Heat Distortion Temperature Modification

of Rigid PVC and Chlorinated PVC: A

Method to Produce Low Smoke
Compositions
ENRICO J. TERMINE
Great Lakes Chemical Corporation
West Lafayette, Indiana 47906

The use of a new low smoke, heat distortion temperature modifier for rigid PVC
and chlorinated PVC is discussed. This material, CN-1427, is a tetrabromobis-
phenol A carbonate oligomer which is compatible with vinyl compositions. The
carbonate oligomer can be compounded into PVC resin to improve heat distortion
temperature of PVC and CPVC by 20-30°C. Unlike conventional HDT modifiers,
brominated carbonate oligomers do not increase smoke evolution during flam-
mability testing. Thus, using carbonate oligomer technology, it is possible to
achieve low smoke, Class I (ASTM E-84) and V-0 flammability (UL-94)perform-
ance. Vinyl compositions, modified with the carbonate oligomer described in this
work, can be utilized as a n alternative to expensive engineering thermoplastics.
This paper reports recent studies on the use of carbonate oligomers a s heat
distortion temperature modifiers for low smoke vinyl applications. Formulation
information addressing flammability and physical property performance is pre-
sented in detail.

INTRODUCTION test standard must be met. In the building construc-

oday, the polyvinylchloride (PVC)industry faces
T many regulatory issues ranging from smoke tox-
icity to the formation of acid gas emissions during
combustion. A need exists for a heat distortion tem-
perature modifier for PVC that meets smoke-related
concerns and produces a PVC composition with phys-
ical properties acceptable for engineering thermo-
plastic applications.
Several approaches are used to increase the heat
distortion temperature properties of PVC. These
methods are based on acrylic acid derivatives and
copolymers, styrene maleic anhydride copolymers, or
acrylonitrile-butadiene-styreneterpolymers. Typi-
cally, these additives are incorporated into PVC resin
at a ten to forty percent load level, and can improve
heat distortion temperature (HDT)by 20-25°C.
Although effective in modifying the heat distortion
properties of PVC, commercial HDT modifiers have
limited usefulness in engineering thermoplastic ap-
plications. These modifiers, being combustible poly-
mers, detract from the inherent flame retardant
properties of PVC resin, and cause an unsatisfactory
increase in smoke evolution.
Many engineering thermoplastic applications must
pass strict flammability and smoke development re-
quirements. For example, in the computer housing
market and other areas in which electrical compo-
nents are fabricated, the UL-94 vertical flammability
tion area, structural components should meet the
ASTM E-84 test (25’tunnel test) of similar large scale
test which measures flame spread and smoke devel-
opment.
Recently, a novel heat distortion temperature mod-
ifier was introduced by Great Lakes Chemical Cor-
poration (1). This material, CN-1427, is a tetrabro-
mobisphenol A carbonate oligomer containing 58
weight percent bromine. Vinyl compositions, con-
taining this additive received very low smoke per-
formance ratings during flammability testing.
This paper describes new studies to broaden the
utility of carbonate oligomer technology in vinyl ap-
plications. Formulation information for improving
heat distortion temperature and meeting low smoke
Class I ASTM E-84 flammability requirements is pre-
sented for PVC and CPVC resin.
EXPERIMENTAL
Preparation of PVC and CPVC Compositions
BF Goodrich Geon 86 polyvinylchloride (IV = 0.60)
was used a s the injection molding grade resin; Occi-
dental Petroleum 225SG PVC (IV = 0.92)was used a s
the extrusion grade resin; and BF Goodrich Temprite
3104 was used for chlorinated PVC. The following
general formulation was used in the study.

204 J0URN A L OF VINYL TECHNOLOGY, DECEMBER 1990, VOL. 12, NO. 4

 Heat Distortion Temperature Modgication of Rigid PVC and Chlorinated PVC

Component PHR Performance in PVC and CPVC

PVC resin 100 The ability of carbonate oligomers to increase heat
CN-1427 Modifier varied distortion temperature is evident in Figs. 2 through
Wax 165 0.8 4. The results showed that as much as a 15°C in-
AC 629 Wax 0.1 crease in the heat distortion temperature over the
Calcium Stearate 1 .o
control PVC resin, and a 21°C increase over the con-
trol CPVC are obtained, using 30 percent carbonate
The components were pre-blended by hand in a mixing oligomer.
bowl and compounded on a two roll mill a t 180-200°C. Test The effect of carbonate oligomer concentration on
specimens were processed a t 200°C by either injection mold- flammability performance and heat distortion prop-
ing or compression molding techniques.
erties for injection molding grade and extrusion grade
PVC resin are shown in Figs. 2 and 3.
Flammability Test Procedures Carbonate oligomer reduced the smoke develop-
The following flammability tests were used ment of the PVC resin as measured by four foot
throughout the study.
Glass Transition Temperature, Tg, C
Test Method Description 160 I I

Four Foot Tunnel Apparatus to measure flame spread

and smoke development in accordance
with ASTM-84 test procedures. Low
values indicate better flame retar-
120 f--- /
dancy.
ASTM D-2863 Measurement of the minimum oxygen
Limiting Oxygen necessary to sustain burning of a ver-
Index tically supported sample for three min-
utes. High values indicate improved 60 '
c 10 20
I
30
resistance to burning.
Carbonate Oligorner, w t %
UL-94 Vertical A test method which ranks specimen
Flame Test based on time to extinguish a flame A P V C -cpvc
after ignition. A V-0 rating is needed
for most thermoplastic applications. Fig. 1 . Carbonate oligomer in PVC & CPVC Tglloading
relationship.

RESULTS AND DISCUSSION

HDT Modifier and Flame Retardant
The new polymer additive described in this study
is available from Great Lakes Chemical Corporation
under the developmental product designation CN-
1427. The physical properties of this phenyl-termi-
nated carbonate oligomer are given in Table 1 .
The combination of high bromine content and low
molecular weight are unique design features which
allow carbonate oligomers to be intimately blended
with rigid PVC resin. There is strong evidence that
low molecular weight brominated oligomers form a n Fig. 2. HDTlsmoke performance effect of carbonate oli-
alloy with PVC. gomer loading in injection molding grade PVC.
PVC and CPVC blends of carbonate oligomers were
studied by differential scanning calorimetry. The ef-
fect of carbonate oligomer concentration on glass
transition temperature of PVC and CPVC is shown in
Fig. 1. The Tgfor a 30/70(w/w) carbonate oligomer/
PVC mixture is 102°C. The Tgfor a similar blend in
CPVC is 149°C.

Table 1. Carbonate Oligomer HDT Modifier/Flame Retardant

Typical Physical Properties.
Percent Bromine 58
Meltina Ranae. OC 240-260
Molec;lar Wleight, Mw 10-1 5,000
Specific Gravity 1.6 Fig. 3. HDTlsmoke performance effect of carbonate oli-
gomer loading in extrusion grade PVC.

JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1990, VOL. 12. NO. 4 205

 Enrico J . Termine

tunnel test method, and maintained UL-94 V - 0 per-

formance. Impact strength of carbonate oligomer
modified PVC blends were lower than the un-modi-
fied PVC base resin.
Figure 4 contains carbonate oligomer performance
results in CPVC resin. Modified CPVC exhibited low
smoke performance. Unlike the PVC system, the car-
bonate oligomer did not suppress the total smoke
evolution when compared to the base CPVC resin.

Comparison of Carbonate Oligomer to

Conventional HDT Modifiers
A comparison of flammability and physical prop- F i g . 5. HDTlsmoke performance in PVC HDT modtfier
erty performance of carbonate oligomer versus com- comparison.
mercial heat distortion temperature modifiers is pre-
sented in Table 2 and Figs. 5 and 6.
Carbonate oligomer modified PVC blends showed
the best combination of HDT improvement and
flammability properties. Carbonate oligomer received
very low smoke development values in the four foot
tunnel test, whereas other HDT modifiers increased
the smoke evolution of the PVC resin. Tensile and
flexural strength performance were similar for each
additive in this study.
A comparison of carbonate oligomer to other com-
mercial HDT modifiers based on oven sag testing is
presented in Fig. 7. Significant differences are no-
ticed when the modified PVC blends were tested at
90°C for one hour.
Fig. 6 . HDT/smoke performance in CPVC modtfier com-
parison.

Fig. 4 . HDTlsrnoke Performance effect of carbonate oli-

gomer loading in extrusion grade CPVC.
TEMPERATURE I C )
Fig. 7.Oven sag test effect of modifier type and load level
Table 2. Comparison of Carbonate Oligomer with Commercial in PVC resin.
HDT Modifiers in PVC Resin.
Base I I1 111 IV
Loading, wt % - 30 30 30 30 Carbonate oligomer incorporated at a 10 weight
lzod Impact, J/M 43 27 16 16 54
Gardner Impact, J 81 18 102 68 140 percent loading performed as well as a 25 weight
Tensile Yield, MPa 57.2 61.4 56.5 68.9 53.8 percent loading of a SMA-type modifier. Likewise, a
Elongation, YO 5 4 5 5 4 25 weight percent loading of carbonate oligomer
Flexural Yield, MPa 104 98 91 115 85 showed very little sag a s compared to the unmodified
Flexural Mod, MPa 3700 3200 2900 3200 2900
UL-94, 1.6 mm v-0 v-0 v-2 v-2 v-2
PVC base control at this temperature.
Oxygen Index 42
- 52 35 35 34
CONCLUSIONS
Great Lakes CN- 1427 carbonate oligomer is a very
effective heat distortion temperature modifier for

206 JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1990,VOL. 12, NO. 4

 Heat Distortion Temperature Modification of Rigid PVC and Chlorinated PVC
PVC and CPVC compositions. In these resins, carbon-
ate oligomer improves heat distortion temperature by
20-30°C and lowers smoke evolved during flamma-
bility testing, a s compared to other heat distortion
temperature modifiers.
The enhancement in heat distortion temperature
and smoke-related properties provided by carbonate
oligomer technology permits several interesting op-
tions to PVC fabricators. For example, carbonate
oligomer modified PVC blends can be used as a n
alternative to straight CPVC systems, or carbonate
JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1990, VOL. 12, NO. 4
oligomer modified CPVC blends as alternatives to
engineering thermoplastics.
ACKNOWLEDGMENT
The author acknowledges the assistance of Mr.
John P. Stallings for his efforts in formulating and
testing of flammability and physical properties.
REFERENCE
1. E. J . Termine, Society of Plastics Engineers RETEC,
Toronto, paper no. R89-110, September 1989.
207