TAP CHI HOA HOC T. 51(6)686-690 THANG 12 NAM 2013
NGHIEN CLPU T 6 N G HaP BIS(1.10-PHEN)Eu{NO3)3, LPNG DUNG LAM PHU GIA CH^ TAO MANG POLYME HAP THU VA CHUYEN HOA BLFC XA
Mai Van Tign'*, Pham The Trinh', Le Thi Hai' Vien Hod hoc Cong nghiep Viet Nam
^Trudng Dgi hgc Tdy Bdc Den Toa soan 24-5-2013
Abstract
The conqilex bis( 1,10-Phen)Eu(NO3)3 was synthesized from EU2O3 with complexing ligand 1,10-phenanthroline.
Composition, structural characteristics and the nature of the complexes were detennined by the methodS: SEM-EDX, IR spectra, ihermal analysis- TGA, 'H-NMR, '^C-NMR spectmm. UV-VIS spectras and fluorescence spectroscopy. Bis (1,10-Phen)Eu(NO;)3 was used to make the masterbatch, apphcaUon in polymer as light absorption and convertion additives the basis of LDPE.
Keywords: Functional polymer, 1,10-Phenanthrohne, Europium, complex, absorption and convertion of radiation.
l.DATVANDE
Trong nhii'ng nam gan day, nghien cim tdng hgp va iing dung phirc chat ciia cac nguyen td dat hiem (NTDH) dang rat dugc quan tam [1], dac biet phiic chat tren ca sd ciia cac nguyen td dat hiem nhu: Eu, Tb, Nd, Sm...vdi nhieu loai phdi tu tao phirc khac nhau. Phirc chat tren ca sd nguyen td dat hiem Europi vdl phdi tir tao phuc 1,10-phenantrolin dugc nghien cim tdng hgp va img dung trong nhieu ITnh virc nhu: ITnb vuc dien tir, quang tu, huynh quang, ndng nghiep, lam ngu nghiep... [2-^5]. Bao cao nay gidi thieu phuang phap tdng hgp, phan tich dac trung cau friic tinh chat ciia phuc bis(l,10- Phen)Eu(N03)3 va djnh hudng iing dung phirc chat nay de che tag phu gia phuc vu cho viec nghien cuu che tao mang polyme hap thu va chuyen hda buc xa tren ca sd nhira LDPE img dung trong ndng nghiep va ddi sdng
2. THUC NGHIEM 2.1. Nguyen lieu, hoa chat
- EU3O3: 99,99 %, Merck (Dire).
- 1,10 phenantrolin 98 %, Aldrich (My).
- HNO3: 63,5 % (Trung Quoc).
- Etanol: 98 % (Viet Nam).
Nhua polyetylen ty trgng thap (LDPE) (Malaysia); khdi lugng rieng 0,92 g/cm^, chi sd chay
(190 °C/2,I6 kg), MFI 2,5 g/10 phut.
- Cac loai hoa chat phan tich can thilt khac.
2.2. Phuffng phap nghien cuu 2 2 I Tdng hgp bisfflO-PhenJEufNOjJj
Phirc chit bis(l,!0-Phen)Eu(NO3)3 dugc tdng hgp tir EU2O3 vdi phdi tir tao phuc 1,10-phenantrolin qua hai giai doan:
Giai dogn 1: Chuyin EU2O3 sang dgng muoi Eu(NOj)s:
Hda tan EujOj trong dung dich HNO3 2 N (du) cd gia nhiet va khuay nhe. Khi EU2O3 tan hoan toan, tiln hanh cd dung dich dk duoi axit du chua phan img het cho tdi khi xuat hien ket tiia thi dimg lai, bd sung nudc cat va lap Iai qua trinh cd cho tdi khi loai bd het axit (khoang 3-5 lan). Eu(N03)3 ket tiia dugc lgc va siy tai 80^0 trong thdi gian 3 gid den khdi lugng khdng ddi.
- Giai dogn 2: tiin hdnh long hgp phirc chdl bis(1.10-Phen)2Eu(NO3)3
Hda tan Eu(N03)3 trong etanol va di6u chinh den pH = 6-^7 b ^ g kiem. Song song, hda tan lugng 1,10-phenantrolin (Phen) trong etanol (lugng Phen dugc tinh trudc theo ti 1? mol phan Cmg) trong binh phan img 3 cd, cd pheu nhd gigt va cd lap may khuay. Tien hanh tdng hgp phirc bang each cho dung dich Eu(N03)3 vao pheu nhd tir tir timg gipt dung dich Eu(N03)3 da pha cho tdi h8t vao dung dich 686
TCHH, T. 51(6), 2013
phenantrolin. Phan img thuc hien tai nhiet dp trong khoang 60-75 °C, khuay lien tuc cho den khi dimg phan ling theo cac khoang thdi gian nhat dinh lira chgn tir 1 -5 gid. Hdn hgp phan iing sau dd dugc lam ngudi tdi nhiet do phdng. Tiln hanh lgc rira thu san pham bis(l,10-Phen)2Eu(NO3)3 dudi dang kSt tiia mau hdng nhat trong etanol, say san phim tai 70-80
°C cho den khdi lugng khdng ddi. San pham phirc chat thu dugc dudi dang bgt min, mau hdng nhat dugc dem di phan ti'ch va che tao hat nhua gdc chiia phu gia.
2.2.2. Chi tgo hgt nhua goc chira phu gia Can djnh lugng phirc chat, nhua va phu gia khac theo dan phdi lieu dinh san, dua toan bp hdn hgp nhua vao may trdn vat lieu da gia nhiet trudc do d khoang 70-^80 °C, tien hanh trdn ky hdn hgp trong khoang 30 phut.
Td hgp nhua dugc tnit ra sau may trdn dua ngay sang may dim true vit da gia nhiet san. Td hgp nhua di qua may dim true vit, vdi 3 vimg gia nhiet da dugc dieu chinh trudc: viing 1: 150 °C, vimg 2:
170 "C, viing 3: 180 °C. San pham td hgp nhua ra khdi dau dim (dau pep cd tir 5^7 Id, dudng kinh Id pep cd 3H-4 mm) dugc keo thanh sgi di qua mang nudc lam lanh den may chem hat. Tai day nhua dugc cat Ihanh hat nhd. Dp dai hat dugc dieu chinh nhd may chem hat de cd dugc kich thudc mong mudn (thudng la tir 2 mm den 4 mm). Hat nhira dugc say d 80 °C, trudc khi ddng gdi, bao quan hay dugc sir dung de thdi mang.
2.3. Cac phucng phap phan tich dac trung cau true tinh chat cua san pham
- Phd hong ngoai IR dugc thuc hien tren may Impact-410 NICOLET (My).
- Phuang phap phd cgng hudng tir NMR dugc thirc hi?n fren thiSt bj AVANCE-500 hang BRUKER (Dire).
- Phd tan xa nang lugng SEM-EDX tien hanh fren may JED-2300 ciia hang JEOL (Nhat Ban).
- Kinh hian vi dien tii: quet SEM-JSM 5410- JEOL (Nhat Ban).
- Phan tich nhiet TGA-DSC tren may LABSYS STEARAM (Phap).
- Phan tich tinh chat quang tren thiet bi do phd huynh quang FL3-22 (My).
Tinh nang ca ly xac dinh theo tieu chuan ASTM tren may do LLOYD (Anh).
3. KET QUA VA T H A O LUAN
3.1. Tong h9p, dac trung cau true, tinh chat ciia phiic bis(l,10-phen)2Eu(NO3)3
Mai Vdn Tien vd cgng sir 3.1.1. Tdnghgpphuc
Phirc chat bis(l,I0-Phen)Eu(NO3)3 da dugc nghien cim tdng hgp nhu md ta trong muc 2.2.1, trong qua trinh thuc nghiem khao sat anh hudng cua dieu kien phan va nit ra dugc cac dieu kien thich hgp de tdng hgp phiic chat nhu sau:
Bdng T. Dieu kien thich hgp de tdng hgp phiic chat bis(l,10-Phen)Eu(NO3)3
SIT 1 2 3 4 5 6 7
Dieu kien Ty le so mol giffa Eu'71,10-phen
Nong do mol ion Eu *, mmol
Nong do mol cua phoi tu (1,10-phen), mmol Nhiet do phan ung, °C Then gian phan ung, h Hieu suat phan iing, % Ngoai quan san pham
Gia tri 1/2
2 4 70 3 82,7 Bot min, mau
hong nhat 3.1.2. Dgc trung cdu'triic, linh chdt phirc bisfl.lO- Phen)Eu(NOj)s
• Phd SEM-EDX cua bis(l,10-Phen)Eu(NO3)3
Hmh !: Gian dd phan tich SEM-EDX ciia bis(l,10-Phen)Eu(NO3)3
De xac dinh thanh phan nguyen td ciia phirc chat bis(l,I0-Phen)Eu(NO3)3, phuong phap SEM-EDX da dugc sii dung. Ket qua xac dinh thanh phan phan cac nguyen td ciia phirc bis(l,10-Phen)Eu(NO3)3 (hinh 1) va so sanh vdi Iy thuyet cho thay sd lieu giu'a ly thuyet va thuc nghiem la kha gan nhau. Tir ket qua thu dugc cd the khang dinh cdng thirc cau t^o ciia phirc chat Bis(l,10-Phen)Eu(NO3)3 la phii hgp vdi cdng thirc gia djnh theo ly thuyet cua phirc Bis(],10- Phen)Eu(N03)3 va dugc rmnh chimg them tren phd hdng ngoai IR va phd cgng hudng tir NMR
Phd hdng ngogi IR, phd cgng hudng tir ' H - N M R va "C-NMR ciia bis(l,10-Phen)Eu(NO3)3.
Phd hong ngo^i ciia phirc bis(1.10-phen)Eu(NO3)j (hinh 2b) cho cac tan so dao dgng dac tnmg nhu UC-N
TCHH, T. 51(6), 2013 Nghien dm tdng hgp bis(1.10-Phen)Eu(NO3)3,-.
= 1572,79 cm"', x>cA\{<h<m>) = 3074,69 cm'', Uc=c = dao ddng cua nhdm -OH khong th6 hien ro (UQ-H = 1627,19 cm"'. So vdi phd IR cua 1,10-Phen cac tin so 3383,13 cm"'), chiing td cd sir tao thanh lien ket gitra dac tnmg nay d6u cd sir dich chuyen dang ke, ngoai ra 1,10-phen va ion Eu *
Hmh 2: Pho IR ciia 1.10-Phenantrolin (a). bis( 1.10-Phen)Eu(NO3)j (b) Pho cpng huong tir hat nhan ciia bis(l,10-Phen)Eu(NO3)3
Hinh 3: Phd 'H-NMR cua 1,10-phenantrolin (a), phirc bis(l,10-Phen)Eu(NO3)3(b)
Ket qua chi ra: sau khi tao phirc vdi ion Eu^"^ do djch chuyen ciia cac nguyen tii H va C cua phdi tii 1,10-Phen trong phirc cd su thay ddi so vdi phdi tii 1,10-Phen. Dp dich chuyen hda hgc ciia nguyen tu H the hien ro tai cac vi tri ddi vdi 2 ^ 1 , 9—*-10, Ddi vdi nguyen tir C tai cac vj tri 2 , 9, 11 va 12 quanh nguyen tii N, dieu nay minh chimg cho su hinh thanh cac lien ket phdi tir tao phiic.
Tinh chat quang cua phiic bis(l,10-Phen)Eu(NO3)3 De xac dinh tinh chat quang ciia phirc chat, phuong phap phd kich thich huynh quang da dugc sir dung de phan tich cudng dp hap thu va phat quang ciia phiic.
Ket qua phan tich tinh chat quang ciia phiic bis(l,10-Phen)Eu(NO3)3 cho thay, phiic cd kha nang thu hoan toan anh sang cd budc sdng tir 20CH-400 run va phat quang tai budc sdng trong khoang tir 580-^688 run. Chimg td phiic chat cd kha nang hap thu tdt anh
sang cd budc sdng ngan tir 200-400 nm va phat quang tai vimg anh sang nhin thay (580-^688 nm).
Ket qua nay md ra trien vgng irng dung phirc chat lam phu gia che tao mang polyme hSp thu va chuyen hda birc xa, thiic day qua trinh quang hgp nham tang nang suat cho cay trdng.
3.2. NghiSn cihi phan tan bis(l,10-Phen) Eu(N03)3 Ien nen nhira LDPE dl che tao phu gia (hat nhua goc) hap thu va chuyen hoa birc xa 3.2.1. Dan phoi lieu va cdc dieu kien cdng nghe che tgo hgt nhua gdc (masterbatch)
Da tien hanh nghien cuu phan tan thanh cdng phiic chat Ien nen nhi/a LDPE dk che tao phu gia (hat nhua gdc) va lira chon cac dieu kien thich hgp (bang 2).
TCHH, T. 51(6), 2013 Mai Van Tien vd cgng su
.tsoooooo .10000000 3 5 0 0 0 0 0 0
Hinh
Budc sdng, nm
: Phd kich thich va phat xa ciia phiic bis(l,10-Phen)Eu(NO3)3 Bdng 2 Don phdi lieu va cac dieu kien che tao phu gia (hat nhua gdc) STT
I 1 2 3 4 5 II 1 2 3 4 5
Dieu kien cong nghe Thdnh phdn dan phdi lieu che tgo hai nhua goc Ty le phiJc chat bis(l,10-Phen)Eu(NOj)j/LDPE Ty le chat chong oxi hoa Irganox 1010 Ty le chat chong oxi hoa Irgafox 168 Chat on djnh quang HALS Chat chong dong suong
Dieu hen gia cong tren mdy dim true vit Nhiet dp vung 1
Nhiet do vCing 2 Nhiet dp VLing 3 Thoi gian lim Toe dp quay cua true vit
Gia tri 1%
0,02 % 0,04 % 0,2 % 1%
150 °C 170°C 180°C 3phul 30 v/phut 3 2 2 Tinh chdt ddc trung cua phu gia (nhua hgt
goc) hdp thu vd chuyin hga hire xg
- Nhua hat gdc (phu gia) chira phu gia phirc chat cd cac dac trung tinh chdt (bang 3).
Bdng 3: Tinh chat ciia nhua hat goc Tinh chat
Chisd MFI (190 "0/2,16 kg), g/10 phiit Dp ben keo dirt 5K, MPa Dp dan dai khi dut e, % Ng09i quan san pham
Hat nhua gdc 2,34 24,1 285,2 Hat trang, trong md, kich thudc ddng deu, be mat bdng mm.
- Tinh chat nhiet ciia hat nh\ra goc:
Gian dd phan tich nhi?t TG-DSC cua hat nhira goc (hinh 5) xuat hien hai hieu ling thu nhi?t va hai hi?u img tda nhi?t. Hi?u iing thu nhi?t thii nhSt tai 116
"C tucmg img vdi qua trinh ndng chay ciia nhua LDPE, hieu ling tda nhiet tai 244 "C va 344 "C tuong img vdi su phan hiiy pha va cau tnic ciia phdi tir Phen trong phirc chat bis(l,10-Phen)Eu(NO3)3. Hieu img thu nhiet tai 480 °C tucmg ung vdi qua trinh phan hiiy ciia phiic chat. Ket qua phan tich nhiet cho thay rang nhira hat chii, cd tinh chat nhiet tdt, dam bao dii dieu kien sir dung de gia cdng che lao mang polyrne hap thu va chuyen hda birc xa tren ca sd LDPE.
4. KET LUAN
I. Da tien nghien cim tdng hgp thanh cdng phirc chat bis(l,10-Phen)Eu(NO3)3 tir nguyen lieu dau la EU2O3 vdi 1,10-phenantrolin. Vdi cac dieu kien thich hgp la: ty 1? mol Eu^*/Phen la 1/2, nhiet dp phan iing 70 "C, thin gian phan img 3 gid. hieu suat tdng hgp phirc dat dugc la 82,7 %. Sir dung cac phuang phap:
SEM-EDX, pho IR, pho 'H-NMR, '^C-NMR, TGA- DSC... de phan tich thanh phan, djc
T C H H , T. 51(6), 2 0 1 3 Nghien ciru tdng hap his(}.10-Phen)Eu(NO3)3....
t r u n g cau t n i c , tinh chat san p h a m . d u n g d e c h e t a o m a n g p o l y m e h a p thu v a chuyen 2. Da n g h i e n ciiu p h a n tan phirc chat Ien n e n h d a biic xa. San p h a m t a o ra c d tinh c o , ly, nhiet tdt, n h u a L D P E de c h e t a o p h u gia (hat n h u a g d c ) iing cd t h e sii d u n g d e gia c d n g c h e tao m a n g m d n g .
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Hinh 5: G i a n d o p h a n tich nhiet T G - D S C c u a hat n h u a gdc T A I L I E U T H A M K H A O
1. Shiroki Iwanaga. Emission ProperUes. Solubility, Thermodynamic Analysis and NMR Studies of Rare- Earth Complexes with Two Different Phosphine Oxide, Materials, (3), 4080-4108 (2010).
2 Le Chi Kien, VO Kim Thu. Tong hap vd nghien ciru su tao phiic trong he ion ddt hiem (lll)-anion antramlat-phenantrolin. Tap chi Hoa hoc, 44(2), 147-151 (2006).
3. Nguyin Diic Vugng, Nguyen Dinh Luyen. Tong hgp vd xdc dinh cdu true phirc chdt cua neodim (HI) vdi
phoi tir 1.10-phenantrolin vd nitrat. Tap chi Khoa hgc, (65), 121-130(2011).
4. Jiun-Pey Duan, Pei-Pei Sun, Chien-Hong Cheng.
Europium complexes having an Aminophenanthrobne Ligand as red dopants in electroluminescent devices, Azojomo, (1), 1-11, (2005).
5. Zhibin Zhang, Changrui Zhang, Meigong Fan, Wenpeng Yan. Synthesis and complexation mechanism of europium ion (Eu^^) with spirofindoline-phenanthrolineoxazine], Dyes and Pigment, 1-5 (2007).
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