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Патент USA US3037971

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” nited, States Patent
Patented June 5, 1962
Finally, another group of compounds known as stabilizers
are organotin xanthates of the general formula
William E. Leistner and Olga H. Knoepke, Brooklyn,
‘N.Y., assignors to Argus Chemical Corporation, Brook
lyn, N.Y.
No Drawing. Filed Aug. 11, 1959, Ser. No. 832,902
5 Claims. (Cl. 260—45.75)
Where R stands for an alkyl, \aryl, hydroaromatic orv
heterocyclic radical and
It is well known that organotin oxides and organotin
halides react with mercaptans to form organotin mer
for an anion of an alkyl xanthic acid, andn for an integer
capto compounds in which part of the four tin valencies
from 1 to 3.
is linked directly to sulfur.
These compounds have, however, one drawback that
is formation of odor in processing and still more serious,
These compounds are ex
cellent stabilizers for polyvinyl chloride resins.
sometimes a mercaptan odor in the ?nished products.
Such compounds are for instance organotin mercap
tides of the general formula (RS)XSn.R’4_x, wherein R 15 It is the object of this invention to prevent this forma
tion of odor.
and R’ are hydrocarbon radicals, e.g. alkyl such as
The odor problem can be solved by adding in process
methyl, ethyl, butyl, octyl, dodecyl, and octadecyl; aryls,
ing a peroxide compound which may be inorganic or
such as phenyl, tolyl, xylyl, oxyalkyl and oxyaryl; and
organic. Examples of inorganic peroxides are sodium
the furfuryl and tetrahydrofurfuryl groups; x is an in
perborate, potassium persulfate and sodium percarbo-nate.
tegral number between 1 and 4. The following tin mer
Examples of organic peroxides are dicumyl peroxide, ter
captides are listed by way of example:
tiary butylhydroperoxide, and benzoyl peroxide.
Tin tera-dodecylmercaptide
In general, the amount of the peroxide compound
S11 (S-C12H25) 4
Tin tetra-phenylmercaptide
Tin dibutyl di-dodecylmercaptide
(C4H9) 25B‘ (S~C12H25 ) 2
Tin dibutoxy di-octylmercap tide
(C4H9O )2SI1(S-CsH17)2
Tin dibutoxy di-phenylmercaptide
(C4H9O ) 2SI1(S-CsH5 ) 2
added will range from 0.05 to 0.5% calculated on the
25 weight of the resin.
The invention will now be more fully explained with
reference to a number of speci?c examples, but it should
be understood that these are given by way of illustration
and not of limitation and that many changes in the
details can be made without ‘departing from the spirit of
the invention. In the following all parts are given by
Tin diphenoxy di-butylmercaptide
(Cal-I50 ) 2511 (S-C4H9 ) 2
Tin diphenoxy di-phenylmercaptide
Example 1
100 parts Geon 101 EP (a polyvinyl chloride homo
polymer) are mixed in a pan with 50‘ pts. dioctylphthalate,
(Cal-I50 ) 2511 (s-csHs) 2
0.75 pt. A-C polyethylene 8416 (a low-molecular weight
Another group of organotin stabilizer compounds are
polyethylene used as lubricant) 3 pts. dibutyltin bis (octyl -
represented by the general formula Rn—Sn—X4_n,
rthioglycolate) and 0.25 sodium perborate.
wherein R again stands for a radical as listed above, while 40 The mixture is fused on a heated two-roll mill at 320°
X stands for an ester of a monobasic mercapto acid having
F. until a homogeneous sheet is obtained which takes
from 2 to 6 carbon atoms, with a monohydric alcohol,
about 5 minutes. Neither in processing nor in the
and n represents an integral number from 1—3. ‘In all
?nished sheet is any merca-ptan odor apparent. A simi
the compounds, the sulfur atom is directly linked to tin.
lar composition prepared without using sodium perborate
As acids, the following may be used; thioglycolic, thio 45 gave oif a strong mercaptan odor during the milling and
propionic, thiobutyric, thiovaleric or thiocapronic; as
the ?nished sheet also smelled of mercaptan.
alcohols, n-butyl, sec. butyl, tert. butyl, hexyl, octyl,
Slabs were made by molding pieces of the sheet in
dodecyl, cetyl alcohols, butylcarbitol, benzyl, cyclohexyl,
methyl cyclohexyl, tetrahydrofurfuryl and -tetrahydro—
abietyl alcohols.
Speci?c examples of such esters are: dibutyltin dithio
a form under pressure at 350° F. and kept at this tem
perature for one hour. The slabs so obtained were odor
50 less only When the peroxide was used.
Heat stability of
the composition was not impaired by the use of sodium
glycolic acid cyclohexyl ester
Example 2
dibutyltin dithioglycolic acid tetrahydroabietyl ester,
The procedure was the same as in Example 1, but
instead of sodium perborate 0.25 pt. potassium persulfate
was used. ‘In this case, too, the odor during processing
and in the ?nished product was non-existent.
monobutyltin tri-?-thiopropionic acid hexyl ester
dilauryltin dithiobutyric acid butyl ester,
(C12H25) 2.8m. (S.CH2CH2CH2COOC4H9 ) 2
and triphenyltin thioglycolic acid benzyl ester
Example 3
100 parts Vinylite VYNW (96% vinyl chloride and 4%
vinyl acetate copolymer) were treated as in Example 1
with 50 pts. dioctyl phthalate, 0.75 polyethylene and 3 pts.
dibutyltin bisdodecylmercaptide and 0.11 pt. dicumyl per
(C6H5) 3 .Sn-—SCH2CO OCH2C6H5
An odorless product was obtained and no odor
65 was observed during processing.
Instead of the mercapto acid esters listed above, mer
Example 4
capto acid amides have been described and used; esters
The procedure of Example 3 was repeated, using this
of monovalent mercapto alcohols with monocarboxylic
time 0.1 pt. benzoyl peroxide. The results were equally
acids; esters of glycols with mercaptocarboxylic acids. 70 satisfactory.
‘ .
4. A method of preventing odor-formation in the sta
bilization of polyvinyl chloride resins with organotin mer
capto compounds, which comprises adding to the resin in
processing benzoyl peroxide in an amount of 0.05-0.25
By the expression a “peroxide” 3. compound is under
stood having the group -V-O-—O—-.
What is claimed is:
1. A method of preventing odor-formation in the sta
bilization of polyvinyl chloride resins with organotin mer- ' 5 by weight of the resin.
5. A composition of matter containing a polyvinyl chlo
eapto compounds, which, comprises adding to the resin in
ride resin stabilized with, an organotin mercapto com
processing-sodium perborate in an amount ranging'from
pound and as an addition a peroxide in an amount of
0.1 to 0.5% by weight of the resin.
p 2. A method of preventing odor-formationrin the sta
'0.05,-0.5% by Weightgogf the resin.
bilization of polyvinyl chloride resins with. organotin mer
capto compounds, which comprises adding to the resin 19
in processing potassium persulfateiing an amount ranging
from 0.1 to 0.5% by weight of the‘ resin. 0
i '
3. A method of preventing odor-formation in the sta
bilization of polyvinyl chloride resins with organotin mer
capto. compounds, which comprises adding to, the resin in
processing dicumyl-peroxide in an amount ranging from
0.05-0.25 ‘by. Weight of'the resin.
References Cited in the ?ler of this patent
Weinberg et a1. ____ _____ Apr. 29, 1958
May 9. 1950
; Ramsden ____Ve _______ __ Sept. 15, 1959
781,452 I
Great Britain _i__'__v__j_l___' Aug. 21, 1957
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