry (DSC).

2 MATERIALS AND METHODS

2.1 Materials

The material used in this study is 80% solution of 2-

(acryloyloxy)-ethyltrimethylammonium chloride were

purchased from Sigma-Aldrich Chemicals (USA) and

used without any purification, ammonium persulfate

ICOCSTI 2019 - International Conference on Chemical Science and Technology Innovation

306

(NH

)

≥90% from China, maleic anhydride with

weight molecul 98.06 g/mol, acetone and toluene

from Mallinckrodt Chemicals (USA). Belangke

bamboo that is used comes from Pangkalan Brandan,

Sei Lepan Subdistrict, Langkat Regency, North

Sumatra, located on the east coast of the island of

Sumatra, about 60 km north of Binjai City.

2.2 Methods

2.2.1 Preparation of Belangke Bamboo

The bamboo Belangke obtained is washed with

water until clean then dried in the sun to dry then cut

with a grinding cutter until it becomes powder.

2.2.2 Isolation of α-cellulose from Belangke

Bamboo

As much as 75 grams of Belangke Bamboo Powder

then put into a glass beaker and added 1 L mixture

of 3.5% HNO

and 10 mg NaNO

heated on a hot

plate at 90

C for 2 hours. After that filtered and

washed pulp until neutral filtrate. Then added with

750 ml of solution containing 2% of NaOH and 2%

of Na

at 50

C for 1 h then filtered and washed

pulp until neutral filtrate. Then bleaching with 500

ml of 1.75% of NaOCl solution at boiling

temperature for 30 minutes. The pulp is filtered and

washed until neutral filtrate. After that, α-cellulose

was purified from a sample of 500 ml of 17.5%

NaOH solution at 80

C for 0.5 hours then filtered,

washed until neutral filtrate. Continuing bleaching

with 10% H

at 60

C for 15 minutes. Washed and

filtered cellulose to neutral. Oven drying was carried

out for 3 hours at 60

C and stored in a desiccator

(Ohwoavworhua, 2005). Characterization of α-

cellulose produced includes: % yield, chemical-

physical properties analysis, functional groups

(FTIR), morphology (SEM), thermal analysis

(DSC).

2.2.3 Modification of α-cellulose with Maleic

Anhydride

Modification of α-cellulose bamboo belangke with

maleic anhydride was done by reflux for 2 hours

using toluene as a medium. Reaction optimization

was carried out with fixed cellulose levels (100 phr)

with maleic anhydride variations (5, 10, 15, 20 phr).

The toluene solvent was evaporated at 110

then washed with acetone to remove free maleate.

The result of cellulose / AM is dried in an oven at

C until the weight remains, then characterized by

functional group analysis (FTIR).

2.2.4 Modification of Cellulose Fibers

with [2-(Acryloiloxy) Ethyl]

Trimethyl Ammonium Chloride

(AETAC)

Surface modification of Belangke bamboo cellulose

fibers with [2- (acryloyloxy) ethyl]

trimethylammonium chloride (AETAC) 80% was

carried out in the reflux phase modification reactor

and stirring with toluene solvent and the addition of

maleic anhydride (AM) and ammonium persulfate as

comonomers and initiators. Reaction optimization

was carried out by varying the levels of maleic

anhydride and AETAC reagent levels by adding

10% ammonium persulfate from the optimum level

of maleic anhydride. The toluene solvent was taken

back by a vacuum evaporator and the AM-AETAC-

modified cellulose was dried in a 70

C vacuum oven

to a fixed weight. Characterization of α-cellulose

modified with [2- (acryloyloxy) ethyl]

trimethylammonium chloride (AETAC) produced

included: functional groups (FTIR), morphology

(SEM), thermal analysis (DSC).

3 RESULTS AND DISCUSSION

3.1 Isolation of α-cellulose from

Belangke Bamboo

Based on a series of delignification, swelling and

whitening processes that have been carried out in

this study in order to obtain white α-cellulose. At the

isolation stage, α-cellulose is used 75 grams of

belangke bamboo powder and at the end of the

process produces pure α-cellulose of 10.95 grams (as

much as 14.6% of the initial weight of belangke

bamboo used). Figure 1: shows the α-cellulose

results obtained from this study.

Figure 1: α-cellulose powder isolated from bamboo

belangke.

Modiﬁcation of Pulp Cellulose of Belangke Bamboo (Gigantochloa pruriens) using [2-(Acryloyloxy)Ethyl] Trimethyl Ammonium Chloride

and Maleic Anhydride

307

Figure 2: FTIR spectrum of cellulose.

Functional group analysis with FT-IR has been

carried out, for the cellulose spectrum shown from

FT-IR data to provide cellulose support that has an -

OH group with the emergence of vibration peaks at

wave number 3448.72 cm

-1

and supported by peak

absorption at wave numbers 1026.13 cm

-1

which

shows the vibration of the symmetric CO group and

the absorption peak at wave number 1373.32 cm

-1

shows the anti-symmetric CO vibrations. The peak

vibrations at wave number 2900.94 cm

-1

are

stretching C-H vibrations supported by bending C-H

vibrations at wave number 671.23 cm

-1

. The

emergence of the vibration peak at wave number

2368.59 cm

-1

shows the C-C stretching vibration and

is supported by the wave number 894.97 cm

-1

which

shows the C-C bending (Penjumras et al., 2014).

3.2 Modification of Belangke Bamboo

Cellulose α-Maleic Anhydride

In order to optimize the conditions for grafting of

maleic anhydride onto cellulose, we did this by

varying the concentration of monomers. The grafting

mechanism of anhydride groups onto cellulose in the

melt, it has been shown that the grafted polymer

generally contains residual amounts of free

(ungrafted) maleic anhydride as well as free

ungrafted polymaleic anhydride sequences. It has

been shown that the free maleic anhydride can be

removed by vacuum-drying while the free

polymaleic anhydride is removed by washing.

Cellulose grafting with maleic anhydride can be

calculated from the peak FTIR characterization.

Because the absorption coefficient was calculated,

the content of the grafted maleic anhydride onto the

cellulose form can simply be determined by

measuring the FTIR spectra (Krump et al., 2005).

Table 1: Cellulose grafting results with variations in the

concentration of maleic anhydride.

Cellulose

(php)

Maleic anhydride

(php)

100

13.6544

0.0269

0.0775

0.1612

0.1131

From the data in Table 1 it appears that the

optimum conditions for the addition of maleic

anhydride at 15 phr. This shows that the increase in

the degree of grafting caused by the cross-ring

formation of polymers and poly (maleic anhydride)

increases. the degree of grafting begins to decrease

when the concentration of maleic anhydride is more

than 15 phr, this is due to the homopolymerization

that causes maleic anhydride monomers tend to form

a polymer themselves compared to sticking to

cellulose.

Figure 3: FTIR spectrum of α-cellulose with various AM

levels.

From the data in Table 2: it can be seen that the

optimum conditions of adding AETAC to 20 phr are

0.6393, when the addition of AETAC 30 phr to the

condition of grafting decreases. This is because the

number of AETAC additions causes the reaction

between maleic anhydride and cellulose not to the

maximum possibility of maleic anhydride monomers

with less colliding cellulose. Grafting is increased if

maleic anhydride monomers with cellulose and

AETAC collide with each other.

Figure 4 shows the results of grafting between

the optimum conditions of AM-cellulose produced

previously with variations in AETAC levels. Of the

three FTIR results obtained, all three AM-cellulose

have been successfully grafted with AETAC. This

can be seen with the emergence of new peaks at

wavelengths of 1463, 1465 and 1467 cm

-1

which are

the tops of the methyl groups of antimicrobial

compounds (AETAC). But after calculating the

surface area by using the previous formula which

ICOCSTI 2019 - International Conference on Chemical Science and Technology Innovation

308

compares the peak of maleic anhydride with one of

the cellulose peaks, it can be produced that the

optimum condition of cellulose-AM-AETAC

modification is on the addition of 20 php AETAC.

Figure 4: FTIR spectrum of α-cellulose-AM with various

AETAC levels.

3.3 Analysis Results Scanning Electron

Microscope (SEM)

The results of the SEM analysis can provide

information about the shape and change of the

material being tested. In principle, if there is a

change in a material such as fractures, indentations,

and structural changes, the material tends to

experience energy changes. The changed energy can

be emitted, reflected, and absorbed and converted

into electron waves that can be captured and read the

results on SEM photographs.

Figure 5: SEM test results of bamboo cellulose surface

with 100x magnification.

Figure 6: SEM test results of bamboo cellulose surface

with 500x magnification.

Figure 7: SEM test results for MA-AETAC cellulose

grafting with 100x magnification.

Figure 8: SEM test results for MA-AETAC cellulose

grafting with 500x magnification.

Modiﬁcation of Pulp Cellulose of Belangke Bamboo (Gigantochloa pruriens) using [2-(Acryloyloxy)Ethyl] Trimethyl Ammonium Chloride

and Maleic Anhydride

309

The SEM results shown Figure 7: shows that the

structure is uniform, homogeneous and has small

pores which are cellulose structures from bamboo

belangke. Cellulose has an ion -OH bond that can

cause the adsorption process.

Figure 8: shows that the structure of cellulose has

changed due to the addition of maleic anhydride and

aetac. These changes state that the surface of

cellulose has been grafting maleic anhydride and

aetac, there are some areas where clots occur and

enlarged pores.

3.4 Differential Scanning Calorimetry

(DSC) Analysis

DSC analysis is used to study phase transitions, such

as melting, glass transition temperature (Tg) or

exothermic decomposition and to analyze the

stability of oxidation and heat capacity of a material.

A technique used to determine the temperature of a

material transformation by quantifying its heat. The

data generated in the form of a heat flow curve to the

sample minus the heat flow to the reference to time

or temperature.

In thermal analysis, cellulose decomposes at

temperatures between 270oC to 400oC. In this area,

cellulose decomposes into D-glucopyranose

monomers (Yang, 2008). This can also be seen in

Figure 5: which shows that cellulose is degraded at

400oC and also on the DSC results of cellulose

modification with AM-AETAC degradation at

300oC.

Figure 9: DSC analysis of cellulose and cellulose / AM-

AETAC.

4 CONCLUSIONS

Optimization and reaction mechanism of the

modification process and surface characteristics of

cellulose pulp from Belangke bamboo with the help

of maleic anhydride through FTIR test that is found

in the addition of 15 phr maleic anhydride by

calculating the surface area of FTIR which compares

the peak of maleic anhydride with one of the peaks

of cellulose.

Characterization of functional groups (FTIR),

morphology (SEM) and thermal strength (DSC) of

cellulose, cellulose / AM and AM-AETAC cellulose

grafting namely the emergence of new and

characteristic peaks from cellulose and from maleic

anhydride. The change in cellulose morphology to

cellulose grafting AM-AETAC is marked by a

change in the surface structure in the form of pores,

indentations and faults. In thermal analysis, cellulose

decomposes at temperatures between 270

C to

400

C. In this area, cellulose decomposes into D-

glucopyranose monomers. This can be seen from the

endothermic and exothermic reactions that occur.

The FTIR results can be calculated the optimum

conditions from the addition of AETAC, namely by

calculating the surface area of the peak maleic

anhydride with one of the cellulose peaks obtained

the optimum conditions for the addition of AETAC

of 20 phr.

ACKNOWLEDGEMENTS

Authors would like to thank to Ministry of RISTEK-

DIKTI, the Republic of Indonesia for financial

support through DRPM program 2018. Furthermore,

additional support from all those who helped the

completion of this research are gratefully

acknowledged.

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