Transcript Slide 1

“Synthesis and study of a crystalline epoxy resin for high heat resistance”
Pradip K. Dubey*, Hitesh. K. Soni, Mahesh Soni, Samir Kanitkar
Thitikan, Patcharaporn
Aditya Birla Chemicals (Thailand) Ltd- Epoxy Division
Sept,11, 2006
TRFA Annual Meeting- Montreal, Canada
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Introduction
Emerging needs
 Miniaturization of electronic components
 High speed data transfer
 Lower dielectric constant and high heat resistance
Possible to apply in lower thickness
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TRFA Annual Meeting- Montreal, Canada
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Introduction
 High Purity resin
 Low melt viscosity
 High heat resistance
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Chemical structure and characteristics
 Hydrophobic/ saturated backbone – lower dielectric constant
 Higher aromatic content - higher heat resistance
 Purity/ symmetry- crystalline / lower melt viscosity
 High functionality/ high crosslink density – high heat resistance
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TRFA Annual Meeting- Montreal, Canada
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High performance resins
O
O
H2C
CH CH2
O
O
CH2
CH
CH2
Difunctional DCPD type epoxy resin
O
O
O CH2
CH
CH2
O CH2
CH
O
CH2
O CH2
CH
CH2
n
Multifunctional DCPD type epoxy resin
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TRFA Annual Meeting- Montreal, Canada
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High performance resins
O
O CH 2
CH
CH 2
O
O
H2C
CH CH 2 O
O
H2C
H2C
CH
CH 2
O
O
CH 2
CH 2
O
CH CH 2 O
O
CH 2
CH
CH 2
CH CH 2 O
Difunctional 1,5-Dihydroxy Naphthalene type
epoxy resin
Tetra functional Naphthalene type epoxy resin
O
H2C
O
CH CH2
O
O
CH2
CH
CH2
Difunctional Dihydroxy Biphenyl type epoxy
resin
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TRFA Annual Meeting- Montreal, Canada
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Epoxy resins used for present study
CH 3
C
CH 3
O
H 2C
CH CH 2
O
O
O CH 2 CH
CH 2
O
Diglycidyl ether of Bisphenol-A (DGEBA)- YD 128
H 3C
O
H 2C
CH CH 2 O
H 3C
O
S
O
CH 3
O
CH 2
CH
CH 2
O
O
H2
C
CH 2
CH
CH 2
O
O
CH 2
CH
CH 2
H2
C
O
2 .6
O
CH 2 CH CH 2
CH 3
Epoxy Phenol Novolac (EPN)- YDPN 638
Epoxy Tetramethyl Bisphenol-S (ETMBPS)
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TRFA Annual Meeting- Montreal, Canada
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Preparation of ETMBPS
Schem e I
H 3C
OH
H 3C
CH
+
2
3
HO
H 2 SO
CH
3
O
S
4
OH
O
H 3C
2 ,6 - D i m e t h y l p h e n o l
CH
+
2 H 2O
3
B i s ( 3 ,5 - d i m e t h y l - 4 - h y d r o x y p h e n y l ) s u l p h o n e
S ch em e II
H 3C
HO
O
CH
S
H 3C
O
3
OH
CH
O
+
O
NaOH
CHCH
2 Cl
H 2C
CHCH
2O
H 3C
3
B i s ( 3 ,5 - d i m e t h y l - 4 - h y d r o x y p h e n y l )
su lp h o n e
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H 2C
H 3C
E p ic h lo r o h y d r in
O
CH
S
O
3
O H 2C H C
CH
O
CH
2
+ NaCl
+
3
D ig ly c id y l e th e r o f
b i s ( 3 ,5 - d i m e t h y l - 4 - h y d r o x y p h e n y l ) s u l p h o n e
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H 2O
Properties of various epoxy resin used for present study
Properties
YD 128
YDPN 638
ETMBPS
Epoxy equivalent weight (g/eq)
188.0
175.1
216.7
Hydrolysable chlorine (% w/w)
0.0574
0.072
0.0034
0.17
0.18
0.062
12200
@25oC
29094
@ 52oC
119.1
@ 120oC
380
(2)
600
(3.6)
421
(2)
-
-
114
Total chlorine (% w/w)
Viscosity (oC), cPs
Number average molecular weight (g/mol)
(Functionality)
Melting point (oC)
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TRFA Annual Meeting- Montreal, Canada
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GPC of ETMBPS
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DSC of ETMBPS
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Physical form of various epoxy resin used for present study
Diglycidyl ether of Bisphenol-A (DGEBA)
Epoxy Phenol Novolac (EPN)
Epoxy Tetramethyl Bisphenol-S (ETMBPS)
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TRFA Annual Meeting- Montreal, Canada
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Melt viscosity Vs. Temperature of various epoxy resins
Melt Viscosity
1800
1600
Viscosity, cPs
1400
1200
1000
800
600
400
200
0
120
130
140
150
160
170
180
Temperature, oC
ETMBPS
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ECN
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EPN
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Curing agents used for present study
OH
H2
C
OH
OH
H2
C
HO
H
C
OH
2 .6
OH
Phenol Novolac (PN)
Tris(4-hydroxyphenyl) methane (THPM)
HRJ 1583
H 2N
O
NH 2
S
O
3,3’-Diaminodiphenyl Sulphone (3,3’-DDS)
Omicure 3,3’-DDS
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Properties of curing agent used for present study
Properties
Hydroxyl equivalent weight (g/eq)
(Functionality)
Amine equivalent weight (g/eq)
(Functionality)
Softening point (oC)
Melting point (oC)
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PN
THPM
DDS
106
(3.6)
97
(3)
-
-
-
62
(4)
78
102
-
-
-
177
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Mixing ratio used for laminate preparation
Ratio (Part by weight)
Resin
Hardener
Catalyst
Resin
Hardener
Catalyst
YD 128
3,3-DDS
Anchor 1040
100
33.0
1
YDPN 638
3,3-DDS
Anchor 1040
100
35.0
1
ETMBPS
3,3-DDS
Anchor 1040
100
28.6
1
YD 128
HRJ 1583
TPP
100
56.4
0.5
YDPN 638
HRJ 1583
TPP
100
60.5
0.5
ETMBPS
HRJ 1583
TPP
100
49.0
0.5
YD 128
THPM
TPP
100
51.6
0.5
YDPN 638
THPM
TPP
100
55.4
0.5
ETMBPS
THPM
TPP
100
45.0
0.5
Binder- Fiber ratio : 30: 70
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Glass transition
tenperature, oC
Glass transition temperature of different
systems
200
180
PN
160
3,3'-DDS
140
THPM
120
100
DGEBA
EPN
ETMBPS
Epoxy resin system
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% Weight loss Vs. Temperature by TGA
TGA- 10% degradation
420
440
400
420
380
DGEBA
360
EPN
340
ETMBPS
320
Temperature, oC
Temperature, 0C
TGA- 5% degradation
300
400
DGEBA
380
EPN
360
ETMBPS
340
320
PN
DDS
THPM
PN
Curing agent system
DDS
Curing agent system
TGA-50% degradation
TGA-20% degradation
600
420
400
DGEBA
380
EPN
360
ETMBPS
340
Temperature, oC
440
Temperature, oC
THPM
500
400
DGEBA
300
EPN
200
ETMBPS
100
0
320
PN
DDS
Curing agent system
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THPM
PN
DDS
THPM
Curing agent system
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Tensile strength, MPa
Tensile strength Vs. Curing agents
400
350
300
250
200
150
100
50
0
DGEBA
EPN
ETMBPS
PN
DDS
THPM
Curing agents
Tensile Modulus, MPa
Tensile Modulus Vs. Curing agents
30000
25000
20000
DGEBPA
15000
EPN
10000
ETMBPS
5000
0
PN
DDS
THPM
Curing agents
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TRFA Annual Meeting- Montreal, Canada
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Flexural strength, MPa
Flexural strength Vs. Curing agents
500
400
DGEBA
300
EPN
200
ETMBPS
100
0
PN
DDS
THPM
Curing agent system
Flexural Modulus, MPa
Flexural Modulus Vs. Curing agents
25000
20000
DGEBA
15000
EPN
10000
ETMBPS
5000
0
PN
DDS
THPM
Curing agent system
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TRFA Annual Meeting- Montreal, Canada
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Impact strength, KJ/sq.mt
Impact strength of various epoxy systems
200
180
160
140
120
100
80
60
40
20
0
DGEBA
EPN
ETMBPS
PN
DDS
THPM
Cring agents
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TRFA Annual Meeting- Montreal, Canada
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Stress distribution during fracture by Impact
YD 128/ DDS/ Anchor 1040
YDPN 638/ DDS/ Anchor 1040
ETMBPS/ DDS/ Anchor 1040
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YD 128/ HRJ 1583/ TPP
YDPN 638/ HRJ 1583/ TPP
ETMBPS/ HRJ 1583/ TPP
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YD 128/ THPM/ TPP
YDPN 638/ THPM / TPP
ETMBPS/ THPM / TPP
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Electrical properties of various systems
YDPN
638/
DDS/
Anchor
1040
ETMBPS
/ DDS/
Anchor
1040
YD128/
HRJ1583/
TPP
YDPN638/
HRJ1583/
TPP
ETMBPS /
HRJ1583/
TPP
YD128
/THP
M/
TPP
YDPN638/
THPM /
TPP
ETMBPS /
THPM /
TPP
Property
Test
Method
Unit
YD128/
DDS/
Anchor
1040
Volume
resistivity
IEC60093
Ohms
-cm
1016
1016
1016
1016
1016
1016
1016
1016
1016
Surface
resistance
IEC60093
Ohm
1013
1013
1013
1013
1013
1013
1013
1013
1013
Dielectric
constant
IEC60250
-
3.50
4.30
3.23
3.85
3.79
3.50
3.71
3.28
2.51
Dielectric
loss
IEC60250
%
1.5
1.9
1.9
1.5
1.9
1.9
1.5
1.6
1.0
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TRFA Annual Meeting- Montreal, Canada
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Conclusion:
High purity ETMBPS exhibits lower melt viscosity in uncured form.
 ETMBPS shows higher Tg compared to conventional epoxy resin system.
 ETMBPS cured systems shows better dielectric constant and dielectric loss
compared to other systems.
 Mechanical properties of ETMBPS systems are comparable or lower compared
to other systems.
Properties at elevated temperature need to be studied further to establish true
potential of this resin
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TRFA Annual Meeting- Montreal, Canada
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Potential application areas
• Laminates involving high temperature and
electrical properties
• Electronic molding compounds
• Powder coating of electrical and electronic
components
• One component adhesives
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TRFA Annual Meeting- Montreal, Canada
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Thank You
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