ANTEC

Poly(arylene ether)-polysiloxane multiblock copolymers

r
Fo
Journal:

Manuscript ID:

Wiley - Manuscript type:

Complete List of Authors:

PENG-10-2010-0038
Proceeding
27-Oct-2010

Re

Date Submitted by the

Author:

ANTEC

ew

vi

Chowdhury, Rajesh; GE India Technology Center Pvt Ltd, Sabic

Innovative Plastics Program
Chatterjee, Gautam; GE India Technology Center Pvt Ltd, Sabic
Innovative Plastics Program
Mahanth, Satish; GE India Technology Center Pvt Ltd, Sabic
Innovative Plastics Program
Dey, Rima; GE India Technology Center Pvt Ltd, Sabic Innovative
Plastics Program
Fisher, Scott; Sabic Innovative Plastics
Guo, Hua; Sabic Innovative Plastics

This study focuses on the evaluation of novel, linear, poly(arylene

ether)-polysiloxane (PPE-Siloxane) multiblock copolymers prepared
by the reaction of a hydroxyl terminated oligomeric bifunctional
poly(arylene ether), a hydroxyl terminated telechelic bifunctional
polysiloxane, and an aromatic diacid chloride. The resulting
copolymer chains had multi (greater than or equal to 2) siloxane
blocks and multi arylene-ether blocks. The overall siloxane
incorporations were varied and at high levels (>60 wt %) yielding
flexible compositions with improved flow, ductility, flame retardancy
and low smoke generation during burn.

ly

Abstract:

Polyphenylene Ether (PPE) < Polymers, Silicone (Silicone) <

Polymers, Thermoset Elastomer (TSE) < Polymers

On

Keywords:

Page 1 of 7

ANTEC

Poly(arylene ether)-polysiloxane multiblock copolymers

Authors : Rajesh Chowdhury*,Gautam Chatterjee*, Satish Mahanth*,Rima Dey*
Scott Fisher#, Hua Guo#,
*: GE India Technology Center, SABIC Innovative Plastics Program, Bangalore, India,
#: SABIC Innovative Plastics, Selkirk, NY, USA,
Abstract

r
Fo

This study focuses on the evaluation of novel, linear,

poly(arylene
ether)-polysiloxane
(PPE-Siloxane)
multiblock copolymers prepared by the reaction of a
hydroxyl terminated oligomeric bifunctional poly(arylene
ether), a hydroxyl terminated telechelic bifunctional
polysiloxane, and an aromatic diacid chloride. The
resulting copolymer chains had multi (greater than or
equal to 2) siloxane blocks and multi arylene-ether
blocks. The overall siloxane incorporations were varied
and at high levels (>60 wt %) yielding flexible
compositions with improved flow, ductility, flame
retardancy and low smoke generation during burn.

vi

Re

Introduction

This article reports the performance of PPE-polysiloxane

multiblock copolymers prepared by polyesterification of a
bihydroxyaryl
terminated
oligomeric
PPE,
a
bihydroxyaryl terminated polysiloxane, and an aromatic
diacid chloride like terephthaloyl chloride in a polar protic
solvent. The resultant multiblock copolymers were
capped by a benzoylation process with benzoyl chloride,
added as an end-capper to ensure requisite melt stability.

ew

Since polyphenylene ethers (PPE) s discovery, there has

been continued effort to improve the melt processability
and ductility of PPE. The strategy that has successfully
been used to offset the above limitation is to blend PPE
with high impact polystyrene or other rubbery styrenic
block copolymers like styrene-ethylene-isobutylenestyrene (SEBS). The downside of this strategy, however,
is that such blending leads to reduced heat and flame
performances, glass transition temperature (Tg) and
smoke, relative to virgin PPE.

reagents and hence may not be suited for commercial

scale-up due to economic reasons. Also, in few cases, the
PPE-siloxane copolymer thus formed exhibits poor
thermal and hydrolytic stability, due to C-O-Si linkages.
Others were found to be applicable only for low intrinsic
viscosity (IV) PPE, as extensive gelation was observed
when higher IV PPEs were employed. Moreover truly
flexible copolymers with high levels of siloxane
incorporations could not be achieved.

ly

The synthesis of PPE-siloxane copolymers was earlier

achieved by the following routes(3-8): The above
procedures used to make PPE-siloxane copolymers are
mostly multi-step, employ expensive and sensitive

The hydroxyl terminated oligomeric bifunctional PPE

used as the hard block was Noryl MX 90 resin, obtained
from Sabic Innovative Plastics NV, Netherlands. Three
eugenol terminated telechelic bifunctional siloxane fluids
of varying D-lengths (DI, DII and DIII, with
DI>DII>DIII), incorporated as the soft blocks at 60 and
70 wt percentages, were obtained Momentive
Performance Chemicals, USA. The copolyesterifications
with varied siloxane feeds were carried out at room
temperature in dichloromethane using the process as
described in US Patent Application No 12/644144.

On

Polysiloxanes are known to retain the elastomeric

property even at sub zero temperature owing to very low
glass transition temperature. They are reported to exhibit
excellent low smoke and good FR properties (1,2). The
major deficiencies which prevented the wide spread use
of polysiloxane impact modifiers in thermoplastic resins
are raw material costs, relatively poor rubber integrity and
the incompatibility between silicone based rubber
modifier and thermoplastic resin. One of the solutions
envisaged is to have covalently linked siloxane domains
or copolymers with siloxane blocks.

Experimental

Six different copolymer compositions DI60, DII60 and

DIII60 at 60 weight percentage and DI70, DII70 and
DIII70 at 70 weight percentage of the incorporated
siloxanes as detailed in Table1, were evaluated in the
present study. The neat copolymers were extruded and
pelletized using co-rotating 25mm twin-screw extruder
(Werner and Pfleiderer) with L/D ~40 at 220 C. Tensile
bars (ISO 527-1), UL94 flame bars at 1.6mm and 2mm
were all injection molded. The flame testing was done
according to the UL94V standards. The data reported here

ANTEC

r
Fo

was based on 2mm and 1.6mm thick flame bars. In this

test, ten bars at a specific thickness were vertically held at
10mm (3/8) from a Bunsen burner tip in a 20mm (3/4)
blue flame for 10 seconds in a draft free hood. After
removing the flame, the first flame out time (FOT-1) was
recorded and the flame was reapplied immediately for 10
seconds and the second flame out time (FOT-2) was
recorded. The smoke density measurement plaques
(ASTM E662-06) were molded using L&T Demag
injection molding machine (60 tons). The tensile tests
were conducted on Instron 5566 machine at a strain rate
of 500mm/min. Smoke measurements were performed in
NIST smoke density chamber from Newport Scientific,
U.S.A. The samples were conditioned at 23C and 50%
humidity for 48 hours, prior to testing. The smoke
densities reported here are the smoke densities at 4
minutes and at the maxima.

Results and Discussion

density at 4 minutes and the maximum smoke density

were lower in the 70 wt% siloxane based copolymers. At
a given level of siloxane incorporation, the smoke
densities however registered higher values as the mole%
of siloxane incorporations decreased. Thus DI based
copolymers exhibited the highest values followed by the
DII siloxane based copolymers. PPE-Siloxane based
copolymers based on eugenol capped siloxanes with dlength of DIII exhibited the lowest smoke densities.

Conclusion
Linear PPE-Siloxane multiblock copolymers using three
types of d-lengths of the siloxane building units, made in
our pilot plant, were evaluated at 60 and 70 wt% of
siloxane incorporation. At a given level of incorporation,
the copolymers with the lowest d-length of the
incorporated siloxanes (DIII), exhibited best balance of
properties. Thermoplastic compositions at 70 wt% of
siloxane incorporation in DIII based copolymers also
exhibited best flame and smoke performance.

Acknowledgement
The authors would like to acknowledge Vivek
Karambelkar, Radha Kamlakaran and MH Shridhar for
their analytical support.

ew

vi

Re

Tensile and elongations of the molded specimens of

copolymers with based on DI, DII and DIII eugenol
siloxanes at 60 and 70 wt% of incorporations are shown
in Figures 1 and 2 respectively. At incorporations of 60
wt%, copolymers based on DIII siloxane d-lengths led to
the best balance of properties with a tensile strength of 12
Mpa at an elongation of 60%. With DIII siloxanes, true
thermoplastic elastomeric behaviour was obtained with a
elongation at break exceeding 190% at a tensile strength
of about 8.7 Mpa.(Figure 2.) The DI based copolymers
showed significant delamination in the molded parts and
had inferior mechanical properties. The tensile modulus
and hardness of the copolymers at 60 and 70 wt%
siloxane incorporations are shown in Figures 3 and 4
respectively. At a given level of siloxane incorporation,
the modulus and hardness increased with the d-lengths of
the starting siloxanes. The DIII based copolymers
exhibited highest values on account of lower mole
percentages of the incorporated soft blocks though at
same weight percentages of incorporations.

Page 2 of 7

Hamdani S, Longuet C, Perrin D, Lopez-cuesta

J.M, Ganachaud F, Polymer Degradation and
Stability, 94, 465 (2009)

2.

Brydson J.A., Plastics Materials

Edition), Pages 814-852 (1999)

3.

I. Mamalis and C.DiFede, GE Internal Reports

(Seventh

ly

The smoke performances are shown in Figures 7 and 8. In

general the smoke densities were less in copolymers with
70 wt% of the soft blocks as compared to the copolymers
with 60 wt% of incorporated siloxane. Both the smoke

1.

On

Comparisons of the UL94 flame out times (FOT) for all

the copolymer compositions are shown in Figures 5 and
Figure 6. DIII-based copolymers showed lowest FOTs
and in general the same increased with the d-lengths of
the starting siloxane building blocks. Longer siloxane
blocks led to deterioration in flame performance.
However, the FOTs did not exhibit definite correlation
with the thickness of the flame test bars. Similar trends
were observed in copolymers at 60 and 70wt% of
siloxane incorporations.

References

4.

T.J. Shea, J.R. Campbell, D.M. White and L.A.

Socha, General Electric Company, US 4814392
(1989).
5. M.L. Blohm, T.E. Banach, K.M. Snow, R.T.
Heisler and G.T. Seeger, GE Internal Report,
(1993).
6.

G.W. Yeager GE Internal Report (2006).

7.

Jean-Jacques Toublan, Farah

application series 12/277835

8.

M.L. Blohm, T.E. Banach and C.M.E. Bailly,

General Electric Company, US 5596048 (1997)

et.

al,

US

Page 3 of 7

ANTEC

Figures and tables are provided for general information

and are not for the purpose of warranty or specification.
Any flame or ignition resistant rating presented herein is
NOT intended to reflect hazards presented by this or any
other material under actual fire conditions. All resins and
mixtures discussed herein should be thoroughly tested in
actual parts under end use conditions before incorporation
into any device.

Keywords
Copolymers, Siloxane, Polyphenylene ether, Multi-block,
Flame Resistance, Smoke density

r
Fo
ew

vi

Re
ly

On

ANTEC

Page 4 of 7

Table 1: Evaluated PPE-Siloxane multiblock copolymers

PPE-Siloxane Multiblock Copolymers
Incorporated PPE MX90 Hard Block (Mole %)
Incorporated Eugenol Siloxane Soft Block of D-length DI (Mole%)
Incorporated Eugenol Siloxane Soft Block of D-length DII (Mole%)
Incorporated Eugenol Siloxane Soft Block of D-length DIII (Mole%)

DI60

DII60

DIII60

DI70

DII70

DIII70

72.04
27.96

49.32

41.01

62.36
37.64

38.48

30.87

50.68

61.52
58.99

69.13

14

70

Tensile Strength (Mpa)

Elongation (%)

60

50

r
Fo

Tensile Strength (MPa)

10

40

30

Re

10

DII60

ew

DI60

20

vi

Elongation (%)

12

DIII60

Figure 1: Tensile strength and elongation of the PPE-Siloxane copolymers with 60wt% incorporated siloxane

Tensile Strength (Mpa)

8

Elongation (%)

ly

Tensile Strength (MPa)

250

200

150

4
100

Elongation (%)

On

50

0
DI70

DII70

DIII70

Figure 2: Tensile strength and elongation of the PPE-Siloxane copolymers with 70wt% incorporated siloxane

Page 5 of 7

ANTEC

350

70
Tensile Modulus (Mpa)

250

50

200

40

150

30

100

20

50

10

r
Fo

60

Hardness (ShoreD)

Tensile Modulus (MPa)

Hardness (ShoreD)
300

DI60

DII60

DIII60

Re

Figure 3: Tensile modulus and hardness of the PPE-Siloxane copolymers with 60wt% incorporated siloxane

120

45

vi

Tensile Modulus (Mpa)

35

ew

110

30

25

105

On

Tensile Modulus (MPa)

40

100

ly

95

90

20

Hardness (ShoreD)

Hardness (Shore D)
115

15

10

0
DI70

DII70

DIII70

Figure 4: Tensile strength and elongation of the PPE-Siloxane copolymers with 70wt% incorporated siloxane

ANTEC

Page 6 of 7

10

12

2mm bars

1.6 mm bars

FOT-1 (Secs)

FOT-1(Secs)
FOT-2 (Secs)

FOT-2 (Secs)

10

7
UL94 Flame Out Time (FOT) Secs

UL94 Flame Out Time (FOT) Secs

2
1

DI60

DII60

DIII60

DI60

DII60

DIII60

r
Fo

Figure 5: UL94 Flame Out Times of the PPE-Siloxane copolymers with 60wt% incorporated siloxane

2mm bars
8

12

1.6 mm bars

FOT-1 (Secs)

FOT-1 (Secs)

FOT-2 (Secs)

6
5

FOT-2 (Secs)

vi

Flame Out Times (FOT) Secs

Re

UL94 Flame Out Times (FOT) Secs

10

ew

0
DI70

DII70

DIII70

DI70

DII70

DIII70

On

Figure 6: UL94 Flame Out Times of the PPE-Siloxane copolymers with 70wt% incorporated siloxane

ly

Page 7 of 7

ANTEC

350

DS4 (Smoke Density at 4 mins)

300

DSmax (Maximum Smoke Density)

Smoke Density

250

200

150

100

50

r
Fo

DI60

DII60

DIII60

Figure 7: Smoke densities of the PPE-Siloxane copolymers with 60wt% incorporated siloxane

Re

250

DSmax (Maximum Smoke Density)

vi

200

ew

Smoke Density

DS4 (Smoke Density at 4 mins)

150

100

0
DI70

DII70

ly

On

50

DIII70

Figure 8: Smoke densities of the PPE-Siloxane copolymers with 70wt% incorporated siloxane