IRRADIATION GRAFTING OF HYDROPHYLIC MONOMER

ONTO CHITIN FOR ION EXCHANGE APPLICATION

Gatot Trimulyadi Rekso

Center for Research and Development of Isotopes and Radiation Technology

Jl . Lebakbulus raya No 49, Jakarta 12240, INDONESIA Fax 62 21 7691607, E-Mail : Gatot2811@yahoo.com

INTRODUCTION

INDONESIA DEVELOPING COUNTRY

INDUSTRIAL DEVELOPMENT

BESIDE PRODUCT

ENVIRONMENTAL PROBLEM

LIQIID WASTE WITH THE HEAVY METAL CONTENT IN THE LARGE SCALE OF PRODUCTION CAN BE

HAZARDOUS TO ENVIRONMENTAL

ION EXCHANGE ADSORBENT CHEAP SIMPLE

USEFFULL IN WASTE TREATMENT

The natural chelating marine polymer chitin, poly(N-acetyl-D-glucosamine) and its deacetylated derivative chitosan is useful for removing heavy metal ion waste from discharge water .

Chitin , the most abundant naturally is undoubtedly one of

the most promising and attracting resources present in quantity. Among some interesting properties of chitin , chelating ability arising from its characteristic structure is especially noteworthy. Many researchers have explored the feasibility of this approach. Kurita.K et.,all, conducted experiments with a number of heavy metals

Shell seafood waste such as shrimps shell and craps are abundantly in Inonesia

Shrimps shell Craps shell

The remarkable rapid and successful expansion of shrimps processing industry in Indonesia suggests the possibility of utilizing shrimps-processing waste as raw material for the manufacture of many valuable products such as chitin and chitosan for industrial and health care product

Indonesian shrimps production in 2006 had been projected 350.000 tons

SHRIMPS SHELL

DEPROTEINATION

DEMINERALIZATION

CHITIN

NaOH, 1M

HCl, 1M

WASTE

WASTE

Organic Fertilizer

Chitosan

The adsorption behavior of chitin and its concerns with various degree of deacetylization. This high adsorption capacity was ascribable primarily to its remarkable hydrophilicity in cooperation with the relatively high amino

group content. It is indicate that the importance of hydrophlicity and suggest that, in order to develop adsorbents of high capacity, it is make

indicate the importance of hydrophilicity essential to make chitin derivatives highly hydrophylic and yet insoluble in water.

In this present study, the purpose of the experiments is to study graft-copolyimerization reactions as well as to study the absorption properties as ion exchange of grafted chitin.

Hydrophilic monomers such as acrylic acid will be employed for these experiments. The functional group of graft –copolymers is

expected to be useful in the attaching test of metal ions.

PolysaccharidesPolysaccharidesChitin/Chitosan, Chitin/Chitosan,

and their derivativesand their derivatives

PolysaccharidesPolysaccharidesChitin/Chitosan, Chitin/Chitosan,

and their derivativesand their derivatives

DegradationDegradationIrradiation

・ Solid stateDilute aq. solution

CrosslinkingCrosslinkingPaste-like condition

Irradiation

Carboxymethylchitin

Carboxymethylchitosan

ApplicationsIn Agriculture, Industry, Food, Medicine, Cosmetic

Fields

MODIFICATION OF CHITIN AND CHITOSAN BY IRRADIATION TECHNIQUE

Pencangkokan/ graftingPencangkokan/ grafting

WHY RADIATION TECHNOLOGY IS IMPORTANT?HealthEnvironmentSafetyNew materials

Address all aspects of Millennium Project !!!

HIGH QUALITY MATERIALS

CrosslinkingGraftingDegradation

Electron Beam Machine Specifications No EPS-300 Type GJ-2 Type

1 Installation year 1984 1994

2 Origin Nissin High Voltage, Japan

Shanghai Xian-Feng Electrical Manufacturing Work, China

3 Type Cockroft-

Walton Dynamitron

4 Max tension 300 kV 2000 kV

5 Max energy 300 keV 2000 keV

6 Max flow 50 mA 10 mA

7 Sample transportation

Konveyor Konveyor

Latex Irradiator, the Control Panel

IRRADIATION GRAFTING

GRAFTING MECHANISM 1.  Initiation Pembentukan radikal akibat radiasi IRADIASI

a. Chit Chit + H

b. Chit + M Chit-H + M

 

2. Propagation M + nM Mn+1

  

3. Terminanation Chit + Mm grafted Mm + Mn+1 Homopolymer

Reaction of graffting acrylic acid onto chitin

..

.

IradiasiPemanasan

O

HO

H

NHCCH3

OO

CH2HO

CH2

O

OH NH

C OCH3

H

O

OO

HO

H

NHCCH3

OO

CH2HO

CH2

O

OH NH

C OCH3H

O

O

O

HO

H

NHCCH3

OO

CH2O

CH2

O

OH NH

C OCH3H

O

O O

HO

H

NHCCH3

OO

CH2O

CH2

O

OH NH

C OCH3

O

O

CH2 CO

OHCH

O

HO

H

NHCCH3

OO

CH2O

CH2

O

OH NH

C OCH3

H

O

OO

HO

H

NHCCH3

OO

CH2O

CH2OH NH

C OCH3

O

O

CH2

CO

OHCH

CH2

CO

OHCH

O

n

n

n

CH2

CO

OHCH

EXPERIMENTAL

Material and Experiment Chitin extracted from prawn shell (Penaeus Monodon), it was got from Muara Karang , North Jakarta. The were initially washed by water and then dried at 800 C overnight and conditioned at room temperature for 24 hr. Acrylic acid monomer, and white crystalline powder, obtained from E Merck, and other chemicals of reagent grade were used without purification.

Radiation Source Gamma radiation source of Co-60, IRKA batch irradiator , with irradiation dose rate about 9,0 kGy/hr was employed in these experiments. This radiation source is located at Pasar Jumat, Center for Application of Isotopes and Radiation Technology, Jakarta, Indonesia.

Grafting reaction

In the present experiment, the pre irradiation graft co polymerization method was employed. In this method a sample of chitin powder of about 500 mg , was put into a glass tube, then irradiated in air atmosphere at room temperature.

A monomer acrylic acid solution was deairated by bubbling with nitrogen gas, then introduced into the pre irradiated sample and the graft polymerization was carried out in a nitrogen atmosphere at certain temperature . The grafted chitin obtained was washed toughly with aquadest and soaked overnight in aquadest, then subjected to sox let extraction with methanol for 8 hours to extract homopolymer. The grafted chitin then was dried in vacuum until they reached a constant weight at 500 C.

The percentage of graft yield was calculated from the difference in weight ;

o Graft yield = ( Wg - Wo ) / Wo x 100 %

Where Wo and Wg are the weight before and after grafting.

Measuring off adsorption of metal ions by chitin and its modified

The experiment was done with chitosan with degree of the deacetylization of 78,5 % and modified chitin were Chitin-g-Aac. Measuring the rate of adsorption about 100 mg of powder material (chitin,chitosan and it’s modifications) equilibrated with 100 ml 0f solutions ( HgSO4 , CuSO4.5 H2O, K2Cr2O7) 0,1 M, at pH 4,0 and stirred for 60 min. The metal ion uptake concentrated after equilibrating were determined by using AAS and for Hg(II) using CV-AAS.

RESULTS AND DISCUSSION

Evidence of grafting : The increase in weight of the extracted grafted sample, as compare with that the original chitin and their FTIR spectra , was used as evidence of grafting.

The FTIR spectra of chitin and grafted chitin are shown in Fig 1. It can be seen that a band around at 1660 cm –1 arises from carbonyl absorption of chitin and anew band appear at 3400 cm -1

which correspond to the hydroxyl absorption of grafted chitin with acrylic acid and at 3500 cm -1 is asymmetric stretching of NH2 for grafted chitin with acrylamide.

FTIR

300240180120600

160

140

120

100

80

60

40

20

0

Reaction time (min)D

egre

e o

f g

raft

ing

(%

)

10 % Acrylamide

20 % Acrylamide

30 % Acrylamide

40 % Acrylamide

6543210

100

80

60

40

20

0

Reaction time (hr)

Pe

cen

tag

e o

f g

raft

ing

(%

)

Acrylic acid 10 %

Acrylic acid 20 %

Acrylic acid 30 %

Acrylic acid 40 %

Effect of monomer concentration and reaction time.

The effect of acrylic acid and acrylamide monomer concentration on the percentage of grafting with reaction period of 1 hr, 2 hr, 3 hr and 4 hr are presented on Figure above.

It can be seen that the percentage of grafting is independent of the monomer concentration

6543210

100

80

60

40

20

0

Time of reaction (hr)

Pe

rce

nta

ge

of

gra

ftin

g (

%)

Temp 50 C

Temp 60 C

Temp 70 C

Temp 80 C

300240180120600

200

160

120

80

40

0

Reaction time (min)

Deg

ree

of

gra

ftin

g

(%)

React. Temp 50 C

React. Temp 60 C

React. Temp 70 C

React. Temp 80 C

Effect of grafting temperature

It is oblivious that the degree of grafting is largely by the reaction temperature. The higher temperature the higher of degree of grafting obtained.

The reason is that the increase in temperature improves the monomer diffusibility as well as the mobility of the monomer.

It is recommended that the optimum reaction for this grafting system is 70 0 C more than that the increasing of degree of grafting is not so much, there is a nearly constant value.

Materials

The capacity of adsorption ( mg / g)

Hg(II) Cr(VI) Cu(II)

Chitin

Chitosan

Chitin-g-Aac

Chitin-g-Aam

Chitosan-g-Aac

Chitosan-g-AAm

92,6

174,5

294,3

257.3

488,9

464,2

30,6

48,4

109,5

94,8

318,5

325,8

24,4

44,2

180,1

154.6

362,8

398,2

The ion exchange adsorption of metals ions by grafted chitin and its derivatives

These results clearly show that chitin modified as chitin grafted acrylic acid have higher capacity of adsorption for ion metal such Hg, Cr, and Cu.

The highest one is for metal ion Hg. The chitin modified

have an excellent adsorption capacity due to the advantageous location of -COOH, -OH and –NH2 group in the molecule of chitosan to form complex formation and functional group of monomer act as ion exchger for ions metal.

Using acryl amide give percentage of grafting higher compare with acrylic acid.

The presence of monomer grafted onto chitin is demonstrated by FTIR spectrum with the appearing of carbonyl functional group.

The optimal condition of monomer acrylic acid or acryl amide concentration was 30 %, temperature 700 C and reaction period of 3 hours.

Chitin grafted with acrylic acid give a higher capacity of adsorption of metal ion Cr, Cu and Hg compare grafted with acryl amide.

The high rate of adsorption is for metal ion Hg it was found 488,9 mg/g for chitosan-g-Aac and 464,2 mg/g for Chitosan-g-Aam.

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