DE1917847A1 - Stabilization of halogen-containing polymers - Google Patents

Description

Bill.xton-M & T Chemische Industrie N, Τ *, The Hague / NiederJande

g _yon ha3.og8nhaltige polymers.

ö-. April ; 968 V _{; ä} bt.A ..

Db? Έ? ΤΊ &Ιν.ί> £ refers to a \ '. F oin? Er: rab; cen zx> .r stabilizer,;.;, ·> .- 9';? I aalogen-containing polymers; like ζ-B, polyvinyl chloride _r . U "i! .R>. AL'-f new atabill-isie-rrs containing halogens © Polymerzussjnmensetaun- KQn vsö. Iasbasonäere on stabilized © halogen-containing polymer to« total solutions .. the \ a dex sound recording.rrhmmgsj.ndindustrie are used

¹ I? - -ns' if & cblenten beko-iirit, is _:. different halogeniLi. ";." -! /?; '-: organic polymers; especially vinyl halide polymers _;

909845/1690

SAD ORIGINAL

as a, B ₃ Honiopolymers of vinyl chloride and copolymers of vinyl chloride with other monomers, degrade if they are exposed to heat for a longer period of time = which is expressed by the resin darkening and by an increase in brittleness *. These disadvantages can the resin for many uses make it unfit _t since the darkening a unansehliehes appearance yields and increased brittleness mechanical unfit ness have the effect may = A large number of materials has been to stabilize hai ogenhalt strength polymer ene "Many these additives have had some success in stabilizing halogen-containing resins against the degradative effects of heat, but there are still many uses? in which a greater degree of via stability is desired 'than can easily be achieved up to now *

It is a particular characteristic of the known stabilization systems that they cannot completely prevent the degradation of parcels or polymers such as polyvinyl chloride during the period during which the resins and the stabilizer composition are kept on a hot mill, , on which they are mixed. During this side space, which can be 5-30 min or more, the various ingredients such as zoB, pigments, plasticizers, "stabilizers", lubricants, etc. are mixed with the resin, whereby the content is mixed with the infiltration of Heat and pressure is applied to produce a substantially homogeneous mixture. During this period of high heating (typically 150 G or more) the resin can degrade much more quickly than under normal working or use conditions product that of a Banbury mixer or an extruder is to be darker than it is _f er'.riinscht.

For this reason, the experts have tried so far to eliminate this degradation caused by heat by _{using various materials, such as ζ, B 0} auxiliary heat stabilizers _? added xtfurden ,. It has been found, however, that the presence of these additional materials has undesirable side effects which result in the desired properties of the hair or the polymer ^. 909845/1690 *

be modified in an unsatisfactory way «Aue this Basically, it has not been possible so far to identify Harssus compounds which are stabilized in a completely satisfactory manner against the degradative effects of heat

It is an object of the present invention to provide a method for stabilizing halogen-containing organic polymer or HarE compositions. In particular, Viitylhalogenidpolymeren _t create against the degradation caused by heat. It is a further object of the invention to create new stabilized halogen-containing polymers = further objects emerge from the following description.

Thus, according to the invention, a method for producing a proposed new, against the degrading effect of heat-stabilized halogen-containing polymer, which thereby carried out is that one adds a stabilizing amount of the following substances to the halogen-containing resin: a first stabilizer the

Formula (RSnX, _c ) ^ _t where X is sulfur or a mixture of; 10 f »ρ η

Parts of oxygen with 10-1 parts of sulfur and η means one Integer of 2 1000 means? and a second stabilizer of

Formula R 'SnY, wherein at least one Y -O0C-R "-CQCR or a g e '

R''YSnY- or -OOC ~ a ⁿ -COO ~ iet mA g equals 4 and a equals 1-5 if Y is -OOC-A ^ -OQOR ,, - and g equals * Ibt and a equals 2 eats "white Y -00 (X-EVCOO: · {. · ΐ and less than all of the groups Y -OOCR; where R vn &'£..-." rushes unconditionally from the -ir.aa.' the alkyl with 1-20 Köhlenetoffato? Iöii ~ aryl, alkaryl, aralkyl and cycloalkyl and R "alk? ^ Lenyl * Arylenyl, Älkarylenylr Arylalkylenyl and Cycloalkylenyl tsdeuiet,

The polymers or resins * which can be made according to the above statements can be halogenated organic polymers, and typically were such; oil. o (Jhlor;). tome toi the poly merket te contain- this foJ. ywerti körjaen. Homopolymers like. ε »B. Polyn? are der Pblyvit; jrl chlor iä type, .- be.isijielsweaee Poly vinyl chloiad. Polyvin ^ - 'idenohloria χίεντ: _f 3-sin, Pie Brfindung bet their most important application aa> in: _$ \ wirn. the pole, vir.er a mixed

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polymer is j ¥ ärmestabilität reaches _f where _f is unexpectedly hocli _f namely fall by a factor of more than JQfo or .more "Among these copolymers, the nically unsaturated by copolymerization of vinyl chloride or vinylidene chloride with other äthyle- 'monomers are obtained »Ethylenically unsaturated monomers are compounds _{containing 5} diq polymerizable carbon-carbon double bonds? such as Z ₀ B ₀ acrylates such as acrylic acid, ethyl acrylate _t acrylonitrile etc .; Vinyl monomers such as styrene. Vinyl acetate, etc .; Maleates such as maleic acid, maleic anhydride, maleate ester, etc. * For the sake of convenience, reference is made to vinyl chloride homopolymers and vinyl chloride / vinyl acetate copolymers »

The polymers can be either hard or soft. If hard polymers are used then they can be impact modifiers. Pigments and / or fillers "lubricants, etc." contain "in addition" to the resin and the stabilizer. If soft polymers are used because they can in "plasticizer (primary and secondary) & c _o contain pigments and / or fillers, lubricants in addition to the resin and the stabilizer *

The VinylchloridpolymereiL and -mischpolymeren to as Z ₀ Bo Dioctylphthalatf also contain plasticizers, lubricants, such as ζ _O B.> tStearinsäure _f pigments, fillers, etc. ""

The first stabilizer which is used according to the invention WiTd ₈ has the formula (RSnX, _f ^) _n = In this compound, R can be a hydrocarbon radical, which is preferably selected from alkyl, cycloalkyl, aralkyl, aryl _f alkaryl including such 'inertly substituted radicals is selected. When R is alkyl, it may typically be _f straight chain alkyl or branched alkyl such as methyl, ethyl, n-propyl, isopropyl "iB.utyl ,. isobutyl. Sec.-butyl, tert" -Buty3., N .... Arayl, Heopentyl Isoarayl _f n-Hexylf Isoheryl, heptyl, octyl tiecyl j - "> odecyl _r Te trade cyl, octadecyl, etc, be ,, the preferred alkyl groups are iiiearige alkylene groups containing 8 or less Eohlenctoffstome a-JLfirüijen! , W-ie ζ ß the octyls and lower groups, ί / βϊ? Νΐ B is cycloalkyl,

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then it can typically be cyclopentyl »cyclohexyl, cyclo- .heptylj. Cyclooctyl etc. _o if R is aralkyl _s then it can typically be benzyl, ß-phenylethyl ,, "f" -phenylpropyl, ß-phenylpropyl etc. _o If R is aryl- * then it can typically be phenyl, naphthyl, etc ₀ be "When R is alkaryl ISTJ, - then it may be typically tolyl * xylyl _r p" ethylphenyl, p-nonyl "phenyl etc _u * R may be inertly substituted, d _o h _O9 it may be non-reactive Substituents carry, such as Z ₀ Be alkyl »Arylg Cycloalkyl> Aralkyl _f . Alkaryl ,. Ether etc. ₅ Typical substituted alkyls are 2-ethoxyethyl etc. Substituted cycloalkyls are SoB ₁₃ 4-- ~ methylcyelohexyl etc. _o Inert substituted aryls are z- ₀ B <· anisyl ,, biphenyl etc. _o Inert substituted aralkyls are z _a B _ü Chlorobenzylj, p ~ _T p-phenylbenzyl Methylbenayl etc .. inertly substituted ■ Alaryle are, for example, _e, 2,, 6 "Di-tert-butyl = 4-methylphenyl etc,

The first stabilizer ,, which is used according to the invention may be a * Thiostannonsäure, namely a Alkylthiostannonsäure, a Arj-lthiostannonsäure, a Gycloalkylthiostannonsäure _r a / _f Lralkylthiostannonsäure one Alkarylthiostannonsäure

/ Polymeric thiostannonic acids comprise the condensation products of stannonic acid and bawe thiostannonic acid, the products having degrees of condensation of about 2 to about 1000 and preferably 2-1:00 o

These compounds can be represented by the following formula, "f earth?

(RSnX _{1 5} ) _n ■ "(I)

"in which J. is sulfur or a mixture of 1- · 1ΰ parts of oxygen with 10-1 parts of sulfur, these are mixtures which contain these elements in a weight ratio between ίϊΙΟ and 10ϊ1, and in which ώ. 2-1000 _s preferably 2-100 _f can be «

Polymers -thiostannonic acids correspond to the formula (II) given _below. In the cocondensation products, units of, for example, stannonic acid with units of, for example, thiostannonic acid in accordance with that given below

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Alternate formula III, in which case m and η can each be 2-1000 _f, preferably 2-10Op *

(RSnO _{1 t5} ) _m (BSnS _U3 ) _n (in)

The group H of the polymeric Thiostannonsäuren preferably contains alkyl groups having 1-20 carbon atoms and most preferably 4 carbon atoms "Other I'hiostannonsäuren as _f s _o B" polymeric and Arylthiostannonsätrren and Gyeloalkylthiostannonsäuren are effective but preferably ₅ are the alkyl compounds ο

The above compositions can be prepared for example by "that one ™ iiatriumsulfidj RöiiOl. Typically Butylzinntrichloride with, for example, Na ^ S * reacting ,, for example to produce (RSNs. _{K) s} wherein η as defined further just mentioned has ₃ If RSnCl ^ for example, If the aqueous medium is reacted with less than the equivalent amount of sulfide, then the product can. (RSNO, -) to be (. RSNs _{F) ä} the both sulfur and oxygen contains ₃

The preferred compounds are those of the formula (RSnS,, -). where the group R is a lower alkyl group ο Most particularly butyl is preferred. Preferably those used are Compounds those in which η is about 2-100

Preferred first stabilizers are ζ, B, methylthiostannonic acid

(GH-SnS. _Κ ) _f in which η can be 2- »10000- butylthiostannonic acid j ι ί y n."

), where η can be 2-1000j n-Ootylthiostannon-

acid (H-CoH ₁₁₇ SnS ₁ , -), where η 2-1000 be kai οι / ι j ρ η

The second stabilizer _? which is used according to the invention _f is a compound of the formula R ¹ SnT _$ wori.na an integer xL

& g ^ a

from 1 _S 2 or 3 isto In this formula, R ¹ can be a hydrocarbon radical from the group alkyl ₅ cycloalkyl, aralkyl »alkaryl i? nd, arpl: pein ^ In the above formula is at least one T

90 9845/169 0 © AD ORlQiNAL

-0OC-R "-COOR or E ^ YSnY- or -QOC-R" -COO- (where each Y can be the same or different), where g is 4 and a is 1-3 when Y -U0C- R "-C00R _t . And g is 3 and a is 2 when Y is -GOC-R" -C00 ~., And less than all of the groups Y are -00CR. R "is a divalent äthyienisch unsaturated hydrocarbon radical from the group alkylenyl Arylenyl _r Alkarylenyl, Arylalkylenyl and cycloalkylenyl., Second Typical stabilizers are ζ.Β., Dibutylainnmaleat, dimethyltin bis- (iso-octyl maleate), Dibutylzinncitraconat, Dibutylzinnmonoäthylmaleat (which is the Reaction product from dibutyltin oxide and monomethyl maleic acid).

Typical preferred second stabilizers are ζ »Β _α

Dibutyltin-bis-methyl aaleate ■

Dibutyl tin bis octyl hialeate Dibutyl tin-biB-benzyl maleate Dibtttyltin-bis-sylyl-maleate Dibutyltin bie-cyclohexyl maleate Dibutyltin-bis-phenyl-maleate Dioctyl tin bis methyl maleate Dioctyltin-biB-octyl-maleate Dioctyl tin bis-benzyl maleate Dioctyl tin bis xylyl maleate Dioctyltin bis-cyclohexyl maleate Dicyclohexyltin bis-laurylinaleate

Dimethyltin-A) is-lauryl-maleate ■

Dimethyltin bis-maleate benz3'l D imethylzinn-bis-cyclohexyl-times at dimethyltin bis-xylyl-maleate Butylsinn-tris-iso-octyl maleate Octj ^r lzinn-tr is-iso-octyl ~ times at dibutyltin laurate ~ -isO "octyl maleate tributyltin iso-octyl maleate

The preferred second stabilizers are BiTnitylsirm-bis- (l3ü - prcpyl-! T5aleate), Dibui ^ lziim-bis-iisiO-octyl-rnales- ¹ :} and dibvitylsinn-maleate j

X 909845 / 1690-

The first and second stabilizers can be used in stabilizing Crowds are present «.

Typically, the first stabilizer (RSnX ₁ , -) can be used in amounts of 0.01-5 parts by weight per 100 parts by weight of halogen-containing resin, preferably in amounts of 0.05- 2 weight parts _o ~ _f in particular from 0.5 'parts by weight per 100 parts by ₀ halogen-containing resin used _f *

Ih typical example, the second stabilizer in amounts of 0.01-10 Gewo parts per 100 wt, parts by hälogenhaltiges resin to be present, "Preferably, the amount used is 0.25-4 wt ~ _e parts, for example 1.0 wt Parts per 100 parts by weight of its halogenated resin o Preferably the second stabilizer is used in an amount at least equal to that of the first stabilizer, Preferred results are obtained when the second stabilizer is present in an amount at least twice the first stabilizer is.

Thus, the preferred heat-stable vinyl chloride polymer compositions according to the invention contain: 100 parts by weight of a vinyl chloride polymer and a stabilizing amount (typically 0.01-5 parts) of a first stabilizer of the formula (RSnX _{1 c} ) "wherein X is sulfur or a mixture of 1 Means -10 parts of oxygen with 10-1 parts of sulfur and η means an integer of 2 ~ 1000; and a second stabilizer of the formula R 'SnY. wherein at least one Y ~ OOO-R "-COOR or

a g a ■

R ' _{2 is} YSnY- or -OÜC ~ R "-COO- and g is .4 and a is 1-3 when Y is -OÜO-R" -OOOR. vuä.g is 3 • and a is 2 if Y is -OOC - R "-COO.- _; and less than all of the groups Y are -OüCR; where R and R ^{1 are} each independently alkyl with 1-20 Carbon atoms, aryl, alkaryl * aralkyl and cycloalkyl and R "signifies A3.kylenyl, arylene ^ ^r l _r alkarylenyl; Arylalkylenyl and Cj'cloalkylenyl means =

^T jie new wari "e - and light-stable-sn additions:.; N ^T> ieriSierungen according to rter £ rfindui) .g kömiei · by such OJechnike-i as Matlen, dry '■ iiiich & n. Bant-ury-Miscnen oae :: · Ä-y _: cb i. "· Erts: - η other norrsaler-

909845/1690.

wisely used mixing process can be produced »

One of the blending methods that "is particularly useful * is" to make a stabilizer composition that contains the first stabilizer and the second stabilizer * This stabilizer composition is then added to the vinyl chloride polymer and carefully mixed with it "If this technique is used" then eiithält the Stabilisatorsusammensetzung typically _0? 01-5 wt _e parts by the first stabilizer and 0.01 "10 wt parts by * of the second stabilizer" Preferably, it contains approximately Q _f 05-2 weight parts by _G}, for example, 0 , 5 weight parts ,, ~ _e of the first Stabilisatora and about 0.25-4 wt "parts * example _1? 0 parts by weight of "the second stabilizer" Preferably the second stabilizer should be present in an amount at least equal to that of the first stabilizer ο whichever mixing method is used _f it is desirable that the first stabilizer and the second stabilizer largely completely and uniformly distributed throughout the vinyl chloride polymer composition «

Eb is a feature of the neat stabilizer system of the present invention; that with this stabilized halogen-containing copolymers and resins can be obtained "and in particular vinyl halide copolymers _s such as _Q B _o vinyl chloride / vinyl acetate copolymers, which are characterized by a high resistance to heat degradation. * The degree of stabilization obtained in such systems is considerably better than before could be obtained by the known stabilizer systems ».

Because of the extraordinary properties of this new stabilizer system, it can be _? to bring about a stabilization with smaller amounts and thereby a more effective system zj. receive »which reduces costs and increases the effectiveness of the process *

Πια to clearly demonstrate the novel features of the invention and to show the unexpected and extraordinary results _f

909845/1690 _BÄD

which can be obtained by the invention are as follows Examples given in which all parts are parts by weight j. unless otherwise stated ο

Examples

In these examples a hard vinyl chloride polymer was used which had a specific gravity of 1 _f 40 _s, a Shore Durometer "D" hardness of 80 and a final tensile strength of 490 kg / cm and is sold under the trademark Diamond 450 o.

In some of the examples, the vinyl chloride blend polymer used was one with a vinyl chloride / vinyl acetate ratio of 90/10, a specific gravity of 1 * 36 and a specific viscosity of 0 ^ 59 * which was sold under the trademark Gary 380A by the Tenneco Corp »is sold _o

The exemplary first stabilizer used was butylthiostannonic acid with an η value of 4? 5 »The second used The stabilizer in these examples was dibutyltin maleate, dibutyltin-bis- ( iso-oetyl-maleate), dibutyltin-bis- (isopropyl maleate, Di-n-octyltin maleate ,. Bis- (dibutyltin-laura.t) -maleatej. Bis (tributyl tin) maleate, dibutyl tin bis (benzyl maleate) and dibutyltin bis (cyclohexyl maleate) o

The selected compositions were carefully mixed by placing a polyvinyl chloride on a two roll mill _. which was heated by oil (to a temperature of 175 ⁰ G for the homopolymer compositions and 163 G for the mixed polymer compositions), was applied together with the specified amount of the first and second stabilizer and the G-mixture was ground for about 5 min these tests was 2 _i b-Di "tert ~ butyl-p-cresol (in an amount of u _s T entirety) also added to the resins" Am continuous ribbon of the composition .-- formed around one of the rollers., this tape was au ^ geschhitten "and the composition was removed from the hot orphan squares of this material in _2? 54 cm χ 2 _S 54 cm" srurden "for

^ - 9 0 9 8 4 5/1690 _{aÄD 0RlG1NAU}

Thermal stability tests excised * For the thermal stability test, the squares were placed in an oven which was maintained at a temperature of 19O ⁰ C in the Homopolymerzusaiainensetzungen and to a temperature of 170 ° C at the mixed polymer compositions "samples of each composition were removed from the oven at intervals of Taken for 15 minutes and examined visually for the color change and classified as follows:

7 - clear, water-white

6 - just white

5 - lightest degree of yellowing 4 - pronounced yellow color 3 - deep yellow-brown color

2 - deep brown color

1 - dark brown to black color

The time in minutes required to reach a value of 3 or less * was referred to as the thermal stability value.

Examples 1-6

In Example 1, 100 files of the vinyl chloride homopolymer composition were tested without the addition of a stabilizer. They served as a comparison. In comparative experiment 2, 100 parts of vinyl world ainylacetate copolymer composition were tested without the addition of a stabilizer; it served as a further comparison, "In Vergleichsbeispieleh 3 and 4, the first stabilizer Butylthiostannonsäure was of a η value of 4» 5 _f exhibited in an amount of 1.5 parts to 100 parts Homopolymerpolyvinylchloridzusammensetzung (Example 3) and in an amount from 1.5 parts to 100 parts of vinyl chloride / vinyl acetate Mischiiolymerziusammensetzung (example 4) _t is added with no other stabilizer Toggle

deii
was essential. In / Comparative Examples 5 and 6, the stabilizer was dibutyltin maleate in an amount of 1.5 parts per 100 parts of homopolymer _{polyvinyl chloride compound (Example 5) and in an amount of i t} 5 parts per 100 parts of vinyl chloride / vinyl acetate mixed polymer ( Example 6) present, with none

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Another stabilizer was present.

In Example 7, 100 parts of homopolymer polyvinyl chloride were - present composition and two stabilizers as follows;

Butylthiostannonic acid 0.50 part dibutyltin maleate x 1.00 part

Ci -

Total amount of stabilizer 1.50 parts

In Example 8, 100 parts of vinyl chloride / vinyl acetate composition and two stabilizers were present as follows:

Butylthiostannonic acid 0 * 50 parts of dibutyltin maleate 1 «00 parts

Total amount of stabilizer 1 * 50 parts

The results of the thermal stability tests are given in Table I. specified:

Table I.

Example., Heat stability stability value color according to value in minutes on the mill * grinding

™ - T

2 ■ --.- ■

. ■ 4 22 min 6

6 29 min 6.

* Stability value -on the case · ■■ -: time until gluing,.

From Table I it can be seen that Example ^{Γ ϊ} is substantially ..besser than the comparative examples'and> .BOT !. Baispisl 7 resulted in a Wö.r.mests.b.iJ.itätswei't of 90 minutes, which is three-way larger JL ^: t than with. Test I3r 3 ^ ^er d'ir beet-) of the three comparable

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- ■: - ■■ - ■ * - ^ "'■ - bad original

1 no
lity
after
mill Heat stabilizer
- stuck
1 min at the 2 Il 3 30th 4th 30th 5 90 6th 45 7th 90 8th 60

trials isto Furthermore, the stability value on the mill of Example 7 is more than 25 $ better than that of Comparative Example 5. Table I also shows that Example 8, compared to all comparative examples, has the vinyl chloride / vinyl acetate composition (Example 2 _f . 4 and 6 ), is exceptionally superior and has a thermal stability value of 60, which is more than 305S greater than the best comparative test, namely Example 6 _u. Thus, the new compositions are at least 30% longer effective than the best known heat stabilizers in vinyl chloride copolymers «In addition is superior to stabilizers for homopolymer polyvinyl chloride according to the state of the art in terms of stability on the mill "

In further examples, the thermal stability values and the Color after grinding intended for other preferred systems, where other stabilizers were used as follows:

Vinyl chloride homopolymer composition 100 parts butylthiostannonic acid 0 _? 5

Bis (tributyltin) maleate 1.0

Vinyl chloride homopolymer composition 100 parts of butylthiostane saturation O ₉ 5

Dibutylainn-bis (iso-octyl-maleate) 1 _? 0

Vinyl chloride homopolymer composition. 100 parts of butylthiostannonic acid 0 * 5

Di-n-octyl sense maleate 1 _s 0

Vinyl chlorideh-OBiopolymer composition 100 parts

Bu tylthio stannbns acid 0 " 4

Bibutylzinii-MsCisopropyl-Maeate) 1 _s 0

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Example 15

Vinyl chloride homopolymer composition 100 parts

Butylthiostannonic acid 0.5

Bis (dibutyltin laurate) maleate 1.0

Example 14

Yinyl chloride homopolymer composition 100 parts

Butylthiostannonic acid 0.4

Dibutyltin bis (benzyl maleate) 1 _r O

Example 15

Vinyl Chloride Homopolymer Composition 100 Parts

Butylthiostannonic acid O ₅ , 4

Dibutyltin biscyclohexyl maleate) 1 _y 0

The results of the heat stability tests of Examples 9-15 are given in Table II below:

Tabel 90 II Example. Thermal stability value 90 Color after the missing ea in min 90 9 90 6th 10 90 6th 11th 90 6th 12th 90 β 13th 6th 14th 6th 15th 6th

From Table II it can be seen that the heat stability values far exceed those of Comparative Example 3 in which butylthiostannonic acid is the only stabilizer _? and are at least equivalent to the heat stability value of Comparative Example 5 _? in which Dibuty3.ainn-inaleate is the only stabilizer o As can be seen from Table I ₉ , the stability value on the mill of the new compositions according to the invention allows the processing times to be increased by 25%

90 9 845/1690 em '«WälRAL

stickiness occurs.

Further tests were carried out with vinyl chloride / vinyl acetate mixed _{polymer * compositions, for example Cary 380A resin r} that is a polymer _f that consists of 90 $ polyvinyl chloride and 10% vinyl acetate and has a specific gravity of 1.36 and a specific viscosity of 0 , 59 (measured as a 1% solution in methyl isobutyl ketone at 25 C). The batches were prepared as before, and the heat stability and the color after grinding were determined as above

BeJBp ₁ JeI 16

Vinyl chloride / vinyl acetate composition 100 parts butylthiostannonic acid 0 _£ 5

BiB (tributyltin) maleate IjO "

Example 17

Vinyl chloride / vinyl acetate composition 100 parts

Butylthio stannonic acid 0.5

Dibutyltin-bisCiBO-octyl-malea · ?;) 1 _f C

Example 18

Vinyl chloride / vinyl acetate composition 100 parts

Butylthiostannonic acid 0.5

Di-n-octyltin maleate 1.0

Example 19

Vinyl chloride / vinyl acetate admixture 100 parts

Butylthiostannonic acid 0 4

Dibutyltin biscisopropyl maleab) I 0

Example 20

Vinyl chloride / vinyl acetate composition 100 parts

Butylthiostannonic acid Or 5

ßis (dibutyl £ inn-laurate) nia3-eat 1.0

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Example 21 -

Vinyl chloride / vinyl acetate composition 100 parts

Butylthiostannonic acid 0 _f 4

Dibutyltin bis (benzyl maleate) 1 _t 0

Example 22

Vinyl chloride / vinyl acetate composition 100 parts

Butylthiostannonic acid 0 _f 4

Dibutyltin bis (cyclohexyl maleate) 1 _f 0

The results of the thermal stability tests of Examples 16-22 are given in Table III below:

Tabel 60 III example . WMrmestability value 60 Color after grinding in min 60 16 60 6th 17th 60 6th 18th 60 6th 19th 60 6th 20th 6th 21 6th 22nd 6th

Aue Table III it is seen that the thermal stability value compared to Comparative Examples 3 and 4 in which Butylthioetannoneäure is used alleiae _r, is remarkably improved. The thermal stability value is up to 30% greater than in the best comparative example, Example 6, of the prior art. In addition, the color after grinding is 6 in all cases, ie. equal € · ■ best stabilizer of the prior art and will be better used as Comparative Example 4 "wherein Butylthiostannoneäure alone as a stabilizer" For this reason, it is clear _r that the new method of the invention allows the preparation of polymeric resins for a person skilled in the -a have an extremely high degree of thermal stability ?.

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ORlGiWALlNSPECTEO

B,

Further examples of preferred stabilizer systems within the scope of the invention are given below: (in mixture with 100 parts resin):

Vinyl chloride homopolymer 100 parts

Butylthiostannonic acid 0 ^, 3

Dibutyl tin bis (iso-octyl maleate) 0.80

Vinyl chloride / vinyl acetate copolymer 100 parts

Butylthiostannonic acid 0.31

Di-n ^ octyltin ~ bis (iso-octyl maleate) 0.85

Vinylidene chloride homopolymer 100 parts

Butylthiostannonic acid 0 "51

Dimethyl tin bis (iso-f octyl maleate) 1.47

Vinyl chloride homopolymer 100 parts

Butylthiostannonic acid 0 _f 42

Di-η · octyltin »bis (iso-octyl maleate) 0.87

Vinyl chloride homopolymer 100 parts

Octylthiostannonic acid 0.29

Di-n "octyltin ~ bis (iso-octyl ~ maleate) 1 _? 0

Vinyl chloride homopolymer "100 parts

Gyclohexylthiostannonic acid 0 ^ 36

Di-n-octyltin bis (iso ~ octyl ~ maleate) 0 _f , 87

E,

90984 5/1690

Claims (2)

Godparent claims marriage Process for the production -7On against the degrading influence of heat-stabilized halogen-containing polymers, characterized in that a stabilizing amount of the following substances is added to a halogen-containing resin: a first stabilizer of the formula (RSnX ₄ c L, in which X is sulfur or a mixture of 1- 10 parts of oxygen with 10-1 parts of sulfur and η is an integer from 2-1000; and a second stabilizer of the formula R ^s _a 3 _b Sn _c or the formί Η ^ Ζ ^ ηΥεηΖ ^ ίΓ ^ where Y - "0OC- R ^{8] is} --COOR or -0OC-R ° ' -COO- and Z is -OOCR, a is 1-3, _f b is 0-2 and c is 1-3j where R and R ^! Are each independent of one another Alkyl with 1-20 carbon atoms, aryl, alcaryl, aralkyl and cycloalkyl and R ⁵ denotes alkylenyl, arylenyl, alfcarylenyl. • means lalkylenyl and cycloalkylenyl, 2. The method of claim 1, characterized in that the first _r stabilizer polymer is added in an amount of 0.01-5 parts per iOO parts Method according to claim 1 _? characterized in that the second stabilizer χλ is added in an amount of 0.1 »10 parts per 10 parts of polymer 4, The method according to claim 1, characterized in that the second stabilizer in one Amount at least twice the amount the first Stabilizer added effectively 5 _; Process according to claim 1, characterized in that the first stabilizer is butylthiostannonic acid (C ₄ H ₉ SnS., ^) _N , where η is 2-1000, 909845/1690 6 :, The method according to claim 1, characterized in that the second stabilizer is butylzirmbis (iso-octyl-maleate) is" a method according to claim 1, characterized ; draws that the second stabilizer is dibutyltin maleate is" Process according to claim 1 _f, characterized in that the second stabilizer is dioetyltin bis (ieo-octyl maloate), 9 "Process according to Anapruch 1, characterized in that the halogen-containing polymer contains a copolymer iet _t the vinyl chloride, 1Oo method according to claim 1, characterized that the halogen-containing polymer is a copolymer of vinyl chloride and vinyl acetate » 11 ", Halogen-containing polymer stabilized against the degrading influence of heat, characterized in that it contains a stabilizing amount of the following: a first stabilizer of the formula (RSnX ₁ r)""in which X is sulfur or a mixture of 1-10 parts of oxygen with 10-1 parts means sulfur and η means an integer of 2 * 1000? and a second stabilizer of the formula R ⁵ SnY ", in which at least one Y -OOC-R" -GOOR or ti g-β / - 'YSY- or -OOG-R "is -COO- and g is 4 and a is the same 1-3 iet _f if Y -0OC-R ¹ ^ COOR iet, and g equals 3 let and a equals H 2 iet if ¥ -000-R "-COO- and less all groups T are -OOCR; where R and R 'each independently denotes alkyl having 1-20 carbon atoms, aryl, alkaryl, aralkyl and cycloalkyl and R "denotes alkylenyl, arylenyl, alkarylenyl, arylalkylenyl and cycloalkylenyl. Polymer according to claim 11, characterized in that that the first stabilizer butylthio- etannonic acid "(0.H ₀ SnS ₄ ._> iet, where n eats 2-1000, # y", y η ORIGINAL JNÖPECTED 909845/1690 ί 3 'polymer according to claim 11, characterized in that the second stabilizer is dibutyltin bis (iBo-oct.yl-maleate) is.:. PcljKiei- according to claim 11, characterized in that that the second stabilizer is dibutyltin maleate ^ 15 ,. Polymer according to claim 11, characterized in that the polymer is a mixed polymer. which contains vinyl chloride. - Polymer according to claim 11, characterized in that the polymer is a mixed polymer of vinyl chloride and vinyl acetate _o 17 <: Stabilizer composition for the stabilization of a halogen-containing polymer against the degrading influence of heat, characterized in that it contains the following: a first stabilizer of the formula (RSnX. _R ), in which X is sulfur or a mixture of 1-10 parts of oxygen with Represents 10-1 parts of sulfur and η represents an integer of 2-1000; and a second stabilizer of the formula R-SnY, wherein at least one Y ~ OOC ~ R "~ COOR or R ³ _{2 is} YSnY- or -OOC-R ^I! -.COO- and g is 4 and a is 1-3 when Y is.-00C ~ R "~ COOR and g is 3 and a is 2 when Y is -OOC-R" -COO ~ and less than all of the groups Y are -OOCR, where R and R ¹ , independently of one another, denote alkyl with 1-20 carbon atoms, aryl _{f alkaryl f} aralkyl and cycloalkyl and R "denotes alkylenyl _f arylenyl _f alkarylenyl _s , arylalkylenyl and cyeloallcylenyl 18c stabilizer composition according to claim 17j, characterized in that the first stabilizer is buty3.thiostamionic acid (C-HoSnS _{1 r} ) ^, where η is 2-1000. 19 <: Stabilizer composition according to claim 17, characterized in that the second stabilizer is dilutyltin-bis (iso-octyl-maleo-t) _{or the like} 9 0 9 8 4 5/1690 bad original 20, Stabilisatorzusammensetzimg according to claim 17, dad u rch in that the second stabilizer dibutyltin - is maleate. MfBWMlWXITH • 14M0H. (114CKE ₁ OlFL-INO.Il OWUINO.S-STAfOB BATH ORIGINAL 9098AB / 1690