Tổng hợp một số dẫn xuất của xenlulozơ và nghiên cứu khả năng tách loại một số ion kim loại nặng từ nước sinh hoạt đề tài NCKH QGTĐ 08 03

DAI HOC QUOC GIA HA NOI
TRirONG DAI HOC KHOA HOC TlT NHIEN

a
KET QUA THLTC HiEN OE TAI NGHIEN CU'U
KHOA HOC TRONG DIEM CAP DAI HOC QUOC GIA HA NOI

TONG HOP MOT SO DAN XUAT CUA
XENLULOZO VA NGHIEN CUU KHA NANG
TACH LOAI MOT SO ION KIM LOAI NANG TCT
NlTOC SINH HOAT
MA SO: QGTD.08.03

Chu nhiem de tai: PGS. TS. Nguyen Dinh Thanh
Cac can bo tham gia:

ThS. Pham Hong Lan
ThS. Nguyin Thi Thanh Mai
ThS. Hoang Kim Van
Mot so NCS, HVCH va sinh vien Phong Tong hop hOu ca 1
DA! HOC QUOC C - rlA N(J1

i pr/m
HaN6i-2010


BAO CAO TOM TAT
1. Ten 6h tai: TONG HOP MOT SO DAN XUAT CUA XENLULOZO VA NGHIEN
CLTU KHA NANG TACH LOAI MOT SO ION KIM LOAI NANG TLT NLTOC SINH
HOAT
M A S 6 : QGTD.08.03

2- Chu nhiem d^ tai: PGS. TS, Nguyin

Dmh

Thanh

3. Cac can bo tham gia:
PGS. TS. Nguyen Dinh Thanh - Khoa Hoa, tnrang DH KHTN - DHQG Ha ngi
ThS. Pham H6ng Lan- Khoa Hoa, trucmg DH KHTN - DHQG Ha npi
ThS. Nguyen Thi Thanh Mai- Khoa Hoa, truong DH KHTN - DHQG Ha npi
ThS. Hoang Kim Van - Khoa H o i truong DH KHTN - DHQG Ha noi
Mot so NCS- HVCH va sinh vien- Khoa Hoa, truong DH KHTN - DHQG Ha noi
4. M u c tieu va noi dung nghien ciiu
a. Muc tieu
a I. Dua nhom chuc c6 kha nang tao phirc vao phan tu xenluloza bang cac phan img hoa hoc
dac Iruiig cua xenluloza {dupe gpi Id cac phan icng hien tinh xenluloza)^ mot pohme thien
nhicn. de tao ra mot loai vat lieu than thien vcri moi truong, c6 the phan huy sinh lioc sau qua
trinh su dung thuc te. Nguon xenluloza su dung trong de tai la bong hoac hot gidy.
a2. Khao sat kha nang lao phuc va kha nang hap phu (hoa hoc va vat li^j cua cac hop chai
tong hop dugc vai mot so ion kim loai nang (cation Cd"^. Pb"^^ va/hoac Mn""*" va anion AsO^
va AsO;J') nham dua nhung ket qua nhan dugc vao che tao vat lieu hap phu kim loai nang.
a3. Nghien cun kha nang ung dung cac san pham bien doi hoa hoc cua xenluloza vao thuc te
nham tach mot so ion kim loai nang (cation Cd~ , Pb" va/hoac Mn' va anion AsO^" va
AsO^') thuong gap trong nguon nuac an uong va sinh hoat (6 day goi tat la ngudn nirac sinh
hocU).
a4. Xay dung qui trinh che tao cot hap phu dung cac vat lieu xenlulozo bien tinh nay. buoc
dau nghien cuu che tao Ihiet bi loc nuoc trong phong thi nghiem de dat duac ham lugng cac
ion kim loai nang phu hop vai TCVN.
b. Not dung nghien

cuu

b l . Nghien cuu tong hop \'a chuyen hoa mot so dan xuat este va ete cua xenluloza. mot s6
vat lieu xenluloza c6 cau tri'ic mang luoi tren co so dan xuat ete va este cua xenlulozo.
b2. Cau true cua cac hop chat nhan duac se dugc xac nhan bang cac phuong phap vat ly hien
dai (pho hong ngoai, pho cgng huong tu hat nhan proton va cacbon-13. trong lugng phan tu
trung binh dugc xac dinh bang phuong phap sac ki tham ihau gel).
b3. Nghien cuu kha nang tao phuc va hap phu cua dan xuat este va ete cua xenluloza. cua \at
lieu xenlulozo c6 cau true mang luoi tren co so dan xuat ete va este cua xenluloza tong hgp
dugc va kha nang tai sinh cac \ at lieu xenluloza bien tinh nay.


b4. Nghien cuu kha nang ung dung cac san pham bien doi hoa hgc cua xenluloza vao thuc te
nham. tach mot so ion kim loai nang (cation Cd"", Pb^^ va'hoac Mn"* va anion AsOj" \ a
AsO^') thuong gap trong nguon nuac sinh hoat.
b5. Nghien cuu thiet ke thu nghiem thiet bi Igc nuoc tren co so xenlulozo bien tinh.
5. Cac ket qua dat du'O'c
* Ket qua ve khoa hgc va

kithuat

a. Da tong hgp dan xuat clo cua xenluloza bang phan ung cua xenluloza vai POCI3 trong
dung moi DMF va chuyen hoa vai dietanolamin va axit p-aminobenzoic. Kha nang hap phu
cac dan xuat dietanolamin va axit/7-aminobenzoic cua xenluloza vai Pb^' a nong dp 10 " M
da dugc khao sat. Cau true ciia cac san pham dugc xac nhan bang phuong phap pho IR, HNMR va phuong phap kinh hien vi dien tu quet SEM.
b. Da thirc hien phan ung bien tinh xenluloza qua NaCMC vai epiclorohydrin va
etylendiamin vai cac ty le moi cua NaCMC, epiclorohydrin va etylendiamin Ian lugt la
1:1,5:1,5; 1:2:2; 1:3:3 va 1:4:4. Da tien hanh khao sat kha nang hap phii kim loai chi cua dan
xuat
amit

ciia
dietanolamin
ciia
xenluloza
va
dan
xuat
xenlulozo-gepiclorohydrin/etylendiamin o cac nong 6.0 lOOOOppm, 2000ppm. lOOOppm, 600ppm,
400ppm va lOOppm. Be mat ciia dietanolamin/xenlulozo va NaCMC bien tinh voi
epiclorohydrin/etylendiamin voi cac ty le moi khac nhau da dugc xem xet bang phuong phap
Sl:M.
c. Da khao sat anh hirong ciia mot so dieu kien phan ung (ti le moi cac chat phan ung, thai
gian phan ung) den tinh chat hap phu cua xenlulozo bien tinh CMC-g-ECH va CMC-,^ECH/EDA. San pham CMC-g-ECH dugc tong hgp trong dieu kien khuay trpn tot, 0 nhiet do
phong trong 9 gio va ti le moi CMC;ECH=1:3 va san pham CMC-g-ECH/EDA dugc tong
hgp bang each dun hoi luu each thiiy a 55-65°C trong 8 gia voi ti le moi CMC-gECH:EDA=^1:3 deu co kha nang hap phii ion nhat. Kha nang hap phu cua cac san pham
CMC-^^-ECH/EDA va CMC-g-ECH/EDA da dugc khao sat voi cac dung dich Pb"*, Cd'^ va
Mn^^ CO nong dp thay doi trong cac khoang 500 ppm, 1000 ppm, 1500 ppm, 2000 ppm, 2500
ppm, 3000 ppm va nhan thay rang kha nang hap phu cua xenluloza bien tinh \'6i cac ion kim
loai thay doi theo trat tu: Pb"*>Cd"*>Mn"^.
d. Cac mau CMC-o^-MA da dugc tong hgp bang phan ung ciia carboxymethyl cellulose vai
methyl acrylat va dugc chuyen hoa thanh dan xuat amit \'6i dicthanolamin thanh san pham
bien tinh CMC-^i,^-MA/DEA trong cac dieu kien phan iing khac nhau: thai gian phan ung tir 1
gia den 10 gio va ti le CMC-g-MA: DEA thay doi tir 1:6 den 1:12, va da nhan thay rang dieu
kien toi uu cho phan img bien tinh la thai gian phan img 5 gio voi ti ie C\IC-g-MA:
DEA= 1:10. Kha nang hap phu cua cac mau vat lieu xenluloza bien tinh a dieu kien toi uu doi
ximg du'gc khao sat vai cac ion Pb;", Cd""^ va Mn"^ va tuan theo thir tu Pb"%Cd'"--Mn"^
e. Da tong hgp \i\ khao sat tinh chat hap phu ion kim loai Pb"' \"a Cd""' cua xenluloza bien
tmh bang acid citric \'a cho thay rang san pham xenlulozo bien tinh bang acid citric dugc
tong htTp trong dieu kien nhiet 6.0 120°C trong 12 gia va ti le khoi luong xenluloz(r:acid
citric=l:3 co kha nang hap phu Ion nhat. Kha nang hap phu cua san pham da duoc khao sat

citric=l :3 co kha nang hap phu Ion nhat. Kha nang hap phu cua san pham da dugc khao sat
vai cac dung dich Pb ^. Cd ^ co nong dp thay doi \a cho tha\' dung lugng hap phu tang theo
nong dp ion trong dung dich hap phu. Cau true cua cac san pham xenluloza bien tinh da dugc
xac nhan bang pho IR va be mat cua san pham da dugc xem xet bang phuong phap S1:M.
f. Da tong hgp va khao sat tinh chat hap phu cac anion AsO^. AsO;^' cua xenlulozo bien tinh
bang muoi BCDMAB va cho thay rang san pham xenluloza bien tinh dugc tong hgp trong
dieu kien nhiet dp 55°C trong 3,5 gio va ti le khoi lugng xenluloza:BCDMAB=l :1.25 co kha
nang hap phu lan nhat. Kha nang hap phu ciia san pham da dugc khao sat \x7i cac dung dich
arsenat co nong dp thay doi \'a cho thay dung lugng hap phu can bang tang theo nong do ion
AsOJ', AsO^'trong dung dich hap phu. Cau triic cua cac san pham xenlulozo bien tinh da
dugc xac nhan bang pho IR va be mat cua san pham da dugc xem xet bang phuong phap
SEM.
g. Da khao sat cac dieu kien hap phu tinh va kha nang giai hap cac ion Pb~'. Cd~'. Mn^' cua
xenlulozo bien tinh bang axit citric vai cac ion Pb~*. Cd"" va Mn"". Ket qua nhan dugc nhu
sau: pIIioiLRi "" 6 doi \ a i Pb~\ pHtoi im = 5 doi voi Cd"". pHio, ^ru = 6.6 doi \oi Mn^*; Thoi gian
can bang: 80 phiit \ai ion Pb"'. 60 phiil \xVi ion Cd"" \ a 30 phiit \6i ion Mn"': Dung lugng
hap phu tinh: 500 mg/g \'ai Pb"'. 476 mg/g \'ai ion Cd"" \a 227.3 mg/g \ a i ion Mn"'. Kha
nang giai hap cac ion Pb"\ Cd"*, Mir' ciia xenlulozo citrat: Voi ion Pb"* m,, = 200 f.ig thi
hieu suat giai hap la 87.6%; Vai ion Cd"' lUo = 250 ),ig thi hicu sual giai hap la 77.5%; Voi
ion Mn"' m,, = 250 f,ig thi hieu suat giai hap la 56.0%.
h. Da khao sal cac dieu kien hap phu tinh va kha nang giai hap cac anion AsO-^"\a AsOj .
Ket qua nhan dugc nhu sau: pi li.-,, uu = 2 doi \'ai AsO;'- AsO;]"; Thai gian dat can bang hap
phu: 45 phiit doi \'ai AsO^". 60 phiit doi \-ai AsO_j"; Dung lugng hap phu tinh: 3-85mg.g \6i
AsO; ; 227.55 mg/g voi AsO;;". Kha nang giai hap cac anion AsO;"\a AsO^" cua xenluloza
bien tinh: voi AsO;' a lUp ^ 500 |ig thi hieu suat giai hap la 61.6%; AsO^" \'ai o m,, = 500 (.ig
thi hieu suat giai hap la 74.7**o.
i. Da nhan thay rang xenlulozo bien tinh (tir bong) \ a i axit citric va BCDMAB thich hgp hon
ca de lam \at lieu hap phu cac cation P b ' \ Cd"^. Mn"' \'a anion AsOj". AsO^'tuong irng.

* Ket qua ling dung thirc te
Vai lieu hap phu ion kim loai nang (Pb"". Cd"". Mn"" va AsO: . AsO;^") lii' bone
(xcnlulo/o) bien tinh bang axil citric va muoi BCDMAB tuong iing.
* Ket quii ddo tao
- Si) cu nhan dugc dao tao trong khuon kho cua dc tai: Gdp pluhi ddo lao 02 cu- n/u'in.
1. .\gu\vn Vict Dung
2. Do Thanh Turen
- So thac SI dirge dao lao Irong khuon kho cua dc tai: (jdpphan ddo lao 04 ihac \i
1. Trinh Thi Hd
2. Le Thi Thiiv Hdii
iii


3. Hd Lam Nhung
4. Luu Nhu Quynh
- So NCS dugc dao tao trong khuon kho ciia de tai; Gap phan ddo too 04 NCS ve ede van de
CO lien quan cua de tdi (ve hod hoc cachohidrcU).
1. NCS Pham Hong Lan
(da bao ve cap co so)
2. NCS Nguyen Thi Thanh Mai
(da bao \'e cap co so)
3. NCS Hoang Kim Van
(dang thuc hien luan an)
4. NCS Le The Hoai
(dang thuc hien luan an)
\ Trong nam hpc 2009-2010: 04 sinh vien NCKH. 04 sinh vien khoa luan. 04 HVCIl
khoa 2008-2010.
* Ket qua cong bo
Da dang dugc 04 bai bao a Tctp ehi Hod hoe vd Ung dijng. 02 bai bao o' 'Tap chi Hod
hoc. 03 bao cao khoa hpc o Proceedings of 13'^ International Electronic Conference on

Synthetic Organic Chemistry (ECSOC-13) 11/2009.
1. Nguyen Dinh Thanh. Luu Nhu Quynh. Nguyen Thi Thu Huong. Xenlulozo' bien tinh
bang (N-bulyLN-cloropropyl-N.N-dimelyl)amonium bromua \a kha nang hap phu
ascn cua no. Tap ehi Llod hoe vd Ung dung. No. 19. tr. 30-34 (2009).
2. Nguyen Dinh Thanh, Ha Lam Nhung, Nguyen Thi Ciic. long hgp cellulose bien linh
bang acid citric va sir hap phu ion kim loai nang cua n6. Tcip ehi Hod hoe vd I 'ng
dung. No. 17(101). 33-37(2009).
3. Nguyen Dinh Thanh. Le fhi Thuy Ilau, Study on modified reaction of sodium
carbox\ lmcth>i cellulose with methyl acrylale. Tap ehi Hod hoe. 1.47. N.4A. 228-233
(2009).
4. Nguvcn Dinh Thanh. Trinh Thj I la. Nghien ciru long hgp \'a linh chal cua xenlulozo'
bien linh voi epiclorohydrin va etylendiamin. Tap ehi Hod hoc. T. 47. N.2A. pp.543549 (2009).
5. NguycMi Dinh Thanh. Nguyen Viet Dung. Mot so dan xual cua xenluloza \6'i
dietanolamin \a et\ lendiamin. Tap ehi Hod hoe & [ 'ng dung. No. I I (95). pp. 39-42
(2009).
6. Ngu>cn Dinh 'Thanh. Do Thanh Tuyen. Dan xuat clo cua xenluloza. 7'ap chi Tlod hoe
c^ Ung dung. No. 10 (94). pp. 40-43 (2009).
7. Nguyen Dinh Thanh. Do Thanh Tuyen. Some Dcrivati\cs of Cellulose with
Dietanolamin and Ethylendiamine. 7/'^ International Eleelonie Conference on
Synthetic Organic Chemistty (LX'SOC-13). 1-30 November 2009. F002.
8. Nguyen Dinh Thanh. Ha Lam Nhung. Cellulose modified with citric acid and its
absorption of Pb"" and Cd"' ion. / i " International Eleelonie Conference on Synlhelie
(hganieChemisiry(l-CS()C-}3).
1-30 November 2009. F003.
9. Ngu\cn
Dinh
Thanh.
Luu
Nhu
Quynh.

(N-butyl-N-chloroprop\l-N.Ndimelh\i)aminonium bromide salt of cellulose: preparation and its absorption of
ascnic ions. 15'' bUernalional Eleelonie Conterenee on Svnlheiie Organic Chei}}/\lr\
(EC \S(K '-I3), 1-30 No\ember 2009. TT)()4.

w


6. Tinh hinh kinh phi cua de tai
- Kinh phi dugc cap cho de tai trong 2 nam la 300 trieu dong. trong do chu \eu de mua
hoa chat va dung cu tieu hao. thue khoan chuyen mon.
- Kinh phi cap cho nam 2008 la 150 trieu dong (da quyet loan xong).
- Kinh phi cap cho nam 2009 la 150 trieu dong (da nop chirng tir de cho qu}el loan).
KHOA QUAN LI

Chu nhiem de tai

Pho Chii nhiem khoa Hoa hoc

yducL
PCS.TS. Trinh Ngoc Chau

PGS.TS. Nguyin Dmh Thanh

TRUONC DAI HOC KHOA HOC TU NHIEN
•^""•''t-

r^:x .•'^o Hijtj TPaana

Gc.isM,./^^J>'j,^.,^^;^v^

SUMMARY

1. Tilte: SYNTHESIS OF SOME DERIVATIVES OF CELLUOLOSE AND STUDY ON
TTS SEPARATION CAPACITY OF SEVERAL HEAVY METALLIC IONS FROM
WATER
CODE: QGTD.08.03
2. Director: Assoc. Prof. Nguyen Dinh Thanh
3. Members:
Assoc. Prof Nguyen Dinh Thanh
Master of Science Pham Hong Lan
Master of Science Nguyen Thi Thanh Mai
Master of Science Hoang Kim Van
Some Ph.D. students, post-graduated students and students
4. Researching attitudes and contents
a. Researching

attitudes

al. Modification of cellulose using different reagents.
a2. Investigation of complex and (chemical and physical) absorption capacity of synthesized
modified cellulose with some heavy metallic ions (cations: Cd" , Pb" and/or Mn ^ and
anions: AsO^", AsO^").
a3. Study on application of modified cellulose for separation of some heavy metallic ions
(cations: Cd"^, Pb"^ and anions: ASO3", AsO;,') from water.
a4. Design of absorption column using modified cellulose in lab according to Vietnamese
Standard for water.
b. Researching

contents

bl. Study on synthesis and transformation of some ester and ether derivatives from cotton's
cellulose, some cellulose materials containing cross-link based on ester and ether cellulose
derivatives.
b2. Structures of products are confirmed by modem spectroscopic methods (IR. NMR....).
b3. Study on the obtained products' capacity in complex formation and adsorption of heavy
metallic ions.
b4. Estimation of applicable products for separation of some heavy metallic ions (cations
Cd"^. Pb"^ and/or Mn~^and anions AsO^' and AsOj") in water.
b5. Study on design of water-filler instrument based on modified cellulose materials.
5. Main results
- Results in science and technology:


a. Cellulose from cotton was modified through reaction with oxyphosphorous chloride in
DMF at ISC^C. Obtained cellulose chloride was transformed with diethanolamine and
sodium p-aminobenzoate in DMF at 25°C. The surface of obtained products have been
investigated by SEM images.
b. Cellulose from cotton was modified through reaction of NaCMC with diethanolamine and
epichlorohydrin-ethylenediamine system in molar ratio of 1:1,5:1,5; 1:2:2; 1:3:3 and 1:4:4.
respectively. The modification with epichlorohydrin-ethylenediamine system have carried out
in two steps: in the first step, NaCMC reacted with epichlorohydrin. and in the second step,
oxiran-2-ylmethyl carboxymethylcellulose reacted with ethylenediamine gave cellulose-gepichlorohydrin/ethylenediamine. The surfaces of obtained products have been investigated
by SEM images. Their capacity in adsorption of Pb(II) ion (in concentration of 10000 ppm,
2000 ppm, 1000 ppm, 600 ppm, 400 ppm and 100 ppm) have been investigated.
c. The affects of some reaction conditions (molar ratio of reactants, reaction time) to property
of modified CMC-^-ECH and CMC-g-ECH/EDA have been estimated. It's shown that these
affects remarkably infiuenced to the heavy metallic absorption capacity of reaction products.
Absorption of some ion (such as Pb ^, Cd ^ and Mn ^) has been investigated with different
concentrations in range of 500-3000 ppm. CMC-^-ECH/EDA adsorbed Pb~^, Cd""^ and Mn""*^

ions well and the absorption capabilities varied in the order: Pb ^> Cd ^> Mn ^.
d. Samples CMC-^-MA have been synthesized by reaction of carboxymethyl cellulose with
methyl acrylate and transformed into amide derivative with diethanolamine (CMC-gMA/DT^A) in different reaction conditions: reaction time changing from 1 hr. to 10 hrs. and
ratios of CMC-^-MA:DEA changing from 1:6 to 1:12. and it's shown that optimum condition
was reaction time 5 hrs. with ratio of CMC-^-MA:DEA^l :10. Absorption capacity of
synthesized samples in optimum condition have been investigated with Pb"^. Cd"^ and Mn"^
ions and indicated that this property obeyd in order Pb^^>Cd"^~Mn"^.
e. Cellulose was modified with citric acid in high temperature. Investigations of its absorption
of heavy metal ions (such as Pb"^ and Cd"^) showed that modified cellulose in conditions
120°C and 12 h and in mass ratio of cellulose :citric acid=l:3 had highest absorption
capacity. Absorption capacity of modified cellulose increased in accordance with increase of
concentrations of ions. Structure of modified cellulose was confirmed by IR spectra and SEM
pictures.
f. Cellulose was modified by reaction with (:V-butyl-;V-chloropropyLiV,7V-dimethyl)
ammonium bromide (BCDMAB). The optimum reaction conditions were as follows:
temperature 55°C. reaction time 3.2 h and mass ratio of ceIlulose:BCDMAB=l:2.5.
Equilibrium adsorption capacity of modified cellulose for arsenate ion has been estimated.
It's shown that this capacity increased with concentrations of arsenate ion. Structure of
modified cellulose was confirmed by IR and SEM images.
g. Static absorption conditions for modified cellulose as follows: pHopt,mum = 6 (for Pb""). 5
(for Cd"^). 6.6 (for Mn"*): equilibrium time - 80 min (for Pb"*). 60 min (for Cd"") and 30 min
(for Mn~^): static absorption capacity - 500 mg/g (for Pb"*). 476 mg/g (for Cd"*) and 227.3
vii


mg/g (for Mn'''); deabsorption capacity ^ 87,6% for Pb"^ with mo = 200 fig, 77.5% for Cd"^
with mo = 250 ng, 56,0% for Mn^"" with mo ^ 250 ^g.
h. Static absorption conditions for modified cellulose as follows: pHopumum = 2 (for AsO^,
AsO^"); equilibrium time = 45 min (for AsOj"), 60 min (for AsO^"); static absorption
capacity = 3.85 mg/g (for ASO3'), 227.55 mg/g (for AsO^"); deabsorption capacity ^ 61.6%

for ASO3" with mo = 500 ^ig, 74,7% for AsO^" with mo = 500 ^g.
i. Cellulose (from cotton) modifying with citric acid and was suitable to make the absorption
materials
Cd^^, Mn^^ cations and AsO;^", AsOj'anions, respectively
laterials for Pb^^, Cd^"^,
Results in practical application:
Absorption materials for heavy metallic ions (cations Pb , Cd . Mn"^ and anions
AsOj", AsO^") from modified cotton (cellulose) with citric acid and BCDMAB.
- Results in training:
- Number of Bachelors: 02
J. Nguyen Viet Dzung
2. Do Thanh Tuyen
- Number of Masters of Science: 04.
J. Trinh Thi Ha
2. Le Thi Thuy Llau
3. Ha Lam Nhung
4. Luu Nhu Quynh
~ Number of Post-graduated students: 04
1. Pham Hong Lan
2. Nguyen Thi Thanh Mai
3. Hoang Kim Van
4. Le The Hoai
- Publications:
Four articles were published in Journal of Chemi.stry and Apply (CSV), two ones in
Journal of Chemistry (VAST), three ones in Proceedings of 13^*" Intemational Electronic
Conference on Synthetic Organic Chemistry (ECSOC-13) 11/2009.
1. Nguyen Dinh Thanh. Luu Nhu Quynh, Nguyen Thi Thu Huong. Xenlulozo bien tinh
bang (N-bulyl-N-cloropropyl-N,N-dimetyl)amonium bromua va kha nang h^p phu
ascn cua no. Tcip ehi Hod hoe vd Ifng ditng. No. 19. tr. 30-34 (2009).
2. Nguyen Dinh Thanh. Ha Lam Nhung, Nguyen Thi Cue. Tdng hop cellulose bien tinh

bang acid citric va su hap phu ion kim loai nang cua no. Tap ehi Hod hoe vd Ung
diwg No. 17(101). 33-37(2009).
3. Nguyen Dinh Thanh. Le Thi Thuy Hau. Study on modified reaction of sodium
carboxyimethyl cellulose with methyl acrylate. Tap ehi Hod hoe. T.47. N.4A. 228-233
(2009).
viii


4. Nguyen Dinh Thanh, Trinh Thi Ha, Nghien cuu tong hgp va tinh chat cua xenlulozo
bien tinh voi epiclorohydrin va etylendiamin. Tap chi Hod hoc, T. 47. N.2A- pp.543549 (2009).
5. Nguyin Dinh Thanh, Nguyen Viet Dijng, Mot so dan xuat cua xenlulozo vai
dietanolamin va etylendiamin, Tap chi Hod hpc <& ifng dung. No. 11 (95), pp. 39-42
(2009).
6. Nguyin Dinh Thanh, Do Thanh Tuyen, Dan xuat clo cua xenluloza, Tap chi Hod hoc
& Ifng dung No. 10 (94), pp. 40-43 (2009).
7. Nguyen Dinh Thanh, Do Thanh Tuyen, Some Derivatives of Cellulose with
Dietanolamin and Ethylendiamine, 13' Lnternational Eleelonie Conference on
Synthetic Organic Chemistry (ECS()C-I3), 1-30 November 2009, F002.
8. Nguyen Dinh Thanh, Ha Lam Nhung, Cellulose modified with citric acid and its
absorption of Pb ^ and Cd ^ ion, 13' International Electonic Conference on Synthetic
(Jrganic Chemistry (ECSOC-13), 1-30 November 2009, F003.
9. Nguyen
Dinh Thanh, Luu Nhu Quynh,
(N-butyl-N-chloropropyl-N,Ndimethyl)ammonium bromide salt of cellulose: preparation and its absorption of
asenic ions, 13'^ International Electonic Conference on Synthetic Organic Chemistry
(ECSOC-13), I-30 November 2009, F004.

IX

MUC LUC
•

•

.Chu-angl-TdNGQUAN

1

1.1. CAU TAO PHAN TLf, HINH THAI CAU TRUC VA DUNG DICH CUA XENLULOZO. 2
^.^.^. C i u tao phantu-xenlulozo'

2

1.L2. Hinh thai c l u true xenluloza

3

L L 3 . Dung djch xenluloza

5

1.1.4. Khoi lu-ang phan tu-va do da phan tan cua xenluloza

6

1.2. PHAN

UNG BI^N

DOI

MACH XENLULOZO 11-5]

7

1.2.1. Phan huy mach xenluloza

7

1.2.2. Tao nhanh tren phan ttr xenluloza

7

1.2.3 Tao mang lien k§t giO-a cac phan tCr xenluloza

7

1.3. ESTE CUA XENLULOZO

7

1.3.1. Este cua xenluloza vai axit v6 ca

8

1.3.2. Este cua xenluloza vai axit huu ca

8

1.4. ETE XENLULOZO

9

1.4.1. Cac phu'ong phap tong hap ete xenluloza

9

1.4.2. Mot s6 d i n xu^i ete xenluloza

11

1.5. XENLULOZO BI^N TiNH DUNG LAM VAT LIEU HAP PHU

13

Chifcng 2. PHU'aNG PHAP NGHIEN CU'U VA THl/C NGHIEM

15

2.1. XU'Li B^ MAT BONG

15

2.2.

TONG

HOP

DAN

15

2.3.

TONG

HOP

DAN XUAT

DIETANOLAMIN QUA XENLULOZO

15

2.4.

T6NG

HOP

DANXUAT

AXITp-AMINOBENZOIC

16

2.5.

T6NG

HOP NATRI CACBOXYMETYLXENLULOZa

16

2.6.

T6NG

HOP ETYL ESTE QUA CACBOXYMETYLXENLULOZO

17

XUAT CLO QUA XENLULOZO

CUA XENLULOZO

Xac dinh m u c d p t h l (DS)
2.7. TONG HOP AMIT QUA DIETANOLAMIN VOI CACBOXYMETYL-XENLULOZO....
2.8.
T6NG
HOP
XENLULOZO-g-EPICLOROHYDRIN/ETYLENDIAMIN
ECH/EDA) (Qui trinh 1 bucrc)

17
18

(CMCI-g18

2.9. T6NG HOP VA KHAO SAT KHA NANG HAP PHU CUA CMC-g-EPICLOROHYDRIN
(CMC-g-ECH) VA CMC-g-EPICLOROHYDRIN/ETYLENDIAMIN
(CMC-g-ECH/EDA) (Qui
trinh 2 birac)
79
2.9.1. Tong hap CMC-g-ECH

19

2.9.2. T6ng hgp CMC-g-ECH/EDA

20

Mi


2 10 T6NG HOP COPOLYME GHEP QUA CACBOXYMETYL-XENLULOZO
ACRYLAT (CMC-g-MA) VA AMIT QUA N6 VOI DIETANOLAMIN

VOI METYL
21

2.10.1. Tong hgp CMC-g-MA

21

2.10.2. T6ng hgp dan xuit amit cua CMC-g-MA vai dietanolamin (CMC-g-MA/DEA) 21
2.11 TONGHQP

DAN XUAT

ESTE CUA XENLULOZO VOI ACID CITRIC

22

2.11.1. Mo hinh hoa thirc nghiem phan ung giira xenluloza vai axit citric

22

2.11.2. Xu- ly so lieu theo mo hinh hoa thuc nghiem

23

2.11.3. Khao satdi4u kien pH anh huang tai kha nang hip phu cua xenluloza citrat 23
2.11.4. Khao sat thai gian dat can b^ng h^p phu

24

2.11.5. Khao sat kha nang giai hip

24

2.12. TdNG HOP MU6l
BROMUA CUA XENLULOZO

N-BUTYL-N-(3-CLOROPROPYL)-N,N-DIMETYLAMONIUM
24

2.12.1. T6ng hgp (N-butyl-N-cloropropyl-N,N-dimetyl)ammonium bromua

24

2.12.2. Mo hinh hoa thyc nghiem phan u-ng giOa xenluloza vai mu6i BCDMB

25

2.12.3. Xu ly s6 lieu theo mo hinh hoa thyc nghiem

25

2.12.4. Khao sat thai gian dat can bing hip phu

26

2.12.5. Khao sat di^u kien pH anh huang tai kha nang hap phu cua muoi amoni bac 4
cua xenluloza
26
2.12.6. Khao sat kha nang h i p phu Asen a cac n6ng do khac nhau cua xenluloza biln
tinh
26
2.12.7. Khao sat kha nang giai hip

27

Phin 3. K^T QUA VA THAO LUAN
3.1. V^ TONG HOP DANXUAT

28

CLO CUA XENLULOZO

3.2. V^ TONG HOP DANXUATDIETANOLAMIN
3.3. V£ T6NG

HOP

28

CUA XENLULOZO

DAN XUA T AXIT p-AMINOBENZOIC CUA XENLULOZO

3.4. V£ TONG H(JP NATRI CACBOXYMETYL-XENLULOZO
3.5. V^ T6NG
3.6. V^ T6NG
birac)

HOP
HOP

AMIT CUA DIETANOLAMIN VOI

30
33
34

CACB0XYMETYL~XENLUL0ZO36

XENLULOZO-g^EPICLOROHYDRIN/ETYLENDIAMIN

(Qui trinh 1
38

3.7. V^ TONG
HOP
VA KHAO SAT KHA
NANG HAP
PHU CUA CMC-gEPICLOROHYDRIN VA CMC-g-EPICLOROHYDRIN/ETYLENDIAMIN
(Qui trinh 2 bw&c)
41
3.7.1. T6ng hgp cacboxymetylxenluloza-g-epiclorohydrin (CMC-g-ECH) va chuyin hoa
thanh cacboxymetylxenluloza-g-epictorohydrin/etylendiamin (CMC-g-ECH/EDA)
41
3.7.2. Khao sat cac y§u t6 anh hudng d§n kha nang h i p phu ion kim loai cua san
p h i m CMC-g-ECH va CMC-g-ECH/EDA
42

Mii


3.7.3. Ket qua khao sat hap phu

45

3.8. TONG HOP COPOLYME GHEP COA CACBOXYMETYL-XENLULOZO VOI METYL
ACRYLAT (CMC-g-MA) VA AMIT CUA N6 VOI DIETANOLAMIN (CMC-g~MA/DEA)....46
3.8.1. T6ng hgp CMC-g-MA va chuy§n hoa thanh CMC-g-MA/DEA

46

3.8.2. Khao sat cac yeu to anh huang d§n kha nang h i p phu cua CMC-g-MA/DEA ..49
3.9

T6NG

HOP

DAN XUAT

ESTE CUA XENLULOZO VOI ACID CITRIC

55

3.9.1 Tong hgp cellulose biln tinh bing acid citric

55

3.9.2. Mo hinh hoa thyc nghiem phan ung giua xenluloza vai axit citric

56

3.9.3.

57

XLF

ly s6 lieu k i t qua nghien

CLPU

3.9.4. Khao sat kha nang h i p phu ion kim loai Pb^*, Cd^* va Mn^"^

62

3.9.5. Khao sat kha nang giai h i p cac ion kim loai tren vat lieu

74

3.10. TONG HOP MUdi
BROMUA CUA XENLULOZO

N-BUTYL-N-(3-CLOROPROPYL)-N,N-DIMETYLAMONIUM
76

3.10.1. T6ng hgp mu6i N-butyl-N-(3-cIoropropyl)-N,N-dimetylamonium bromua cua
xenluloza
76
3.10.2. Mo hinh hoa thuc nghiem phan ung giua xenluloza vai mu6i BCDMAB

79

3.10.3. X u ly s6 lieu mo hinh hoa thuc nghiem

79

3.10.4. Khao sat kha nang h i p phu anion AsO^", AsO^

84

3.5. Khao sat kha nang giai h i p

93

K^TLUAN

96

TAI LIEU THAM KHAO

98

Phu luc

Miii


CAC CHlT VIET T A T
BCDMAB
CMC
CMC-g-ECH
CMC-g-MA
CMC-g-ECR^DA
CMC-g-MA/EDA
DMF
DEA
ECH
EDA
g

IR
NaCMC
SEM

(N-Buty!-N-chloropropyl-N,N-dimethyl)amnionium
bromide
Carboxymethyl cellulose
Cellulose-g-epichlorohydrin
Carboxymethyl cellulose-g-methyl acrylate
Ccllulose-g-epichlorohydrin/ethylenediamine
Carboxymethyl cellulose-g-methyl acrylate/ethylenediamine
Dimethyl formamid
Diethanolamine
Epichlorohydrin
Ethylenediamine
grafted
Infrared
Natrium carboxymethyl cellulose
Scaned electronic ...


MO DAU
Xenluloza la mot trong nhung polyme tu nhien phong phu nhat tren trai dat va co
vai tro quan trong trong sir phat trien cac ung dung cong nghiep cua polyme, dua tren cac
tinh chat da dang cung vai kha nang phan huy sinh hoc va co the tai tao cua chung. Tuy
nhien chung cung co mot so nhugc diem nhu: tinh chat ca ly thap, kha nang chong chju
vai tac dung ciia vi sinh vat kem.... Vai nguon nguyen lieu doi dao va san co, ITnh vuc
hoa hoc tren ca sa xenluloza tren the giai ciang nhu a nuac ta da va dang dugc nghien
cuu rong rai trong nhieu nam qua de tao ra cac loai xenluloza bien tinh vai cac tinh chat
dugc lua chon. Ben canh do, van de xu ly 6 nhiem moi truong, dac biet la xu ly cac

nguon nuac bj 6 nhiem cac ion kim loai nang dang la van de het sue cap bach, thu hut
dugc sir quan tarn ciia nhieu nha khoa hoc. Tu xenluloza co the chuyen hoa thanh cac
dan xuat ete hoac este ciia xenluloza, hoac bien tinh xenluloza bang con duang dong
trung hgp. Bang each nay tinh chat cua xenluloza ban dau dugc ma rgng, cac vat lieu
xenluloza bien tinh nay co the dung lam vat lieu hap phu kha tot.
Nham gop phan vao viec tim kiem cac vat lieu hap phu kim loai nang co nguon goc
xenluloza than thien vai moi truong, chung toi da de xuat va thuc hien de tai nghien cuu
-TONG HOT MOT SO DAN XUAT CUA XENLULOZO VA NGHIEN CLTU KHA NANG
TACH LOAI MOT SO ION KIM LOAI NANG TLT NU'OC SINH HOAT\


Chirong 1. TONG QUAN
1.1. CAU TAO PHAN TU^, HINH THAI CAU TRUC VA DUNG DICH CUA
XENLULOZO
7.7.7. Cau tao phan tuxenlulozXenlulozo la hgp chat cao phan tu, dan vi mat xich !a anhydro-P-D-giucopyranoza
(ggi ng4n ggn la D-glucoza). Di6u nay dugc xac nhan nha thuy phan xenluloza, thu dugc
D-glucoza vai ham lugng 96-98% so vai ly thuyet. Cac dan vi mat xich cua xenluloza
chua ba nhom hydroxyl tu do (khong a dang lien ket), mot nhom hydroxy! rugu bac mot,
hai nhom hydroxyl rugu bac hai. Dilu nay co the chung minh bang thuc te la cac phan
ung ete hoa d^n cung luon tao ra san pham chua ba nhom the tren mot dan vi mat xich.
Cac nhom hydroxyl nay khac nhau ve kha nang phan ung. Cac nhom hydroxyl a moi dan
vi mit xich lien ket vai nguyen tu cacbon a vj tri 2.3 va 6. Cac don vi D-glucoza trong
xenluloza co dang vong 6 canh (pyranoza), chu khong phai dang vong 5 canh
(furanozo), vi xenluloza tuang doi ben trong moi truong axit. trong klii do furanozit de
dang bj thuy phan trong dieu kien tren. Dua tren cac nhan xet rut ra tu thuc nghiem. ta co
the bieu dien cau tao phan tu xenluloza nhu a sado 1.1 [1-5].
CH2OH

OH

OH

OH
Sa d6 1.1. C l u tao hoa hpc cua phan tu xenluloza t h i hien theo phuang phap phoi canh
Haworth; n: do trung hgp (DP).

Xet ve thanh phan hoa hgc, don vi mat xich cua xenluloza la anhydro-P-Dglucopyranoza. Ve phuang dien cau tao mach, cur sau hai don vi mat xich, cau tao mach
lai dugc lap lai. Do do. ta co the coi xenluloza la polyme dieu hoa khong gian {sa do
1.2).
CH^OH

OH

OH

Ch20H

CH^OH

OH

OH

J

CH2OH
n-2

2

Sa 66 1.2. Phan tu xenluloza dugc bilu di§n tren ca sa coi xeniobioza la dan vi clu true

Cau lao don vj mat xich ve phuong dien cau hinh cung da dugc nghien cuu. Cac
nha khoa hgc da xac djnh rang cac dmi vj mat xich cua xenluloza co cau dang hinh ghL
Co the ton tai hai hinh thai cau true dang ghe. ung vai su dinh huang khac nhau cua
nhom the. Cac nhom the co the huong ngoai (thuat ngu nay ti^ng nuac ngoai ggi la dinh
huong xich dao), trong do. lien ket giua vong vai nhom the co xu huc'mg song song voi


mat ph^ng so sanh cua vong pyranoza. Cac nhom the cung co the lien ket vai \6ng
pyranoza theo huong trac, tuc la xu huong vuong goc vai mat phang so sanh cua vong
pyranoza.
d cac hinh thai dang ghl khac nhau, cac nhom hydroxyl co hoat tinh khac nhau. Vi
du, trong phan ung ete hoa, nhom hydroxyl huong ngoai tham gia phan ung thuan Igi
ban. Noi chung, cac don vi m§t xich xenluloza, a dieu kien thuong, co cau hinh dang ghe
"^Ci (CI) ung voi sir dich huong xich dao cua cac nhom hydroxyl (sa do 1.3).
OH

HOH2C

HOH2C

HOH2C

HOH2C

Sa do 1.3. Mach xenluloza t h i hien theo c l u hinh dang g h l "Ci cua cac dan vi m i t xich.

Dual tac dong cua mot so yeu to ben ngoai, cau hinh co the a dang ghe C4 (IC), vi

du, phan ung thuy phan xenluloza trong moi tixrong kiem.
7.7.2. Hinh thai can true xenlulozo^
Tu nhijrng thap ky dau tien cua the ky hai muoi, phuang phap tia X da dugc
Nishikawa va Ono su dung de nghien cuu cau tmc cua xenluloza. Cac tac gia nay nhan
thay bieu do tia X cua xenluloza co nhirng net dac tiomg cho vat lieu tinh the, trong do
tinh the djch huong theo true cua xo sgi. Nhieu cong trinh nghien cuu cua cac tac gia
khac da dugc thuc hien doi vai xenluloza tu nliien co nguon goc khac nliau va bieu do tia
X cung CO dac trung tuong tu. Mot so tac gia da v J u c i 1 Ci J^.y do mang tinh the. MG hinh
dugc thua nhan dau tien la mo hinh do Mayer va Misch de xuat 1937. Theo mo hinh nay,
mang tinh the la khoi hop dung co tiet dien binli hanh. Bon mach phan tu djch huong
song song voi true cua khoi hop va nam doc theo cac canh dung cua hop. Khoang each
giua cac nguyen tu cacbon la 0,154 nm, khoang each giija cac nguyen tu cacbon vdi
nguyen tu oxy la 0.135 nm. Cac nguyen tu nam gan nhau nhat cua hai doan mach trong
cung mat phang co cu ly 0,25 nm. Voi kich thuoc nay. co the xuat hien lien kh hydro,
tao thanh tu nhom hydroxyl. Doan mach xeniobioza la phan tham gia vao cdu tao mang
tinh the. Trong doan mach do. cac don vi mat xich nkm quay 180' d6i voi nhau. Trong
mang tinh the. cac doan mach dau xep theo mot huong va song song vdi nhau. Doan
mach xenlobiozo co hai lien ket hydro ngi phan tu. Mot lien k^t hydro tao ra do H cua
nhom hydroxyl d C2 cua mot mat xich tac dung vdi O thugc nhom hydroxyl d Ce cua mk
xich lien ke. Mot lien ket hydro khac tao thanh do H cua nhom hydroxyl d C3 cua mot
don vj mat xich tac dung vdi O nam trong vong cua don vi mat xich li6n k^.


/^""

H ^CH

H ^CK
O
H

OH

Hinh 1.1. He thing lien ket hydro trong xenluloza 1. Moi dan vj mIt xich D-glucoza co 2 lien kit
hydro ngi phan tu va mot lien kit hydro giua cac phan tu.
Hai doan mach n^m trong mot mat phang cua mang tinh the tuong tac vdi nhau,
hinh thanh mot Idp. Trong lop nay, cd lien ket hydro giua H cua nhom hydroxyl d C6 cua
don vi D-glucopyranozo trong mot doan mach va O cua nhom hydroxyl d C3 trong doan
mach kliac. Cac tac gia da xac dinh dugc rang, trong xenlulozo tu nhien (xenlulozo 1),
khong cd lien ket hydro giua cac lop vdi nhau. Giira chung chi ton tai tuong tac van der
Waals. Nhu vay, cd the noi xenluloza tu nhien vua cd mang tinh the vira cd mang cua
Idp.
Xenlulozo hoan nguyen. tuc xenlulozo II, cd mang tinh the khac vdi xenlulozo I.
Cung nhu doi vdi xenlulozo I, xenlulozo hoan nguyen van cd cau true Idp trong mang
tinh the. Cac mach dai phan tu van nam song song nhau. Nhung khac vdi xenlulozo I. d
xenluloza II, cac doan mach xenlulozo d cung phia cua mang tinh the khong cung nam
tren mot mat phang ma nghieng mot goc nhu nhau so vdi mat phang cua mang tinh the.
Mach trung tam van song song vdi cac mach ben, nhung nam ngugc chieu so vdi cac
mach ben.
() xenluloza II van ton tai lien ket hydro ngi phan tu trong tung doan mach
xenlulozo. Xenluloza hoan nguyen la xenluloza thu dugc nhd dong tu dung dich
xenlulozo, nhu dung dich xanlhogenat, dung dich phuc dong amoniac ciia xenlulozo.
Nhu vay. sau qua trinh dong tu tir dung dich, mot trang thai tinh the mdi da dugc thiet
lap, do la xenlulozo II. Xenlulozo II cung hinh thanh sau khi cho xenluloza I trucmg


trong k'lhm manh rdi rua sach b§ng nude. Do qua trinh truong nd, trang thai tinh the cu bj
bi^n ddi, hinh thanh trang thai tinh the mdi.
Sir khac nhau ro ret giira xenluloza I va xenluloza II cd the thay dugc tren bieu do
nhilu xa tia X, nhieu xa electron va phuang phap pho hong ngoai. Nhd cd them lien ket

hydro nen xenluloza II b^n v^ mat nhiet dong hon so vdi xenluloza I. Do do, xenluloza
II khong chuyen trd lai thanh xenlulozo I. Xenlulozo tap hgp thanh tinh the co ban theo
trat tu nhit dinh. Nhin chung, trong xenluloza tu nhien, cau true co ban cua xenlulozo cd
chi^u dai khoang 100 - 250 nm, vdi tiet dien ngang hinh chu nhat cd canh khoang 3 nm
va 7 ^ 10 nm. Vdi kich thudc cua dai phan tu xenluloza khoang 5000 nm, cac mach
xenluloza cd thi trai qua nhieu vung tinh the va vd dinh hinh hoac ton tai d dang gap nep
trong pham vi mot tinh the. Cac tinh the cung vdi cac vung vd djnh hinh tap hgp thanh to
chuc Idn hon ggi la vi xo (microfibril). Theo mot so tac gia. vi xo cd kich thudc thay doi
tuy thudc vao loai thuc vat. Chieu ngang cua vi xo khoang 10-20 nm (ciang cd y kien cho
ring kich thudc cua vi xo con Idn ban). Cac vi xo lai tap hgp thanh to chuc Idn hon ggi
la xo (fibril).
Cac bd mach cd dang sgi nay, theo mot so tac gia, cd kich thudc ngang khoang
100-300 nm. Cac bd mach nay tham chi cd the quan sat dugc qua kinh hien vi thong
thuong, khi xenluloza bi truong.
Cac bd mach dang sgi nay tap hgp lai thanh Idp. Lop la dang to hgp cd the bj bong
ra tir te bao. dudi tac dung co hgc. Nhu vay, xenluloza khong tap hgp hoan toan thanh
cac tinh the, ma mot phan d trang thai vd dinh hinh, trong do tuong tac giira cac phan tu
khong dang ke. (Jiua cac vung tinh the, djnh hudng va vung vd dinh hinh, khong djnh
hudng, cung khong cd ranh gidi that ro ret. thudng trai qua mot viing chuyen tiep. Nhieu
cong trinh da xac dinh ty le giira cac vung tinli the va vung vd dinh hinh. Nhung ket qua
thudng khac nhau, khong pJiijng phu thudc vao ngudn goc lay mau ma con phu thudc vao
phuong phap nghien cuu.
Khi chuyen xenluloza vao dung dich, trang thai td hgp bi thay doi, hinh dang mach
phan tu cung thay doi. Tuy nhien. cau tao hda hgc ciia mach xenlulozo. vdi nhieu nhom
phan cue manli, cung anh hudng nhieu tdi tinh chat cua dung dich xenlulozo. Mac du
tuan theo quy luat chung cua hgp chat cao phan tu, dung dich xenlulozo cung cd nhieu
net rieng.
7.7..?. Dung djch xenlulozo'
Xenluloza. mot loai polyme vua phan cue manh vira ket tinh cao, chi hda tan trong
mot so it dung mdi. Cijng nhu doi vdi cac polyme kJiac, \'h phuang dien nhiet dong hgc.

qua trinh hda tan xenlulozo chi xay ra khi AG trdn lan am. Do tuong tac hydro manh, kit
tinh cao. gia trj AII duong va Idn, tuc la c^n nhilu nang lugng (nhiet) dua vao he dl k h k
phuc trd ngai do. AS ducmg nhung do Idn lai nho. Mach xenlulozo vdn cung nhdc. Trong
dung dich. mach xenlulozo cOng co cum lai nhung muc do hh ddi vin vk cao. vin cung
nhac. khdng uyen chuyen nhu nhieu loai polyme khac. nen entropy it tha}' ddi. nghia la
AS nhd. Nhu vay. ve phuong dien nhiet dong. xenlulozo khd bi hda tan. Tuy nhien. cung
cd mot so he dung moi dac biet. hay dung hon la mot sd he chat lone, cd the lam truonu


manh xenluloza va din tdi hda tan. Su truong ciia xenluloza cd the la truong giira cac
tinh the va truong trong tinh the.
Sir truong trong tinh thi xay ra khi chit gay truong cd ai lire manh hon tuong tac
giua cac phan tiJ xenluloza. Luc do trang thai tinh the ban dhu bi bien ddi. Sir thay ddi
nay thi hien qua bilu do nhilu xa tia X. Sir truong trong tinh the cd hai kha nang. Qua
trinh truong cd thi huu ban hoac vd ban. Dung dich natri hydroxit 16 - 18% chi hda tan
dugc phSn xenlulozo mach ng§n, san phim phan buy cua cac qua trinh gia cong nhu nau
hda chit va tly t r ^ g . D6i vdi xenluloza tu nhien hoac a-xenlulozo, dung djch natri
hydroxit nhu tren khdng the hda tan dugc.
Xet vl phuong dien hda hgc, dudi tac dung ciia dung djch kiem, giua xenlulozo va
NaOH hinh thanh hgp chit phan tu cd thanh phin (C6H,o05)x-(NaOH)v.(H20)z. Do Ion
ciia x, y, z la vin dl dang dugc tranh luan. Tac dung gay truong cua dung dich NaOH ddi
vdi xenlulozo cd y nghia rit Idn trong thuc tien, vi du, qua trinh tao alcalixenlulozo trong
sam xuat sgi viscozo va mang xenlophan. Qua trinh gia cong xenlulozo bang dung dich
NaOH dugc ggi la mercer hda - mercerization - mang ten ngudi de xuat la John Mercer
(1844). Chat gay truong cd the tich Idn va cd kha nang tao phuc manh vdi xenluloza, cd
thi pha vd cac lien kit hydro giua cac mach phan tu xenlulozo, lam chung tach ra khdi
nhau va dan tdi hda tan. Qua trinh truong dan tdi hda tan ggi la truong vd ban. Chat gay
truong luc nay chinh la dung mdi ciia xenlulozo. Nhu vay, tuy thudc vao ban chat cua
chat gay truong, qua trinh truong trong tinh the cd the la huu han hoac vd ban. Chat gay
truong rdi dan den hda tan xenlulozo cd the la cac dung djch cd tinh bazo, nhu dung dich

phuc dong - amoniac Cu(NH3)4(OH)2, cuprietylendiamin, cadimietylendiamin, bazo
amin bac bdn [(C2H5)4N]OH hoac dibenzyl dimetyl amoni hydroxit. Mot so axit cung cd
the hda tan xenlulozo, dd la dung dich axit H2SO4 72%, dung dich axit H3PO4
85%...Dung dich dam dac cua mot sd muoi vd co cung cd the hda tan dugc xenlulozo,
nhu mot sd muoi kem, bari...Da sd cac he dung mdi tren day deu it nhieu cd tac dung pha
buy xenlulozo, nhat la khi rihiet do cao va cd vet oxy. Mot sd he dung mdi khac cung
dugc thu nghiem, nhu bdn hgp DMA/LiCl, DMF/LiCl, DMSO/LiCl..
7. L4, Khoi Iwong phan tu va do da phan tan cua xenlulozo
Khdi lugng phan tu la mot trong nhung thong sd quan trgng, quyet dinh tinh chat
vat lieu cao phan tu, trong dd cd xenluloza va dan xuat. Hon nua. trong nguyen lieu thuc
vat con cd bdn hgp chat cao phan tu khac. Khdi lugng phan tii ciia polyme cd thi dugc
xac djnh theo cac phuang phap hda hgc hoac phuong phap vat ly. Phuong phap hda hgc
chi dugc ap dung khi polyme chiia mot lugng xac dinh cac nhdm chiic d diu hoac cudi
mach va khdng cd ngoai le. Ddi vdi polyme mach th^ng, khi da xac dinh dugc toan bd
nhdm chirc dau hoac cudi mach, ta cd the biet tdng so phan tir polyme, tu dd tinli dugc
khdi lugng phan tii trung binh cua polyme. Xenlulozo va din xult cd nhdm cacbonyl
cudi mach. ta cd the dua vao dd de xac djnh khdi lugng phan tu. Tuy vay. nhdm
cacbonyl cung cd the xuat hien them d cac vi tri khac trong mach phan tu. do tac dong
oxy hda trudc dd. Vi vay. trong nhieu truong hgp, ta cSn ap dung nhilu phuong phap de
so sanh. bao dam thu dugc ket qua tin cay. Hien nay. nhilu phuong phap vat ly dugc ap
dung de xac djnh khoi lugng phan tu cung nhu phan bd khoi lucmg phan tu. Irong so cac
phuang phap vat ly. dang luu y nhat la cac phuong phap ap suit tham ihlu. tan xa anh


sang, sieu ly tam, do do nhdt va sac ky qua gel.
Do da phan tan hay muc do khac nhau ve khdi lugng phan tir trong mot mau
polyme la thong sd quan trgng, lien quan tdi nhieu tinh chat ciia dung dich pol}ine cung
nhu vat lieu polyme. D I hieu ro do da phan tan, ta can phan doan va xac dinh phan bd
khdi lugng phan tir.
1.2. PHAN ITNG BIEN DOI MACH XENLULOZO [1-5]

7.2.7. Phan huy mach xenluloz(T
1. Thuy phan xenlulozc

Xenluloza cd the bj thiiy phan, vdi tdc do cham, trong mdi truong nude, d nhiet do
cao. Dudi tac dong ciia xuc tac axit, qua trinh thiiy phan xay ra vdi tdc do Idn hon.
2. Nhiet phan xenlulozo^

Dudi tac dung ciia nhiet, d nhiet do du cao, xenluloza bj depolyme hda, do triing
hgp giam dan. Qua trinh nhiet phan xay ra theo co che gdc.3. Phan huy mach do oxy hda
Tac nhan oxy hda cd the phan huy manh dudi hai dang :
Oxy hda pha vd cau triic vdng pyranozo;
Oxy hda true tiep lam dirt mach hoac tao dieu kien dirt mach xenlulozo
Xenluloza la rugu da chirc, vira cd OH rugu bac mot, vira cd OH rugu bac hai kieu
glycol. Do dd, xenluloza de bj oxy hda. Chi cd mot sd it tac nhan oxy hda tuong ddi chgn
Igc, cdn lai, da phan cac tac nhan oxy hda la klidng chgn Igc. Mire do pha buy mach tiiy
thudc vao loai tac nhan va dieu kien phan img.
7.2.2. Tao nhdnh tren phan turxenlulozo
Tao nlianh la qua trinh bien xenlulozo tir phan tu mach thang sang phan tu mach
nhanh. Cac phan tir xenlulozo cd nhanh ggi la copolyme ghep.
Phuong phap ghep mach dat nhieu ket qua la phan irng triing hgp. Phan ung cd the
theo CO che triing hgp goc. triing hgp ion, trong do, phuong phap dugc nghien ciiu va ap
dung vao thuc tien nhieu hon ca la triing hgp goc.
7.2. J Tao mang lien ket giira cac phan tu xenlulozo
Ddi vdi cac hgp chat cao phan tir, de dat dugc yeu cau vl tinh chit co ly. hda ciia
vat lieu, trong nhieu trudng hgp, can tien hanh tao mang khdng gian giira cac dai phan tu.
Qua trinh tao mang dugc sir dung ddi vdi xenluloza ciing khdng ngoai nhimg muc dich
tren.
Cd the khau mang bang each tao cau noi nhd lien kit ete hoac este. Tuy vay. lien
ket este kem ben hon. nen thudng tao mang nhd lien k^t ete.
L3. ESTE CUA XENLULOZO

Cung nhu este ciia rugu phan tu thap. cac este cua xenlulozo cd the tao ra khi
xenluloza tac dung vdi axit vd co. axit hu-u co. anhydrit hoac cloanhydrit cua cac axit.
Qua trinh este hda xay ra khi khi su dung tac nhan axit vdi su tham gia hoac ving mat
chat pha loang tro. Phuong phap nay thudng dugc su dung de tdng hgp esie cua
7


xenluloza vdi axit vd ca (sulfat, phosphat, nirtrat) va este ciia xenluloza vdi axit formic.
Este hda bIng anhydrit cua axit, dudi tac dung ciia xiic tac. la phuong phap thudng
diing dk tdng hgp este ciia xenlulozo va axit cacboxylic, vdi do dai mach cacbon tdi C4
hoac C5. Qua trinh nay cung cd thi ap dung dk tdng hgp mot sd este cua xenluloza vdi
axit vd ca. Este hda cung xay ra khi diing cloanhydrit ciia axit, cd mat bazo hiru co lam
chit lien kit vdi HCl tach ra tir phan ung.
7.5.7. Este cua xenlulozo voi axit vd cot
1. Xenluloza nitrat

Xenluloza nitrat la este ciia xenlulozo vdi axit nitric. Cong thuc tdng quat ciia este
nay dugc the hien d so dd sau:
-[C6H,02(OH)3.,(ON02),^
n

Qua trinh phan img tao este tir xenlulozo va axit cd the bieu dien theo so dd sau:
Cell-OH +

HONO2

^

Cell-0N02 +

Hp

2. Xenluloza xanthat

Xenlulozaxanthat (hoac xenluloza xanthogenat) cd cong thuc tdng quat nhu
sau:

f

C6H702(OH)3.,(OCSSNaVT4
^';

(1.6)

Xenlulozo xanthat la muoi cua axit xenlulozoxanthogenic. Axit
xenlulozoxanthogenic la este cua rugu (trong trudng hop nay la xenlulozo) vdi
axit dithiocacbonic.
7.i.2. Este cua xenlulozo voi axit hHu co
1. Xenluloza axetat

Xenlulozo axetat hoac axetylxenlulozo la este ciia xenlulozo vdi axit axetic. Cong
thirc tdng quat ciia xenlulozo axetat dugc bieu dien d so do sau:
-=C6H,02(OH)^,(OCOCH3),-^

n

(1.7)

Xenluloza axetat cd nhieu tinh chat quy nhu kha ben co hgc, bin anli sang, khdng
bj chay... Do dd, dan xuat nay dugc diing trong nhieu ITnli vuc. nhu to nhan tao. phim

anh. son, chat deo. mang Igc, sgi Igc...
2. Este hon tap cua xenluloza

Tdng hgp este hdn tap, trong dd nhdm the bao gdm nhilu loai gdc axit. la mot trong
nhung phuong phap hda hgc nham bien ddi tinh chat cua eslc xenluloza.
Cac este hdn hgp dugc san xuat nhieu hon ca la este chira nhdm axctyl va mot loai
nhdm the khac, nhu este axetobutyrat. axetonropionat. axelophtalat. axctovalerat va mot
8


sd din xult khac. Khi dua them vao xenluloza khoang 5 - 15%> tdng sd nhdm the loai
gdc axit thiir hai, tinh chit ciia xenluloza thay doi mot each dang ke.
a. Axetobutyrat va axetopropionat
Xenluloza axetobutyrat (CAB) la este ciia xenlulozo vdi axit axetic va axit butyric.
—[CeH702(OH)3.,.y(OCOCH3),(OCOC3H,)y-5—
n

Xenlulozo axetopropionat la este cua xenluloza vdi axii axetic va axil propionic.
Phuang phap san xult hai loai este hdn hgp nay tuong tu phuong phap san xuat
xenluloza axetat. Hai tac nhan este hda tren cd kha nang gan nhu nhau ve este hda nhdm
hydroxyl va depolyme hda mach xenluloza.
h. Axetophtalat
Xenluloza axetophtalat (CAP) cd cdng thirc tdng quat nhu sau:
^ '

CeH,02(OH)^,.y(OCOCH3),(OCOC6H,)COOH

CAP cd do deo kha cao, trong dd cac nhdm the phtalat ddng vai trd ngi hda deo.
CAP dugc sir dung lam nguyen lieu tao mang va phim.
L4. ETE XENLULOZO

Dan xuat ete ciia xenlulozo dugc bieu dien dudi dang cdng thuc tdng quat d so dd
sau
-j-C6H,0,(CH)^,(0A),-^
n

trong dd: x la chi sd bieu dien mire do the DS; A la gdc ciia tac nhan tham gia phan
img tao ete vdi xenluloza. A cd the la ankyl, dan xuat vdng ciia ankyl hoac dan xuat
ankyl mang cac nhdm chirc kliac nliau nliu OH, COOH. CN, halogen, lien ket C=C,
C-C...
Tiiy thudc ban chat ciia nhdm the dua vao xenlulozo. tiiy thudc mire do the DS cung
nhu do trimg hgp DP. cac san pham cd the cd cac tinh chat khac nhau. dap irng nhu cau
sir dung, nhu kha nang hda tan trong nude, kha nang chdng tham nude, kha nang hda tan
trong dung mdi hiru co, kha nang each dien, kha nang trao ddi ion...Cung nhu ddi vdi cac
hgp chat cao phan tu khac. ete xenlulozo khdng ddng deu ve klidi lugng phan tir. Hon
nura, cac phan img ete hda thudng tien hanh trong dilu kien di the nen san pham khdng
ddng nhat ve hda hgc. Do dd, tiiy yeu cau ve chat lugng san pham. cac nha san xult cin
chgn phuong an cdng nghe thich hgp de dat dugc muc dich dh ra vl kinh tl va chat lugng
san phan..
7.4, L Cac phuong phap tong hop ete xenlulozoDan xuat ete ciia xenlulozo rat phong phii va da dang. Tiiy thuoc vao han chit cua
nhdm the dinh dua vao xenlulozo. ta cd the lira chon phuang phap etc hda thich hgp de
dat hieu qua mong mudn.


1. Ete hoa xenluloza b4ng ankylsulfat va ankylhalogenua

Phan ung O-ankyl hda (hay ete hda) bIng ankylsulfat xay ra theo so dd :
—^C6H702(OH)3-^

+

nx(R)2S04

—[C6H702(0H)^,(0R),^

+

+

nxNaOH

nxR0S020Na

+

nxH20

R: ankyl.
Phu thudc dilu kien phan ung. ta cd thi thu dugc cac san pham vdi miic do the khac
nhau. Phuang phap ankylhalogenua rIt thich hgp dl tdng hgp metyl- va etylxenlulozo.
Ddi vdi cac din xult ankyl Idn hon. phuong phap nay van cd the sir dung, nhung mire do
ban chi hon va dilu kien phan img khit khe hon, nhu nhiet do cao ban, thdi gian phan
img dai ban.
2. Ete hoa b^ng este cua axit tham chira gdc ankyl
Xenluloza cd thi tac dung vdi este cua axit tham, vi du, este ciia axit sulfonic, tao
thanh ete cua xenluloza theo so dd sau :
£C6H702(0H)^
n

+

nxArS03R

£•C6H,02(OH)^,(OR)-

nxArS03H

Trong phaii irng nay, tac nhan O-ankyl hda la este ciia axit thorn phan hiiy uianh
axit sulfonic, ddng thdi gdc ankyl dugc dua vao xenluloza de tao thanh hgp chat ete.
Ar cd the la gdc ciia benzen, toluen, naphtalen. Phan img cd the ddng the hoac dj
the. Tdc do O-ankyl hda Idn nhat khi tien hanh phan img trong bazo hiru co. Do Idn ciia
gdc R trong este cua axit sulfonic cung cd anh hudng tdi tdc do tdi tdc do tdi ete hda.
Gdc R cang Idn, tdc do phan irng cang cham.
3. Ete hoa nha muoi onium

Oni la dang mudi. trong dd N^ ket hgp vdi anion. Nhdm hydroxyl ciia xenlulozo la
tac nhan nucleophil. phan irng vdi mudi oni dien ra theo so dd sau:
f
Cell-OH

+

H35C17OCHNH2CN

Cell-0-CH2NHCOCi7H35

CI

+

Dan xuat ete xenlulozo. vdi nhom the mach cacbon dai, co tinh ky nude cao. Bang

phuong phap nay. cac nha san xuat co the tao ra vai khdng tham nude.


4. Ete hoa bIng hop c h i t dj vong

Xenluloza cd thi tao thanh din xult ete khi tac dung vdi hgp chat dj vdng. Cac
vdng ba hoac bdn canh chira O, S, N, cd sue cang vdng Idn, cd the md vdng va ket hgp
khi tac dung vdi cac hgp chit chua nguyen tir hydro linh ddng, nhu rugu, amin, axit...
Xenluloza la polyhydroxy, cd thi tac dung vdi hgp chat dj vdng ba hoac bdn canh
dl tao thanh din xult ete. Phan img ete hda vdi vdng ba canh tien hanh theo so dd sau:
xt
-fc6H702(OH)3~^
n

+

nxH2C—CH2
Y

-

—[CeH702(OH)^,(OCH2CH2YH)-

Qua trinh ete hda cd thi tiln hanh vdi xiic tac bazo hoac xuc tac axit.
5. Ete hoa b^ng hgp chit vinyl
Xenluloza cd thi tao ra din xult ete, khi tac dung vdi hgp chat vinyl. Mot sd hgp
chit khdng no, dac biet la hgp chit vinyl, cd the tac dung vdi xenlulozo, tao thanh ete
theo so dd:
Cell-OH

+

xt
H2C=(:H

Y

Cell-OCH^CH,
I
X

Cac hgp chat vin\'l cd the tao thanh ete vdi xenlulozo la acrylonitril, acrylamit,
vinylsulfonic...
1,4,2. Mot so dan xuat ete xenlulozo
1. Metylxenluloza

Metylxenlulozo la ete ciia xenlulozo vdi rugu metylic. Cdng thuc tdng quat ciia
metylxenlulozo dugc bieu dien d so dd sau:
•C6H,02(OH)^,(OCH3),-

Metylxenlulozo cd the tdng hgp theo phuang phap O-ankyl hda bang diazometan.
dimetylsulfat hoac met)iclorua. Trong cdng nghiep, cac nha san xuat thudng diing tac
nhan metylclorua.
2. Etylxenluloza

Htylxenluloza la ete ciia xenlulozo. cd cdng thirc tong quat nhu sau:
C6H,02(OH)^,(OC2H5)"^-

Etylxenlulozo la mot trong sd cac dan xuat ete cua xenlulozo dugc su dung rong rai
nhat. Nhd cd do ben co hoc cao. tuong ddi ben nhiet. tuong ddi ben ve hda hoc. nen dan