CS250899B1 - Mixed non-coloring synthetic rubber stabilizer with improved processability - Google Patents

Abstract

The solution relates to a mixed non-staining stabilizer for synthetic rubbers with improved processability, which contains 72 to 96.9 wt. % tris(aralkylphenyl)phosphite, 3 to 26 wt. % anionic emulsifier based on alkyl- or aralkylphenolpolyglycol ether sulfate, 0.1 to 2 wt. % hydrogen chloride deactivator and optionally 2 to 9 wt. % auxiliary substances of the diluent type. The solution can be used in the chemical and rubber industry.

Description

250839

BACKGROUND OF THE INVENTION The present invention relates to a blend of non-coloring, synthetic stabilizer rubber with improved processability, comprising tris- (aralkylphenyl) phosphite, anionic emulsifier and optionally diluents and hydrogen chloride deactivators.

The industrially produced synthetic rubbers are needed in the process of their manufacture, at least the storage and processing, to protect against undesirable thermo-oxidative degradation, which results in the deterioration of the ρδ-void physiological-mechanical properties of the substrate. A number of phenol-type stabilizers (e.g., 2,6-di-tert-butyl-4-methylphenol, ...), amines (e.g., phenyl- (2-naphthylamine, ...) are commonly used to protect against thermo-oxidative degradation. and phosphites (e.g., tris / n-phenylphosphite, resip. tris / 1-phenylethylphenyl) -phosphite) The type of stabilizer used determines the grade of dyeing, weakening or non-dyeing rubbers (Pech J. - Synthetic rubber, Prague, 1971).

The introduction of stabilizers into latexes of synthetic rubbers is based on the use of the technology and type of stabilizer. The dosage stabilizer may be in suspension, solution diluent or oil, or directly, without further treatment, into a solution of the emulsifiers of the metal soaps of organic acid with water, and the emulsion formed by vigorous stirring is then directly used to stabilize the synthetic rubber latex (CS 207). 241). In the case of the phosphite stabilizer, the problem of phospholysis of phosphite in the process is that of hydrolytic stability, especially in the case of the hydrolysis stability, which in practice means irreversible destruction of the prepared emulsion and thus its evaluation. Therefore, a certain alkaline reserve of the prepared emulsion is needed, guaranteeing the stability of the emulsion until the time of processing.

A disadvantage of the aforementioned process of preparing a stabilizer emulsion is the necessity of a preparation solution of a mixture of emulsifiers, which also increases the coloring. The preparation of the emulsion itself, which can only be carried out at temperatures of 50 to 60 ° C, consists in the addition of phosphite under vigorous agitation, sparse, rapid sedimentation and standing of the aqueous phase. The prepared emulsion is flexible and thus the shelf life is limited to a maximum of 24 to 48 hours (CS AO 207 241).

It has now been found that the abovementioned drawbacks accompanying the synthetic rubber stabilization process can be removed with a mixed non-coloring stabilizer for base-phenylaphenylphenyl) phosphite of general formula I 3 (i) wherein R - represents α-methylibenzyl or α, α1-dimethylbenzyl and n is an integer of 1 to 3, wherein when R is α-menthylsulfyl, n is an integer of 1 to 3 alk R is N, - dimethylbenzyl, n is an integer of 1.

SUMMARY OF THE INVENTION The present invention is based on the fact that the mixed non-coloring synthetic rubber stabilizer with improved processability comprises 72 to 96.9% by weight of the tris- (aralkylphenyl) phosphite of general formula I,

3 to 26% by weight of an alkyl- or aralkylphenol-polyglycol ether sulfate-based anionic emulsifier of the general formula (IIa) wherein R is α-methylbenzyl, and, and - dimethylbenzyl or nonyl n is an integer of 1 to 3 and m is an integer of 10 to 20, wherein when R is α-methylbenzyl, it is an integer of 1 to 3 when R is α, α'-dimethylbenzyl, nonyl, n is 1 X is hydrogen, sodium, potassium, ammonium or ammonium, derived from an aliphatic or cyclic amine and having from 2 to 10 carbon atoms. 0.1 to 2% by weight of a chloroform deactivator and optionally 2 to 9% by weight of diluent type excipients.

The use of a mixed non-colorant stabilizer according to the invention has many advantages. The high active substance content of the stabilizer is maintained, the long-term compatibility of the emulsifier with the phosphite stabilizer is guaranteed, starting from the same, or very chemically very, in the synthesis of the phosphite component such as 250899 5 similar raw material, while the secondary raw material is also being valued. In the ultimate in the superiority of the raw materials, there is no change in the physical-mechanical properties, including the emulsifying and stabilizing properties of the altered stabilizer, by storage.

Mixing non-bleaching stabilizer ensures a simple preparation of high-quality water emulsions in the range of 20 to 50 ° / o, without or by careless demands for heating, without compromising the composition of the feedstock - eg tris (met-methylbenzylphenyl phosphite preparation and emulsion quality, with a uniform appearance the stabilizer in the emulsion at the state in the reservoir due to the low sedimentation rate.

Furthermore, we note a high hydrophilic stability of the emulsion in the range of tens to hundreds of hours without changing the quality of the prepared emulsion. The present stabilizer, when used in the synthetic rubber manufacturing technology, implies a reduction in the cost of emulsifiers and the preparation of their aqueous solutions at temperatures of about 70 ° C and allows smooth icoagulantation of the latex.

By combining a non-coloring stabilizer, it guarantees a high degree of processing reliability and provides a well-watered and stable aqueous emulsion, which fully meets the requirements of the processors for a modern, efficient and easy-to-process phosphate stabilizer.

The uncoloured non-coloring stabilizer retains the high stafbilization efficiency of the phosphates, alcohols such as trisnonylphenylsulfite or tris (α-methylbenzylphenyl phosphite, with the use of readily available raw materials.

In fact, aqueous emulsions of mixed non-colorating stabilizers are prepared by simple mixing of water into the stabilizer, the desired concentration of stabilizer in the emulsion in one apparatus, without the need for intensive mixing and without rollers for additional heating. Prepared milky-bile emulsion, low viscosity liquid, unusual foaming, almost non-sizing, with high stability, very good compatibility and unchanged stabilizing effect of phosphite.

These examples illustrate, but are not intended to, the invention. 1 and 1 In a beaker equipped with a laboratory stirrer, the following non-blending stabilizers A to F prepared by mixing the molten anionic emulsifier into a basic phosphite, heated to 90-120 ° C, were added, followed by solvents based on high boiling aromatic-paraffinic hydrocarbons, declared as kerosene, and / or disintegrating hydrogen chloride. The phosphite solution used is as follows:% P = 3.2 to 4,% C1 = max. 0.1, acid number, mg KOH / g = max 0.8 kinematic at 50 ° C, mm 2 / s - max. 550.

Mixed stabilizer composition by weight% A. tris (α-methylbenzylphenyl) phosphite 82 nonylrenol-based emulsifier, m = 15 12 kerosene-j-propylene oxide 5: 1 6 mixture B. tris (α-methylbenzylphenyl phosphite 72 emulsifier based on α-methylbenzylphenol, im = 10 18 mixture of kerosene-β-propylene oxide 9: 1 10 C. tris (α-methylbenzylphenyl phosphite 88 α-methylbenzylphenol-based emulsifier, m = 20,5 mixture) avian .petrole-j- + propylene oxide 10: 1 5.5 d. trisj (α-methylbenzylphenyl phosphite 91 aa-idimethylbenzylphenol-based emulsifier, im = 20 5 kerosene 4 E. tris (α, α'-dimethylbenzylphenyl) -phosphite 90 a, a'-dimethyl-Ibenzylphenol based emulsifier, m = 20 9.4 proipylene oxide 0.6 F. tris (α, α'-dimethylbenzylphenyl) phosphite 96.3 emulsifier based on α-methylbenzylphenol , m = 20 3.5 trietanolaimine 0.2 The 20 to 50% aqueous emulsions prepared from the prepared non-coloring stabilizers were prepared so that they were placed in a beaker, coated with a shovel. with a laboratory stirrer (n = 450-600 rpm) with a stabilizer of laiborate temperature, gradually adding 230899 7 8 with stirring for 20 to 30 minutes, adding a corresponding amount of voldy, preferably to pH = 9 A low-viscosity milk-white emulsion was obtained without foam and no signs of decomposition: the pH of the emulsion prepared was 9 to 9.5. Example 2

An aqueous emulsion of iris (nonylphenyl) phosphite or tris (α-methylbenzylphenyl phosphite of the prior art: In a 250 ml beaker, dissolve 7 g of potassium stearate in 143 g of water, buffered to pH 10, heated to 70 ° C. 50 g of tris (α-methylbenzylphenylphosphite, characterized by Example 1) are added dropwise to the aqueous phase with a mixed-bladder mixer. The resulting emulsion is a foamed, white to yellowish-white color that rapidly settled on standing.

The properties of the prepared phosphite stabilizer emulsions according to Examples 1 and 2 characterize the thrust. 1. Example 3

A mixed non-coloring stabilizer, formulated as a 25% emulsion of Example 1, was fed at a concentration of 1.5% by weight with respect to the rubber hydrocarbon content of the latex to the conventional latex latex of butadiene styrene rubber (SBR). type 1501 used to make Kralex rubber 010.402. A stabilized rubber containing a stabilizer was prepared by a reduction of the technological operations. Its stabilizing effect was monitored by thermo-oxidative stress in an air circulating oven 130 ° C for 0 to 8 hours. The measure of stabilizing efficiency is always the change in the viscosity of MOONEY 1-47100 ° C of the rubber to which the effect of thermo-oxidative degassing occurs - see Tab. 2.

For comparison, the values obtained with commonly used phosphites are given.

Table 1

Properties of aqueous phosphite stabilizer emulsions

Aqueous emulsion, 25% onset of sedimentation stability to irreversible [hour] emulsion distribution (days) stabilizer from example 2 0.5 to 1 to 2 mixed stabilizer A 18 50 B 10 20 C 30 60 D 24 55 E 48 60 F 8 14 Table 2 Thermal stability of SBR rubber, exposure at 130 ° C Used stabilizer Mooney viscosity, 1 - 4 '(100 ° C / ° ML) 0 I 2 4 6 8 h delta - 46 77 90 96 99 105 +59 from example 2 52 50, 51 51 49 47 - 5 tris (nonylphenylphosphine 47 46 44 44 46 46 - 1 mixed stabilizer C 47 46 47 47 46 46 - 1 of example 1 E 48 47 46 45 46 46 - 2

The trisfonylphenyl phosphite emulsion was carried out according to Example 2.

Claims (2)

Mixed non-staining stabilizer of synthetic gums with improved processability based on trisjaralkylphenol phosphite of formula I (a) where R is α-methylbenzyl or a, α'-diVYNALEZU methylbenzyl and n is an integer of 1 to 3, where R is α-methylbenzyl, n is an integer of 1 to 3 when R is a, n ', dimethylbenzyl, n is an integer of 1 to 72 to 96.9% by weight of tris jaralkylphenyl phosphite of formula I, 3-26% by weight of anionic emulsifier, based on the alkyl or ¹ · · arailkylfenoloolyglykolétersulfátu of formula II wherein R is' methylbenzyl, <x, a-dimethylbenzyl, or nonyl, n is 1-3 and m represents an integer of 10 to 20, wherein when R is α-methylbenzyl, n is an integer from 1 to 3 and when R is a, n-dimethylbenzyl, nonyl, n is an integer of 1 X is hydrogen, sodium, potassium, an ammonium residue, or an ammonium group de-bonded from an aliphatic or cyclic amine of 2 to 10 carbon atoms, 0.1 to 2% by weight of hydrogen chloride inactivator and optionally 2 to 9% by weight of diluents. REPAIR to PVAO no. 250,899 (51) Int. Cl. ⁴ C 08 C 13/08 // (C 08 C 13/08, (C 08 K 5/49, C 08 K 5/36) The last word in the "Object of the invention" should be: ... type of thinners.