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Патент USA US3078301

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United States Patent
3,018,290
ice
1
Patented Feb. 19,
.
‘2
.
..
where n, R and R1 are as‘de‘?ned above and R7
alliyl,
'aralkyl or ar'yl.
3,078,290
DIHYDROCARBUNTIN SALTS 0F
.
CARBOXY MERCAPTALS
Ingenuin 'Hechenbleikner, Kenwood, Robert ‘E. 'Bresser,
Sharonville, ‘and Otto A. Homberg, Woodlawn, (ihio,
assignors to Carlisle Chemical Works, Inc., Reading,
Ohio, a'corpo'ration of Ohio
No Drawing. Filed Apr.'17, ‘1961, Ser. No. 103,256
8 Claims. (Cl. 260-42937)
The present invention relates to novel thioacetals and
10 where ‘R,"R1, and n are de?ned as above, R8 is alkyl,
aralkyl or and and m is an integer from 0 to.8.
_
In another form of the invention certain thioacetal's
"and thioketals are mixed with dihydrocarbon tin oxides
thioketals and their use as stabilizers for halogen-con
taining resins.
or sul?des.
Y It is an object of the present invention to prepare novel
“ thioacetals and thioketals.
_
(VI)
I
I A further object is to extend the heat and light sta
bility of halogen-containing resins.
I
,
‘
, a,
\r /
,
H
noo<ona..—sv
v/G\'R,
noo(onz)n—"s
An additional object is to provide novel stabilized vinyl 20
resin‘ compositions.
r
formulae:
v ‘Another object is, to prepare novel dihydrocarbon tin
salts of acids having a thioketal or thio'acetal group.
.
The thioacetals and thioketals have the following
>
‘II
_ Yet another object is to provide novel synergistic sta~
bilizers for halogen-containing resins.
or
Still further objects and the entire scope of applicability
of the present invention will become apparent from the 25 (VI/1)
detailed description given hereinafter; it should be under
stood, however, that the detailed description ‘and spe
ci?c examples, while indicating preferred embodiments
of the invention, are given by way of illustration only,
since various changes and modi?cations within the spirit
and scope of the invention will become apparent to those
H
nooooni
nooo- —s
H
R,
\
nooo-ons/ \Ra
HOOCCH?
(v11)
skilled in the art from this detailed description.
,
(sin
||
droca'rbon tin salts of acids having a thioacetal or ithio
~ke£al grouping. Such compounds belong to one of the 35
‘following groups
'
.
.
v/
moownnao.
Ru SR5
, In one form of the invention there are prepared dihy
(VIII)
'0
u
.
,R
/ '
> 1100-
_
/ -o\
S
a
R:
I(IX) I
H
mson'zswnnnoon
(X)
'
45
H0 (I'l (OHzlr-S
O
S (CH2) no 0011
.
.
.
,
‘
g In Formulae VI through X the de?nitions of m,j_n, ‘R5,
50 R3, R4, R5, R6, R7 and R8 are the same as those de?ned
where n is an integer from 1 to 8, R and R1 are alkyl,
above and R9 is hydrogen or alkyl.
aralkyl or ar‘yl and R2 and Raare hydrogen, alkyl, alken
As the dihydrocarbon tin oxide or sul?de there can- be
9-1, aralkyl, aryl, hydroxyaryl, alkoxyaryl or taken ‘together
used dimethyl tin oxide, dibutyl tin oxide, dioctyl tin
oxide, dilauryl tin oxide,'butyl lauryl tin oxide, dioctadecyl
complete a cyclohexane ring, i.e. the pentamethylene
radical.
(II)
R
in)
tin oxide, diph‘enyltin oxide, dimethyl tin sul?de, dibutyl
/SR‘
>sn<o (oni)n(lJ\ )
R1
tin sul?de, dioctyl tin sul?de, dilauryl tin sul?de, diphenyl
tin sul?de, dioctadecyl tin sul?de, dicyclohexyl tin ‘oxide,
R0 SE5 2
etc.
alkyl, aralkyl, aryl, mercaptocarboxylic acidor mercapto
60 tin propane-2,2-bis (mercaptopropionate) _
carboxylic acid ester and R6 is hydrogen, alkyl benzyl or
0411K / oooomonls\ /CH2
R:
(III)
‘ [ 04H»/S“\ oooonzonzs/0\ CH3
65
2
Ba
where R, R1, R2 and R3 are as de?ned above.
(IV)
1
Typical examples of compounds in group I are dibutyl
where n, R and R1 are as de?ned above, R4 and R5 are
R
70
dibutyl tin benzaldi (mercaptoacetate), dibutyl tin ben
zaldi (mercaptop-ropionate), dibutyl tin 2-hydroxyben
zaldi (mercaptopropionate), dineopentyl tin propane-2,2
bis (mercaptopropionate), dibutyl tin isodecane ‘LL-bis
(mercaptopropionate), dioctyl tin propane >2,2-bis.(_n'1_er
captopropionate), dibutyl tin cyclohexyl 1,1.-bis ,(mercap
topropionate), dimethyl tin propane 1,2-bis (omega mer
3,078,290
3
4
captooctanoate), dioctadecyl tin methane bis (mercapto
acetate), diphenyl tin propane 2,2-bis (mercaptopro
pionate), dibutyl tin propene 3,3-bis (mercaptopro
pionate), butyl lauryl tin phenylacetaldi (mercaptoace
tate), dihexyl tin 2-butene-l,1-bis (mercaptopropionate),
dibutyl tin diphenyl methane bis(mercaptopropionate)
captoacetic acid), diphenylmethane-bis (mercaptopro
picnic acid), propene-3,3~bis (mercaptopropionic acid),
2-butene-l,1-bis (mercaptopropionic acid), propane-2,2
bis (mercaptosuccinic acid), 2-hydroxybenzaldi (2’-mer
captobenzoic acid), propane-2,2-bis (mercaptooctanoic
acid), phenylacetaldi (mercaptoacetic acid), propane-2
mercaptoacetic acid-Z-mercaptopropionic acid, and 2-hy
droxy-4-methoxybenzaldi (mercaptobutyric acid).
Typical examples of compounds in group VII are 4,4
0
10
dibenzyl tin propane-Z-mercaptoacetate-2-mercaptopro
pionate, dibutyl tin 2-hydroxy-4-methoxybenzaldi (mer
captobutyrate) and dibutyl tin propane 2,2-bis (mercap
tosuccinate) .
bis (carbobutoxyethylthio) valeric acid, 4,4-bis (dodecyl
thio) valeric acid, 4,4-bis (phenylthio) valeric acid, 4,4
bis (carboxyethylthio) Valerie acid, ethyl~3,3-bis (car
boxyethylthio) butyrate
SOHzCBzCOOH
[01 3 301320 0 C21 3]
15
Typical examples of compounds in group II are dibutyl
SCHsCHaCOOH
tin di [4,4-bis (dodecylthio) valerate]
C4Hn
\
/
3,3-bis (benzylthio)-3-phenylpropionic acid.
SOuHza
Typical examples of compounds in group VIII are 2
20
/Sn OOCOHaCHaCQH:SOnHz:
hydroxybenzaldi (2'-mercaptobenzoic acid), propane-2,2
bis (2'-mercaptobenzoic acid), methane-bis (4-mercap
n
tobenzoic acid), methane bis (3-mercaptobenzoic acid),
dibutyl tin di [4,4‘-bis (phenylthio) valerate], dioctadecyl
ethane-1,1-bis (2'-mercaptobenzoic acid), phenylmethane
tin di [4,4-bis (phenylthio) valerate], dioctyl tin di [4,4
(2-mercaptobenzoic acid).
,
bis (carboxyethylthio) valerate], butyl octyl tin di [4.4 25 bisTypical
examples of compounds in group IX are dodec
bis (carbobutoxyethylthio) valerate], dimethyl tin di [4,4
ylthiomethyl mercaptoacetic acid, methylthiomethyl mer
bis (dodecylthio) valerate], dioctyl tin di [ethyl 3,3-bis
captopropionic
acid, phenylthiomethyl mercaptooctanoic
(carboxyethylthio) butyrate]
acid, benzylthiomethyl mercaptoacetic acid, butylthio
04H.
‘ methyl mercaptopropionic acid.
30
Typical examples of compounds in group X are ethane~
diphenyl tin di [3,3-bis (benzylthio)-3-phenyl propio
nate].
‘
,
l,l,2,2-tetrakis (mercaptopropionic acid), l-methylethane
,1,l,22~tetrakis (mercaptoacetic acid), pentane-2,2,4,4
tetra (mercaptopropionic acid), ethane-1,1,2,2-tetrakis
(mercaptoacetic acid), 1,1,4,4-tetrakis-(mercaptopropi
Typical examples of compounds in group III are di 35 onic acid) hexane l,1,6,6-tetrakis (mercaptooctanoic
butyl tin Z-hydroxybenzaldi (2'-n1ercaptobenzoate), di
acid).
butyl tin propane-2,2-bis (2'-mercaptobenz0ate)
The compounds in groups VI, VIa, VII, VIII, IX and
CH3
5
C4Ho\
X can be prepared by any of procedures A to D below.
Unless otherwise indicated all parts are by weight and
40 are expressed in grams.
PROCEDURE A
G
I
SH 0000
C4HI/
‘
\CH'
2
The aldehyde or ketone and mercaptan are mixed in a
diphenyl tin methane-bis (4-mercaptobenzoate), dilauryl
1 to 2 molar ratio. This procedure is particularly effec
tin diphenyl methane bis (3-mercaptobenzoate), dimethyl
tive with mercaptans such as mercaptoacetic acid which
45
tin ethane-1, l-bis (2'-mercaptobenzoate).
are su?iciently strong acids for an exothermic reaction
Typical examples of compounds in group IV are di
to occur. The product if a solid is air dried. It can‘be
butyl tin di (dodecylthiomethyl thioacetate)
further puri?ed if desired by recrystallization from an
appropriate solvent such as water, benzene-hexane mix
dilauryl tin di (methylthiomethyl-thiopropionate), di 50 tures for example. If the product is a liquid it is recov
ered by stripping o?? lower boiling materials by vacuum
methyl tin di (phenylthiomethyl-thiooctanoate), diphenyl
distillation.
tin di (benzylthiomethyl-thioacetate).
PROCEDURE B
Typical examples of compounds in group V are di (di
butyl tin) ethane 1,l,2,2-tetrakis (mercaptopropionate)
04H’
OOOCHzCHr-S
SOHzOHgGOO
C4H9
This procedure is the same as procedure A except that
55 the reaction is catalyzed by a small quantity of acid, tag.
1 cc. of concentrated hydrochloric acid.
PROCEDURE C
01H,
OOCCHaCHr-S
SOHzOHgCOO
O4Hv
This procedure is the same as procedure A, except that
di (dioctyl tin)-1-methyl ethane 1,1,2,2-tetrakis (mercap
toacetate), di (diphenyl tin) butane-l,l,4,4-tetrakis (mer 60 a small quantity of zinc chloride, e.g. 0.5 gram is used
to catalyze the reaction.
captopropionate), di (dilauryl tin) hexane-1,l,6,6-tetralds
(mercaptooctanoate) .
PROCEDURE D
Typical examples of compounds in groups VI and VIa
A solution of one mole of carbonyl compound and two
are benzaldi (mercaptoacetic acid), benzaldi (mercapto
moles of mercaptan in 200 ml. of toluene was heated
propionic acid), 2-hydroxybenzaldi (mercaptoacetic acid), 65 under
re?ux in the presence of a catalytic quantity of acid,
Z-hydroxybenzaldi (mercaptopropionic acid), 4-hydroxy
e.g. 0.5 gram of p-toluenesulfonic acid until the calculated
S-methoxy-benzaldi (mercaptopropionic acid), cyclohex
quantity of water had been collected. The reaction solu
y1-1,1lbis (mercaptoacetic acid), cyclohexyl-l,l-bis (mer
tion was then washed with water, dried and the solvent
captopropionic acid), methane-bis-(mercaptoacetic acid), 70 removed under reduced pressure.
methane-bis (mercaptopropionic acid), isodecane-l,l
bis (mercaptoacetic acid), isodecane-1,l-bis (mercap
topropionic acid), propane-2,2-bis (mercaptoacetic acid),
‘propane-2,2-bis (mercaptopropionic acid), 4-methylpen
tane-2,2-bis (mercaptoacetic acid), butane-Z-Z-bis (mer
, Example 1
Using procedure A one mole of benzaldehyde and two
moles of mercaptoacetic acid were mixed together. An
exothermic reaction occurred. The product was air dried.
3,978,290
5
6'
It was benzaldi (mercaptoacetic acid) having a melting
to produce propane-2,2_-his (mercaptopropionic acid) ‘as
a solid having a melting point of 76-78° C.
Example 14
Using procedure B (Example 2) one mole of methyl
point of 127° C. and the formula
SCHzCO OH
641%
.
isobutyl ketone and two moles of mercaptoacetic acid were
sGHiQ 0 0H
reacted to produce 4-methylpentane-2,2-bis (mercapto~
Example 2
Using procedure B one mole of benzaldehyde, two moles
of mercaptopropionic acid were mixed together along with
acetic acid) as a solid having a melting point of 81—84° C.
Example 15
Using procedure B (Example 2) one mole of methyl
one ml. of 37% hydrochloric acid. The product was air
dried to yield benzaldi (mercaptopropionic acid) as a
ethyl ketone and two moles of mercaptoacetic acid were
waxy solid.
as a solid having a melting point of 102-104" C.
reacted to produce butane-2,2-bis (mercaptoacetic acid)
.
Example 3
Example 16
Using procedure A one mole of salicylaldehyde and
two moles of mercaptoacetic acid were reacted to produce
Z-hydroxybenzaldi (mercaptoacetic acid) as a waxy solid.
Using procedure B (Example 2) one mole of levulinic
acid and two moles of mercaptopropionic acid were re
acted to, produce 4,4-bis (carboxyethylthio)-v'aleric acid
as a solid having a melting point of 146-149‘‘7 C. and
Example 4
having the formula
Using procedure B one mole of salicylaldehyde and 20
SOHzCHzOOOH
two moles of mercaptopropionic acid where reacted to pro
CHzOHzCOOH
duce Z-hydroxybenzaldi (mercaptopropionic acid) as an
SCHzCH2C O OH
oil.
Example 1.7
Example 5
25
Using
procedure
D.
one
mole of levulinic acid and two
Using the procedure of Example 2 (procedure B) one
moles of butyl mercaptopropionate were added to 200
mole of vanillin and two moles of mercaptopropionic acid
ml. of toluene, 0.5 gram of p-toluenesulfonic acid added
were reacted to produce 4-hydroxy-3-methoxybenzaldi
and the mixture heated under re?ux. The distillation was
(mercaptopropionic acid) as a solid having a melting
continued until the theoretical amount of water had been
point of 124-126” C.
30 collected. The toluene solution was then washed with
Example 6
water and the toluene removed by distillation under a
Using procedure B (Example 2) one mole of cyclo
vacuum (about 20 mm)- There was recovered 4,4»bis
hexanone and two moles of mercaptoacetic acid were re
(carbobutoxyethylthio)-valeric acid as an oil having the
acted to produce cyclohexyl-1,1-bis (mercaptoacetic acid)
formula
as a solid having a melting point of 124-129” C.
35
Example 7
Using procedure B (Example 2,) one mole of cyclo
hexane and two moles of mercaptopropionic acid were
reacted to produce cyclohexyl-l,1-bis (mercaptopropionic
"
sornomo o o O4Ha
OHa CHzCHzCOOH
0113011200 0 04119
40
Example 18
‘ Using procedure C one mole of levulinic acid and two
acid) as a solid having a melting point of _87-91° C.
moles of lauryl mercaptan were mixed together along
with 0.5 gram. of zinc chloride. The product obtained
Example 8
was a waxy solid and was further puri?ed by recrystallizar
mole of 37% aqueous formaldehyde and two moles of 45 tion' from hexane to. yield 4,4»bis-(dodecylthio) valeric
acid‘ as a- waxy solid.
mercaptoacetic acid were reacted to produce methane-bis
(mercaptoacetic acid) as a solid having a melting point
Example 19
of 119-122° C.
Using the procedure of Example 2 (procedure B) one
Using procedure D (Example 17)‘ onemole. of levulinic
Example 9
acid and two moles'of thiophenol were added to 200 ml.
50
Using procedure B (Example 2) one mole of 37%
of toluene and 0.5 gram of p-toluenesulfonic acid and the
aqueous formaldehyde and two moles of mercaptopropi
onic acid were reacted to produce methane-bis (mercapto
propionic acid) as a solid having a melting point of 140
141° C.
Example 10
Using procedure A (Example 1) one mole of isodec
mixture re?uxed. When the theoretical amount of water
had collected the toluene solution. was washed with water
and the toluene removed under vacuum. There was re
55 covered 4,4-bis-(phenylthio) valeric acid as an oil.
Example 20
Using procedure B (Example 2) one mole of ethyl
aldehyde and two moles of mercaptoacetic acid were re
acted to produce isodecane-1,1-bis (mercaptoacetic acid)
as a liquid.
Example 11
Using procedure B (Example 2) one mole of isodec
acetoacetate and two moles of mercaptopropionic acid
60 were reacted to produce ethyl-3,3-bis (carboxyethylthio)
butyrate as an oil having the formula
SGHzOHzOOOH
aldehyde and two moles of mercaptopropionic acid were
reacted to produce isodecane-l,l-bis (mercaptopropionic 65
acid) as a liquid.
Example 12
Using procedure A (Example 1) one mole of acetone
and two moles of mercaptoacetic acid were reacted to
CH3 ~ 011200002135
SCHzCHzCOOH
Example 21
Using procedure B (Example 2)‘ one mole ofibenzo
phenone and two moles of mercaptopropionic acid were
reacted. to produce diphenylmethane-bis (mercaptopro
produce propane-2,2-bis (mercaptoacetic acid) as a solid 70 pionic acid) as a solid having a melting point of 130° C.
'having a melting point of 129—l30° C.
and having the formula.
C5135
SCHzCHzCOOH
Example 15’
\ /
Using procedure B (Example 2) one mole of acetone
and two moles of mercaptopropionic acid were reacted 75
3,078,290
7
Example 22
Using procedure B (Example 2) one mole of acrolein
and two moles of mercaptopropionic acid were reacted to
PROCEDURE F
A mixture of one equivalent of carbonyl compound
and two equivalents of mercaptoalkanoic acid or similar
compound were heated under re?ux in 300 ml. of toluene,
containing a catalytic quantity, e.g. 0.5 gram, of
produce propene-3,3-bis (mercaptopropionic acid) as a
waxy solid having the formula
p-toluenesulfonic acid until the calucuated quantity (one
SOHaCHzCOOH
equivalent) of water had collected. One equivalent of
dialkyl tin oxide (or diaryl tin oxide or diaralkyl tin
CHFCH H
omomooorr
oxide) was then added and re?ux continued until a
Example 23‘
Using procedure B (Example 2) one mole of proton
aldehyde‘and two moles of mercaptopropionic acid were
reacted to produce 2-butene-1,1-bis (mercaptoproplonic
10
produce ethane-1,l,2,2-tetrakis-(mercaptopropionlc acid)
20 other mercaptal) in 200 ml. of acetone and ?ltered. The
second equivalent of water had distilled. The product
was then ?ltered warm and the solvent removed under
reduced pressure.
I
PROCEDURE G
15
acid) as a waxy solid.
A solution of one mole of dialkyl tin dihalide in 300
Example 24
ml. of ether was shaken with two moles of 50% aqueous
sodium hydroxide to form the dialkyl tin hydroxide.
Using procedure B (Example 2) one mole of glyoxal
The ethereal solution was then poured into a solution of
and four moles of merca-ptopropionic acid were reacted to
as a solid having a melting point of 162“ C. and having
the formula
one mole of his (mercaptoalkanoic acid) mercaptal (or
product was isolated by evaporation of the solvent and
trituration of the residue with hexane. Diary] tin dihalides
HOOCCHzCHz-S
sornomcoon
can be used in place of the dialkyl tin dihalides.
CHO
PROCEDURE H
25
noooomom-s
somomooon
The mercaptoalkanoic acid (or similar compound) was
Example 25
treated with an amount of the dialkyl tin oxide (or diaryl
tin oxide or diaralkyl tin oxide) suf?cient to give a neutral
Using procedure B (Example 2) one mole of acetone
tin salt (e.g. 1 mole of a mercaptoalkanedioic acid for
and two moles of mercaptosuccinic acid were reacted to
30
each mole of dialkyl tin oxide). Then 300 ml. of benzene
produce propane-2,2-bis (mercaptosuccinic acid) as a
or toluene was added and the mixture was re?uxed under
waxy solid having the formula
a moisture trap‘ until the calculated quantity of water had
01110003
been removed. The solvent was stripped and the product
crystallized if solid and remained as a high boiling residue,
35
if liquid.
Example 28
\SCHOO OH
. One mole of dibutyl tin oxide and one mole of propane
HaOO OH
2,2-bis (mercaptopropionic acid) were heated under re
Example 26
Using procedure D (Example 17) one mole of sali
40 ?ux in 300 ml. of toluene until one mole of water had
collected. The reaction mixture was ?ltered warm and
cylaldehyde and two moles of 2-mercaptobenzo1c acid
stripped of toluene under reduced pressure (20 mm.) to
were added to 200 ml. of toluene and 0.5 gram of
yield dibutyl tin propane-2,2-bis (mercaptopropionate) of
p-toluenesulfonic acid and the mixture re?uxed. When
the formula
the theoretcial amount of water had collected the toluene
solution was washed with water and the toluene removed 45
04H]
under vacuum. There was recovered Z-hydroxybenzaldi
(2’-mercaptobenzoic acid) as a solid having the melting
point 141-145" C. and having the formula
C4Hn
80
/ do OH
Q OH
A. \
0 0 UCHzCHrS
\ /
/s§
CH1
0
OOCOHJCHQS/ \CHI
as a solid having a melting point of 58-60” C.
50
Example 29
Using procedure E (Example 28) one mole of dibutyl
tin oxide and one mole of benzaldi (mercaptoacetic acid)
'were reacted to produce dibutyl tin benzaldi (mercapto
00 on
55 acetate) of the formula
s
04H:
O O C CHaS
Sn
ESQ
Example 27
Using procedure B (Example 2) one mole of 37%
aqueous formaldehyde was reacted with one mole of 60 as a solid having a melting point of 157—l62° C.
dodeycl mercaptan and one mole of mercaptoacetrc acid
Example 30
to produce dodecylthiomethylthioacetic acid.
Using procedure E (Example 28) one mole of dibutyl
The compounds in groups I, la, II, III, IV, and V can
tin oxide and one mole of benzaldi (mercaptopropionic
be prepared by any of procedures E to H below.
65 acid) were reacted to produce dibutyl ‘in benbaldi (mer
PROCEDURE E
captopropionate) as a solid having a melting point of 79—
89 C.
Equimolar quantities of dialkyl tin oxide (or diaryl tin
oxide or diaralkyl tin oxide) and the his (mercaptoalkano
Example 31
ic acid) or similar compound were heated under re?ux in
300 ml. of toluene until the calculated quantity of water 70
(one equivalent) had collected. The reaction mixture
was ?ltered warm and stripped of solvent under reduced
pressure (e.g. 20 mm.). The residue normally solidi?ed
on standing. The products can be further puri?ed by
trituration with hexane.
-
A mixture of one mole of salicylaldehyde and two moles
of mercaptopropionic acid were heated under re?ux in 300
mol. of toluene containing 0.5 gram of p-toluenesulfonic
acid until one mole of water had collected. Then one
'mole of dibutyl tin oxide was added and re?uxing con
75 tinued until a second mole of water had- distilled. The
3,078,290..
9 .
10.’
Preferably, the resin is a vinyl halideresin, speci?cally,v
a vinyl chloride resin. Usually, the vinyl chloride resin
warm mixture was ?ltered and the solvent removed in a
vacuum ('20. mm.) to yield dibutyl tin 2-hydroxy-benzaldi
is made from monomers consisting of vinyl chloride alone.
or a mixture of monomers comprising at least 70% vinyl
(mercaptoproprionate) as a solid having a melting point of
131-134“ C. and having the formula.
chloride by weight. When vinyl chloride copolymers
are stabilized, preferably the copolymer of vinyl chloride
.
\
\
with an ethylenically unsaturated compound copolymer
izable therewith contains at least 10% of polymerized
)5 OOCCHzCHgS'/§_
‘
C4H9
vinyl chloride.
Example 32
As the chlorinated resin there can be employed chlo
10’
rinated
polyethylene having 14 to 75%, e.g., 27%, chlo~
A solution of one mole of dineopentyl tin dibromide in
rine by weight, polyvinyl chloride, polyvinylidene chloJ
OH
04139
QOCCHzCHzS
|
300 ml. of ether was shaken with two moles of 50%
aqueous sodium hydroxide. The ethereal solution was
then poured into a solution of one ‘mole of propane-2,2
ride, polyvinyl bromide, polyvinyl ?uoride, copolymers
of vinyl chloride with 1 to 90%, preferably 1 to 30%,
of a copolymerizable ethylenically unsaturated material
bis (mercaptopropionic acid) in 200 ml. of acetone and 15 such as vinyl acetate, vinyl butyrate, vinyl benzoate, via
?ltered. The product was isolated by evaporation of the
nylidene chloride, diethyl fumarate, diethyl maleate, other
solvents and trituration of the residue with hexane. The
alkyl fumarates and maleates, vinyl propionate, methyl
product was dineopentyltin propane-2,2-bis (mercapto
acrylate, Z-ethylhexyl acrylate, butyl acrylate and other
alkyl acrylates, methyl methacrylate, ethyl methacrylate,
20 butyl methacrylate and other alkyl methacrylates, methyl
Example 33
alpha chloroacrylate, styrene, trichloroethylene, vinyl
‘One mole of isodecane-1,l-bis (mercaptopropionic
ethers such as vinyl ethyl ether, vinyl chloroethyl ether
acid) and one mole of dibutyl tin oxide were added to
and vinyl phenyl ether, vinyl ketones such as vinyl methyl
300 ml. of toluene and the mixture re?uxed under a mois
propionate) .
ketone and vinyl phenyl ketone, l-?uoro-l-chloroethylene,
acrylonitrile, chloroacrylonitrile, allylidene diacetate and
chloroallylidene diacetate. Typical copolymers include
ture trap until one mole of water was removed. The sol
vent was then stripped off and dibutyl tin isodecane-l,1
‘bis (mercaptopropionate) recovered as the product.
vi‘ny choride-vinyl acetate (96:4 sold commercially as
Example 34
Using procedure H (Example 33) one mole of (dioctyl
tin oxide and one mole of p-ropane-2,2,,-bis (mercapto
VYNW), vinyl chloride-vinylacetate (87: 13), vinyl chlo
ride-vinyl acetate-maleic anhydride (8621311)‘, vinyl chlo
ride-vinylidene chloride (95:5), vinyl chloride-diethyl
fumarate (95:5), vinyl chloride-trichloroethylene (95 :5),
vinyl chloride-Z-ethylhexyl acrylate (80: 20).
propionic acid) were reacted in toluene as the solvent
and dioctyl tin propane.'2,2-bis (mercaptopropionate)re
covered as a high boiling liquid.
The stabilizers of the present invention can be incor
porated with the resin by admixing in an appropriate
Example 35
35
mill or mixer or by any of the other well-known methods
Using procedure E (Example 28) one mole of dibutyl
which provide for uniform distribution throughout the
tin oxide and one mole of propane-2,2-bis (mercaptosuc~
resin compositions. Thus, mixing can be accomplished
cinic acid) were reacted to produce dibutyl tin propane.-,
by milling on rolls at IOU-160° C.
2,2-bis (mercaptosuccinate) having the formula
40
nooo-orn
04m
000 HS
\
as plasticizers, pigments, ?llers, dyes, ultraviolet light ab
sorbing agents, densifying agents and the like.
OH;
/sn\OOCCHS/0\ om
04110
In addition to the novel stabilizers there can also be
incorporated with the resin conventional additives such
'45
H000 H2
Example36
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-Z-ethylhexyl phthalate, dibutyl
sebacate, dioctyl sebacate, tricresyl phosphate.
The tin containing stabilizers in groups I, Ia, II, III,
Using procedure H (Example 33) one mole of dioctyl
IV and V are normally usedin an amount of 0.01 to 10%
Example 38
Using procedure H (Example 33) one mole of 'di-.
of the present invention with vinyl chloride resins with
out exception there was greater stabilization than when
tin oxide and two moles of 4,4-bis (carbobutoxyethyl 50 by weight of the resin. Morepreferably 0.2 to 5%
of the tin compound is used by weight of the resin.
thio) Valerie acid were reacted in toluene as the solvent
When a mixture of dihydrocarbon tin oxide or sul?de
and there was recovered dioctyl tin di [4,4-bis (carbobu
is employed with the thioacetals or ketals of groups VI,
toxyethylthio) valerate] as the product.
VIa, VII, VIII, IX and X there is normally used 0.01
to 10% of the tin oxide or sul?de by weight of the resin
Example 37
55
and the thioacetal or thioketal is also normally used in
Using procedure E (Example 28) one moleof dibutyl
an amount of 0.01 to 10% by weight of the resin. More
tin oxide and one mole of 2-hydroxybenzaldi (2’-mer~
preferably 0.2 to 5% of the tin compound and 0.2 to 5%
captobenzoic acid) were reacted to produce dibutyl tin
of the thioacetals or thioketal is employed based on the
Z-hydroxybenzaldi (2'-mercaptobenzoate).
weight of the resin.
60
In the following examples employing the stabilizers
the equivalent amount of dibutyl tin dilaurate was em
phenyl tin oxide and one mole of benzylthiomethylthio~
ployed. Many of the compounds and compositions were
acetic acid were reacted to produce diphenyl tin div
65
superior to dibutyl tin bis(isooctylthioglycolate) as stabil
(benzylthiomethylthioacetate) .
izers for vinylchloride resins.
Example 39
The following examples (except comparison Examples
40 and 41) illustrate the stabilizing effect of the addi
tin oxide and one mole of ethane-1,1,2',2-tetrakis (mer 70 tives of the present invention. It should be noted that the
?rst yellowing does not necessarily limit the usefulness
captopropionic acid) were reacted to produce di (dibutyl
Using procedure H (Example 33) two moles of dibutyl
tin) ethane 1,1,2,2-tetrakis (mercaptopropionate).
The stabilizers of the present invention, can be used,
with halogen containing vinyl and vinylidene resins in
of the stabilizer.
The stabilizer tests were carried out
at 360° F. (216° C.) in the conventional forced draft
oven. In the tables 101 EP and 103 EP designate Geon
which the halogen is attached directly to the carbon atoms. 75 101 EP and Geon 103 EP which are vinyl chloride homo
3,078,290
11 ‘
12
polymers manufactured by B. F. Goodrich. VYNW
designates a 96:4 vinyl chloride'vinyl acetate copolymer
and St. Gobain, a commercially available vinyl chloride
Example 43
[Dibutyl tin benzaldi weight
(mercaptoéiropionate)--m01ecular
53 ]
resin. In the tests all parts are expressed as parts per 100
parts by weight of the resin. The letter Y designates the time in minutes at which color ?rst appeared. The letter
B designates the time in minutes at which the resin be
time very dark.
Example 40
Parts stabilizer ___________________ .__
1.60
Resin
_
Dioctyl phthalate (parts) __________ __
103 EP
50
Results __________________________ -. Y-—75, 13-120
Example 44
1 0 [Dioctyl tin propane-2,2-bls (mercaptoproplon ate)—-molecular weight 594]
[Dlbutyl tin dJlaurate-molecular weight 528]
Parts stabilizer ....................... ..
Parts stabillzen ........... _-
0.95
0.94
1.88
Resin ______________________ __
103 EP
101 EP
103 E1’
Dloctyl phthalate (partsL--.
Ywg
Y its)
Y 23
Results -------------------- "
B___60
B_45
B_75
0. 875
Epoxtdized soya. oil ................... _.
_
0. 453
0. 453
2.82
103 EP
__
0
0
5
Epoxidized isoetyl oleate-
0.875
0. 453
0. 453
Y 3 15 Resin ................... --
1%? E71:
10% E72
1011,1371;
{ 13-405
B~90
B~135
__
B_-75
_.
Results """" "
o
_.
_
Example 41
[Dibutyl tin (isooctylthioglycolate)—-molecular weight 580]
Parts stabilizer ......... _.
0. 94
0.775
0.95
Resin ................... -_
103 EP
103 EP
103 EP
Dloetyl phthalate (parts).
Results
----------------- --
1.0
1. 67
101 EP
1.11
VYNW
(1)
50
50
0
0
0
50
Y-45
Y-45
Y——45
Y-30
Y—75
Y-00
13-90
13-75
13-00
13-75
3-75
12-75
I St. Gobain.
Example 45
[Dibutyl tin beuzaldi (mercaptoacetate)-—molecular weight 502]
Parts stabilizer .......... -_
0.76
1.5
0.75
0. 75
1.48
1. 48
Resin ___________________ __
103 EP
103 EP
103 EP
103 EP
103 EP
103 EP
Dioctyl phthalate (Karts).
Trieresyl phosp ate
0
0
50
0
50
0
(parts) ................ ._
0
0
0
0
0
Y-GO
Y--15
Y-45
Results
""""""""""" "
{ Y~60
B-75
13-120
13-75
Y-30
13-75
Y-30
13-165
13-165
Example 46
Example 42
r
[Dlbutyl tin isodocane-1,1-bis (mercaptoproplonnte)-—
molecular weight 580]
45
Parts stabilizer ____ __‘ ______________ -.
0.86
Resin ____________________________ _.
103 EP
Dibutyl tin propane-2,2-bis (mercaptopropi on ate)—mole cular weight 482]
Part5 stabmzer-?-
0-715
Epp’f‘l‘jffffiff’in
Results -------------------------- —— Y—45: B~75-
1-07
0
103121;J
""""" "
5
(7-905
0
Results
0
0-715
gesngin?gg?u
103 E61; VYNW‘; 1011213 1011313
100
p
a a e.
0
0
0'72
Y--90
Y-76
Y~—75
Y-75
Y-75
13-105
B—-75
B-120
13-90
13-75
0. 37
0. 46
0. 37
0. 23
0. 37
0. 46
101 EP
101 EP
Example 47
(Compound: Benzaldi bis (mercaptopropionic acid)-molecn.lar weight 300)
Dibutyl tin oxide (parts) ...... __
Above compound (parts) --
0. 74
0.88
0. 74
0. 45
0. 74
0. 88
0. 74
0. 45
0. 74
0.88
0. 74
0. 49
0.37
0.25
0. 37
0.30
-
103 EP
103 EP
103 EP
103 EP
103 EP
103 EP
103 EP
101 EP
Trlcresyl phosphate (parts) .... __
0
0
0
50
0
0
0
0
0
0
{ Y—75
Y~—00
Y-120
Y-GO
Y——75
Y-15
Y-30
Y-—30
Y—00
Y-30
esm ____________________ _-
Dioctyl pllthalate (parts).T
Results
__
"""""""""""""" "
50
13-135
50
B—-135
Y—-60
13-465
50
13-105
13-165
50
13-155
0
13-105
101 E
13-75
0
13-75
£0
13-75
13-00
Example 48
(Compound: O-hydroxybenzaldi (mereaptopropionlc acld)—molecular weight 316)
Dibutyl tin oxide ...... _-
0. 74
0. 74
0. 74
0.37
0. 37
0.37
0. 37
0.37
0. 37
0.37
0. 555
0.37
Above compound.
-_
0.50
0. 59
0. 59
0.30
0.275
0.26
0.30
0.32
0.35
0.50
0.77
0. 475
0. 44
Resin ___________ _-
--
1 103
1 103
1 103
1 103
1 103
(2)
l 101
l 103
I 103
1 101
1 101
l 101
Dioctyl phthalate.
Tricresyl phosphat -
__
50
0
50
0
0
50
50
0
50
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
0
{ Y-—90
Y——90
Y—-00
Y-—75
Y——00
Y-—60
Y-60
Y-—30
Y-—15
Y—30
Y—15
Y—30
Y—~75
Results
----------------- -- 13.435 a13_165
1 EP.
13-75
13-120
13-120
3-105
1 St. Gobain.
8 Indicates resin was not very dark when test was terminated after 165 minutes.
13-105
13-75
13-90
13-90
13-120
13-90
0. 37
13-405
3,078,290
Example 65
Example 73
[ Compound: cyc1ohexy1-1,1,~bis (mercaptoproplonie acid)—mol. wt. 292]
[Compound: Cyclohexyl-1,1-bis (mercaptopropionic acld)—mo1.wt.264]
Dibutyl tin oxide _____________________ __
Above compound."
._
0.37
0. 45
Droctylfiht-lia-la-te:
0.37
0_ 23
0.37
0.45
Dibutyl tin sul?de .............................. _.
Above compound ............................... ..
5
‘m E13 1°; E15 1‘: E513
~
Results------------------------------- --{ Y-eo
13-45
—60
3-75
0. 40
0' 28
101 EP
Hg
101E}?
Rem":
{ B—75
—
B-105
nigé‘lylphrhm
’-"5
B_1[')5
Example 66
0. 40
0. 28
_.
'
10
Y g3
‘The term thioacetal as used in the claims in accordance
lCompound: Propane>2,2-bls (mercaptosucclnie ncld)—mo1. wt. 340]
wlglleagfgilzsd termmology 1S geneuc to thloketals‘
Dibutywn Oxide ____________________ __
[137
‘137
[L37
1. A dihydrocarbon tetravalent tin salt of a carboxy
?bqve compound":
0. s1
0. 2a
103 05%
mercaptal containing 2 to 4 carboxyl groups in the mole
Y 30
Y 30
~
——
85111 ............. ....
-
Dioctylphthalate ____________________ __
Rmm‘
{ 13-45
B-75
Y
-
.
15 cule ealtlnd WhlCh is connected to the tin atom through
—
ox
13-115
.
gg
R
Example 67
[Compoundz Propene-3.3-bis (mercaptopropionic acid)——mol. wt. 250] 20
SD
OOO(GH2) —S
n
R/ \00 C(CH ‘
1
Dibutyl tin oxide-
-
as??? compound"
Res
101%?
1010b‘?
from the group consisting of alkyl, aryl and aralkyl and
_-
B45
Y-o
R2 and R3 are selected from the group consisting of hydro
B_75 25 gen, alkyl, alkenyl, aryl, hydroxyaryl, aralkyl and to
gether the pentamethylene radical.
3. A compound according to claim 2 wherein R and
_
_
0.37
0. 37
?boveyeompound ............................... -- 101 0E4}?
Dibut 1 tin oxide ............................... --
101 01-32%
es1n_.
Y-o
Results.
B-75
R are alk l and n is an inte er from 1 to 2.
14. A Sgt according to claim 1 having the formula
30
CHRO O OH
R
Y-O
B——75
000 HS
\Sn/
35 _
Ri/
\
0000118
7
_
_
wherein R and R1 are selected from the group consisting
Dnmm an oxide _____________________ __
0.37
a 37
?lgove compound..-
.-__ 10101.51}? 1010;?
ma?a-1.555555%;-
:: r Y 1g
Results ............................... -.
I
l B 75
M7
of alkyl, aryl and aralkyl and R2 and R3 are selected from
10305412 40 the group consisting of hydrogen, alkyl, alkenyl, aryl,
Y 38
Y 5g
I
I’
B 75
B 90
hyéimiltyaryl, aralkyl and together the pentamethylene
“1 lca-
Example 70
_
45
weight 488]
HOOCCHICHIS
CH
e
R 8
P
'
(
R1
scmcmcoo?
‘
_
006 CH O/SR'
n
9“
Rs SR5 I
'
_CH_ CH
130099319315
,
5. A salt according to clalm 1 having the formula
lcompound: Pentane-2,2,4,4-tetre (mercaptoproplonic acid)—molecular
>
B.
_
(
‘
/ \
HZOOOH
and: Ethyl»3,3-bls carboxyethylthio)butyrnte—mol.wt.324]
Formula:
R:
\O/
Example 69
m
I
where n is an integer from 1 to 8, R and R1 are selected
[Compound: 2-butene-1,1-bis (merceptopropiomc acid)-—mol. wt. 264]
l
s/ \R
1 21-’
0. 37
Example 68
Com
R;
0.37
_
'
\C/
_
_
wherein R and R1 are selected from the group consisting
'
50 of alkyl, aryl and aralkyl, R4 and R5 are selected from
SCHICHWOOH
Dibutymn oxide _______________________________ __
(137
$2328 compound ------------------------------- -- IOIOEQLQ
y_15,
Result‘:
B—-7o
the group consisting of alkyl, aralkyl, aryl, mercapto
carboxylic acid and mercaptocarboxylic acid ester, R,
[)_37
is selected from the group consisting of hydrogen, alkyl,
10101-391}
benzyl, and aryl and n is an integer from 1 to 8.
y_30 55
6. A salt according to claim 1 having the formula
13-75
R
S
\
Example 71
R:
' /
/SD 000G C\
[Compoundz Propane-2,2-bis (mercaptopropionic acid)—mol. wt. 2321 60
_
R‘
l
1
R‘
wherein R and R1 are selected from the group consisting
ii‘é‘éiyéoiii‘pi‘i?i?:::::::::::::::::::::::::::::::
Resim- M1 1 f
D “Y1? " “ ''
Rpm!“
8:53
8:52
of alkyl, aryl and aralkyl and R2 and R3 are selected from
101EP
Y_3g
101 EP0
F20
the group consisting of hydrogen, alkyl, alkenyl, aryl,
hydroxyaryl, aralkyl and together the pentamethylene
{ B—~75
‘ B—105 65 radical.
Example 72
7. A salt according to claim 1 having the formula
R
[Compoundz Benzaldi (mercaptopropionic acld)—mol. wt. 300]
(msoHzswHzhooo) 2S1<
glijbutyl tin sul?ge .............................. ._
Resin101 EP
0V8 compoun
------------------------------- _-
21°C?‘ Ph'hmm
m <
-
70
-
101 EP
R1
wherem R and R1 are selected from the group consisting
.
,
,
Yjg
Y__1g
of alkyl, aryl and aralkyl and R7 is selected from the
{ 13-105
B~—75
group consisting of alkyl, aralkyl and aryl and n is an
75 integer from 1 to 8.
3,078,290
17
R1/ \O00(0H2>n-s
2
wherein R and R1 are selected from the group consisting
of alkyl, aryl and aralkyl and R8 is selected from the
group consisting of alkyl, aralkyl and aryl and m is an
integer from 0 to 8 and n is an integer from 1 to 8.
18
References Cited in the ?le of this patent
UNITED STATES PATENTS
8. A salt according to claim 1 having the formula
5
2,786,813
2,789,106
2,805,234
2,872,468
2,910,452
McDermott __________ __ Mar. 26, 1957
Tomka et a1 ___________ __ Apr. 16, 1957
Gloskey ______________ __ Sept. 3, 1957
Leistner et a1 ___________ __ Feb. 3, 1959
Crauland ____________ __ Oct. 27, 1959
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