DE2549332A1 - DIORGANOZINNMALEINATE - Google Patents

Description

Case 3-965 3 / CGM 11 9 / +
Germany

Diorganotin maleate

The present invention relates to a mixture of oligomeric Dialkyl or dibenzyltin maleic acid half esters, their Ester groups are built up from diols and higher aliphatic alcohols.

Diorganotin bismaleates have been around for a long time as effective stabilizers against the varine- and light-induced Degradation of polyvinyl chlorides known, the simultaneous light stabilization of particular Advantage is. Particularly well-known representatives at this point are di-n-butyltin-bis- (i-butylmaleate) and Called di-n-butyltin bis (i-octylmaleate).

On the other hand, however, the low inherent thermal stability of these compounds is felt to be particularly disadvantageous. as this is known to act as an irritant during the processing of the PVC thermoplastics stabilized in this way

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active and volatile maleic anhydride: is formed (see e.g. J.Macromol. SCI-REVS.Macromol.Chem., C3 (2), 1969, page 274). As a result, a higher processing-technical effort is necessary, so that the resulting Maleic anhydride does not enter the surrounding atmosphere.

In British Patent 718,741, inter alia, polymeric diorganotin maleic acid esters are made from diols and diorganotin oxides, optionally also additionally from alcohols such as butyl glycol or monocarboxylic acids such as linoleic acid to stabilize vinyl chloride resins suggested. Due to the high molecular weights, these products are highly viscous or solid, which is what the Incorporation of the stabilizers into the polymer is disadvantageous. Next is the thermostabilizing effect these polymeric organotin maleate not satisfactory, which is partly due to the nature of the products can be. The process described in more detail in Example 1 of the British patent is produced also tin alkoxy groups and it is common knowledge that tin alkoxylates have a lower stabilizing effect Have an effect as, for example, organotin maleate.

The object of the present invention is to provide a stabilizer based on organotin maleate for chlorine-containing To provide thermoplastics, in particular for polyvinyl chloride, their effectiveness against the known diorganotin maleic acid half-esters is practically not reduced and the thermal during processing dux-ch Breakdown of less volatile components, especially less volatile irritants.

75 M.529a

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ORIGINAL INSPECTED

The present invention relates to binding mixtures of the general formula I.

RR ¹

I OOC ~ CH = - CH-COO-Sn- [OOC-CH ^ CH-COO-R ^ OOC-Ci ^ CH-COO-Sn-] 00C-CH = CH-COOR ' a ι ι - a

R l · ⁿ

(D

wherein

R and R 'independently of one another, represent an alkyl radical with 1 to 12 carbon atoms or the benzyl radical, R an alkylene radical with 2 to 12 carbon atoms or a polyethylene glycol residue with 2 to 6 units, R and R 'independently of one another a linear or branched alkyl or an alkenyl radical with 12 to 18 carbon atoms and η as the mean value for a rational number between 0 and 2, with up to 1/3 of the terminal maleic acid half-ester residues by monocarboxylic acid residues with 12 to 18 carbon atoms can be replaced.

R and R ¹ are preferably the same, R and R ¹ denote an alkyl radical having 1 to 8 carbon atoms, particularly preferably methyl, n-butyl

or n-octyl. Further examples of R and R ¹ are: ethyl, propyl, η-butyl, i-butyl, pentyl, hexyl, 2-methyl-pentyl, heptyl, octyl, i-octyl, decyl, undecyl, dodecyl.

R is preferably a linear or branched alkylene radical with 2-6 carbon atoms or a polyethylene glycol radical with 2 to 4 units, especially an ethylene radical, which can also be substituted, or the diethylene glycol radical, in particular but the ethylene residue itself.

R _a and R ^ 'are preferably an alkyl radical having 12 to 16, in particular 12 to 14 carbon atoms, which is particularly preferably branched and η is preferred as the mean value

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a number between 0.5 and 1.5, especially between 0.8 and 1.2 and in particular the number 1. It is further preferred that the tin content in the compound mixture is at least 16% by weight. Particularly valuable mixtures of compounds are those in which R and R 'are an alkyl radical with 1 to 8 carbon atoms, in particular a butyl radical, R and R 'is an alkyl radical having 12 to 14 carbon atoms, R an ethylene radical and η as the mean value is a number between 0.5 and 1.5.

The compound mixtures are used according to one for the production known from organotin maleic acid half-esters Receive step-by-step procedures. First of all, alcohols are used

of the formula R -OH, optionally together with alcohols of the

^a 1

Formula R ¹ -OH and diols of the formula HO-R-OH with maleina

sMureanhydride around, whereby essentially the corresponding half-esters are formed. In a second stage, the half-esters thus obtained are reacted with an organotin oxide of the formula RjSnO, optionally together with an organotin oxide of the formula R ¹ ^ SnO, with removal of the water of reaction to give the compound mixtures according to the invention. The reaction is illustrated by the following scheme:

2R -OH + nllO - R ¹ - OH + (2n 4- 2)

2R - 0OC-CH = CH - COOH + nR ¹ - (0OC-CH = CH-COOH)

el. '

+ (η + I) R ₉ SnO

¹ 1

R OOC-CH = CH-COO-Sn- [OOC-CH = CH-COO-R-OOC-CH = CH-COO-Sn-] OOC-CH = CH-COOR

^a II ή ^a

^R R

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The reactions of both stages v / ground generally performed at elevated temperatures, preferably at 50 ° 180 ⁰ C, particularly 80 to 14O ⁰ C. It also a solvent may be used, however, is more advantageous if no solvent is used. The water of reaction of the second stage can be distilled off under normal pressure or vacuum and heating, if appropriate together with a solvent. In a preferred embodiment, the water of reaction is removed only by applying a vacuum with simultaneous heating of the solvent-free reaction mixture.

The maleic acid half-esters of the intermediate stage can in some cases, preferably up to 1/3, be replaced by monocarboxylic acids, which contain 12 to 18 carbon atoms, e.g. oleic acid, Stearic acid or palmitic acid without doing so the valuable properties of the invention Mixtures are affected too much. Suitable alcohols are:

n-dodecanol, n-tridecanol, n-tetradecanol, i-tetradecanol, Pentadecanol, 2-ethyltridecanol, n-hexadecanol, 3-methylpentadecanol, n-octadecanol, i-octadecanol, n-dodecen-l-ol-12, 2-methyl-dodecen-l-ol-12, n-tetradecenol, 2-ethyl-tetradecen-l-ol-14, 2-methylpentadecenol-1, oleyl alcohol. from i-Tridecanol should be mentioned in particular as the preferred branched alcohols.

The following representatives are examples of diols called: diethylene glycol, triethylene glycol and tetraethylene glycol lycol, hexaethylene glycol and general diols Formulas HOC H ^ -OH, where η is an integer of 2 can be up to 12, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,3-pentanediol, 1,6-hexanediol, Trimethylhexanediol, 1,8-octanediol, 1,4-octanediol,

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75.11.329a

2b49332

1,12-dodecanediol. Preference is given to 1,2-diols such as ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-IIexanediol, 2,3-butanediol, 2,3-pentanediol, 2,3- or 3,4-hexanediol, 1,2-octanediol, 1,2-dodecanediol and diethylene glycol and especially ethylene glycol. It is also possible Use mixtures of diols.

The mixture of compounds according to the invention represents a statistical one Mixture of monomers and oligomeric organotin maleic acid half-esters -dar what is expressed by η. There can also be proportions of the starting products be included in the first reaction stage. Ever The larger η is, the more proportions are contained in the mixture which have a higher degree of condensation. The distribution in relation to the number of connections and thus the size of η is determined by the proportions the starting components and influenced by the reaction conditions. -

In the first reaction stage, it is advantageous per mole Alcohol group used one mole of maleic anhydride. Becomes the ratio of diol to alcohol at this stage of the reaction set to approximately 1: 2, one can expect that η in the mixture of compounds according to the invention will be around 1. If the ratio of 1: 2 is shifted in favor of Diole, then predominance in the second reaction stage chain-building reactions of the glycol esters with the diorganotin oxide versus the termination reaction of diorganotin oxide with alcohol half-esters and as a result η will become larger. When postponed of the ratio 1: 2 in favor of alcohol, the opposite occurs and η becomes smaller. Particularly preferred the ratio is adjusted so that η is approximately in the range of 1.

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The so-called cracked mixtures are ideal for stabilizing thermoplastic molding compounds made of or based on vinyl chloride, especially in calender and extrusion technology.

The present invention therefore also relates to thermoplastic, chlorine-containing plastic mixture, containing:

a) a polymer made of or based on vinyl chloride and

b) 0.1 to 5% by weight, preferably 0.5 to 2% by weight of a mixture of compounds of the formula I.

With the compound mixers according to the invention can Vinyl chloride polymers or copolymers are stabilized. Suspension and bulk polymers are preferred as well Emulsion polymers. As comonomers for the copolymers for example: vinylidene chloride, transdichloroethane, ethylene, propylene, butylene, maleic acid, Acrylic acid, fumaric acid, itaconic acid.

The. The stabilized molding compositions are produced by known processes by incorporating the stabilizer and, if appropriate, further stabilizers into the polymer. A homogeneous mixture of stabilizer and polymer may, for example, using a two-roll mixer at 150-210 ⁰ C are obtained. Depending on the intended use of the molding compound, further additives can be incorporated before or with the incorporation of the stabilizer, such as lubricants, preferably montan waxes or glycerol esters, plasticizers, fillers, modifiers such as impact additives, pigments and / or light stabilizers.

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2 b 4 9 3 3

The successfully measured V erb inching sg erni see are more fluid or waxy consistency and can work well in vinyl chloride polymers be incorporated. They are stable in storage and have a very good stabilizing effect and favorable processing properties. They are not prone to plate-out .-- Appearances and in addition to being good Initial color, practically no cloudiness is observed in the press plate test and the plasticizing time (determined in the. Plastograph test) is favorable. It is surprising and particularly advantageous that it is essential when heating less volatile components are formed, and it is particularly surprising that even the proportion of Maleic anhydride is reduced in the volatile mixture, Xtfenn with known orgaiio tin maleic acid half-esters compares.

The following examples elucidate the invention in more detail. Herein parts are parts by weight and percentages are percentages by weight.

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Manufacturing examples

Example 1-1 7

According to the Mo! Ratios given in Table 1, maleic anhydride, glycol and alcohol, optionally together with a monocarboxylic acid, are ^{heated to 110 °} C. for minutes. The temperature is then ^{lowered to 80 °} C. and the specified amount of diorganotin oxide is introduced. After about 30 minutes, a vacuum of 10 to 40 Torr is applied and ^{the mixture is heated to 110 °} C., the water of reaction being removed. The reaction mixture is then filtered while it is still warm.

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75.11.323 «

Tabel

No.

Raw materials

Diorgano-

ίzinc oxide

Maleinanhvdrid

(molar amounts used in clauses)

Diol j monovalent! Alcohol exnoase

Carboxylic acid

% Sn
(found)

consistency

DBTO
(0.2)

(0.4)

Ethylene glycol (0.1)

i-tridecanol (0.2) 13.0

viscous liquid
flows well

j 2 j DBTO
«(0.2)

(0.4)

Ethylene glycol (i-tridecanol (0.13) j (0.1) 20.0

highly viscous liquid not very fluid

ί DBTO
! (0.2)

(0.4)

Aethy1engIyco1 (0.1)

Tetradecanol (0.2) j 17.8

waxy firm

] DBTO ί

KO, 2) ^ι (0.4)

ι (comparative example)

Ethylene glycol j i-T-butanol (0.1) I (0.2) 22.7 {viscous liquid
good flowability

iDBTO ίAethylene glycol} i-0ctanol

i (0.2) ^! (0.4) j (0.1) i (0.2); (comparative example) j ' \

\ 20.7! viscous liquid

) · Speed

j good flowability

DBTO
1 (0.2)

(0.4)

Ethylene glycol \ Oieylalkohol (0.1) I (0.2) 16.4 j viscous liquid jj ness I

j good flowability \

1) = dibutyl tin oxide

Table 1 (continued)

Starting materials diorgano \ Maleinzinnoxid ιanhydrid

(molar quantities in brackets)

Diol ι monovalent monobasic

! kit * * 4

Alcohol carboxylic acid

% Sn
(found)

consistency

DBTO (0.2)

(0.4)

Hexanedio1 (0.1)

i-tridecanol 17.4

Liquid, j which after some i

! Weeks waxy 'ι solidified'-

DBTO- (0.2)

(0.4)

Trimethylhexane-j i-tridecanol diol (0.1) I (0.2)

16.7 ι viscous, flowable

DBTO (0.2)

(0.4)

Neopentyl glycol! i-tridccanol (0.1) I. (0.2) 17.9 viscous, flow-

able

DBTO (0.2)

Ethylene Glyco1 (0.1)

I-Tricecanoi . (0.15)

i-octo.decanol (0.05) '17.5

j viscous liquid, fiiess-

able to

DBTO (0.2)

j ethylene glycol (0.4) j (0.1)

i-tridecanol (0.15)

Oleyl alcohol (0.05) 17.5

! viscous liquid, flowable

D3T0 "(0.2)

j (0.35)

j ethylene glycol (0.1)

i-tridecanol (0.15); Lauric acid i 18.6
(0.05) j

; viscous liquid

j speed,

easy to flow

Table 1 (continued)

No. I raw materials male

jDicrgano {tin oxide

anhydride

! (molar inserts in brackets) I. Diol; monovalent; egg:

Alcohol ι carboxylic acid

monobasic

% Sn
(found)

least

DBTO
(0.2)

(0.35)

Ethylene glycol (0.1)

i-Tridecanol (0.15.) Oleic acid
(0.05)

18.6

viscous liquid
good flowability

DBTO
(0.2)

(0.35)

Ethylene glycol (0.1)

i-tridecanol (0.15) i-stearic acid (0.05)

18.3

viscous liquid
good flowability

CjD j j

.σο 15 JDBTO

(0.2). i (0.3) (comparative example)

i-tridecanol (0.2) 20.5

viscous liquid, easy to flow, not bearing stable ,. Precipitation

j DBTO j

(0.2) i (0.3) (comparative example)

Oleyl alcohol (0.2) 18.3

viscous liquid, easy to flow, not stable in storage, formation of precipitates

! 17 j DBTO
(0.2)

(0.4).

Triethylene glycol (0.1)

j i-tridecanol (0.2) j 17.0

viscous liquid, good flowing

able to

Application-specific examples

Example 18

To check the formation of volatile components the evaporation losses after the two following Methods determined.

a) 5 g of the substances shown in Table 2 are heated in a Umlufttrockensc.hrank at 160 ⁰ C for 45 minutes. Then the weight loss is measured.

b) 5 g of the substances given in Table 2 are used

^{Heated to 120 °} C. in a vacuum drying tank at 0.1 torr for 3 hours. Then the weight loss is determined.

Table 2 shows the weight loss in percent,

Table 2

product Weight ¹
160 ° C test / loss
120 in the
° C test
α) Dibutyltin-bis-
(i-butyl maleate)
No. 4 25th
12th 16
7th No. 5 13th 10 number 1 5 7th No. 6 4th 1 No. 17 5 8 ■

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ORIGINAL INSPECTED

Example 19

Subsequent mixtures are made using press plates Continuous whale test checked the thermal stability.

Mixture Λ

S -PV C, K-YJ & rt: Montan wax

2, G-di-t-but; yl-4-diethylphenol

stabilizer

Mixture B: S-PVC, K-value:

Vinnol K.510 / 68 (Propfpolytuerisat from vinyl chloride to ethylene vinyl acetate)

Montan wax

2,6-di-t-butyl-4-methylpheno1

stabilizer

100 , 25 Parts 0 , 2 Parts 0 Parts 2 Parts 50 Parts 50 Parts

0.25 parts 0.2 parts 2.0 parts

Test press plate (PP):-rolled sheets, samples are taken and atm in a press at 200 and thermal load 180 ⁰ C. (Time: 2.5 minutes). The thickness of the samples is 2.5 mm.

Endurance roller test (DWT): The mixture is ^{plasticized at 190 °} C. on a mixing roller mill. After 10 and 35 minutes, respectively, samples 0.3 mm thick are cut from the middle of the film. The thermal stability is measured with the help of the yellowness index (η. ASTM-D 1925-70) as a measure of the yellowing

degree (YI, YIn ₀ or YI-n). The contrast ratio (KV) as a measure of opacity is also given in Table 3 (device: Elrepho from Zeiss).

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75.11.329a

) -) 4 η ' ^J - 3 2

Tabe.Ue 3

PreGsplntten- and permanent rolling csts

Test: PP _YI (2) K7 < ³ > A. YI I. Readings 33 2.3 28 KV DWT ^ ¹ ^ YT
■ 35 B. 5.8 37 Kess size: 31 1.9 28 ^YI 10 8.1 63 mixture 36 2.1 31 6.0 30th 40 2.6 31 3.7 7.2 58 Stabilizer: Dibii-
tylzinn-bis- (i-bu-
tylmaleate) 36 2.1 30th 3.4 7.5 69 number 1 36 2.2 30th 3.1 5.0 33 No. 9 39 2.3 32 3.9 6.5 54 No. 10 3.3 No. 11 4.0 No. 12 3.9 No. 13

Note: (1)

In the DWT, the yellowing is after 10 and 35 minutes Rolling duration specified (YInQ or ΥΪ05)

YI = Yellowness Index (yellowing)

KV = contrast ratio (opacity)

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ORIGINAL INSPECTED

Claims (1)

Claims ^a II, η ^a (D R and R ¹ independently of one another are an alkyl group with 1 to 12 carbon atoms or the benzyl group, R is an alkylene group with 2 to 12 carbon atoms or a Pol \> - "ethylene glycol group with 2 to 6 units, R and R ¹ a a independently a linear or branched one Alk} * ·! - or alkenyl radical with 12 to 18 carbon atoms and η is the mean value for a rational number between 0 and 2, up to 1/3 of the terminal MaleinsMure half ester residues by monocarboxylic acid residues with 12 to 18 carbon atoms can be replaced. 2. A mixture of compounds according to claim 1, characterized in that R and R ^{1 are the} same. 3. Compound mixture according to claim 1, characterized characterized in that R and R ^{1 are the} same. 3. a 4. A mixture of compounds according to claim 1, characterized in that R and R ^! are independently an alkyl radical having 1 to 8 carbon atoms. 609821/1040 ^; '-. 2b49332 5. Connected according to the claim. 4, thereby marked j that S raid R * ftfr the methyl, π-btity Ιο the n-octyl radical. 6. Yerbindtmgs mixture, according to claim "L _% thereby 1
characterized ^ that It is an alkylene radical with 2 rock 6 carbon atoms, or a folyethylene glycol radical. with 2 to units is * 7. '■ Verbiädtmgsgeiisch. according to claim 6 _y · characterized · 'that R Εϊϊι
Diet glyko.lires-t "·" stands. « germinated, · that R Eür the Äethyienrest or the B. ■ '■■ IFE rblnd-ängsgeittisck: gemiiss _Ansprtrch: 1, characterized geitattii2eichnefe _:( - .. R. tHtdT that R "AIkylreste with .. 12: Up c & et 16'Karbonaficuäea-mean. -. . ...... 9. '' ^: ¥ erMÄdiQßgsgemisck. geaöfss, Aaspnreii Β », gekennz-eiehnet ^ 'iiaiss-R- ■■' ■■ « imFE ¹ for a branched one. Alkyl radical with 12 to 16 carbon atoms. 10. Verb i-iidiing sgeasisdk- 'geeßf s s Aasprtrci ». .9. i: 'by this marked in zv ichnet, dai: s *, R vsad R for the i-tridecyl. 11,:. . · .., compound mixture according to claim _1 »thereby characterized in that η as the mean value means a number from 0.5 to 1.5. - ... 609821/1040. ORIGINAL INSPECTED 12 * Verbiradrangsgemiseh according to claim 1, thereby gefeaaHZ & iefnaeE: j, fess whose tin content is at least ·· 16 C? ew .-%. - · ■ - - ^ ■ · - ^: - · ■ "- ■ - ^; '..:' :. IS. ? er ^ iaifeogsgemi ^ eh .gciiiäss-Claim 1 ,, thereby-, · ■■ "g.efeHazeiehnet _$: that R .and R ^! '' / for an alkylresfc- ^: with - '1 Ms S KohJenstö'ffatomen and R and Ri, for Onea alkyl -. HBi t 12 to 14 feiilens to ff atoms are a ,. R ■ -., and η is as mean ψφτι ö, 5 Ms means I ₅₁ S a- number .... _..,, .,., .. T 14 "^ erbiimiäEmgsverbindungen according to claim 1 -,> a & ämzeh ■ geitenn- et ^ that R mid R ¹ for n-Butjl ,, R and R ^r for Isotri- T SE. SL tmd BL. f ^ r ^ ethylene, keopeatylene or 2 _S 2 _S 4-trimethyl 15 ·. ¥ er £ aljreiE zor-Hers division: from ¥ mixed ethnic groups Formula I. R OOC-CH-GH-COQ-Snr- [0 <D! C-CS = CH-COO-R ¹ -CKJG-CH = CS-eOO-Sn-IJJaC-Ga = ^^ a · j _; la E tmd. R * mna & Bttamgig ^ oneinaadier einea Älkylrest EELt: 1 "to 12. Kbltleiffi'S-toffattceeTa or the Betiaylrest, R a
itlkjlenrest mij!:. 2_ | j £ s ,, 12th carbon atoms, or one j ^ feeslxest ^ t 2 bis _; 6 units ,, R _& and JR ^ wnseJbiEaaeler a linear, or branched Alkyl or alkemyl resfc with 12 Ms IS iOahlens to ff atoms
mean ,, and.η as the mean value for a rational number
strives between O and 2 ^ being up to 1/3 of the terminal ORIGINAL INSPECTED Maleic acid half-ester residues through moiiocarboxylic acid residues can be replaced with 12 to 18 carbon atoms, characterized in that first diols of the general formula HO-R -OH and alcohols of the formula R-OH, optionally together with alcohols of the formula R'-0H reacts with maleic anhydride and then optionally together with monocarboxylic acids with 12 to 18 carbon atoms with a diorganotin oxide of the formula R ^ SnO, optionally together with a diorganotin oxide of the formula R ^! ₉ Sn0, V7 with R, R ', R, R ¹ and R as given above ^ - SL ei Have meaning, converts with removal of the water of reaction formed. 16. The method according to claim 14, characterized in that that R and R 'are the same. 17. The method according to claim 14, characterized in that R and R ^{1 are the} same. * aa ° 18. The method according to claim 15, characterized in that R and R 'independently of one another Denote an alkyl radical having 1 to 8 carbon atoms. 19. The method according to claim 18, characterized in that R and R ¹ stand for the methyl, n-butyl or n-octyl radical. 6098 217 10 40 2 D ^ b 33 Δ 20. The method according to claim 15, characterized in that that R 'is an alkylene radical having 2 to 6 carbon atoms or a polyethylene glycol residue with 2 to 4 units is. 21. The method according to claim 2O _5, characterized in that R stands for the ethylene rust or the DiethylengIyko1rest. 22. The method according to claim 15, characterized in that draws that R and
'a atoms mean. indicates that R and R ^{1 are} alkyl radicals with 12 to 16 carbon a a 23. The method according to claim 22 _} dadui-ch characterized in that R and R ^{1 represent} a branched alkyl est with ^ 12 to 16 carbon atoms. 24. The method according to claim 23, characterized in that R and R ¹ stand for the i-tridecyl radical a a. 25. The method according to claim 15, characterized in that η. the mean value is a number from 0.5 to 1.5 means. 26. The method according to claim 15, characterized in that the tin content in the compound mixture is at least 16% by volume. 609821/1040 PRIGiNAL INSPECTED 2543332 27. The method according to claim 15, characterized in that R and R. ' for an alkyl radical I have to 8 carbon atoms and R and R ¹ for an alkyl radical with 12 to 14 carbon atoms, R is an ethylene radical means and π means a number from 0.5 to 1.5 as the mean value. 28. The method according to claim 15, characterized in that R and R ¹ for η-butyl, R and R ¹ for isotridecyl and R 1 a a for ethylene, neopentylene or 2,2,4-trimethylhexylene-l, 6 stand. 29. Stabilized with organotin nuilein acid half-esters thermoplastic, chlorine-containing plastic mixture, containing: a) a polymer made of or based on vinyl chloride and b) 0.1 to 5% by weight, preferably 0.5 to 2% by weight of a mixture of compounds of the formula I according to claims 1 to 13. 609821 / 10A0