TP CH KHOA HC V CNG NGH

Tp 46, s 5, 2008

Tr. 43-48

TNG HP V NGHIN CU VT LIU HP TH DU T B

MA
PHN 2. NGHIN CU CU TRC V TNH CHT NHIT CA MT
S DN XUT A-X-TAT XENLULOZ T B MA
PHM TNG SN, BCH THANH

1. M U
Hin nay, vt liu hp th du ch yu c ch to t cc loi polyme hu c tng hp,
khng b phn hu sinh hc nh PP, PE, PU, polyeste, polyamit, sau khi s dng li gy ra s
nhim mi trng th cp nghim trng[3]. gii quyt vn ny, ngi ta tp trung
nghin cu v pht trin l vt liu hp th du mi, thn thin vi mi trng v b phn hu
sinh hc t cc sn phm v ph thi nng nghip nh rm r, b ma...[2 - 9].
Trong cng trnh trc, chng ti trnh by mt s kt qu nghin cu mt s yu t nh
hng ln ng a-x-tyl ho xenluloz t b ma ph thi vi tc nhn a-x-tyl ho l anhydrit ax-tic v xc tc l N-bromosuccinimide (NBS). xc nh cc iu kin tt nht ca phn
ng ny l: nhit phn ng khong 110-120oC; thi gian phn ng khong 6 - 7 gi; hm
lng ca xc tc NBS nm trong khong t 1,25 g n 1,50 g trong 100 ml anhydrit a-x-tic.
Vi cc iu kin trn, c th tng hp c cc dn xut a-x-tat xenluloz khc nhau t b
ma ph thi vi mc a-x-tyl ho (DAc) thay i t 0,18 n 2,92 [10].
Trong bi bo ny, chng ti tip tc trnh by mt s kt qu nghin cu cu trc v tnh
cht chu nhit ca ca mt s dn xut a-x-tat xenluloz t b ma bng phng php ph
hng ngoi FTIR v phng php thay i trng lng theo nhit TGA.
2. PHN THC NGHIM
2.1. Tng hp cc dn xut a-x- tat xenluloz t b ma ph thi vi anhydrit a-x-tc v
xc tc N-bromosuccinimide (NBS)
Cho 10 g b ma th c loi b lignin, hemixenluloz, cc hp cht phenol,
pectin phn trn vo bnh thu tinh 4 c dung tch 500 ml c trang b sinh hn hi lu,
my khuy t, nhit k thu ngn 200oC v ng dn kh ni-t (N2). Cho 300 ml anhydrit a-x-tc
v mt lng xc tc NBS vi nng l 1 g/100 ml anhydrit a-x-tc. Phn ng c tin hnh
nhit khong 110oC v ko di trong thi gian khong 6 - 7 gi. Sau hn hp phn ng
c h xung nhit phng, c lc loi xenluloz t b ma th cha phn ng v sau
c kt ta trong metanol. Sn phm kt ta l cc dn xut a-x-tat xenluloz th c lm
sch bng phng php chit Soxhlet vi cn etanol loi b xc tc v anhydrit a-x-tc d.
Sau cng, sn phm a-x-tat xenluloz sch c sy trong t sy chn khng 50oC 60oC
n trng lng khng i.
2.2. Cc phng php nghin cu
43

Nghin cu phn ng a-x-tyl ho v dn xut a-x-tat xenluloz bng phng php ph

FTIR. Cc iu kin o: nghin nh mu, p vin to mng KBr v chp trn my Nexus
670-FTIR- Nicolet trong vng t 500 cm-1 n 4.000 cm-1.
Nghin cu kh nng chu nhit ca cc mu ca xenluloz t b ma trc phn ng v
cc dn xut a-x-tat xenluloz bng phng php phn tch s thay i trng lng theo nhit
TGA trn my (Thermogravimetric Analysis). Cc mu c chp trn my TGA (Shimadzu
TA50, Japan) vi cc iu kin o: trong kh ni-t, vn tc nng nhit l 10oC/pht trong
khong nhit t nhit phng n 700oC.
3. KT QU V THO LUN
Hnh 1 trnh by ph hng ngoi FTIR ca xenluloz b ma trc khi phn ng v Hnh 2
l ph hng ngoi FTIR dn xut a-x-tat xenluloz vi DAc ~2,92. Ta thy c tt c cc di
hp th quan trng nht c trng cho xenluloz ban u nh 3000-3500, 2844, 2.723, 1662,
1447, 1373, 1085, 836 cm-1. Vng hp th kh rng 3300 - 3500 c trng cho dao ng ho tr
ca lin kt O-H trong cc nhm hydroxyl. Thng thng, di hp th c trng cho dao ng
ho tr ca lin kt O-H nm vng 3400 - 3500 cm-1 v kh hp, song do c s to cu hydro
ni v ngoi phn t xenluloz nn di hp th b m rng. nh hp th 2844, 2723 cm-1
c trng cho dao ng ho tr ca lin kt C-H trong cc nhm metylen (CH2) v metin (CH).
nh 1662 cm-1 lin quan n cc dao ng ca nc b xenluloz hp th. nh hp th
1447 cm-1 lin quan n dao ng ho tr ca lin kt -C-O-C- trong kt glycosidic -(14) v
nh hp th 836 cm-1 tng ng vi s dao ng bt i xng ca C1-H trong kt glycosidic
-(14).

Hnh 1. Ph hng ngoi FTIR ca xenluloz b ma trc khi phn ng

Trong ph hng ngoi FTIR (Hnh 8) ca dn xut a-x-tat xenluloz vi DAc ~2,92 ta
cng nhn thy c tt c cc di hp th quan trng nht c trng cho cu trc n v mt xch
l anhydro--D glucopyranoz (vit tt l AGU) ca phn t xenluloz ban u nh 3400 3500, 2844, 2723, 1662, 1447, 1373, 1085, 836 cm-1. Tuy nhin y, ta d dng nhn thy
rng, vng hp th c trng cho dao ng ho tr ca lin kt O-H trong cc nhm hydroxyl
(OH) khng rng nh trong hnh 6 (vng 3300 - 3500 cm-1) m hp li rt nhiu (3400 - 3500
44

cm-1). iu chng t cc nhm hydroxyl (OH) trong phn t xenluloz phn ng vi

anhydrit a-x-tic to thnh cc dn xut a-x-tat, ph v cc cu hydro. c bit, s xut hin
ca mt nh hp th mi vi cng mnh 1731 cm-1 c trng cho dao ng ho tr ca
lin kt (C=O) ca nhm este (a-x-tat xenluloz), chng minh rng, phn ng gia cc
nhm hydroxyl (OH) trong phn t xenluloz vi anhydrit a-x-tic xy ra dn n s to
thnh lin kt este este trong phn t a-x-tat xenluloz.
Trong ph hng ngoi FTIR (hnh 2) ca dn xut a-x-tat xenluloz vi DAc ~2,92 (mu
M36 trong bng 4), khng thy xut hin ca cc di hp th 1840, 1760 v 1700 cm-1 [14],
c trng cho anhydrit a-x-tic cha phn ng v a-xt a-x-tic, sn phm ph ca phn ng a-x-tyl
ho xenluloz b ma (S 3). iu ny cng chng t a-x-tat xenluloz, sn phm chnh ca
phn ng a-x-tyl ho xenluloz b ma, c lm sch hon ton t cc sn phm ph.

Hnh 2. Ph hng ngoi FTIR dn xut a-x-tat xenluloz vi DAc ~2,92

Cc tnh cht nhit ca xenluloz b ma trc khi phn ng v ca dn xut a-x-tat

xenluloz cng c nghin cu bng phng php phn tch s thay i trng lng theo
nhit TGA. Hnh 3 l gin TGA ca xenluloz b ma trc khi phn ng. Hnh 4 l gin
TGA ca dn xut a-x-tat xenluloz vi DAc ~0,97. Cn hnh 5 l gin TGA ca dn
xut a-x-tat xenluloz vi DAc ~2,92.T gin TGA ca xenluloz b ma trc khi phn
ng (hnh 3) ta thy rng xenluloz b ma trc khi phn ng bt u phn hu khong 250
255oC; nhit m xenluloz b ma trc khi phn ng mt 50% trng lng l khong
371oC. Dn xut a-x-tat xenluloz vi DAc ~0,97 li bt u phn hu khong nhit thp
hn, khong di 200oC ( thp hn ti 55-600C) (hnh 4) v nhit m mu a-x-tat
xenluloz vi DAc ~2,92 mt 50% trng lng cng thp hn, khong 367oC (thp hn khong
3-40C).
45

a)

b)

Hnh 3. Gin TGA ca xenluloz b ma trc khi phn ng(a) v ca dn xut

a-x-tat xenluloz vi DAc ~0,97(b)

Hnh 3. Gin TGA ca dn xut a-x-tat xenluloz vi DAc ~2,92

46

iu l th l khi dn xut a-x-tat xenluloz c gi tr DAc cao hn, ~2,92 (mu M36
trong bng 4) th khong nhit bt u phn hu li thp hn rt nhiu khong trn di
200oC (thp hn ti 55 60oC) (hnh 4) v nhit m mu a-x-tat xenluloz vi DAc
~2,92 mt 50% trng lng cng thp hn rt nhiu, khong 358oC (thp hn khong 13oC) so
vi xenluloz b ma trc khi phn ng. Ni mt cch khc, cc dn xut a-x-tat xenluloz c
gi tr DAc cng cao th kh nng chu nhit cng thp. Tt c nhng quan st trn cho thy,
xenluloz b ma trc khi phn ng c kh nng chu nhit cao hn so vi cc dn xut a-x-tat
xenluloz. Kh nng chu nhit thp hn ca cc dn xut a-x-tat xenluloz so vi kh nng
chu nhit xenluloz b ma trc khi phn ng lin quan cht ch n s hnh thnh cc lin kt
cu hydro ni v ngoi phn t xenluloz.
4. KT LUN
nghin cu phn ng a-x-tyl ho xenluloz b ma vi anhydrit a-x-tic bng bng
ph hng ngoi (FTIR). Cc tnh cht nhit ca xenluloz b ma trc khi phn ng v ca dn
xut a-x-tat xenluloz cng c nghin cu bng phng php phn tch s thay i trng
lng theo nhit ( TGA). Cc kt qu nghin cu khng nh rng, phn ng gia cc
nhm hydroxyl trong phn t xenluloz vi anhydrit a-x-tic xy ra, to thnh cc dn xut ax-tat, ph v cc cu hydro lm thay i v c bn tnh cht chu nhit ca vt liu, trong
cc dn xut a-x-tat xenluloz c gi tr DAc cng cao th kh nng chu nhit cng thp.
TI LIU THAM KHO
1.

T. Lim, X. Huang - Evaluation of kapok (Ceiba pentandra(L.) Gaertn.) as a natural hollow

hydrophobic-oleophilic fibrous sorbent for oil spill cleanup, Chemosphere 66 (5) (2007)
955-963.

2.

T. R. Annunciado, T. H. D. Sydenstricker, S. C. Amico - Experimental investigation of

various vegetablle fibres as sorbent materials for oil spills, Marine Pollution Bulletin 50
(2005) 1340-1346.

3.

C. Teas, S. Kalligeros, F. Zanikos, S. Stournas, E. Lois, and G. Anastopoulos Investigation of the effectiveness of absorbent materials in oil spills cleanup, Desalination
140 (3) (2001) 259-264.

4.

X. F. Sun, R. C. Sun, J. X. Sun - Acetylation of sugarcane bagasse using NBS as a catalyst

under mild reaction cobditions for the production of oil sorption-active materials,
Bioresource Technology 95 (2004) 343-350.

5.

G. R. Fiho, S. F. da Cruz, D. Pasquini, D. A. Cerqueira, V. de S. Prado, R. M. Nascimento

de Assuncao - Water flux through cellulose triacetate films produced from heterogeneous
acetylation of sugar cane bagasse, J. Mem. Sci. 177 (2000) 225-231.

6.

M. O. Adebajo, R. L. Frost - Acetylation of raw cotton for oil spill cleanup application: an
FTIR and 13C MAS NMR spectroscopic investigation, Spectrochimica Acta, Part A60
(2004) 2315-2321.

7.

H. El-Saied, A. H. Basta, B. N. Barsoum, M. M. Elberry - Cellulose membranes for

reverse osmosis, Part 1.RO cellulose acetate membranes including a composite with
polypropylene, Desalination 159 (2003) 171-181.

47

8.

B. Karimi, H. Seradj - N-bromosuccinimide (NBS), a novel and highly effective catalyst

for acetylation of alcohols under mild reaction conditions, Synlett 4 (2001) 510-519.

9.

G. R. Filho, R. M. N. Assuncao, J. G. Vieira, C. S. Meireles, D. A. Cerqueira, H. S.

Barud, S. J. L. Ribeiro, Y. Messaddeq - Characterization of methylcellulose produced
from sugar cane bagasse cellulose: Crystallinity and thermal properties, Polymer
Degradation and Stability 20 (2006) 1-6

10. Phm Tng Sn, Bch Thanh - Tng hp v nghin cu vt liu hp th du t b ma.
Phn 1: Nghin cu mt s iu kin phn ng a-x-tyl ho xenluloz t b ma, Tp ch
Khoa hc v Cng ngh 46 (4) (2008) 99-105.
SUMMARY
PREPARATION AND CHARACTERIZATION OF OIL ABSORBENTS FROM
SUGARCANE BAGASSE CELLULOSE
PART 2. STUDY ON THE STRUCTURE AND THERMAL PROPERTIES OF
CELLULOSE ACETATES DERIVED FROM SUGARCANE BAGASSE
CELLULOSE
The acetylation reaction between sugarcane bagasse cellulose and acetic anhydride using
N-bromosuccinimide as a catalyst was investigated by Infrared Spectroscopy (FTIR). The
thermal properties of the cellulose acetates obtained were characterized by Thermal Gravimetric
Analysis (TGA). The analytical data showed that the acetylation reaction between sugarcane
bagasse cellulose and acetic anhydride took place, and that the higher the degree of acetylation
the cellulose acetates have the lower the thermal stability they exhibit.

a ch:
Vin Ho hc, Vin Khoa hc v Cng ngh Vit Nam.

48

Nhn bi ngy 15 thng 8 nm 2007