Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
.
~0~128~ ~
In applicant's Canadian patent 974,688 issued September
16, 1975r organotin stabilizer systems are described, particularly ~
suited for the stabilization of vinyl halide resins against de- ~;
gradation by heat. Such stabilizer systems permit resins to be
molded and ~orked under the action of heat into many useful arti-
cles. It was found/ as disclosed and exemplified in this patent,
that a metal base component, alone~ contributed to the heat sta~
bilization of vinyl halide resins in the presence of the organotin ~-
sulfur-containing compound. The present application develops more
.fully the combination of an organotin sulfur-containing compound
and a metal compound and the stabilizing synergisms embodied by
~ . such combinations.
SUMMARY OF T~E INVENTION . ~`
The present invention is directed to improvements in
resin stabilizer systems of organotin sulfur-containing compounds.
~: This invention.is predicated in part upon the unexpected heat ;~
: stabilization of vinyl halide rèsins by organotin sulfur-contain-
: ing compounds in.combination with certain types of me.~al compounas~
~ ~ . Specifically, the in~ention relates to a resin stabilizer
..~ 20 composition which consists essentiàlly of, an or.ganotin sulfur-
containing compound having a -C~Sn-S group, and a metal compound
. .
~. selected from the group consisting of an alkali metal bisulfite,
~ . .
; ~ carbonate, hydroxide, oxide, thiocarbonate, bicarbonate and meta-
bisulfite, and mixtures of the metal compounds, the organotin and ~.
metal.compound compon~n~s in`re-lative amounts which toyether pro-
vide a synergistic stabilizing ef~ectiveness upon the resin.
~. ' .
, .~l
rw/~ `
Z85
In particular, a metal compound selected from the group
of an alkali metal bisulfite, carbonate, hydroxide, oxide, thio-
carbonate, bicarbonate and metabisulfite, and an organotin sulfur-
containing compound together contri~ute highly unexpected heat
; stabilization to a vinyl halide resin. We have found that
synergistic heat stabilizations are provided by our compositions,
i.e., the sum of the stabilizin~ effects of an amount of each
component alone upon the resin is exceeded when the same amounts
o~ components are together in the resin formula.
Other seemingly chemically similar metal compounds
have not been found by us to provide synergistic effects with
the organotin component. For instance, based upon our findings
of syneryisms and amounts of components where synergism might
be found, other seemingly chemically similar~metal compounds
do not display heat stabilizing synergism with the organotin
component. The exact chemical mechanisms for the unexpected
:. ., .~.
behav-iors of our stabilizer compositions in vinyl halide resins
'. , ' : -
, - ' '
'
,., , '
:'
,~
~w/) ~7
11)41Z85
are not completely understood. Nevertheless, such unexpected
i result~ and other advantages are empirically demonstrated in
.¦ numerous operatlng examples oS tnis inven~ion, ana a ruriner
understanding thereof will become apparent in view of the
detailed de~cription herein. In the stabilizer compositions of
organotin sulfur-containing compounds and metal compounds of
: . .this inventionl the benefits of stabilization Can be realized .
¦ ~ over ~road ranges of both total parts by weight of the stabilizer
compositions in the vinyl halide resin and the weight ratios
of each of the components with respect to the other. Particularly
¦ ~ usefu1 stabilizer compQsitions of this invention are achieved
with a total parts by weight rangè on the order of about 0.2
I ~ to about 15 parts by weight based upon 100 parts by weight ~phr)
o~ the vinyl halide resin. A mOQt useful range of total parts
; by weight of stabilizer composition is on the order of about
~! ~ 0.5 to about 10 phr and this depends upon the desired heak
~ stabllity in a particular vinyl halide resin composition
- ~ consi9tent with other requirements and economiesO
; There are certain generally preferred wsight ratios
~ 20 of the organotin sulfur-containing compounds relative to à
i particular metal component. This will become apparent in view
of the detailed operating examples. However, it is ~o be
emphasized that the most desirable weight ratios o~ each of
the essential components of the composition of this invention
¦ for a particular application and resin system can be arrived
l at in accordance with the teachings of ~his invention. Thus,
.q in its broader aspects, this invention is not limited to weight
~1 '. ~
lU41Z85
ratios of components. It has been found that synergistic
~tabilization levels of a particular metal compound and a
particular organotin sulfur-containing compound Wlll vary as
exemplified by the combination of sodium carbonate and dibutyltin
bis (isooctylthioglycolate). This combination has a synergistic
effectiveness when an amount in the range of 0.1-10 phr of
sodium carbonate is combined with an amount of organotin in
the range of about 0.1-4 phr. Higher levels of each component
may be used. In contrast, the sodium carbonate alone in the
vinyl halide resin will not materially contribute any heat
stability when present in the range of 0.1-10 phr, or higher.
On the other hand~ the heat stability of a vinyl halide resin
` is enhanced with increasing amo~mts of the dibutyltin compound -
employed by itself in the 0.1-4 phr range. But, when the
amounts of such à dibutyltin compound are employed with amounts
~ of othexwise ineffective sodium carbonate, heat stabilities
Xj ~ are achieved which far exceed the expected results. In general,
~ ~the combination of metal compound with the organotin sulfur-
3 containing compound is utilized at total parts on the order of
about 0.2 to about 15 phr; and where the metal compound i~
within the range of about 0.1 to about 10 phr and the organotin
compound is i~ tbe range of about 0.1 to about 5 phr.
ORGA~OTIN SULFUR-CONTAINING COMPONENT
The vrganotin sulfur-containing compounds which are
of use in this invention are generally characterized as having
a sulfur-co aining radica, or atom attached to the tin through
~ .
i, '
"
104~ 5
the sulfur atom and a hydrocarbon cr sub~tituted hydrocarbon
~ group directly attached to the tin through a carbon atom, i.e.,
:, compounds containing the -C-Sn~S group. These compounds can
also be characterized by the ~ormula R-Sn-S wherein R represents
a mono or polyvalent hydrocarbon or non-hydrocarbon substituted
hydrocarbon radical. As mentioned, this combination of R-Sn-S
,~ . bonds has been heretofore recognized as glving optimum stabili-
zation. The tin bonds are usually derived from polyvalent tin
: by having at least one valence for bondLng to the sulfur atom
while the remaini~g valence or valences are for bonding with a .
. hydrocarbon radical. Tin usually acts as a hi- or tetra- valent
, . atom, but coordination complexes of tin are known where the tin ~
, behaves in even a higher valence state and, therefore, the .
. ` ~ valence state of tin can vary in the organotin compounds which
~ can be used in this invention. ` '
,~ : . Generally,, however, most organotins suitable for use .
; ~ , in this invention are derived ~rom tetravalent tin. Of the
types`of organotin compounds contemplated, inoluded are organotin
~ mercaptides which may be characterizPd by the Formula I: , .
: 20 ~Sn (SR ) 4-X
wherein R and R' represent hydrocarbon or substituted hydroc,arbon
, radicals selected from the group consisting of alkyl,'aryl,
' oxyalkyl, oxyaryl and the furfuryl and tetrahydrofurfuryl radical ,
. and x is an integral number from 1 to 3. Examples of such groups
. are alkyls such as methyl, ethyl, butyl, octyl, dodecyl J and
. octadecyl; aryls such as phenyl, tolyl, naphthyl or xylyl; .
oxyalkyl and oxyaryl, such as propyloxide, hutyloxide, octyloxide,
. ~ ~
lO'llZI~S
benzyloxide; and the furfuryl and tetrahydrofurfuryl groups.
Specific examples of organotin mercaptides in which R and
are butyl, for examplP, and x varies from 1 to 3 are mono-
butyltin tributylmercaptide, dibutyltin dibutylmercaptide and
tributyltin monobutylmercaptid-e~ Patents exemplifying this
formula RxSn(SR')4 x or a similar formula and a definition
of compounds represented thereby include U. S. Patents 2,641,588;
2,641,596; 2,648,650; 2,726,254 and 2,789,963, among o~hers.
While the simplest representatives of the organotin .
sulfur-containing compounds are the organotin mercaptides of
the Formula I, RxSnlSR')4_x, as stated herein above, the
important components of the compounds are the organotin group . .
and the tin~sulfur group. The organotins are therefore~ not :
limited to the components of this ~ormula, but are shown by
all compounds in which a sulfur atom or mercapto radical is
bound ~hrough the sulfur atom to~the tin atom of the organo~in
radical, iOe~ ~ those organotins containing the R-Sn-S bonds.
These compounds may be further defined by the Formula II.
¦ 20 ~ R" Sn SX
,. . .
wherein R", R' ", SX and Z have the following significance:
R" and R" ' may be different monovalent hydrocarbon radicals
or substituted hydrocarbon radicals, but will be generally
the same radicals because the starting materials ~or the
preparation of the organotin mercapto compounds will be generally .
the di-lor tri-) hydrocarbon tLn halides or oxides available
1,
~,
1~ ,
~4iea5
in commerce. The nature of these groups has in most cases no,
or only a very minor, influence on the properties of the end
products. R" and R''' may be aliphatic, aromatic, or alicyclic
groups such as methyl, ethyl, propyl, butyl, amyl, hexyl,
octyl, lauryl, allyl, benzyl, phenyl, tolyl, naphthyl and cyclo-
hexyl, or substituted hydrocarbon groups of these groups having
-OH, -NH2, -CN, etc., radicals~in the molecule such as cyanoethyl
(of the type described in U. S. Patent-3,471,538), ànd the likeO
The group SX of Formula II, for instance, may be
~sulfur alone, the rest of a mercaptan, or a mercapto alcohol,
or o~ an ester of a mercapte alcohol or mercapto acid. The
;~ patents mentioned above in the background of our copending
application give examples of this. Aliphatic and aromatic
mercaptans may be employed to form the group SX. In the case
of aliphatic mercaptans, those having 8 to 18 carbon atoms, e.g.,
decyl or dodecyl mercaptan are usually pref~rred because the
lower m=rcaptans are unsuitable for the prepar tion and use of
the stabilizers on account of their offensive smell. Suitable
aromatic mercaptans are, for instance, thionaphthol, thiobenzyl
alcohol, phenoxyethyL mercaptan, phenoxyethyl mercaptan, and
, others. As examples of suitable mercapto alcohols, monothio-
ethylene glycol, monothiopropylene glycol, thioglycerol, thio-
diethylene glycol, and others may be mentioned. Particularly
suitable are the esters of these mercapto alcohols in which
the hydroxy groups are esterified by an aliphatic, aromatic,
i or alicyclic saturated or unsaturated monocarboxylic acid.
1 Readily available mercaptoacid ester~ are the esters of
~ I I
~ 85
thioglycolic acid, such as ethyl thioglycolate, isooctyl-
thioglycolate, and generally the esters of mono and dibasic
aliphatic and aromatic mercapto acids, such as esters of beta
thiopropionic acid, thiolactic acid, thiobutyric acid and
mercapto lauric acid. It will be understood that the recited
examples for group SX apply to SR' of Formula I and the examples
of R" or R''' apply to R or R' of Formula I.
The group Z of Formula I~ may be a monovalent hydro-
carbon radical like R" and R''', in which case the compound is
a tri-hydrocarbon tin mercapto compound. The three hydrocarbon
groups may have the same or different composition. Z may also
be a sulfur alone or ~he rest of a mercapto compound linked
through the S atom to the tin atom, in which case it may have
the same composition as SX or a different composition. The
former case represents a dihydrocarbon tin dimercapto compound
and the latter case represents a mixed mercapto derivative of
the dihydrocarbon stannanediol. In another sub-group, Z may
be the rest of an alcohol or of a carboxylic acid linked through
the oxygen of the alcoholic hydroxyl group or of the carboxylic
acid group to the tin atom. Such compounds can be defined as
monoesters or monoethers of hydrocarbon substituted stannanediol,
in which the second hydr~x~l group of the stannanediol is re-
placed by a mercapto compound. Thio alcohols and acids which
are capable of forming such ether and ester groups are illustratel I
in the patents cited in the background of our copending app-
lication along with their methods of preparation. Other
specific references to organotin sulfur-containing compounds as
widely described in the'patent art include U. S. Patent
~ 9
2,641,588, col. 1, lines 32~53 to col. 2, lines 13-46; U. S.
Patent 2,641,596, col. 1, lines 10-44; . U. S. Patent 2,726,254,
col. 1, line 63 to col. 2, line 19; U. S. Patent- 2,789,963,
col. 2, lines 35-60; U. S. Patent 2,914,506, col. 1, line 59
to col. 4, line 8; U. S. Patent 2,870,119, col. 1, lines 27- :
53 and U. S. Patent 3~126,400, col. 1, lines 21-61. Other
patents exemplifying these organotin sulfur-containing compounds.
include U. S. Patents Nos. 3,069,447; 3,478,071; 2,998,441,
2,809,956; 3,293,273; 3,396,185; 3,485,794; 2,830,067 and
2,855,417.
: Other organotin sulfur containing compounds which
are within the scope of this invention are characterized by
the following E~ormula III: ~.
wherein R is deined as above, S is sulfur and n is an integral
number ~rom about 2 to about 1000. These polymeric compounds
are described in the patent literature, for example, at U. S.
.::
Patent 3,Q21,302 at col. 1, line 60 to col. 2, line 17,
U.: S. Patent 3,424~,712 at col. 3, line 34 to col. 4, line 2;
2:0 :and U. S. Patent 3,92~,717 at col. 3, line 1:3, to col. 4, line
21. ~Specifla refer~nce is made to these patents at the reer-
enced columns for more details. Other polymeric tin mercaptide
type compounds having the R-Sn-S bonds characterizing the ~
organotin sulur-containing compounds suita~le for use in this
invention are exemplified in U~ S. Patents 2,809,956; 3~293,2i3;
3,396,185 and 3,485,794,
.
~ 1 0
. . .
~0~L285
Of course, it i5 obvious that organotin mercaptides,
oryanotin mercapto acids, organotin~ mercaptoacid esters, etc,,
per se form no part of this invention and the mentioned patents
and their specific disclosures clearly teach these compounds
and their method of production to enable anyone of o~dinary
skill to use them in carrying out this invention. Other
literature references which pertain to the organotin sulfur-
containing component ha~ing the R-Sn-S yroup to exemplify the
scope intended for this component in accord with the principles
of this invention, include "The Development of The Organotin
Stabilizers", by H. Verity Smith, Tin Research Institute,
Greenford, Middlesex, Pp. 15-22/ (December 1959).
METAL COMPOUND
A metal compound for use in our compositions is
selected from one of the groups of (1) an alkali metal bi-
sulfite, carbonate, hydroxide, oxide, thiocarbonate, bicar-
bonate or metabisulfite, (2) an alkaline earth metal oxide
: . 1 .
or hydroxide and ~3) an organic over based complex of Group I
or~ a metal bases. Compounds in group (lj have been found
to provide heat stability synergism in our composition. Seem-
ingIy~ similar alkali compounds~have not been found by us as
mentioned above to provide such results. Group (1~ compounds
also offer premium stabilization with the organotin compounds
at considerabl~ sa~ings; and wide flexibility of amounts
~ox different resin molding and working temperatures.
- Compounds in group (2) also provide synergism with other
.
ci/
~ 41~
advantages similar to group (1) metal compounds. For example,
calcium hyclroxide, barium hydroxide and strontium hydroxide
synergistically function; whereas other seemingly similar
alkaline compounds we have found do not so function. Compounds
or complexes in group (3) also provide a synergistic dimension
to the compositions of this invention. Each group (1) to (3)
or each metal compound within the group offers separate and
distinct advantages in the stabilization of resin systems.
While our invention brings these metal compounds together as
~ 10 a class principally because of their unique behaviours with
- organotin sulfur-containing compounds and their unobvious
properties, it will be appreciated, in view of this description,
that distinct advantages are associated with each of the members
o~ this class.
As reported in our Canadian patent 974,688, the
organic alkali or alkaline earth meta]. basic complexes or
~compounds of group (3) have been very well developed in
the patent literature~ They are commonly referred to as
"organic alkali or alkaline earth basic metal complexes" or
: ~ .
"basic salts"-or "super-based salts". These terms are generic
to well-known classes of metal-containing organic materials
which have generally been employed as lubricant additives.
Such over-based materials were commercialized principally
by the Lubrizol Corporation and, therefore, are also
commonly referred to`in the trade as "Lubrizolates". The
fundamental technique for preparing such over-based mater-
ials evolved in the preparation of a soap or salt of an
.
cbj r 12
104~Z~35
organic acid where the use of an excessive amount of a
neutralizing agent, such as a metal oxide or hydroxide, results
¦ in the fo~nation of a stable product which contains an amount
1 of metal in substantial excess o~ that which is theoretically
-;¦ requir~d to replace the acidic hydrogens ~f the organic acid,
e~g., a carboxylic or sulfonic acid, used as the starting
material. Thus, if a monosulfonic acid,
R~SO H
;is neutralized with a basic me~al compound, e.y., barium oxide,
the "normal" metal salt produced will contain one equivalent
of barium for each equivalent of acid, i.e.,
~- ~R-SO3)2Ba
However, as is welt known in the art, various processes are
a~ailable for reacting one equivalent of an organic acid or
an alkali or alkaline salt thereof (e.g., alkyl benzene
sulfonic acid~ with a stoichiometric e~cess, i.e., 2-10
equivalents o~ an alkaline earth inorganic base (e.g., barium
oxidel in a suitable inert organic solvent to produce a basic
complex in solution or dispersion form con~aining more than
the stoichiometric amount of metal. Following these procèdures,
~for example, an excess of 1 equivalent of barium oxide reacted
with an organic sulfonic acid may be regarded as a double salt
which is indicated by the structure,
(R-S03)2Ba-BaO
Alternatively, this type of product may be regarded as a ~asic
salt which is indicated by the structure,
¦ R-503-Ba-OH
,
~ -13-
~ 1041Z~S
~i or a combination of these structures, -
i R-SO3-Ba-OH-BaO
1 Regardless of whichever of these structures is
accepted, it has been shown that such products contain metal
~¦ in stoichiometrically larger amounts than the organic acid
I radical and thus, the term "over-based" or "super-based" or
"basic complex" is employed. The ac~ual stoichiometric excess
; of metal can vary considerably, for example, from about 0.1
equivaIent to about 30 or more equivalents depending on the
reactions, the process conditions and the like. In the
present specification and claims, the term "organic over~
based complex" is used to designate materials containing a
stoichiometric excess of metal and is, therefore, inclusive :
of those materials which have been referred to in the art as
over-based, super-based, basic complex, etc., as discussed
supra. ~enerally, the ~toichiometric excess of metal for the
organic over-based complexes lS at least about 1 equivalent,
as presently preferred, it being understood`that the excess
can vary from about 0.1-30 equivalents, even up to 60 or more
equivalents.
Generally, most of these over-based organic complexes
are prepared by treating a reaction mixture comprising the
organic material to be over-based, a reaction medium of at
least one inert organic solvent for the organic material, a
. stoichiometric excess of a metal base, and optionally a promoteri
Also, the reaction product may optionally be treated with an
1 acidic gas (e.g. C02) to reduce the free basicity of the complex.
~.
The free basicity is regar~e ~ ~ ~ at amount of metal base
which is titratible to a pEI of about 8; whereas, the total
basici-ty of the complex is titratible to a pH of about 3.
The methods for preparing the over-based materials as well
as an extremely diverse group of over-based materials are well
known in the prior art as disclosed in the followin~ U. S.
Patents.
2,616,904 2,616,905 2,616,906 2~616,911 2,616,924
2,616,925 2,617,049 2,695,910 2,723,234 2,767,209
2,777,874 2,7g9,852 2,839,470 2,~15,517 2,959,5~1
2,368,642 2,971,014 3,001,981 3,027,325 3,147,232
3,172,855 3,194,823 3,232,883 3,242,079 3,242,080
3,256,186 3,274,135 3,350,308
These patents disclose exemplary processes for synthesizing
the over-based organic complexes used in the systems of the
. ~ . .
invention and are referred to for their discussion of these
processes, materials which can be over-based, suitable metal
.
bases, promoters and acidic materials, as well as a variety
of specific over-based products.
Organic over-based complexes of metal bases useful
n ~his invention may be represented by the following Formula
IVj it being undexstood that this formula is only representative
of the actual over-based complexes which exist and their pro-
perties, since, as discus~sed above, various structural theories
have~been proposed and the precise structure of these organic
complexes has not conclusively been established, nor is such
necessary for the purposes of this invention.
~ .
Formula IV RnM.xM'A
29 whereln R is an organic radical or residue of an organic
cb/
~ 15
.
Z8S
material, includin~ sulfonic or carboxylic acids or phenols;
n is 1-2; M and M' are the same or dissimilar alkali or
alkaline earth metals of Group I and II-a of the Periodic
Table; x is a positive number greater than zero, preferably
at least about 1 and usually in the range of about 1~30 or
more; and A represents the anion portion of the basic metal
compounds used in preparing the over-based complex~s. The
~ . :
~ excess basicity is sometimes referred to in the art as "metal
~.
ratio" and these organic over-based complexes or salts have
a metal ratio of at least about 1.1. The term "metal ratio"
: ~ .
is used herein to designate the ratio of the total chemical
equivalents of the metal in the salt to the chemical equiva-
lents of the metal which is in the form of a normal salt, i.e.,
neutral salt of the organic acid. To illustrate, a salt
containing two equivalents of the metal per equivalent of ~
the organic acid radical (i.e., R in the above formula) has
a me~tal ratio of 2, whereas a neutral salt has a metal ratio
of l, ~
~ ~ -
Organic materials which can be over-based are gener-
20 ally organic acids including phosphorus acids, thiophosphorus
acids,~sulfur acids, carboxylic aclds, thiocarboxyllc acids, and
the like, as well as the corresponding alkali and alkaline earth
metal salts thereof. Representative examples of each of these
classes of organic acids as well as oth r organic ~acids,
e,g.~ nitrogen acids, arsen~c acids, etc., are disclosed alon~
wLth methods of preparing over-based products therefrom in
the above cited patents.
.
:
~ 16 -
cb/
~0~2~3Si
Patent No. 2,777,874, identlfies orcJani.c acicls
suitable for preparing over-based or~anic complexes which can
be used in the compositions of the invention. Similarly, a
number of the patents disclose a variety of organic acids,
metal bases, etc., suitable for preparing organic over-based
complexes as well as representative examples of over-based
products prepared therefrom and these include: U. S. Patent
2,695,910, at col. 2, line 37 to col. 8, line 67; U. S.
Patent 3,194,823 at col. 3, line 40 to col. 6, line 44;
U. S. Patent 3,274,I35 at col. 3, line 43 to col. 6, line
49; U. S. Patent 3,350,308 at col. 1, line 45 to col. 11,
line 75~ U. S. Patent 3,471,403 at col. 4, line 1 ~o col. 9,
line 15; and U. S. Patents 2,717,714; 2,G16,904; 2,767,209
and 3,147,232. Over based acids wherein the acid is phosphorus
acid, a thiophosphorus acid, phosphorus acid-sulfur combination,
and sulfur acid prepared from polyoleins are disclosed in
2,883,340, 2,915,517; 3,001,981; 3,108,960 and 3,232,883.
Over-based phenates are disclosed in 2,959,551, while over-
; . ~
based ketones are found in 2,798,852. A variety of over-based
materials:derived from oil-soluble metal-free, non-tautomeric
neutral and basic organic polar compounds such as esters,
amlnes, amides, alcohols, ethers, sul~ides, sul~oxides, and
- the like are disclosed in 2j968,642; 2,971,014 and 2,389,463.
:: Another class of materials which can be over-based are the
~; oil-soluble~, nitro-substituted aliphatic hydrocarbonsj parti~
~- : cularly nitro-substituted polyolefins such as polyethylene,
, ,
,
~ 17 ~
c~,/
:
IO~lZ85
polypropylene, polyisobutylene, etc. Materials of this type
are illustrated in 2,959,551. Likewise, the oil-soluble
reaction products of alkylene polyamines such as propylene
diamine or N-alkylated propylene diamine with formaldehyde or
formaldehyde producing compound ~e.g~, paraformaldehyde) can
~e over-based. Other compounds suita~le for over-basing are
d~s~losed in the above cited patents or are othe~tise well=
known in the art.
A class of particularly suitàble organic materlals
which may form the R group of Formula IV above include oil-
soluble organic acids, preferably those containing at least
twelve aliphatic carbons although the aclds may contain as
few as eight aliphatic caxbon atoms if the acid molecule :
includes an aromatic ring such as phenyl, naphthyl, etc.
Representative organic acids arle discussed and identified in
detail in the above-cited patents. Particularly, 2,616,904
and 2~777,874 disclose a variety o very suitable organic .
acids.. For reasons o~ economy and pexformance, oil-soluble
carboxylic and sulfonic acids are particularly suitable.
Illustrative of the carhoxylic acids are palmitic acid, stearic
acid, myristic acid, oleic acid, linoleic acid, behenic acid,
hexatriacontanoic acid, tetropropylene-substituted glutaric
acid, polyisobutene (M. W. -- 5,000)-substituted succinic acid,
polypropylene (M. W. -- 10,000)-substituted succinic acid,
octadecyl-substituted adipic acid, chlorostearic acid,
9-methyl-stearic acid, dichlorostearlc acid, stearylbenzoic .
acid, eicosane-substituted naphthoic acid, dilauryl-decahydro-
. ,~, .
~ 104~LZ85
naphthalene carboxylic acid, didodecyltetralin carboxylic acid,
dioctylcyclohexane carboxylic acid, mixtures of these acids,
their alkali and alkaline earth metal salts and/or their
anhydrides. Of the oil-soluble sulfonic acids, the mono-,
di-, and tri-aliphatic hydrocarbon substituted aryl sulfonic
acids and the petroleum sulfonic acids (petro-sulfonic acids)
are particularly suitable. Illustrative examples of suitable
sulfonic acids include mahogany sulfonic acids, petroleum
sulfonic acids, monoeicosane-substituted naphthalene sulfonic
àcids, dodecylbenzene sulfonic acids, petrolatum sulfonic
acids, monoeicosane-substituted benzene sulfonic acids, cetyl-
chlorobenzene sulfonic acids, dilauryl beta-naphthalene sulfonic
acids, the sulfonic acid derived by the treatment of polyiso- :
butene having a molecular weight of 1500 with chlorosulfonic
acid, nitronaphthalenesulfonic acid, paraffin wax sulfonic
acid, cetyl-cyclopentane sulfonic acid, lauryl-cyclo-hexanesul-
fonic acids, polyethylene (M. W. -- 7503 sulfonic acids, etc.
; Within this group of over-based carboxylic and
sulfonic acids, the barium and calcium over-~ased mono-, di-, ~
and tri-alkylated benzene and naphthalene (including hydrogenated
forms thereof) petrosulfonic acids, and higher fatty acids
are especially suitable. Illustrative o~ the synthetically
produced alkylated benzene and naphthalen~ sul~onic acids are
those containing alkyl substituents having from 8 to about 30
carbon atoms therein~ Such acids include di-isododecylbenzene
sulfonic acid, wax-substituted benzene sulfonic acids,
polybutene-s stituted sulion c acid, cetyl-chlorobenzene
10a.L~2~5
sulfonic acid, di-cetyl~naphthalene sulfonic acid, di-lauryl-
diphenylether sulfonic acid, diisononylbenzene sulfonic acid,
di-isooctyldecyl~enzene sulfonic acid, stearylnaphthalene
sùlfonic acid, and the like. The petroleum sulfonic acids
are a well-known art recognized class of materials which have
been used as starting materials in preparing over-based
products since the inception of over-basing techniques as
illustrated by the above patents. Petroleum sulfonic acids are
obtained by treating refined or semi-refined petroleum oils
with concentrated or fuming sulfuric acid. These acids remain
in the oil after the settling out of sludges. These petroleum
sulfonic acids, depending on the nature of the petroleum oils
from which they are prepared, are oil-soluble alkane sulfonic
acids, alkyl-su~stituted cyclo-aliphatic sulfonic acids, includinc
cycloalkyl sulfonic acids and cycloalkene sulfonic acids, and
alkyl, alkaryl, or aralkyl substituted hydrocarbon aromatic
sulfonic acids including single and ~ondensed aromatic nuclei
as well as partially hydrogenated forms thereof. Examples of
such petrosulfonic acids include mahogany sul~onic acid, white
oil sulfonic acid, petrolatum sulfonic acid, petroleum naphtXene
sulfonic acid, etc~ This especially suitable group of aliphatic
fatty acids includes the saturated and unsaturated higher
fatty acids containing from 12 to about 30 car~on atoms.
Illustrative of these acids are laurlc acid, palmitic acid, oleic
acid, linoleic acid, linolenic acid, oleo-stearic acid, stearic
acid, myristic acid, and undecalinic acid, alpha-chlorostearic
acid, and alpha-nitrola~ric acid. The organic acids may
. '`'
I ',.~., .
10~::a28S
contain ~on-hydrocarbon substituents such as halo, nitro,
alkoxy, hydroxyl! and the like.
The over~based organic complexes used in the
stabilizer systems of the invention usually contain from about
10% to about 70% by weight of metal-containing components.
As explained, the exact nature of these metal containing com-
ponents is not known. The material which is over-based may
itself be a metal-containing compound, e.g., a carboxylic or
sulfonic acid metal salt. Furthermore, the over-based organic
complexes may be in colloidal non-Newtonian form as disclosed
; and described in U. S. Patent 3,384,586 in contrast to single
phase homogeneous systems. However, this depends upon the
reaction conditions and the choice of reaotants in preparing
the over-based materials. Sometimes there is present in the
product insoluble contaminants. These contaminants are normally
`~ un~reacted ba9ic materials such as calcium oxide, barium oxide,
calcium hydro*ide, barium hydroxide, or other mstal base -
~` ~ ~materials used as a reactant in preparing ove~-based material.
It should be understood, howev~r, that the removal of these
contaminants is not absolutely essential to the performance of
this invention.
The metal compounds used in preparing the organic
over-based complexes are the basic salts of metals in Group I
~ and Group II a of the Periodic Table. The anionic portion of
¦ the salt can be hydroxyl, oxide, carbonate, bicarbonate,
1 ~hiocarbonate, nitrate, sulfite, bisulfite, sulfide, bisulfide,
1 halide amide, sulfate, etc., as disclosed in the above cited
:1 2~
Z~5
patents. The presently preferred over-based materials are
prepared from the mentioned alkali and alkaline earth metal
oxides, hydroxides~ and carbonates.
As mentioned above, promoters (materials which per-
mit the incorporatlon of the excess metal into the oyer-based
material) may be used and are also quite diverse and well-
known in the art as evidenced by the cited patents. For
further discussion of suitable promoters, acidic materials,
examples of preparation of the over-based complexes, etc.,
reference is made to our Canadian Patent 974,688.
The principles of this invention and its operating
parameters will be further understood with reference to the
following detailed examples which serve to illustrate the
types of specific materials and their amounts as used in typi-
cal vinyl halide resin formulations and the synergisms dis-
played by the essential combination of components in the
stabilizer composition according to this invention. These
examples are considered to be exemplary of this invention,
and should not be considered as limi~ing, especially in view
20~ of applicants' broad disclosure of principles of this invention.
In the examples which follow, a standard resin fo~mula
~; was employed which contained 200 parts by weight of polyvinyl
- ; chloride homopolymer which is characterieed as a white powder
having a particle size such that 100~ passes through a 42 mesh
screen at a specific gravity of 1.4Q (Geon ~ 103 EP by B. F.
Goodrich). Included in the standard resin formula is also
6 parts by weight of a processing aid which is an acrylic polymer
:~ .
- 22 -
cb/
~L041Z~IS
in powdered form which improves the hot processing of rigid
and plasticized vinyl compounds. (Acryloi ~K120N by Rohm and
Haas Company). This material is a fine, white free flowing
powder having a bulk density at about 0.30 gramq per cc and
a viscosity, 10% in toluene, at 600 cps (Brookfield). The
processing aid merely acilitates hot processing and forms
no part of this invention. A para~fin wax lubricant, i.e.,
a commercial wax designated 165 (H. M. Royal, IncO) was also
employed at ~ parts by weight in the resin formula. The
term "standard resin blank" or just "blank" is used hereinafter
to designate the standard resin formula wi~hout heat stabilizer
additiYes. Various combinations of the organotin sulfur-
containing compounds and metal compounds were mixed into the
standard resin formula according to the following examples on
a parts by weight basis. All amounts of such stabilizer com-
ponents, in the tables and examples unless otherwise indicated,
are on a parts per hundred resin basis, or as indicated above,
cllimply "phr". The blank resin formula wi~h and without stabi-
liæer additives are tested in the following examples by first
milling the mixtures to form a uniform polyvinylchloride
composition for five minutes at 350F., after which time long
term heat stabilities of test samples were determined by oven
treatment at either of two temperatures, 375F. or 400F~, as
~ndicated. The heat stability contribution of the stabilizer
compositions (or components thereof) hereinafter are determined
by ascertaining the number of minutes at the test temperature
required for the samples to degrade by darkening usually to dark
red or black. Thus, the term "heat stability contribution" is
I
1041Z85
used to indicate the amount of heat stability in minutes contri-
. I buted by a composition or component to the resin blank formula.
EXA~LES 1-55
; In Examples 1-55, the synergistic performance of
the combination of sodium carbonate and dibutyltin bis
~isooctylthioglycolate), hereinafter "DBT", was demonstrated.
For this purpose, the heat stability of the standard resin
blank in the absence of either the organotin compound Dr
metal compound was determined by milling at 350F. and long term
heat stability testing at 375F. The standard resin blank was
pink or orange off the mill and darkened within 10 minutes
at 375F. This demonstrated ~lat the blank resin will degrade
quickly~ This blank was thus given the numerical designation "0" :
at zero parts of either component, as shown in the upper left
hand corner of Table I. For comparison with the standard resin
blank,~ varying amounts of sodium carbonate over the range of
about 0~1 to about 10 phr were employed alone. The results of
these examples are shown in the first horizontal line of Table I.
-i~ Also, a series of examples in which the standard resin formula
was combined with DBT alone were performed for comparison.
-~ The results of these examples are shown in the first vertical
line of Table I. Then, the combination of sodlum carbonate
¦ and DBT varying in ampunts of 0.1-10 phr of sodium carbonate with
~`1 0.1-4.0 phr DBT wexe performed to illustrate the synergistic
heat stabillzing effects ln minutes.
Table I which follows demonstrates the results of
! the fifty-five examples (the one blank space in the table
,, . ,.
1041Z8S
indicates no ~est was made), The times in minutes repor~ed in
J Table I for darkening or blackening ta~e into accounk the
~ . st~ndard resin blank which degraded within about 10 minukes
:~ ~ of heat stability testing. In other ~lords, the time in
. . minutes recorded at various levels for sodium carbonate and
. DBT alone, and in combination with one another, represent the
. "contribution" in minukes of either one or both of these
t ~ ta~ ~ rd ~-~ bl~
: ~
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i
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:- ~ H 14 ~1 f~l u~ a~ u~ a~ 1_
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: ~ O . ~1 N
~ H ~ H --- = = :1----
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,~ ' . ~ _ __
,~ : ,~ $ _ _ _ _ _ _
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l . ~1 ~t N ~ a~ N
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1~41S~5
Referring to Table I, at 0.1-.5 phr of sodium
¦ carbonate alone, stability of the blank was not improved.
At higher levels on the order of about 1 to about 10 phr of
sodium carbonate alone, the heat stability of the blank was
improved, at most ~bout 10 minutes. In contrast, the DBT
alone at about 0 l phr contributed about 10 minutes of heat
stabilizing ef~ectiveness to the blank and, with increasing
amounts up to 4 phr, the heat stability was enhanced to about
;~ 200 minutes. Therefore, in general, the sodium carbonate
I0 component of the stabilizer combination contributed only
- slightly at higher levels on the order of 1 to about 10 phr
to the heat stability of the blank ormula. Whereas, DBT
with increasing amounts contributed significantly to the heat
stability of the blank~
When the sodium carbonate and DBT were combined in
varying amounts as Table I demonstrates, at lower~levels of
sodium carbonate on the order of 0.1 to about 1 phr in
- combination with 0~1 phr DBT, unexpected heat stability was
i ~ not clearly observed. Quite similarly, when DBT on the order
-~ 20 of 0.1-0.5 phr was combined with .1 phr of sodium carbonate,
unexpected heat stability was not clearly observed. However,
when sodium carbonate within the range of 0.1 to about 10 phr
was oombined with DBT at various levels from about 0.1 to 4
phr, significant synergism was observed. To illustrate this,
reference is made to Table I in which 1 part of sodium carbonate
alone contributed at most about 10 minutes of heat stability
1 to the blank. For comparison, one part of DBT contributed
. 27
," . . ..
.
about 40 minutes of heat stability to the blank. Thus, the
expected heat ~tability of a combination of 1 phr of sodium
car~onate ana i pnx ~ shoula nave ~een aboui ~u minu~Y.
However, as demonstrated by Table I, the heat stability of such
a combinatian was 90 minutes and synergism thus was clearly
demonstrated.
In the range of 0.1-10 phr of sodium carbonate,
th~re was a level of DBT in the range of 0.1-4 phr which
when combined wit~ the sodium carbonate provided for a
synergistic result. Such levels are easily determined from
Table I. It was only at a lower level of about 0.1 sodium
carbonate when the DBT was between 0.1 and 0.5 phr that
synergism was not clearly demonstrated at 375F.; and
similarly at levels between about 0.25-1 phr sodium carbonate
at 0~1 phr DBT. However, as highlighted in the area encom-
passed by the double black lines of Table I, with few
exceptions, principally in the lower phr of each component
of the combination tested, synergism was observed. Such a
comprehensive demonstration can be extended to other higher
levels of components and a similar table can be prepared to
ascertain all levels of syner~ism for the combinations of
all components according to the principles of this invention.
However, within the teachings of this invention, one of
ordinary sk 1 can attend to such further details.
~ - 2~
~,
E ~ P I E 5 b 104 ,z~5
These examples demonstrated the synergistic combination
of calcium hydroxide and an organotin sulfur-containing com-
pound, that is DBT, for comparison with previous examples.
In Examples 56 and 57, calclum hydroxide ~as employed alone
at levels of 0.1 phr and ~0 phr, respectively, in the standard
resin formula. Examples 58-61 aemonstrated the combination
of calcium hydroxide and DBT for synergistic heat stabilizing
effectiveness upon milling and oven testing at 375F. as
indicated above. The results are recorded in Table II.
- The Table II results can also be compared with
. . ,
Examples 3 and 5 of our above mentioned copending application
attached hereto as page 29' realizing the different reporting
method and di~ferent test conditions employed.
' '
-
~'
, :
, ' : '
-29
i! 1041Z85 ' " . 1 ~
, EXAMPLI~'S 3-5
Thrcc di~crent vinyl halide resin compositions were
then preparcd by adding one part o~ di.but.yltin bis (isooctyl- , ~
thio~lycolate, i.e. (DBT), to the standard ~ormula mentioned l, ¦
Qbove (Example 3); one par~ each of DBT and calcium steara~e
- . (Examl~le 4); and one part eacl of DBl' and calcium hydroxide ,
(Example 5). Eac.h of these formulas were then mi].led and their I
I heat stabilities determined by ovcn exposure at 400F. as ' i
~i mentioned above. The results are s~,o-~n in Table II.
~ ' ' . ~
TABL~ II J
400F. I
. Com~_nents Hea~ s.abili-ty
~Exa~ple 3 ~ DBT 15'
. ., , , . . . .,, , ., , . . .. , ,... .. . . . . . . ' i
Example 4 l D~T . . ,~
1 calcium stearate 20'
~Example 5 l D~T . .
1 calcium hydroxide _ .
_ __ . -
:~' ~
~ ~ ~.The DBT ~hen employed above blackened ater about
;D~ ~ fifteen minutes ~Example 3). The combination of DBT and
calcium stearate blackened after ab~lt twenty minutes of ex-
I . posure (Example 4). Similarly, the combination of DBT and
¦calcium hydroxide b,lackened after about twenty minutes expo-
sure (Example 5). Thus,Table II demonstrates that calcium -
: stearate as well as calcium hydroxide alone can mar~inally
increase the heat stability of the orgsnotin mercaptoacid ester.
. ................... , ..
,
- ~ ~ ~
~ : ~
~ :
:: : l :
~ 104~z85
.
: ~
:, :: :` . TABLE II
: ~ ~ : 375 F
~:~ ~ : Heat
:~ ~ Components Stability
~: ~ _ _ Contri~ution
; ~ ~ : . :Example 56 0.1 calcium hydroxide 0'
Example 57 lO calclum hydroxide 0' ~;
~:~' ~ Example 58 0.25 DBT
: 0~25 calcium hydroxide 10'
. :~ :~
~:~ ~ Exàmple 59 0.25 DBT
~' ~ 0 calcium hydroxide 40'
Example 60 0.5 DBT ;
, ~ 0.25 calclum hydroxide 25'
.~ ~5 ExampIe 61 : 0.5 DBT~
~ 1.0 calcium hydroxide 60'
,,; _ _ :
,
~ ~ .
:
'; ~ , ' ' -
'
' .
. ' , ' .
.
. 3~~ ... . .
lu~
In Examples 56 and 57 of Table II, calcium hyd~oxide
at levels of 0.1 and 10 phr did not contribute to the heat
. ` stability of the blank. In both instances, even a~ such low
. and high levels, no extension of heat stability was observed
. at 375F. As previously demonstrated in Table I, DBT alone
i exhibited a heat stabilizing-effectiveness over the range of
0.1 to about 4 phr. In Example 58 where 0.25 phr DBT and
~¦ 0.25 phr calcium hydroxide were employed in combination, ~he .
~! heat stability of the combination was about 10 minutes. .
;~ 10 Therefore, at this low level of each component in the stabilizer
: . combination, synergistic results were not clearly observed.
: ~: However, in Example 59 at 0.25 phr DBT and 1.0 phr calcium
hydroxide, a heat stability of 40 minutes was contributed .
to the blank. In contrast, the expected heat stability of
~ such a combination would have been only 10 minutes since 0.1
;~ ~ . ~ to 10 parts of calcium hydroxic;e alone did not contribute
~, ~ to the heat stability of the blank and 0.25 part DBT contri- -
; ~ ~ buted only 10 minutes 5Table I). Accordingly, the 40 minutes
-1 1 heat stability for the combination far exceeded the expected
heat stability of only 10 minutes, judging from the performance
.. of each of the components alone~ Quite similarly, Examples
60-61 at the leveIs of the DBT and calcium hydroxide shown,
1 illustrated a synergistic effectiveness of about 25 minutes
and 60 minutes, respectively, in comparison to th~ expected
, heat stability of only 20 minutes based on the performance .
of each of the components alone (See Tables I and II). .
Therefor2, Examples 56-61 demonstrated that an
,
,' .
1 -31- l
1041Z85
organotin sulfur-containing compound (DBT) and a metal component
~calcium hydroxide) in combination provided a vinyl halide resin
tabilization which was indeed superior and highly unexpected.
Having demonstrated the stabilizing effectiveness of the com-
bination of calcium hydroxide and DBT at certain levels within
the ranges of 0.1-10 calcium hydroxide and 0.1-5 DBT, there
are other levels within these ranges whers synergistic results
can be achieved.
EXAMPLES 62-64
~` : , .
To further lllustrate the principles of this invention
employing other organotin sulfur-containing compounds and metal
components and the synergistic effects achieved by such
~ combinations, Examples 62 64 were performed. In ~hese examples,
;~ ~ monobutyltin tFis (isobctylthioglycolate) was substituted for
the dibutyltin bis (isooctylthioglycolate) of the previous
examples. ~ereinafter, the monobutyltin tris (isooctylthiogly-
colate) is designated "MBT'~. Milling and oven testing for
¦ heat stabiIity was performed as above. In Example 63, 0.5 phr
¦ MBT and 0.25 phr sodium carbonate were employed. In Example 6i,
; 20 0.5 phr MBT was comhined with l.0 phr sodium carbonate. All
examples were compared with a standard resin~blank, and the
results are shown in Table III.
;l . .- : .
11 32 1~
.
. '.
,.
. ..
.
o4~z85
. :
, ~ : . .
~ :
.~ ~
Table III
: ~
~: ~ . 375F
- Hea~ :
~: ~ : Components Stability
Contribution_
:1 ~ Example 62~0.5 MBT 30'
. ~
Example 63 0~5 MBT
~ 0 . 2 5 sOaillm carbonate 45'
:-' ~ Example 64 0.5 MBT
~ : 1.0 sodium carbonate
':, ~
,
: ~ :
: ~ : ,
,~
: :
~1
~ ~ .
33
'
~1
1 '
lU_lZ~l5
As reported in Table I, sodium carbonate alone at
a level of 0.25 phr contributed no heat stabili~ing effective~
ness upon the blank. At a level of 1.0 phr alone, sodium
car~onate contributed at most 10 minutes of heat stability
to the resin blank. Also, as reported in Table III above,
MBT at 0.5 phr contributed 30 minutes of heat stability to
a resin blank. ~owever, a combination of 0.5 phr MBT and
0.25 phr sodium carbonate displayed a heat stabilizing
effectiveness of about 45 minutes upon the resin (Example 63~.
In comparison, the expected heat stability contribution of
such a combination was 30 minutes because at a level of 0.25,
sodium carbonate alone did not contribute to the heat stability
of the resin and the MBT alone contributed about 30 ~inutes
of heat stability. Accordingly, the synergistic effectiveness ,
was demonstrated. In Example 64, quite similarly, at a le`vel
~f 0~5 phr MBT and 1.0 phx sodium carbonate, a heat stability
of 70~minutes was observed. This is to be compared with an
expected heat s~ability of each of the components in the com-
bination on the order of about 40 minutes. Again, quite
unexpectedly, the heat stability of the combination was 30 '
minutes grea~er and far exceeded the expected heat stabilizing
effectiveness.
EXAMPLES 65-70 ,
For the purpose of illustrating the,synergistic
activity of the stabilizer compositions of this invention at
a higher tempe~ature, Examples 65-70 were performed. A
resin blank ~7as formulated in accordance with the standard
- !
procedure above identified except that-the wax was eliminated
as a lubricating additive. Example 65 was the blank formula-
tion which was milled for about S minutes at 350F. followed
by oven treatment at 400F. The blank degraded within about
0-5 minutes. Examples 66-70 were performed under identical
formulation and milling conditions with oven testing at 400F.,
except that 1 phr of DBT was employed alone as a stahilizer
in Example 66, 2 phr of sodium carbonate alone was added in
Example 67, and 2 phr of calcium hydroxide alone was added
in Example 68. Examples 69 and 70 employed the combination of
Gomponents according to the principles of this invention.
1 phr DBT and 2 phr sodium car~onate were combined in
Example 69; and 1 phr DBT and 2 phr calcium hydroxiae were :
combined in Example 70~ The results of oven heat st~bility
testing appear in Table IV.
.' ~ . , .
~` ~ . , . .
' ,,
' '' .. '' .
'1 I
I I -35-
~!
.~ ,
, :; '
.
~:; ~ TABLE IV
: ~ 400 F
Heat
~ Components Stability
:` ~ Contribution
~ ~:~. Example 65 Resin blank formula --
~,
~. ~ ~ Example 66 1 DBT 15-20'
: ~ : . . .
: ~ ~ Example 67 2 sodium carbonate 0-5'
~ , .
:~ ~ ~ Example 68 2 calcium hydroxide 0-5'
Example 69 1 DBT
~ ~ 2 sodium carbonate 50'
:: :~ Example 70 . 1 DBT ::
i ~ 2 calcium hydroxide 50'
~ :
:, - .
, . .
.
:!
~ ~ .
~ .
1 ... .
. . ,
- `1 .
. ~ , .
6-
~: ' , ' ;, ' : 1
~O~lZ85
i Examples 65-70 demonstrated the heat stabilizing
synergistic effectiveness of the composition of this invention
. at the higher (400Fo) temperature. For example, control blank
. formulation in Example 65 became pink off the mill at 375F.
and degraded by darkening significantly within 5 minu~es at
400F~ The sodium carbonate or calcium hydroxide at 2 phr
. alone provided little or no con~ribution to the heat stabilizing
; effectiveness of the resin blank it~elf (as demonstrated by
Examples 67 and 68 which became red or dark red upon milling and
a color degradatlon similar to the resin itself within about 5 .
~:~ . . minutes at 400F.) In Example 66, 1 phr DBT alone contributed
:~ a heat stabilizing effectiveness of about 15-20 minutes. How-
. ever, the synergistic combination of either 2 phr sodium car- .
: . bonate or 2 phr calcium hydroxide with l phr DBT (as demonstrated
by Examples 69 and 70) did not blacken even a~ter 50 minutes
: ~ of oven heat stability testing at 400F. Examples 69-70 were
discontinued at 50 minutes. Indeed, where one would expect the
~:: . combination of sodium carbonate or calcium hydroxide with
1 . DBT to be comparable to that o~ the DBT alone, rather a
¦ 20 superior degree of stabilizing effectiveness was achieved.
EXA~LES 71-72
. . __
¦ The synergistic effectiveness of sodium bisulfite in
combination with .an organotin sulfur-containing compound (DBT) .
was demonstrated by Examples 71-72. To the standard resin
¦ . formula,. 1 phr sodium bisulfite was added alone (Example 72). .
¦ For comparison, 1 phr so.dium bisulfite and 1 phr DBT were added
;l to the resin blank (Example` 72). The xesults are reported in
l Table V, after milling ~or 5 minutes at 350F. and oven testing
I at 375F.
"t
1 ` ~04~5
.
~ ~ .
::~,
~:
~, ~
:~ ~ TABLE V
375 F
. ~leat
:. ~: : Components Stability
~ ~ ~ Contribution
. ~
:~; : Example 71 1 DBT
: 1 s.odium bisulfite 70'
;~ Example 72 1 sodium bisulfite 0'
:, ~
-
: ~ '
;''~ . ' ,
.~
~:
: . .
,~ .
.~ ,j ' ~
I
1 -38~
1041Z85
l As reported earlier, DBT alone at 1 phr contributed! ` about 40 minutes to the heat stabili~y of the standard resinblankO As demonstrated by Example 72, 1 phr.sodium bisulfitè
made no material contribution to the heat stability o~ the
blank. Elowever, at 1 phr DBT and 1 phr sodium bisulfite in
co~bination, the heat stability contribution was 70 minutes
which demonstrated the synergism of sodium bisulfite as a
metal component in the composition of this invention.
~ : .~
EXP~IPLES 73-77
Potassium carbonate and bicarbonate have also been
, demonstrated to possess unique stabilization properties in
our compositions with vinyl halide resins. E~amples 73-77
were performed employing the combination of potassium carbonate
or potassium bicarbonate with an organotin sulfur-containing
compound (DBT). The standard resin formula ~Jas used with
DBT alone, potassium carbonate alone, potassium bicarbonate
alone, and combinations of each alkali metal component with
~ DBT, on a parts per hundred resin basis as reported in Table VI
! as follows. Milling and heat stability testing were per~Qrmad
as above.
~1
.
! ~39
~1 . ,
:
ss
::~ ~
~ TABLE VI
'` ,
375F
Heat
~ . Components Stability
; ~ Contribution
: Example 73 1 DBT 40'
., ::
:~ ~ Example 74 2 potassium carbonate 0'
: .
Example 75 1 DBT
. 2 potassium carbonate 95'
, : .
~: ~ ; Example 76 2 po~assium bicarbonate 0'
- . Example 77 1 DBT
: 2 potasslum bicarbonate 65'
~ :: ~ .
.~1
,1 ~ , `
'
.
~.'
~ j
, .
,',,
.
~ .
-
1 . , .
I ~ -40-
10=lZ85
Again, the organo~in component alone at 1 phr
exhibited a contribution of 40 minutes to the heat stabllity
of the resin blank (Example 73). Also, potassium carbonate
at 2 phr did not materially contribute to the resin blank
formula as demonstrated by Example 74. However, the combination
of 1 phr DBT and 2 phr potassium carbonate contributed 95
minutes of heat ~tability to the resin blank which is an
order of magnitude clearly unexpected for the combination in
comparison to the performance of each of the components.alone. .
Similarly, in Example 76, 2 phr potassium bicarbonate did
not materially contribute to the performance of the blank. .
~Jhereas, the.combination of 1 phr DBT and 2 phr potassium .
bicarbonate contributed 65 minutes of heat stability to the .
blank resin formula which rar exoeeded the expected contribution.
EXAMPLE5_78-83
: Other alkali bisulfites or metabisulfites in com-
bination wlth an organotin sulfur-containmg component have
been~demonstrated to possess remarkable heat stability. For
this purpose, Examples 78-83 were performed in a manner similar .
to the precedin~ examples employing the standard blank resin
and conducting heat stability tests at 375F. This series .
of examples demonstrated the performance of potassium metabisul-
fite and sodium metabisulfite for comparison with an alkali
bisulfite. The amounts of each of the.components in phr and
the test re llts are reported in Tab1e VII as follows.
' . ,
''I ,
. I
. _
,1 ,
:l
`¦ TABLE VII
:~ 375~ F
~eat
;~ ` . - . ComponentsStability
: . Contribution
:~ Example 78 0~5 DBT 20'
~; ~ Example 79 .l potassium meta-
bisulfite 0'
:,
. Example 801 sodium bisulfite - 0'
~,
. ::~ : : Example 81 0.5 DBT
: 1 potassium meta- . :
. ~ : bisulfite 3S'
~: ~
Example 82 0.5 DBT
; - :1 sodium bisulfite 40'
Example 83 0.5 DBT
.1 sodium meta-
. : bisulfite. 35'
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1041Z195
Examples 78 80~demonstrated that DBT alone contributed
20 minutes of heat stability to the blank, whereas either the
potassium metabisulfite or sodium bisulfite did not materially
contribute to the blank. Similarly, sodium metabisulfite
alone at levels comparable to the level exemplified in
Example 83 does not materially ccntribute to the blank. However,
when the same amounts of the metal compounds were combined
with the same amount of the organotin compound as demonstrated
in Examples 81-83, synergistic performances were observed by
comparison with previous Examples 78-80.
~ : . .
EXAMPLES 84-88 -
Other alkaline earth metal hydroxides have been
demonstrated to provide the synergistic results fox comparison
with calcium hydroxide as above reported. Examples 84-88
were performed to demonstrate the synergistic results of barium
hydroxide, Ba~OH)2 H2O, and strontium hydroxide, Sr(OH)2 8H2O,
with the organotin component. Amounts o~ each of the components
are reported in Table VIII alone and in com~ination as added
to the standard resin blank on a phr basis along with the~results
of hea~ st~ lity testing at l75F.
I
11 . '
.~
I -~3-
:
: . ~
: ~ :
:::
: 1~41~5
.
: ;~
ABL~ VIII
.~ ~ 375 F
~ ~; ~leat
: : ComponentsStability
Contribution
Example 84 0.5 DBT 20 '
; Example 85 0.5 barium hydroxide 0'
.
: ~ Example 86 0~5 strontium hydroxide 0'
:
. ~ ~Example 87 0.5 DBT
¦ ~ 0.5 barium hydroxide 35'.
Example 88 0.5 DBT
0.5 strontium hydroxide 30'
: ~-
. ~ .
. ~ , .
~. ~ .
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1 . .
,
.
1041Z85
The organotin componen$ alone at 0~5 phr demonstrated
again a heat stability contribution of 20 minutes. Whereas,
~he barium hydroxide or.strontium hydroxide component alone
l demonstrated no material contribution to the resin blank as
:~ reported in Examples 85-86 of Table VIII. IIo~ever the com-
-! bination of the organotin component and either of the metal
components demonstrated a synergistic heat stability as shown .
by Examples 87-88 of the table.
: , .
: : EX~SPLES 89-93
Synergisms have also been found for the combination
; . . of an alkali metal h~droxide and an organotin sulfur-containing
: ~. compound. In Example 89, sodium hydroxide at 0.25 phr was
: employed alone in the standard resin blank formula and tested
: ~ for heat stability by milling at 350F. for about 5 minutes ' .
followed by oven tes~ing at 375F. No material heat stability
; : contribution was observed. For comparison, 0.25 phr was .
.' comhined with DBT at 1 phr and tes'ted under identical conditions
,1 . in Example 90 and the heat stability contribution of the
combination was a~out 70 minutes. When these results are
compared with the DBT alone at 1 phr with the standard resin
~1 blank as for example, in Table I above, synergism i5 demonstrated
~¦ In Example 91, lithium hydroxide ~LioH~H2o) was .
.1 tested under conditions similar to sodium hydroxide,above
1 except that 1 phr of lithium hydroxide was employed with the
,~ standard resin blank and 0.5 phr dioctyltin bis (isooctyl-
. thioglycolate) was substituted for DBT. A heat stability ,
contribution of about 80 90 minutes was observedO For
-45-
1041Z85
;l comparison, Example 92 was run in which 0.5 phr of dioctyltin
bis (isooctylthioglycolate) was employed alone and a heat
! stability contribution of abou~ 20 minutes was observed.
i }lowever, when Example 93 was run for 1 phr lithium hydroxid-~
¦ alone~ no material contribution was observed. Thus, Examples
91-93 demonstrated that the combination of lithium hydroxide
and organotin, like sodium hydroxide at certain levels with
organotin, exhibits synergism according to the principles of
this invention.
As discussed in the detailed description of this
invention above, organic over based complexes have been
demonstrated by us to possess the desirable activity in our
. novel compositions. It has been explained that the exact :
; physical or chemical structure of these compositions is not
known except that, empirically, these compositions are stable
and have reserved basicity by having associated therewith
axcess inorganic metal bases either in chemically combined
form or in colloidal form. Regardless of the precise form of
;¦l basicity, these organic complexes of metal bases such as
lithium hydroxide, barium oxida, baxium hydroxide, calcium
oxide, calcium hydroxide, strontium hydroxide, etc., have been
found to possess the desired properties for use in this
invention. Several over-based complexes are commercially
available from Lubrizol Corporation. Examples of these
,. ~
f~ ~ include "Lubrizol LD2106" which is an over-based barium
phenate which features a high barium metal content in a
liquid form. Typical properties o~ "Lubrizol LD2106" are a
, . .
~ ~6-
1041 Z85
i specific gravity at 50F. of 1.3; a Brookfield viscosity at
71F., 20 ~PM, of 3000 cps.; a viscosity (SSU) at 210F. of 95;
a Gardner Color of 18+; and a percent weight barium content
of 27.5%. Another typical of such basic metal complexes is
¦ a material sold by Lubrizol Corporation under the trademark
"Lubrizol LD2103" which is an over-based barium carboxylate
characterized by viscosity at 210F. (SUS~ of 78; color, ASTM
of 4; sulfated ash of 40%; a weight of 10 lbs./gal. and a percent
~;~ weight barium content of 23.5~. Other products of this type
are commercially available, for example, Ba-190 by Bryton
Chemical Company which is a basic barium organic sulfonate,
; ~"C-300" which is a highly basic oil solu~le, calcium sulfonate
having excess basicity of calcium carbonate and the like.
Bryton "C-300" is a 300 base numbered calcium sulfonate, the
300 designation being derived by the chemical base number of
, ~ the composition which is approximately 295; and a typical
{ ~ analysis of such product demonstrates that it has a specific
gravity at 60F. of 1.13; a visoosity at 210F. (SUS) of
1 ~ 800; a base number of 295; calcium in percent by weight of
11.8~; sulfur in percent by weight of ?.0% and sulfonate in
percent by weight of 29%. These mentioned commercial products
are widely available and are orms of basic organic complexes
` which have been described in detail herein and by reference
to the patents cited. Indeed, ~hey are not limiting upon
. the scope of this invention, but it is found convenient to
employ some of them in examples which follow because of their
availability as commodities o commerce. To further illustrate
~L~4~Zl~S
the typical preparation of o~ganic ov~r-based complexes .:
Examples 14-17 of Canadian Patent 974,688 are referred to.
~: EXAMPLES 94-98
Examples 94-98 were perfor~ed to demonstrate syner-
gism between dibutyltin bis (isooctylthioglycolate), i.e.,
DBT, and over-based barium phenate (LD2106, identified supra).
The standard formula was used with milling and heat stability
testing at 375QF. The amounts of each of the components alone
and together in the vînyl halide resin are reported in Examples
~ ~lO 94-98 of Table IX.
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~ j; - TABLE IX
~ ~ ~ .
: 1~ 375 F
~:. ~leat
:j . Components Stability
Contribution
: ~ .
:~ `~ Example 94 0~5 DBT 20'
~' :~:
:' ~ ~ ~ Example 95 0.5 LD21061 0'
..
~ Example 96 1 LD2106 0'
I ~ Example 97` 0.5 DBT
~i ~ 0.5 LD2106 50
`~` ~ Example 98 0.5 DBT
~ ~ 1 LD2106 60'
il
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,,
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1 '
.
., , I .
~(1 4~Z1~5
Again, as demonstrated by Example 94, 0.5 phr DBT
provided a 20 minute heat stability contribution to the resin
blank. In contrast, elt~er 0 5 or l phr LD210~ provided no
material contribution to the heat stability of the resin blank
as demonstrated by Examples 95-96. However, the combination
of each of the components in the same amounts together in
the vinyl halide resin provided a synergistic heat stabiliza-
~ion of 50' and 60', respectively, in Examples 97 and 98.
For comparison with Examples 9~-98, reference is
made to Canadian Patent 974,688 above identified, Examples
3, 29,~32, 35, 40, 43, 46, 49 and 51. These examples of our
patent demonstrated the performance of an organotin component
in combination with an organic over-based complex (LD2106 or
C-300~ identified above). The organotins employed in the
examples of that application include dibutyltin bis (isooctyl~
thiaglycolate), monobutyltin tris ~isooctylthioglycolate) and
dibutyltin dilaurylmercaptide. Under the 400F. heat stability
evaluations made in our patent it will be appreciated that
; the;~heat stability contribution of the combination was greater
than the expected contribution. It is to be observed that the
~ heat stabilities ln minutes were reported as times until black-
;~ ~ ening or darkening of the formulations under test, rather
than in~terms of "contrIbution" as used herein. However, the
~ ~ .
~ results are clear for comparison. The LD2106 and C-300, alone,
; provide no material contribution to the resin formula. However,
in combination with the organotin, heat stability was observed
.
cbj - 50 -
.. . . . ..
1041285
which exceeds the expected sum of each of the components in
the same amounts alone.
ln eacn o~ tne a~ove examples, ~ne vinyl naliae
resin which was employed is a homopolymer of vinyl chloride,
i.e., polyvinyl chloride. It is to be understood, however,
that this invention is not limited to a particular vinyl
halide resin such as polyvinyl chloride, of course. Other
halogen-containing resins ~hich are employed and illustrate
~; ~ the principles of this invention include chlorinated poly-ethylene, chlorinated polyvinyl chloride and thb vinyl halide
resin type~ Vinyl halide resin, as understood herein, and
as appreciated in the art, is a common term and is adopted
to define those resins or polymers usually derived by poly-
~" ~ ~ merization or copolymerization of vinyl monomers including~inyl chloride with or without other comonomers such as
ethylene, propylene, vinyl acetate~ vinyl ethers, vinylidene
chloride, methacrylate, styrene, etc. A simple case is the
conversion of vinyl chloride H2C:CHCl to polyvinyl chloride -
(CH2-CHCl-)n wherein the halogen is bonded to the carbon
atoms of the carbon chain of the polymer~ Other examples _
of such vinyl halide resins would include vinylidene chloride
1, polymers, vinyl chloride vinyl ester copolymers, vinyl
~ chloride-vinyl ether copolymers, vinyl chloride-vinylidene
i copolymers, vinyl chloride-propylene copolymers, chlorinated
polyvinyl chloride, and the like. Of course, the vinyl halide
J commonly used in the industry is the chloride, aithough others
such as bromide and fluoride may be used.
. ' ~
1, , .'
l -51-
~ 5
It is also to be understood that other components
i such as lubricants, processing aids, pigments, other stabilizers,
other non-halogenated resins, etc., can be incorporated in
. the resin compositions and the benefits of this invention
can be achieved. Accordingly, other modifications will
~; become apparent in view of the teachings herein without
t ~ tr~ d ~
~:' ~ `
,.................... .
.
