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Advances in the Stabilization of Flexible PVC

by Using a Liquid Calcium-Zinc Technology


JAMES E. REDDY cud JEREMY A. HACKETT

OMG Inc., 81 1 Sharon Drive, Westlake,OH 44145


The global market for liquid mixed-metal stabilizers is migrating toward heavy-
metal-free products. Historically, these systems have not been performance and
cost competitive. High efficiency calcium-zinc stabilizers have the potential to
replace heavy-metal-based products. The intrinsic value of non-phenolic lubricating
calcium intermediates and calcium-zinc stabilizers is discussed.

IUICKGROUND Heavy-metal additives for plastics are performance


and cost competitive, but their environmental implica-
P VC is processed under high thermal and shear
conditions. An artifact of this process is hydrogen
chloride (HCl) evolution that results in degradation of
tions remain severe. The market trend toward heavy-
metal-free products limits the type of heat stabilizers
that c a n be used to satis@ the aforementioned mech-
the polymer network. This degradation manifests itself
anisms. High-efficiency mixed-metal stabilizer sys-
as an undesirable color shift and rheology change.
tems offer a viable alternative (8).Specifically,liquid
A polymer of ideal constitution [-(CH&HCl),-] is less
calcium-zinc (Ca/Zn) blends centered on novel cal-
susceptible to dehydrochlorination. During WC pro-
cium intermediates provide a cost and performance
cessing, HCl is most readily liberated at initiation sites
competitive product. The characteristics of the novel
on the PVC backbone. Labile chlorine atoms can be
intermediate must include internal lubricating proper-
found where auylic and tertiary structures exist (1-4).
ties and a high calcim concentration. This stabilizer
Subsequent fonnati80nof polyene sequences result as
system contains components that scavenge HC1 (calci-
a rapid zipper elimination reaction takes place. Six con-
um),prevent propagation of HCl elimination (zinc),and
secutive areas of unraturation are enough to cause dis-
remain forgiving to the forces of shear (fatty anion).
coloration of the substrate (5).Areas of unsaturation
Ca/Zn stabilizer systems are promising candidates
have a propensity tci crosslink with adjacent polymers
for the replacement of conventional heavy-metal-based
and increase the viscosity of the substrate. Degradation
by physical and chi-miical variations complicates the
stabilizers.Ca/Zn stabilizershave been viewed as poor
performers and expensive when compared to their
processing of WC.
heavy-metal counterparts (5).Fractional and full fac-
Heat stabilizers auld in reducing the adverse effects
torial experimental designs were applied to optimize
of the process conditions. The eflRciency of a heat sta-
the stabilizer component blends. The blends were
bilizer is measured by its ability to prevent degradation.
evaluated against high-efficiency barium-zinc (Ba/Zn)
The stabiking function follows two primary mechan-
stabilizers. The discovery and introduction of novel
isms: reacting with liberated HCl and reacting with the
calcium intermediates, the optimization of Ca/Zn sta-
polymer to prevent I-IC1loss (6).
bilizer blends, and a comparison of Ca/Zn and Ba/Zn
The HC1 that is liberated in the early stages of deg-
technologies are discussed.
radation must be nleutralized to prevent an inherent
autocatalytic effect (7). The HCl absorption reaction is
ExPmUHEmAL
a common property of most metal organic complexes
(8).Chloride ions displace the metal ligand to yield a Standard W C compounds, OMG commercial stabi-
less catalytic species. A chloride sink is essential to lizers,and conventional test methods are used in the
inhibit mild early color damage to the polymer. evaluation. The experimental Ca/Zn stabilizem made
The reaction of stabilizers with the polymer to pre- from the novel calcium intermediate are optimized for
vent HCl loss is a more critical function. The appropri- each application via experimental designs. A fractional
ate metal organic complex can terminate the zipper factorial statistical design is employed to discern criti-
elimination reaction 115).This substitution reaction pro- cal variables. The critical variables are incorporated
ceeds in three steps: removal of labile chlorine atoms, into a full factorial design to determine main effects
conjugation shift and ligand transfer. and interactions. Statistical software is used to act as

JOURNAL OF VINYL & .ADD/TWE TECHNOLOGY,SEPTEMBER 2002, Vol. 8, No. 3 171


James E. Reddy and Jeremy A. Hackett

I+ C a n Heat Stabilizer

Scheme 1. Degradation and stabilization

a graphical interface and evaluate the data generated complexing agents. An initial screening design (2”2
from each design (9).The optimized formulations un- fractional factorial) is applied to determine the critical
dergo a performance assessment against Ba/Zn for- formulation variables for clear and filled applications.
mulations. Static thermal stability is tested using a The design pattern for each variable creates aliases,
Blue M Electric Forced Air oven at 191OC and color and the main effects may be confounded by interac-
readings are taken using a Minolta CR 200 colorimeter. tions that exist. The zinc carboxylate, calcium car-
Dynamic mill stability is measured by milling a W C boxylate, and phosphite compound appear to have the
compound for a timeframe that ends when the film highest impact on stabilization in each PVC com-
adheres to the heated mill (185OC).Portions of the film pound. A full factorial design (23) is applied using the
are taken at 5-minute intervals and color readings are critical variables from the screening design. The de-
taken using the Minolta CR 200 colorimeter. Braben- sign space is optimized for each response in filled
der stability measurements are taken using a Braben- compounds (FQ.1). The variables, design pattern, and
der Plasti-Corder machine with a 60 g sample, a tem- responses are listed in the design matrix (Table1).
perature of 190°C, and mixer head #5 at 60 rpms. A The summaries of fit, parameter estimate, and effect
sample is pulled from the mixer head at 5-minute in- test values for each response are listed in the least
tervals and color readings are taken using the Minolta squares fit analysis (Table2 ) .
CR 200 colorimeter. The standard plate-out test meth- The levels of zinc carboxylate. calcium carboxylate,
od using the 2B red pigment is applied to the compari- and phosphite compound are optimized for clear (Ca*)
son between Ba/Zn and Ca/Zn technologies, and it is and filled (Ca**) W C compound in each application.
quantified by using a-values from the Minolta CR 200
colorimeter. The L*a*b values that are generated from
the colorimeter readings are used in the evaluation.

RESULTS AND DISCUSSION


There are several proposed mechanisms for the role
of heat stabilizers in W C stabilization. Results that
support metal complex formation, transmetallation
couplings, and anion exchange reactions are com-
monly reported (10).The source of W C degradation is
also well published and is in accord with the following
reaction (5)(SchemeI). Zn
The treatment of W C with a varying shear modulus
(G) and high temperatures (A) causes the polymer to
discolor. The role of a heat stabilizer is to inhibit this
reaction, where M is calcium or zinc, and R is oxygen
or an alkyl group.
The functional formulation components that con-
0
tribute to stabilizing PVC are metal carboxylates,
phosphite compounds, antioxidants, free acid, and Flg. 1. Fullfmrialdesign space.

172 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, SEPTEMBER 2002, Yo/. 8, No. 3
Advances in Stabilization of Flexible W C

Table 1. Design Matrix.


~~ ~~

Run Ca Zn P Thermal1 Dynamic1 Brabender' Plate-Out2


2.74 6.54 5.42 -2.66
2.62 6.14 8.60 -3.83
6.65 10.87 5.04 -4.23
5.65 13.81 4.83 -4.48
2.67 5.00 5.16 -1.21
2.69 6.29 9.08 -0.78
4.91 12.59 5.63 -4.30
5.83 19.07 6.27 -2.83
3.93 7.71 7.09 -2.55
'Thermal, Dynamic and Brabender performance values equal the invetse slope ofa line formed fmm b-valuesas a function of time
2A stabilizer with better plate-csut resistanceyields a more negative a-value.

Table 2. Least Squares Fit Data Values.


Response Thermal Response Brabender
Summary of Fit Summary of Fit
RSquare 0.97713 Rsquare 0.96868
RSquare Adj 0.908522 RSquare Adj 0.874719
Root Mean Square Error 0.485183 Root Mean Square Error 0.558178
Observations (or Sum \Ygts) 9 Observations (or Sum Wgts) 9
~

Parameter Estimates Parameter Estimates


Term Estimate t Ratio Prob>ltJ Term Estimate t Ratio Prob>(tl
Intercept 4.1$577778 25.89 0.0015 Intercept 6.3466667 34.1 1 0.0009
Ca -0.195 -1.14 0.3735 Ca 0.28125 1.43 0.2902
Zn 1.54 8.98 0.0122 Zn -0.81 125 -4.1 1 0.0544
P -0.0225 -0.13 0.9076 P 0.94125 4.77 0.0413
Ca'Zn -0.195 -1.14 0.3735 Ca*Zn 0.22625 1.15 0.3703
Ca'P 0.2575 1.50 0.2721 Ca*P 0.19875 1.01 0.4199
Zn'P 0.0025 0.01 0.9897 Zn'P -0.83375 -4.22 0.0517
Effect Tests Effect Tests
Source Sum of Squares F Ratio Prob>F Source Sum of Squares F Ratio Prob>F
Ca 0.:)04200 1.2923 0.3735 Ca 0.6328125 2.031 1 0.2902
Zn 18.972800 80.5972 0.0122 Zn 5.2650125 16.8987 0.0544
P O.CW050 0.0172 0.9076 P 7.0876125 22.7486 0.0413
Ca*Zn 0.:104200 1.2923 0.3735 Ca'Zn 0.4095125 1.3144 0.3703
Ca'P 0.530450 2.2534 0.2721 Ca*P 0.3160125 1.0143 0.4199
Zn'P 0.c1oo050 0.0002 0.9897 Zn'P 5.5611125 17.8491 0.0517
Response Dynamic Response Plate-out
Summary of Fit Summary of Fit
RSquare 0.969956 Rsquare 0.985218
RSquare Adj 0.879825 RSquare Adj 0.940872
Root Mean Square Error 1.619927 Root Mean Square Error 0.328041
Observations (or Sum Wgts) 9 Observations (or Sum Wgts) 9
Parameter Estimates Parameter Estimates
Term Estimate t RatiC Prob>ltl Term Std Error t Ratio Prob>ltl
Intercept 9.78 18.11 0.0030 Intercept 0.109347 -27.30 0.0013
Ca 0.63875 1.22 0.3468 Ca 0.11598 6.55 0.0225
Zn 4.04625 7.06 0.0195 Zn 0.11598 -7.93 0.0155
P 1.213875 2.25 0.1533 P 0.11598 0.52 0.6565
Ca'Zn 1.04625 1.83 0.2093 Ca'Zn 0.11598 -3.15 0.0879
Ca*P 0.6!5375 1.14 0.3719 Ca'P 0.11598 3.58 0.0700
Zn'P 1.Of5625 1.86 0.2037 Zn'P 0.11598 2.1 1 0.1690
Effect Tests Effect Tests
Source Sum of Squares F Ratio Prob>F Source Sum of Squares F Ratio Prob>F
Ca 3.90601 1A885 0.3468 Ca 4.6208000 42.9398 0.0225
Zn 130.97711 49.9120 0.0195 Zn 6.7712000 62.9229 0.0155
P 13.;!8701 5.0633 0.1533 P 0.0288000 0.2676 0.6565
Ca'Zn 8.75711 3.3371 0.2093 Ca'Zn 1a658000 9.9042 0.0879
Ca'P 3.41911 1.3029 0.3719 Ca*P i.~naooo 12.8035 0.0700
Zn'P 9.CI9511 3.4659 0.2037 Zn'P 0.4802000 4.4624 0.1690

JOURNAL OF VINYL & ADDiTiVE TECHNOLOGY,SEPEMBER20U2, Vol. 8, NO. 3 173


James E. Reddy and Jeremy A. Hackett

I
T
I ,

2.75 4.1'25
I

,825
.
1.2375 4 . k 4.65

j 1. :

Most of the data analysis showed agreement with the


conservative model chosen. This is evidenced by high I
R-squared adjusted values and narrow confidence in-
tervals. A strong effect from a term applied to each re-
sponse can be identified by a small Prob>ltl value and
large F ratio. The graphical representation of the per-
formance values is illustrated in the prediction profiler -T--7--
2.75 4.125
(Fig. 2). Non-parallel lines evidence the presence of
interactions and can be found in dynamic and Bra- a.
3. Intemctionpbts.
bender responses (a. 3).These interactions are taken
into consideration when developing optimized formu-
lations. The optimized samples are used in the evalu- The barium carboxylates that are chosen for clear
ation against high-performance I3a/Zn stabilizers. (Ba*) and filled (Ba**)applications are high-efficiency
A significant magnitude of Merence can be observed commercial-grade materials. The barium and calcium
between static and dynamic performance testing. This optimized formulations were evaluated in dynamic, Bra-
can be explained by the variables incorporated in each bender and plate-out applications (Table 3).The clear
test method. Static stability simply measures the per- dynamic stability results show performance matches
formance efficiency of the metals. Dynamic stability in early and mid-term stability (Fig.4). The filled dy-
incorporates a shear variable and measures the per- namic stability results illustrate the Ca/Zn perform-
formance efficiency of the stabilizer system. As previ- ance advantages in early, mid, and long-term stability
ously mentioned, a critical component of the stabilizer
is the metal carboxylate. Careful consideration must be Table 3. B a n and C a n Technolwies.
taken when choosing the carboxylate. A balance be-
~~

Dynamic2 Brabende$
tween short, mid and long chain length acids must be Stabilizer Plate
maintained. The novel calcium intermediate imparts Sample' Clear Filled Clear Filled Out3
an internal lubricating functionality and a rapid ex- Ca' - 53.16 - 7.09 -4.30
change anion via the fatty acid and carbonate, respec- Ca" 15.07 - 1.37 - -3.92
tively. This dynamic functionality may reduce the force Ba' - 31.63 - 6.67 -2.13
of shear and accelerate the stabilization mechanism. W" 19.38 - 0.97 - -0.67
It is worth mentioning that the novel calcium interme- 'Ca" and Ba" were developed for clear applications, whereas Ca' and Ba' were
diate is a heavy-metal-free, phenol-free, low-viscosity, developed for filled.
*Dynamic and Brabender pedormance values equal the inverse slope of a line formed
mild-odor, mild-color, shelf-stable. isotropic, and ther- from b-values as a function of time.
modynamically stable liquid with high metal content. 'A stabilizer with batter plate-out resistanceyields a more negative a-value.

174 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, SEPTEMBER 2002, Vol. 8, No. 3
Advances in Stabilization of Flexible W C

Clear Dynamic Stability (185°C) Filled Dynamic Stability (185°C)

15
7
l
ll-
l__
l

.
4

=?
0
10

5
0 10 20 30
Time (min!

Fig. 5. mdynamicstability.
Fig. 4. clear dynamic stability.

(Fig. 5 ) . An additional benefit within Ca/Zn technol- ACElllowLEDollllElllT8


ogy is the favorable: color reading maintained during
The authors wish to express their thanks to OMG
the early process stige. This is apparent in filled com-
Inc. for the support of responsible care efforts.We com-
pounds for calendering and extrusion applications.
municate additional thanks to Dr. Chester E. Ramey
The Brabender results also show that the Ca/Zn tech-
for inventive contributions and to Ms. Yelena Pirogov
nology can remain competitive with high-efficiency
for assistance with technical applications.
Ba/Zn stabilizers. ?his is apparent in both clear and
filled applications. ;Plate-out resistance has been re-
garded as a dimcu:lt barrier to overcome for Ba/Zn
m a s
stabilizers. This is due to the components that are in- 1. A. Michel. J. Vinyl T e c M . 7,77 (1985).
corporated into making the barium and zinc carboxy- 2.A. Guyot, J. VilTechnoL, 7.92 (1985).
3. R Bacaloglu and M. Fisch,Pohjm Deg. Stab.. 45, 301
lates. The calcium technology is very forgiving in this "94).
nature. Comparatively speaking, the fatty acid is non- 4.R Bacaloglu and M. Fisch, pdym Deg. Stab., 45, 315
volatile and does not show a tendency to migrate to (1994).
the surface of the film. This permanency is of value to 5. R Gfichter and H. Miiller, PlasticAdditSes, pp. 271-325
Hanser/Gardner Publications. Inc. (1996).
process efficiency and printability applications. 6. B. Ivb, T. klen,and F.Tiidbs, Dqmdaim * nandStabi-
lizationofPolyners, Vol. 2,pp. 483-714. H. H. G. Jelli-
C~OlrpCLUSIOlllS nek and H. Kachi, eds., Elsevier Science, Amsterdam,
Netherlands ( 1989).
Future efforts to (developW C heat stabilizers are 7. J. W. Burley and R. E. Hutton, PoZyrn Deg. Stab., 8,
focused on providing alternatives to products that are 285 (1980).
suspected to be environmentally hazardous. The Ca/ 8. E.J.Wickson, Handbook of Pohjuinyl ChlorideFormulat-
ing, pp. 303-37,J o h n Wiley, New York (1993).
Zn technology is a viable alternative to Ba/Zn stabiliz- 9.SAS Institute, 'JMP: Statistical Discovery Software,"
ers. The novel calcium intermediates make perform- Version 4,Cary, N.C. (2000).
ance and cost competitive heavy-metal-free stabilizers 10.R. Bacaloglu, M. Fisch, U. Stewen, M. Shah,J. Fakin-
a reality. Furthermctre, this technology allows us to lede, E. Krainer, P. Kleinlauth, and I. Bacaloglu, "New
provide a comparable -green" stabiker that is free of Intermediates for Calcium Zinc Stabilizers," Pushing
Pro$t&i&g RET%C conference(2001).
heavy metals and phenol-based compounds. This new
Ca/Zn technology can produce effective heat stabiliz-
ers for most applications, given the proper testing
conditions.

JOURNAL OF VINYL & AIDDKIVE TECHNOLOGY, SEPTEMBER 2002, Vd. 8, No. 3 175