Note: Descriptions are shown in the official language in which they were submitted.
105'~80'~
The present invention is directed to a new meth-
od of preparing organotin mercaptide It i8 based on
the reaction of organotin sulfides with active organic
halides in the presence of specific aprotic solvents or
more preferably in the presence of water. Preferably,
wet, newly prepared organotin sulfides are used. The re-
action~ involved are as follows:
S S, Rl S, Rl
(1) (RSn)2S + 2RlX -~ RSn - S - Sn - R
.
X X
R~ R2 / SR
(2) / SnS + RlX ~~ Sn
R3 R3 X
R4 \ / R4 R4 ~ R ~
(3) Rs; Sn - S - Sn - R5 + RlX ~ R5 j Sn - SRl + R5j SnX
R6 R6 R6 R~
S X X
,. . .
(4) (RSn)2S + 3RlX--~RSn(SRl)2 + RSn - SRl
X
S SR
(S) RSn - SRl + RllX -~ RSn
X SR
wherein:
R~ R2, R3~ R4~ R5, and R6 are alkyl, usually of
25 1 to 20 carbon atoms, cycloalkyl, usually of 5 to 6 carbon
--3--
, ~
.
loS~ 4
atoms in the ring, alkenyl, usually of 2 to 20 or more
frequently 3 to 18 carbon atoms, aryl, usually phenyl or
alkyl phenyl having 1 to 4 carbon atoms in the alkyl
group, or aralkyl, usually of 7 carbon atoms (R, R2, R3,
R4, R5, and R6 preferably are methyl);
O O
ll ll
1 ~cH2~nC - OR7, ~CH2~m~C ~ R12~ benzyl~
,R14
CH2 = C - CH2 - where R14 is hydrogen or methyl;
Rll is defined as Rl;
R7 is alkyl usually of 1 to 20 carbon atoms,
cycloalkyl usually having 5 to 6 carbon atoms in the ring,
alkenyl, usually of 2 to 20 carbon atoms, more commonly 3
to 18 carbon atoms, or aralkyl, usually of 7 carbon atoms;
R12 is alkyl, usually of 1 to 19 carbon atoms,
or alkenyl usually of 2 to 17 carbon atoms;
X is a halogen of atomic weight 35 to 80, i.e.,
chlorine or bromine;
n is an integer of 1 or 2; and
m is an integer of 2 to 3.
When aprotic solvents are employed as catalysts
said solvents are:
O Rg
(a) R8C - X
Rlo
105~80~
Rg
(b) / S = 0
Rlo
Rg
(c) N P = 0 , or
Rlo _ 3
(d) N - methyl - 2 - pyrrolidone,
where R8 is hydrogen or methyl and Rg and Rlo are methyl
or ethyl. The preferred aprotic solvent catalyst i9 di-
methyl formamide. The amount of aprotic solvent (whenemployed) can vary, for example, from 0.1 to 10 moles
per mole of organotin sulfide, preferably 0.8 to 8 moles
per mole of the organotin sulfide.
It is critical to use the catalyst or water
since in the absence of the catalyst or water degradation
reactions predominate and little or no product is formed.
As aprotic solvent catalysts there can be used
for example, dimethyl formamide, dimethyl acetamide, di-
ethyl formamide, diethyl acetamide, dimethyl sulfoxide,
diethyl sulfoxide, tris(dimethylamino)pho~phine oxide,
tris(diethylamino)phosphine oxide and N-methyl-2-pyrrol-
idone.
It has further been found that water wet, pref-
erably freshly prepared, wet, organotinsulfides are much
more reactive than dried organotinsulfides and will react
--5--
'105'~8B4
with isooctylchloroacetate or other active organic halides
in the absence of catalysts such as dimethyl~ormamide or
the others set forth above. Most preferably a slurry of
organotin sulfide in water is employed.
Organotin sulfides are usually prepared by re-
acting aqueous Na2S with organotin chlorides. The insol-
uble organotin sulfides precipitate and are removed by
filtration. Moisture is removed from the wet sulfides by
heating at elevated temperatures. During the drying op-
eration, it is possible that the polymeric sulfides are
further polymerized and thus become less reactive. For
these dried and less reactive sulfides, a catalyst, e.g.,
dimethylformamide) is required to effect reaction with
active organic halides.
Unexpectedly, by contrast, wet newly prepared
organotin sulfides react readily in the absence of a cata-
lyst.
As compounds of the formula R1X or R11X there
can be used in the present invention: methyl chloroace-
tate, methyl bromoacetate, ethyl chloroacetate, propylchloroacetate, propyl bromoacetate, butyl chloroacetate,
butyl bromoacetate, hexyl chloroacetate, hexyl bromoace-
tate, octyl chloroacetate, octyl bromoacetate, isooctyl
chloroacetate, isooctyl bromoacetate, 2-ethylhexyl chloro-
acetate, 2-ethylhexyl bromoacetate, isodecyl chloroacetate,
105'~8¢4
isodecyl bromoacetate, decyl chloroacetate, decyl bromo-
acetate, dodecyl chloroacetate, dodecyl bromoacetate,
hexadecyl chloroacetate, hexadecyl bromoacetate, octadecyl
chloroacetate, octadecyl bromoacetate, eicosanyl chloro-
acetate, eicosanyl bromoacetate, cyclopentyl chloroacetate,cyclopentyl bromoacetate, cyclohexyl chloroacetate, cyclo-
hexyl bromoacetate, benzyl chloroacetate, benzyl bromo-
acetate, vinyl chloroacetate, vinyl bromoacetate, allyl
chloroacetate, allyl bromoacetate, methallyl chloroacetate,
methallyl bromoacetate, crotyl chloroacetate, crotyl bromo-
acetate, 3-bromopropyl octoate, 2-bromoethyl pelargonate,
3-bromopropyl acetate, 3-bromopropyl stearate, 2-chloro-
ethyl linoleate, 2-chloroethyl linolenoleate, oleyl chloro-
acetate, oleyl bromoacetate, 2-chloroethyl acetate, 2-
bromoethyl acetate, 2-chloroethyl propionate, 2-bromoethyl
propionate, 2-chloroethyl butyrate, 2-bromoethyl butyrate,
2-chloroethyl valerate, 2-bxomoethyl valerate, 2-chloro-
ethyl pivalate, 2-bromoethyl pivalate, 2-chloroethyl cap-
roate, 2-bromoethyl caproate, 2-chloroethyl octoate, 2-
bromoethyl octoate, 2-chloroethyl decanoate, 2-bromoethyl
decanoate, 2-chloroethyl laurate, 2-bromoethyl laurate,
2-chloroethyl palmitate, 2-bromoethyl palmitate, 2-chloro-
ethyl stearate, 2-bromoethyl stearate, 2-chloroethyl eico-
sanate, 2-bromoethyl eicosanate, 2-chloroethyl acrylate,
2-bromoethyl acrylate, 2-chloroethyl me~hacrylate, 2-
~05'~80~
bromoethyl methacrylate, 2-chloroethyl crotonat~, 2-bromo-
ethyl crotonate, 2-chloroethyl oleate, 2-bromoethyl ol~ate,
allyl chloride, allyl bromide, methallyl chloride, meth-
allyl bromide, benzyl chloride, benzyl bromide, methyl 2-
chloropropionate, methyl 2-bromopropionate, methyl 3-
chloropropionate, methyl 3-bromopropionate, ethyl 2-chloro-
propionate, ethyl 2-bromopropionate, ethyl 3-chloropropi-
onate, ethyl 3-bromopropionate, propyl 2-chloropropionate,
propyl 3-bromopropionate, butyl 2-bromopropionate, butyl
3-chloropropionate, octyl 2-chloropropionate, octyl 3-
chloropropionate, octyl 2-bromopropionate, octyl 3-bromo-
propionate, isooctyl 2-chloropropionate, isooctyl 2-bromo-
propionate, isooctyl 3-bromopropionate, isodecyl 2-chloro-
propionate, isodecyl 2-bromopropionate, isodecyl 3-chloro-
propionate, n-decyl 3-bromopropionate, dodecyl 2-chloro-
propionate, tetradecyl 3-chloropropionate, hexadecyl 2-
chloropropionate, hexadecyl 3-chloropropionate, octadecyl
2-chloropropionate, octadecyl 3-chloropropionate, octa-
decyl 2-bromopropionate, octadecyl 3-bromopropionate, 2-
ethylhexyl 3-chloropropionate, 2-ethylhexyl 2-chloropro-
pionate, eicosanyl 3-chloropropionate, cyclohexyl 2-chloro-
propionate, cyclohexyl 3-bromopropionate, cyclohexyl 3-
chloropropionate, benzyl 2-chloropropionate, benzyl 3-
chloropropionate, benzyl 2-bromopropionate, vinyl 2-chloro-
propionate, vinyl 3-bromopropionate, allyl 2-chloropropi-
105'~804
onate, allyl 3-chloropropionate, allyl 2-bromopropionate,
allyl 3-br~mopropionate, methallyl 3-chloropropionate,
crotyl 2-chloropropionate, oleyl 2-chloropropionate,
oleyl 3-chloropropionate, oleyl 2-bromopropionate, oleyl
3-bromopropionate.
Examples of starting materials of the formula:
S
(RSn)2S
are monomethyltin sulfide, monoethyltin sulfide, mono-
butyltin sulfide, monooctyltin sulfide, monododecyltinsulfide, monooctadecyltin sulfide, monoeicosanyltin sul-
fide, monocyclohexyltin sulfide, monocyclopentyltin sul-
fide, monovinyltin sulfide, mono-2-ethylhexyltin sulfide,
monoallyltin sulfide, monomethallyltin sulfide, monooleyl-
tin sulfide, monophenyltin sulfide, mono-p-tolyltin sul-
fide, mono-p-butylphenyltin sulfide, monobenzyltin sul-
fide.
Examples of starting materials within the for-
mula:
R2
/ SnS
R3
are dimethyltin sulfide, diethyltin sulfide, methyl butyl-
tin sulfide, dipropyltin sulfide, dibutyltin sulfide, di-
hexyltin sul~ide, dioctyltin sulfide, di-2-ethylhexyltin
~ 0S'~804
sulfide, diisooctyltin sulfide, bis(dodecyltin) sulfide,
bis(octadecyltin) sulfide, bis(eicosanyltin) sulfide, bis
(cyclohexyltin) sulfide, divinyltin sulfide, diallyltin
sulfide, dimethallyltin sulfide, dicrotyltin sulfide, di-
oleyltin sulfide, diphenyltin sulfide, mono-methyl-mono-
phenyltin sulfide, di-p-tolyltin sulfide, di-p-butylphenyl-
tin sulfide, dibenzyltin sulfide.
Examples of starting materials within the for-
mula:
. R4 \ / R4
R5 - Sn - S - Sn - R5
R6 R6
are: bis(trimethyltin~sulfide, bis(triethyltin)sulfide,
bis(tributyltin)sulfide, bis(trioctyltin)sulfide, bis(tri-
octadecyltin)sulfide, bis(trivinyltin)sulfide, bis(tri-
allyltin)sulfide, bis(trimethallyltin).sulfide, bis(tri-
oleyltin)sulfide, bis(triphenyltin)sulfide, bis(tri-p-
tolyltin)sulfide, bis(tribenzyltin)sulfide.
Many of the products prepared in the present in-
vention are old. Thus, Leistner U.S. Patent 2,641,596discloses some of the non-chlorine containing compounds
prepared by reaction (3). Brecker U.S. Patent 3,565,931
shows many compounds which can be prepared from the com-
pounds made by reaction (1). Hoye U.S. patent 3,542,825
discloses many compounds prepared by reaction (2) and (4)
--10--
~OS'~804
as does the similar Briti~h Patent 1,117,652. Wowk U.S.
Patent 3,665,025 and British Patent 1,297,550 disclose
some of the compounds prepared by reaction (4) as well as
compounds somewhat similar to those prepared in reaction
S (1).
The organotin mercaptides prepared by reactions
(1), (2), (3) and (4) are useful for the same purposes as
Leistner, Brecker U.S. Patent 3,565,931, Brecker U.S.
Patent 3,630,992, Hoye, Wowk or British Patents 1,117,652
and 1,297,550. ~hey are particularly useful not only as
stabilizers but as intermediates for making stabilizers
for polyvinyl chloride resins by replacing the halogen
atom or atoms with oxygen, carboxyl, mercaptyl, or ester
mercaptyl; they are also less expensive than organotin
mercaptides prepared from mercaptans and organotin oxides
or halides.
The organotin mercaptide stabilizers prepared
in reactions (1), (2) and (3) of the present invention
can be used with halogen containing vinyl and vinylidene
resins in which the halogen is attached directly to the
carbon atoms. Preferably, the resin is a vinyl halide
resin, more preferably, a vinyl chloride resin. Usually,
the vinyl chloride resin is made from monomers consisting
of vinyl chloride alone or a mixture of monomers compris-
ing at least 7~% vinyl chloride by weight. When vinyl
105'~8~4
chloride copolymers are stabilized, preferably the copoly-
mer of vinyl chloride with an ethylenically unsaturated
compound copolymerizable therewith contains at lea~t 10%
of polymerized vinyl chloride.
As the halogen resin there can be employed
chlorinated polyethylene having 14 to 75%, e.g., 27h
chlorine by weight, polyvinyl chloride, polyvinylidene
chloride, polyvinyl bromide, polyvinyl fluoride, polyvinyl-
idene fluoride, copolymers of vinyl chloride with 1 to 90/0,
preferably, 1 to 3~% of a copolymerizable ethylenically
unsaturated material such as vinyl acetate, vinyl buty-
rate, vinyl benzoate, vinylidene chloride, diethyl fumar-
ate, diethyl maleate, other alkyl fumarates and maleates,
vinyl propionate, methyl acrylate, 2-ethylhexyl acrylate,
butyl acrylate and other alkyl acrylates, methyl metha-
crylate, ethyl methacrylate, butyl methacrylate and other
alkyl methacrylates, methyl alpha chloroacrylate, styrene,
trichloroethylene, vinyl ethers such as vinyl ethyl ether,
vinyl chloroethyl ether and vinyl phenyl ether, vinyl ke-
tones such as vinyl methyl ketone and vinyl phenyl ketone,l-fluoro-l-chloroethylene, acrylonitrile, chloroacrylo-
nitrile, allylidene diacetate and chloroallylidene di-
acetate. Typical copolymers include vinyl chloride-vinyl
acetate (96.4 sold commercially as VY~W), a vinyl chlor-
ide-vinylacetate (87:13), vinyl chloride-vinyl acetate-
-12-
105'~804
maleic anhydride (86:13-1), vinyl chloride-vinylidene
chloride (95:5), vinyl chloride-diethyl fumarate (95:5),
vinyl chloride-trichloroethylene (95:5), vinyl chloride-
2-ethylhexyl acrylate (80:20).
The stabilizers of the present invention can be
incorporated with the re~in by admixing in an appropriate
mill or mixer or by any of the other well-known methods
which provide for uniform distribution throughout the
resin compositions. Thus, mixing can be accomplished by
milling on rolls at 100-160C.
In addition to the novel stabilizers there can
also be incorporated with the resin conventional additives
such as plasticizers, pigments, fillers, dyes, ultraviolet
light absorbing agents, densifying agents and the like.
If a plasticizer is employed, it is used in
conventional amount, e.g., 30 to 150 parts per 100 parts
of resin. Typical plasticizers are di-2-ethylhexyl phthal-
ate, dibutyl sebacate, dioctyl sebacate, tricresyl phos-
phate
The tin containing stabilizers are normally used
in an amount of 0.01 to 10% by weight of the resin, more
preferably 0.1 to 5% of the tin compound is used by weight
of the resin. The organotin mercaptide products of reac-
tions (1), (2) and (3) are clear, mobile liquids that are
soluble in hydrocarbon and polar solvents such as benzene,
-13-
~05'~8~4
toluene, acetone, and ethyl acetate. The mono- and dl-
organotin sulfides used as starting materials in re~c-
tions (1) and (2) are polymeric, high-melting solids and
are insoluble in the reaction products and in most solvents
that dissolve the reaction products. It is evident, t~ere-
fore, that the reaction products are not mere solutions
of the organotin sulfides.
Specific combinations of organotin sulfides and
RlX compounds in addition to those set forth in the work-
ing examples and mentioned as illustrative only and not
as limiting are given below. The numbers indicate the
number of moles of catalyst (and in reaction 1, also the
moles of other reactant) per mole of starting sulfide.
Reaction (1)
1. Monomethyltin sulfide + 2 methyl chloroacetate
2, Monooctyltin sulfide + 2 methyl bromoacetate
Monooctadecyltin sulfide + 2 isodecyl chloroacetate
4~ Monobenzyltin sulfide + 2 butyl chloroacetate
5. Monophenyltin sulfide + 2 cyclohexyl chloroacetate
6. Monoallyltin sulfide + 2 benzyl chloroacetate
7. Monomethyltin sulfide + 2 2-chloroethyl stearate
8. Monobutyltin sulfide + 2 2-chloroethyl oleate
9. Monocyclohexyltin sulfide + 2 2-chloroethyl acetate
10. Monomethyltin sulfide + 2 2-chloroethyl methacrylate
11. Monomethyltin sulfide + 2 dodecyl 3-chloropropionate
12. Monobutyltin sulfide + 2 allyl chloride
Reaction (2)
13. Dimethyltin sulfide + ethyl chloroacetate
14. Dibenzyltin sulfide + propyl bromoacetate
5 15. Dioctyltin sulfide + decyl chloroacetate
16. Dibutyltin sulfide + sec. butyl chloroacetate
17. Di-p-tolyltin sulfide + cyclohexyl bromoacetate
18. Dioleyltin sulfide + phenylethyl chloroacetate
19. dimethyltin sulfide + 2-chloroethyl palmitate
10 20. Dibutyltin sulfide + 2-bromoethyl crotonate
21. Dicyclohexyltin sulfide + 2-chloroethyl pivalate
22. Dimethyltin sulfide + 2-chloroethyl acrylate
23. Dimethyltin ~sulfide + isooctyl 3-bromopropionate
24. Dibutyltin sulfide + methallyl bromide
Reaction (3)
25. Bis (trimethyltin)sulfide + isopropyl chloroacetate
26. Bis(tribenzyltin)sulfide + 2-ethylhexyl chloroacetate
27, Bis(trioctyltin)sulfide + nonyl bromoacetate
28. Bis (tributyltin)sulfide + hexyl chloroacetate
20 29. Bis(triphenyltin)sulfide + isooctyl chloroacetate
30. Bis (triallyltin)sulfide + benzyl chloroacetate
31. Bis (trimethyltin)sulfide ~ 2-chloroethyl eicosanate
32. Bis(tributyltin)sulfide + bromoethyl methacrylate
33. Bis(tricyclohexyltin)sulfide + 2-chloroethyl myristate
25 34. Bis (trimethyltin)sulfide + 2-bromoethyl oleate
--15--
~05'~804
35. Bis(trimethyltin)sulfide + dodecyl 3-chloropropionate
36. Bis(tributyltin)sulfide + allyl chloride
Reaction (4)
37. Monomethyltin sulfide + 3 methyl chloroacetate
38. Monooctyltin sulfide + 3 methyl bromoacetate
39. Monooctadecyltin sulfide + 3 isodecyl chloroacetate
40. Monobenzyltin sulfide + 3 butyl chloroacetate
41. Monophenyltin sulfide + 3 cyclohexyl chloroacetate
42. Monoallyltin sulfide + 3 benzyl chloroacetate
43. Monomethyltin sulfide + 3 2-chloroethyl stearate
44. Mono~utyltin sulfide + 3 2-chloroethyl oleate
45. Monocyclohexyltin sulfide + 3 2-chloroethyl butyrate
46. Monomethyltin sulfide + 3 2-chloroethyl methacrylate
47. Monomethyltin sulfide + 3 hexyl 3-chloropropionate
48. Monobutyltin sulfide + 3 allyl bromide
The temperature is not critical, but heating is
usually employed, preferably between 130-155C. The tem-
perature is usually at least 90C. and can be as high as
200C. for example.
Unless otherwise indicated, all parts and per-
centages are by weight.
The lack of reaction by a dried sulfide without
the use of an aprotic solvent is shown in Example 1.
EXAMPLE 1:
One-tenth mole of dried dimethyltin sulfide was
-16-
~oszsO~
mixed with one-tenth mole of isooctylchLor~aceta~e arld
heated under nitrogen. At 90C, solution of the solid
dimethyltin sulfide was complete and a clear, nearly col-
orless liquid resulted. After a 2-hour reaction period
at 135-145C., the reaction mixture was cooled. At 90C.,
precipitation of unreacted dimethyltin sulfide began.
Precipitation was completed by cooling to 20C. The un-
reacted dimethyltin sulfide was removed by filtration and
freed of isooctylchloroacetate by washing with heptane.
~inety-seven percent of the starting dimethyltin sulfide
was recovered unchanged.
The reactivity of wet, freshly prepared sulfides
is shown by the following examples
EXAMPLE 2:
To 0.4 M of ~a2S in 100 g water was added 0.4
M of aqueous (50% H2O) Me2SnC12 over a 30-minute period
at 50-70C. The resulting slurry of Me2SnS was heated to
90C. and then mixed with 0.4 M of isooctylchloroacetate.
After heating to 95-105C. for 15 minutes, two clear lay-
ers formed. The lower organic layer was removed and re-
acted for 2 hours at 135-140C. under nitrogen. After
cooling to 25C. the reaction mixture was filtered to re-
move a trace of salt carried over from the wet sulfide.
The product is soluble in benzene in all proportions and
is believed to have the following structure
lOS'~:804
o
CH3\ S -- CH2C -- C8H17
Sn
CH3 C 1
Yield = 151 grams (155 calc)
Cl - 9.0% (cal'c 9.16%)
S - 8 . 3% (cal'c 8 . 2 6%)
Two-tenths of a mole of the above product was reacted with
O . 2 M of isooctylthioglycolate and 0.2 M of aqueous am-
10 monia to form dimethyltin bis (isooctylthioglycolate) ingood yield. This compound was tested as a stabilizer for
PVC and compared with dimethyltin bis(isooctylthioglyco-
late) prepared in the conventional manner from dimethyltin
dichloride and isooctylthioglycolate. Both performed
15 equally well,
EXAMPLE 3:
To 0.2 M (mole) of Na2S in 50 g of H20 was added
0.2 M of aqueous Me2SnC12 in 30 minutes at 50-70C. The
resulting slurry of Me2SnS was heated to 90C. and then
20 mixed with 0.2 M of 2-chloroethyloctanoate. After mixing
and heating for 15 minutes at 95-105C. the Me2SnS dis-
solved in the organic phase and two clear layers developed
upon settling. The lower organic phase was removed and
reacted for 2 hours at 145-155C. under nitrogen. Upon
25 cooling to 25C, no Me2SnS precipitated indicating com-
--18--
~0~'~8~4
pletion of the reaction. This intermediate was reac~ed
with 0.2 M of 2-mercaptoethyl octanoate and 0.2 M of aque-
ous ammOnia to form dimethyltin bis(2-thioethyloctanoate).
Yield - 94.8% (based on Me2SnC12)
5Appearance - colorlesq oil
PVC Stabilizer Performance - equivalent to the
same compound prepared from Me2SnC12 and 2-
mercaptoethyl octanoate.
The reactions involved in this example are believed to be:
10 Me2sncl2 + Na2S ~ Me2SnS
..
S - CH2CH20 - C -- C 7H15
Me2SnS + ClCH2CH20CC7H15 ~ Me2Sn
Cl (I)
O O
.. ..
(I~ + HSCH2CH2OCC7Hls--~Me2Sn(S-CH2CH2oc C~H15)2
EXAMPLE 4:
To a mixture of 50 g water, 0;2 M MeSnC13 and
0.2 M isooctylthioglycolate was added .2 M of dilute
aqueous NaOH then .2 M of dilute aqueous Na2S. The mix-
ture was heated to 80C and then settled. The lower or-
ganic phase was removed and mixed with 0.2 M iqooctyl-
chloroacetate and heated under nitrogen to 145-155C. for
2 hours. Upon cooling, this intermediate wa3 converted
to a finished stabilizer by treating with 0.1 mole of
--19--
s.~ . .
105Z~04
aqueous ~a2S. The reactions involved are believed to be:
O S o
,. .. ..
MeSnC13 + HSCH2C-OC8Hl7 + NaOH + ~a2S ~ MeSn-SCH21-C8H17
O .,
~ ClCH2C-OC8H17
MeSn(, ~CH2C-OcgHl7)2 <
ClO
MeSn(ScH2c~Oc8Hl7)2
S O
~a2S
~ MeSn(ScH2c~OcgHl7)2
Yield - 105 g (94.4%)
Appearance - colorless oil
PVC Stabilizer Performance - equivalent to the same com-
pound prepared from MeSnC13, isooctylthioglycolate
and Na2S.
EXAMPLE 5:
To a mixture of 50 g water, 0.2 M MeSnC13 and
0.2 M isooctylthioglycolate was added 0.2 M of dilute
aqueous ~aOH then 0.2 M of dilute aqueous ~a2S. The mix-
ture was heated to 80C. and then settled. The lower
organic phase was removed and mixed with 0.2 M isooctyl-
chloroacetate and heated under nitrogen to 145-155C. for
2 hours. Upon cooling, this intermediate was mixed with
0.2 M isooctylthioglycolate and 0.2 M of aqueous ammonia
to form methyltin tris-isooctylthioglycolate.
-20-
~05'~80~
Yield - 146 g (148.8 cal'c)
Appearance - colorless oil
PVC Stabilizer Performance - equivalent to the
same compound made from MeSnC13, i900ctyl-
thioglycolate and aqueous ammonia.
Reactions: O S O
.. .. ..
3 OH ~ ~a2S + HSCH2C-OcgHl7 ~ MeSnS-CH2C-1~8H17
~ ClCH2C-OC8H17
Me I D ( I CH2C -OC~3N17 ) 2 ~ .
.. O
l HSCH2c-Oc8Hl7 ~ Mesn(scH2c-oc ~ 17)3
NH40H
EXAMPLE 6:
The process of Example 4 was repeated except
that 2-mercaptoethyl octanoate was used in place of iso-
octylthioglycolate and 2-chloroethyloctanoate was used in
place of isooctylchloroacetate in the same molar amounts
to form thio-bis[methyltin bis(2-thioethyloctanoate)] in
good yield.
Appearance - pale yellow oil
PVC Stabilizer Performance - equivalent to the
same compound prepared from MeSnC13, 2-
mercaptoethyloctanoate and Na2S.
105'~8~4
Reactions: o S 0
,.
MeSnC13+HSCH2CH20-CC7H15+MaOH+Na2S ~ Mesn-s-cH2cH2-oc77Hl5
o
o ClCH2CH2-o-cc7Hl5
" ~ .
MeSn(S-CH2CH2-O-cc7Hl5)2 0
Cl "
¦ MeSn(SCH2cH2O-c-c7Hl5)2
10 ¦ ~a2S S O
~ MeSn(SCH2cH2O-c-c7Hl5)2
Example 7:
The process of Example 5 was repeated except
that 2-mercaptoethyl octanoate was used in place of iso-
octyl~hioglycolate and 2-chloroethyloctanoate was used
in place of isooctyl chloroacetate in the same molar
amounts to form methyltin tris(2-thioethyloctanoate) in
good yield.
Appearance - colorless oil
PVC Stabilizer Performance - equivalent to the
same compound made from MeSnC13 and 2-mer-
captoethyl octanoate.
Reactions:
-22-
105'~80g~
o S o
ll ll ll
MeSnC13+HSCH2CH20CC7Hls+NaOH~H2S ~ MeSn-SCH2CH20-CC ~7H15
o
o c lCH2CH20C-c 7H15
5MeSn(sCH2cH2Oc-c7Hl5)2 (
~1
¦ HSCH2CH2C-C7H15 MeSn(scH2cH2O-cc7Hl5)3
NH40H
EXAMPLE 8:
To 0.2 M of ~a2S in 50 g of H2O was added 0.2 M
of aqueous Me2SnC12 in 30 minutes at 50-70C. The result-
ing slurry of Me2SnS was heated to 90C. and then mixed
with 0.2 M of benzyl chloride. After mixing and heating
for 10 minutes at 95-100C. the Me2SnS dissolved in the
organic phase and two clear layers developed upon settling.
The lower organic phase was removed and reacted for 2 hours
at 145-155C. under nitrogen. Upon cooling to 30C., this
intermediate was reacted with 0.2 M isooctylthioglycolate
and 0.2 M of aqueous ammonia to form dimethyltin isooctyl-
thioglycolate-benzylmercaptide in good yield.
Appearance - yellow oil
Performance - when tested in PVC this compound
was found to be an effective stabilizer.
Reactions~
~ .
los~sa4
Me2SnC 12 + Na2S ~ Me2Sn 3
SCH2Ph
Me2Sn PhCH2Cl
\ Cl
,S-CH2Ph
NH40H
) Me2Sn O
SC~2C-0c8Hl7
HscH2c-oc8Hl7
EXAMPLE 9
To a mixture of S0 g H20, 0.2 M MeSnC13 and
0.2M isooctyl-thioglycolate was added 0.2 M of dilute
aqueous NaOH then 0.2 M of dilute aqueous Na2S. The mix-
ture was heated to 80C. and then settled. The lower prod-
uct layer was removed and mixed with 0.2 M of benzyl bro-
mide and heated under N2 to 145-155C. for 2 hours. Upon
cooling, this intermediate was mixed with 0.2 M of iso-
octylthioglycolate and 0.2 M of aqueous ammonia to form
methyltin bis(isooctylthioglycolate)benzylmercaptide in
good yield.
Appearance - yellow oils
Performance - when tested in PVC this compound
was found to be an effective stabilizer.
Reactions-
-24-
1~5'~80~
o S o
ll ll ll
MeSnC13 + HscH2c-oc8Hl7 ~ NaOH + Na2S ~ MeSn 5CH2c )C8Hl7
o
S-CH2C-Oc8Hl7 PhCH2Br
5MeSn-S-CH2-Ph
HscH2c-oc8Hl7
¦~ MeSn(SCH2c-ocgHl7)2
NH40H
S -CH2Ph
EXAMPLE 10:
To 0.2 M of Na2S in 50 g of H20 was added 0.2 M
of aqueous Me2SnCl2 over a 30 minute period at 50-70C.
The resulting slurry of Me2SnS was heated to 90C. and
then mixed with 0.2 M of isooctyl-3-chloropropionate.
After mixing and heating for 15 minutes at 95-105C., the
Me2SnS dissolved in the organic phase and two clear layers
developed upon settling. The lower organic phase was re-
moved and reacted for 2 hours at 145-155C. under nitro-
gen. Upon cooling, this intermediate was reacted with
0.2 M of isooctyl-3-mercaptopropionate and 0.2 M of aque-
ou~ NaOH to form dimethyltin bis-isooctylthiopropionate
in good yield.
Appearance - colorless oil
Performance - when tested in PVC this compound
was an effective stabilizer
-25-
lOS'~804
Reactions:
Me2SnC12 + Na2S ~ Me2SnS
O O
1 ..
SCH2CH2cOc8Hl7 ClCH2CH2C-C8H17 ,
Me2Sn
\ Cl
O O
.. ..
HscH2cH2c-oc8Hl7 MeSn(scH2cH2c~OcgHl7)2
~,
NaOH
EXAMPLE 11:
A slurry of 0.5 mole of monomethyltin sulfide
in water made by reacting aqueous Na2S with methyltin
tri-chloride is mixed with 1.0 mole of isooctyl chloro-
acetate and heated and further treated in the manner de-
scribed in Example 2. The structure of the product isbelieved to be:
fl fl
CH3 ,n-S-SnCH3 O
SCH2-cOc8Hl7
..
SCH2C-C8H17
EXAMPLE 12
Example 2 is repeated replacing the isooctyl
chloroacetate by the same molar amount of isooctyl-3-
chloropropionate to form:
~OS'~804
\ /
Sn
CH3 SCH2c~2cOc8Hl7
EXAMPLE 13:
Example 2 i~ repeated replacing the dimethyltin
dichloride by the same molar amount of dibutyltin dichlor-
ide to form:
C~Hg / Cl
Sn
C4H / SCH2COc8~17
EXAMPLE 14:
Example 11 is repeated replacing the methyltin
trichloride by the same molar amount of butyltin trichlo-
ride to produce the corresponding butyl analogue of the
product of Example 11.
EXAMPLE 15:
Example 2 is repeated replacing the i800ctyl
chloroacetate by the same molar amount of i~ooctyl bromo-
acetate to produce:
CH3 ~ r
Sn 0
CH3 SCH2cOc8Hl7EXAMPLE 16:
Example 8 i~ repeated replacing the benzyl chlo-
ride by the same molar amount of benzylbromide to fonm as
_27-
105'~84
the intermediate:
CH3\ Br
Sn
CH3 CH2-Ph
EXAMPLE 17
The procedure of Example 11 is repeated except
that 1.5 moles of isooctyl chloroacetate is employed.
The product is believed to be a mixture of equal molor
amounts of:
Cl C
CH3Sn(ScH2cOcgHl7)2 and
Cl O
CH3Sn-SCH2cOc8Hl7
Cl
In making the starting compounds for reaction
5, there can be reacted a compound of the formula RSnC13
with a compound of the formula HSRl + alkali metal ~e.g.,
sodium or potassium) or ammonium sulfide in water. The
compound HSRl can be any of the HSRl analogues of the
compounds RlX set forth above.
In the process of the invention as illustrated
in Examples 4-7 and 9, the organic phase reacted with the
isooctyl chloroacetate, 2-chloroethyl octoate or the
benzyl bromide was not dried and hence contained water.
As stated above, the temperature is not critical
-28-
lOS'~804
but is preferably between 130-155C. The temperature is
usually between 100C. and the boiling point of the cata-
lyst when a catalyst is employed. All of the catalysts
are liquids at the reaction temperatures.
EXAMPLE 18:
One-half mole of dlmethyltinsulfide was mixed
with 0.5 M of isooctylchloroacetate and 75.0 grams of di-
methylformamide and heated to 130 - 135C. for 2 hours.
Dimethylformamide was distilled from the reaction mixture
by heating to a final pot temperature of 110C. at 10 mm
Hg. The residue (product) was clarified by filtration
yielding 188.5 gms (97.3% of theoretical) of pale yellow
oil. It is soluble in heptane and acetone. An NMR spec-
trum of the product was consistent with expected struc-
ture:
O
C~ ~ S - CH2C - C8H17
CH "' ~ Cl
Cl - 9.2% (calculated 9.16%)
S - 8.4% (calculated 8.26%)
EXAMPLE 19:
One-half mole of monomethyltin sulfide
(CH3SnS)2S was mixed with 1.0 M of isooctylchloroacetate
and 150 gms of dimethylformamide and heated to 130 -
135C. for 2 hours. Dimethylformamide was recovered by
-29-
1Os~so4
vacuum stripping to 110C. at 10 mm Hg. The residue was
clarified by filtration yielding 370.0 gms of yellow oil
(95.0/O of theoretical). The product is soluble in benzene
and acetone. The structure is believed to be
fl Icl
CN3Sn --S ' SnCH3
O ~ Q
, ~CH2COC8H17 SCH2CC8H17
Cl - 9.4% (calculated 9.12%)
S - 11.9% (calculated 12.3%)
EXAMPLE 20
A mixture of 0.1 ~ of dimethyltin sulfide, 0.1
M of ben yl chloride and 40 gms of dimethylformamide was
heated to 130 - 135C. for 2 hours. After stripping to
110C. at lO mm Hg there remained 30.5 gms of pale yellow
oil. The theoretical yield is 30.7 gms for:
CH3 / Cl
/ Sn
CH3 SCH2Ph
S - 10.2% (calculated 10.4%)
Cl - 11.6% (calculated 11.5%)
EXAMPLE 21
A mixture of 0.1 M of dimethyltin sulfide, 0.1
M of 2-chloroethyloctoate and 40 gms of dimethylformamide
was heated under an atmosphere of nitrogen for 4 hours at
-30-
~05'~804
150C. After stripping to 120C at 10 mm Hg and filter-
ing to clarify, there was obtained 34.2 gms of yellow
oil. The theoretical yield is 39.7 gms for:
CH3 Cl
Sn O
CH3 S - CH2 - CH2 - oC - C7H15
Cl - 8.6% (calculated 8.94%)
S - 8.3% (calculated 8.06%)
EXAMPLE 22:
One-half mole of dimethyltinsulfide was mixed
with 0.5 M of isooctyl-3-chloropropionate and 75 grams of
dimethylacetamide and heated at 145-155C. for 4 hours.
After stripping to 120C. at 10 mm Hg and filtering to
clarify, there was obtained 194.6 grams of a yellow oil.
The theoretical yield is 200.7 grams for:
CH~ Cl
Sn O
CH3 S - CH2 - CH2C - C8Hl7
Cl - 8.5% (calculated 8.84%)
S - 8.1% (calculated 7.98%)
EXANPLE 23:
A mixture of 0.1 M of dimethyltin sulfide, 0.1
M of isooctylchloroacetate and 40 gms of dimethylsulfox-
ide was heated under nitrogen at 130C. for 1.5 hours.
After stripping to 110C. at 10 mm Hg there remained 32.0
-31-
~o5',~804
gms of red oil.
\ /
Sn 0
CH3/ S ~ CH2COC8H17
5 S ~ 8.5% (calculated 8.26~/o)
EXA,~lpLE 24
A mixture of 0.1 M of dimethyltinsulfide, 0.1 M
of isooctylchloroacetate and 30 gms of tris(dimethylamino)
phosphine oxide was heated at 130C. for 2 hours. After
stripping to 120C. at 10 mmHg there remai ned 37.1 gms
of yellow oil.
CH3\ Cl
Sn 0
/ \ 11
CH3 S - CH2COC8H17
15 Cl - 9. 3% (calculated 9.16%)
EX~MPLE 2 S:
A mixture of 0.2 M of dibutyltin sulfide, 0.2 M
of isooctylchloroacetate and 40.0 gms of dimethylformamide
was heated under ~2 for 2 hours at 130 - 135C. After
stripping and filtering there was obtained 93.8 gms of
yellow liquid. The theoretical yield is 94.3 gms for:
Sn
/ \
C4H9 S ~ CH2C ~ OC8H17
25 Cl - 7.2% (calculated 7.51%)
. ., ,~
~(~5'~804
S - 6.5% (calculated 6.7Ph)
EXAMPLE 26:
A mixture of 0.1 M of monobutyltin sulfide
S
(C4HgSn)2S, 0.2M of isooctylchloroacetate and 40.0 gms of
dimethylformamide was heated under nitrogen to 130 -
135C. for 2 hours. After stripping to 120C at 10 mm Hg
there was obtained 83.7 gms of viscous amber oil. The
theoretical yield is 86.1 gms for:
10Cl Cl
C4Hg- n S Sn - C4Hg
I I
SCH2COC8H17 SCH2CC8H17
Cl - 8.Gh (calculated 8.22%)
15 S -10.7h (calculated 11.1%)
EXAMPLE 27:
A mixture of 0.1 M of bis(tributyltin) sulfide,
0.1 M of isooctylchloroacetate and 20 gms of dimethylfor-
mamide was heated for 2 hours at 130 - 135C. After
20 stripping and filtering there remained 91.3 gms of yellow
oil.
Cl - 4.1% (calculated 4.32%).
EXAMPLE 28:
A mixture of 0.1 M of dimethyltin sulfide, 0.1
--33--
~05'~804
M of isooctylbromoacetate and 20.0 gms of dimethylforma-
mide, was heated under nitrogen for 2 hours at 130 -
135C. After stripping to 110C. at 10 mm Hg there re-
mained 37.8 gms of yellow oil. The theoretical yield is
43.2 gms for
CH3\ Br
Sn o
/ \
CH3 S - CH2 - C - OC8H17
Br - 17.9% (calculated 18.5%)
EX~MPhE 29
A mixture of 0.1 M of dimethyltin sulfide, 0.1
M of benzylbromide and 30 gms of dimethylformamide was
heated to 130C. for 2 hours. After stripping there re-
mained 33.8 gms of yellow oil. The theoretical yield is
35.2 for:
CH3 Br
Sn
CH3 CH2 - Ph
Br - 21.9% (calculated 22.P~)
EXAMPhE 30:
ne-half mole of monomethyltin sulfide
(CH3SnS)2S was mixed with 1.5 M of isooctylchloroacetate
and 150 gms of ~-methyl-2-pyrrolidone and heated to
130 - 135C. for 2 hours. The ~-methyl-2-pyrrolidone
was recovered by vacuum stripping to 120C. at 10 mm Hg.
-34-
~05'~8~)4
The residue was clarified by filtration yielding 465 gms
of amber oil (94.~/O of theoretical). Sulfur - 9.6% found
(9.76% calculated); chlorine - 10.9% found (10.82% cal-
culated). The postulated reaction is:
oCl O
~cat ' "
(CH3SnS)2S + 3ClCH2C-O-C8Hl7 ~ CH3Sn(S-CH2c-oc8Hl7)2 +
Cl O
"
CH3Sn-S -CH2C-OC8Hl7
Cl
lO As shown in Example 30 by varying the mole
ratio of monoorganotin sulfide to RlX compound from 1:2
to 1:3 the products obtained are changed. In place of
the (CH3SnS)2S in Example 30 there can be used any of the
S
other compounds of the formula (RSn)2S set forth above
and in place of the isooctyl chloroacetate there can be
used any of the other compounds of the formula RlX set
forth above,
