CS217817B1 - Lubricants with stabilizing effects for chlorine-containing polymers - Google Patents

Abstract

The invention relates to lubricants with stabilizing effects for chlorine-containing polymers, especially for polyvinyl chloride and vinyl chloride copolymers. These lubricants improve the thermal stability of polymer mixtures and their processability. Lubricants with stabilizing effects according to the invention consist of ionic surfactants containing a phosphatidyl or bisphosphatidyl anion and the cation is a higher-valent metal ion. Lubricants according to the invention are suitable for use in both softened and hard mixtures of chlorine-containing polymers and copolymers.

Description

(54) Lubricants with stabilizing effects for chlorine-containing polymers

The invention relates to lubricants with stabilizing effects for chlorine-containing polymers, in particular for polyvinyl chloride and vinyl chloride copolymers. With the help of these lubricants, the thermal stability of polymer mixtures and their processability are improved. Lubricants with stabilizing effects according to the invention consist of ionic surfactants containing a phosphatidyl or bisphosphatidyl anion and the cation is a higher-valent metal ion.

The lubricants according to the invention are suitable for use in both softened and hard mixtures of chlorine-containing polymers and copolymers.

The invention relates to lubricants with stabilizing effects for chlorine-containing polymers, in particular for polyvinyl chloride and vinyl chloride copolymers.

Currently produced polyvinyl chloride and its copolymers cannot be processed without the addition of other components, such as stabilizers, lubricants, fillers, etc., because during the processing of these polymers, hydrogen chloride is split off due to thermal stress, thereby gradually degrading the mixtures.

A number of lubricants, stabilizers with lubricating effects and stabilizing additives are commonly used, which have a variety of chemical compositions and are mainly applied in combinations. By combining individual stabilizers and possibly lubricants and stabilizers, a synergistic effect can be achieved to improve the thermal stability of mixtures and their processability. The effect of lubricants used so far is mainly focused on improving the processability of mixtures of chlorine-containing polymers, whether they are internal or external lubricants. Some substances used as lubricants have a high stabilizing effect and at the same time exhibit lubricating properties, for example metal stearates, and can be referred to as stabilizers themselves.

The disadvantage of most lubricants used so far, such as stearin, ester waxes, fatty acid esters, alcohols, etc., added to stabilizing systems is the fact that during processing they do not exhibit a synergistic effect with the stabilizers used and only facilitate processing.

This disadvantage is not present in a lubricant with stabilizing effects for chlorine-containing polymers based on ionic surfactants containing phosphatidyl (I) or bisphosphatidyl anion (II), of the following general types:

IR,-O-CH ₂ r ₂ -o-ch ch ₂ -op-oII 11,-0-(¾ ch ₂ -or ₄

Ro-O-CH 0 CH-0-R ₃ ² I t I ³

CHo-O-P-O-CH,

I ^am

where

R, is ^c n ^H 2n+,C0 and/or ^c n ^H 2n-1 ^C0 ®/ ^{or C} n ^H 2n-3 ^{CO and//or C} n ^H 2n-5 ^CO '

R ₂ » is R, or H, wherein the number of carbon atoms in R,, R ₂ , Rj or R ₄ is 6-26, i.e. n is equal to 5-25, and the cation is a higher valence metal ion such as Ca ⁺⁺ , Lig ⁺⁺ , Zn ⁺⁺ , Sn ⁺⁺ or Ba ⁺⁺ .

The above compounds are prepared from phosphatidic or biphosphatidic acids (obtained e.g. by the procedure according to Czechoslovak Patent Application No. 173 220 or Czechoslovak Patent Application No. 203 421 by neutralization with a suitable alkali or amine of the above composition. Binders with stabilizing effects according to the invention are used in combination with conventional stabilizers based on organotin or organoantimony compounds, based on Pb compounds and metal soaps Ba, Zn, Ca, Cd and with conventional lubricants. Their use makes it possible to reduce the dosage of conventional stabilizers in order to achieve the desired thermal stability.

The binders according to the invention are suitable for use in both plasticized and hard mixtures of polymers and copolymers containing chlorine, and optionally also for these mixtures containing a blowing agent.

The binders are commonly available and, depending on the type of bound cation, are harmless to health. The essence of the invention is explained in more detail in the following examples.

Example 1

100 parts by weight of polyvinyl chloride were mixed with 82 parts by weight of diisooctyl phthalate, parts by weight of organotin stabilizer and 0.4 parts by weight of stearin. The mixture was mixed in a fluid mixer up to 120 °C and then granulated in a KO-kneader at a temperature of 130 °C. The resulting granulate was subjected to a thermal stability degradation test at 180 °C. The beginning of hydrogen chloride splitting occurred after 45 minutes, the graphically determined thermal stability was 95 minutes.

Example 2

100 parts by weight of polyvinyl chloride were mixed with 82 parts by weight of diisooctyl phthalate, parts by weight of organotin stabilizer and 0.4 parts by weight of lubricant according to the invention application in the form of Ca ⁺⁺ salt. The mixing and granulation procedure of the mixture were the same as in Example 1. During thermal stress, no free hydrogen chloride was released for 110 minutes, the thermal stability, determined graphically, was 115 minutes.

Example 3

100 parts by weight of polyvinyl chloride were mixed with 82 parts by weight of diisooctyl phthalate, parts by weight of a stabilizer based on Ba-Cd-Zn soap and 0.4 parts by weight of stearin. The granulate produced in the same manner as in Example 1 was stable for 135 minutes in the thermal stability test, the thermal stability determined graphically was 138 minutes.

Example 4

100 parts by weight of polyvinyl chloride were mixed with 82 parts by weight of diisooctyl phthalate, parts by weight of a stabilizer based on Ba-Cd-Zn soap and 0.4 parts by weight of the lubricant according to the invention in the form of a Ca ⁺⁺ salt. The mixing and granulation procedure of the mixture was the same as in Example 1. The granulate was stable for 152 min., the thermal stability determined graphically was 160 min.

Example 5

100 parts by weight of polyvinyl chloride were mixed with 82 parts by weight of diisooctyl phthalate, parts by weight of tribasic lead sulfate and 0.4 parts by weight of stearin. The granulate produced in the manner as in Example 1 was thermally stable for 75 minutes, the thermal stability determined graphically was 135 minutes.

Example 6

100 parts by weight of polyvinyl chloride were mixed with 82 parts by weight of diisooctyl phthalate, parts by weight of tribasic lead sulfate and 0.4 parts by weight of the lubricant according to the invention in the form of the Ca ⁺⁺ salt. The granulate, produced in the same manner as in Example 1, was thermally stable for 110 minutes, the thermal stability determined graphically was 215 minutes.

2.7317

Example 7

100 parts by weight of polyvinyl chloride, 6 parts by weight of chalk, 5 parts by weight of tribasic lead sulfate, 0.6 parts by weight of lead stearate, 0.6 parts by weight of calcium stearate and 0.6 parts by weight of ester wax were mixed in a fluid bed mixer. The mixing temperature was 140°C. The mixture was granulated on a KO-kneader at a temperature of 140°C. The resulting granulate was subjected to a thermal stability test at 200°C. The thermal stability was 71 minutes.

Example 8

A mixture was prepared with the same composition as in Example 7, except that 0.6 parts by weight of the ester wax was replaced by 0.6 parts by weight of the lubricant according to the invention, in the form of the Ca ⁺⁺ salt. The granulate, prepared in the same manner as in Example 7, was stable for 90 minutes at 200°C in a thermal stability test,

Salts of Mg ⁺⁺ , Zn ⁺⁺ and other metals have a similar effect to Ca ⁺⁺ salts.

Claims (1)

SUBJECT OF THE INVENTION Lubricants with stabilizing effects for chlorine-containing polymers based on ionic surfactants containing phosphatidyl (1) or bisphosphatidyl anion (II), of the general formulas: AND Ro-O-CH 0 I t CH-O-P-O II r ₂ -o-ch ₂ -or ₄ CH-OR, CH ₂ -O-CH ₂ O where R, 3e ^C n ^H 2n + 1 ^{C0 and} / ^{or C} n ^H 2n-, C0 and / or ^C n ^H 2n- jCO and / or θ _η ^Η 2η-5θθ ' R 1 -> is R 1 or H, wherein the number of carbon atoms in R 1, R ₂ , R 3 or R ₄ is 6-26, i.e. q is ^R 4j equal to 5-25, and the cation is a high metal ion such as Ca ⁺⁺ , Mg ⁺⁺ , Zn ⁺⁺ , Sn ^++, or Ba ⁺⁺ .