DE1815168A1 - Organotin mercaptocarboxylic acid ester sulfide with more than 18% tin content, stabilizers and resin compounds - Google Patents

Description

.-SNG. WA LTE R A BITZ DR. DIETER MORF Patent Attorneys

8 MQnchtn 27, Pienzenauerstrcae 28 Telephone 483225 and 486415 Telegrams: Cbemindus Mönche;

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The organotin sulfides ss «B. have the highest tin and sulfur sehalta per organosense group and are, nevertheless, not the best stabilizers and are never all stabilizers on the market because they have, among other things, a bad initial color ίϋ """?. * κ Trots their considerably lower sense and Sch '' fei - (iahflte are the most wirkeae currently in ferwendung befindlloi'sn Organozitro-S ¹ * λ ** ^"f1 capacitors and recognized StanderJ ^ roducts to Beurt" Hi "i others Organotin stabilizers, the organoeln-mereeijplouarbonaäureester. The main part of diflaer materials unAililifn "dearly all of the most used Üandela products" loaded either liquid with low actaeluead solids the hot deformation temperature and the impact resistance of polyvinyl chloride resins As a result, it is difficult to achieve a high degree of chemical stability and tiitem ho hen ERAI structural stability and equilateral Xrietallklarbtit 3SU achieve "- these problems are ia general Bandi in" Hand "weiia stares resins conditions of high temperature are subjected To achieve all these goals", it is necessary a Men ^ e of stabilizer which as' small as possible is' to be applied 'so that the structural. Wideratan-: looseness of the resin * is least affected. Bleaea 2iel is naturally relieved if the stabilizer has a very high tin content, but from this point of view the organic tin-capto-carbonic acid esters are not satisfactory.

BIe use of örga ·. ,, ^ »carbonic acid esters ale

Stabilizers, for PoIv ^ · β is well known

3 O 9 8 3 B / 1 p

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and is generally ready in eo early patents such as U.S. Patents 2,752,325, 2,641,596, and 2,648,650 described. ,

They are organosense sulfides in the United States patent 2 746 946 concreted. Also polymeric organofsense sulfides with a high proportion of tin and sulfur are already been geeohlagen. Examples of such materials are described in U.S. Patent No. 5,021,302 which describes polymeric Condensation products of Köblenwaeeerstoff-etanoic acid, Hydrocarbyl thioitonic acid and odor condensation products of these materials, but all of these suffer Materials under, dent one or the other disadvantage »of. until now prevented them from being widely used in commerce.

You Dutch Patent®® & rift 6700014t which refers to the United States patent applications Serial Numbers 517,967 from "J.January 1966 and 531 805 of March 2, 1966, describes combinations of monoalkylsense sulfides with tri-substituted hindered phenols and possibly susätelioh with org & notin-mercaptocarboxylic acids, meroaptooarboxylic acid esters or - Mercaptids. The purpose of adding the phenol is evident to the adverse properties of the organon sulfide to avoid and the further additives of the Organoinn-mercaptide the mercapto acid or the mercapto acid ester complements the Effect of phenol and organotin sulfide in this regard.

Further disclosures of polymeric organosense compounds which generally include a chain of tin atoms

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the oxygen or sulfur atoms are connected, bind, in U.S. patent documents 2,597,920, 2,626,993 »2,620,211, 2 746 946, 3 184 430 and 2 933 013 included.

US Pat. No. 2,809,956 discloses polymeric organotin compounds which have mercapto-meter groups attached to the sense one oh, one and the general formula

RR t · ·

t * ■ '♦ ft »R«

beeitien, where SX is a mercapto, mercapto alcohol or -ester- or Äercaptoettureeeter-Oruppe can »Bieee compounds tend to see, however, as not eo effective stabilizers like the monomeric organo-internal meroaptostittreeeter» like B.B. Dibutyllinn ~ bie (ieoootyl * thioglycolate).

Me VSA-fatenteehriften 3 078 390, 3 196 129 and 3 217 004 describe a number of thioacetal and thioketal organoin-ee.rboxylatöalss stabilizers which can be prepared in situ by converting thioacetal and Shioketal-oarbonstturen with aweifaoh Kohlenwaeeeretoff-eub-. Substituted xin oxides or sulfides or the corresponding mono- or triple-carbon-substituted oxides Tin compounds »'

The present invention classifies organosinn-O (- or β -meroaptooarboxylic acid ester sulfide · · with a relatively high concentration within the range ·· of about 18%

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about 35 % tin and a relatively high concentration of soulfur within the range of about 10 to about 25 % sulfur and a method of making them are available which are effective polyvinyl chloride impact buffers.

The term "sulfide" in this connection relates to the sulfide-sulfur group, * S, in which the valences of the sulfide-sulfur are bonded to the same tin atom or to different tin atoms. Each organotin compound contains 1 or 2 hydrocarbon or heterocyclic groups per tin atom, which are bonded to tin via soles, a sulphide and at least one / c & ~ or / S-meroaptocarboxylic acid ester group. In order to achieve the best results · and to achieve a synergistic stabilizing effect, a mixture is made which consists of at least one compound? which contains only one Koblenwaseeratoffgruppe per tin atom (and is referred to here as ^ Moü ^ rganoainn compound ") and at least one * rbind that contains 2 hydrocarbon groups per Zinnatoa (and is here referred to as" Diorganoeinn compound ¹ *) susamuene "is» wherein each hydrocarbon group Wa & t a Koblenstoffatoa of tin is bonded · piping Iomblmtl®n improved ia general, the Anfangefarbe a -Harssaaoe during Srhitaene, ie during ü, bt contact 30 Hinuten a Bitzetestes and may also be the ^ emg3 @ it stable, it & t before the final charring

H®rst @ iliangeverf € itir®B goes from the corresponding orgotin

from »wel © h © a @ ®i @@ ^ on the one hand from the organotin oxide or the Stann ^ ns ^ r®! © F can be divided * Sas Organo-

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Tin halide is carboxylic acid ester with an Ot- or A-Mercapt © converted to ale intermediate product an organossin mercaptocarboxylic acid ester balogenide ssu form and this is reacted with an alkali or alkaline earth sulfide} to the Organotin mercapto acid ester sulfide eu "

The Organozinn-mercaptosaureeBter-halogen1.de are new compounds, which are not only all intermediates in these "processes" but also as stabilizers for Polyvinyl chloride bars are valuable in the same way like the organotin mercapto acid ester sulfides. They are given by the general! Formula

₁ ) _m

defined * where mean:

η is an integer from ί to 2,

m is the number of COOK.} groups and is an integer of

1 to 4 ₉

χ is an integer from 0 to 1, X is halogen «

R, R ₁ , R ₂ and 2 correspond to the definition below.

The organotin iaeroapto acid ester sulfides obtained from these intermediates can be defined as organotin compounds »which organic reeds only over carbon bound to tin * Hercapto sulfur and sulphide sulfur groups have and the general formula

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1)

R.
t

possess «in which meaning

η a whole number from 1 to 2,

β is the number of 00OR ₁ groups and is a whole range 1 to 4,

χ is a whole number from 0 to 1,

H is a hydrocarbon radical with about 1 to about 18 carbon atoms and preferably 4 to β carbon atoms, B ₁ is an organic dnapp ·? wtleh © from "inea monohydric or Eüöhrwertigen alcohol ύ @ τ F ^ Israel E (CEi) ₁ , is derived" where n * a gans® Isfel of 1 Ms about ⁴ 4 _t but before "" occasionally "1 or 2 let"" -

Hg is 1 or 82 (0001 «, ) .jo

2, i © t @ia »weiweFfeäfGs? Altcjleairest, ämr öie S-Örtsppe in o (- odey: H-position gi% © i ^ ier 0OQR ₁ -GrUpPe carries and Eusäteliehe free Carboneäus? £ has 1 to about 5 carbon atoms.

The groups S - 2 - (COOR ₁ ) _a are derived from mono- or poly-Ot- and jd-mercaptocarboxylic acid by removing the hydrogen atom from the mercapto group. These include the esters of aliphatic acids which contain at least one mereapto group, such as β.B. Esters of mtrcaptoesslgeic acid, ok- and / 3-meroaptopropionic acid, oli- and / ^ - heroaptobutric acid and oC- and / ^ - mercaptevaleric acid, ^ - and

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Meroaptohexanoic acid, thio malic acid, oi- and r-mercaptoadipic acid and ^ - and ρ-mercapt © pimelic acid.

The Koblenwasssrstoffgruppen E can be found under the groups Alkyl, aryl, cycloalkyl, alkylcycloalkyl, cycloalkyl! Alkyl and arylalkyl are selected which have 1 to 18 carbon atoms and can be the same or different.

The R groups, which are bonded to tin via carbon, can be, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert.i-butyl, sec-butyl, atnyl, hexyl, Octyl, 2-ethylhexyl, isooetyl, dodecyl, palmityl, myrietyl, S. tearyl, phenyl, benzyl, cumyl, tolyl, xyIyI, cyolohexyl, Oyclooctyl, Cycloheptyl and Cyclopentyl.

R ₁ can be alkyl, alkylene, alkenyl, aryl, arylene, mixed alkyl-aryl, mixed aryX-alkyl, cycloaliphatic or heterocyclic and can contain from about 1 to about 12 carbon atoms and can also contain ester groups, alkoxy groups, hydroxyl groups, halogen atoms and other inert Containing substituents R ₁ is preferably derived from a monohydric alcohol which contains 1 to about 15 carbon atoms, such as methyl, ethyl, propyl, sec-butyl, η-butyl, tert-butyl, isobuty! ~ , Oetyl-, Iscocfcyl-, 2- 'ethylhexyl-, 2-octyl-, decyl-, lauryl alcohol, of cyclic, monohydric alcohols such as cyclopropanol, 2,2-dimethyl-1-cyclopropanol, cyolobutanol, a-phenyl -i-cyclobutanol, cyclopentanol, oyclopentenol, cyclohexanol, cyclohexene !, 2-kethyl ~, 3 * -methyl- and 4 ~ methyl-eyelohexanol ,. 2-phenylcyclohexanol, 3,3 »5-trimethyl-cyclohexanol, cycloheptanol,

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2 ~ methyl-, 3-methyl- and 4-methyl-cyeloheptanol, cyclooctanol, cyclononanol, cyclodecanes, oyclododecanol or of a 2 we i. word weight alcohol, such as glycols containing 2 bit about 15 carbon atoms _t einschliesslicb ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol »tetramethylene glycol, Neopentylglykol.und Becamethylenglykol» 2,2,4-Tritaetbylpentan-diol, 2>2.4> 4-Tetrametbylcyolobutändiol , 0yelohexane-1,4-dimethanol and poly oils, such as glycerine »TrimatbylolUthan, Mannitol» Sorbitol, Erytbritol, Dlpentaerythritoli Pentaerythritol and Iriiaethylolpropane »

The alcohol R ₁ (OH) _n does not need a single compound

"Many of the cheap alcoholic drinks available in the trade are suitable and advantageous. The branched-chain primary alcohols, which are produced according to the Oxo-Syntheae and are known as isooctyl, isodecyl and isotridscyl alcohols, are mixtures of isomers, but they can be used whether individual compounds are present. Other alcohol compounds that can be used include mixed homologs primary alcohols, which result from the oxidation of the reaction product of ethylene with triethylaluminum »isomeric and homologous secondary alcohols from the addition of water to linear olefins with 5 to 15 carbon atoms or the oxidation of linear paraffins with 6 to 15 carbon atoms, isomeric and homologous straight-chain and methyl branched primary alcohols, which result from the application of the oxo-synthesis to linear O ^ -oiefine with 6 to 14 carbon atoms, homologous mixtures of reaction products of ethylene oxide with alcohols, phenols or carboxylic acids with the appropriate carbon content and the like.

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From the above it can be seen that the organoisense moroaptooarbottBäm-eester-sulfide of the invention in one of the following general categories can fall »

Il

R-Sn-

'■ ^m / 2

ι).

SZ- (GOOR ₁ )

The organotin mercaptocarboxylic acid ester sulfides, which according to the invention can be used ala polymers with the general formula

2)

R ₀ -Sn

S-

■ S-

Sn-R,

'ia

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occur, where mean R and 8-2-give »

) Y _n and

as stated above

R ₂ is R or 8-2-

y is a number from 1 up to a practical limit of 5 #

Such polymers can be built up on a) Monoalfcylziiragruppen alone »with the general formula

Sn-S

«■

-Sn-SZ- (COOR ₁ ) _m R

or b) mixtures of mono- and dialkyl tin groups with the general formula

R-

Sh.
t

where ρ is a number of 2 feie to a ^ practical limit of 5

from A unä / o & ev B and / or E with C and also D © ö®rf alone aiai ia their stabilizing efficacy each of the compounds A, B, C unfl E _{p taken} faithfully superior and therefore preferred «

You according to invention

can by tfeaetsen of Diorgano2inn-halogeniden _t Monoor-

11th

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ß.

ganosinn halogens or mixtures thereof at a temperature within the range of about 25 ° to about 200 ° G with less than stuchiometric amounts of mercapto-carboxylic acid ester in the presence of water or inert organic ! solvents and an alkali «* or alkaline earth base, such as an oxide or hydroxide or a tertiary amine base in an amount »the sum of meroapto acid ester stochiometrisoh equivalent, can be prepared and the resulting organoeihnmeroaptos & ureeater halide intermediate product can be further with Alkali or alkaline earth sulfides, such as sodium sulfide, reacted to give the organoin mercapto acid ester sulfide au. ! The following formula shows the conversions which occur in the case of monoorganon compounds (I) and diorganotin compounds (II)!

B-Sn-X + n HS-Z- (OOOR ₁ ) _m + n-Ha0H- ^ R-Sn - jS-Zi ^OOOR i) | n] ⁺ ^ nX

l-Sn- Js-Z- (OOOR ₁ ) _a l + 3-n NaX

3-n

When η is 1, the molecular structure corresponds to the formula Aj when η is 2, the molecular structure corresponds to For mel B *

~ 12 -

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R 'K

t a

H-Sn-X + HS-Z- (OOOR ₁ ) *. + NaOH-f R-Sa-SZ- (COOR ₁ V _n -f NaX

X ί

R t

R-Sn-SZ- (COOH ₁ ) _m + NaX ^ -

1/2 Na ₂ S.

S.
R-Sn-SZ- (COOR ₁ ) _m (II).

In the above formula series, X denotes halide and η is 1 or 2. The formula series I explains the production of monoorganotin-mereaptosäureeater-sulfiden and formula series II the reaction for the production of diorganotin mercapto acid ester sulfides.

In another way, monoalkyl sensory oxides, stannonic acids and / or dialkyltin oxides for the preparation of the invention Organoainn compounds are used. Daa Alkyl tin oxide is one? approximately atoichiometric amount up to a 25% excess of a dilute mineral acid, such as. Salic acid, at elevated temperatures of around 25 ° C up to about 200 ° C converted to an aqueous solution (in the case of the Monoalkylzinii-Yerbindungen) or a suspension (in the case of the dialkylin compounds) of the organotin salt, e.g. des Form chloride in water. i) ae procedure is as indicated above continued} except that »if there is an excess of acid has been applied by adding alkali should be neutralized before adding alkali or alkaline earth will.

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SA Argus Chemical NV 9 * 162 M.

At the stages of implementation of the organotin halide old the mercapto acid ester and the implementation dea Organotin-mercapto-acid-halides with alkali or earth ~ alkali sulfld it is important »to ensure» that the pH value of the reaction mixture does not exceed about 10, this is due to the rapid addition of alkali hydroxide or -8Ulfid or addition of excess alkali hydroxide or sulfide is strongly alkaline, since the hydrolysis of the Mercapto acid ester can lead.

When to manufacture the monoorganotin mercapto acid ester sulfide If "it is understandable" that the product can have the formula shown under A or B above "or both in the mixture exist »corresponding to the relative proportion of the mercapto acid ester and the sulfide» which with the or » nanotin halide are implemented. You connection B asked the Half of the equivalents of sulfide sulfur of compound A.

Mixed mono- and diorganotin compounds are obtained in a corresponding manner of the Compound D type by employing mixed mono- and diorganotin oxides or halides as Starting materials. If other than stoehiometric proportions of organotin halide or oxide »mercaptocarboxylic acid ester and / or alkali sulfide are converted »one obtains polymers. If, for example, the ratio of mercaptocarboxylic acid ester to alkali sulfide is increased from η * 1 to η »2 in scheme I, compounds of type B are obtained. Other variations within of the general formula of the invention are apparent to those skilled in the art from the description given above.

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As can be seen from the above series of formulas I and II, it runs the process of the invention starting from the organotin halides in two stages or, starting from the organosense oxides or stannic acids, in three stages. It is but not necessary, the reaction product after each stage disconnect or isolate. Uacb the conversion of the organon halide «Sum organosense-mereaptosate-halide the alkali * or alkaline earth suifid can be added »during the pH is maintained below 10 and the sulphide conversion is then effected.

The reaction in each stage takes place in the presence of water, which acts as a solvent or carrier for the alkali or Alkaline earth hydroxide or sulfide and the inorganic halide formed as a by-product, as well as for the organotin compound 8-Beagdnsien and reaction products is used. The amount Water is not critical, but since the organoin-mercaptoacid-sulfld of which must be separated at the end of the reaction, there is a major advantage in using more, ale is required to make a fluid suspension or Iiöoung to build.

The reaction participants can be mixed in any order. Provided that the alkalinity is kept at a pH value below 10, if the free mercaptic acid ester or a mercapto acid ester group is present, the alkali can be in an aqueous solution or an aqueous suspension solution of the organotin compound used as Äusgangsmaterial be jsugefügfc, wherein the pH value is checked to _t slcherzugehen that the addition do not. occurs quickly and does not exceed the severity of the hydroxide or sulphide severity.

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It can be any alkali or alkaline earth hydroxide or sulphate fid can be used, such as sodium hydroxide, potassium hydroxide, aramonium hydroxide, calcium hydroxide «barium hydroxide or ' Strontium hydroxide? Sodium sulfide, lithium sulfide, potassium sulfide, calcium sulfite, barium sulfide or strontium sulfide. Strong amine bases can also be used as an acid accessory such as Fyrldln, triethylamine, tributylamine, triethanolamine, monoethanolamine or diethanolamine.

The mineral acid used to convert an organotin oxide or a stononic acid to an intermediate product with which a mereaptic acid ester is reacted is preferably a halogenic acid, such as hydrogen chloride, hydrogen bromide or hydrogen iodide.

The reaction proceeds at tree temperature and is usually complete within less than 1 hour. However the reaction can be accelerated by using an elevated temperature Temperatures as high as 200 ° C are usually used, but the reaction temperature naturally becomes a value at which the reaction product decomposes. A preferred range is 35 to 150 ° C.

The organotin mercapto acid ester sulfides are soluble in Paraffin hydrocarbons and can thus at the end of the Process can be extracted from the Reakticmsverbindungen. if if they are visibly insoluble in the reaction, they can also get through Filtration or centrifugation can be separated. Internship

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ned crystallization is satisfactory if they are insoluble in the reaction mixture.

It has already been mentioned that a synergistic stabilizing Effectiveness through the use of mixtures of monoorganotin and diorganotin mereaptoic acid ester sulfides is achieved according to the invention. You can share of everyone within the range of 10 to 9Q # monoorganotin ester sulfide and from 90 to 10 56 of the diorganotin ester sulfide, preferably varied between 20 to 80 # and 80 to & 0 # will. Compounds of type D or polymers of type P show a remarkably increased stabilizing effectiveness compared to any of compounds A, B or C or polymer B. Accordingly, semiae are any of compounds A and / or B and / or E with C or the above compounds B or F are preferred according to the invention.

For special combinations of organotin-mercaptocarboxylic acid ester-sulfideo., which can be used according to the invention * include the following:

1. Mono-n-butyltin ffionoisooctyl thioglycolate sulfide * Bis- {di-n »butyltin monoisoootyl-thioglycolate sulfide.

2 ♦ Mono-n-octylian-mosiocyclohexyl-thi oglycolate sulfide. + Bis-Cdi-n-octyltin monocyclohexyl thioglycolate J sulfide.

3. Bis- (n-butyltin-di ~ n-butyl-thiomalate) -eulfide + bis- (di-n-butyltin-'mono (iaooctyl-thioglycolate) -sulfide.

4. Bis (n-octyltin-di-2-ethylhexyl-yβ-mercaptopropionate) sulfide + Bis (di-n-octyltin monoisooctyl thioglycolate) sulfide.

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5. Bi8 ~ (n ~ octylainn-diisooetyl ~ thioglycolate) ~ 3ul £ id + Bis- (di-n ~ octylinn-mono-octyl-thioglycolate) -ealfide.

6. n-Oetylainn-moon disooctyl-thioglycoXate-sulfide + Bi3- (dln-butylBinn-TBonoiaooctyl-thioglycolate ) -aulf id

7 "Oyclobexyl-tri-monoieooctyl-thioglycolate-sulfide + bis- (dicyclohexylsinn-aonoisooctyl-thioglycolate-sulfide.

8. Bis (mono-tt-propylainn-dicyclohexyl-tbioglycolate) -sulfide + Bia- (di-2-ethylhexyltin-mono-2-ethylbutyl-thioglycolate ) «8Ulfid,

pionate) sulfide + bis-i (iöobutylKinn-di-tetrahydrofurfuryl- ß -meroaptopropionate) -3ulfide.

10. tert-butyl tin mono (methyl thioglycolate) sulfide + bis (diphenyl tin monophenoxyethyl thioglycolate) sulfide.

11. Ethyltin ~ monaisooetyX ~ thiogXycolate-3ulfide + Bia «(dibeuzyltin ~ mono-2-ethylhexanoyloxyethyl-thi oglycolate) sulfide.

12. Bis (i-propyltin-di "2,2-dimethylpentyl thioglycolate) sulfide + BiB-idiiaoamyltin-mono ^ -octyX-OC-Tnercaptopropionat) sulfide.

13 "Bis-Cn-butylainn-dicyclobexyl-thioglycolaijJ-su.li'id + Bie- (di-n-butyltin monoglyceryl thi oglycolate) sulfide.

The following examples explain preferred embodiments for the production of the inventive organosin mercapto acid ester sulfides and their mixtures.

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Example A.

. Production of Monobutyleinn-monoisooctyl-thioglycolate aulfld · "; _{in ti} _ _t -

51 g (0.25 mol) of isooetyl thioglycolate are added to 70 g (0.25 mol) of monobutylin tricbloride, warmed to 50 ° 0, in 200 ml of water, whereupon slowly 10 ge (0.25 mol) of sodium hydroxide, dissolved in 15 ml Water »can be added. The mixture is stirred for 1 hour. The product formed is monobutylin monpisooctyl thioglycolate diobloride.

Then 52.5 g (0.25 Hol) of 60 # aqueous sodium sulfide, dissolved in 100 ml of water, are added. After stirring for 10 minutes, the reaction mixture is extracted with 150 ml of hexane and washed twice with 150 ml of water. Bas hexane is then added. Vacuum removed. A yield of 100 g of honobutyl monoisooctyl thioglycolate sulfide is obtained. This corresponds approximately to 97 »5 ^ of the theoretical yield. The salary is 28.2? £ (calculated 29 f>) and the sulfur content is 15.9 # (calculated 15 ₉ 6 #)

Production of bis (monobutyl «inn-diisooctyl thioglycolate) - gulfld _m ^ _{j ι;.} - ^ , -. ,, .., - "-". _r ^ ._ ^^. "·

To 70 g (0.25 mol) of monobutyltin trlehlo heated to 50 ° C riä, dissolved in 100 ml of water, 102 g (0.5 mol) of isό-oatyl thioglycolate are added 20 g (0.5 mol) of sodium hydroxide, dissolved in? 0 ml of water, are then added. The addition of the NaOH is added dropwise, the temperature being below

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The reaction mixture is stirred for 1 hour. The product formed is monobutylin diisooctylthioglycolate monochloride

16.25 g (0.125 mol) of 60% aqueous sodium sulfide (dissolved in 50 ml of water) are added dropwise to this end, the reaction temperature being kept at 50.degree. The reaction mixture is then stirred for 1 hour at 50.degree. C., cooled to below 40.degree. C., 150 ml of hexane are then deposited, the mixture is allowed to cool for 15 minutes, the hexane layer is separated and washed twice with 150 ml of water. The aqueous phases are neutral. The hexane is removed in vacuo at 100.degree. C., 150 g of product being obtained, which corresponds to a yield of 100 tilings. The product is analyzed and contains $ 20.6 sense (theoretical 19.9 #) and 15.1 lbs sulfur (theoretical 13.4 #). '

Example C Production of (Monobutylzinh-diisooctyl-thioglycolate) - (dibutylginn-monoiBOOotyl- thioglycolate ) -8ul fid

A solution of 70 g (0.25 Hol) of monobutyltin trichloride in 400 ml of water at 50 ° C, in which 75.5 g (0.25 mol) of dibutyl-2inn dichloride are suspended, one adds 152.5 g (0.75 mol) Isoctyl thioglycolate, then slowly eetet 30 g of sodium hydroxide (0.75 mol) in 45 ml of water, the temperature is kept at 50 ° C and continues stirring for 1 hour away. The product formed is an equimolar mixture of Monobutylainn-diisoootyi-thioglycolate-monocblorid and Dibutylei.nn- * munoie ooctyl-thioglycolate-monochloride.

Then 32.5 g (P, 25 mol) of 60 ^ igea Ha ₂ S, dissolved in 100 ml

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Water, poured slowly in and stirred for 1 hour. then the reaction mixture is cooled and treated with 300-1 hexane extracted. The hexane is washed with water and then stripped under vacuum at about 100 ° C. The product obtained has a tin content of about £ 22 (theoretically 22.5 and a sulfur content of 12.0 Ji (theoretically 12.3 pounds)

Example D

Production of bis-cdibutyltin-monoiaoootyl-thioglycolate) sulfide

98.6 g of concentrated hydrochloric acid and 50 ml of water are heated to about 70 ° 0, then adds slowly during the period of 1 hour 124.5 g (0.5 mole). Bibutyl sense oxide, cool the mixture to 55 ° C. and add 102 g (0.5 mol) of isoootyl bioglycolate, followed by the dropwise addition of 20 g of sodium hydroxide (0.5 mol), exoiled in 30 ml of water. The product formed as a base is Dlbutylzlnn-monoiaoootyl-thiogiykolat-mono-chloride.

32.5 g (0.25 mol) of sodium sulfide (60%) dissolved in 90 ml of water are then slowly added. The mixture is stirred for 1/2 hour at 60.degree. The product separates from the aqueous solution as a lower layer. The aqueous upper layer is decanted and fresh water is added and the mixture is stirred for 10 minutes at 50.degree. C. / "Oils water washing is repeated once more. The organic layer is separated off and dried under vacuum at 80.degree. C. The yield is 226 g or 100 g The tin content is 26.2 % and the sulfur content 10.5 %.

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Beta P ₁ ie 1 E

Manufacture of bis-imonobutylainn-diiaooctyl-thioglycolate) sulfide ,

To 74 g of concentrated hydrochloric acid in 30 ml of water is added 52.2 g (0.25 mol) of monobutylstannonic acid au, then heated the reaction mixture to 65 ° C, holds 10 minutes at this temperature and then, after cooling, adds the reaction mixture to 50 ° C, 102 g (0.5 mol) isoootyl thioglycolate and 20 g (0.5 mol) sodium hydroxide (dissolved in 30 ml waaeer). The sodium hydroxide is added drop by drop, the temperature being maintained at about 50 ° C. The product formed is monobutyltin diisooetyl thioglycolate monochloride.

16.25 g (0.125 mol) of sodium sulphide (60% solution in water) are then added dropwise and stirring is continued until the brown color that resulted from the addition of the sodium sulphide does not lighten any further, which indicates is that the sodium sulfide has completely reacted. In this state the pH value is around 3, feie ο very slightly on the basic side. The reaction mixture is extracted with 150 ml of hexane at room temperature and washed with water until the aqueous layer is neutral. The hexane is then stripped off at about 100 ° under vacuum. Mari wins 14! 5 g of colorless product ( $ 97> the! Cheorie). The tin content is 19 * 5 $> and the swing sequence maintenance 13.5 i "(calculated 19.9 # Sn and 13.4 # S).

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BATH

9-162 M.

Example P

Production of monobutyl tin monoisooctyl thioglycolate sulfide

To 74 g of concentrated hydrochloric acid in 30 ml of water is added 52.25 g (0.85 mol) of butyl-atatmonic acid au, βrhitut then that The reaction mixture at 65.degree. C. is kept at this temperature for 15 minutes and, after cooling, the mixture is added to 50.degree 5 g (0.25 mol) isooetyl thiol glycolate and 10 g KaOR (0.25 mol) Mol) in 15 ml of water dropwise eu, whereby the (temperature is kept at about 50 ° C for 1 hour »The obtained The product is Mohobutylsinn-monoieoootyl-thioglycolate-dicblorid

Then 32.5 g (0.25 Hol) of Ha ₂ S (60 $) are put into 100 ml of water and the mixture is stirred for 1 hour. After stirring for 15 minutes, the reaction mixture is extracted with 150 ml of hexane and washed with 150 ml of water. Then the hexane is removed under vacuum. A yield of 100 g of monobutyltin-monoieooetyl-thioglycolate-eulfld is obtained. This corresponds to about $ 100 of the theoretical yield. The tin content is 29.0 #, (calculated 29.0 #) and the sulfur content is $ 15.3 (calculated 15.6 #). ^:

B el a ν 1 e 1 ß

Preparing a mixture of Monobutyleino-diieooctyl thioglycolate-sulfidj bis (dibutyleinn-monoieoootyl thioglycolate) sulfide, and (Moriobutyleinn-diifiooctyl thioglycolate) - (dibutyl beginning-monolaopetyl-tbioglykola t) -sulfi d

52.25 g (0.25 mol) of monobutylstannonic acid are added to 148 g of concentrated hydrochloric acid in 60 ml of water heated to 60.degree au, heat the mixture to 65 ° 0, whereby the oxide is long-

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Sam dissolves, then adds 93.4 g (0.579 NoI) of dibutylin oxide more slowly over a period of 1 hour eu, the dibutylin diohloride formed remains suspended in the warm (65 ° O), aqueous solution as Sohmelee. 155 g (0.79 mol) of isootyl thioglycolate are slowly added and then 30 g of sodium hydroxide, dissolved in 45 ml of water, are added dropwise at a rate to keep the temperature at about 50 ° without external heat ventilation. The product is a full-molar mixture of monobutyl chloride-dl ~ w isoootyl-thioglycolate-monochloride and dibutyltin-monoieooctyl-thioglycplate-monochloride.

Then 48.5 g (0.575 Hol) of 60% hatriura sulfide (dissolved in 150 ml of water) are added, the addition at 50 ° 0 takes place dropwise and is slightly called to Maintain this temperature. After 50 minutes at this temperature, additional sodium sulfide is slowly added Just neutralize the reaction geoisch and make it weakly basic at a pH of about 3. There are 300 ml Hexane added and the mixture stirred for 10 minutes to extract the organic product into the hexane mixture is transferred to a Seheidetriohter and the watery thread removed * Then the hexane layer with water until eur Washed neutrality and the hexane finally removed under vacuum at 100 ° 0. The yield is 265 g of a pale yellow liquid, corresponding to about 90.5 Ji of theory, with a chin content of 25.0 1> and a sulfur content of 12.4 $.

Example H

The procedure of Example 0 is repeated, with 50.2 g (0.1 mol) of dibutyl chloride, 28.0 g (0.1 mol) of monobutyl

'■ ■■ - 24 - · ^{t

^909836/1649 _BAD OR _IGI NAL

9-162 M.

tin trichloride, 51 »0 g (0.25 mol) isooctyl thioglyl colate, 10 g (0.25 mol) NaOH and 16.25 g (0.125 mol) sodium sulfide (as a 60 # aqueous solution) can be used. Bas product contains # 23.7 tin and $ 12.6 sulfur.

B e i ^ _s ρ ie 1 I

Example C is repeated, using 30.2 g (0.1 mol) of dibutyltin dichloride, 14.0 g (0.05 mol) of monobutyltin trichloride, 51.0 g (0.25 mol) of laooctyl thioglycolate, " 10 g (0.25 mol) NACM and 6.5 g (0.05 mol) latriuaaulfid be used. The product obtained contains 21.0 # tin and 11.4 ° F of sulfur.

At SiJeI J

Example C is repeated, using 33 »5 g (0.11 mol) of dibutylsense dichloride, 28.0 g (0.1 mol) of monobutyltin tricloride, 65 g (0.32 mol) of isgoctyl thioglycolate, 12 _S 8 g of latritam hydroxide and 13.0 g (0.1 mol) of sodium sulfide (as a 60 # sodium sulfide solution) are used. The yield is 98 # _m of a product domestic product with a content of 22.1 <f "tin and IS # sulfur.

BjB_i_ g__ia_ji ejl K

Example C is repeated, with 48.4 g (0.16 mol) of dibutyltin dichloride, 28.0 g (0.1 MpI) of monobutyltin trichloride, 69.5 g (0.34 mol) of isoootyl thioglycolate and 13, 6 g of sodium hydroxide can be used together with 18.2 g (0.14 mol) of sodium sulfide (as a 60% aqueous solution). The product obtained shows a tin content of $ 23.8 and a sulfur content of 12-6.

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Example I.

Repeating the procedure of Examples G, wherein 45t0 6 monobutyl "inn-oxide, _f 41 5 g Dlbutylzinn-oxide, 138 g leooctylthioglykolat, 27 g of sodium hydroxide and 21» 7 g of sodium sulfide (60 #ige aqueous solution) are used. The product obtained shows a tin content of 21.9 # and a sulfur content of 11.9 #

Example M

Example β is repeated, using 58.8 g (0.21 mol) of monobutyltin trichloride, 24.8 g (0.1 mol) of dibutyltin oxide, sufficient hydrochloric acid to form the dibutyltin oxide chloride, 143 g (0.7 mol) isooctyl thioglycolate, 28 g sodium hydroxide and 8.5 g (0.065 mol) sodium sulfide are used as a 60 fiige aqueous solution. Baa erhaltsne product has a tin content of 18.5 ^c fc and a Schirefelgehalt of 11.5. ^.

Example N

92 g {0.33 mol) Monobutylaisin trichloride dissolved in 260 ml of petroleum ether (boiling range 60-80 ° C), one adds 103.5 & (0.5 mol) Jsooctyl thioglycolate to, then stirring the obtained Kami sch, heated at 55 ° C., then 50 parts of triethylamine are added dropwise while the temperature is maintained at 55 to 60 ° C. and, after cooling, the product is washed three times with an equal volume of water. The organic solvent layer is separated off and then the solvent is distilled off under vacuum. The product is filtered and an equimolar mixture of HonobutylKinn-

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monoisooctyl-thioglycolate-diehlorid and honobutylinn-diisooctyl-thioglycolate-monochloride «

The organotin mercapto acid ester halides and sulfides according to the invention can be used as stabilizers for any polyvinyl chloride hair. The term "polyvinyl chloride ^11" as used here includes any polymer which is at least partially selected from the recurring group

—CH- C- * t ■■ «

Cl X

is formed and has a chlorine content of over 40 % . In this group, the X groups can be either hydrogen or chlorine. In the polyvinyl caloride homopolymers, each of the X groups is hydrogen. Benmach includes not only polyvinyl chloride homopolymers but also semi-chlorinated polyvinyl chlorides, as they are described in British patent specification 893 286 and also copolymers of vinyl chloride as the main component and other copolymerizable monomers in a minor proportion, such as copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride with shark mono- or furaaric acid or esters and copolymers of vinyl chloride with styrene, propylene and ethylene. The invention is also applicable to mixtures of polyvinyl chloride as the main part with other synthetic resins, such as chlorinated polyethylene or a mixed polymer of acrylonitrile, butadiene and styrene. Among the stabilizable polyvinyl chlorides

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are the non-axially stretch-oriented polyvinyl chlorides "which" he UBA-Patenteohrift 2 934 59? described Bind, dae are syndiotactic polyvinyl chloride, as well as atactic and ieotactic polyvinyl chlorides. .

The inflammation-class organolines-mercaptoeaureeter-halides and sulphides are excellent stabilizers for both softened and non-softened polyvinyl chloride hares both with and without any other stabilizers. If plasticizers are to be used, they can w the Polyvlnylohlorldharsen by conventional methods, a · be verleibt. The conventional plasticizers can be used such as dioctyl phthalate, bloctyl sebacate and trioresyl phosphate. When a plasticizer is used, it can be used in an amount within the range of 0 to 100 parts by weight of the resin.

Particularly valuable plasticizers are the higher epoxy fatty acid ethers, which have about 20 to about 150 carbon atoms » eiteen. Such esters originally had unsaturated bonds in the alcohol or acid portion of the molecule, which were added by the formation of the Bpoxy group.

"Ba can also contain a small amount, usually not more used as 1.5 Ji of a release agent or lubricant will. Typical release agents are the higher aliphatic acids and salee with 12 to 24 carbon atoms, such as stearic acid, lauric acid, palinitic acid and myristic acid, lithium stearate and oaloluapalmitate, male aliphatic oils, polyvinyl stearate, polyethylene and paraffin wax.

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BATH ORIGINAL

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Impact modifier used to improve the toughness and impact resistance of non-softened products Resins can be the Haremaasen stabilized according to the invention also in small amounts, usually not more than 10? 6 «can be added. Examples of such modifiers for the vision ability include chlorinated polyethylene, ABS polymers and polyacrylate-butadiene graft polymers.

The organic internal mercapto acid ester halide or sulfide stabilizer of the invention is used in sufficient amounts to impart the desired resistance to heat damage at operating temperatures of 177 ° C. and above. The longer the time and the harsher the conditions to which the hair is subjected during processing and mixing, the greater the amount required. In general, as little as 0.25% by weight of the resin total stabilizer will improve resistance to heat damage; to enhance. There is no critical upper limit for the amount of "give, however quantities above about 10 wt .- # of Har Zee no increase of the stabilizing effectiveness" wtlohe the stabilizer additionally applied appropriately 1st · Preferably you amount is from about 0.5 to about 5 wt. - »56 of the resin.

The organosense mercapto acid ester sulphide has a sulfur content in the range from about 10 to about 25% and a tin content in the range from about 10 to 35 % - the best results are a total of about 20 to about 30% by weight. -56 preferred

- 29 -909836/1549

9-162 "IQ

The invention doesntisB · stabilizer let extremely effective, though it is applied alone, but it can busanmen old other Polyvinyl chloride resin stabilizers can be used, but if special effects are required, not with others Organotin Compounds · In this Pail, the stabilizer according to the invention will be the main tabilleator and the additional stabilizer will be the stabilizing effectiveness of the the former supplement, the amount of organotin ester sulfide stabilizer in the range from about 0.25 to about 10 parts by weight per 100 parts of resin and the additive in the amount of about 0.05 to about 10 parts each 100 parts resin is present.

The additional MetallctaMlieators include polyvalent ones Metal salts of medium and high molecular weight fatty acids and phenols with metals such as calcium, tin, cadmium, Barium, zinc, magnesium and strontium. To non-metallic Stabilizers include phosphites, epoxy compounds, phenol flat antioxidants, polyhydric alcohols, and the like. Epoxy compounds are particularly useful and typical compounds are described in U.S. Patent No. 2,997,454.

You can use stabilizers according to the invention for sale be compiled by mixing the organotin-mercäptoeäureedter-sulflds with an inert diluent or with any liquid lubricant or plasticizer in suitable concentrations which are suitable to be added to the Harzraaaae in order to obtain a suitable stabilizer and Lubricant or plasticizer concentration in the resin

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9-162 M.

ben. Other stabilizers or additives may be used be incorporated just as easily.

You manufacture the Polyvinylchlorldharis-Maeee reached nan simply in conventional ways. You selected stabilizer » Combination is formed as described above and then with the polyvinyl chloride hair constricted or in another way misoht nan the constituents an in the whore a »where for example a 2 or 3 whale mill is used at a temperature at which the mixture is fluid and Thorough mixing is facilitated, and the Haremaaee grinds together with any plasticizer at temperatures of 121 ° C to 191 ° C for a sufficient time to form a homogeneous hatred, usually 5 minutes As soon as the mass is uniform, it is sucked off in the usual way as fur

In the technical processing of rigid PVO, the stabilizer is reactivated with the whole or a proportion of the bu stabilizing polymer mixed with vigorous agitation and under such conditions and temperature that the stabilizer is sufficiently Way is absorbed by the polymers to form a dry «free-flowing powder bu. The known Hensohel mixer is suitable for this process.

The following examples explain preferred embodiments of Polyvinylchioridhare Maeaen, including incorporation of the inventive mono- and Si-organo & lnn-mercaptocarbotH acid ester sulfides as stabilizers.

-. 31 -909836/1549

9-162 M.

B eia ρ i ^ e \ _it e ^., I ₁ to?

A number of rigid or non-plasticized recipes are produced »which have the following composition)

Components parts by weight

Polyvinyl chloride homopolymer (Trade name "Diamond 40") 100

w Acrylonitrile-butadiene-styrene-copoly-

merisat (trade name "Blendex 40") 12

Stabilizer 'sufficient to one

Tin weight of 0.40 g as indicated in Table I

The stabilizer concentrations tested in each bara sample contain the same amount of tin, i.e. 0.40 parts of tin per 100 parts of hair.

The stabilizer is mixed into the resin in the amount given in Table I below on a 2-Walsen mill } to form a homogeneous whale skin and suck it off as a pell. Ouch Strips are cut out of the pell and placed in an oven Heated for 2 hours at 191 ° 0 to determine the heat stability. Pieces of each strip are taken every 15 minutes and placed on cards to show the progressive heat damage.

Compounds A through D below are used as controls used which stabilizers of the next stand representι the technology

- 32 -909836/1549

181, "Ί6ϋ

S.A. Argus Chemical N.V. 9-162 M.

A * Dibutylainn-bie- (isooc ^ yl- «ihioglycolate) B w monobutylainn-tris-cieooctyl-thioglycolate) C - Dibutylsinn-eulfid D η monobutyltin-eeequiaulfide

The heat decomposition is determined according to the parbintenality that has occurred, i.e. the extent of the discoloration on the controls. Ee two scales are used »around the Characterize the amount of color formation. Scale A covers the Color range from colorless to brown and amber to greenish brown. Scale B covers the color range from colorless to yellow and orange to reddish brown. Each scale ranges from ßi £ - remotely from zero (colorless) to 9 (brown).

Scale A Scale B 0 clear and colorless clear and colorless 1 Color purple yellow stitch 2 very light brownish very pale yellow 3 light brown pale yellow 4th very light amber yellow 5 light amber yellow - brown ribbons 6th medium dark yellow light orange-brown 7th dark amber orange brown θ green Brown reddish brown 9 green-black brown-black

You two colored bezels are needed because of the fact »that the degradation of the polyvinyl chloride hares stabilized with organotin compounds does not follow a single uniform theme. Scale A is for the heat removal from

* new page

909836/1549

ORONAL INSPECTED

9-168 m

Recipes applicable »which monoorganotin compounds and Mixtures of monoorganoain and diorganotin compounds included, while scale B is applicable for recipes, v / elohe Di organotin compounds contain. Daa look of the Samples are given in Table Z below.

- 34 909836/1 549

!Table 1

τ, », *" - K _0n ^ Bei- Bei- Bei- Kon- »

game SSle A should B game 1 game 2 game 3 trolls C trolls D g

Stabilizer A B Bei- BeJ- Bei- C D »

game C game B game D

1.02 1.05

«Tight 2.15 2.65 1.75 Be ^! l-_ _ At- _ 0.9 0.75

cn go

S 105

120

A. B. at
game C at
game B
1.02 at
game D
1.05 0 2.15 2.65 1.75 at
game E
0.68 at
game F
0.45 0.9 B-O A-O A-O A-O A-O B-O B-4 A-I A-O A-I A-1 B-5 B-4 A-3 A-1 A-1 A-1 B-5 B-4 A-4 A-1 A-2 A-2 B-5 B-5 A-4 A-2 A-3 A-3 B-6 B-7 A-4 A-3 A-3 A-4 B-7 B-8 A-6 A-4. A-5 A-4 B-8 B-9 A-7 A-6 A-7 A-7 B-9 B-9. A-8 A-8 A-3 A-8 B-9

A-O

_m I ₅ B-4 A-1 AO AI A-1 B-5 A-3

ο ^, ο B-4 A-3 A-1 A-1 A-1 B-5 A-4

S ^ 45 B-4 A-4 A-1 A-2 A-2 B-5 A-6

£ '60 B-5 A-4 A-2 A-3 A-3 B-6 A-8 oo

75 B-7 A-4 A-3 A-3 A-4 B-7 A-9 _m

σ »

1815188 9-162- M

The marketing results clearly indicate the improved effectiveness of the Invention agem & ssen organonic mercaptoic acid ester sulfides in a rigid polyvinyl chloride hair formulation. Pies is from Of particular importance, as it is known that rigid polyvinyl chloride requires the strongest stabilizers for effective processing and Langeelt aging.

In Table X, Examples 1, 2 and 3 are the preferred stabilizer combination, that is to say a combination from mono- and dibutylin-mereaptosäureester-sulfides contain "the controls A, B, 0 and D markedly superior.

In Example 1, after 60 minutes of heating at 191 ° C, one obtained better color than in controls A, 0 and D after only 15 minutes heating and 'in control B after 30 minutes heating. This means, for all practical purposes, that the Example 1 about four times the stabilizing effectiveness compared to controls A. C and B and about the cwel- to three * are twice as effective as control B »

Similarly, Examples 2 and 3 have twice the effectiveness compared to Control B (the best control sample). Bas the amount of discoloration that Control B After only 30 minutes of heating, examples 2 and 3 do not achieve heating after 60 minutes.

The special advantage of the steel isolators according to the invention can be even better appreciated by considering the fact that the costly and primary stabilizing ingredient in Controls A through D and the Examples

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ι "*

1 bia 3 (the pray the tin η equal amounts of 0.40 g of tin per 100 parts Hare vorbanden 1st while diar entire amount of stabilizer of example © 1, 2 and 3, only 66 #, 64 i bew. 5 έ? Yon Control B is.

Examples , _{n [} 4 big 6

Another series of hara recipes is produced, which have the following composition

Components parts by weight Polyvinyl chloride homopolymer

(Diamond 40) 100

Stabilizer 1.5

In making and checking the connections, one follows the same procedure as in Examples 1 to 3t wherein Same stabilizer weights instead of the weight, which result in equal amounts of tin, are used. Sas appearance of the samples is given in Table II below

•• ν

- 37 -

909836/1549 BAD ORKHNAl

Table II vo Example control S control? Example 4 Example 5 Example 6 Control g <*

A Example H Example I Example Ii C as ns 1_ * 5 n5_ 1.5 1.5

B-O A-O A-O

B-3 A ^ O A-O

B-4 A-O A-0-1

B-5 A-1 A-1

B-6 A-2 A-2

B-8 A-5 A-4

B-8-9 A-8 A-8 ~ "-. _OQ

B-8-9 A-9 A-9

B-8-9 A-9 A-9 " ^Λ * ^A * ^Ä ° *

° · σ » α>

Stabilizer B. lot 1.5 0 A-O 15th A-O 30th A- * 1 909836 / «60
? 75
90
105 A-2
A-8
A-9 120

A-O A-O A-O A-4 A-O A-4 A-0-1 A-5 A-2 Δ-5 A-8 Δ-6 A-9 A-7 A-9 A-8 A-9 A-9

9-162 M 33

The results of Table II clearly indicate the improved efficacy achieved with the use of mixtures of Mono- and dibutylinn isooetyl thioglycolate sulfides even contribute the low overall weight ratio of 1.5 cures per 100 Share Hare Receives. The samples, which according to the invention Containing stabilizer, Examples 4, 5 and 6, prevent damage to the resin when heated at 191 ° 0 during a Much longer time than either monobutyl tin trisulfide (isooetyl thioglycolate), dibutyltin bi- (ieooctyl thioglycolate) or dibutylsense sulfide. Examples 4, 5 and 6 keep a beaeer looking color during the first JC minutes of the Erhiteens. In addition, the Haremaasen de * At ** games 4, 5 and 6, which contain the new stabilizers, only show a light discoloration even after 60 hours of heating subject, while control E, honobutyltin- »tris- ~ (iso« octyl thioglycolate), takes on a considerable discoloration after 30 hours of heating and turns dark green after 60 hours of heating. Controls F and S are completely yellow after only 15 minutes of heating and turn to color with further heating progressively darker.

B ei sρ ie 1 e 7 and 8

Another series of resin formulations is produced which have the following composition]

Components Weight weight part Polyvinyl chloride homopolymer

(Diamond 40) 100

Xsooctyl epoxy etearate 3 Stabilizer 2.2

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9-162 H.

The same procedure as in Examples 1 to 3 and the appearance are followed in the preparation and testing of the compositions of the samples is given in Table XXI below.

B. Tabel III Control M 2.2 I »Example 7 Example 8 0 Examples control A-O Example J Example K 2.2 stabilizer A-1 2.2 2.2 A-O lot "A-2 A-O A-O A-3 O A-3 A-O A-O A-3 15th A-6 A-0-1 A-O • A-3 30th A-9 A-1 A-C-1 A-4 45 A-9 A-2 A-1 A-5 60 Ar-2-3 A-2 A-6 75 A-4 A-3 A-7 90 A-7 A-6-7 A-7-8 105 A-9 A ~ 8 120

The results clearly show that when used in the same total oewiobto concentration, the mono- and dibutylsense isooctyl thioglycolate sulfides damage the hair Prevent leg heating to 191 ° 0 for a considerably longer period of time than either monobutylrin ~ tris- (ieooctyl ~ thioglycolate) or dibutylin sulfide »and thus extend the time for processing before a harmful · Discoloration occurs. The control L assumes a very light discoloration within 15 minutes of heating, but the example 7 does not achieve this discoloration until after 45 minutes Krhiteen and Example 8 only after 60 minutes of heating. This is the same the three and fourfold stability of the control υ

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Examples 7 and 8 show a slight discoloration after 75 and 90 minutes submit to Urhitsen at 191 ° C while Control L, the Maas ©, which contains the Mcnobutylssinn-tr & a- (isooctyl-thioglycolate) contains a dark color after 60 minutes anniiai & t and after 75 minutes Erhitaen black 1st · Wenn Control H also does not calibrate until after 2 hours of heating discolored black, it immediately takes on a yellowish discoloration after 15 minutes of heating, which on further Heating becomes progressively darker.

B eia το ie 1 e _n ^ ₁ and 10

33s are given oath of harshness, which has the same basic oath as in Examples 1 to 3, the stabilizers of Examples 33 and F being used. All recipes contain 0.40 g of sense per 100 parts of resin.

The same test procedure is followed and the results are in Table XV.

41

909836/1549

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March 10, 1969 9-I62 M

Example Control B Example 9 Example 10 Control 3D

Stabilizer B amount 2.65

Example E Example F D 2.02 1.35 0.75

0 A-O A-O A-O A-O 15th Ä-1 A-1 A-1 A-3 30th A-3 A-2 A-2 A «4 45 A-4 A-3 A-3 A-6 60 A-4 A-4 A-5 A-8 75 A-4 A-4 A-6 A-9 90 A-6 A-6 A-8 105 A ~ 7 A-8 A-9 120 A-8 A-9 A-9

Examples 9 and 10 show the advantage of the monobutylsense meroapto acid ester sulfides over either monobutyltin maroaptoacid or monobutyltin sulfides alone.

Examples 9 and 10 have better color stability after 30 minutes of heating than monobutyltin-tri- (ieooctyl ~ thioglycolate), control B and the monobutyltin suequieulfide, Control D with the same tin content and this is only 76.5 # and 57 £ of the Qesamtatabiliaatorhalt of control B. Control D shows severe discoloration after 15 minutes same tin content and would only result in stronger discoloration at higher concentrations.

Examples 11-13

Eb another set of resin formulas is made, which have the following composition:

• new page 42 -

909836/1549

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«Fs

Components, Qewi c htateile

Example Example Example 11 game 12 game 13

Polyvinyl boride homopolymer

sat (Diamond 40) 100 100 100

Isooctyl epoxy stearate 3 3 Stabilizer of Example M 1.5 2.2 3.5

The same procedure as in Examples 1 to 3 is followed in dividing and testing the hates.

The results clearly show the effectiveness which one is at Use of mixed monobutyltin nono- and diisooctylthioglycolate di- and non-chlorides, even at the base Total weight ratio of 1.5 parts per 100 parts of hair. The samples containing the stabilizer of Example H have a good initial color when heated 191 ° C. Examples 11, 12 and 13 obtained excellent color appearance during the first 30 minutes of cooking.

The Stabilizer Maesen according to the invention are with a gate part Applied for resins * which can be processed for many basic structures, including extruded ones Polyvinyl chloride pipes, which are used for water, brine, raw oil, Benisin, natural and artificial heating gas and house and induatrle waste can be used, furthermore for flat and reinforced profiles for the construction industry, as well as for blow-molded Bottles! Typical recipes are as follows

- 43 -909836/1549

BATH ORIGINAL

9-162 M.

ZuaamaenaetBuag weight parts Polyvinylohlorid-Hooopolymeriaat with

mean * molecular weight (K-55) 100

ABS polyamide 10 C & loiueetearate 1 Product of Example I 1.4 Pigment as desired

Külbel gum yiaachenblaeen ZuaaaaeneetViohtateile

Polyynyl chloride HomoFOlyaerisat with

average molecular weight (K-55) ■ 100 Styrene-butadiene-methyl methacrylate polyesters 10 Stearic acid. 0.5

Product of Example I »1.6

blue dye 0.0005-0.002

yiaaohen for HahrungemitteXverp ack clothes

Qawai parts

Polyrinyl chloride honopolymer with Average molecular weight (K * 55) ABS polynoreate n-Octylinn-ioootyl-thioglycolate-sulfide Bia- (di-n-oc tyleiim-tnonoia ooo tyl-thi oglycolate) -eulfide

Di-n-ootylBinn-oKid

100 .9 10 • 95 0 , 05 0 0

- 44 -

909836/1549

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Profile" Zuaameneetsung Qevldhta file

Polyvinyl chloride high-quality polyether belt Molecular Weight Loss (MO) 100

chlorinated polyethylene (51 # 31) 15

Ieoootyl-epoxyeteax ** t 2 Dl-a-ootylaiiiJi-bia-iaonoieooetyl-thioglylcolate) -

euifid · 1.0

n-Butylinn-IIoetyl-tbioglycolat-aulfid 0 * 55

Magneaeetearate 0.2?

All ditee Reiep ^ uyoE develop sufficient erXinduiagegeaSsera Stabilieator "tm bai increased YeBpemtt $?" St int the mentioned foraen obne eohädXicbe discoloration ofer brittleness

ι> ₍ · '». -» - ■ »-Wnlin.

9 0 9 θ? 6/15 4 9

BATH ORIGINAL

Claims (1)

Claims 1. Organoelnn-mercaptooarboxylic acid ester sulfide, which has at least one tin shade, to the organic groups only Are bonded via carbon and sulfur and in which at least one tin atom per molecule is at least one hydrocarbon group bonded to tin via carbon, at least one of- or A-meroaptocarboxylic acid ester group is bound to tin via the sulfur of a mercapto group and at least one sulphide-sulphurous group is bound, the organotin compound having a tin content in the range from about 18 to about 35% by weight and a sulfur content generally from about 10 to about 25% by weight * 2. Organoeinn compound according to claim 1 with the general formula (H ₂ J ₃ where η is an integer from 1 to 2, χ zero or 1, m a whole number of. 1 to 4, R is a hydrocarbon radical with about 1 to about 18 carbon atoms, B _{1 is} a monohydric or polyhydric alcohol - 46 - 909836/1549 9-162 M. 1815188 Conducted organic group with 1 to about 4 hydroxyl « Groups and 1 to etv, a 18 carbon atoms, R ₂ öen Reet R or SZ- ( ⁰ OOR ₁ ) _a and a divalent alkylene residue which carries the 3-Q group in <& - or yS-position to a COOR ₁ -QrUpPe and has 1 to about 5 carbon atoms, and optionally additional radicals from the group free carboxylic acid groups »carboxylic acid ester groups, Contains carbonic acid salt groups and mercapto groups. 3. Organotin connection according to claim 1, characterized in that the organic bonded to tin via carbon Group is η-butyl or n-octyl. 4. OrganOBinn compound according to claim 1 with the general formula S where m »R» R ₁ and £ correspond to the above meaning. 5 «organosense compound according to claim 1 with the general Formula. or ) J ₂ (R) ₂ -Sn-SZ- (COOR ₁ ) _m S, S ) _ffl j (R) ₂ -Sn-SZ- (COOR ₁ ) - 47 -909836/1549 9-162 N R - 8 ι where β, R, R ₁ and Z correspond to the above meaning » 6. Organotic sense connection according to Anspruoh 1 with the general formula R » V? » ■ s »Btt ■ '! ■■ o t . ^c Sn — 8— SZ- (COOR ₁ where y is a number from 1 to 5 and m, R, R ₁ , R ₂ and correspond to the above meaning. 7 «organotin compound aaoh Anepruoh 1, characterized in that the hydrocarbon group 1 to about 18 Carbon atom and the meroaptocarboxylic acid ester group is an alkyl conductor of a meroaptocarboxylic acid with 2 to 5 carbon atoms, the alkylate having 1 to 18 carbon atoms. 3. organoisense compound according to claim 7, characterized in that the hydrocarbon group is butyl and the jMercaptooarbonsttureester-uruppe is a thioglycolateeter. 9. Mixture of organotin compounds according to claim 1, which contains at least one monoorganorian compound and at least one diorganorian compound » - .48 - L ' 909836/15 49 9-162 M. 1Oi mixture of organosimi compounds according to claim 9, characterized in that the "Honoorgano & inn ~ compound a compound according to claim 4 or 5 and the diorganosense compound is a compound according to claim 5 11 · Qrganosinn-oeroaptoparbonsttureeeter-halide with the all common! formula where X is halogen and η, χ »α» H, S ₁ 1 B ₂ and 2 correspond to ^{the above meaning} 12. Organoeinn compound according to claim 11 »daSuroh kennseiehnet» that the group bonded to Zim via carbon is η-butyl or n-octyl. 13 * Qrganoeinh connection according to claim 11, characterized net that the hydrocarbon group has 1 to about 19 carbon atoms and the itercaptocarbonate ester group is an alkyl ester of a mercaptocarboxylic acid with 2 to The Allcyl-Heat has 5 carbon atoms and 1 to 18 carbon atoms. 14. 0rgaTiosini3- "V © rbiiaöung according to claim 13""ladurcb gekesinzeich nrlt daise üln ilo ^ jLanv / aaaers-Soff-Sruppa is butyl and the mercapto acid ester soup is a fhioglycolate-sister * 3 0 9 B 3 B / 1 5 L 9 9-162 M. 15. Mixture of organotin compounds according to claim 11, which contains at least one MonoorganoEinn compound and at least one Diorganoainn compound. 16 · Use of organotin compounds according to one or more of claims 1 to 15 for stabilizing vinyl chloride polymer is at s against damage from increased to higher temperatures. 17 · Embodiment of the use according to claim 16, characterized gekennseietraet that there is a vinyl chloride polymer Polyvinyl chloride hoopolymer * or a copolymer from a major part of vinyl chloride and a minor part Amount of other vinyl monomer. 18. AusfUhrungeform the use according to claim 16, characterized marked that the amount of stabilizer wet in area from about 0.25 to about 10% by weight of the mass. 19 »embodiment of the use according to claim 16, characterized in that characterized in that a polyvalent metal salt of a carboxylic acid or an alkylphenol is also used. 20. embodiment of the use according to claim 16, characterized characterized in that one also has a Bpoxy compound used. 21. Ausführungsfona of the use according to claim 16, characterized marked that nsan additionally has a 'plasticizer for the hair is used in an amount above about 10% by weight. - 50 - 909836/1549 8.A. Argue Chemical M.V. 9-162 N 22. Embodiment dtr use according to Anepruoh 16, thereby known that Mn stands for etarree Polyvinylohloridhari a plasticizer in a hangt bit eu about 10 Gtv.-Jt the Naase used. 23 · Design for use according to claim 16, characterized in that marked that nan euaätelioh tin uses phtnolieoha antioxidant. 24. Embodiment of the use according to claim 16, characterized marked that «an susätslioh uses a modification agent for the impact resistance · 25. A process for the preparation of organoicinn-mercaptocarbonate-aulfiden naoh claim 1, characterized by gtktnnstithntt, that one can bit an organoslim halide in the presence of water a Meroaptos & urttsttr and an alkali or alkaline earth base in less than stuohiometrlsohsn amounts, and then the product until a pH value that does not exceed 10 is cleaned with an alkali or alkali metal sulfide and then the organotin meroaptooarbonaKureester from the v.Sserigen phase separates ^: 26. The method NaOH Anspruoh 25 »characterized gtkennceiohnet" that, starting from the corresponding Organozlnnoxid or DTR Stannonsäure with -Iner wüesrigen dilute hydrohalic acid at a temperature of 25 to 200 ⁰ C to form the Organosinnhalogenids reacting these. - new page 51 - 909836/1549 8-162 M 10th March 1969 87 · Proceed according to Anspmieh 25 »characterized in that ·« one makes connections according to Antprueti 2. 86. Traversing · * naoh Anepmeh 25 "gekennseiohnet! Dadureh because ·" to V "rbtndw« «n htratellt, b 'ld' nan dl" bound to cinnamon over Kohlenetoff "oreaitlaehe group n-butyl S9. Verfahr «» naöh Aaepruoh 25, dadureh gekenisaelohnet, that "makes" connections "where the over Carbon attached to an organic group n-Ootyl let. - new since © 52 - 9 0 9836/1 54 ^ ßAD ORIG