PVC Stabilizers of the Past, Present, and

Future
R. D. DWORKIN
Akzo Chemicals Znc.
New Brunswick, New Jersey 08903

When chemical additives were found that could minimize the loss of chemical
and physical properties of a thermally-processable but heat-sensitive polymer
called poly(viny1chloride) (PVC),a n industry was born. And with it grew the world
of plastics additives. Stabilizers for PVC became a n industry itself, feeding into
and off of this versatile polymer industry, in a n almost symbiotic relationship.
There have been so many types of stabilizers in use throughout the past fifty
years: inorganics, leads, organics, barium/cadmiums, calcium/zincs, organotins,
and antimony. And so very many more have been conceived but not commercial-
ized: organoleads, organoantimonys, bismuths, indiums, and a myriad of organic
chemicals. What are the merits and deficiencies of these stabilizers? Which of
yesterday's products are still with us? What are the newer types? What might be
tomorrow's products? This paper will attempt to review and discuss the past,
present, and future of PVC stabilizers; the factors that are responsible for their
variety, for influencing their research, development, and commercialization, and
how these factors change with time.

INTRODUCTION thermal instability, a German company (1) let its

hen there's a vinyl fabrication problem, invar-
W iably, the stabilizer supplier the first to be
is
blamed. The resin supplier is next, followed in rapid
succession by the other additive producers. Why
question the stabilizer first? Because the fabricator
understands just how fundamentally important sta-
bilizers are in successful processing of PVC. Recog-
nition of this type can be very stressful, however.
It all started in 1872, quite a long time ago. In that
year, a potentially marvelous and versatile new poly-
mer was created. A white powdery material, which
on heating could be formed into useful shapes-but
not without partial decomposition. Thus treated,
color and physical properties would suffer and many
processing difficulties were to be encountered, not
least of which were the liberation of extremely nox-
ious and corrosive HC1 and sticking of the hot poly-
mer to the metallic equipment shaping it.
It was hopeless! A waste of time! Nothing would
ever come of poly(viny1chloride) until some scientists
would find certain relatively simple chemical addi-
tives that would minimize thermal decomposition.
The PVC industry and the world of stabilizers was
yet to be born.
A lot happened since PVC was first made in a
laboratory in 1872. Mostly, however, time passed.
In the mid-1920s. owing to the lack of available
machinery which could process PVC, overcoming its
vinyl chloride monomer (VCM) and PVC patents
lapse.
Industrial interest picked up in the 1930s in the
U S . with the patented (2) use of certain phosphate
and phthalate iqmpounds to produce flexible, shap-
able PVC adhesive compositions. White lead and so-
dium silicate are believed to have been employed, in
this case, as heat stabilizers.
Probably, the stabilizers of the 1930s grew out of
the rubber industry additive technology (3), where
litharge was likely, among the earliest successful
products. Then came metal soaps, patented in 1934
(4).a n obvious offshoot of the use of alkali metal and
alkaline earth oxides and hydroxides (5).
During the 1940s both calcium-zinc and barium-
cadmium soap synergism was discovered, as were
highly effective organotin salts, including unsatu-
rated carboxylic acid ester derivatives (6, 7).
In the 1950s. one of the most long-lived, commer-
cially successful, organotin mercaptoacid ester sta-
bilizers was invented (8) along with other notable
organotin sulfur-containing products (9, 10). Anti-
mony mercaptoester stabilizers ( 1 1). use of polyols
(12),and mixed alkyl/aryl phosphites (13)for mixed
metal soap stabilizers were also patented.
Look at the literature and patents of the 1960s and
1970s and you'll find a seemingly endless and amaz-
ing variety of proposed new stabilizer products, stud-
ies of mechanisms of PVC decomposition and stabi-
lization, and reviews.

JOURNAL OF VINYL TECHNOLOGY, MARCH 1989, VOL. 11, NO. 1 15

 R. D. Dworkin
Among the highlights of this era were the intro-
duction of food grade octyltin stabilizer, high tin/high
efficiency and overbased butyltin stabilizers, com-
mercialization of methyltin stabilizers, one-pack tin
stabilizers, estertin stabilizers, non-dusting lead sta-
bilizers, and sulfur-based organic stabilizers. The
VCM/angiosarcoma relationship, industry’s better
than hoped for technical response to decreasing re-
sidual vinyl chloride monomer (RVCM) in PVC, the
Bureau of Alcohol, Tobacco, and Firearms banning
of PVC containers for alcoholic beverages, cadmium
bans in Scandinavia, and the implementation of the
Toxic Substances Control Act (TSCA)were some of
the more dramatic events of this time.
By comparison to the past two decades, the 1980s
have been technologically relatively slow, but envi-
ronmentally, quite active. Some of the more interest-
ing stabilizer developments of this period involved
the introduction of stabilizers for gamma-irradiated
PVC medical articles (14, 15), growth of liquid cal-
cium/zinc stabilizer use in FDA applications, high
flash-point, i.e., low volatility, barium-cadmium sta-
bilizers, safer-to-handle lead stabilizers, and a
keener interest in cadmium-free and low fogging (au-
tomotive) products.
The emphasis on safety, health, and the environ-
ment has been dramatic, to say the least. A s a n
example, the Palisades Section of the Society of Plas-
tics Engineers held a one-day symposium at Poly-
technic Institute, Brooklyn, New York, on April 22,
1981. The theme was “Cadmium and Lead Additives
for PVC: Where are they headed?” Ten papers were
presented, transcribed, and later published in a sin-
gle volume of the Journal of Vinyl Technology (I6).
A s you see, a lot has happened since PVC was first
synthesized. Let’s now take a look at the additives
which have most helped the PVC industry grow to its
present position of commercial and practical promi-
nence.
STABILIZERS
Leads
Litharge PbO
Basic Lead Carbonate 2PbC03. Pb(OH)2
(White Lead)
Normal Lead Stearate Pb(OCOCi7H35)2
Dibasic Lead Stearate 2Pb0. Pb(OCOCi7H35)z
Triibasic Lead Sulfate 3Pb0 * PbS04. H z 0
Dibasic Lead Phosphite 2Pb0. PbHP03 ’hH20
Dibasic Lead Phthalate 2Pb0. Pb(OCO)zCsH4
Dibasic Lead Carbonate 2Pb0 * PbC03
Basic lead carbonate quickly replaced litharge as
one of the earliest stabilizers because it was non-
yellowing. At higher temperatures, however, it can
liberate C02.
Normal lead stearate and dibasic lead stearate sta-
bilize poorly but are very lubricating.
16 JOURNAL OF VINYL TECHNOLOGY, MARCH 1 9 8 9 , VOL. 1 1 , NO. 1
Tribase lead sulfate is one of the most effective
and commonly used stabilizers.
Dibasic lead phosphite is a n excellent and highly
efficient stabilizer, which unlike other lead com-
pounds, provides excellent weatherability to PVC.
Dibasic lead phthalate is another excellent product
which has superior long term stabilization proper-
ties.
These products, often called commodity leads, are
now sold in non-dusting forms or compounded into
stabilizer “one-packs.”A typical one-pack might con-
tain one or more inorganic lead salt, some lead stear-
ate, wax lubricants, oxidized polyethylene wax, and
auxiliary compounds. The products are formed into
non-dusting prills, strands, pastilles, or flakes.
Lead stabilizers’ major use is attributable to their
non-conductive electrical properties. These stabiliz-
ers and their decomposition product, lead chloride,
are the least conducting compounds of all stabilizer
types. Thus, they are used in PVC primary electrical
wire insulation and jacketing. Their drawbacks in-
clude potential toxicity, sulfide/cross-staining, and
opacification of PVC.
Barium-Cadmium Mixed Metals
Barium/Cadmium Carboxylates: M(OCOR)2
-0COR Types: Stearate
Laurate
Naphthenate
Neodecanoate
Octanoate
Benzoate
p-t-Butylbenzoate
Oleate
Tallate
Barium (Alky1)Phenates Ba ( O a R l2
Types: Octylphenate
Nonylphenate
-OQR Phenate
Barium (Ba) and Cadmium (Cd) soaps are most
frequently used in combination to take advantage of
synergistic behavior. Additionally, zinc salts or or-
ganic auxiliaries, such as organophosphites, antiox-
idants, and epoxidized oils may be used to further
boost performance.
Solid Ba/Cd soaps, the stearates and laurates, are
very powerful stabilizers which also contribute lu-
brication to PVC formulations. Their major draw-
backs are toxicity, especially of dusty powders, and
plateout.
The other Ba/Cd soaps are generally produced as
liquid solutions, with or without synergistic adju-
vants. Selection of one or more carboxylic acid li-
gands is made on the basis of the flexible vinyl prod-
uct’s desired end properties, e.g., clarity, low plate-
out, inhibition of early color development, and eco-
nomic considerations.
Barium alkylphenates and their basic analogs are
 PVC Stabilizers of the Past, Present, and Future

used to enhance plateout resistance compared to car- S

boxylates. Diphenylthiourea
Liquid barium-cadmium stabilizers are available
for virtually any application which does not require Beta Diketones 0 0
non-toxicity, e.g., according to the approval guide- II II
lines of Health and Welfare Canada, U S FDA, etc. R--C --CHz--C-R’
Because of their general applicability, this class of Mercaptans (Thiols) R-SH
mixed metal products has had the lion’s share of the Sulf ides/Disulf ides R-S-R, R-S-S-R
primary stabilizer market for flexible PVC. Thioanhydrides 0 0
Aside from their toxicity and plateout potential, all II II
barium-cadmium stabilizers may sulfur/cross-stain. R--C --s--C -R
Epoxies 0
Calcium-Zinc Mixed Metals / \
RI4! 4-R3
Calcium-Zinc Carboxylates M(0COR)z
-0COR types: Stearate I I
Laurate Rz R4
Octanoate Organophosphites
Benzoate
Neodecanoate
Hindered Phenolics
Oleate
Tallate
Rosinate
Calcium (Ca) and zinc (Zn)soaps, like Ba/Cd prod- Bisphenol A H
Io
*o
I-
ucts, respond synergistically and are, therefore, most Phenols
often used in combination. Weaker stabilizers than Pentaerythritol C(CHzOH)4
Ba/Cd’s, Ca/Zn’s usually require additional syner- Sorbitol HMHz(CHOH)4CHZ-
gists in the form of organophosphites, antioxidants, OH
and polyols. Trimethylol CH&HzC(CHZOH)3
The major use of Ca/Zn’s is in non-toxic applica- Propane
tions. The solid soaps are the basis of many commer-
cial powder and paste, non-toxic stabilizer composi- There are thousands upon thousands of organic
tions. The laurates, however, are no longer believed chemicals known to us. It isn’t surprising, therefore,
to be of commercial significance. that a large number of them have been evaluated as
Many of the other carboxylates are approved by co-stabilizers for PVC. It’s even less surprising that
the US FDA for food-contact PVC applications, but a substantial variety of organic compounds have
some are not. When even one ingredient of a Ca/Zn been shown to possess genuine activity. In general,
stabilizer is not sanctioned by FDA, it may not be it would seem that nitrogen, sulfur, and oxygen func-
used in non-toxic applications. These products would tionality are most effective.
still be considered to be low in toxicity compared to Alpha-phenylindol (18)was used in Europe, for a
other mixed metal stabilizers. time, a s a co-stabilizer (19) with Ca/Zn’s for PVC
Efficient, non-toxic, liquid, Ca/Zn stabilizers for mineral water bottles. In 1978, it was removed from
clear, flexible PVC applications were scarce until the French approval list. Its further use anywhere in
solubilized rosinate technology was developed ( 17). the world is in doubt.
Ca/Zn stabilizer drawbacks include plateout, haze As recently as 1985, beta-aminocrotonates were
development in thick’ cross-sections of clear sub- being used in Germany for food-contact and non-
strates, water-blush characteristics, and early yel- food packaging and phonograph records. These or-
lowing. ganic compounds, even today, are mostly used in
conjunction with Ca/Zn’s (20): they have never
Organic fC-1 Stabilizers caught on anywhere else, probably due to poor early
color properties.
Diphenylthiourea (21) was used in several Euro-
Alpha-phenylindole
pean countries for food packaging. Since the switch
from alkaline-prestabilized emulsion resin to suspen-
sion PVC, their use has apparently dwindled.
Beta-diketones (22), specifically stearoyl-benzoyl-
Beta-Aminocrotonic 0 methane, which is USFDA approved for food contact
Esters use in PVC, are good Ca/Zn stabilizer boosters (23).
At $8.50/lb, the PVC bottle industry is slow to re-
spond, even though usage levels of this co-stabilizer
may be quite small.

JOURNAL OF VINYL TECHNOLOGY, MARCH 1989, VOL. 11, NO. 1 17

 R. D. Dworkin

Mercaptans have been shown to help stabilize PVC or suggested, but I would be remiss for not mention-
(24, 25).but odor, cost, and marginal effectiveness ing dicyandiamide and melamine. Both nitrogen com-
are not conducive to widespread application. When pounds were used years ago in conjunction with
used in combination with organotin mercaptoesters, metal salts, for vinyl/asbestos tile, as a way to retard
beta-mercaptopropionic acid can improve early color the development of the bluish discoloration that
inhibition of clear PVC compounds. could otherwise form.
Of all the sulfides and disulfides which have been
tried in PVC, only esters of thiodipropionic acid con- Inorganics
tinue to find limited use in primary stabilizer com- The only material worth mentioning in this cate-
positions. gory is a complex magnesium-aluminum salt known
Thioanhydrides, especially thiolauric anhydride, as talcite or hydrotalcite (30).Two specific products
are quite interesting organic stabilizers. While they have the formulas:
promote significant early yellowing, they provide
good long term stability and can be performance Mg6A12(OH)16C03and Mg4.5A12(OH)1&03.
3.5 H 2 0
boosted by small amounts of organotin mercaptoester
co-stabilizers (26-28). The main drawbacks to these These products do show some activity with certain
products are cost and poor shelf-stability. organotin mercaptoesters and zinc carboxylates, co-
Epoxy compounds, mentioned earlier to be excel- stabilized with beta-diketones. However, usage levels
lent synergists for mixed metal Ba/Cd and Ca/Zn and costs are high and they cause opacity.
stabilizers, are one of the most widely used co-stabi- I t is interesting to note that they have almost world-
lizers (19, 29). Activity is essentially keyed to the wide governmental health and safety approvals for
amount of oxirane oxygen, but plasticization, lubri- use in polyolefins and PVC.
cation, and cost parameters play a role in their selec- Organotins
tion and use.
The most common products are epoxidized soya Di-Alkyltin Carboxylates:
oil, linseed oil, castor oil, sunflower oil, epoxidized Laurate
tall oil esters, and some polymerics. Probably the
biggest problem with epoxy compounds, particularly (7 )
R2Sn -0C C11H23 2
those derived from vegetable oils, is their propensity
to titer out at cold temperatures.
Organophosphites constitute another class of ex-
Maleate
(;
R2Sn - 0 C CH==CHC0-
7)
tensively used co-stabilizers for Ba/Cd and Ca/Zn Maleate Esters
soaps. Tri-phenyl phosphite has been used for gen-
eral purpose applications where the possibility of
releasing free phenol does not pose environmental, Alkyltin Chlorides:
II
R2Sn( 0
OCCH4HCOR’ 7 ) z

health, or safety problems. Tris (nonylphenyl) phos- Butyltin Trichloride C4H9SnC13

phite is commonly used in non-toxic applications Dibutyltin Dichloride(C4Hg)zSnC12
where U S FDA approval is required; other “non-toxic” Alkyltin Sulfides:
types are available too. Mono Butyltin Sul-
The most effective general purpose types, however, fide
are the mixed alkyl/aryl products. Diphenyl decyl and Dibutyltin Sulfide
didecyl phenyl are among the most effective mate- Di-Alkyltin Mercap-
rials (13). Nonetheless, most all organo-phosphites tides:
have as their biggest drawback, hydrolytic instabil- n-Dodecyl Mercap-
ity. tide
Antioxidants help stabilize PVC; and while the Mono-/Di-Alkyltin
variety of potential products is quite large, two gen- Mercaptoacid Es-
eral types work well in most applications: BHT and ters:
bisphenol A. The difference in steric hindrance is Isooctylthioglycolate 0
enormous but both products have a place in solid and
liquid mixed metal stabilizers.
Polyols are organic compounds, containing three Di-Alkyltin Mercapto-
or more alcohol functional groups, which find some carboxylates:
utility in mixed metal stabilizers (12).Most of this Mercaptopropionate
class of products exhibits some water solubility and
can, therefore, contribute to water-blush problems.
On the other hand, polyols are limited in solubility in Mono-Alkyltin Mercap-
typical solvents used to make liquid mixed metal toalcohol Esters:
products and are, therefore, more generally employed 2-Mercaptoethyl 0
in solid stabilizer systems. Oleate
Many other organic costabilizers have been used RSn

18 JOURNAL OF VINYL TECHNOLOGY, MARCH 1989, VOL. 1 1 , NO. 1

 PVC Stabilizers of t h e P a s t , Present, and Future
Mono-/Di-alkyltin Mer-
captoester Sul-
fides:
Mixed Ligands SR’ R to Lewis-acidity of alkyltin chlorides, particularly
I I
R - S n - S - S n-R
I I
SR’ SR’
Organotin stabilizers are the most universally appli-
cable of all stabilizer types. While they find greatest
utility in rigid PVC, homopolymer, and co-polymer
applications, some products perform quite well in
flexible vinyls too.
Unlike lead stabilizers, organotins may be used in
the fabrication of crystal clear PVC articles. In Eu-
rope, lead stabilizers are the dominant type, finding
utility in potable water pipe and profile extrusion. In
the U S . tin stabilizers have the strongest foot-hold
and leads are mostly used for wire and cable insula-
tion and credit card stock.
From the beginning, butyltin stabilizers dominated
the market for general purpose applications. Octyltin
products were later introduced for food-contact ap-
plications and commanded a premium price.
When they were finally commercialized in the early
1970% methyltins successfully challenged butyltins
in a number of areas, eventually including some FDA
approved applications.
The most recent development in organotin stabi-
lizer technology (mid-1970s)was in the form of ester-
functional products called “Estertins.” Only sulfur-
containing products are commercially available for
both general purpose and FDA approved food-contact
PVC applications.
While each family of organotin stabilizers has
some undesirable properties, their advantages f a r
outweigh their disadvantages. Barring any unforseen
problems or radical new technologies, they are prob-
ably here to stay.
Mono-/Di-alkyltin combinations usually offer syn-
ergistic performance properties, but there are a num-
ber of all-mono or all-di stabilizers being used in
certain applications.
Dibutyltin dilaurate is a very lubricating, low odor
product which has been substantially replaced by
more cost-efficient compounds. It has good long term
stability but develops a yellow discoloration immedi-
ately. Mixtures of this material with dibutyltin ma-
leate solved the color problem but shelf stability of
the blend was too poor to maintain commercial inter-
est.
Dibutyltin maleate provides excellent early color
ihhibition to PVC in addition to the strongest UV
light stabilizing properties of any organotin product.
Drawbacks of this solid compound include polymer
de-lubrication, lacrymatory properties, and high cost.
Dibutyltin bis(ma1eate esters) also provide decent
early color and U V stability. The usual liquid nature
of this family of products is conducive to ease of
handling, but does not completely eliminate potential
eye, nose, and throat irritation during use.
JOURNAL OF VINYL TECHNOLOGY, MARCH 1 9 8 9 , VOL. 1 1 , NO. 1
Alkyltin chlorides are not, themselves, sold as PVC
stabilizers. but can be formed in vinyl via reaction of
liberated HCl with typical organotin stabilizers. Due
monoalkyltin trichloride, one would imagine these
products to de-stabilize PVC. On the contrary, they
have been found to have a slightly stabilizing effect
(31,32, 33).
Dibutyltin sulfide is not a good stabilizer by itself
as it causes initial discoloration. On the other hand,
monobutyltin sulfide provides PVC with very good
early color and was used for years as a sole stabilizer
in rigid calendered goods. High cost and poor disper-
sion in vinyl resin were among its drawbacks.
Dibutyltin bis(n-dodecyl mercaptide), like its di-
laurate counterpart, causes immediate yellowing of
PVC but provides good lubrication. When color
boosted with a little zinc carboxylate, it becomes
more efficacious as a stabilizer/activator for chemi-
cally blown, extruded PVC (34).
Dibutyltin bis(isooctylthioglyco1ate) had been the
work-horse of the tin stabilized PVC industry for over
20 years. Mixtures of mono- and di-butylin com-
pounds were used in every conceivable rigid PVC
application, except food packaging. Its dominance
was successfully challenged by higher tin content,
slightly more efficient methyltin analogs.
Once the methyltin process was refined enough,
low-trimethyltin products were approved by FDA for
non-toxic applications. Thus, dioctyltin bis(iso-
octylthioglycolate)also met with stiff competition.
Diestertin bis(isooctylthioglyco1ate)is representa-
tive of the newest in tin stabilizer technology. Prod-
ucts based on this type of molecule have been known
to possess somewhat better UV light stabilizing effi-
cacy than alkyltins. The FDA approved estertins per-
form closest to octyltin types, with slightly better
early color inhibition.
Dibutyltin mercaptopropionate is a most interest-
ing solid stabilizer with excellent early color and
moderately good UV properties. This product is,
chemically, very closely related to the cyclic thiogly-
colate compound which usually precipitates out of
solution from methyltin and butyltin isooctylthiog-
lycolate based products. However, the mercaptopro-
pionate’s performance far outshines the thioglyco-
late’s.
So called “reverse ester” monoalkyltin stabilizers,
based on mercaptoalcohol derivatives instead of mer-
captoacid derivatives, were found to be useful in
giving PVC pipe compound a “whiter-white” color.
The combination with organotin sulfides fast became
the basis for potable water pipe stabilizers, despite
their strong odor and in spite of the fact that a white-
white pipe is only esthetically better than a pale-
yellow-white pipe.
Mixed ligand alkyltin stabilizers, i.e., those con-
taining mercaptoesters and sulfides, were the basis
for highly diluted (5%to 13%tin) PVC pipe stabilizers.
Since reverse ester products replaced these materials
in this application, the mixed ligand stabilizers have
19
 R. D.Dworkin
found utility in other rigid, opaque applications.
For a short time, overbased organotin mercaptoes-
ters were commercially available: these high tin-con-
tent, low odor, high efficiency materials had the
unique property of minimizing blue toner exhaustion
in PVC bottle compounds.
Made from dibutyltin oxide and butyltin mercap-
topropionate esters, these moderately viscous stabi-
lizers were somewhat deficient in long term dynamic
properties.
As with lead stabilizers, some liquid tins were con-
verted to solid (powder) one-packs by mixing with
wax, calcium stearate, oxidized polyethylene, and a n
absorbant, such a s synthetic silicates. While just a
few of these products are still commercially active,
the concept fills a very logical need in the PVC pipe
market, as it minimizes the handling of micro-ingre-
dients and decreases raw material inventories for
some fabricators.
It should be mentioned that many of the original
alkyltin mercaptoacid esters invented in the U S .
were based on 2-ethylhexyl alcohol. The same type
products are today’s standards in Europe, whereas,
U S . products use isoctyl alcohol rather exclusively.
Cost and availability were the deciding factors. For
the most part, both esters give stabilizers of equal
overall performance.
Tin-Based Mixed Metals
Also for a time during the 1970s.low tin-content
liquid stabilizers, containing either barium or cal-
cium, were used in considerable volume for PVC pipe
extrusion (35).The first products were based on mon-
obutyltin mercaptoacid esters and barium alkylphen-
ates. Later materials contained more complex mer-
captoacid ester derivatives. While they were darkly
colored, these low cost tin-based mixed metal stabi-
lizers gave reasonably good-looking white pipe with
only a very slight yellow cast to it.
Antimonies
Essentially all commercial antimony stabilizers
consisted of antimony tris(isooctylthioglycolate),
though the initial invention was based on the 2-
ethylhexyl ester. A s originally commercialized, for
high usage level processing on single-screw ex-
truders, antimony stabilizers were no match for or-
ganotins, although they did find some utility in vinyl
phonograph records.
Antimony stabilizers got a second chance when
they were found to have some potential cost-perform-
ance advantages over mixed-ligand organotins, at
low stabilizer usage levels. Additionally, it was found
that certain metal soaps responded synergistically
with antimony and di-hydroxybenzenes boosted UV
light and storage stability (36).
Of all the drawbacks to using antimony stabilizers,
the most serious may be their cross-staining potential
with any sulfide-based tin stabilizer. To insure
20 JOURNAL OF VINYL TECHNOLOGY, MARCH 1 9 8 9 , VOL. 1 1 , NO. 1
against this, a fabricator must dedicate his plant to
handle only one type of product, antimony or tin.
THE ISSUES BEHIND STABILIZER
DEVELOPMENT
A Need
Without the need to solve a problem, meet a chal-
lenge, or explore a n opportunity, we’d all become
blissfully complacent. In the past, there was a very
strong need to find the solution to the problem of
PVC decomposition during attempts to fabricate it
into useful articles. W h p Because this new polymer
was begging to be used. It could be made from chem-
ical industry by-products and plentiful raw mate-
rials. Machinery couldn’t do it so the answer had to
be chemical.
Once some solutions were found, the need shifted
emphasis to deal with newer process resins. Pres-
ently, the need is more economic and one of technical
survival. How much more so in the future, when the
emphasis changes once again to stronger competi-
tive, regulatory, and environmental concerns?
Creativity
This factor is the cornerstone of success. It seems
to come naturally to some people; one idea building
upon another. Curiosity is creativity’s middle name.
There was a starting point for stabilizer develop-
ment in the past. Some breakthroughs were discov-
ered which formed the basis for rapid growth in the
number of useful products; and this led to present
breakthroughs. If the stabilizer industry uses its cre-
ative powers, we will also see slow but steady growth
in the future.
Economics
The great opportunity of the past to find ways to
stabilize PVC had financial motivation as its partner.
Today’s opportunity is no less financially motivated,
but profitability has erroded so much that several
companies have been driven out of business. For
technology to grow, stabilizer manufacture must be
profitable. This will be a n issue in the future, too.
Performance
The early stabilizers were barely satisfactory but
they rapidly got better in performance. Today’s per-
formance criteria are even more stringent. Fabrica-
tors want to use less and get more out of their stabi-
lizers. To survive in the future we must and will meet
the industry’s expectations.
Health, Safety, and Environment
This issue only seemed to be less important in the
past than it is today. We now strive to protect our
workers, customers, and the environment. Our chal-
lenge for the future, then, is to make less toxic sta-
 PVC S t a b i l i z e r s of t h e P a s t , P r e s e n t , and Future
bilizers by safer methods and handle them in ways
which will prevent water, air, or land contamination.
Regulatory Matters
In the past, you couldn’t exactly do anything you
wanted to, but from the uncovering of toxic waste
dump sites nowadays, its keenly obvious that a num-
ber of irresponsible chemical manufacturers were
unreasonably careless.
Due to lack of regulatory concerns in the past, we
seem to be facing over-regulation in the present.
Unfortunately, even though the chemical industry is
doing a very respectable job now, things will only get
tighter in the future. More and more world-wide leg-
islation and regulation will be drawn up by relatively
chemically-uneducated people who may be trying to
.
please their constituents or succumb to the pressure
of special interest lobbying groups. The stabilizer
industry must play a stronger role in guiding fair and
warranted regulations.
Competition
Imitation may be the sincerest form of flattery, but
everyone would like to have uniquely advantageous
products.
In the past, competition among stabilizer suppliers
had to be a whole lot weaker than it is in the present.
Now it is a significant driving force in the develop-
ment of better PVC stabilizers. Should economic in-
centives for R&D investment improve, competition
may get keener still in the future.
Despite the problems that stabilizer manufactur-
ers may have because of competition, it is good for
the PVC industry in the long run.
Technology
In the past, the budding PVC stabilizer industry
borrowed products and ideas from available rubber
technology: but as soon as possible, patents were
sought for newly developed products in addition to
keeping certain things proprietary. The technology
base has built up almost exponentially to the present.
However, emphasis has shifted from a more theoret-
ical approach to more applied concepts.
The future should continue to see significant im-
provements in stabilizer technology. Even though
much of it will be patented, and that means restricted
use of the invention by the assignor for many years,
the driving force will be there to stimulate and chal-
lenge us to create newer and even better products.
LOOKING TO THE FUTURE
The outlook for survival of lead stabilizers into the
future is bright. Just as the PVC industry survived
the first black days of realization, that long term
exposure to RVCM can cause angiosarcoma, the lead
stabilizer industry will survive the ever tightening
regulatory demands for reduced worker exposure to
JOURNAL OF VINYL TECHNOLOGY, MARCH 1 9 8 9 , VOL. 1 1 , NO. 1
these products. Will there be substantially new
breakthroughs in lead stabilizer technology? Most
likely for Europe but possible for the U.S. too. Will
the National Sanitation Foundation ever approve
leads for potable water pipe? I’m afraid my crystal
ball won’t give up its secret answer to this question.
How much longer will Ba/Cd mixed metals be
around? After all, cadmium is toxic and now the cost
of the metal has escalated. The answer is that l3a/
Cd’s will indeed survive for some time to come.
Cadmium containing, liquid and solid, metal soap
stabilizers have been successfully and safely manu-
factured and handled for dozens of years. Just as
importantly, hundreds of vinyl processors have
safely and effectively used these products during that
time. Low-cadmium and cadmium-free products will
make inroads into automotive and sensitive applica-
tions, but these highly efficient Ba/Cd products will
continue to be used in the most demanding applica-
tions.
Highly efficient PVC stabilizers for low-foggingau-
tomotive applications are still in great demand. Sta-
bilizer and plasticizer manufacturers have been well
aware of it in the past. Their customers periodically
remind them of the need for better products, as well
as the Trade Journals (37). The future should witness
significantly improved stabilizers and other com-
pound additives to help solve the automotive fogging
problem.
Just like certain metal carboxylates and di-hydrox-
ybenzene synergists gave new life to a long known
but virtually forgotten stabilizer, antimony mercap-
toester, this author believes that the future may see
breakthroughs in synergists for several types of pri-
mary stabilizers. Special, high-efficiency additives
may be found for Ca/Zn’s, Ba/Zn’s, and organotins;
perhaps through reawakening a forgotten or aban-
doned technology: perhaps through the use of new
metal soap combinations, such as bismuth and bar-
ium (38).
It’s very likely that we shall see better PVC stabi-
lizers in the future, but there never will be a univerr
sally applicable one. Even if PVC could be made with
zero defect sites and totally free of residual initiators,
emulsifiers, etc., stabilizers would still be required-
even at lower usage levels.
Some of the stabilizer products of yesterday have
outlived their usefulness, but only time will tell how
many will survive in the future.
REFERENCES
1 . Chemische Fabrik Griesheim-Elektron (1926).
2. W. L. Semon, U S . Patent 1 , 9 2 9 , 5 4 3 (1933).
3. M.Morton, ed., R u b b e r Technology, 2 n d ed.. V a n Nos-
trand Reinhold, N.Y. (1973).
4 . R. Groff, Canadian Patent 3 4 6 , 1 6 4 (1934).
5. T.C. Jennings. a n d C. W. Fletcher, Chapter 2 i n En-
c y c l o p e d i a of PVC. L. I. Nass, ed., 2 n d ed., 2. Marcel
Dekker, N.Y. (1988).
6 . V. Yngve, U S . Patent 2.2 1 9 , 4 6 3 ( 1940).
7. W. Quattlebaum, e t a l . , U S . Patents 2 , 3 0 7 , 1 5 7 ;
2,307,675; 2,344,002.
21
 R. D. Dworkin
8. E. L. Weinberg, U S . Patent 2,648,650.
9. C. E. Best, U S . Patent 2,731,484(1955).
10. W. E. Leistner, U S . Patents 2.726,254:2,726,277
(1955).
11. E.L. Weinberg, US. Patent 2,680,726(1954).
12. Lally, et al., U.S. Patent 2,734.881 (1956).
13. W.E. Leistner, bt al., U S . Patent 2,716,092(1955).
14. M.Foure, a n d P. E. Rakita, Med. Deuice & Diagnostic
Ind., 5 , No. 1 1 , November 1983.
15. D. S.Housel, SPE 43rd ANTEC Preprints 1068 (1985).
16. J. Vinyl Tech., 4. No. 1, (1982).
17. D. S.Housel, U S . Patent 4,340.514 (1982).
18. German Patent 862,512(1942).
19. T.Van Hoang, e t al., Eur. Polyrn. J., 12, 357 (1976).
20. T.Van Hoang, et al., J. Macrornol. Sci. Chern., A12.3
41 1 (1978).
21. German Patent 746,081(1940).
22. French Patents 2,297,227: 2,324,681(1975).
23. M.Gay, a n d L. Carette. SPE Polyrn. Modifiers a n d Ad-
ditives Dir. 1st Inten'l Conf., November 1985;not in
Preprints.
24. Handbuch der PVC-Additive, 1971,Ciba-Geigy, Mar-
ienberg GmbH.
22 JOURNAL OF VINYL TECHNOLOGY, MARCH 1989, VOL. 11. NO. 1
25. W. H. Starnes, et al.,Macrornol., 11, No. 2,373 (1978).
26. L. B. Weisfeld, a n d C. H. Stapfer, ACS Div. Org. Coat-
ings a n d Plastics Chem., 161st Meeting, 31 (1). 732
1971.
27. W. Stamm, et al., ibid 26,720.
28. Stapfer, e t al., SPE Journ., 28, No. 5,22 (1972).
29. D. F.Anderson, a n d D. A. McKenzie, J. Polyrn. Sci. 8,
2905 (1970).
30. Mfg'd by Kyowa Chem. Ind. Co., Ltd., Kagawa, Japan:
dist. by Mitsui & Co., (USA), Inc.: trade n a m e "Alcam-
izer."
31. H. 0.Wirth, e t al., J. Vinyl Tech. 1, No. 1. 51 (19791.
32. T. Van Hoang. e t al., J. Polyrn. Deg. and Stab. 3, No.
2,137 119811.
33. H. 0.Wirth, a n d H. Andreas, Pure a n d Applied Chern.,
49,627(1977).
34. R. D. Dworkin, a n d A. J. Ejk, U.S. Patent 3,953,385
(1976).
35. T. C. Jennings, et al., U S . Patent 3,764,571(1973).
36. D. J. Dieckmann, U S . Patents 3,887,508(1975):
4,029,618(1977).
37. D. Smock, Plastics World, 62-65,April 1988.
38. R. G. Weiler, J. Vinyl Tech., 5 , No. 1, 27 (1983).