Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 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 2

Introduction

Emerging needs

Miniaturization of electronic components

High speed data transfer

Lower dielectric constant and high heat resistance

Possible to apply in lower thickness

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 3

Introduction

High Purity resin

Low melt viscosity

High heat resistance

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 4

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

Chemical structure and characteristics

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 5

CH2CH

O

H2C CH2 CH CH2

O

O O

O O OCH2 CH CH2

O

CH2 CH CH2

O

CH2 CH CH2

O

n

High performance resins

Multifunctional DCPD type epoxy resin

Difunctional DCPD type epoxy resin

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 6

High performance resins

O

O

CH2 CH CH2

O

CH2CH

O

H2C

CH2CH

O

H2C

CH2 CH CH2

O

O

CH2

O

OO

CH2 CH CH2

O

CH2CH

O

H2C

Difunctional 1,5-Dihydroxy Naphthalene type epoxy resin

O CH2 CHOCH2CH

O

H2C CH2

O

Difunctional Dihydroxy Biphenyl type epoxy resin

Tetra functional Naphthalene type epoxy resin

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 7

C

CH3

CH3

O CH2 CHOCH2CH

O

H2C CH2

O

O H2C

OH2C

O

2.6

CH2

CH

CH2O

CH2

CH

CH2O

CH2

CH

CH2O

S

O

O

O CH2 CH

O

CH2OCH2CH

O

H2C

H3C

H3C

CH3

CH3

Diglycidyl ether of Bisphenol-A (DGEBA)- YD 128

Epoxy Phenol Novolac (EPN)- YDPN 638

Epoxy Tetramethyl Bisphenol-S (ETMBPS)

Epoxy resins used for present study

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 8

OHH3C CH3

H2SO4

S

O

O

H3C

HO

H3C

CH3

OH

CH3

Scheme I

2,6-Dimethyl phenol Bis(3,5-dimethyl-4-hydroxyphenyl) sulphone

2 H2O

H2C

O

CHCH2ClS

O

O

H3C

HO

H3C

CH3

OH

CH3

S

O

O

H3C

O

H3C

CH3

O

CH3

H2C

O

CHCH2 H2CHC

O

CH2

Scheme II

Bis(3,5-dimethyl-4-hydroxyphenyl) sulphone

Epichlorohydrin

+2 +

+ NaCl+ H2O+NaOH

Diglycidyl ether of bis(3,5-dimethyl-4-hydroxyphenyl)sulphone

Preparation of ETMBPS

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 9

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

Total chlorine (% w/w) 0.17 0.18 0.062

Viscosity (oC), cPs 12200 @25oC

29094 @ 52oC

119.1 @ 120oC

Number average molecular weight (g/mol)(Functionality)

380(2)

600(3.6)

421(2)

Melting point (oC) - - 114

Properties of various epoxy resin used for present study

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 10

GPC of ETMBPS DSC of ETMBPS

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 11

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)

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 12

Melt Viscosity

0

200

400

600

800

1000

1200

1400

1600

1800

120 130 140 150 160 170 180

Temperature, oC

Vis

co

sit

y,

cP

s

ETMBPS ECN EPN

Melt viscosity Vs. Temperature of various epoxy resins

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 13

OH H2C

OHH2C

OH

2.6

C

H

OHHO

OH

S

H2N NH2O

O

3,3’-Diaminodiphenyl Sulphone (3,3’-DDS) Omicure 3,3’-DDS

Phenol Novolac (PN)

HRJ 1583 Tris(4-hydroxyphenyl) methane (THPM)

Curing agents used for present study

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 14

Properties PN THPM DDS

Hydroxyl equivalent weight (g/eq)(Functionality)

106(3.6)

97(3)

-

Amine equivalent weight (g/eq)(Functionality)

- - 62(4)

Softening point (oC) 78 102 -

Melting point (oC) - - 177

Properties of curing agent used for present study

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 15

Resin Hardener Catalyst

Ratio (Part by weight)

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

Mixing ratio used for laminate preparation

Binder- Fiber ratio : 30: 70

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 16

Glass transition temperature of different systems

100

120

140

160

180

200

DGEBA EPN ETMBPS

Epoxy resin system

Gla

ss t

ran

siti

on

te

np

erat

ure

, o

C

PN

3,3'-DDS

THPM

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 17

% Weight loss Vs. Temperature by TGATGA- 5% degradation

300

320

340

360

380

400

420

PN DDS THPM

Curing agent system

Tem

per

atu

re,

0C

DGEBA

EPN

ETMBPS

TGA- 10% degradation

320

340

360

380

400

420

440

PN DDS THPM

Curing agent system

Tem

per

atu

re,

oC

DGEBA

EPN

ETMBPS

TGA-20% degradation

320

340

360

380

400

420

440

PN DDS THPM

Curing agent system

Tem

per

atu

re,

oC

DGEBA

EPN

ETMBPS

TGA-50% degradation

0

100

200

300

400

500

600

PN DDS THPM

Curing agent system

Tem

pera

ture

, o

CDGEBA

EPN

ETMBPS

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 18

Tensile strength Vs. Curing agents

050

100150200250300350400

PN DDS THPM

Curing agents

Ten

sil

e s

tren

gth

, M

Pa

DGEBA

EPN

ETMBPS

Tensile Modulus Vs. Curing agents

0

5000

10000

15000

20000

25000

30000

PN DDS THPM

Curing agents

Ten

sil

e M

od

ulu

s,

MP

a

DGEBPA

EPN

ETMBPS

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 19

Flexural strength Vs. Curing agents

0

100

200

300

400

500

PN DDS THPM

Curing agent system

Fle

xu

ral

str

en

gth

, M

Pa

DGEBA

EPN

ETMBPS

Flexural Modulus Vs. Curing agents

0

5000

10000

15000

20000

25000

PN DDS THPM

Curing agent system

Fle

xu

ral

Mo

du

lus,

MP

a

DGEBA

EPN

ETMBPS

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 20

Impact strength of various epoxy systems

020406080

100120140160180200

PN DDS THPM

Cring agents

Imp

act

stre

ng

th,

KJ/

sq.m

t

DGEBA

EPN

ETMBPS

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 21

Stress distribution during fracture by Impact

YD 128/ DDS/ Anchor 1040

YDPN 638/ DDS/ Anchor 1040

ETMBPS/ DDS/ Anchor 1040

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 22

YD 128/ HRJ 1583/ TPP

YDPN 638/ HRJ 1583/ TPP

ETMBPS/ HRJ 1583/ TPP

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 23

YD 128/ THPM/ TPP

YDPN 638/ THPM / TPP

ETMBPS/ THPM / TPP

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 24

PropertyTest

MethodUnit

YD128/ DDS/

Anchor 1040

YDPN 638/ DDS/

Anchor 1040

ETMBPS / DDS/ Anchor

1040

YD128/ HRJ1583/

TPP

YDPN638/ HRJ1583/

TPP

ETMBPS / HRJ1583/

TPP

YD128/

THPM / TPP

YDPN638/ THPM /

TPP

ETMBPS / THPM /

TPP

Volume resistivity

IEC60093Ohms-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

Electrical properties of various systems

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 25

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 26

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

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 27

Potential application areas

• Laminates involving high temperature and electrical properties

• Electronic molding compounds

• Powder coating of electrical and electronic components

• One component adhesives

Sept,11, 2006

TRFA Annual Meeting- Montreal, Canada 28

Thank You