Correlation of Test Methods to evaluate the

Thermal Stability of neat PVC Resin

PVC 2008 - The 10th International Conference on PVC
Innovation – Technology – Sustainability – Networking
Brighton Dome, UK
April 22nd, 2008

Alex Wegmann; Shandy Li

Ciba R&D Center, Plastic Additives, Shanghai, China

1
Contents
• Introduction
• Chain stoppers / antioxidants used
in Suspension-PVC (S-PVC) polymerization
– Efficiency of chain stopping
– Sterically hindered phenols as chain stoppers
• Thermal stability of PVC (degradation and discoloration)
• Evaluating thermal stability of PVC by different methods
– Evaluation of neat PVC resins
– Evaluation of PVC compounds
– Correlation between different methods
PVC industry

3
S-PVC Polymerization Process
Deionized water VCM
Suspension agent Initiators

PVC Polymerization PVC slurry

Stripping
Chain stoppers
Antioxidants
Drying
• Chain stoppers terminate the polymerization and quench
catalyst residues, thereby avoiding further polymerization
reactions that can lead to polymer deposits in strippers and
dryers
• Some sterically hindered phenols also demonstrate a quite
good efficiency as chain stoppers; in addition, they are also
very effective antioxidants, protecting PVC under thermo-
oxidative conditions

4
Structure of chain stoppers / antioxidants

Acetone-thio-semi- Bisphenol A (BPA) Ciba® IRGANOX® 1076

carbazone (ATSC)

CGX AO 145 (80%) IRGANOX® 1076 (20%) Ciba® IRGANOX® 245

= Ciba® IRGASTAB® PVC 11

5
Evaluating chain stopping performance
Pressure drop during PVC polymerization:
Chain terminator is added at 70% conversion rate to check its efficiency in the lab process
12
Reaction Pressure (bar)

10

8
Delta P ≈ 0
6 Ideal chain stopper (100% effective)

4 Delta P < Delta P’ < Delta P’’

partial chain stopping effect
2 Delta P’’ :
No chain stopper (Maximum pressure drop)
0
0 2 4 6 8 10 12 14
Reaction Time (hour)

No chain-stopper: VCM consumption causes pressure drop

Ideal chain-stopper: Terminates polymerization completely (no pressure drop)
„Non-ideal“ chain-stopper: Pressure drop only reduced (not 100% effective)

6
 Efficiency of different chain stoppers
50ppm ATSC

150ppm IRGASTAB PVC 11

150ppm IRGANOX 245

150ppm IRGANOX 1076

without chain stopper

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Pressure drop (bar)

• Hindered phenols can be almost as good as ATSC in chain terminating.

• The degree of sterical hindrance of the phenol group seems to determine the efficiency in
chain stopping:
• Full sterical hindrance (2 tert-butyl groups), like in Ciba® IRGANOX® 1076,
shows a very low chain stopping efficiency.
• Less hindered molecules, like IRGANOX® 245 (1 tert-butyl, 1 methyl group) and
CGX AO 145 (1 methyl, 1 secondary alkyl group) are better in chain terminating

7
Thermal degradation of PVC

• Dehydrochlorination
(DHC):

• Autoxidation:

• DHC and autoxidation proceed simultaneously and influence each other

• HCl (autocatalytic) and O2 (defects formed by autoxidation) catalyze DHC
• DHC is reduced during processing by adding heat stabilizers (metal soap)
• Autoxidation is reduced by antioxidants during production and processing

8
Discoloration occurs during degradation
H H H
oxygen R
R R + 3 HCl
polyene (light colored) O
Cl Cl Cl O
cyclic peroxides
PVC
not conjugated (colorless)
HCl halochromism
start of DHC at structural defects R
("irregular structures"): oxygen
H O
R Cl keto-polyene
R +
C (deeply colored)
Cl H H via peroxy radicals
O R
carbenium ion (polymethine)
Cl deeply colored (mesomeric) oxygen chain scission:
R
terminal carbonyl
Cl Cl and carboxyl groups

A direct consequence of the dehydrochlorination (“unzipping”),

also involving oxidation and chain-scission reactions,
is discoloration of PVC

9
Evaluation of thermal degradation of PVC
• Evaluation of neat PVC resin
(without any heat stabilizer or other components added):
– Dehydrochlorination (DHC)

– Discoloration after compression molding

– Static oven aging of PVC powder (discoloration)

• Evaluation of PVC compounds

(formulated with heat stabilizers and possibly other components)
– Discoloration after processing on a 2-roll-mill (dynamic heat stability)
– Discoloration of PVC sheets in a gradient oven (static heat stability)
– Measuring the molecular weight decrease due to chain-scission of
PVC with a torque rheometer

10
Evaluation of neat PVC resin
Dehydrochlorination Compression molding

carrier gas conductivity

+ HCl cell
carrier gas

HCl

heating
block sample holder
Evaluation of dehydrochlorination (DHC)
Control IRGANOX 1076 IRGASTAB PVC 11
160
Conductivity (micro Siemens / cm)

120

On heating,
80 PVC releases HCl,
that increases the
conductivity or pH
40 of an aqeous solution
in which HCl is trapped.

0
0 10 20 30 40 50
Time (min)

12
Dehydrochlorination (DHC) performance
150ppm IRGANOX 245

150ppm IRGASTAB PVC 11

50ppm ATSC+100ppm BPA

50ppm ATSC+100ppm IRGANOX 1076

150ppm IRGANOX 1076

50ppm ATSC

30 35 40 45 50 55 60 65 70
Time (minutes) to reach a conductivity of 200 micro Siemens/cm

• Sterically hindered phenols can increase the stability of PVC resin. Especially, partially
hindered phenols are very effective, e.g. IRGASTAB® PVC 11, IRGANOX® 245.
• Fully hindered phenols, like IRGANOX® 1076, or completely unhindered phenols,
like Bisphenol A (BPA), show lower efficiency.
• IRGANOX® 1076 shows lower DHC performance than IRGANOX® 1076 + ATSC,
because part of the IRGANOX® 1076 is used up for chain stopping
• Pure Chain stoppers, like ATSC, show low performance in DHC test

13
Discoloration during compression molding
150ppm IRGANOX 245

150ppm IRGASTAB PVC 11

50ppm ATSC+100ppm IRGANOX 1076 Yellowness index

Lightness
50ppm ATSC+100ppm BPA

150ppm IRGANOX 1076

50ppm ATSC

30 45 60 75 90 105 120

• The lower the yellowness index (YI), the higher the

lightness (L*) of PVC plaques made from neat PVC
resin, and thus the better the thermal stability.
• Sterically hindered phenols can effectively reduce the
discoloration of PVC resin at high temperature

14
Evaluation of PVC compounds

D
t
torque

A B X C

time
Discoloration after 2-roll-mill processing
30
50ppm ATSC
26 250ppm IRGASTAB PVC 11
250PPM IRGANOX 245
Yellowness index...

22

18

14

10
5mins 10mins 15mins 20mins 25mins 30mins
PVC resin 100 phr
Processing times (minutes)
Tin stabilizer 1.5 phr
Process aid 1.9 phr

PVC sheets containing sterically hindered phenols have better color

retention compared to PVC sheets with only chain stoppers
16
Correlation between DHC and molding
150 75
Yellowness index

Time to reach a conductivity..

Lightness*1.5 65

of 200 micro Siemens/cm

120 DHC stability
Yellowness index /

55
lightness*1.5

90
45

60
35

30 25

SC 6 A 6 11 45
07 BP 07 2
AT 1 1
PV
C
OX
p m N OX p pm N OX B AN
p 0 TA
50 GA + 10 RGA S I RG
IR C I A m
p pm A TS p pm I RG 0 pp
0 0 m 15
15 p pm +10 0 pp
50 SC 15
AT
m
0 pp
5
17
Correlation between DHC and molding
• DHC measurements reflect the first phase in the degradation process
of PVC; it is based on the release of HCl from the PVC resin.
• Measuring the discoloration of PVC resins (e.g. by compression molding)
reflects the final stage of the degradation process, involving different
degradation mechanisms (DHC and autoxidation)
• A correlation exists between DHC and the discoloration of PVC plaques:
the higher the DHC stability, the better the color in the compression test

18
Conclusion and summary
• Partially hindered phenols show the best performance in
thermal stabilization of neat PVC resin
(during polymerization, stripping, and drying)
• Partially hindered phenols show, at concentrations needed
for good thermal stability of the resin, chain stopping almost
as good as ATSC
• Good correlation between DHC (HCl release) and
compression molding (discoloration)
Thank you for your attention!
Please visit our internet site:
www.cibasc.com

For further information, please contact:

Alex Wegmann
Application Technology
alex.wegmann@cibasc.com

Shandy Li
Application Technology
shandy.li@cibasc.com

20
20