685 - 690, 2009 MOT SO HE KHAU MACH QUANG TREN CO s 6 GLYXYDYL ETE CUA NHl/A 0-CREZOLFOMANDEHYT I - ANH HLfdNG CUA TY LE CHAT KHOl MAO QUANG CATION TAS DEN PHAN L/NG KHAU MACH QUANG HO
Trang 1Tgp chi Hoa hoc, T 47 (6), Tr 685 - 690, 2009
MOT SO HE KHAU MACH QUANG TREN CO s 6 GLYXYDYL ETE
CUA NHl/A 0-CREZOLFOMANDEHYT
I - ANH HLfdNG CUA TY LE CHAT KHOl MAO QUANG CATION TAS DEN PHAN L/NG KHAU MACH QUANG HOA QUA HE CG-BGDE-TAS
Den Tda soan 5-5-2008
LE XUAN HIEN, D 6 THI NGOC MJNU, NGUYEN THI VIET TRIEU
Vien Ky thuat nhiet ddi, Vien Khoa hgc vd Cong nghe Viet Nam
ABSTRACT
The influence of the content of cationic photoinitiator-triarylsulfonium salt (TAS) on the photocrosslinking of the systems containing glyxydyl ete of o-crezolformaldehyde resine (CO), hiscycloaliphatic diepoxy monome (BCDE) with the mass ratio CGIBCDE = 111 has been studied The study of the photopolymerization of the epo.vy group in the 20 jjin thickness film of the system
hy IR - Spectroscopy in the presence of TAS in the range from 1% to 7% of the total mass of the
CO and BCDE showed the fastest convertion rate of the TAS and epoxy groups at the content of TAS 5% leading to the final convertion of TAS, epo.xy groups of BCDE and the total epoxy groups ofCG and BCDE 99% 98% and 82% respectively after exposure under 250 mW/cnr intensity
UV - lamp
I - MO DAU
Do cd nhieu uu dilm ndi bat, viee che tao
cac idp phu bao ve, trang tri bing phuang phap
quang hda dang ed tdc do phat trien nhanh va
iirng dung trong nhilu ITnh vuc ky thuat, ddi
sdng [1,2] Trong dd, khau mach quang hda cae
hgp cha't chiia nhdm epoxy cd hieu qui cao, tao
mang ddng rin chit lugfng tdt dang thu hiit su
quan tam chii y ciia nhilu nha nghien cii*u [3, 4]
Nhua epoxy novolac sau khi ddng ran cd
nhilu tinh nang quy, cd do bin hda chit, bin
nhiet cao [5] Tuy nhien, cac kit qui nghien ciiu
khau mach quang hda nhua epoxy novolac vi
tfnh chat ciia sin phim cdn it dugc cdng bd
Phan irng khau mach quang hda ciia he khau
mach quang tren ca sd nhua va monome chiia
nhdm epoxy, chat khai mao quang cation chiu
anh hudng ciia nhilu yeu td nhu bin cha't va ty
le cac hgp phin, chilu day mang, cudng do biic xa [1 - 4, 6 - 11] Bai bao nay trinh bay kit qua nghien ciiu anh hudng ciia ham lugng chat khai mao quang cation TAS de'n qua trinh khau mach ciia he khau mach quang tren ca sd glyxydyl ete ciia nhua o-crezolfomandehyt, bisxycloaliphatic diepoxy monome va chit khai mao quang cation - mudi triarylsunfoni
II - THUC NGHIEM
1 Nguyen lieu va hda chat
- Glyxydyl ete cua nhua o-crezolfomandehyt (CG) ciia hang Sigma-Aldrich, Dire, ham lugng nhdm epoxy 2,7 mol/kg
- Monome bisxycloaliphatic diepoxy (BCDE
- loai Cyracure 6105 ciia hang UCB, cd ham
685
Trang 2lugng nhdm epoxy = 7,9 mol/kg
- Chit khai mao quang cation: mudi
triarylsunfoni (TAS) - loai Cyracure UVI - 6974
ciia hang Ciba
- Clorofom - loai P cua Ba Lan
2 Tao he khau mach quang
He khau mach quang dugc tao bing each
trdn diu cac td hgp nhua CG vdi monome
BCDE va chit khai m i o quang cation TAS theo
ty le trgng lugng CG/BCDE = 50/50, chiia tir 1
-7% TAS so vdd tdng trgng lugng eiia CG va
BCDE
3 Khau mach quang
Miu khau mach quang dugc tao mang ed do
day 20 jam tren vien KBr, dugc chilu dudi den
tir ngoai cudng do 250 mW/em' tren miy
FUSION UV model F 300S (My) tai Vien Ky
thuat nhiet ddi (Vien KTND), Vien Khoa hoe vi
Cdng nghe Viet Nam (Vien KHc&'CNVN)
4 Phan tich hong ngoai
Phan tich hdng ngoai dugc thuc hien tren
may FT-IR NEXUS 670 NICOLET (My) tai
Vien KTND, Vien KH&CNVN Biln ddi cac
nhdm dinh chdc ciia he khau mach quang trong
thdi gian chieu tia tir ngoai dugc xac dinh dua
vao sir thay ddi cudng do hip thu dac trung cua
chiing tren phd hdng ngoai Cic bien ddi nay
cdn dugc xac djnh dinh lugng theo phucmg phap
ngi chuin dua vao hip thu dae trung eiia dao
dgng hda tri eiia lien ket doi trong vdng tham tai
1506 cm"', khdng thay ddi trong qua trinh chilu
tia tir ngoai
Ill - KET QUA VA THAO LUAN
Nghien ciiu phd hdng ngoai cua ming trong
qua trinh chieu tia tir ngoai cho thiy eae hip thu
dac trung cho lien kit CH no trong dai 2847
-2935 c m ' , 1470 - 1434 c m ' , 1393 - 1300 c m '
va hip thu dac trung eho dao dgng hda tri cua
lien kit ddi trong vdng tham tai 1506 c m ' cung
nhu cudng do cua chiing khdng thay ddi Cudng
dd cac hip thu cd sd sdng 3475 em"' va 1084
e m ' dac trung cho nhdm hydroxyl v i nhdm ete
tang len Cae hip thu cd sd sdng 914, 790, 1798
c m ' dac trung cho tdng lugng nhdm epoxy ciia
686
CG va BCDE, nhdm epoxy cua BCDE va TAS giam rat manh Vi vay, sir thay ddi cudng do cua eae hip thu niy da dugc khao sat bing phuang phap ngi chuan theo cudng do hip thu dac trung eho dao dgng hda tri ciia lien ket ddi trong vdng tham tai 1506 em"'
Bie'n ddi ham lugng TAS trong cac he cd ty le chit khai mao khic nhau khi chieu tia tir ngoai mang diy 20 )im dugc trinh bay tren hinh 1 Tir hinh 1 ed thd thay khi ham lugng TAS trong he cd gia tri 1%, 3%, 4%, 5%, 7% lugng TAS cdn lai sau 18 giay chieu tir ngoai tucmg ling 22%, 8%, 6%, 1%, 15% gia tri ban diu Bie'n ddi tdng lugng nhdm epoxy ciia nhua
CG va monome BCDE cung nhu bien ddi ham lugng nhdm epoxy ciia monome BCDE trong cac he ed ty le chit khai mao khac nhau khi chieu tia tir ngoai mang day 20 )j.m dugc trinh biy tren hinh 2 va 3
Tir hinh 2 cd the thay khi ham lugng TAS thay ddi tir 1% de'n 7%, tdng lugng nhdm epoxy cua nhua CG v i monome BCDE giam nhanh trong khoang tir 0,3 - 1,2 giay dau ciia phan ung, dat eae do chuyin hoa 22%, 38%, 42%, 54%, 30% tuong irng vdi ham lugng TAS trong
he 1%, 3%, 4%, 5%, 7% Sau dd, chuydn hoa nhdm epoxy cham dan va hau nhu biSn ddi khdng dang ke, dat cic gia tri 28%, 64%, 72%, 82%, 46% sau 18 giay
Chuyen hoa nhdm epoxy ciia BCDE trong qua trinh chieu tia tir ngoai cung cd quy luat tuang tu nhu chuyen hda tdng lugng nhdm epoxy cua nhua CG v i monome BCDE (hinh 3), giam manh trong khoang 1,2 giay diu ciia phan iing vdi miic chuyen h o i 64%, 76%, 82%, 86%, 66% khi ham lugng TAS tucmg dng 1%, 3%, 4%, 5%, 7%, bie'n ddi cham din va hiu nhu khdng thay ddi, dat cac gia tri chuyen hoa 7 3 % , 92.%, 94%, 98%, 82% sau 3,6; 6; 12; 18 giay chieu
Ciing vdi bie'n ddi ham lugng nhdm epoxy, mat do quang tai 1084 em"' dae trung cho hip thu ciia lien ket ete C-O-C (hinh 4) va tai 3475
cm ' dae trung cho hap thu eiia lien kit O-H (hinh 5) tang len ro ret trong q u i trinh chiiu tia tir ngoai
Trang 3<;
CO
5-_5
E
X
100
80
60
40
20
Ham lugng TAS (%): • 1; -3; A 4; x 5; * 7
20 Thai gian chieu, sec
Hinh 1: Bie'n ddi ham lugfng TAS trong qua trinh chieu tia tu ngoai he khau mach quang
CG-BCDE-TAS
g o
a
.a
c
S
/rt
0
Thai gian chieu, sec Ham lugng TAS (%): • I ; • 3 ; A 4; x 5; * 7
Hinh 2: Bien ddi tdng lugng nhdm epoxy eiia CG vi BCDE trong qua trinh chieu tia tir ngoai he
khau mach quang CG-BCDE-TAS
687
Trang 4^ 100 f
X
o
n
E
^o
J2
C
60
g
S
E
.•rt
80
60
40
20
0
Thdi gian chieu, see Ham lugng TAS (%): • 1; • 3; A 4; x 5; * 7
Hinh 3: Biln ddi ham lugng nhdm epoxy ciia BCDE trong qua trinh chieu tia tir ngoai he khau
mach quang CG-BCDE-TAS
D1084cm"'/D1506cm"'
0.8 n
0.6
0.4
0.2
5 10 Thdi gian chieu (giay)
Ham lugng TAS (%): • I ; 3 ; A 4; x 5; * 7
Hinh 4: Bien ddi ti sd D1084 cm"'/D1506 cm"' tren phd hdng ngoai ciia he khau mach quang
CG-BCDE-TAS trong qua trinh chieu tia tir ngoai
688
Trang 5D3475cm"'/D1506cm"'
0.8
0.6
0.4
0.2
5 10 15
Thdi gian chieu, sec Ham lugng TAS (%): • I ; • 3 ; A 4;
20
x 5 ; * 7
Hinh 5: Bien ddi ti so D3475 cm"'/D1506 cm"' tren phd hdng ngoai cua he khau mach quang
CG-BCDE-TAS trong qua trinh chie'u tia tir ngoai Nhiing kit qua trinh bay tren cac hinh 1 - 5
cho thiy he vdi ham lugng TAS 5% cd chuyen
hda nhdm epoxy cao, tao nen nhilu lien kit ete
va lugng TAS du sau khi chieu tia tir ngoai
khdng nhilu Kit qua nay dugc giai thich bing
hieu ling chin anh sang ciia cac phin tir trong
chat khai mao quang Ham lugng chit khai mao
tang thiic day phan iing triing hgp quang do tang
kha nang tao thanh proton de khai mao phan
iimg nhung ddng thdi ciing tang sir che chin anh
sang tir ngoai lim giim tdc do phan quang ciia
chat khai mao Su canh tranh eiia hai xu the nay
la nguyen nhan lam he chiia lam lugng TAS ban
dau 5% ed chuyen hoa TAS, cac nhdm epoxy
nhanh va nhilu nhat trong qua trinh chilu tia tir
ngoai
IV - KET LUAN
Da khio sat qua trinh khau mach quang cua
mang tren ca sd nhua epoxy novolac CG,
monome epoxy Cyracure BCDE, chit khai mao
quang cation - mudi triarylsunfoni TAS vdi ty le
chat khai mao khac nhau
Da lua chgn dugc he khau mach quang vdi
ty le cac hgp phin CG/BCDE/TAS = 50/50/5 cd tdc do chuyen hoa TAS, cac nhdm epoxy cao va
cd gia tri chuyen hoa TAS cao nhit, cd chuyin hoa nhdm epoxy ciia BCDE va tdng lugng nhdm epoxy tucmg iing 99%, 98% va 82% khi chilu tia tir ngoai
Ldi cam ofn: Tap the tdc gid chdn thdnh cdm an chuong trinh nghien cihi co bdn trong ITnh vifc Khoa hoc Tii nhien dd ho trg kinh phi de hodn thdnh cong trinh ndy
TAI LIEU THAM KHAO
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Trang 65
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Anthony Kelly, Carl Zweben, Comprehensive
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Le Xuan Hiln, Vu Minh Hoing, Nguyin
Thi Viet Trieu Tap chi Khoa hoc v i Cdng
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Le Xuan Hien, Nguyin Thi Thanh Phong,
Dd Thu Hien, Nguyin Thi Viet Trilu Tap
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690