CA1041285A - Resin stabilizer systems of organotin sulfur-containing compounds - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A resin stabilizer composition which essentially contains an organotin sulfur-containing compound having a ?-Sn-S group, for example, organotin mercaptides, organotin mercaptoacids, organotin mercaptoacid esters, organotin sulfides, organothiostan-noic acids and the like, and metal compound selected from the group consisting of an alkali metal bisulfite, carbonate, hydroxide, oxide, thiocarbonate, bicarbonate and metabisulfite, and mixtures of said metal compounds, said organotin and metal compound compon-ents in relative amounts which together provide a synergistic stabilizing effectiveness upon said resin. These compositions remarkably contribute to the long term heat stability of vinyl hal-ide resins. Furthermore, among other advantages, significant econ-omies and synergistic resin heat stabilization are offered by these stabilizer compositions.

Description

.

~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/~ `

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 .

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 :~ .

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

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 ,, . ,.

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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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.
' ' -~' , :

, ' : ' 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.
. ................... , ..

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~ : ~
~ :

:: : 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' ,,; _ _ :
, ~ ~ .
:
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.
. 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 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.

~` : , .
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.
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: ~
~: ~ . 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 ':, ~
, : ~ :
: ~ : , ,~
: :
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' ~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.
.' ~ . , .
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~:; ~ 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' ~ :
:, - .
, . .
.

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1 ... .
. . , - `1 .
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~: ' , ' ;, ' : 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 .
~ ~ .
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:~ ~ TABLE V

. ~leat :. ~: : Components Stability ~ ~ ~ Contribution . ~
:~; : Example 71 1 DBT
: 1 s.odium bisulfite 70' ;~ Example 72 1 sodium bisulfite 0' :, ~

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~:

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1 -38~

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
'` , 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 ~ , `
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,',, .

~ .
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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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1. .

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.
~ : . .

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 . ' .~

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: ~ :
:::
: 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 . . .
1 . .

, .

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 ;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-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.

:;,:

-:.
'; :~ :

' ~ . ' , ~
:,: :
,.,~.

., .

~'~ : ' .

cb~ ~ 4 ~ ~

:~i !

~ 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 :,: : ~ ~
', ,, ,:

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 -.. . . . ..

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 ~

~:' ~ `

,.................... .
.

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A resin stabilizer composition which consists essentially of, an organotin sulfur-containing compound having a ?-Sn-S group, and a metal compound selected from the group consisting of an alkali metal bisulfite, carbonate, hydroxide, oxide, thiocarbonate, bicarbonate and metabisulfite, and mixtures of said metal compounds, said organotin and metal compound components in relative amounts which together provide a synergistic stabilizing effectiveness upon said resin.

2. The composition of claim 1 wherein said organotin sulfur containing compound is selected from the group con-sisting of an organotin mercaptide, organotin mercaptoacid, organotin mercaptoacid ester, organotin sulfide, and organo thiostannoic acid, and mixtures thereof.

3. The composition of claim 1 wherein said components are present in a weight ratio in the range of about 0.1-5 of the organotin component to about 0.1-10 of the metal component.

4. A vinyl halide resin composition which comprises a vinyl halide resin and, as a heat stabilizer, an effective amount of a composition consisting essentially of, an organotin sulfur-containing compound having a ?-Sn-S group, and a metal compound selected from the group consisting of an alkali metal bisulfite, carbonate, hydroxide, oxide, thio-carbonate, bicarbonate and metabisulfite, and mixtures of said metal compounds, said organotin and metal compound com-ponents in relative amounts which together provide a syner-gistic stabilizing effectiveness upon said resin.

5. The composition of claim 4 wherein said organotin sulfur-containing compound is selected from the group consisting of an organotin mercaptide, organotin mercaptoacid, organotin mercaptoacid ester, organotin sulfide, and organo thiostannoic acid, and mixtures thereof.

6. The composition of claim 4 wherein said effective amount is on the order of about 0.2 to about 15 parts by weight per 100 parts resin.

7. The composition of claim 4 wherein the relative amount of said organotin component is in the range of about 0.1 to about 5 parts by weight per 100 parts resin and the relative amount of metal compound present is in the range of about 0.1 to about 10 parts by weight per 100 parts resin.

8. The composition of claim 4 wherein the organotin sulfur-containing compound is selected from a group consisting of dibutyltin bis (isooctylthioglycolate), monobutyltin tris (isooctylthioglycolate), dibutyltin dilaurylmercaptide, butyl thiostannoic acid, dioctyltin bis (isooctylthioglycolate), dimethyltin bis (isooctylthioglycolate), monomethyltin tris (isooctylthioglycolate), dibutyltin bis (isooctyl-beta-mercapto-propionate), and mixtures thereof.

9. The composition of Claim 4 wherein the metal compound is selected from a group consisting of sodium bisulfite, sodium carbonate, potassium carbonate, sodium metabisulfite, potassium metabisulfite, lithium hydroxide, sodium hydroxide, and mixtures thereof.

10. The composition of claim 8 wherein the relative amount of said organotin component is in the range of about 0.1 to about 5 parts by weight per 100 parts resin and the relative amount of metal compound present is in the range of about 0.1 to about 10 parts by weight per 100 parts resin.

11. A vinyl halide resin composition which comprises a vinyl halide resin and, as a heat stabilizer, an effective amount of a composition consisting essentially of, an organotin sulfur-containing compound selected from the group consisting of dibutyltin bis (isooctylthiogly-colate), monobutyltin tris (isooctylthioglycolate), dibutyltin dilaurylmercaptide, butyl thiostannoic acid, dioctyltin bis (isooctylthioglycolate), dimethyltin bis (osooctylthioglycolate), monomethyltin tris (isooctylthioglycolate), dibutyltin bis (isooctyl-beta-mercapto-propionate), and mixtures thereof, and a metal compound selected from the group consisting of sodium bisulfite, sodium carbonate, potassium carbonate, sodium metabisulfite, potassium metabisulfite, lithium hydroxide, sodium hydroxide, and mixtures thereof, said organotin and metal compound components in relative amounts which together provide a synergistic stabilizing effectiveness upon said resin.

12. The composition of claim 11 wherein said effective amount is on the order of about 0.2 to about 15 parts by weight per 100 parts resin.

13. The composition of claim 12 wherein the relative amount of said organotin component is in the range of about 0.1 to about 5 parts by weight per 100 parts resin and the relative amount of metal compound present is in the range of about 0.1 to about 10 parts by weight per 100 parts resin.