DE1469952B2 - Stabilization of halogen-containing vinyl polymers. Note: Deutsche Advance Produktion GmbH, 6l4l Lautern - Google Patents

Description

I 2

The present invention relates to a stabilizer. The carboxylic acids can be wholly or partially tion of halogen-containing vinyl polymers, which are replaced by phenols. To do this, verder as basic stabilizers salts of carboxylic acids, butylphenols or octylphenols are used in particular metal soaps, and / or metal phenates, other substituted phenols. The cationic Bever turns and a component of these salts that enhances the effect can be magnesium, calcium, Secondary stabilizer is added. Be polymers, barium, strontium, cadmium, zinc or lead, which can be stabilized according to the invention NEN, are polyvinyl chloride, chlorinated polyethylene using thioethers correspond in the simplest with about 14 to 75% chlorine content, polyvinylidenes case of the general formula R — S — R '. In this chloride, polyvinyl bromide, polyvinyl fluoride and ent- ίο Formula are R and R 'aliphatic or aromatic, Speaking copolymers or mixtures die- .. heterocyclic, cycloaliphatic, straight-chain or these connections. . . ; . branched, saturated or unsaturated radicals, in It is well known that heat and light also exert functional groups on halogenated groups, such as ester groups, containing polymers from a harmful influence. Carboxyl groups, amide groups, carbonyl groups, Here, in addition to other disadvantageous changes, 15 alcohol groups and other thioether groups, the use value can be particularly due to discoloration. R and R 'can be identical, but Exercise and deterioration of the mechanical intrinsic also be different. Are particularly advantageous shafts impaired. Compounds that in the molecule have several sulfur sub the multitude of known stabilizers contain ether-bonded atoms, the thio having the carboxylic acid metal salts have the advantage that there are 20 ether bridges between different carbons easy and relatively cheap to manufacture and atoms of matter are or even of a carbon odorless are as well as mostly regarded as non-toxic atom can go out such. B. in the mercaptols can be. However, they have man and mercaptals opposite.

Chen other stabilizers, e.g. B. Compared to the tried and tested, the following thioethers: Di-octyl organotin compounds, a lower stabilizing sulfide, di-lauryl sulfide, lauryl cyclohexyl sulfide, lauryl end Effect. stearyl sulfide, di-stearyl sulfide, lauryl allyl sulfide, Lau-Zur Improvement of the stabilizing effect ryl tert-butyl sulfide, phenyl stearyl sulfide, di-phenylvon Metal salts and phenolates is already presulphide, di-lauryl-thiodipropional, 1,2-di-thiolauryl whipping been added to the basic stabilizer, additional ethane, 1,2,3-tri-thiolaurylpropane, tetra-lauryl-tetra-sentences to mix in. These as secondary stabilizers 30 thiopentaerythritol,!, Δ-di-tert-butyl-di-thiohexane, dioder Additives called synergists are substances that contain thiolauryl methane, "Acetontilaurylmethyl-mercaptol, Applied alone, little or no stabilizing methyl ethyl ketone dioctyl mercaptol, acetaldehyde disator effect exercise, but in combination with octylmercaptal. . the metal salts or -phenolates their effective- As sulfoxides in the simplest case increase speed. Known secondary stabilizers are 35

z. B. alkylphenols, higher alcohols, phosphites and R - S - R '

Epoxy compounds. The addition of the well-known Il

Secondary stabilizers, however, usually result in undesirable side effects. By

Phenols or nitrogen-containing compounds will be the 40 are all suitable that have the above-mentioned light resistance group often worsened. Other pen R or R ', in particular those secondary stabilizers, lead to a considerable reduction in thio that is different from the named thio of transparency. Derive another post-ether. Mixtures of thioethers and Part of the known secondary stabilizers consists of sulfoxides are particularly effective and show a in that they often have poor compatibility of the mixture components with the polymers, are detrimental and consequently in processing if the thioethers and sulfoxides have the same Aufoder Storage migrate or build in any form with respect to groups R and R 'or the excreted will. have the number and arrangement of the sulfur atoms. * It has been found that by avoiding the place of thioethers and sulfoxides previous disadvantages of both the heat stabilizing .5 ° '. also by exchanging the sulfur for them as well as the light-stabilizing effect of the selenium isologues produced by the metal selenium, salts and phenolates can be increased significantly. For stabilization according to the invention, the if thioethers, such as metal salts and / or metal phenolates, are used as secondary stabilizers in amounts of 0.01 R — S — R ', or their oxidation products, the SuIf-. to 10, preferably from. 0.2 to 5 percent by weight, oxides, such as 55 and the thioethers and / or sulfoxides or the ent-R - S - R 'speaking selenium compounds in amounts of 0.01

II to 5, preferably from 0.1 to 1.5 percent by weight, O based on the polymer to be stabilized, mixed into this.

or a mixture of such compounds is added. Straight-chain or branched ali-AIs basic stabilizers, the metal salts phatic thioethers with a carbon number of aliphatic cyclic, alicyclic and aromatic about C ₁₂ to about C _{40 are} advantageous. These Verbinscher acids are used: Salts of stearic fertilizers usually have a solid consistency and are acid, lauric acid, caprylic acid, caproic acid, ethyl - completely odorless. Thanks to their waxy behexanoic acid, oxyacids and oxo-synthesis properties, they also give the acids, naphthenic acids, benzoic acid mixtures obtained from the polymerizate a particularly high and good lubricity that is advantageous for further processing, such as tert-butylbenzoic acid, maleic acid and crotonic acid. Lower thioethers like their higher homologues. with a carbon number below C ₁₂ show themselves

also the effects according to the invention, but are unsuitable because of their strong odor.

Both the thioethers and the sulfoxides can be used on their own as secondary stabilizers will. In many cases, however, a mixture of thioether and sulfoxides will give one even better effect than with the individual components.

The claimed secondary stabilizers are highly compatible with the halogen-containing polymers mentioned and are not excreted by them even after prolonged storage. In addition to the excellent stabilization, increased transparency is achieved, which is particularly important in the case of films. The stabilizers can be incorporated completely uniformly into each polymer, with no odor occurring. ^V:::

So far, the viewpoint has been that sulfur-containing compounds should not be used together with metal salts, since colored compounds can result. These undesirable reactions that lead to discoloration of the plastics can be triggered by the effects of both heat and light ^! will. Particularly in the presence of lead or cadmium salts, there is a risk of strongly colored sulphides being formed during processing. Surprisingly, it has been shown that when the claimed thioethers and sulfoxides or the corresponding selenium compounds are used, no discoloration occurs.

In addition to the stabilizer mixture according to the invention, the usual additives and processing aids, such as plasticizers, pigments, fillers, dyes and plasticizers, can be added to the polymer Absorbers are added . "" ·. ■ - · -; '7 .. .. ;;;> ■ · ■ ■■; -;' :. ■.: ·: .- ■?: ■■ '

According to the invention: it is possible with the same Absolute amount of stabilizer; much higher heat and light resistance than with the. known Secondary stabilizers. to achieve: without that: undesirable Side effects occur.

.. In the subsequently listed for the "explanation of the invention examples, two Vergleichsfolien- A and B are each faced Both films were, _apart. Yom ^stabilizer: each made of the same mixtures under the same conditions on a heated, roller. Foils A were stabilized in accordance with the invention, while foils B (if there are no other details in the example) each contained 1.5% bearium cadmium laurate, the 0.5% 2,2- (4,4 ^ -dihydroxy-diphenyl) -propane (bis-phenol A) would be added as a secondary stabilizer .: This corresponds roughly to .: the composition of a complex barium-cadmium stabilizer as it is currently used. In the recipes, the amounts are given as parts by weight. the thermal tests were performed in a drying oven at: 170 ° C performed the exposure tests were conducted in einem.Atlas fadeometer at 55 ⁰ C and a humidity of 65% Λ,: -.....-j

..... Example 1

To produce a stabilized polyvinyl chloride molding compound, a mixture was prepared from the following components: '■.:.

100 parts of polyvinyl chloride (K value 70),

30 parts of di-octyl phthalate, 0.92 parts of barium laurate,

1.1 parts of cadmium laurate, 0.6 parts of di-lauryl sulfide.

Film A made from the above mixture was placed in a drying cabinet for 75 minutes Maintained 170 ° C without yellowing occurring, ίο After the same treatment, the comparison film B showed significant yellowing after just 45 minutes. A comparison of the two foils in the fadeometer showed that foil B already had a exhibited significant discoloration, while film A was still unchanged after 800 hours. , :::

■■ ■■■■ Example 2 '■;"■'

The following ingredients were used to produce a stabilized polyvinyl chloride molding compound a mixture prepared: ... ■.: .-.

100 parts of polyvinyl chloride (K value 70); 30 parts of di-octyl malate; : / 0.92 parts barium laurate, ". :;

1.1 parts of cadmium laurate,. 0.6 parts of lauryl stearyl sulfide. ,

The film A 'produced from this mixture was

Maintained in a drying cabinet at 170 ° C. for 60 minutes without yellowing occurring. The comparison slide After the same treatment, B showed clear yellowing after just 45 minutes.

A comparison of the two foils in the fadeometer

showed that: FoKeB showed a clear discoloration after 400 hours, while film A was still unchanged after 800 hours. .: -. ··. ■■; ■. .-., ■ ' ' : ·.

Example 3

To produce a stabilized polyvinyl chloride molding compound, a mixture was prepared from the following ingredients: -. | - _{r Ί} ■ '.- ;,

100 parts of polyvinyl chloride. (K value 60),. , .. · ;; .0.68 parts of barium laurate; ''; ^Λ: "- · ^1: -; ' ^{! 1 ;; tj} - '0.92 parts Cadmiumlaurat; Γ P ^Ui f ^{::' :: ':} ■' / ^ '-; 0.5 parts of 1,2-di-thiola'urylpropän, .. ^v:; '} - ■' _ .0.7 parts of phenyl-di-decylphosphite. ; . . -. ^:?

_-The: from this mixture:; prepared. Film A was kept in a drying cabinet at 170 ° C. for 60 minutes without yellowing occurring; The comparative film B, which also contained 0.7 parts of phenyldi-decylphosphite, showed significant yellowing after just 5 minutes after the same treatment: - ~ ; ν.) - ::> \ _: \: '\\ ^ ν: ■ :: '_ · \':.:;M; ■: ■ / \:: ~ \ ■■■: When comparing the light resistance in the fadeometer, film A was unchanged after 700 hours, while film B already changed color after 400 hours. _. . , ". · '.' Example 4

For the production of a stabilized polyvinyl chloride molding compound a mixture was prepared from the following ingredients:

100 parts copolymer of 87% vinyl chloride. and 13% vinyl acetate (K value 55),. :; '.: 0.55 parts of barium laurate,; '' · ^':

0.66 parts of gadmium laurate,. . -

0.6 parts of 1,2,3-triethiolaurylpropane, 0.7 parts of phenyl-di-decyl phosphite.

Claims (4)

5 6 To compare the heat resistance, the color was displayed, while film A still had Slide A was unchanged for 75 minutes in an oven 900 hours. kept at 170 ° C without yellowing _Ώ . . kicked. Comparative film B, also containing 0.7 parts of Example 8 Phenyl-di-decyl phosphite, showed in the same 5 For the production of a stabilized polyvinylchloride After only 45 minutes of treatment, a deuterium molding compound was made up of the following components lent yellowing. When comparing the lightfastness- a mixture prepared: ability in the fadeometer was film A after 1200 hours _{100 parts polyvinyl chloride)} unchanged, while slide B already after 400 hours _{0 68 parts} ßarium laurate, which showed a clear yellowing. io _{092 TdleCa} dmium laurate, Example 5 0> 25 parts of di-lauryl sulfide, r, _TT ". ,.,. . τ,,. , ,, 0.25TeIIeDi-IaUrVlSuIfOXVd.
For the production of a stabilized polyvinyl chloride Ride molding compound was made up of the following components: The film A produced from this mixture was a mixture prepared: 15 for 60 minutes in a drying cabinet at 170 ° C 100 parts of polyvinyl chloride, check whether yellowing has occurred. The Ver- 1 ς TpIIp -Ripictparst equal film B already showed with the same treatment JLjJ 1 Clic XJlCIt) ICdTdI, **,. . · ·. .1 ·, -r 7 -n S · τ τ 0.6 parts of di-lauryl sulfide. after 45 minutes a clear yellowing. A comparison of the two foils in the fadeometer showed that the foil A 20 foil B produced from this mixture showed a clear discoloration for 45 minutes in a drying cabinet, while foil A was still kept at 170 ° C. after 400 hours, without any yellowing remaining unchanged for 700 hours.
kicked. The comparison film B, which with 1.5 parts _. . α
Lead stearate and 0.5 part bisphenol A stabilized Example 9
For the production of a stabilized polyvinylchloride, it showed clear yellowing after only 25 minutes with the same treatment. A comparison of rid molding compound was made from the following components of the two foils in the fadeometer that foil B prepared a mixture:
already after 400 hours a clear discoloration 100 parts of polyvinyl chloride,
exhibited, while film A still after 800 hours un- q 55 x _e ü _e barium laurate
was changed. '' .; Γ ₃ o 0 * 66 parts cadmium laurate / /
Example 6 0.4 parts of di-lauryl sulfide, ' _TT "" ■■■. ■ ", ........ ■■' -. '■' . , ,, 0.1 part of di-lauryl sulfoxide. To produce a stabilized Polyvinylchlo- ^ Ride molding compound was made up of the following components: The film A produced from this mixture was a mixture prepared: 35 for 75 minutes in a drying cabinet at 170 ° C 100 parts of polyvinyl chloride apply without yellowing occurring. The Ver- 30 parts of di-octyl phthalate, .. .. gjei ^ rfoje B "already showed in gleidier'BehMidlun V ■ 0.92 TeUe barium caprylate, /. . ⁿ ™ \ ^A5 _A ^Mmu .t ^en e ^ e clear yellowing. A verse 1 1 part of cadmium caprolate resulted from the two foils in the fadeometer; that 0 ^ 4 parts of di-lauryl selenide, '^{;; 4} ° Foil B already after 400 hours a significant _- ·:: · ■■. ·. ι. _; had colouration, while film A was still after The film A produced from this mixture was unchanged for 1000 hours: " For 60 minutes in a drying cabinet at 170 ° C ■ '■ U · - · ^; ι in ^! held without yellowing. The supply - VB ⁶¹ SP ¹⁶¹ _IU:. film B already showed 45 for the same treatment. For the production of a stabilized polyvinyl chloride significant yellowing after 45 minutes. A Verrid molding compound was made up of the following ingredients the same as the two foüen in the fadeometer showed that i prepared a mixture: "' ^: FoHeBbereiteych ^ OOStodenemedeuth-cheVer- ^{100TeUePolyvinylchlorid;} ' ^r oniT ^g / ^ ^ε8 '.. ^ ^{ahrend Fohe} : ^{A. still} - ° ^oh 0.60 TeUeBariumphenolät ,. .. 800 hours was unchanged. ν ν 50 1.1 TeUe cadniium caprylate, _r _: \ _; . · .- ': .. ■. Example 7 -. 0.6TeUeMethylethyl-di-laurylmercaptoi. For the production of a stabilized polyvinylchloride, the film A produced from this mixture was used Ride molding compound was made from the following ingredients for 60 minutes in a drying cabinet at 170 ° C a mixture prepared: ν 55 held without yellowing. The Ver- 100 parts of vinyl chloride film B already showed the same treatment 30 parts of di-octyl phthalate, marked yellowing after 45 minutes. . ... 0.6 parts of barium laurate,. . Em comparison of the two foils in the fadeometer _r:, 0 9TeileCadmiumbenzoat. ' _fi *' ΑΚ ^Β already after 400 hours ^: '0 5 parts of di-lauryl sulfoxide ^: · ^! 60 clearly discolored, while film A was still ' . ^y . ■ J '' ^{:: -:} - was unchanged after 800 hours .. The film A produced from this mixture became ■ · '. ; ' 60 minutes in a drying cabinet at 170 ° C Claims: held without a yellowing occurred. The Ver- . _{: r} same film B showed 65 1 with the same treatment. Stabilization of halogen-containing vinyl poly- clear aging after 45 minutes. A note against the effects of heat and the same of the two foils in the fadeometer showed that light, with metal salts as the basic stabilizer Film B shows a significant change in carboxylic acids and / or metal phenates after only 400 hours. used alone or in a mixture by using a basic stabilizer in amounts of 0.01 to 10 percent by weight and a secondary stabilizer in the form of simple or mixed thioethers and / or their corresponding sulfoxides with 12 to 40 carbons in amounts of 0.01 to 10 percent by weight individually or in Mixture. 2. Stabilization according to claim 1, characterized by the use of polyvalent ones Thioethers or sulfoxides, where the thioether bridges lie between different carbon atoms or from one carbon atom can go out. 3. Stabilization according to claim 1 or 2, characterized in that when using Mixtures of thioethers and sulfoxides make the mixture components have the same structure with regard to the organic radicals R and R 'or the number and arrangement of the sulfur atoms exhibit. 4. Stabilization according to claim 1 to 3, characterized in that instead of the thioether or sulfoxides whose selenium isologues are used. 909586/178