DD226292A1

DD226292A1 - LIQUID METAL CARBOXYLATE-BASED STABILIZER SYSTEM FOR VINYL CHLORIDE POLYMERS

Info

Publication number: DD226292A1
Application number: DD26589384A
Authority: DD
Inventors: Uwe Jacob; Rainer Maedler
Original assignee: Greiz Doelau Chemie
Priority date: 1984-08-02
Filing date: 1984-08-02
Publication date: 1985-08-21
Also published as: DD226292B1

Abstract

Ziel und Aufgabenstellung der Erfindung besteht darin, sowohl die thermostabilisierende Wirksamkeit als auch die Anfangsverfaerbung von cadmiumfreien Stabilisatorsystemen zu verbessern. Erfindungsgemaess entsprechen fluessige Stabilisatorsysteme obiger Zielstellung, wenn neben Erdalkalisalzen von aliphatischen verzweigtkettigen oder aromatischen Monocarbonsaeuren und/oder Alkylphenolen, fluessigen Gleitmitteln sowie gegebenenfalls weiteren ueblichen Costabilisatoren als Zink-Komponente ein basisches Zink-hydroxycrotonat/2-ethylhexoat-Mischsalz, bei welchem der Ueberschuss an Metallkomponente bis zu 10% betragen kann, in Mengen von 5,0 bis 20,0 Gew.-% im gesamten Stabilisatorsystem vorliegt.The aim and object of the invention is to improve both the thermostabilizing effectiveness and the initial staining of cadmium-free stabilizer systems. According to the invention, liquid stabilizer systems correspond to the above objective if, in addition to alkaline earth salts of aliphatic branched or aromatic monocarboxylic acids and / or alkylphenols, liquid lubricants and optionally other customary costabilizers as the zinc component, a basic zinc hydroxycrotonate / 2-ethylhexoate mixed salt in which the excess of metal component can be up to 10%, in amounts of from 5.0 to 20.0 wt .-% throughout the stabilizer system.

Description

25,S T Barium-2-ethylhexoat 25,8 T Barium-isononylphenolat ' 5,0 T Zink-hydroxycrotonat/^-ethylhexoat-Mischsalz (mit 10% Überschuß Zink)25, S T barium 2-ethylhexoate 25.8 T barium isononylphenolate '5.0 T zinc hydroxycrotonate / --ethylhexoate mixed salt (with 10% excess zinc)

23.2 T Triisononyiphenylphosphit 5,2 T Di-tert,-butyl-p-kresol23.2 T Triisononyiphenyl phosphite 5.2 T di-tert-butyl-p-cresol

10,0T Paraffinöl 5,0 T epoxidiertes Sojabohnenöl10.0T paraffin oil 5.0T epoxidized soybean oil

Diese Mischung wurde auf einem Walzwerk bei 165⁰C zu Folien von 0,2 mm Stärke verarbeitet. Die Folien wurden außerdem in einer Presse bei 180°C zu 4-rnm Prüfplatten verpreßt.This mixture was processed on a roll mill at 165 ^° C. into films of 0.2 mm thickness. The films were also pressed in a press at 180 ° C to 4-rnm test plates.

Die statische Thermostabi.lität wurde in üblicherweise in einem Stabiümeterofen bei 18O⁰C bestimmt, wobei die Zeit bis zurThe static thermostability was usually determined in a static oven at 18O ⁰ C, the time to the

Schwarz- bzw. Dunkelfärbung des Streifens ermittelt wurde. Die dynamische Stabilität ermittelte man auf einem Walzwerk bei 17P⁰C, wobei die Zejtbis zürn K[ebeji bestimmt wurde. Die 4-mm-Prüfpiatten wurden anhand der SYNMER0³-Farbskala auf den Grad der Anfangsverfärbung hin untersucht.Black or dark color of the strip was determined. The dynamic stability was determined on a rolling mill at 17P ⁰ C, the Zejtbis was determined to K [ebeji. The 4 mm test plates were examined for the degree of initial discoloration using the SYNMER0 ³ color scale.

Die Ergebnisse der Ausprüfungen sind am Ende der Ausführungsbeispiele in einer Tabelle zusammengefaßt dargestellt. 2. Zu 100 Teilen Suspensions-Polyvinylchlorid mit einem K-Wert von 65 werden^O Teile eines Stabilisatorsystems, bestehend ausThe results of the tests are summarized at the end of the embodiments in a table. 2. To 100 parts suspension polyvinyl chloride having a K value of 65 are ^ O parts of a stabilizer system consisting of

30.7 T Calcium-p-tert.-butyl-benzoat30.7 T calcium p-tert-butyl benzoate

20,0 T Zink-hydroxycrotonat/^-ethylhexoat-Mischsalz (mit 5% Überschuß Zink)20.0 T zinc hydroxycrotonate / --ethylhexoate mixed salt (with 5% excess zinc)

20.3 T Diphenyialkyl(C_l2-C₁₅)-phosphit 20,0 T epoxidiertes Rapsöl20.3 T Diphenyialkyl (C ₁₂ -C ₁₅ ) phosphite 20.0 T epoxidized rapeseed oil

9,0 T Paraffinöl9.0 T of paraffin oil

sowie 43,0 T Dioyctylphtnalat hinzugegeben und gründlich vermischt. Die Herstellung der Folien sowie der Prüfplatten erfolgte gemäß Beispiel 1.and 43.0 T dioctyl phthalate added and mixed thoroughly. The production of the films and the test plates was carried out according to Example 1.

3.100 Teile eines Suspensions-Polyvinylchlorid mit einem K-Wert von 65 sowie 43 Teile Dioxtylphthalat werden mit 2,0 Teilen eines Stabilisatorsystems, bestehend aus3,100 parts of a suspension polyvinyl chloride having a K value of 65 and 43 parts Dioxtylphthalat be with 2.0 parts of a stabilizer system consisting of

.1,8 T Strontium-dodexylphenolat.1,8 T strontium dodexylphenolate

10,0 T Zink-hydroxycrotönat/^-ethylhexoat-Mischsalz (mit 3,0% Überschuß Zink) 16,2 T Diphenyldecylphosphit 7,0 T Bisphenol A 15,OT Paraffinöl10.0 T Zinc hydroxycrotonate / --ethylhexoate mixed salt (with 3.0% excess zinc) 16.2 T diphenyldecyl phosphite 7.0 T bisphenol A 15, OT paraffin oil

gründlich vermischt und ebenfalls zu Folien und Prüfplatten verarbeitet. Die Auswertung erfolgte wie im Beispiel 1 beschrieben. Ergebnis der Ausprüfungen:thoroughly mixed and also processed into films and test plates. The evaluation was carried out as described in Example 1. Result of the tests:

Rezepturrecipe

statische Thermo-static thermal Dynamische Tnermo-Dynamic Terno AnfangsAt first stabilitätstability stabilitätstability farbecolour (min.)(Min.) (min.)(Min.) (nach(to SYNMEROSYNMERO Grad)Degree)

Beispiel 1example 1 8080 3535 2,02.0 Beispiel 2Example 2 5050 2525 2,52.5 Beispiel 3Example 3 4545 3030 2,22.2

Claims

Invention claims:

1. liquid Metailcarboxylathaltiges stabilizer system for Vinylchioridpoiymere, consisting of Erdaikalisalzen of aliphatic branched or aromatic monocarboxylic acids and / or alkylphenols, liquid lubricants, other common costabilizers and a zinc compound, characterized in that as zinc component of a basic zinc hydroxycrotonate / 2 ethylhexoate mixed salt is included.

2. stabilizer system according to item 1, characterized in that the stoichiometric excess of metal component in the zinc hydroxycrotonate / 2-ethylhexoate mixed salt is up to 10%.

3. stabilizer system according to item 1 and 2, characterized in that the basic zinc hydroxycrotonate / 2-ethylhexoate mixed salt is present in the stabilizer system in amounts of 5.0 to 20.0 wt .-%.

4. stabilizer system according to item 1 to 3, characterized in that the basic zinc hydroxycrotonate / 2-ethylhexoate mixed salt has arisen from a common manufacturing process in the presence of the other stabilizer constituents.

Field of application of the invention

The invention relates to a liquid metailcarboxylathaltiges stabilizer system for vinyl chloride polymers, which is used as a cadmium-free product as a thermal or light stabilizer in homo- and copolymers of vinyl chloride. This stabilizer system is particularly suitable for the stabilization of plasticizer-containing suspension and emulsion polymers. It can be used in a wide variety of processing forms of polyvinyl chloride, such as extruder, calender or injection molding.

Characteristic of the known technical solutions

Liquid metal carboxylate-containing stabilizers for polymers of vinyl chloride are already widely described and well known.

Particularly cadmium-containing metal salts of branched-chain long-chain carboxylic acids or alkylphenols have, in connection with metal salts of alkali metals and alkaline earth metals as well as with zinc salts, due to their very good stabilization properties of great importance.

For toxicological reasons, however, efforts have recently been made to replace cadmium-containing cadmium-free systems to a greater extent. In particular, the alkaline earth / zinc salts are frequently mentioned as possible substituents in the literature.

However, such stabilizers have disadvantages over cadmium-containing systems, which manifest themselves in particular in insufficient thermostability and inferior initial color, that is, increased yellowing, of finished polyvinyl chloride products. Therefore, attempts are being made to deliberately influence the negative manifestations by special modifications of such cadmium-free systems. One possibility, for example, is to achieve an improvement by changing the metal carrier component, ie the anion component. Also, various suggestions are known from the literature. Thus, in addition to the very frequently mentioned and frequently used 2-ethylhexanoic acid, other branched-chain acids, such as trialkylacetic acids (cf., German Offenlegungsschrift 1 869 802) or substituted aromatic carboxylic acids, such as p-tert-butylbenzoic acid (cf. OS 1 694 624), as a metal carrier.

In particular, the anion of the zinc component, which is considered essential in cadmium-free Metallcarboxylatstabilisatoren, is given for certain utility properties of crucial importance. In addition to the purely static thermal stability, this also includes the initial discoloration or yellowing of the finished products. The patent closest to the invention, GS-PS 2,110,697, describes a particular basic zinc component which can be used in conjunction with other conventional stabilizers for vinyl chloride polymers, e.g. Caicium stearate and epoxidized oils, to ensure an improvement in the thermostabilizing effectiveness.

This described basic zinc compound with the empirical forms! (R-COO) ₆ -Zn ₄ -O significantly increases the static methylation in cadmium-free systems. A particular disadvantage, however, is that the initial discoloration is not improved to the same extent and thus the moldings produced with such a zinc compound are significantly yellowed.

In addition, the stabilizers described in said patent have an insufficient sliding action, which has an unfavorable effect on the dynamic rolling stability.

Ziei the invention

The object of the invention is to provide a liquid metal carboxylate-containing stabilizer system which, both in terms of thermostabilizing activity and initial discoloration, largely eliminates the prior art deficiency of cadmium-free stabilizers.

Explanation of the essence of the invention

The invention has for its object to develop a liquid metallcarboxyiat.hsitices stabilizer system for predominantly plasticized Vinylchloridpoiymerisate. In particular, a cadmium-free stabilizer system is to be produced by a modification of the zinc component which, in addition to good thermostabilizing effectiveness, also has an excellent initial color and sufficient dynamic rolling stability.

According to the invention, the object is achieved in that in addition to an alkaline earth metal salt of an aliphatic branched or aromatic monocarboxylic acid and / or an alkylphenol and other customary for the stabilization of Vinyichloridpolymerisaten costabilizers, such as organic phosphites, antioxidants or epoxidiertsn O'en, as a zinc compound sin basic zinc -hydroxycrotonate / ^ - ethylhexoate mixed salt is used.

Essential to the invention in this context is that in this mixed salt sin stoichiometric excess of metal component is present, which may be up to 10%. This zinc hydroxycrotonate / --ethylhexoate mixed salt, which is present in amounts of 5.0-20.0% by weight in this liquid stabilizer system, has arisen from a co-production process in the presence of the other stabilizer ingredients.

embodiments

1: To 100 parts of suspension polyvinyl chloride having a K value of 65, 2.0 parts of a stabilizer system and 25.0 parts of dioctyl phthalate are added and thoroughly mixed at room temperature. The Stabiiisatorsystem is composed of the following Eirzelkomponenten: