DE2501007A1 - STABILIZING AGENTS FOR HALOGENIC SYNTHETIC RESINS - Google Patents

Description

Stabilizing agent for synthetic resins containing halogens (additive to (patent application-P 23 29 039.3))

In the patent (patent application P 23 29 039.3) it is described that dimethyltin bis (thioalkanoate) of the general formula

S (CH ₉ ) COOR ^ n

Sn

S (CH ₀ ) COOR ζ η

in which R is a hydrocarbon radical with 1 to 20 carbon atoms and η is an integer from 1 to 3, physiological represent harmless stabilizers for halogen-containing synthetic resins, especially polyvinyl chloride resins, if they contain less than 0.5% trimethyltin thioalkanoate as an impurity.

It has now been found that an even better, physiologically harmless stabilization of these resins is achieved if one used for the stabilization mixtures that

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(1) 2 to 96% of the dimethyltin compound of the general formula

CH- S (CH ₉ ) COOR

CH-. S (CH ₀ ) COOR

(2) 98 to 4% of the monomethyltin compound of the general formula

CH., - Sn - Fs (CH ₀ ) COOR ~ L and

(3) not more than 0.6%, preferably not more than 0.4% the trimethyltin compound of the general formula

(CH ₃ J ₃ Sn - S (CH ₂ J _n COOR

contain as an impurity, where R is a hydrocarbon radical having 1 to 20 carbon atoms and η is an integer from 1 to 3 is.

The LD _{50 of} these mixtures when administered orally to rats is at least 695 mg / kg, preferably at least 1000 mg / kg. They are therefore extremely suitable for the stabilization of synthetic resins which are used for the packaging of foodstuffs and luxury foods and for drinking water pipes. Resins stabilized in this way have excellent heat and color stability.

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Advantageous stabilizer mixtures according to the invention contain .96 to 60% by weight, in particular 81 to 71% by weight, of the compound (1) and 4 to 40 % by weight, in particular 19 to 29% by weight, of the compound (2).

Typical compounds of the general formula (2) are:

Methyl tin tris (isoooctyl thioglycolate), methyl tin tris (isooctyl S-mercaptopropionate) , methyl tin tris (2-ethylhexyl thioglycolate), methyl tin tris (2'-ethylhexyl-S-mercapto-propionate) , Methyl tin tris (isooctyl-4-mercaptobutyrate), methyl tin tris (n-octyl thioglycolate), methyl tin tris (n-octyl-S-mercaptopropionate) , methyl tin tris (methyl thioglycolate), methyl tin -tris- (methyl-3-mercaptopropionate), methyltin-tris- (methyl-4-mercaptobutyrate), methyltin-tris- (ethyl-thioglycolate), methyltin-tris- (propyl-3-thiopropionate), methyltin-tris- ( butyl thioglycolate) ,
Methyl tin tris (butyl 3-thiopropionate) , methyl tin tris (butyl 4-thiobutyrate), methyl tin tris (isooctyl 2-thiopropionate), methyl tin tris (decyl thioglycolate) , methyl tin tris (isodecyl thioglycolate), methyl tin tris (dodecyl thioglycolate),

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-A-

Methyl tin tris (dodecyl 3-thiopropionate), methyl tin tris (isodecyl 3-thiopropionate), methyl tin tris (dodecyl-4-thiobutyrate) , methyl tin tris (octadecyl thioglycolate), methyl tin tris (octadecyl-3-thiopropionate), methyltin-tris- (octadecyl-4-thiobutyrate),, methyltin-tris- (eicosanyl-thioglycolate), methyltin-tris- (eicosanyl-3-thiopropionate), methyltin-tris- (cyclopentyl- thioglycolate) , methyl tin tris (cyclohexyl thioglycolate), methyl tin tris (cyclohexyl-S-thiopropionate), methyl tin tris, (benzyl thioglycolate), methyl tin tris (benzyl-3-thiopropionate), methyl tin tris (phenyl thioglycolate), methyl tin tris (p-tolyl-3-thiopropionate), methyl tin tris (allyl thioglycolate), methyl tin tris (allyl 3-thiopropionate), methyl tin tris (allyl -4-thiobutyrate) , methyl tin tris (crotyl thioglycolate), methyl tin tris (oleyl thioglycolate), methyl tin tris (oleyl 3-thiopropionate), methyl tin tris (oleyl-4-thiobutyrate), Methyl tin octyl thioglycolate bis (decyl) thioglycolate, methyl tin tris (meth allyl thioglycolate), methyl tin tris (methallyl 3-thiopropionate), methyl tin tris (dodecenyl thioglycolate).

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As compounds of the general formula (1), the corresponding Dimethyl tin compounds and dimethyl tin bis (isodecyl thioglycolate) and dimethyl tin bis (isodecyl thio-3-propionate) can be used.

The trimethyltin compounds of the general formula (3) are impurities that occur in the production of the Dimethyltin compounds, for example by. Implementation of the corresponding thioalkanoates with dimethyltin dichloride, the largely purified from trimethyltin chloride, are still present.

The later named ADVASTAB TM-181 FS contains about 24% by weight Monomethyltin tris (isooctyl thioglycolate), 0.6% by weight trimethyltin isooctyl thioglycolate and the remainder is dimethyltin bis (isooctyl thioglycolate).

It has proven to be a stabilizer for synthetic resins that come into contact with foodstuffs and luxury foods Furthermore, a similar formulation as satisfactory, which contains approximately 24% by weight of monomethyltin tris (isooctyl thioglycolate) contains. This agent is used in Germany, the Netherlands and England for the stabilization of synthetic resins, that come into contact with foodstuffs and luxury items are permitted on a trial basis.

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Polyvinyl chloride bottles containing 2.2% ADVASTAB-TM-1 81 FS, In tests carried out over 3, 10 and 24 days at 23 and 50 C, the migration of the stabilizing agent in (a) distilled water, (b) 3% acetic acid, (c) 10% ethanol, (d) 50% ethanol and (e) peanut oil were examined. In all cases it was found that the migration of the stabilizer was well below 1 ppm. the

maximum migration barely exceeded 0.2 ppm even at 50 ° C,

2
corresponding to about 0.03 mg / dm, which indicates that ADVASTAB TM-181 FS is well suited as a stabilizer for polyvinyl chloride, which is used for the production of packaging material for food and luxury items.

A polyvinyl chloride tube with an inside diameter of 10 cm and a pipe wall thickness of 3 mm containing about 0.7% ADVASTAB as a stabilizing agent was added to its Suitability as drinking water pipe investigated. ·

Sections of the tube were filled with sodium bicarbonate solution and with sodium bicarbonate solution containing chlorine. It was then stored for 2, 5 and 10 days. Both solutions were tested for tin stabilizer migration. In

In all cases the migration was less than 0.01 mg / dm. Of the The potassium permanganate consumption of the sodium bicarbonate solution was below 3 mg / l in all cases. The sodium bicarbonate-chlorine solutions

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gave a mean value of less than 2 mg / m in the 10-day test per day. There is therefore no health risk when using the pipe for drinking water.

Subchronic toxicity studies on ADVASTAB TM-181 FS were carried out on rats for 90 days, "to which one o, 10, 30, 100 or 300 ppm fed. No toxic effect was found at 100 ppm, or only a slight toxic effect Effect at 300 ppm.

As a result of other research with ADVASTAB TM-181 FS, it is stated by the British Industrial Research Association that that it is at a maximum content of 2.5% in polyvinyl chloride intended for contact with food in the BIBRA / BPF Code of Recommendations can be included.

The following examples show that the stabilizers according to the invention, polyvinyl chloride, have excellent resistance to lend. The color ratings were made using the customary 0 to 10 scale, 0 being colorless and 10 being black indicates, with the exception of Example 4, in which the scale used indicates 0 milky white and 10 milky brown.

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example 1

Polyvinyl chloride (Geon 103 Ep-8) 100.0% by weight

Stearyl alcohol 0.5% by weight

Stabilizing agent (Table 2) 2.0% by weight

The above ingredients were tested on a laboratory differential roll mill mixed together at 170 ° C for 5 minutes until the mixture was homogeneous. The film obtained was with a Thickness of 0.6 mm was taken from the roller and samples thereof were heated in an oven to 175 ° C. "These samples were visually examined for the speed of color development. In another test, the film was used a pressure of 150 kg / cm for 50 minutes at 180 C in pressed a press to a thickness of 1 mm. The obtained films were visually checked for the speed of color development examined.

Table 1 - Stabilizers

a dimethyltin bis (isooctyl thioglycolate)

b monomethyltin tris (isooctyl thioglycolate)

c trimethyltin isooctyl thioglycolate

d dimethyltin dilaurate

e monomethyltin trilaurate

f dimethyltin bis (isooctyl maleate)

g monomethyltin tris (isooctyl maleate)

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T able 2 - Results

Ver
am
manure
No. Stabilizing
lisie-
guessing
middle Phr g < Weight
share , 5
, 0
, 5 Color of the sample
(Minutes) *
20 40 60 90 120 0
0
0 0
0
0 U) U) U) 00 00 00 Color of
pressed
foil 1
1
1 a
b
C. 1.8
0.2
0.01 89
10
0 , 5
, 0
, 5 0
0
0 0
0
0 0
0
0 00 00 00 00 00 CO colorless
Il
Il CM CM CM a
b
C. 1.6
0.4
0.01 79
20th
0 , 0
, 0 0
0
0 Ul ul 10
10 Il
Il
Il oo cn d
e 0.8
0.2 90
10 , 0
, 0 5
5 7th
7th 10
10 orange
orange 4th
4th d
e 1.6
0.4 80
20th , 0 VO VO U) U) 7th
7th 10
10 yellow-brown
Il in in f
G 1.8
0.2 90
10 , 0
, 0 1
1 3
3 VO VD 10
10 colorless
Il VD VO f
G 1.6
0.4 80
20th , 0 1
1 1 2 7th 9 Il
Il 7th a 2.0 100 , 0 1 10 Il 8th b 2.0 100 , 0 8th 5 10 yellow 9 d 2.0 100 , 0 5 10 orange 10 e 2.0 100 , 0 6th 2 3 10 Brown 11 f 2.0 100 , 0 1 colorless 12th G 2.0 100 (3) 10 brown I [7) yellow * colorless (0) älb black (10)

The results obtained clearly show that changes in the acid component lead to significant differences in heat resistance.

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- ίο - 2 5 0 Ί η 0

The thioalkanoates cause a significantly better effect than the aliphatic carboxylate and the alkyl maleate.

Example 2

Polyvinyl chloride sheets were prepared in a manner similar to Example 1 and tested for color development speed examined.

Table 3 - Stabilizers

a dimethyltin bis (isooctyl thioglycolate)

b monomethyltin tris (isooctyl thioglycolate)

c trimethyltin isooctyl thioglycolate

h dibutyltin bis (isooctyl thioglycolate)

i monobutyltin tris (isooctyl thioglycolate)

j dioctyltin bis (isooctyl thioglycolate)

• k monooctyl tin tris (isooctyl thioglycolate)

1 dimethyltin bis (2-ethylhexyl-ß-mercaptopropionate)

ία monomethyltin-tris- (2-ethylhexyl-ß-mercaptopropionate)

η trimethyltin 2-ethylhexyl-ß-mercaptopropionate

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Table 4 - Results

Ver Rod Phr Weight colour the sample (Minutes) 20th am lisie- 1.9 share 8th manure guessing 0.9 94.5 20th 40 60 90 1 8th No. middle 0.01 5.0 0 0 1 5 8th 1 a 1.9 0.5 0 0 1 • 5 8th 1 b 0.1 94.5 0 0 1 5 8th 1 C. 0.01 5.0 ■ 0 0 0 2 8th 2 1 1.8 0.5 0 0 0 2 8th 2 m 0.2 89.5 0 0 0 2 8th 2 η 0.01 10 _f 0 0 0 0 3 8th 3 a 1.7 0.5 0 0 0 3 8th 3 b 0.3 84.5 O 0 0 3 8th 3 C. 0.01 15 _f 0 0 0 0 3 8th 4th a 1.6 0.5 0 0 0 3 8th 4th b 0.4 79.5 0 0 0 3 8th 4th C. 0.01 20.0 0 0 0 3 8th 5 a 1.6 0.5 0 0 0 3 8th 5 b 0.4 79.5 0 0 0 3 8th 5 C. 0.01 20.0 0 0 0 2 8th 6th 1 1.4 ' 0.5 0 0 0 2 8th 6th m 0.6 69.5 0 0 0 2 8th 6th η 0.01 30.0 0 0 0 4th 8th 7th a 0.5 0 0 0 4th 7th b 0 0 0 4th 7th C.

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Ver
am
manure
No. Stabilizing
lisie-
guessing
middle Phr Weight
share colour
20th the
40 sample
60 (Minutes) *
90 120 9
9
9 > 8th
8th
8th a
b
C. ' ¹ I ² -
0.8
0.01 60 _f 0
40 _r 0
0.5 0
0
0 0
0
0 1
1
1 7th
7th
7th 9
9
9 9
9
9 1
m
η ¹ I ²
0.8
0.01 60.0
40.0
0.5 ■ 0
0
0 0
0
0 1
1
1 5
5
5 10
10
10 10
10
10 a
b
C. 1.0
1.0
0.01 50.0
50.0
0.5 0
0
0 1
1
1 4th
4th
4th 9
9
9 9
9
9 11
11
11 a
b
C. 1.94
0.06
0.01 97.0
3.0
0.5 1
1
1 1
1
1 2
2
2 6th
6th
6th 9
9 12th
12th H
i 1.8
0.2 90.0
10.0 0
0 1
1 2
2 4th
4th 9
9 13th
13th H
i 1.6
0.4 80.0
20.0 0
0 1
1 2
2 4th
4th 9
9 14th
14th j
k 1.8
0.2 90.0
10.0 1
1 2
2 4th
4th 6th
6th 9
9 15th
15th j
k 1.6
0.4 80.0
20.0 1
1 1
1 3
3 6th
6th 9 16 a 2.0 100.0 1 1 2 7th 17th b 2.0 100 8th 10

colorless (0) yellow (3) brown (7) black

(10)

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The results obtained illustrate that with the Methyltin compounds achieved significantly better results than with the butyltin and octyItin compounds. the best results in terms of initial color and heat resistance were obtained at an "a" to "b" ratio of 96: 4 to 60:40 obtained.

Example 3

Polyvinyl chloride (Geon 103 Ep-8) 100 parts by weight calcium carbonate (OMYA-9OT) .3.0 parts by weight

low molecular weight polyethylene
(AC-629A). 0.2 parts by weight

Calcium stearate 0.6 part by weight

Paraffin wax (ADVAWAX 165) 1.2 parts by weight

Titanium oxide 1.0 part by weight

Stabilizer 0.3 parts by weight

The above ingredients were tested on a laboratory differential roll mill mixed together at 200 ° C. for 5 minutes until a homogeneous mixture was achieved. The film obtained was then taken with a thickness of 0.6 mm from the roller, and samples of these were heated to 180 ° C. in an oven. These samples were visually assessed for the rate of color development examined.

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Table 5 - Stabilizers

a dimethyltin bis (isooctyl thioglycolate)

b monomethyltin tris (isooctyl thioglycolate)

c trimethyltin isooctyl thioglycolate

j dioctyltin bis (isooctylthioglycolate)

Stabilizing

bin- lisie-

tion weight to

No. middle phr parts beginning 1O

Table 6 - Results

Color of the sample (minutes)

20th

30 40

a
b
c

a
b
c

1.47
0.52
0.01

1.89
0.09
0.02

2.0

73.4

26.0

0.6

94.3
4.5
1.2

1 1 1

2 2 2

6th
6th
6th

8th
8th
8th

8th
8th
8th

9
9
9

8 8 8

10 10 10

colorless (0) yellow (3) brown (7) black (10)

The results obtained show that an increase in the amount of the incorporated trimethyltin compound improves the heat resistance decreased. The methyl tin stabilizer was better than the octyl tin stabilizer.

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example

Polyvinyl chloride (Geon 103 Ep-8) Calcium carbonate (OMYA-9OT)

low molecular weight polyethylene. (AC-629A) calcium stearate Paraffin wax (ADVAWAX 165) titanium oxide stabilizer

100.0 parts by weight

3.0 parts by weight

0.2 parts by weight

O ', 6 parts by weight

1.2 parts by weight

1.0 part by weight

0.3 parts by weight

The above ingredients were tested on a laboratory differential roll mill mixed at 190 C. The obtained films were with a thickness of 0.3 mm taken from the roller at intervals of 10 minutes and checked for the rate of its discoloration examined.

Table 7 - Stabilizers

a dimethyltin bis (isooctyl thioglycolate)

b monomethyltin tris (isooctyl thioglycolate)

c trimethyltin isooctyl thioglycolate

h dibutyltin bis (isooctyl thioglycolate)

i monobutyltin tris (isooctyl thioglycolate)

j dioctyltin bis (isooctyl thioglycolate)

k monooctyltin tris (isooctyl thioglycolate)

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Table 8 - Results

Ver Stabilizer Phr Weight colour the sample (Minutes) ^x ■ am lisie 1.91 share 50 manure tion s- 0.08 96.0 10 20th 30th 40 9 No. middle 0.01 4 0 1 3 6th 7th 9 1 a 1.51 ojs 1 3 6th 7th 9 b 0J48 76.0 1 3 6th 7th 9 C. OjOl 24.0 1 2 5 6th 9 2 a 1.89 0.5 1 2 5 6th 9 b O ₁ IO 95.0 1 2 5 6th 10 C. 1.89 5.0 3 6th 8th 8th 10 3 H 0.10 95.0 - .3 6th 8th 8th 10 ■ 5.0 4th 7th 8th 9 10 4th • 4th 7th 8th 9 k

milky white (0) milky yellow (5) milky brown (10)

The dynamic heat resistance results illustrate that the combination of the monomethyltin compound with the dimethyltin compound compared to using the monobutyltin compound with the dibutyltin compound and to use the monooctyltin compound with the dioctyltin compound brings about a significantly improved stabilizing effect.

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Example 5

Polyvinyl chloride (Geon 103 Ep-8) 100.0 parts by weight

MBS resin (Kane Ace B-12)

(Monobutyl styrene resin) 10.0 parts by weight

Stearyl alcohol 0.5 part by weight

Stabilizer (Table 10), 2.0 parts by weight

The halogen-containing vinyl resin formulations were processed into films in a manner similar to that described in Example 1 in terms of the speed of their color development.

Table 9 - Stabilizers

a dimethyltin bis (isooctyl thioglycolate)

b monomethyltin tris (isooctyl thioglycolate)

c trimethyltin isooctyl thioglycolate

h dibutyltin bis (isooctyl thioglycolate)

j dioctyltin bis (isooctyl thioglycolate)

(Instead of MBS, ABS (Acrylonitrile-Butadiene-Styrene Terpolymer) can be used, as well as other modifying agents. It can also be conventional, which makes processing easier Substances are added.)

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- 1ö -

Table 10 - Results

Ve.r- Stabili-

bin- lisie-

dung. Weight

No »medium phr parts

Color of the sample (minutes) '

Color of the

to press

Early 20 40 60 90 120 slide

1 al _f 8 89.5 0 1 b 0.2 10.0 0 1 c 0.01 0.5 0 2 a 1.6 79 _f 5 0 2 b 0.4 20.0 0

2 c 0 _f 01 0.5 0

3 a 1.2 59.5 0 3 b 0.8 40.0 0 *

3 " c 0.01 0.5 0

4 a 1.0 49.5 0

4 b 1.0 50.0 0

4 c 0 _f 01 0.5 0

5 h 2.0 100.0 3 5 j 2.0 100.0 , 4th

7 a 2.0 100.0 1

8 b 2.0 100.0 0

9 c 2.0 10 _{O 1} O 3

0 0

4 colorless

2 - 4

0 15

1 5

0 13 5 10 light yellow

0 1 3 5 10 "

0 1 3 5 10

5 5 7 8 9 yellow

* 5 6 8 8 9

2 2 2 3 7 colorless

1 9 7 light yellow

5 5 7 8 9 dark yellow

colorless (O) yellow (3) brown (7) black (10)

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The results obtained show the significantly better effect of the combined stabilizing agent according to the invention in the polymer mixture of MBS and halogen-containing vinyl resin compared to the dibutyltin and dioctyltin compounds.

The amount of Monomethylζinn compound in the invention Mixture of compounds of the general formulas (1), (2) and (3) can be varied so that the mixture 4 to 98% monomethyltin compound and accordingly 96 to 2% dimethyltin compound and no more than 0.6% trimethyltin compound contains. Preferably the amount is the trimethyltin compound . even less, for example not greater than 0.4% down to 0.01% or even less.

It has been found that Dimethylζinnderivate of Alkylthioglycolaten subject to rearrangement during thermolysis with the formation of various trimethylin compounds. This Phenomenon can be determined on the basis of the isooctyl thioglycolate by the following equilibrium

CH ₃ Sn (IOTG) ₃ + (CH ₃ J ₃ SnIOTG DMT

reproduce.

The equilibrium constant was determined as:

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K = = 0.14 ± 0.01 at 180 ° C (1)

Increasing amounts of monomethyltin compound are therefore used the theoretical equilibrium concentration of the trimethyltin compound in that described by the equation (1) Way decrease.

From the figures, Fig. 1 shows a graphical representation of the thermolysis of three different dimethyltin bis (isooctyl thioglycolate) compositions at 180 ⁰ C.

FIG. 2 graphically illustrates a thermolysis similar to that in FIG. 1.

Figure 3 graphically depicts the equilibrium mixtures of methyl and dimethyl tin isooctyl thioglycolates at 180 C as well as using the equation for the Equilibrium constant (1) calculated final concentration of trimethyltin isooctylthioglycolate again.

Fig. 4 shows a graphic representation similar to that in Fig. 3, but with the initial concentrations of monomethyltin tris- (isooctylthioglycolate) are limited to 80% and more.

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The concentrations of D, M and T determined according to equation (1) for the equilibrium constant are given in the table compiled and, as mentioned above, shown graphically in FIGS. 3 and 4.

The rate at which the trimethyltin isooctylthioglycolate is formed depends on the concentration of the monomethyltin compound (see equation (2), below). the higher concentrations of monomethyltin compound slow down the formation of the trimethyltin derivative.

Speed: H = ^k l W * " ^k 2 MM < ² >

There were 100% dimethyltin-bis-isooctylthioglycolate as well with mixtures containing monomethyltin tris-isooctylthioglycolate contained, tests carried out. The mixtures contained 19> 28.6 or 80.0% by weight of monomethylamine derivative. At 180 ° C the composition of the mixtures was determined as a function of time. The results obtained are in the Tables 11, 12, 13 and 14 are compiled and shown in Fig. 1 and 2 are shown graphically.

It can be seen from this that by increasing the amount of the monomethyltin compound in the starting mixture with the dimethyltin compound the formation of trimethyltin compound at increased

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Temperatures is effectively suppressed. This is important when using methyltin compounds for stabilization halogen-containing resins, as these resins are normally processed hot for example at 150 to 2OO ° C. It will thus even if the starting amount of trimethyltin compound in the Stabilizer initially low this gradually became increase, if not together with the dimethyltin compound a substantial amount of monomethyltin compound is used. The amount of monomethyltin compound is advantageously for example monomethyltin tris (isooctylthioglycolate) 75% or more, preferably 80% or more of the Total amount of monomethyl and dimethyl tin compound to ensure formation during hot processing of trimethyltin compound is kept as low as possible.

Thus, in Example 1, 20% (0.4 phr) of (a) and 80% (1.6 phr) of (b) or 2% (0.04 phr) of (a) and 98% (1.96 phr) at (b) can be used to suppress the formation of (c) during processing at 170 ° C, 175 ° C and 180 ° C.

Instead of the isooctyl ester, any other desired monomethyl and dimethyl tin ester can be used for the stabilizing mixture containing large amounts of methyl tin monoester, which is for example 40% monoester and preferably 75% or even more monoester, based on the total amount of monomethyltin

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ester and dimethyltin ester may contain at elevated levels Temperature to suppress the formation of trimethyltin ester. The starting amount of trimethyltin ester is, as already stated, advantageously kept as low as possible, for example to 0.6% or less, in particular to 0.4% or less and with an even greater advantage to 0%.

Table 11

Thermolysis of dimethyltin bis-isooctylthioglycolate

Conc. Of

JTJ-VJUCf
No. (Min.) % By weight MONO- Wt.% DI- Wt.% TRI- I-l 0 - 99+ - la 5 ⁴ I ⁷ 93.0 2 _f 0 2 .10 9.9 87.0 3.0 3 20th 11.8 87.0 4.6 - 4th 35 18.9 73.0 8.3 5 60 20.3 63.0 8.0 6th 90 22.0 61.5 9.5

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2501Q07

Table 12 Thermolysis of methyl tin isooctyl thioglycolate mixtures

Conc. Of methyltin isooctylthiog lycolate, wt.%

rl. uuc,
No. (Min.) % By weight MONO- Wt.% DI- Wt.% TRI- II-l 0 28.6 71.4 - la 5 27.0 69.2 1.0 2 10 25.9 66.5 3 20th 25.8 62.8 1.8 4th 35 28.5 56.2 5 60 31.0 60.1 4.3 6th 90 29.8 53.0 7 _f 3 Table 13

Thermolysis of methyltin isooctylthioglycolate mixture at 180 ⁰ C

Conc. Of

Sample,
No. Time
(Min.) % By weight MONO- h ^ ^^ ^^ ^^ V ^ V ^ b * ^^ ** ^ l * ^ k ^ ^ -Λ ^^ y
Wt.% DI- Wt.% TRI- III-l 0 19.0 81.0 - la 5 ■ - - ". I ₁ O 2 10 20.1 74.3 1.6 3 20th 22.7 73.4 4th 35 25.0 62.9 3.4 5 60 27.1 59.7 5.8 6th 90 27.4
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Table 14 Thermolysis of methyl tin isooctyl thioglycolate mixtures at 180 ° C

Conc. Of methyltin isooctylthioglycolates , % by weight

No. (Min.) % By weight MONO-% by weight DI- Tabel 19.7 Wt.% TRI- IV-I 0 80.0 20.0 0.3 la 5 79.0 18.4 <1 2 10 81.0 19.5 3 20th 75.0 -1 4th 35 19.1 -1.5 5 60 75.9 17.7 -2 6th 90 72.3 15th -2

Equilibrium of the mixtures of mono- and dimethylζinn-

O.

Mole%:

isooctylthioglycolates at 180 C Mono- Pi Tri GeW.% Mono- Di

Tri-

a) 99 _r 0 I ₁ O 0 99.25 0.747 0.000692 b) 99 1 ° 0.997 0.00141 99.25 0.745 0.0 a) 98 _f 66 l _f 34 0.0 99 _r 0 1.00 0.00125 b) 98 _f 66 1,335 0.00253 99.0 0.999 0.0 a) 97 r ° 3.00 0.0 97 _f 75 2 _f 25 0.00637 b) 97 _r 01 2.987 0.0128 97.76 2.23 0.0 a) 95 _r Q0 5.00 0.0 96.22 3.78 0.0179 b) 95 _f 04 4,964 0.0358 96.26 3 _r 72 0.0 a) 93 _f 46 6.54 o _r o 95.0 5.0 0 _# O313 b) 93 r ⁵² 6 _r 42 0.0617 95.07 4 _f 90 0.0 a) 92 r ° 8.0 0.0 93 _r 91 6.09 0.0469 b) 92 , 09 7.81 0.0931 94 _r 01 5.95 a) 90 t ° 10 _f 0 0.0 92 _r 35 7.65, 0.0744 b) 90 _r 15 9.71 0.147 92 _f 5Ö 7.42

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Mole%;

Mono- di- tri- wt.% Mono- di-

Tr ί

87 _p 87.27 85.00

85

12.97 12 _r 47

14.32

0.0 O ₁ 25

15.00 0 _f 00

O ₁ 338 90.0 90.2 6 87.40 88 _f 73

10.0

9.51 12.60 11.10

0.0 0 _f 128 O ₁ O 0.173

80.00 80.61

⁷⁶ I ⁵

77.35

20.0 18 _r 23 _f 21 _r 79

O ₁ O 0.612 0.0 0.853 84.29 84.93 81.37 82 25

15.71 0.0

14.75 18.63 17.31

0.318

0.0

0 _f 438

74.17 75 _t 23 58.07 61.03

25 _f 83 23 41 _f 93 35.99

0.0 1.05 O ₁ O 2.97 79.39 79.87 65.0 68.33

20.61 19.57 35.0 30.03

o _r o

0.550

0.0

1.64

37.88

62.12

0.0

45.01 47.86 7.13 45.0 53 _? 45

55.0 42.37

0.0 4 _f 18

24 _f 35.6

75.6 53 _f

0.0 11 ₁ 2 30.24 44.01-

69.77 44.09

0.0 6 _f 84

23.0

34.65

14.9

77.0

O ₁ O

53.7 11.65 85.1

29.6 0.0 21 _f 385 57 _f 23 21.385

55.7 100.00

0.0 14 _f O ₁ O 28 _f 6

19.0 37 _r 77

0.0 28 66

71.4

81.0 52.97 100.00

0.0

43.06 49.77 7.15

0.0 9 _f 26

57.19 14.15

a) = at the beginning

b) = in equilibrium

509 831/0910

Claims (22)

Claims Stabilizing agent for halogen-containing synthetic resins based on dimethyltin bisr (thioalkanoates) according to patent ....... (patent application P 23 29 039.3) , characterized in that it consists of a mixture of (1) 2 to 96% dimethyl tin bis (thioalkanoate) of the general formula CH-. .S (CH ₉ ) COOR ⁵ / ^{Δ η} Sn
CH ₃ ^ S (CH ₂ ) _n COOR (2) 98 to 4% monomethyltin tris (thioalkanoate) der general formula CH ₃ - Sn [JS (CH ₂ J _n COOR] ₃ (3) no more than 0.6%, preferably no more than 0.4% trimethyltin thioalkanoate of the general formula CH ₃ CH., - ^ Sn - S (CH ₀ ) COOR CH ₃ ' exists as an impurity, where R is a hydrocarbon radical with 1 to 20 carbon atoms and η is a whole Number is from 1 to 3. 5 09831/0910 2. Stabilizing agent according to claim 1, characterized in that it is 2 to 60% of the compound (1) and 98 to Contains 4% of the compound (2), 3. Stabilizing agent according to claim 1 and 2, characterized in that it has an LD ₅₀ of at least 695 mg / kg when administered orally to rats. 4. Stabilizing agent according to claim 1 to 3, characterized in that R is an alkyl, cycloalkyl, alkenyl or benzyl radical and the LDc _{0 is} at least 1000 mg / kg. 5. Stabilizing agent according to claim 1 to 4, characterized characterized in that R is an alkyl radical having 4 to 12 carbon atoms and η is the number 1 or 2. 6. Stabilizing agent according to claim 1 to 5, characterized in that R is an alkyl radical having 8 to 12 carbon atoms is. 7. Stabilizing agent according to claim 1 to 6, characterized in that it does not contain more than 0.5% of trimethyl Contains tin compound. 509831/0910. 8. Stabilizing agent according to claim 1 to 7, characterized characterized in that it contains no more than 0.4% trimethyltin compound contains. 9. Stabilizing agent according to claim 1 to 8, characterized in that it is in the resin in an amount of 0.1 to 5% by weight is included. 10. Stabilizing agent according to claim 1 to 9, characterized in that it is in the resin in an amount of 0.1 to 2.5% by weight is included. 11. Stabilizing agent according to claim 1 to 10, characterized in that it is 2 to 25% of the compound (1) and Contains 98 to 75% of the compound (2) and its trimethyltin compound content is not more than 0.6%. 12. Stabilizing agent according to claim 1 to 11, characterized characterized in that it contains 2 to 20% of the compound (1) and 98 to 80% of the compound (2). 13. Stabilizing agent according to claim 1 to 12, characterized characterized in that it contains 20% of the compound (1) and 80% of the compound (2), based on the total amount of (1) and (2) contains. 509831/0910 14. Stabilizing agent according to claim 1 to 13, characterized characterized in that it is present in the resin in an amount of 2% by weight is present. 15. Stabilizing agent according to claim 1 to 14, characterized characterized in that it contains 2 to 10% of the compound (1) and 98 to 90% of the compound (2) and its content of trimethylin compound is not more than 0.15%. 16. Stabilizing agent according to claim 1 to 15, characterized characterized in that it is 2% of the compound (1.) and 98% of the compound (2) and not more than 0.006% of the trimethyltin compound contains. 17. Stabilizing agent according to claim 1 to 16, characterized characterized in that it consists of a mixture of dimethyltin bis (isooctylthioglycolate) and methyl tin tris (isooctyl thioglycolate). 18. Stabilizing agent according to claim 1 to 10, characterized in that it contains 60 to 96% of the compound (1) and 4 to 40% of the compound (2) and not more than 0.6% of the trimethyltin compound as an impurity. 509831/0910 19. Stabilizing agent according to claim 18, characterized in that that no more than 0.75% of the total tin calculated as metal in the form of the trimethyltin compound are present. · 20. Stabilizing agent according to claim 18 and 19, characterized characterized in that it contains 71 to 81% of the compound (1) and 29 to 19% of the compound (2) Trimethylin compound content not more than 0.6% amounts to. 21. Stabilizing agent according to claim 18 to 20, characterized characterized in that it is about 24% of the compound (2), not more than 0.6% of the trimethyltin compound and the remainder the Contains compound (1). 22. The use of the means according to claim 1 to 21 for Stabilization of chlorinated polyethylenes, polyvinyl halides and polyvinylidene halides, particularly of polyvinyl chloride and polyvinylidene chloride. schjkö 5 0 9 8 3 1/0910