CA1108173A

CA1108173A - Stable liquid antimony organic sulfur-containing compounds

Info

Publication number: CA1108173A
Application number: CA305,116A
Authority: CA
Inventors: Dale J. Dieckmann
Original assignee: Dart Industries Inc
Current assignee: Dart Industries Inc
Priority date: 1977-06-10
Filing date: 1978-06-09
Publication date: 1981-09-01
Also published as: FR2393828A2; BE867990R; ES470671A2; JPS60144343A; NL7806318A; GB1586335A; IT7824339A0; FR2393828B2; JPS5416428A; DE2825472C2; IT1158748B; DE2825472A1

Abstract

Abstract of the Disclosure Liquid antimony organic sulfur-containing compounds are rendered stable at ambient conditions by incorporating an effec-tive amount of a phenol. Liquid antimony organic sulfur-con-taining compounds such as antimony mercaptoacid esters, and the like, are also rendered shelf stable by phenols such as catechol, t-butyl catechol and butylated hydroxy anisole. The stable liquid compositions contribute to the heat stability of vinyl halide resins.

Description

l'l(lt3~73 J:~rJ
Back-3roul1d of tl1c Invention . . .
~ ntimony mercaptides have been proposed a~ stabiliz~r~
for vinyl halide resins to guard again~t deg~adation by heat during molding and working of the re~in intQ u~e~ul a~ticle~.
Prior art patents which disclos~ such antimony organic ~ulur-containing compounds and thei~ utility as ~tabilize~ in~lude U.S. Patent No8. ~,680,726; 2,684,956; 3,340,28$1 3,399,2~0~
3,466,261 and 3,530,158. In pa~t comme~cial practice, ho~ever, the antimony mercaptide~ have not been ~idely u~cd ~ ~tabilizers because of various ~orcomlngg including, ~o~ exampl~, thei~
propensity to exude from molded or wo~ked ~v~ pla~tiç ~t~k, C08t or lack of other advan~ages a~sociat~d ~itb thQi~ u~e which migh~ outweigh uch 6hortcomiP~o~ ~y U,S. ~atcnt No. 3 1 ~7 ~ 50 i~ di~ected to i~provement8 ln th~ utill~atio~ qf antimon~ ~~
ganiC ~ul~ur-containing compound~ in combl~atlon ~itb metal car- :
boxylate~. A~ de~cribed in my U.S. pat~nt No. 3,qB7,5~B, the utility and efficiency of ~uch antlmony co~pound~ ar~ improved in the heat stabilization of vinyl halldc re6in~ to a~ unexpected degree. It has been observed, however, that ~uch antimony com-pound~ which are normally liquld tend to deteriorate or become unstable upon 6torage.

Summary of the Invention , '~
' :~ a. s . Patent 4,029,618 issued June 14, 1977 is directed to further improvements in vinyl halide resin sta-bilizer syfit~ms of antimony organic 6ul~ur-containing compounds.
The invention described therein in one of it6 aspects provided for synergi6tic heat 6tabilizer composition~ of antimony compounds afi stabilizers and ortho-dihydric phenols. In anothe~ of it~

-2-.~ . , ' :1 r ~
38173 r~
j,~

significant fea~urcs, antim~,ny organic sulfur-containing compound~
are provided which are liquid and shelf-stable at ambient tem-peratures. Such stable liquid compositions are ea~ily for~ulated into vinyl halide resin system6 and offer synergistically heat stabilized resin systems with enhanced resi~tance to both early discoloration and long term heat degradation of molded plastic~.
It was found that antimony organic sulfur-containlng compound~
were rendered shelf-stable with certain dihydric phenol~.
This application further amplifies liquid antimony compositions which are rendered ~tabl~ for storage ~ us~ ~t ambient conditions by the addition thereto o~ a phenolic co~pound.
For example, liquid antimony organic ~ulu~-containing compounds, including antimony mercaptoacid e~ter~, tend t~ det~rio~ate upon ~tanding. Such deterioration is ob~erved by ths ~o~matio~ and/or precipitation of ~olids in the liquid compound~. Th~ precl~e reason for this deterioration phenomenon i~ unknown. Neverthe-les8, the re~ulting heterogeneous li~uid~ not only in~rease the problems of measuring and mixing the antimony compounds lnto vinyl halide resins for stabilization, but practlcally 6peaking, heterogeneity causes a dissolute appesrance ~hich reduce~ the marketability of the antimony stabilizers. ~hu~, according to this` invention, liquid antimony compounds are rendered shelf-stable at ambient temperatures by the incorporation of a phenolic component such as an ortho-dihydric phenol.
There are certain generally preferred weight ratios of the antimony organic sulfur-containing compounds relative to a particular phenol in order to achieve ~tability. ~his will become apparent in view of the detailed operating examples.
~owever, it is to be emphasized that the most desirable weiqht ratios of each of the essential components o~ the compo~ition of 8~73 ~ l .. ~ ' this invention for a particnlar application can be arrived at, in accordance with the teachings of this invention, Thu~ ln its broader aspects, this invention iB not limited to wei~ht ratios of components. It has also been found that ~Ve~ ~
particular phenol in a particular antimony o~ganlc sulfu~-con-taining compound to achieve optimum ~tabi~ities un~e~ ceFtain conditions will vary as exemplified herein. But~ -in general, the phenol is combined with the antimony organic sulfur-containing compound in a~ amount ~ abou~ 0,~ to about 20percent by wei~ht o~ the antimony compound , and preferably between about 1 and 10 percent by weight as indicated ln U.S. Patent 4,029,618.
ANTIMONY ORGANIC SULFUR-CONTAINING COMPOUND
~ h~ antimony or~anic ~ul~u~ nta~nlP~ PompQund~ which a~q 6helf-~tabilized acco~din~ tQ thi~ lnvent~oP ~e gene~lly cha~aoterized as having the Sb - S group Q~ linkag~. ~uch anti-mony compound~ may be l~uid~ a~ no~al ~r ro~ tempq~atU~e6 4nd ~tmo~pheri~ condltion~. On the other h~nd~ ~uCh anti~ony com-poundg may be solids at normal temperatur~ ~nd ~py ~ten or melt at elevated temperature~, ~herefore, ll~Uid ~t~bllity at ambient conditions can be achieved ~her~ thq anti~ony compound is either in the normal liquid, hot melt, or ~olyent-containing state at room or ambient tempe~atures and pre~sureB where such compounds tend to undergo degradation due to the ambie~t condi-tions. In a mo6t preferred form, the 6tablliz~tion is achieved in liquid composltions,which are shelf-stable at ~oom o~ ambient temperatures. Such liquid compositions can be readily measured and mixed with other compositions, and are thu~ easy to ~ormulate, market and use.
Generally, most antimony organic compound~ ~ui~able for use in thi~ invention are derived from trivalent ~ntimony and _4_ : ~

0 S ~7 3 .

include merca~tid~s which m.ly be characterized by the ollowing formula:
Formula I. Sb(SR)3 wherein R represents hydrocarbon or sub~tituted hydrocarbon radicals such as those selected from the ~roup conslstin7 of alkyl, aryl or ara1kyl. Example6 of guch ~roupg are alkyl~ ~uch as ethyl, propyl, butyl, octyl, nonyl, lauryl and octadecyl;
aryls and aralkyls such as phenyl, bPnzyl, naphthy~, xylyl o~
phenyl ethyl and the like. The group SR of Formula I~ ~V~ in-stance, may be the rest of a ~ercaptan or ~erc~pto ~lcoho~. A~
indicated, aliphatlc and aromatic me~captan~ ~ay ~e ~mployed to form the group SR. In the ca~e of aliphatic me~apt~n~, those having 8 to 18 carbon atom~, e,g., decyl ~r dedecyl merc~ptan are u~ually pre~erred because the lower mercapta~ a~e un~it~bl~ for the pre~aration and use of the ~tabili~er~ c~ount ~ their offensive ~mell. 8uitable aromatlc mercaptanQ axe, ~u~ tance, thionaphthol, thiobenzyl alcohol, phenoxyethyl mer¢apta~, and others. As examples of ~uitable mercapto alcohol~, ~o~othio-ethylene glycol, monothiopropylene glycol, thioglycerol, thio-diethylene glycol, and other~ may be mentioned, ~pec~fic examples of such antimony mercaptides are antimony trilaurylmercaptide, antimony triphenylmercaptide snd antimony tribenzylmercaptide.
Patents exemplifying this formula Sb(SR)3 or a si~ilar formula and a definition of compounds represented thereby lnclude U.S.
Patent Nos. 2,684,956 and 3,466,261, among othe~.
Antimolly organic ~ulfur-containing compounds other than the antimony mercaptides of the Formula I above, are ~uitable for use according to this invention. Such compounds ~ g~nerally termed antimony m~rcaptoacid ester~ which may be further defined I~LO8173 by t~ followlll<3 formula:
Formula II. Sb(SRCOO~'~3 wherein R is selected from the gxoup consisting of alkylene, arylene, and aralkylene radicals and R' is a sub~tituted or un-substituted alkyl, aryl or mixed aryl-alkyl gXoup. ThUs R may be derived from mercapto acetic, ~ -mercaptopropionic, thiomalic, : thiosalicyclic acids, etc. Similarly, R' may be derived ~ro~
decanols, glycerol, glycol, monoesters, dihydr~abietyl ~lcohol, phenoxyethanol, pentaerythritol, etc. Particularly ~uitabl~ are the esters of mercapto alcohols, 8uCh a~ thioglycol~, in whic~ the hydroxy groups are esterified by an alipbat~c ! ~o~atic or ali-cyclic saturated or un8aturatod mon~çarboxyli~ ~Cid. ~a~ily available mercap~oacid ester~ a~e th~ ~ster~ o~ thiogly~olio acid, such as ethyl thioglycol~te, l~ooctylthiogly~ t'~, and generally the e6ters of mono and diba8ic aliphatic and aroma~lc m~roapo acid~, ~uch a~ esters of beta thlopropionic a~id, tb~laatic acid, thiobutyric acid and mercapto lauric acid. ~pecifia example~ of antimony mercaptoacid ester~ include antimony tri4 ~i~ooctyl-thloglycolate~, antimony tris ~glycoldime~captoacetate~l antimony tris ~dodecy.lthioglycolate), dodecylmercaptoantlmony bi~ ~iso-octylthioglycolate), and antimony tri~ (lsooctyl-~ ~me~captopro-pionate). Patent~ exemplifying Formula II o~ a'~imila~ formula and a definition of compounds represented thereby lnclude U.S.
PaLent No~. 2,680,726 and 3,530,15B, among other~.
The antimony organic sul~ur-containing compounds having the SbS group represented by Formulas I and II come within the scope of a broader characterization illustrated by the following formula;
¦ Pormula III. RnSbX3 n 11 , : ~ I

;38~73 wherein l~ is sclec~ed from lhe ~roup consisting of alkyl, alkenyl, ;
alkynyl, aryl, cycloalkyl, cycloalkenyl, and mixed aryl-alkyl, and substituted groups thereof, where X is eelected from the group consisting of sulfide (sulfur) or mercaptide and n i~ an integer of O to 2. of course, othe~ X group~ are SR and SRCOOR' d~fined by Formulas I and II above wherein R of the group SR is selected from alkyl, aryl, mixed aryl-alkyl, and 6ubstituted groups there-of, where R of the group SRCOOR~ i~ selected f~om ~lkylen~, ary-lene, aralkylene, and substituted group~ thereof, whe~e$n R' of the group SRCOOR' i8 6elected ~rom alkyl, aryl, mixed A~yl-alkyl, and 6ubstituted group~ thereof. Thi~ 1~ al~ ~ppare~ and with reference to the above 4r~~tl~Ye- i 3,530,15~ pate~t, that when X
i8 divalent, e.g. sulfide, t~e ~ompound may ~e RSbX ~ ~xemplified hereinafte~ by n-butyl antimony ~ulfide ~here ~ of ~n ~ Formula III i~ 1 and where n of X3~ 2. It i~ ~h~e~o~ ~ppreciated that the formulas hereip ar~ merely ~epr~6enta~iVe ~ndlci~ o~ the - clas~ of antimony compound6 which re~pond to th~ teaching~ of this invention. In the compound6~ RnSbX3_n which ~y ~e u~ed ln practice of this invention, R may be alkyl~ cyclo~lkyl~ alkenyl, cycloalkenyl, alkynyl, or aryl including ~uch group~ when inertly ubstituted. When ~ i8 alkyl, it may include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-amyl, n-octyl, 2-ethyl-hexyl, etc. a6 well as sub6tituted alkyl~ lncluding phenylethyl, benzyl, etc. Typical alkenyl groups which may ~e employcd may include vinyl, 2-propenyl (i.e. allyl), l-propenyl, l-butenyl, 2-butenyl, etc. as wcll as inertly sub~tituted alkenyl groups typified by 4-phenyl, buten-l-yl, etc. ~ypical cycloalkyl group6 may lnclude cyclohexyl, cycloheptyl, cyclooctyl ag well a~ lnertly substituted cycloalkyl groups including 2-methyl cycloheptyl.

3-butyl cyclohexyl, 3-methylcyclohexyl, etc. ~ypical alkynyl .:

8~3 .~

groups whi~ m~y L~e ~mploye~l include propyn-l-yl, propyn-2-yl, butyn-l-yl, phenlethynyl, ethynyl, etc. Typical aryl gr~ups which may be employed may include phenyl, tolyl, xylyl, chlaro-phenyl, dimethylaminophenyl, etc. Where mo~e than one R o~ X i~
present in Formula III, such groups may be the ~ame ~r dlf~erent.
Typical mercaptide~ include phenyl mercaptide, l~uryl mercaptide, butyl mercaptide~ or dimercaptides includin~ aliphatic, cyclo-aliphatic, or aromatic dimercaptan6 of the ~ groups di~closed herein, etc. Specific compound~ when n is 1 or 2 lnc~ude n-butyl antimony dilaurylmercaptide, n-butyl anti~ony ~ul~ide, di-n-butyl antimony lauryl mercaptide, diph~nyl anti~ony ?au~yl m~qaptide, ditolyl antimony n amyl mercaptlde~ dibenzyl a~timo~y ~nzyl mer-captide, diallyl antimony cyclohexyl me~çapt~d~, diphenyl anti~ony allkylme~captide, dlcyclohexyl antimo~y ~-~exyl merca~tide, di-tolyl antimony phenyl me~captlde~ dl-l~opropyl ~ntimo~y 2-ethyl-hexyl mercaptlde, di-p-chlo~ophenyl antlmony n-~utyl ~rcaptide, diphenyl antimony ethyl me~captoacetat~. Patent~ exem~ ying such antimony compound~ lnclude U.S. Patent ~. 3,53~15~ and 3,399~220. ~here the R ~roup i~ ary~oxy, alkyloxy, a~k~ryloxy, acyloxy, etc., ~peciflc example~ from which th~ group i~
derlved may include 2-ethylhexanol, phenol, nonylphenol~ xylenol, 2-ethylhexoic acid, oleic acid, lauric acid, benzoic acid and the like, Of cour6e, it i~ apparent that antimony merc~ptldes, antimony mercapto acids, antimony mercaptoacid est~r~, et~., per 6e form no part of this invention and the mentloned patent~ and their specific di6closure~ clearly teach these compounds and their method of production to enable anyone of ordinary skill to use e m in carrying out thi~ lnvention.

~ ?
.
:.
.

81~3 PHENOLS

The terms "phenol" and "phenols" as used herein are in-ten~ed to include mono- or polynuclear phenols exemplified by the benzene or naphthalene nucleus, and,the su~stituted forms of such a nucleus. As reported in my earlier mentioned copending appli-cation, the ortho-dihydric phenols of such mono or polynuclear phenols have already been found by me to provide liquid, shelf-stable compositions of antimony compounds at ambient temperatures.
Specific examples of such ortho-dihydric phencls include catechol tertiary butyl catechol, and 2,3 dihydroxynaphthalene. I no~
find that the stability of such antimony compounds Can also be maint~ined b~ ther phenols r ~- ented by the following formula:

wherein Rl, R2, R3, R4 or R5 can be hydrogen, alkyl, aryl, hydroxyl, alkoxy, aryloxy, alkaryl, aralkyl, other substituted groups of said aryl or alkyl, and the like, provided all are not hydrogen, or they may form a part of an aromatic or alkylated aromatic nucleus as in the case when the phenolic nucleus is naphthalene, Alkyl substituted groups of mono or polynuclear phenols of this formula include straight or branched chain groups of C1_12, such as methyl, ethyl, propyl, pentyl, hçxyl, heptyl, dodecyl, or tertiary butyl, isopropyl, e~c., forms. The presently preferred phenols of this invention are the catechol derivatives because of their performance and commercial availability. Other dihydric or trihydric phenols, or other functionally substituted ~1~38~73 mono-, di- or polyhydric ph~llols can be employed. Included in such phellols are mono-, di-, tri- isobutyl or i80ctyl phenolt 2,4,5-trihydroxybutyroPhen0rle; butylated hydroxyanisol~ whlch is a mixture of ortho- and meta-butyl parahydrq~yani~le~ 5ecquinols resorcinol; 2,6-di-t-butyl-~-cresol; reso~cinol mon~benzoate and ~-octylphenyl salicylate. It will be appreciated ~at speci~ic phencls may be used to achieve stabilization result8 along with other advantages as empirically demon~trated in numerQu~ ~pe~ating examples of this invention, and a further understandi~g thereof `~

w111 become apparent in v~eW of the detailed de~crip~i~n he~ein.
Thus, in accordance with the present teachings, a liquid antimony-based composition is provided which is stable under ambient conditions and consists essentially of:
a liquid comprising an antimony organic sulfur-containing compound having the formula:

n 3 where R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, mixed aryl-alkyl, .and substituted groups thereof, where X is selected from the group consisting of sulfur, SR and SRCOOR' wherein R of the group SR is selected from alkyl, aryl, mixed aryl-alkyl~ and substituted groups thereof, where R of the group SRCOOR' is selected from alkylene, arylene, aralkylene, and substituted groups thereof, wherein R' of the group SRCOOR' is selected from alkyl, aryl, mixed aryl-alkyl, and substituted groups thereof, where n is an integer of 0 to 2, and a minor amount by weight of the compound of a phenol chosen from one of the following:
(i) monohydric phenols having alkyl, aryl, alkoxy, aryloxy, alkaryl, aralkyl or other substituted alkyl or aryl constituents on the nucleus thereof (ii) meta- and para-dihydric phenols and substituted ~, -10-.~, .

- . ~ . .

meta- and para-dihydric phenols (iii) trihydric phenols and substituted trihydric phenols.

The principles o~ this lnven~14~ ~nd 1~9 op~dtlp~
parameter6 will be further unde~too~ Wlth r~ ence ~0 following detailed example~ which s~rv~ to illu~t~ate ~h~ type~
o~ ~pecific ~aterial~ and thei~ ~m~unt~ a~ ~s~d in ~h~ fitabil~
zation o~ antimony compounda ~ccording to thi~ inyention. ~heae examples are considered~to be exemplary o~ th~ inventlon, and should not ~e considered a~ limiting, e6pecially ln vi~w o~
applicant' 5 broad di~closure o~ prin~iple~ o~ ~hifi inVe~t$on.
In the examples of Table~ I and TI ~hich follow, various combination's of an antimony organi~ 6ul~ur-containing compound and a phenol were blended together to ~orm ~ liquid composition on a parts by weight basi~. All amou~t~ o~ com-ponents are on a percent by weight ba6is, or a~ ~ndicated, simply "~". The phenols were lncorporated in ~ llquid antimony tris-isooctylt~ioglycolate (ATG) on the ~basi~ o~ a~out 0.1 to about 20 percent by wei~ht of the antimony compound a~ indicated in the Tables. The stabillties of the resulting blend~ of ATG
and t-butyl catechol (T~C) or ATG and butylated hydro~yanisole (~HA) were de~ermined at normal room temperature and p~es6ure ~20-25C an~ atmospheric), as reported in Tables I and II, respectively, in open bottle~.

,: .

B -lOa -r TABLE I

% TBC TIME
1 dày 1 wk. 1 2 wks. 3 wks. 4 Wks.
. . . .. __.
0 Clear Clear Hazy Hazy ~azy _ . ........ ._.. ... _.. __ . .
0.1 Clear Clear Clear Clear Clear ~ . .. .. __ . __ . , ~, _ _ _ ._ r 0.5 Clear Clear Clear Clear Clear 1.0 Clear Clear Clear Clear Clear : L0.0 Clear Clear Clear Clear Cleax .. . ~. . . . ..... _ : 20.0 Clear Clear Clear Clear Clear - -, S~73 _, UJ _ _ . _, _ . . .
Ul '1 ~ ~ h,i ~1 ,~~1 t)' nl rd t~U~ ::~ Ul ~. Ul ~ Ul ':c la O al ~ N N N N
n. ~ ~ ~ 0 ~ ~1 ~ 0 ~ ,d O ~ U l) ~ ~ ~ ~ ~ ~ ,d __ ___ _. . _~
. a~ .
U~ :~ ~, . ~.~ ~n 3 a N N ~1 ~1 ~ C) ~ N
1~ g' ~.C ~.C O U ~1 U 11~1 __ , . ____ - _ __ .
. ~ .
u) ~ ,1 ~ 1~ h ~ h ~' ~ U~ ~ ~ ~ ~ ~
3 (a . N N ~\ O O ~\
~, ~ rd . ~ ~1 ~1 ~ ~ _1 ~O O Ul ~ ~ ~ U U U U U

:~ _I ~ ~ h tl' ~1 U~ ~ 1~ Id Id 1 3 lll ~ N N U a~ 0,~
a. 1-l ~ ' Id r-~ ~1 _1 rl ,_ U~ O Ul ~: ~ U O U ~ t.) . .. . __ . .
n ,~ h ~ ~ ~ .
;~ N ~ U) ~ 1~1~d ~d ~ ~ ~ _~
U~,C ~ 1~ U O 1~ 1,~
H _ _ __ _ _ . .
E~
,X ~ ~ ; I
3 N N N ~\
. ~ ~1 ~ _~ ~ _~
P~ U U U V ~ ' ' i~ _ _ __ .. .- _ __ , ','' U~ ~ ~ ~ ~ ~
~a 3 N N ~J ~ a) a~ ~ a~
~1 ,~ a ,~ ,~ ,~ _, r-~ ~
~ ~.' ~ U U U U ~ U
_ __ _ __ __ .. , . H ~ h 1~ h ~1 h .Y:~1 u~ :~ ~d ~d nl rd nl ,a ~ N N ~1 O O q~ a) ~1 ,a nl -~ ~1 ~1 ~ ~ r~
~1 ~ P~ U U U U U U
_ _ . - _ , ~ ~ ~ h h h h h ~ ~ In ~ ~ ~ ~ ~ ~
N N q~ al ~ ~ ~1 ~U
n~ ,~ ~ ~ ~1 ~_1 ~1 . r~Ul.C ~ .L U ~ V U U U
.

~ h 1~ ~ 1~ h ~ ~ h l~ ~ Id Id n~ Id~d l~ Id a~
~1 ~ ~ ~ . ~ ~ ~1 ., ,~ U U U U U U U U
_ __ m o o c, o 1~ r) r~
~P _ . o _ _ ._ t 1i 8173~ ~

In tl~e ~rables "wk." or "wks." means week(s); "clear"
means homogeneous transparellt liquid; "v. sl. hazy" means Yery minor amount of insolvent partiele appcarance; "s1. hazy" and "hazy" respectively means increasing insolvent appearance; and "opaque" means loss of transparency. Thu~, as can be seen by both Tables, at room temperature and normal atmospher~, the unmodified liquid antimony compound develops haze and becomes opaque on standing for several weeks. In the presence of minor amounts of t-butyl catechol, no deterioration is noted (see Table I). The stabilizing response of TBC would appear to be linear with increasing amounts. However, Table II demonstrates that the stabilizing response of butylated hydroxy anisole (BHA) is not completely linear. Rather, while improvements are observed with varying amounts of O.l to 5.0~, complete clarity is retained throughout an eight week period with about 0.3 to 2% of BHA.
Accelerated shelf stability tests have also been con-ducted. In these tests an apparatus was a~embled to supply air to liquid antimony samples containing varying amounts of phenols.
An alr supply was connected to a ~lowmeter and through a hose to a 1000 ml vacuum flask containing 750 mls water. After bubbl~ng through the water, the air was conducted through a glass tube to a 400 ml beaker containing 150 ~rams of antimony tris- lsooctyl-thioglycolate heated to 260F, for bu~bling throu~h the liquid.
Procedurally, the antimony liquid was charged lnto the beaker and desired percents of phenols were added to liquid samples. Then, the liquid was stirred under a temperature held at 260F with

4 SCF~I of air supplied. With the passage of time in minutes, the moment of opacity was recorded a~ the time at which the centrally located glas~ tube in the beaker evolving ~ir could not be ~een when viewed through the side of the beaker.

Employing the accelerated tests described above, opacity occurred for varying percents of TBC as shown in Table III. The control (0%) opacified in 22 minutes.

:

TABLE I I I
":
96 . Opacity TBC ~min . ) -`. o 22 ~:. 0,5 44 :
"~
~- 1 . 25 61 ., j ~
2.0 6 2 . 5 Bl : 3~ 5 112 ` 5. 0 138 ~' ~
,,~

, ........................................................................ .
. . ~

.: ~ - ' ' '~ , Thus, TBC achieves a linear stabilization of the liquid antimony over a period of time with increasing amounts.
This accelerated data of Table III confirms ambient test results on TBC in the sense that increased stability is achieved with increasing amountC of phenol.
Accelerated tests were also performed for BHA under the same conditions described above and the results are reported in Table IV.

1 IJ8~3 % ûpacity ~A (min. ) O
0.5 31 1. 25 2B
~.0 ~8 ., .
2.5 ~3 3.0 36 3.5 23 g . 25 2S

5.0 26 :-Accelerated data of Table IV thus parallels the data of Table II above and indicates its reliability in similarly predicting long term shelf storage stability for the liquid antimony compositions.
Employing accelerated tests, at 2.5~ phenol component in ATG, improvements of at least about 20 minutes in stability have been observed for butylated hydroxy anisole; p-dihydroxy-benzene; _-dihydroxybenzene; 2,6-di tert-butyl-para-cresol;
resorcinol monobenzoate; p-octylphenyl salicylate; a mixture of di- and tri-alkyl phenols where the alkyl group substituted in the 2, 3 and 5 positions is isobutyl or isooctyl; o-dihydroxy-~` benzene; and 2, 4, 5-trihydroxybutyrophenone. In the case of phenols such as butylated hydroxy anisole; 2,2'-bis (4-hydroxy-phenyl) propane; 4,4'-butylidenebis (6-tert-butyl-_-cresol);
4,4'-thiobis-(6-tert-butyl-m-cresol); and 2-3 dihydroxynaphtha-lene, improvements are observed at levels between 0.5-5.0~, but ` optimums vary depending upon the phenol and the particular antimony compound.
In addition to the above examples, as reported in my earlier application examples, the combination of several o-; dihydric phenols and liquid antimony tris (isooctyl-~-mercapto-propionate), hereinafter "ATP", were demonstrated. Each of the combinations containing 5% phenol were shelf-stable liquids at ambient temperature. The _-dihydric phenols were 4-tertiary butyl catechol, catechol and 2,3-dihydroxynaphthalene.
As developed above, the antim~ny compound may be liquid in its normal state, i.e., at room temperature and atmo-spheric pressure. Also, the antimony compound may be rendered liquid by the addition of a solvent. In this connection, :

,~ -.

l08173 antimony tris ~lauryl mercaptide) is a pasty solid at ambient temperatures~ A composition of 50% hydrocarbon solvent and 50 antimony tris (lauryl mercaptide) was formulated and at room temperature and ambient pressure was a clear liquid. When a sample of such a composition wa6 tested fo~ ~tability under th~
accelerated p~ocedure described above, a control wlthout phenolic stabilizer became opaque after about 35 minutest Upon the addi-bv weight 4-tion of ~%/ tertiary butyl catechol, and the per~ormance ~f the accelerated tests under the same condition~ aq the control, the phenollc containing compo6ition did not be~m~ ~a~ue ~ntil A
passage of 70 mlnute~ Accordin~ly, liquid antim4ny ~abili~er composltions in a normal ~tate or solvat~ 8t~te ~n b~ ~tabilized in accordance with the prlnciple~ ~ this inv~n~lon.
It is als~ to be unde~tood t~a~ ~h~ ~omponent~ can be used and the benefits of this in~ention can bo achl~ved.
Accordingly, other ~odificatio~ will beco~ pa~on~ in Yiew of the teachings hereln wlthout departing from tha tXu~ spirit and Scope of this invention.

Claims

What is claimed is:

1. A liquid antimony-based composition, stable under ambient conditions, which consists essentially of, a liquid comprising an antimony organic sulfur-contain-ing compound having the formula RnSbX3-n where R of the formula is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, mixed aryl-alkyl, and substituted groups thereof, where X of the for-mula is selected from the group consisting of sulfur, SR and SRCOOR', where R of the group SR is selected from alkyl, aryl, mixed aryl-alkyl, and substituted groups thereof, where R of the group SRCOOR' is selected from alkylene, arylene, aralkylene, and substituted groups thereof, wherin R' of the group SRCOOR' is selected from alkyl, aryl, mixed aryl-alkyl, and substituted groups thereof, where n is an integer of 0 to 2, and a minor amount by weight of said compound of a phenol chosen from one of the following groups:
(i) monohydric phenols having alkyl, aryl, alkoxy, aryloxy, alkaryl, aralkyl or other substituted alkyl or aryl con-stituents on the nucleus thereof (ii) meta- and para-dihydric phenols and substituted meta- and para-dihydric phenols (iii) trihydric phenols and substituted trihydric phenols.

2. The composition of Claim 1 wherein said phenol is butylated hydroxy-anisole.

3. The composition of Claim 1 which is liquid and shelf-stable at room temperatures for at least several weeks.

4. The composition of Claim 3 wherein said antimony compound is selected from the group consisting of antimony tris (isooctylthioglycolate), antimony tris (isooctylmercaptopro-pionate), dodecylmercaptoantimony bis (isooctylthioglycolate), antimony tris (glycoldimercaptoacetate), and mixtures thereof.

5. The composition of Claim 4 wherein said phenol is butylated hydroxy-anisole.

6. The composition of Claim 1 containing said phenol in an amount of about 0.1 to about 20% by weight of said compound.

7. An antimony-based composition liquid and shelf-stable at room temperatures consisting essentially of, a normally liquid antimony organic sulfur-containing compound having the formula RnSbX3-n where R of the formula is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, mixed aryl-alkyl, and substituted groups thereof, wherein X of the formula is selected from the group consisting of sulfur, SR and SRCOOR', where R of the group SR is selected from alkyl, aryl, mixed aryl-alkyl, and substituted groups thereof, where R of the group SRCOOR' is selected from alkylene, arylene, aralkylene, and substituted groups thereof, wherein R' of the group SRCOOR' is selected from alkyl, aryl, mixed aryl-alkyl, and substituted groups thereof, where n is an integer of 0 to 2, and as a stabilizer therefor a minor amount of said compound of a phenol chosen from the group consisting of butylated hydroxy anisole, p-dihydroxy benzene, m-dihydroxy benzene, 2,6-di-t-butyl para cresol, resorcinol monobenzoate, p-octyl phenyl salicylate, mono-isobutyl phenol, di-isobutyl phenol, tri isobutyl phenol, mono-isooctyl phenol, di-isooctyl phenol, tri-isooctyl phenol, 2,4,5-trihydroxy butyrophenone, 2,2'-bis (4-hydrotryphenyl) propane, 4,4'-butylidene-bis (6-tert-butyl-m-cresol), and 4,4' thiobis- (6-tert-butyl-m-cresol).

8. The composition of Claim 7 wherein the relative amount of phenol present is from about 1 to about 20 percent by weight of said antimony compound.

9. The composition of Claim 7 wherein said antimony com-pound is selected from the group consisting of antimony tris (isooctylthioglycolate), antimony tris (isooctylmercaptopro-pionate), dodecylmercaptoantimony bis (isooctylthioglycolate), antimony tris (glycoldimercaptoacetate), and mixtures thereof.

10. The composition of Claim 8 wherein said phenol is butylated hydroxy-anisole.