DE1544629A1 - Process for the production of heat stabilizers and stabilized polyvinyl chloride compositions - Google Patents

Description

"Process for the production of heat stabilizers and stabilized polyvinylohloridraasseh ¹¹

Priority:). October 1964. Great Britain

The invention relates to certain organotin compounds which are useful as stabilizers for polymers or copolymers of vinyl chloride.

Many different types of organotin compounds have been described for use as stabilizers for vinyl chloride polymers in recent years, but the search continues

09814/1728

after further ι stabilizers that are economical and / or could have technical advantages over the already known stabilizers, an «It is often assumed that Organotin compounds stabilize vinyl chloride polymers, by acting as a scavenger for the thermal or hydrogen chloride released by light-induced degradation of the polymer. Accordingly, it was assumed that organotin halides worse for this purpose . Would represent organotin compounds, since it would be expected that they would be less effective than organotin stabilizers in absorbing the oxyhydrogen substances released during degradation, which have a direct carbon 'halogen bond contain*

This invention, representative members of a class of organotin compounds prepared by the presence of at least one tin Halogenbind:;. Distinguished ag and at least one tin SchwefBl-carbon bond, and it was _v surprisingly been found that they are effective stabilizers for vinyl chloride polymers * Many members of this class of compounds are new and the preparation of these compounds forms another aspect of the present invention. '

In one aspect, the invention provides a composition comprising a vinyl chloride polymer (which is a homopolymer or a

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Mieohpolamtres , which is formed from little more than 2p wt. Jf of other Ifonoaer ) and 0.1-5 wt, # of the poly tttren a heat stabilizer of the general Perm el

E - 8tt ·· S - Η · '

uofaest, in which R is a hydrocarbon group, X is a chlorine or broitato, H 'is one of an organic meroapto compound H ¹ SH Btamaende organic group and 3 is a group H, X or - SR' or an acyl oxy group R ¹¹ OO ₂ - the of an organic gorboric acid E ¹ OOgH atatarat, mean.

Furthermore, the invention provides novel compounds which are among those which can be used as a HitiseetabiliBatoren in accordance with the objective of the invention. These new compounds are organotin compounds which can be represented by the following general formula.

R-Sn-RV

Wherein R, X and Z have the meanings given above and R * _{2 is} an organic © group with at least 5 carbon atoms which stafinnto from an organic mercapto group R ^f ₂ SH

Third, the invention provides a method of manufacture

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of the compounds according to the invention, which consists in that essentially stbohioiaetriache ilengen a monoorganoainntr! halide or one. Diorganoindihalides with an organoaercapto compound (of which at least 1 mole fraction has at least 5 carbon atoms) and, given- « at least, a Garcojcylat sals, implements «.

Fourth, the invention provides another method for Preparation of those compounds according to the invention formula

■ I. ■

V ~ ²

\ rorin R, R'0 and X have the meanings given above and Z ^{1 is} a group X or -SR ¹ (in which R * di «has the meaning given above) wherein the process, the heating of practically stoichiornGtrieeher amounts of an organotin compound of the formula R ^ Sn (SR *) i _a * where .a is 1 or 2 and at least one group R * has at least 5 carbon atoms, with at least one tin halide of the formula R. SnX .- ^, where b is 0, 1 or 2 , at a temperature of 50-200 ° 0 to cause a disproportionation reaction. It can be seen that the tin halide is a diorganosin halide and / or, if this is appropriate, a tin halide.

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Xn of the following general formula of the compounds which ale Stabilizers can be used in the inventions hates. '.- "' .-

'X ■■■.' '; ;

R-Sn «■. · A H ¹

R can be any hydrocarbon group such as an alkyl group of up to 20 carbon atoms, an alkenyl group such as vinyl, or an aralkyl group such as benzyl, or an ary group such as phenyl, toly or xylyl. Preferably, however, R should be an alkyl group with 4 to 12 carbon atoms, in particular η-butyl or n-oetyl «X can represent a bromine or chlorine atom, but is preferably an oioratum for economic reasons. The group H * is derived from an organic mercapto bond (R ¹ SH). If a group R * which has at least 5 carbon atoms is present in the compounds (hereinafter referred to as the R'g group if necessary), the compounds are new and form the mentioned other aspect of the invention, "Preferably? the mercapto ^{compound R 1} SH is an alkylneroaptan in which the alkyl group has 4-20 carbon atoms, in particular ootyl, dodecyl, oetyl or stearyl meruaptan, but R ^{1 can} also be derived from alkyl ethers, v <? n meroaptocarboxylic acids, such as shioglycolic acid or! Thiomaleal acid, stawmen ₉ where soiohs ester preferably 4 - β carbon atom in the alkyl group on white. The group R · can also

81471728:., -5- BAD above

iron of a thioacid or dithioic acid of the carboxylic acid "or" r Fhösphorsäurereihe derive, such as thiobenisoic acid, or a dialkyldithiophosphoric acid or a di- alkylthiophosphoric acid <,

The group Z in the general formula is normally a group R, X or ~ SR ^f , which can be different τοπ the other E, X or 8R * present in the molecule, but is usually the same. Alternatively, Z can be an aoyloxy group R ¹ OO ₂ - derived from a carboxylic acid R ¹¹ OOgH. For example, Z can originate from an aliphatic honocarboxylic acid with 2 to 20 carbon atoms, in particular acetic acid, 2-ethylhejcanic acid, n-octanoic acid or lauric acid, or from dicarboxylic acids such as maleic acid or succinic acid or half-esters thereof, a, B, benzyl maleic acid; alternatively, Z can be derived from aromatic monocarboxylic acids such as benzoic acid. This last-mentioned feature is, however, less preferred and very particularly preferably f Z should be a further hercaptoreate.

Accordingly, as representative examples of the compounds, which can be used as stabilizers in the founding measures which the following »list (list A) to be named:

Dibutyl butyl mercapto tin chloride; Butyl-dioctylmercapto-zinnohioridi. Butyl-dioctylmercepto-iinnbroBid}.

009814717 28 -, 6 -

Butyl-dodeoylmeroapto-siondiichloridf Butyl-didodeoylmereapto-sinnchloridi Butyl-dodeoylfflercapto-iiim-tthiolienisoatj-cliloridi Qotyl-dodecylmeroapijo-? Lnnohlorid ϊ Bienyl-dioatylmereapto-thimchloridi Btityl * -bis * - (ieoo otylthioglycolate) - tinnehlorid j Octyl bis (butyl thiossalat} - «l? Mehlorid? Dibutyl-dodecylBiercapt-o »ϊ inachlorid ι Bibutyl-oe tylneröapto-? innbromide}

Butyl-dodecylmercapto-aeeto-9innohloridj Butyl-dodtcylaercapto-lauroyl-tijmohloridj and Butyl-dodecyliittercapto- '. Inn- (bottaylm & ieat) -chloride j All "these connections besides the" should advise new ver ties soin.

Compounds for use as stabilizers in the invention can Hassen by reacting a mono- or BI-organotin halide with an organic mercapto compound R ¹ SH in an insufficient amount to react with all the halogen atoms in the Org & nozimüialogenid, and ▼ oreugBvreiee in the presence of a tertiary Aaina be irctsserstoffakfseptcr than halogen produced "in addition to the amounts of Heaktionskomponenten be applied to the normal conditions for the Umeeteung of OrganoBinnhälogeniden mix organic mercapto compounds. So bexapielaweiae there "

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Organotin halide and the captor bond are heated and heated together until the reaction has ended, which results in the evolution of hydrogen halide. A reaction temperature of 40-70 ° C. is usually sufficient, however, preferably a hydrogen halide acceptor, in particular a tertiary amine, such as triethylamine or pyridine. The amine hydrohalide obtained can then be removed from the reaction mixture by filtration or by aqueous extraction. The reaction can also be carried out in an inert solvent such as a hydrocarbon or ether solvent. The products are usually liquids and are usually cleaned only by vacuum stripping. Some of the compounds can also be purified by vacuum distillation. However, they are, at least to some extent, sensitive to solvolysis when brought into contact with hydroacyl containing compounds such as water, acids, and bases.

If Z in the general formula denotes a group R for the stabilizers, a diorganotin halide is reacted with a molar proportion of the MGcapto compound. When Z is a -SR ^f group, a monoorganocin halide is reacted with 2 molar proportions of one or more of the mercapto compounds. If Z represents a halogen atom, an S-jonoorganosin trihalide is reacted with a molar proportion of the BJercapto compound; if desired, mixtures of the compounds according to the invention can be prepared and for the purposes indicated

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3 15Λ4629

be used, baiepielßweiao duroh Uueeteung of a Monoorganoainntrihalogenida with 1 to 2 mol of the Hercapto compound. When 2 is an acyloxy group, a ttonoorganosine trihalide is converted into a halide of both the Hercapto compound and an Oarboxylatealaes / Solhe reactions can be carried out simultaneously or sequentially in any order. The carboxylated! & Used is usually an alkali rope of the carboxylic acid. The metal halide formed as a by-product is removed by filtration or by aqueous extraction. λ

Those of the stabilizers that duroh the generalθ formula

'.' ■% ■: ■ ■ - R-Sn-SR ¹

J.

can be reproduced in which R, R 'and X have the meanings given above and Z ^{1 is} a group R, X or «SR ^} , can also be achieved by a dioproportionation reaction between an organoamine mercaptide of the formula R & Q {SR ^f ). _o , where a is 1 or 2 , and at least one 2innhalogenid of the formula R ^ SaX. ^, wherein b is O ^ 1 or 2, are prepared. The tin halide can be a monoorganosine trihalide RSnX-, a diorganosine dihalide RgSnX ₂ , and / or, if it is suitable, a stannihalogenide SnX ^, eein. Such a reaction is performed only by common zwocknaGig Erhitae.n substantially etöchioiaetrischen appropriate amounts at a temperature of 50 ^0- -.20O -O, wherein οine preferred temperature 70 - is 100 ° C. Öewünechten-

If necessary, an inert diluent, such as a Kohlenwaeeer-009814/1728 _Q

"' ⁹ ~ BAD ORIGINAL

substance or ether. The suitable «etöchiooetriBche Amount for the reaction components for the disproportionation ^ - or equilibrium reaction depends τοη the type of Reaction components and the desired product, .doch the choice of reaction components and their proportions can easily be determined from the respective reaction equations. Examples of these equations are as follows

2RSn (SR '"3 + ₃ RSnX" 3 ReniSROgX;

RSn (SR ') ₃ + 2RSnX ₅ = 3 RSn (8R ») X ₂ ? R ₂ Sn (SR ^f ) ₂ + ³ >> * 4 ^β 2 RSn (SR *) X ₂ ; and R ₂ Sn (SRO ₂ + R ₂ SnX ₂ »2RgSn (SR ¹ ) X

When the disproportionation reaction is carried out with an organotin halide reaction component, the organic groups attached to the tin should be identical to those attached to the tin in the organotin mercaptide if one wants a uniform product. The disproportion nierungsreaktion ^v typically proceeds rapidly to completion bo that little or no purification of the product _r 1st addition to a possible stripping of solvent required. Such a disproportionation reaction can also take place in situ

be carried out in the vinyl chloride polymer or mixed polymer leate during ^{1 of} the calendering by adding the appropriate mixture to the disproportionation reagents.

-J £ '■■■ - - 10-0AD OBtGiNAL

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They special organic tin compounds described here are used as stabilizers for vinyl chloride polyatriate and copolymer "(defined here as those those of not more than 20 units of other monomers ale vinyl chloride, for example vinyl acetate and / or vinylidene chloride, descend). In masses which contain these polymers, the stabilizers should be used in one. Quantity ron 0.1 «· 5 weight * £, preferably 0.5-2% by weight of the polymer or Mieohpoly- ■ erisates are introduced. It has been found that the addition of these compounds to the vinyl chloride polymer or * «Nisohpolymerisat gives a higher degree of stabilization than a conventional organosense meroaptidstftbilieator.

Other stabilizers can also be mixed with the organic sense compounds το · 1 used in accordance with the invention, for example, similar amounts of organic phosphite and / or Thiophosphiteetem and / or Fettettureealise of CaI-oiua and / or zinc and / or oadmium and / or barium and / or Lead, and / or hindered phenols, such as 2,6-di-tert-butyl-4-methyl phenol and 2,4-di-1 er t-butylphenol, and / or basic Lead carbonate or stearate. Gewuntenfalla can other organosine stabilizers are also present. The polymer compositions often contain one or more plasticizers in conventional amounts and other conventionally used ones can be used Contain additives, such as pigments and / or extrusion or Form aids. The polymer compositions according to the invention are in

009814/17 * 28 "'-ti--

usually mixed, for example by calendering or on a two-orphan mixer

The following examples explain the invention without restricting it. All! Sengen are weight-bent. Examples 1 to 5 show the preparation of new compounds obtainable according to the invention, and Examples 6 to 16 show the compositions according to the invention. The term "lauryl" is intended to mean the mixture of alkyl groups "which in a narrowly fraktioniertet" Eokosnußöl exists in which at least $ 50> the alkyl groups are dodecyl groups.

example 1 Butyl-diocty! Mercapto-: inn chloride

94.2 parts (0.33 mol) of monobutyltin trichloride were mixed with 57.5 parts (0.66 mol) of n-oetyl mercaptan and heated to 60 ° 0, 67 _f 2 parts (0.66 mol) of triethylarain were added with stirring The mixture was added over the course of 30 minutes, the temperature being kept at 60-65 ° C. 50 ml of water was added to dissolve the amine hydrochloride. The organic layer was separated and stripped to an internal temperature of 100 ° C at a pressure of 14 mm. Treatment of the product with a filter aid and subsequent filtration gave 115 parts of butyl-dioctylraercapto-ammonium chloride as a colorless liquid «

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Example 2 Semiseh of

and ethyl lauryl mercaptan and dichloride 92 parts (0.33 mol) of butyl trichloride, 101 parts (0.5 mol) of laury mercaptan and 260 ml of petroleum ether (b.p. 60 - 80 ° O) - were mixed and adjusted to 55% 0 raised. 51 parts of triethylamine were added dropwise while the temperature was kept at 55-60.degree. After cooling, the product was washed three times with small amounts of water and the organic layer was stripped of the solvent and filtered as in Example 1, which resulted in an 8 <iuimolarea mixture of butyl-laurylraercaptotin dichloride and butyl-dilaurylmercapton chloride.

example ρ

Qct.yl-'laurylmorpap _M t o > /: inndichlorid

68 parts (0.2 mole) octylamine trichloride, 40 parts (0.2 mole) Laury! Mercaptan and 100 ml petroleum ether (bp * 80 - 100 ° 0) were mixed and heated to 60 ° C and 20 parts of Sri- · I ethylamine as in Example 2 given. The mixture was stirred for another half hour. The Arainhydrochlorid was filtered off and the Piltrat from the solvent up to 80 ° 0 with 14 ram Druok freed. 97.5 tonnes of ootyl-lauryl mercapto-III-dichloride were obtained as a very pale yellow liquid "

Example 4 ,

Butyl-dil- aurylmercapto-frinnchlortd

24.2 parts of monobutylin trilaurylineruaptide were combined with 22.6 0098T4 / 1728 - O «-

BAD OBIGiNAi

Share butyltin trichloride ina equilibrium set by they were heated together at 80 ° C for 1.3 hours. Ale result this dioproportionation reaction became butyl-dilauryl mercapt o- a? innohlorid formed.

Analysis: Cj ₅ -HL

calculate!;: Sn 19.4 £ S 10.4 # oil 5.8 % ) found: Sn 19 »5 & S 9.7 # Cl 5 _f 8 #

Example 5 Pibutyl-laury! Mercapto- ^ inchloride

Example 2 was prepared using 101.5 parts (0.33 mol) of dibutyl-s'dnndichlorid, 67.5 parts (0.33 mol) of lauryl mercaptan, 200 ml of petroleum ether (boiling point 80-100 ° C.) and 34 parts of triethylamine are repeated. Dibutyl lauryl mercapton chloride was obtained.

Examples 6 - 9

Rigid sheets of polyvinyl chloride compound were produced, by 100 parts of a vinyl dispersion polymer with 0.5 Parts of stearic acid and 2.0 parts of stabilizer were mixed on a two roll mixer at 155 ° C for 10 minutes.

The following stabilizers were used! Example 6 Butyl-dilauryl mercapto-chloride

Example 7 1 s 1 mixture of butyl-dilaurylraercapto-ii ** i <3hiorid with butyl-laurylraercapto-tin dichloride;

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Example 8 butyl sense bioctyl mercapto-iii-chloride; and Example 9 Dibutyl-laury / mercapto-tin chloride; and ale Comparative experiment dibutyltin dilauryl mercaptide, which is a common stabilizer.

Samples of the foil material were placed in an oven at a) 170 ° 0 for up to 1 hour? b) 190 ° G for up to 20 minutes and e) Aged 200 ° C for up to 20 minutes. In each of the examples, the initial coloration of the poliet and the coloration g after the aging treatment were lower than in the comparative experiment.

Examples 10 » 13th

Rigid polyvinyl chloride film material was prepared by orphaning the following recipes for five minutes on a two-roll miecher at 150.degree.

share

Polyvinyl chloride (Corrio D-559) 100

atearyl alcohol (lubricant) 1.5 *

Butyl epoxy itearate secondary retabilizer) 3 »0 Organotin stabilizer as in Table I 2.0

The obtained films were cut into strips and aged in a press at 175 ° 0. In the following Table I shows the colors of the samples after various aging periods.

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Tabel

example

stabilizer

Aging time at 135 O in minutes 15 30

Ver>
same

10

11

12th

15th

Dibutyl chin

dilauryl

mercaptid

Butyl ~ dilauryl

mercapto-

tin chloride

ι ί 1 G-eiaiBch before Butyl-laurylraercapto-tin dichloride and butyl-dilauryl mercapto-sinn- ^ chloride

Octyl-dilauryl raeroaptc-ainnühlorid

Butyl-dioctyl> aercapto- ι ΐηη chloride

pale yellow

colorless colorless

yellow

finally

colorless

yellow

very fuzzy

very pale

yellow

pale yellow-brown

pale yellow

colorless

colorless

colorless

colorless

aehr

pale

very pale brown

yellowish brown

pale brown

The examples each show that the compounds, which Tin »carbon - ,, tin-halogen and tin ~ sulfur ~ carbon bonds contain superior stabilizers over a conventional organotin mercaptide stabilizer.

Example H _r 16

The working method of Examples 10 «13 was carried out with the following * lowing recipe and with one carried out in an oven at 170 ° C Aging repeated.

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Parts

Polyvinyl chloride (Oorvio D-559) 100

Stearic acid (lubricant) 0.5

Organotin stabilizer - as indicated in lab. II

Table IX

at stabilizer lot Aging time at 17O ⁰ O in minutes 30th 60 game to Sta
bilisa 15th gate yellow dark yellow Ver Dibutyl tin 2.0 very same dilauryl pale yellow raercaptid colorless very H TsI mixture 1 _r 64 colorless pale brown of butyl di- lauryl-mercap tin chloride and Bu / uyl-lau- ryl-mercaptq- sinn dl ohlorid colorless very 15th ■ butyl dioctyl 1.6 colorless pale yellow merca.pt o ~ sens- chloride colorless very 16 as in Bei 2.0 colorless pale yellow game 14

These examples are again the superiority of the connections, the carbon «tin, tin-halogen and tin-sulfur-carbon -Bonds contain, ale stabilizers for polyvinyl chloride ■

-.17 -

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Claims (1)

15U629 Folder: 20 382 Case »P. 277 0 1. Vinyl chloride polyamide containing a vinyl chloride polyamide and a heat stabilizer, characterized in that that the stabilizer is a compound of the general formula H-Sn-S - R ¹ onthäli; where H is a hydrocarbon group, X is chlorine or bromine, R ^{is an organic group derived from an organic mercapto bond R ¹ SH and Z is a group R, X or -SR ⁵ or an aoyloxy group R ¹¹ CO ₂ , which is derived from a organic carboxylic acid R. ^M 00 ₂ H 3 taram mean. Process for Heratallung as heat restobilizers for Vinyl chloride polymers useful. Connections of general formula E j, - S - H ₂ '
Z 00 981 A / 1728 - ie - 13 15U623 where R is a hydrocarbon group, X is CXor or bromine, Rg * is an organic group with at least 5 carbon atoms, which is derived from an organic mercapto compound Hg ¹ SH, and Z is a group R, X or -SR ¹ _f where R 'is one of an organic Mercapto compound R ¹ SH-derived organic group "means, or an acyloxy group R ¹¹ OOg, which derives from an organic carboxylic acid R ¹¹ COgH, means, characterized in that the compounds are prepared in a manner known per se, such as by reacting suitable stöcliioraetric amounts of a monoorganosine trihalide or morganosine dihalide with an organomercapto.compound of at least 1 molar fraction has at least 5 carbonifera and optionally with a carboxylate salt or by a disproportionate reaction between an organotin mercaptide of the formula K Sn (SR ¹ _af where a is 1 or 2 and at least one group R 'has at least 5 carbon atoms, and one tin halide of the formula Η ^ δηΧ ^^, in which b is 0, 1 or 2. FATENl ANWXl rE H FINCKfi DiPL-IMO. R tOHt DIHMNO I.! TAEGE * ^{0098u / 1728}