TAPrHl HOA HOC

T. 49(2), 177-180

THANG 4 NAM 2011

TONG HOP POLYME SIEU HAP THU NU'OC TREN CO SCy MOT S6 COPOLYME GHEP TINH BOT

Nguyen Thanh Tung, Nguyen Van Khoi, Nguyen Trung Dire, Do Cong Hoan Vi?n Hod hgc, Vi?n Khoa hgc vd Cdng ngh? Vi?t Nam Den Tda soan 3-6-2010

Abstract The superabsorbent polymers (SAPs) were synthesized by graft polymerization of acrylic acid (AA) and acrylamide (AM) onto tapioca starch (AMS-1 and AMS-2, respectively) using potassium persulfate (KPS) as initiator and N,N'methylenebisacrylamide (MBA) as crosslinker. The effects of reaction conditions, such as reaction temperature, crosslinker and initiator contents, starch content and degree of neutralization on the water absorbency were also investigated. Surface morphology of 2 samples of SAP was characterized by SEM.

I.MCIDAU
Polyme sieu hdp thy nude (SAP) Id cdc polyme cdu true mgng ludi 3 chieu cd khd ndng hdp thy vd giu mgt lug-ng nude ldn gdp hdng trdm Idn khdi lugng cua chinh nd, thdm chi dudi dp sudt vd nhigt do cao. Chinh nhd tinh chdt ddc bigt ndy md polyme sieu hap thu nude da Id co sd cho nhieu irng dyng khdc nhau nhu bdng ve sinh [1], he van chuyen thuoc [2], cdm bien [3] vd ndng nghiep [4]. Cdc polyme ndy dd dugc nhieu nhd khoa hgc quan tdm nghien cuu vd hien nay vdn cd nhieu nghien cuu tap trung vdo viec bien tinh nhdm tdng do hdp thu nude, do ben gel vd tdc do hdp thy [5]. Tinh bgt Id ngudn nguyen lieu phong phu, re tien vd C O khd ndng phdn buy sinh hgc. Trong nhQ-ng nam gdn day, viec nghien ciru tdng hgp polyme sieu hdp thy nude tren co sd qud trinh triing hgp ghep cdc vinyl monome nhu axit acrylic, acrylamit, acrylonitrin len tinh bdt dugc tiln hdnh khd pho biln [6-8]. Trong nhung cdng trinh trudc, chung tdi da nghien cuu tong hgp, dieu kign tdi uu vd ddng hgc qud trinh triing hgp ghep axit acrylic (AA) vd acrylamit (AM) len tinh bdt sdn [9-11]. Bdi bdo ndy gidi thieu ket qud tdng hgp hai logi polyme sieu hdp thu nude tren co sd trung hgp ghep AA vd AM len tinh bdt sdn cd mat chat tgo ludi N,N'metylenbisacrylamit (MBA). 2. VAT LIEU VA PHLTONG 2.L Vat lieu Tinh hot sdn (Cdng ty luong thuc Ha Tdy) cd khoi lugng phan tu trung binh -860.000; Natri hypoclorit (Cdng ty Hod chdt Viet Tri) cd ham lugng clo hogt dgng 80 g/l; Axit acrylic (PA- Trung
PHAP

Qudc) dugc cdt Igi dudi dp sudt gidm vd Idy phdn dogn giua trudc khi sir dung; Acrylamit, kali pesunfat (KPS), natri hydroxit (NaOH), N,N'metylen bisacrylamit (MBA), etanol (C2H5OH) deu la hod chdt tinh khiet cua Trung Qudc, dugc su dyng khdng qua tinh che. 2.2. Phuong phap tien hanh 2.2.1. Oxy hod tinh bdt Qud trinh oxi hod tinh bdt sdn bang natri hypoclorit dugc thuc hign theo quy trinh da dugc cdng bd [12]. Su dyng tinh bdt oxy hod cd trgng lugng phdn tir trung binh 1,36x10'* 2.2.2. Tdng hc/p SAP Polyme sieu hdp thy nude dugc tdng hgp tren co sd triing hgp ghep AA (sdn phdm ky hieu Id AMS-1) hodc AM (sdn phdm ky hieu Id AMS-2) len tinh bdt cd mat chdt tgo ludi N,N'-metylenbisacrylamit (MBA) sir dyng chdt khoi mdo KPS dugc tiln hdnh theo quy trinh sau: Tinh bdt dugc phdn tan trong nude cat vd dua vdo binh cdu 3 cd dung tich 250 ml (ty le nudc/tinh bgt = 3/1 ml/g), khuay d 80C din khi hd hod hoan todn, sau dd Idm ngudi den nhigt do phdng. Dung djch chiira 0,2 moi AM hodc AA (da dugc trung hod mdt phdn bdng dung djch NaOH), chat tgo ludi MBA dugc them vdo binh phdn ung, dung nude cdt de dieu chinh ndng do monome la 30%. Hdn hgp phdn ung dugc sue khi N2 dl dudi oxy, gia nhiet din nhigt do phan ung vd khudy diu trong 30 phiit. Phdn irng dugc bdt dau sau khi them chat khoi mao KPS vd duy tri toe do khuay khdng ddi. San phdm phdn ung d dgng gel dugc cdt nhd, ldm khd trong chan

177

TCHH, T. 49(2), 2011 khdng d 60C din khoi lugng khdng doi (irii). Sdn pham khd dugc ngam chilt trong etanol (doi vdi polyme ghep AA) hogc nude cat (doi vdi polyme ghep AM) trong 24 gid sau dd Igi Idm khd trong chdn khdng d 60C din khoi lugng khdng doi (m2). 2.3. Cdc phuang phdp do dgc, ddnh gid *HdiTi lugng phan gel ciia sdn pham dugc xdc djnh theo cdng thirc: Hdm lugng phan gel (%) =
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Nguyin Thanh Timg vd < ,g sudd cdn khoi lugng polyme da hap thy mr- Do hap thy nude can bdng dugc tinh theo phuont trinh sau:
^4

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m. Trong dd mj vd m4 lan lugt Id khoi lugng cua polyme khd vd polyme truong. Q dugc tinh theo g nudc/g polyme. *Chyp dnh kinh hiln vi dign tir quet SEM (Scanning Electronic Microscopy) dugc thgc hien tren mdy FESEM Hitachi S4800 (Singapore). 3. KET QUA VA
THAO

Q (g/g) =

x 100 LUAN 3.1. Anh hudng ciia ham lugng chat tao ludi D I nghien ciiru dnh hudng ciia hdm lugng chat tgo ludi MBA tdi hdm lugng phan gel vd dg hap thu nude ciia cdc sdn phdm, tien hdnh phdn iimg vdi cdc dilu kign dugc trinh bdy trong bdng I vd 2.

Dg hap thy nude cdn bdng (Q): Dg hap thy nude can bdng ciia sdn pham dugc xdc djnh bang phuang phdp tui che. Can chinh xdc 0,05g polyme, dua vao tui che, gdn kin Igi vd ngdm trong 500 ml nude cat (hodc nude muoi sinh ly) d nhigt dg phdng (25C) trong 60 phut. Ldy polyme truang ra khdi tui che, dua len giay Igc de tham het nude lien ket, sau

Bdng 1: Anh hudng ciia hdm lugng chat tgo ludi tdi hdm lugng phdn gel vd dg hdp thy nude cua sdn phdm AMS-I Hdm lugng MBA, % Hdm lugng phdn gel, % Q,g/g 0,01 61,7 228 0,02 83,4 316 0,03 99,3 410 0,04 99,2 389 0,05 99,4 332 0,06 99,2 271

Dilu kien phdn irng: Ham lugng tinh bgt 10%; hdm lugng KPS 0,8%; nhiet dg 70C; mure dg trung hod 75%. Bdng 2: Anh hudng cua hdm lugng chdt tgo ludi tdi ham lugng phdn gel vd do hdp thy nude cua sdn phdm AMS-2 Hdm lugng MBA, % Hdm lugng phdn gel, % Q,g/g 0,016 76,8 204 0,02 87,3 253 0,024 99,4 325 0,028 99,4 281 0,032 99,2 237 0,035 99,3 196

Dilu kien phan irng: Ham lugng tinh bgt 10%; hdm lugng KPS 1,0%; nhigt dg 70''C. Ket qud cho thdy khi tdng hdm lugng chat tgo ludi, ham lugng phan gel d cd 2 sdn pham diu tdng. Dieu ndy Id do ngodi kha ndng noi ket giua cdc nhdnh ghep vdi nhau, giQ-a cdc nhdnh ghep vdi homopolyme, chat tgo ludi cdn cd thi tgo gel trgc tiep nhd phdn iirng trgc tilp vdi monome, hgn chl sg tao thdnh homopolyme bj hod tan vd tdng dg hap thy nude. Dg chuyen hod ciia phdn irng gan nhu hodn todn. Tuy nhien, khi hdm lugng chat tgo ludi cao ban mgt gid trj gidi ban, mat dg tgo ludi trong gel cd thi tdng, Idm gidm trgng lugng phdn tir trung binh giu-a cdc mat ludi, ban chl thi tich tu do dl cdc phdn tu nude xdm nhap ddn din gidm do hap thy nude. Sdn pham AMS-1 cd do hdp thy nude cgc dgi cao hon so vdi sdn phdm AMS-2 do axit acrylic va mudi acrylat cd do phdn cue cao hon acrylamit. 3.2. Anh hud-ng ciia ham lugng tinh hot Anh hudng cua ham lugng tinh bgt din dg hdp thy nude ciia cdc sdn pham dugc trinh bdy tren hinh 1. Khi tang hdm lugng tinh bgt, dg hap thy nude gidm do gidm ty lg cac nhdm chuc phan cue trong gel, ldm gidm di luc ddi vdi nude. Tang ham lugng tinh bgt cung cd thi lam tang mat do cac nhdnh mgng ludi nen cd qud trinh khulch tan cua cdc phan tir dung mdi (nude) vd su md rgng ciia mgch dai phdn tir gidm. 3.3. Anh hudtig ciia nhiet do Anh hudng cua nhigt dg den do hap thu nude cua cdc sdn phdm dugc trinh bdy tren hinh 2. Do

178

TCHH, T. 49(2), 2011 KPS Id chat khoi mao nhiet nen nd phdn ly hieu qud d nhiet do cao hon nhigt do phdn buy. Tdng nhiet dg Idm tdng so gdc khoi mdo, do dd tdng mirc dg phdn ung triing hgp. Ngodi ra, tdng nhigt dg cQng ldm tdng tdc do khuech tdn ciia cdc monome len mgch chinh tinh bdt cung nhu ndng lugng dgng hgc ciia cdc trung tdm goc tdng d nhigt dg cao Idm tdng muc do triing hgp vd do hdp thy nude ciia sdn phdm cuoi.
450 1 400400 350,09300'
-AMS-1 -AMS-2

Tdng hgrp polyme sieu hdp thu nude. Dg hap thy nude gidm khi nhiet do tdng qud cao la do: su phdn huy oxI hod ciia mgch tinh bdt do su phdn buy nhigt ciia KPS, tdng toe do phdn irng ngdt mgch vd chuyin mgch cung nhu sg phdn buy KPS tgo thdnh O2 Id chat bay goc tg do, phdn irng vdi cdc goc tu do C O bdn Idm gidm trgng lugng phdn tir. Cdu true mgng ludi vdi mgch phan tir ngan cd the khdng thuan Igi cho sg hap thy vd giQ- nude.
450

09350

-AMS-1 -AMS-2

<y

i
250 \ 200 ; 150 0

300 I 265 250 5 10 15 20 25 30 55 65 70 75 80 85 H4niliiQii|jtiihbQt(%)

Nhiet do (d$C)

Dilu kien phan irng: Hdm lugng MBA 0,03% (dii vdi Dilu kien phan ling: Ham lugng tinh bgt 10%; hdm AA) hoac 0,024% (dii vdi AM); ham lugng KPS 0,8% lugng MBA 0,03% (dii vdi AA) hodc 0,024% (dii vdi (dii vdi AA) hoac 1,0% (dii vdi AM); nhiet do 70C; AM); ham lugng KPS 0,8% (doi vdi AA) hoac 1,0% (dii mirc do trung hoa 75% (dii vdi AA) vdi AM); muc do trung hod 75% (dii vdi AA) Hinh I: Anh hudng ciia hdm lugng tinh bdt den do hdp thy nude cua sdn phdm 3.4. Anh hudng cua ham lugng chat khoi mao Anh hudng ciia hdm lugng chat khoi mdo tdi do hdp thy nude cua cdc sdn phdm dugc trinh bdy tren hinh 3. Do hdp thy nude tdng khi tdng ndng do chdt khoi mdo den mdt gid trj nhdt djnh, sau dd gidm khi tiep tuc tang chdt khoi mdo. Khi tdng ham lugng KPS, sd goc tu do dugc tgo thdnh tdng ddn tdi nhieu ddu
450 400
.-^350 -2?
w

Hinh 2: Anh hudng cua nhiet do den do hdp thy nude ciia sdn phdm mgch trong mgng ludi vd chieu ddi trung binh ciia mgch ddng hgc ngdn, ldm tang khd ndng hdp thy nude. Tuy nhien, khi tiep tyc tdng hdm lugng KPS se Idm tdng tdc do ngdt mgch qua va chgm ludng phdn tir vd lam gidm trgng lugng phdn tur cua homopolyme dugc tgo ludi, do dd riit ngdn mgch dgi phdn tir, ldm gidm the tich tu do cd sdn trong gel ddn tdi gidm do hdp thy nude [7].
420 1 400 380

-AMS-1 -AMS-2

.29 360 340

-AMS-1

^300

'263 320
250

300
200

0.4

0.8

1.2

1 . 6

60

65

70

75

80

85

90

Ham hong chk khoi mao (%)

Mucdgtninghoa(%)

Dieu kien phdn irng: Hdm lugng tinh bgt 10%; hdm Dilu kien phdn umg: Hdm lugng tinh bgt 10%; hdm lugng MBA 0,03% (dii vdi AA) hodc 0,024% (dii vdi lugng MBA 0,03%; hdm lugng KPS 0,8%; miic do trung AM); mirc do trung hod 75% (dii vdi AA) hod 75% Hinh 3: Anh hudng cua hdm lugng chdt khoi mdo tdi do hap thy nude cua sdn phdm Hinh 4: Anh hudng ciia muc do trung hod den do hap thy nude ciia sdn pham AMS-1

179

TCHH, T. 49(2), 2011 3.5. Anh hudng ciia muc dg trung hoa Anh hudng cua mirc dg trung hod tdi dg hap thy nude cua san pham AMS-1 dugc trinh bdy tren hinh 4. Sdn pham AMS-1 cd dg hap thy nude dgt cgc dgi d muc do trung hod 75%. Dieu nay dugc gidi thich la do khi axit acrylic trong mgng ludi gel dugc trung hod bdng NaOH, nhdm cacboxylat tich dign am trong mgch polyme sc sinh ra mgt lgc day tmh dien Idm md rgng mang ludi. Lgc day tmh dign tdng khi tdng mirc dg trung hod den mgt gid trj nhat djnh. Tuy nhien, tiep tyc tang mirc dg trung hod lam gidm dg hap thy nude do higu ung chan dign tich ciia Na^

Nguyin Thanh Tung vd

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du trong mdi trudng gay truang. C; Mon d^r chdn anion cacboxylat vd ngan chdn Igc day tiih dign higu dyng anion- anion gay md rgng '^g 1"P''Ngodi ra khi tdng mirc dg trung hod, dp 'dt tham thau giua pha dung djch vd pha gel gidm lam giam dg hap thy nude. 3.6. Hinh thai hgc be mat Hinh thdi hgc be mdt cua 2 mdu polyme sieu hap thy nude AMS-1 vd AMS-2 dugc quan sdt bdng each chyp dnh kinh hien vi dign tu quet (SEM). Ket qua dugc bieu dien tren hinh 5.

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(b) Hinh 5: Anh SEM cua mdu polyme sieu hap thy nude AMS-2 (a) va AMS-1 (b) Quan sdt hinh 5 thdy rdng bl mat cdc hgt polyme khdng ddng deu, ggn vd cd cdc vi mao qudn. B I mat ggn vd cd cdc vi bao qudn ndy Id phii hgp cho qud trinh thdm nhap cua nude vdo mgng ludi polyme.
4. KET LUAN

J.

Da nghien ciru dilu kign toi uu dl tdng hgp 2 sdn pham polyme sieu hap thy nude AMS-1 vd AMS-2 (triing hgp ghep AA vd AM len tinh bgt cd mat chat tgo ludi MBA). Dilu kign toi uu dl tdng hgp AMS-1 Id: hdm lugng MBA 0,03%, hdm lugng KPS 0,8%, nhigt dg 70C, mirc dg trung hod 75%, dg hap thy nude cue dgi dgt dugc Id 410 g/g. Doi vdi AMS-2, dilu kign toi uu Id: hdm lugng MBA 0,024%, hdm lugng KPS 1,0%, nhigt dg 70C, dg hdp thy nude cue dgi Id 325g/g. Tdng ham lugng tinh bgt lam gidm dg hap thy nude cua sdn phdm.
TAI LIEU

6. 7. 8. 9. 10. 11. 12.

THAM

KHAO

1. A. Das, V K. Kothari, S. Makhija, K. Avyaya. J.

Appl. Polym. Sci., 107, 1466 i470 (2008). R. H. Todd, S. K. Daniel. Polymer, 49, 1993 2007 (2008). C, Ni, X. Zhu. Eur. Polym. J., 40, 1075 1080 (2004). P. Chen, W. Zhang, W. Luo, Y Fang. J. Appl. Polym. Sci., 93, 1748 1755 (2004). K. Kabira, H. Omidian, S. A. Hashemi, M. J. Zohuriaan- Mehr. Eur. Polym. J., 39, 1341 1348 (2003). V. D. Athawale, V. Lele. Starch, 53, 7 13 (2001). S. Lu, M. Duan, S. Lin. J. Appl. Polym. Sci., 88, 1536- 1542(2003). A. Hashem, M. A. Afifi, E. A. EI-Alfy and A. Hebeish. American Joumal of Applied Sciences, 2(3), 614-621 (2005). Nguyen Thanh Tung, Nguyen Van Khoi. Vie. J. Chem., 47(speeial issue), 148-153 (2009). Nguyen Thanh Tung, Nguyen Van Khoi. Vie. J. Chem., Vol. 48 (5) (2010). Nguyen Thanh Tung, Nguyen Van Khoi, Nguyen Quang Huy, Tran Vu Thang. Advances in Natural Sciences, (in press). Huy N. Q., Ha P T. T., Hung H. T., Tung N. T, Khoi N. v.. Vie. J. Chem., 41(2), 127 131 (2003).

Lien he: Nguyen Thanh Tiing Vign Hda hgc, Vign Khoa hgc va Cdng nghg Vigt Nam - 18 Hodng Quoc Viet, Cau Giay, Ha Ngi. 180