DASB), were used as fluorescence probes for cure monitoring of photocurable polymer system1s. *This technique is based upon the difference in fluorescence, ...
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Intramolecular charge Transfer Complexes as Fluorescence probes fog UV and Vtqjhlp 1.9ghf Indhiwr AM]rynt -Pn1yiViP*in
N00014-91+J1921
jiancheng Song, Afranio Torres-Filho and D.C. Neckers 7.7. EFORINGO~GNIZA.~: NAEIS 7RFO~INGORGAIZATG.' NAMM -ND.~OES~E3~8. -N ACRE55.E.-)
I-ERFORMING ORGANIZATION -EPORT nUMBER I.
Center for Photochemical Sciences Bowling Green State University Bowling Green, OH 43403
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Intramolecular charge transfer complexes (ICTC) of derivatives of 1-diaminonaphthalene-5sulfonamide (DANSYL ANMIE) such as 1-dimethylamino-naphthalene-5-sulfonyl-nbutylanude (l,5-DASB) and 2-dimethylaminonaphthalene-5-sulfonyl-n-butylamide (2'5 DASB), were used as fluorescence probes for cure monitoring of photocurable polymer system1s. *This technique is based upon the difference in fluorescence, intensity from the parallel and ~perpendicular conformations of -the excited state of the complex, and is based on the dependence, of the relative population of each conformation on the mucroviscosity of the system. As the curing reaction proceeds, the steady state fluorescence emission spectra of the probes were all found to exhibit hypsochromic spectral shifts due to the increase in matrix microviscosity. A ~ linear correlation between the fluorescence intensity ratios (R=Ipar./Iper.) and the extent of ~~polymerization, measured by transmission FflR spectrometry, was obtained for different types &.of acrylated polymers, cured with UV or visible (VIS) initiators.
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1a. SUBJECT TERMS
Intramolecuiar-Charge Transfer Visible-Light Induced Acrylate Polymerization 17. SECURITY CLASSIFICATION OF REPOR
18. SECURITY CLASSIFICATION OF THIS PAGE
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OFFICE OF NAVAL RESEARCH GRANT N00014-91-J-1921 R&T Code 413t006 Dr. Kenneth Wynne Technical Report No. 4 Intramolecular Charge Transfer Complexes as Fluorescence Probes for UV and Visible Light Induced Acrylate Polymerization
by Jiancheng Song, Afranio Torres-Filho and D.C. Neckers Prepared for RadTech Center for Photochemical Sciences Bowling Green State University Bowling Green, OH February, 1994 Reproduction in whole or in part is permitted for any purpose of the United States Government This document has been approved for public release and sale; its distribution is unlimited.
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INTRAMOLECULAR CHARGE TRANSFER COMPLEXES AS FLUORESCENCE PROBES FOR UV AND VISIBLE LIGHT INDUCED ACRYLATE POLYMERIZATION J. C. Song, A. Torres-Filho and D. C. Neckers Center for Photochemical Sciences* Bowling Green State University Bowling Green, Ohio 43403, USA
ABSTRACT derivamives ul derivativ~es
of
hg trdiaminonshthieronpexesu(ITC)ofa 1 -diaminonaphthalene-5-sulfonamide
AMIDE), such as I -dimethviamino(DANSYL naphthalene-5-sulfonyl-n-butylamide (1,5-DASB) and 2dimethylaminonaphthalene-5-sulfonyl-n-butylamide (2,5-DASB), were used as fluorescence probes for cure This monitoring of photocurable polymer systems. technique is based upon the difference in fluorescence intensity from the parallel and perpendicular conformations of the excited state of the complex, and is based on the dependence of the relative population of each conformation on the microviscosity of the system. As the curing reaction proceeds. the steady state fluorescence emission spectra of the probes were all found to exhibit hypsochromic spectral shifts due to the increase in matrix microniscosity. A linear correlation between the fluorescence intensity ratios (R=lpar./lper.) and the extent of polymerization, measured by transmission FTIR spectrometry, was obtained for different types of acrylated polymers, cured with UV or visible (VIS) initiators,
INTMODUCIION
initiation, reaction conditions and the rate and degree of polymerization. Thus, a thorough understanding of the photocuring process is essential to property control and process optimization of the final products. Several methods have been developed to study the kinetics of photopolymerization. Among them are photodifferential scanning calorimetry (PDSC), 2 "5 laser interferometry, 6 photoacoustic spectroscopy 7, and UV and FrIR spectroscopy. 8 -10 PDSC is basically like a modified DSC, with a Hg lamp source mounted next to the sample. It has been extensively used to study the kinetics of photopolymerization and the degree of cure can also be measured. However, PDSC is not useful for real time cure monitoring and non-destructive analysis of photopolymers. FMIR is widely used to determine the degree of photopolymerization by monitoring the concentration of residual monomers present in various polymer systems. A real time infra-red (RTIR) technique developed by Decker et al.8, 9 allows one to monitor the polymerization process continuously and rapidly in real time. Both the rate and degree of polymerization can be measured. However, IR techniques can only be used to analyze thin films (less than 20 gm thick). Besides that, transmission IR techniques cannot be used to monitor the degree of polymerization of coatings on opaque substratmes. Also, they are not useful for
Photocurable polymers are used as coatings for various substrates, such as metals, glass, plastics, wood, floors and paper.1 Highly crosslinked polymer networks can be rapidly formed via photopolymerization of
monitonng polymerization of bulk materials, such as parts made by stereolithography, which is a technique designed to form three dimensional objects by the assembly of a series 11 of photopolymers layers.
multifunctional monomers, especially acrylics. The ultimate properties of these polymeric networks depend on various factors, such as monomer structure, forms of
Fluorescence spectroscopy has gained considerable
"Contribution# ISO from the Center for Photochemical Sciences
interest due to its high sensitivity, selectivity, and nondestructive characteristics. Remote sensing is readily
achieved by using fiber-optic cables to transmit optical signals to and from a polymerization system in real time.
* Recently, Neckers et aL.12-15 reported the successful use of fluorescence probes to monitor the photo-cunng process of
the Sartomer Co.). and dipentaervthrvtoi monohvdroxv
polyolacrvlate monomers. Two types of fluorescence probes
Chemucal Co.), on a weight percentage ratio of 20:40:.40,
were found to be particularly useful. The first is based on
respectively.
"excimer" (i.e. excited dimner) forming molecules, such as
18 was utilized as fluorone. DIBF, developed in our group,
pyrene or its derivatives. 16 The ratio of the emission
VIS initiator at a concentration of about Ix 10-3 M. An
intensities of the monomer and excimer was round to
amune co-initiator N-phenyl glycine, NPG (Aldrich) was
correlate well with the degree ot cure. The second is based on intramolecular charge transfer molecules, such as 4(N'N-dimethyl-anuno)benzonitrile (DMABN), and dansyl amide and its derivatives. DMABN exhibits dual fluorescence corresponding to two different singlet excited states called twisted intramolecular charge transfer (TICT) states.I 7 The short wavelength (b) band is due to a
pentaacrvlate. DPHPA (Sartomer 399. from the Sartomer A xanthene dye, 5,7-diiodo-3-butoxy-6
2 also used at a concentration of about 5x10- M. The coinitiator in this case acts as an electron donor to the excited state of the dye, before the generation of free radicals.18
For commercial photocurable resins, two types of acrylated polymer coating formulations (Formulation I and II, both with LV initiators) were investigated.
while the coplanar tnarallel) excited state conformation roma prpediclarAs
fluorescence probes either 1.5-DASB or 2,5-DASB
long waveiength (a') band ongnates from a perpendicular
were used at a concentration of about 5x10 -4 M in the
conformation. The coplanar conformation is more stable in the ground state because of higher delocalization of the it
photopolvmerzable resins.
orbitals. Therefore, the coplanar excited state will be
2.
.engh (*) andoriinaes longwavj
directly populated from the ground state. However, the perpendicular excited state is energetically more stable due to the charge separation. This implies that the molecules are first excited to b" and then "cross" to a', making the
Cure Procedure
An Ar* laser (Qmnichrome. model 543-200 MGS) was used for visible light initiated polymerization of
multifunctional acrylate monomers. To compare samples
population of the perpendicular conformation strongly dependent upon the microenvironment of the TICT molecule.
with different degrees of cure the laser power varied from 30 to 80 mW. To photocure the commercial acrylate
In fact, fluorescence spectra of TICT probes were found to be very sensitive to changes in the microviscosity of the
-coatings a medium pressure Hg-arc lamp was utilized. The degree of polymerization for different samples was varied
medium. In particular. the ratio of the emission intensities
by changing the exposure time to the UV lamp.
at two different emission wavelengths can be correlated
A few drops of the monomer solution being studied
linearly with the degree of cure for various polvolacrylate
were first squeezed between two NaCl plates with a 15.0
lgm thick teflon spacers at the edges to control the final
mom Sytel. In this work we present our recent efforts to develop intramolecular charge transfer (ICT) fluorescence probes for
thickness. The laser beam (2.0 mm diameter) was directed to the sample and scanned at a speed of 13.0 mm/sec using
various photopolymerizable coatings. The ICT probes studied were 1-dimethylaminonaphthalene-3-sulfonyi-n-
computer controlled reflecting mirrors and data files specifically designed for stereolithography purposes.
2-
Steady state fluorescence emission spectra of samples
butylamide
(1,5-DASB),
and
dimethylaninonaphthalene-5-sulfonyl-n-butvlamide
cured for different period of time were obtained via a Spex
(2,5-DASB).
Fluorolog-2 spectrophotometer. Remote measurement was carried using a bifurcated fiber-optic cable attached to the excitation and emission monochromators, respectively. Infra-red measurement of the extent of double bond
1. Materials A mixture of multifunctonal acrvyates was made bv mixing polyethylene glycol-400 diacrylate. PEGA-400
conversion was accomplished using a Mattson Galaxy Series 6020 FT-IR spectrometer with a spectral resolution of 2 cm-
Inc.),
1. The extent of C=C conversion (a) was obtained by using the following equaton.
(Monomer-Polymer
and
Daiac
Labs.
trimethylolpropane triacrvlate, TMPTA ( Saret 331, from
swamn arm an Arl laser as the irradiation source. The data
(1
a wi - A.ryWt.Aref(0)/Aacry(O)/Aref(t)
displayed are the percentages of CC double bond where Aacry(t) and Aacry(O) are the absorbances at 810
converted to single bonds by the photopolvmerization
cm-1 due to the acriytate double bond, after curing times t and zero, respectively. Aref(t) and Aref(O) are the
process. as well as the laser power used for the different samples, and the ratios, R, between the fluorescence
reference peak absorbances at 2945 cm"1 due to the CH
intensites at 430 and 500 nm, respectively, corresponding to
groups, after curing times t and zero, respectively.
the emissions from the two conformations of excited state of
This
reference peak was used as an internal standard to calibrate
2,5-DASB.
any thickness fluctuation during the cunng process. Table 1. Results of IR and fluorescence analyses of the djeree of polyn-nzation of a multifunctional acrAlate monomer solution usine 25-DASB as a E A Urobe. (Initiator = DIBF: Coinitiator w NPC: Irradiation source = Ar1ilau)
1. Comparison of Fluorescence Spectra of 1-5-DASB and 2,5-DASH Probes
Pi (MMW
%C-C
R (1430/IS0)
30
16.7
1.20
Both 1,5-DASB and 2,5-DASB are DANSYL amide derivatives. Previous work by Neckers, et al. showed that 2.5-DASB
was useful as a fluorescent
photopolymerization of polyolacrylates.
13
probe for
5022.7
1.26
Although 1,.5-
DASB differs just slightly from 2,5-DASB in the position of dimethyl amino group on the naphthalene nng, their
80
1.40
36.2 --------
fluorescence spectra differ significantly as shown in Figure
When the R values were plotted against the extent of CwC
1. The excitation peak positions of 1,5-DASB and 2,5-
conversion (Figure 2) a very good linear correlation was
DASB in a dilute THF solution were found to be at 342 rn
obtained (r-0.9999) with the ordinate intercep (0.0 %
and 374 nrm, respectively. This is consistent with their UV
CC) corresponding to the ratio of the fluorescence
as 1,5-DASB absorbs at a
intensities emitted by the excited states of the probe in
shorter wavelength (330 nrm) than 2.5-DASB (374 nm). In
solution, before the photopolymerization process. This first
contrast the fluorescence emission peak position of 1,5-
test clearly indicated that the technique and probe were
DASB is at much longer wavelength (494 nm) than that of
well suited to be used in these highly crosslinked
2,5-DASB (450 nm). Therefore, the Stokes shift of 1,5DASB (152 nm) is twice as large as 2.5-DASB (76 nm). A
photopolymer systems.
larger Stokes shift is a significant advantage for
3.
absorption peak positions,
monitoring photopolymerization since spectral blue shifts
1,5.-DASB as a Fluorescence Probe of the Degree of Photopolymerization.
in the TICr probe fluorescence emission are often observed as the polymerization proceeds due to the increase in
(i). Photocurable resins with UV initiators
The intrinsic fluorescence from the photopolymer (if any) would have less interference to the probe fluorescence with a large Stokes shift value,
To investigate the applicability of 1,5-DASH as a fluorescence probe for photo-polymenzation, we doped 1,5-
matrix viscosity.
DASB at a small concentration into various commercial 2. 2,S-DASB as a Fluorescence Probe for the Degree of Photopolymerization of Multifunctional Acrylate I-MonoMeUs Using Visible Photoinitiators and Visible Lght Emitting Curing S Table 1 presents results corresponding to the
acrylate coating resins. The probe fluorescence enission spectra in the photopolymer systems studied were monitored as a function of irradiation time.
As the curing
reaction proceeds, fluorescence emission peak position exhibits blue shifts due to increases in the medium viscosity which makes it more difficult to form the long wavel ngth Figure 3 compares the
photopolymerization of the mixture of multifunctional
charge transfer excited state.
acrylate monomers using DIBF and NPG as the initiator
fluorescence emission spectra of 1,5-DASB probe in a
commercial photocurable acrylate (Formulation i) betore
degree of polymerization and an incomplele photo-
and after a full curing (30 seconds under a medium pressure
bleaching of the photo-initiators. It is interesting to know
Hg lamp). A total spectral blue shift of about 20 nm was
the effects of visible initiators on the fluorescence spectra
Similar to what described previously,15 I'e
of the 1,5-DASB probe. Thus we investigated the
monitored changes in fluorescence intensity ratios as a
applicability of the new fluorescence probe to monitor the
function of irradiation time as illustrated in Figure 4.
It
photo-cunng reaction of multifunctional acrylates initiated
can be seen that the general trends in the three cases (R
=
via
obtained.
L470/1560,1470/1550 and 1470/1540) are about the same. extent of double bond linear correlations between the
laboratories.
in our
dye initiators developed
the visible 18
The monomer solution contains
TMPTA/DPHPA (1:1 molar), polyethylene
•ycol, DIBF
(initiator) and NPG (coinitiator). The fluorescence emission
conversion of Formulation I vs. the fluorescence intensity
intensity ratio (1470/15W0) of 1,5-DASB probe was found to
ratio of the fluorescence probe were obtained for all the three cases examined (R = 1470/1560, 1470/1550 and
increase from 1.1 (0% conversion) to about 2.2 (32%
1470/1540), as shown in Figure 5. However, the intensity ratio of 1470/1~560 was found to give the best linear
pressure Hg lamp. A linear correlation plot of the probe fluorescence intensity ratio vs. the extent of C=C conversion
correlation. Therefore, we chose to use 1470/1560 as the probe parameter to monitor the photopolymerization of
was obtained as shown in Figure 8. The linear relationship between R (1470/1560) and the extent of conversion (W) is
multifunctional acrylates.
given in Equation 4.
Figure 6 compares the changes in the extent of double
conversion) after 60 seconds of irradiation under a medium
(4)
R = 1.1167 + 3.3908at
bond conversion as a function of irradiation time for the two formulations studied. We can see that the initial cure rate of Formulation I is significantly slower than that of seconds was Formulation I1. An induction time of about two observed for Formulation I while that of Formulation 11
SUMMARY
Intramolecular charge transfer complexes (ICTC)
was less than one tenth of a second. However, the overall
fluorescence probes such as 1-dimethylarmno-naphthalene-
extent of cure of the Formulation 1(-95 %) was much higher
5-sulfonyl-n-butylamide
than that of Formulation 11(-60 %). This is probably due
dimethylaminonaphthalene-5-sulfonyl-n-butyl-amide
to the rapid increase in crosslinking density due to a fast
(2,5-DASB) are useful for cure monitoring of photocurable
cure rate in Formulation II that makes the diffusion of
polymer systems with UV or visible initiators.
radicals difficult,
resulting in a lower extent of
(1,5-DASB)
and
2-
As the
curing proceeds, the steady state fluorescence emission
polymerization.
spectra of the-'piobes were all found to exhibit
Figure 7 gives the linear correlation plots of 1470/1560 vs. the extent of double bond conversion for the two commercial formulations, showing similar slopes. The
hypsochromic spectr"l shifts due to the increases in matrix Linear correlations between the microviscosity.
mathematical expressions given in Equations 2 and 3 can be used to correlate the fluorescence intensity ratio (1470/1560)
With a fiber-optic
fluorescence
intensity
ratios
and
the extent
of
with the extent of C=C conversion (Wi)for Formulations I
polymerization wese obtained. fluorimeter. this fluorsence cure sensing technique based on ITCT fluorescenc\ probes can be readily applied to
and II, respectively.
photopolymerized filn"s, coatings and bulk materials.
R = 1.6284 + 2.3197c
(2)
R = 1.3804+2.6314ct
(3)
(iLi. Multifunctional acrylates with visible initiators
Acknowledgements. [1irtial financial support by the Navy Office of Research P 00014-91-J-1921 and the National Science Foundatiorn, (DMR 93109) is gratefully acknowledged. We als, wish to thank Dr. Hansen Shou for his generous help an4 Mr. Tom Marino and Mr. Dustin Martin of the SGL, Inc.1for their helpful discussions.
/
Visible initiators such as fluorone derivatives exhibit fluorescence emission in photopolvmers with low
/ /
lax 2 ex
. 07
I. Hoy, C E. inhdiaion Curing of Po
Umm
iC
Materials;Hoyle, C. E., Kinstle, J. F., eds.; Society, Washington, DC, 1990, Chapter 1, pl.
,
I
I
ACS Symposium Series 417; American Chemical
2. Tyson, GR.; Shutz, AX 1. Polym.
2m
/
,
\
V
&j,]
/
z
3. Cook, W.D. Polymer 1"Z233,2152. 4. Wang, D.; Canera, L.; Aradie, M.J.M. Eur. Palym. 1.193,29, 1379. 5.
40 Wavelength (rnm) Fig. 1. Fluorescence excitation (EX) and emission (EM)
Hoyle, C.E.; Hensel, R.D.; Grubb, M. B. I. Polym. Sci., Po/ymu. O . Ed. 1984,22, 1865.
6. Moore, J.E. UV Curing: Science and Technology,
spectra of 1,5-DASB (1) and 2,5-DASB (2), respectively, in THF.
Technology Marketing Corporation, 1978.
7. Small, R.D.; Ors, J.A.; Royse, B.S. ACS Sympos 8.
-
Sa eiu # 242.1984, 325.
1.45
Decker, C.; Moussa, K. ACS Symposium Series
1.4
y
1..0276X R. 0.996
1.0277
# 417,1990,439. 9. Decker, C. J. Polym. Sci. Part A: Polym. Chem.
11.35
1992,30,913.
1.3
10. Allen, N.S.; Hardy, S.J.; Jacobine, A.F.; Glaser, D.M.; Yang B.; Wolf, D. Eur. Polym. 1.1990, 26, 1041.
1.25
11. Neckers, D.C. Chlemtech 1990,20, 615.
1.2
12. Paczkowsld, J.; Neckers, D. C. Macromolecules 1992,25,
1.15
.
.
0.1.50s
0.2
13. Zhang, X.; Kotchetov, 1,N.; Paczkowski, J.; Neckers, D. C. 1. Imaging Sc. Tech. 1992, 36, 322. 14. Kotchetov, L. N.; Neckers, D. C 1. Imaging Sci. Tech. 1993, 37,156.
.
.
0.25
.
.
0.3
.
0.35
0.4
EXTENT OF C&C CONVERSION Fig. 2. Correlation plot of the fluorescence intensity ratio (1430/1500) vs. the extent of C=C conversion of a multifunctional acrylate monomer system with a visible initiator (DIBF) and cured by an Ar+ laser.
15. Paczkowski, J.; Neckers, D. C. 1. Polym. Sd., Polym. B
1.J
Chem. Ed. 1993,31, 841.
A
16. Valdes-Aguilera, 0.; Pathak, C.P.; Neckers, D.C.
Macromolecules 199, 23, 689.
'
/
17. Liplnskl, J.; Chojnacki, H.; Rotkiewicz, R.; Grabowski,a/ Z.R. Chem. Phys. Lett. 1980, 70, 449.
9A-4
18. Neckers, D. C.; Tanabe, T., unpublished. 19. We are applying for a patent on this work.
I
"-E z
.l
.(B).
I
/. / /
Cure Time: (A). 0 s 15 s
,
456
--
sis
Wavelength (nm) Fig. 3. Fluorescence emission spectra of 1,5-DASB in a commercial photocurable resin (Formulation I) as a function of irradiation time using a medium pressure Hg lamp. (Excitation at 380 nm).
-
y
1.6284 + 2.3197x Ra 0.9992
-
3.5 6
3
3.5
-
3
2.5
2-470 = o-
s'o0
-2.5
550 1
-251
Iirulto
-1.5
-
-
C--
;
•
1470
~. ~O 0
2
4
6
8
10
1,S-DO
I
12
14
16
1.5
0
Time (s) Fig. 4. Changes in fluorescence intensity ratios of 1,5DASB in a commercial photocurable resin (Formulation 1)as a function of irradiation time using a medium pressure Hg lamp. (Excitation
1.3804 + 2.6314X Ro 0.99473
.&
y
3
-o-____
L
0.8 0.4 0.6 0.2 Extent of C-C Conversion
-
at 380 run).
4-
2.5
,---__0
1470.,0
83
I3 l470 5401 40
-
-1 -~~~
-
11
.Formulation
mExit 2
380 nm
1.5
0
______._.
__.___"_",_
0
0.2
0.6
0.8
1
10.°8 ,o, 0AF
-+
-
"*-
.
/0.8 I
-"
--
0.6
y = 1.1167 + 3.3908x R= 0.99802
2.2
--
.2 1. ZR
I,
1.6
TMPTAADPHPA/I PEGAIDIBF/NPG. ExFci~te 0 380 Tn Il5DS
-
1. 1.2
____________
---
0.5
C-C conversion for two commercial photocurable resins.
01.2
2-0-
0.4
ratio (R = 4170/1560) of 1,5-DASB vs. the extent of
C
0,
0.3
of C=C Conversion
.
0.6
0.2
Fig. 7. Linear correlation plot of the fluorescence intensity
FIg. 5. Linear correlation plot of the fluorescence 1470/1550 and intensity ratios (R - 4170/15[, 1470/1540) of 1,5-DASB vs. the extent of C--C conversion in Formulation 1. 1__2.4
0.1
•Extent
_,_,_,
0.4
% C=C Conversion
0.2
I.
,,Probe Excite0380 nmn
Z
Formul1ation 1 Formulation II
7
X
0
-
02
0
4 6 a Irradiation Time (s)
10
12
Fig. 6. Changes in the C=C conversion of two commercial photocurable resins (Formulations I and 11)as a function of irradiation time using a medium pressure Hg lamp.
0.1
0.2
0.3
0.z
Extent of C=C Conversion Fig. 8. Linear correlation plot of the fluorescence intensity ratio (R - 1470/1560) of 1,5-DASB vs. the extent of C=C conversion of a multifunctional acrylate system with a visible initiator (DIBF) and an amine coinitF~tor (NPG).
