WO2006068627A1

WO2006068627A1 - Use of condensation products of fatty acids, alcohols, phenols, alkyl phenols and amines with ethylene oxide and/or propylene oxide as an essential or sole component of an additive

Info

Publication number: WO2006068627A1
Application number: PCT/SK2005/000024
Authority: WO
Inventors: Karol Kosar; Miroslav Duracka; Jan Sustek; Miloslav Riska; Peter Lehocky; Stanislav Sandtner; Jozef Balko
Original assignee: Vucht, A.S.
Priority date: 2004-12-20
Filing date: 2005-12-15
Publication date: 2006-06-29
Also published as: SK287007B6; SK4122004A3; RU2007123143A

Abstract

The invention concerns the use of condensation products of fatty acids, alcohols, phenols, alkyl phenols and amines with ethylene oxide and/or propylene oxide, either one or a mixture of several types of these condensation products, as a main (essential) or sole component of an additive in compacting wet powders of admixtures to polymers, or an additive for admixtures to polymers in powder form. Using additives according to the present invention low dusting and in polymers well dispersing powders or granulates/pellets are obtained, dispersibility of which is better or comparable to not adjusted form of a given admixture. Additives according to the present invention are added before compaction of admixtures to polymers in an amount of 0.01 to 15 weight parts, preferably of 0.1 to 2 weight parts with respect to 100 weight parts of a given admixture to polymers. They are added in the given range also in the production of final powder forms of admixtures to polymers. Additives according to the present invention may be applied to all types of water-insoluble admixtures to polymers. They are especially suitable for rubber chemicals like, for example, vulcanization agents, vulcanization accelerators, vulcanization activators, pre-vulcanization inhibitors, antidegradants, anti-reversion agents, surfactants, fillers and the like.

Description

Use of condensation products of fatty acids, alcohols, phenols, alkyl phenols and amines with ethylene oxide and/or propylene oxide as an essential or sole component of an additive

Technical Field

The solution concerns the use of condensation products of fatty acids, alcohols, phenols, alkyl phenols and amines with ethylene oxide and/or propylene oxide as an essential or sole component of additives, especially for significant dispersibility improvement and decreasing dustiness of formed or powder admixtures to polymers. The invention may be used in the production of formed and powder admixtures to polymers.

Background Art

Admixtures to polymers are chemicals which adjust and modify final properties of polymers or possibly facilitate, and in some cases make possible at all processing of polymer mixtures, make possible vulcanization of polymers with unsaturated chains, adjust and protect required properties of the resulting polymers/vulcanizates. Here belong mainly peptizing agents, processing agents, vulcanization agents, activators and vulcanization accelerators, pre-vulcanization inhibitors, anti-reversion agents, antidegradants (antioxidants, antiozonants, light and thermal stabilizers), blowing agents, pigments, fillers, and the like. These chemicals are dosed into the polymers usually in an amount of 0.1 to 5.0 weight parts with respect to 100 parts of the polymer, in some cases in amounts even more than 50 weight parts.

From the point of view of i mproving manipulation properties and increasing safety and hygiene, when working with the admixtures to polymers, their non-dusting final form i s important. To achieve their optimal effect in the polymer, their perfect dispersibility in the polymeric matrix is of no less importance, especially in rubber mixtures. To the required processing properties, there belongs also, for example, possibility of automatic weighing, as well as possibility of their automatic transport through various types of conveyors. Non-dusting finish may be achieved by forming, incorporating powder form into dimensionally stable agglomerates of various shapes. In this way, they acquire properties, which are more suitable for packing, storing, transport, weighing and dosing into the polymers. In this way, their dustiness, possible smell and similar undesirable properties will be reduced. To that end, surface treatment of the admixtures by fillers, for example by mineral oils, is often sufficient (Magg, Hans; Kempermann, Theo: Modern delivery forms of rubber c hemicals; Kautschuk Gummi Kunststoffe ( 1982), 35(12), 1 039-46). They a re applied by adding them to suspensions of the admixtures before drying or by mechanical mixing them with a powder admixture, or by spraying.

Some admixtures acquire their processing, form by depositing product melt on a cold surface or into a cold medium. In this way so called pastille, flaky and other processing forms are obtained (Magg, Hans; Kempermann, Theo: Modern delivery forms of rubber chemicals; Kautschuk Gummi Kunststoffe, 35(12), 1039-46, 1982). When stripping solidified admixture from a cooled surface, at subsequent packing, transport and processing at the user, there arises a substantial powder fraction, whereby the solidified melt of the admixture may exhibit limited dispersibility at immixing into the polymer, especially when the temperature of the polymer mixture (especially of a rubber mixture) stirring is lower or equal to the admixture melting point.

The most often used method of increasing grain size of admixtures to polymers, especially of rubber admixtures, is their granulation or pelletizing. Mechanical properties of granulates or possibly pellets may be favourably influenced by adding binders at granulation or possible pelletizing.

Non-dusting granulates/pellets which, at the same time, readily disperse in polymers, may be obtained by preparation of master batches of admixtures with increased content of the admixture in a suitable polymer matrix (Die Rhein-Chemie Retorte Nr50: Chemikaliengranulate fur die moderne Mischungfertigung. Rhein-Chemie Rheinau GmbH, 1974) or in materials of waxy character (CS 277 450 B6), which are subsequently formed in a suitable device, for example in an extruder. The binder content in these composites reaches up to 20 to 30 %. This final form with high content of extraneous substance only rarely satisfies mass users of admixtures to polymers (for example tire manufacturers), who require granulates/pellets of admixtures to polymers in more concentrated form (maximum of up to 2 % of additives). Various low- and high-molecular substances like, for example, aqueous emulsions of polyvinylacetates, aqueous solutions of polyvinylalcohols, and the like are used as binders in preparation of such granulates/pellets (GB 856 312; US 3018261). Although granulation or peptization, performed in this way, decreases dustiness of admixtures to polymers, on the other hand it often impairs their dispersibility in polymers. The use of insufficiently dispersible admixture may result in its inhomogeneous presence in the polymer, lowering of its effectiveness, and in some cases even deterioration of the final product. Therefore, besides the above binders also plasticizers, surface tension reducing additives, and the like, are added into the granulated/pelletized admixture (US4434070; US4367097; EP0169382A2).

Now it has been found that the use of condensation products of fatty acids, alcohols, phenols, alkyl phenols and amines with ethylene oxide and/or propylene oxide as an essential or sole component of additives of a powder or formed admixture enables one to obtain granulates/pellets with reduced dustiness which are well dispersing in polymers or well dispersing low dust-producing powders, both with low content of additives. The use of condensation products of fatty acids, alcohols, phenols, alkyl phenols and amines with ethylene oxide and/or propylene oxide in forming by extrusion allows production of granulates/pellets, which on one hand exhibit a strength satisfactory for their manipulation and transport, and on the other hand they exhibit good dispersibility in polymers at their application.

Disclosure of Invention

The subject-matter of the present invention is the use of condensation products of fatty acids, alcohols, phenols, alkyl phenols and amines with ethylene oxide and/or propylene oxide, either one or a mixture of several types of these condensation products as an essential or sole component of additives in forming wet powders of admixtures to polymers or additives for admixtures to poiymers in the ^'form of powders (hereinafter "additives according to the present invention"). When using additives according to the present invention, low dust-producing and in polymers well dispersing powders or granulates/pellets are obtained, dispersibility of which is better or comparable with not adjusted form of a given admixture.

Additives according to the present invention are added before compaction of admixtures to polymers in an amount of 0.01 to 15 weight parts, preferably of 0.1 to 2 weight parts with respect to 100 weight parts of a given finalized admixture to polymers. They are added in the given range also in the production of final powder forms of admixtures to polymers, which are characterized by reduced dustiness. Additives according to the present i nvention m ay b e a dded to a n admixture, which will be formed ( compacted) o r produced in powder form at any suitable technological stage of the production process. It means that additives according to the present invention may be added already to the selected starting raw material for preparation of a given admixture, in the course of reactions for its preparation, or possibly to a solution of the g iven admixture before its precipitation, or to a suspension of the given admixture before filtration, or into a wet filtration cake of the admixture after filtration, or they may be admixed to a dry powder with the required amount of water.

Pastes of admixtures to polymers with additives according to the present invention may be dried in common types of driers, like a box drier, flash drier, fluidization drier, counter-flow drier, band drier, wherein the resulting product is the final powder form, or the pastes with additives according to the present invention are formed and the granulates/pellets are subsequently dried in common types of driers.

Additives according to the present invention may be applied to all types of water-insoluble admixtures to polymers. Rubber chemicals like, for example, vulcanization agents, peptizing agents, vulcanization accelerators, vulcanization activators, pre-vulcanization inhibitors, antidegradants, anti-reversion agents, surfactants, fillers and the like, are especially suitable. Concrete examples represent vulcanization accelerators from the group of benzthiazoles, examples of which are 2-mercaptobenzthiazole, 2,2'- dibenzthiazolyl disulphide, accelerators from the group of sulfene amides, examples of which are A/-cyclohexyl-2-benzthiazolsu!fene amide, /V-terf-butyl-2-2-benzthiazolsulfene amide, /V-oxydiethylene-2-benzthiazolsulfene amide, Λ/,Λ/-dicyclo-2-benzthiazolsulfene amide, accelerators from the group of sulfene imides, examples of which are N- cyclohexyl-bis(2-benzthiazolsulfene)imide, /V-ferf-butyl-bis(2-benzthiazolsulfene)imide, accelerators from the group of dithiocarbamates, examples of which are zinc dimethylthiocarbamate, zinc ethylphenylthiocarbamate, accelerators from the group of thiurams, examples of which are tetramethylthiuram disulphide, tetraethylthiuram disulphide, tetrabenzylthiuram disulphide, tetra(tert-butyl)thiuram disulphide, accelerators from the group of guanidines, examples of which are diphenylguanidine, diorthotolylguanidine, accelerators from the group of xanthates, a n example of which is zinc ethylxanthate, accelerators from the group of thiophosphates, an example of which is zinc dibutyldithiophosphate. Concrete examples of anti-reversion agents are maleimide derivatives, like 2,2'-dithio-bis-phenylmaleimide, 4,4'-bis(p-maleinimidophenyl)methane, /77-phenylene-bis-maleimide. A concrete example of- peptizing agents is 2,2'- dibenzamidodiphenyl disulphide. A concrete example of a pre-vulcanization inhibitor is N- cyclohexylthiophthalimide. A concrete example of a vulcanization activator is zinc oxide.

Condensation products of fatty acids with ethylene oxide and/or propylene oxide_t according to the present invention may be condensation products of ethylene oxide and/or propylene oxide with oleic acid, stearic acid, ricinoleic acid, coconut acid, and the like. The condensation products contain more than 1 oxyethylene group, preferably 2 to 45 oxyethylene groups.

Condensation products of alcohols with ethylene oxide according to the present invention may be condensation products of ethylene oxide with C₆-C₁₈ alcohols or with their mixtures. The condensation products contain more than 1 oxyethylene group, preferably 2 to 100 oxyethylene groups.

Condensation products of alkyl phenols with ethylene oxide according to the present invention may be condensation products of ethylene oxide with alkyi phenols, mainly octyl-, nonyl-, dodecylphenols. The condensation products contain more than 1 oxyethylene group, preferably 2 to 70 oxyethylene groups.

Condensation products of amines with ethylene oxide according to the present invention may be condensation products of ethylene oxide with linear alkyl amines, terf-alkyl amines and dehydroabietyl amines. The condensation products contain more than 1 oxyethylene group, preferably 2 to 50 oxyethylene groups.

The condensation products of fatty acids, C₆-C₁₈ alcohols, amines, alkyl phenols with ethylene oxide or propylene oxide may be used separately or in any mutual ratio.

The additives are added in concentrated form into the admixture paste (filtration cake or suspension) under stirring, ore they are added in the form of aqueous emulsion.

Additives according to the present invention improve filtration efficiency of suspensions of admixtures to polymers. They make possible to obtain filtration cake with lower moisture content, thus reducing energy demands on the subsequent drying.

Additives according to the present invention reduce dustiness of powder forms of admixtures to polymers, whereby they may improve also dispersibility of the powder form in a polymeric matrix.

Additives according to the present invention serve also as lubricants in forming (for example extruding through a die of wet powder admixtures,^' improve plasticity of wet paste and so facilitate forming to the required shape. Properties of a paste modified by additives according to the present invention reduce energy demands of the forming (for example extruding) operation, and increase the throughput of the forming device. The most important i s the fact that, i n forming the powder admixtures, additives according to the present invention prevent formation of non-dispersible . agglomerates. The resulting strength of the agglomerates can be controlled by the dosing level of additives according to the present invention. The strength of pellets/granules is important at transport, manipulation and dispersing in polymers. If the pellets/granules are too soft, at the conditions of transport and manipulation they fall apart and a great amount of dusty fraction arises. The customer then looses advantages of final shaped form of the admixture in comparison with final powder form. If the pellets/granules are too hard, they cause problems at immixing them in the polymers. Insufficient homogeneity after incorporating causes worse mechanical properties of the vulcanizates, or longer stirring time is necessary, or deviations from the optimum technological treatment are registered.

Moisture I evel of the p aste a ssigned for forming p lays very important role for obtaining expected positive effects when applying additives according to the present invention. Water constitutes environment in which dispersing of the additive and contacting the surface of admixture particles suspended therein takes place, and within the frame of this system the additives act simultaneously as a lubricant between the paste particles, manifesting itself in a plasticity increase at its forming (shaping). The aqueous environment creates a possibility to achieve uniform concentration of additives in the paste before the forming. Water also fulfils binding function between the admixture particles and contributes to cohesiveness by capillary forces in the wet formed product thanks to high surface tension.

The use of additives according to the present invention in forming wet powders of admixtures to polymers ensures preparation of non-dusting and well dispersing pellets/granulates of admixtures to polymers, whereby simultaneous presence of further processing additives at compaction (plasticizers: waxes, stearates, mineral oils, glycerin, propylene ethylene glycol, polyethylene glycol, dioctyl phthalate, dibutyl phthalate, and the like; binding agents: aqueous solutions or dispersions of polymers, like polyvinyl alcohol, polyvinyl acetate, polyacrylamides, copolymers of acrylamtde and acrylic acid, natural and synthetic starches, polymers of acrylic acid, polymers of ethylene oxide, derivatives of alkyl and hydroxycellulose, liquid rubbers, elastomer latexes, and the like), which are added simultaneously with additives according to the present invention or each separately before forming, is not excluded. However, additives according to the present invention must constitute the main (substantial) part of the complex additive. 005/000024

8

In the following, there are given examples of preparation of pellets and powder forms of various admixtures to polymers using additives according to the present invention, application evaluations of processing properties of the prepared compactates and powders and of their effects in polymers.

Strength of pellets/granules has been determined by measuring the force necessary to disintegrate a horizontally lying cylindrical body. The necessary force has been recalculated to the cross section of the cylindrical body (perpendicularly to the force action).

Dustiness was measured by pouring 200 g of admixture into a closed chamber from the height of 30 cm. 1 0 minutes after pouring settled d ust was weighed together with p re- weighed filtration paper located in a part of the chamber, separated from the pouring part by a low partition.

Dispersibility was determined by immixing 30 g of the admixture to 100 g of colored rubber compound of low viscosity (45 ML 100 ⁰C (1+4)) based on natural polyisoprene and synthetic butadiene-styrene rubber on a laboratory open mill at a temperature of 70 ⁰C. After mixing in, dispersibility was assessed by counting not.immixed particles visible to the naked eye on a 40 cm² cut area of the rubber mixture. According to the number of non dispersed particles dispersibility was evaluated using a 4-stage scale from "excellent" (1) to "unsatisfactory" (4).

Abrasion resistance of the pellets was tested by putting 150 g of granulate free of dust fraction by sieving on a 0.8 mm sieve into a plastic container, and after letting the container to fall down 100x from the height of 1 m to the earth, part of fragments smaller than 0.8 mm was determined. The abrasion resistance is given in percents of the product remaining on a 0.8 mm sieve after the treatment. Examples of embodiments of the invention

The following examples illustrate, but do not limit the scope of the present invention.

Example 1

Using filtration cake of Λ/-cyclohexyl-2-benzthiazolsulfeneamide (fk-CBS) the following compositions have been prepared (Table 1):

Table 1: Compositions of CBS

*OK-6: condensation product of oleic acid and ethylene oxide (6 ethoxyl groups)

The additives were admixed to the filtration cake of CBS with given moisture by intensive mixing. A part of mixtures CBS-O and 1 was extruded through a 20 mm thick die with the diameter of holes of 2 mm (obtained samples designated as CBS-O gr and CBS-1 gr). By adjusting the breaking knife, the extruded pellets were broken to a length of 4 mm and, subsequently, dried in a box drier at a temperature of 80 ⁰C to the moisture content in the product of less than 0.5 %. The power, necessary to extrude through the die, when preparing CBS-1 gr, was 20 % lower than that in preparation of CBS-O gr. A part of the compositions CBS-O and 1 was dried in powder form (designated as CBS-O pr and CBS-1 pr) under the same conditions as the pellets.

In Table 2, there are given properties of the obtained samples of CBS, both in powder and pelletized form. Table 2: Properties of the obtained CBS pellets in comparison with powder CBS

Results given in Table 2 show that:

Using condensation products of oleic acid with ethylene oxide according to the present invention one obtains powder CBS with reduced dustiness, and in CBS peptization using condensation products of oleic acid with ethylene oxide according to the present invention one obtains pellets exhibiting low dustiness and dispersing in a rubber compound at the level of the powder product.

Example 2

2 g of the condensation product of oleic acid with ethylene oxide (6 ethylene oxide groups) were added to 300 g of aqueous suspension of /V-cyclohexyl-2-benzthiazolsulfeneamide (CBS) containing 33 % of CBS. Efficiency of filtration of the suspension (CBS-2) was tested on a water vacuum aspirator through a filtration paper, and was compared with a CBS suspension without the condensation products added. (CBS-O). The results are given in Table 3.

Table 3: Efficiency of CBS filtration in the presence of condensation products of oleic acid with ethylene oxide

Presence of condensation products increases the efficiency of filtration of CBS suspension. Example 3

Using filtration cake of diphenylguanidine (fk-DPG) the following compositions have been prepared (Table 4):

Table 4: Compositions of DPG

OK-6: condensation product of oleic acid and ethylene oxide 6 ethoxyl groups

The additives were admixed into the filtration cake having given moisture under intensive mixing. A part of mixtures DPG-O to 2 was extruded through a 20 mm thick die with the diameter of holes of 2 mm (obtained samples designated as DPG-O gr to DPG-2 gr). By adjusting the breaking knife, the extruded pellets were broken to a length of 4 mm and, subsequently, dried in a box drier at a temperature of 80 ⁰C to the moisture content in the product of less than 0.5 %. A part of the compositions DPG-O to 2 was dried in powder form (designated as DPG-O pr to DPG-2 pr) under the same conditions as the pellets.

In Table 5, there are given properties of the obtained samples of DPG, both in powder and pelletized form.

Table 5: Properties of the obtained DPG pellets in comparison with powder DPG

esu ts g ven n a e s ow a :

Using condensation products of oleic acid with ethylene oxide according to the present invention one obtains low dusting powder DPG with excellent dispersibility, and in diphenylguanidine peptization using condensation products of oleic acid with ethylene oxide according to the present invention one obtains pellets which are low d usting and easily and well disperse in a rubber compound.

The reason for improved DPG dispersibility (given in Table 5) both in powder and pelletized form in the presence of condensation products of oleic acid with ethylene oxide according to the present invention is documented also by Table 6, giving the results of sieve analysis of the powder products, according to which powder DPG with additive contains smaller part of agglomerated particles.

Table 6: Results of sieve analysis of powder DPG samples (sieve oversize for given mesh, in %) (STN 666301)

Also the course of drying the products at 80 ⁰C in a box drier has been observe . The results are given in Table 7.

Table 7: Influence of the presence of condensation products of oleic acid with ethylene oxide on the course of drying 100 g of DPG at 80 ⁰C (moisture content, %)

Example 4

20 m l of condensation p roduct of o leic acid with ethylene oxide (6 ethoxyl g roups to 1 molecule of oleic acid) were added to 10 000 ml of 10% aqueous solution of diphenylguanidine hydrochloride (DPG.HCI). After precipitating DPG (with 10% NaOH solution), the obtained suspension was filtered off and a part of the obtained filtration cake was dried in powder form (DPG-3 pr), and a part with 30% moisture content was extruded through a 20 mm thick die with the diameter of holes of 2 mm (obtained product in the form of pellets was designated as DPG-3 gr). The products were dried in a box drier at a temperature of 80 ⁰C to the moisture content of less than 0.5 %. Properties of samples obtained in this way were compared with untreated DPG powder (DPG-O pr) and pelletized form of DPG (DPG-O gr), which were prepared under the same conditions as that without the additive added.

Table 8: Properties of the obtained DPG pellets in comparison with powder DPG

Example 5

Using filtration cake of 2-mercaptobenzthiazole (fk-MBT) the following compositions have been prepared (Table 9):

Table 9: Compositions of MBT

OA-6: condensation product of oleic acid and ethylene oxide (6 ethoxyl groups) **OA-3: condensation product of oleic acid and ethylene oxide (3 ethoxyl groups)

The additives were immixed in the filtration cake of given moisture by intensive mixing. Mixtures MBT-O to MBT-2 were finish dried in a box drier at 80 ⁰C to 35 % moisture content and, subsequently, a part of MBT-O to MBT-3 was extruded through a 20 mm thick die with the diameter of holes of 2 mm (obtained samples designated as MBT-O gr to MBT-3 gr). By adjusting the breaking knife, the extruded pellets were broken to a length of 4 mm and, subsequently, dried in a box drier at a temperature of 80 ⁰C to the moisture content in the product of less than 0.5 %. A part of the compositions MBT-O to MBT-3 was dried in powder form (designated as MBT-O pr and MBT-2 pr) under the same conditions as the pellets.

In Table 10, there are given properties of the obtained samples of MBT, both in pelletized and powder form.

Table 10: Properties of the obtained MBT pellets in comparison with powder forms of MBT

From the results given in Table 10 one can draw the following conclusions: Using condensation products of oleic acid with ethylene oxide according to the present invention in peptization of 2-mercaptobenzthiazole one obtains pellets which easily and well disperse in a rubber compound (dispersibility at the level of that of powder product).

Using condensation products of oleic acid with ethylene oxide according to the present invention one obtains powders and pellets with reduced dustiness.

The resulting properties of pellets can be regulated by adjusting water content in MBT at immixing the condensation products of oleic acid with ethylene oxide according to the present invention in peptization of 2-mercaptobenzthiazole.

Subsequently, influence of presence of condensation products of oleic acid with ethylene oxide according to the present invention in MBT on the course of curing a model rubber compound was tested.

The influence on the course of curing is shown in Figure 1 (variation of the torque moment (axis Y) necessary for rotor oscillation, closed in the rubber compound as a function of curing time (axis X)).

Fig. 1: Curing curves of a model rubber compound (STN 621416, ISO 3417)

It is obvious from Fig. 1, that MBT pellets, prepared using condensation products of oleic acid with ethylene oxide according to the present invention exhibit the same efficiency as powder product, whereby the presence of condensation products of oleic acid with ethylene oxide according to the present invention does not affect the course of curing.

Example 6

Using filtration cake of 2,2-dibenzthiazolyl disulphide (fc-MBTS) the following compositions have been prepared (Table 11):

Table 11: Compositions of MBTS

*S-44P: condensation product of stearic acid with propylene oxide (44 molecules of oxypropylene to 1 molecule of stearic acid)

The additives were immixed in the filtration cake of given moisture by mixing in planetary mixer for 30 minutes. Subsequently, mixtures MBTS-O to MBTS-3 were extruded through a 20 mm thick die with the diameter of holes of 4 mm (obtained samples designated as MBTS-O gr to 3 gr). By adjusting the breaking knife, the extruded pellets were broken to a length of 6 mm and, subsequently, dried in a box drier at a temperature of 80 ⁰C to the moisture content in the product of less than 0.5 %. A part of the compositions MBTS-O was dried in powder form (designated as MBTS-O pr to 2 pr) under the same conditions as the pellets.

In Table 12, there are given properties of the obtained samples of MBTS.

Table 12: Properties of the obtained MBTS pellets in comparison with powder MBTS

Using condensation products of stearic acid with propylene oxide according to the present invention in peptization of 2,2-dibenzthiazolyldisulphide one obtains pellets which easily and well disperse in a rubber compound (dispersibility at the level of that of powder product). Using condensation products of stearic acid with propylene oxide according to the present invention in peptization of 2,2-dibenzthiazolyl disulphide one obtains pellets with reduced dustiness and increased abrasion resistance.

We have tested also the influence of samples on physical-mechanical properties of vulcanizates prepared from the rubber compound, the composition of which i s g iven i n Table 13.

Table 13: Composition of the model rubber compound

The rubber mixtures were immixed on a laboratory twin cylinder 200 x 100 mm at 70 ⁰C under the same conditions. Physical-mechanical properties of vulcanizates prepared from rubber mixtures having the composition given in Table 13 by pressing at 145 ⁰C up to the optimum curing time are given in Table 14.

Table 14: Physical-mechanical properties of vulcanizates prepared with selected samples of MBTS

, T 621431 , STN 621480) Example 7

Using filtration cake of tetramethylthiuram disulphide (fc-TMTD) the following compositions have been prepared (Table 15):

Table 15: Compositions of TMTD

Component MBTS-O MBTS-1 fk-TMTD (30 % of H₂O) 143 weight parts 140

^*AI-3 2

AI-3: condensation product of C12-C15 alcohol with ethylene oxide (3 ethoxyl groups)

The additive was immixed in the filtration cake of TMTD of given moisture by intensive mixing. A part of TMTD-O and 1 was extruded through a 20 mm thick die with the diameter of holes of 2 mm (obtained samples designated as TMTD-O gr and TMTD-1 gr). By adjusting the breaking knife, the extruded pellets were broken to a length of 4 mm and, subsequently, dried in a box drier at a temperature of 80 ⁰C to the moisture content in the product of less than 0.5 %. A part of the compositions TMTD-O and 1 was dried in powder form (designated as TMTD-O pr and TMTD-1 pr) under the same conditions as the pellets.

In Table 16, there are given properties of the obtained samples of TMTD, both in powder and pelletized form.

Table 16: Properties of the obtained TMTD pellets in comparison with powder TMTD

Example 8

Using powder zinc dimethylthiocarbamate (ZDNC) the following compositions have been prepared (Table 17):

Table 17: Compositions of ZDMC

*AF-10: condensation product of nonylphenol with ethylene oxide 10 ethoxyl groups)

The condensation product of nonylphenol with ethylene oxide was immixed in ZDMC by intensive mixing after adding water. A part of mixtures ZDMC-O and 1 was extruded through a 20 mm thick die with the diameter of holes of 2 mm (obtained samples designated as ZDMC-O gr and ZDMC-1 gr). By adjusting the breaking knife, the extruded pellets were broken to a length of 4 mm and, subsequently, dried in a box drier at a temperature of 80 ⁰C to the moisture content in the product of less than 0.5 %. A part of the compositions ZDMC-O and 1 was dried in powder form (designated as ZDMC-O pr and ZDMC-1 pr) under the same conditions as the pellets.

In Table 18, there are given properties of the obtained samples of ZDMC, both in powder and pelletized form.

Table 18: Properties of the obtained ZDMC pellets in comparison with powder ZDMC

Example 9

Using powder magnesium hydroxide (Mg(OH)₂) the following compositions have been prepared (Table 19):

Table 19: Compositions of Mg(OH)₂

*AA-20: ethoxylated octadecylamine (20 ethoxyl groups

Ethoxylated octadecylamine was immixed in Mg(OH)₂ by intensive mixing after adding water. A part of mixtures Mg(OH)₂-O and 1 was extruded through a 20 mm thick die with the diameter of holes of 2 mm (obtained samples designated as Mg(OH)₂-O gr and Mg(OH)₂-I gr). By adjusting the breaking knife, the extruded pellets were broken to a length of 4 mm and, subsequently, dried in a box drier at a temperature of 80 ⁰C to the moisture content in the product of less than 0.5 %. A part of the compositions Mg(OH)₂-O and 1 was dried in powder form (designated as Mg(OH)₂-O pr and Mg(OH)₂-I pr) under the same conditions as the pellets.

In Table 20, there are given properties of the obtained samples of Mg(OH)₂, both in powder and pelletized form.

Table 20: Properties of the obtained Mg(OH)₂ pellets in comparison with powder Mg(OH)₂

spers y was es e n po yv ny ace a e y m x ng at 160 ⁰C Industrial applicability

Present invention may be industrially utilized in final treatment of admixtures to polymers. By its application, one obtains non-dusting and in polymers well dispersing admixtures to polymers. The benefit is reduced dustiness of working environment in industry of rubber and plastics, especially at immixing of modified admixtures to polymers (healthier working environment, reduced danger of forming explosive dusty environment). By perfect dispersion of the modified admixtures in a polymer, the danger of deterioration of the polymeric mixture because of imperfect dispersion of the admixtures is eliminated. Well dispersing admixtures are able to achieve their full effect in a polymeric matrix.

Claims

1. Use of condensation products of fatty acids, alcohols, phenols, alkyl phenols and amines with ethylene oxide and/or propylene oxide as an essential or sole component of an additive to improve dispersibility and suppress dustiness of formed or powder admixtures to polymers.

2. Additive according to claim 1, characterized in that the condensation products of fatty acids with ethylene oxide and/or propylene oxide are condensation products of ethylene oxide and/or propylene oxide with oleic acid, stearic acid, ricinoleic acid, coconut acid.

3. Additive according to claim 2, characterized in that the condensation products of fatty acids with ethylene oxide and/or propylene oxide contain 2 to 70 oxyethylene and/or oxypropylene groups.

4. Additive according to claim 3, characterized in that the condensation products of fatty acids with ethylene oxide and/or propylene oxide contain 2 to 45 oxyethylene and/or oxypropylene groups.

5. Additive according to claim ^characterized in that the condensation products of fatty alcohols with ethylene oxide are condensation products of ethylene oxide with Cβ-Cis alcohols or possibly with their mixtures.

6. Additive according to claim 1, characterized in that the condensation products of alkyl phenols with ethylene oxide are condensation products of ethylene oxide with octyl-, nonyl- and dodecylphenols.

7. Additive according to claim ^characterized in that the condensation products of amines with ethylene oxide are condensation products of ethylene oxide with linear alkyi amines, tert-alkyl amines and dehydroabietyl amines.

8. Additive according to claims 5 and 6 and 7, characterized in that the condensation products contain 2 to 100 oxyethylene groups.

9. Additive according to claim 8, characterized in that the condensation products contain 2 to 50 oxyethylene groups.

10. Additive according to claim 1, characterized in th at they can be applied to all types of water-insoluble admixtures to polymers.

11. Additive according to claim 10, c h a racte rized i n th at the water- insoluble admixtures to polymers are rubber chemicals I ike vulcanization agents, vulcanization accelerators, peptizing agents, vulcanization activators, pre- vulcanization inhibitors, antidegradants, anti-reversion agents, surfactants, fillers.

12. Additive according to claim 11, c h a r ac t e ri z e d i n t h at the vulcanization accelerators are accelerators from the group of benzthiazoles, like 2- mercaptobenzthiazole, 2,2'-dibenzthiazolyl disulphide, accelerators from the group of sulfeneamides, like Λ/-cyclohexyl-2-benzthiazolsulfeneamide, Λ/-ferf-butyl-2-2- benzthiazolsulfeneamide, /V-oxydiethyIene-2-benzthiazolsulfeneamide, Λ/,Λ/-dicyclo- 2-benzthiazolsulfene amide, accelerators from the group of sulfeneimides, like N- cyclohexyl-bis(2-benzthiazolsulfene)imide, Λ/-terf-butyl-bis(2- benzthiazolsulfene)imide, accelerators from the group of dithiocarbamates, like zinc dimethylthiocarbamate, zinc ethylphenylthiocarbamate, accelerators from the group of thiurams, like tetramethylthiuram disulphide, tetraethylthiuram disulphide, tetrabenzylthiuram disulphide, tetra(tert-butyl)thiuram disulphide, accelerators from the group of guanidines, like diphenylguanidine, diorthotolylguanidine, accelerators from the group of xanthates, like zinc ethylxanthate, accelerators of vulcanization from the group of thiophosphates, like zinc dibutyldithiophosphate.

13. Additive according to claim 11, c h a r a c t e r i z e d i n t h a t the vulcanization agents are sulfur, donors of sulfur, ϋke dithiomorpholine.

14. Additive according to claim 11, characterized in that the peptizing agent is 2,2'-dibenzamidodiphenyl disulphide.

15. Additive according to claim 11, ch aracteri zed i n th at the anti- reversion agents are maleimide derivatives, like 2,2^l-dithio-bis-phenylmaleimide, 4,4'-bis(p-maleinimidophenyl)methane, m-phenylene-bis-maleimide.

16. Additive according to claim 11, c h a r a c te r i z e d i n th at the antidegradants are 2-mercaptobenzimidazole, zinc salt of 2- mercaptobenzimidazole.

17. Additive according to claim 11, ch a ra cte ri ze d i n th at the pre- vulcanization inhibitors are Λ/-cyclohexylthiophthalimide or phthalic anhydride.

18. Additive according to claim 11, c h a r a c t e r i z e d i n t h a t the vulcanization activators are zinc oxide, magnesium oxide.

19. Additive according to claim 11, characterized in that the fillers are magnesium hydroxide, chalk, kaolin.

20. Additive according to claim 11, characterized in that it is added to admixtures to polymers in an amount of 0.01 to 15 weight parts, preferably of 0.1 to 2 weight parts with respect to 100 weight parts of a given finalized admixture to polymers.

21. Additive according to claim ^characterized in that it is added to the formed/adjusted admixture at any suitable technological stage of its preparation.