CA1045804A - Processing aids for natural and synthetic rubber compounds - Google Patents
Processing aids for natural and synthetic rubber compoundsInfo
- Publication number
- CA1045804A CA1045804A CA212,200A CA212200A CA1045804A CA 1045804 A CA1045804 A CA 1045804A CA 212200 A CA212200 A CA 212200A CA 1045804 A CA1045804 A CA 1045804A
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- CA
- Canada
- Prior art keywords
- processing aid
- thioether
- acid
- rubber
- aid according
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
NOVEL PROCESSING AIDS FOR NATURAL
AND SYNTHETIC RUBBER COMPOUNDS
Abstract of the Disclosure Compositions containing salts of aromatic sulfonic acids, long chain fatty acids and thioethers are useful in the processing of natural and synthetic rubber by permitting the usual peptizing step of such processing to be omitted.
AND SYNTHETIC RUBBER COMPOUNDS
Abstract of the Disclosure Compositions containing salts of aromatic sulfonic acids, long chain fatty acids and thioethers are useful in the processing of natural and synthetic rubber by permitting the usual peptizing step of such processing to be omitted.
Description
sackground of the Invention Crude natural rubber is generally quite high in viscosity and therefore does not mix easily and quickly with the many additives used during processing. To facilitate the addition of these additives, the rubber usually is softened by undergoing a preliminary step called mastication.
The rubber is placed into a usual mixer, such as the Banbury*, and is subjected to heat and a plasticizer (peptizer), while being mixed for several minutes. The resulting mixture is then dumped, sheeted on a roll mill and cooled. The softened rubber then undergoes the mixing step.
The processing aids of United States Patent No.
3,787,341 were developed to eliminate the need for the mastica-tion step. These compositions are added directly to the crude rubber in the mixing cycle along with the other additives. In addition to facilitating the breaking of the polymer and the elimination of the need for both the mastication step and the peptizer, these compositions have other beneficial effects in rubber compounding. They reduce the mixing time required for rubber compounding and provide for better dispersal of additives than traditional methods. In addition, they enable'"~he use of ; lower mixing temperatures and provide for improved flow, improved physical properties, improved mixing and extruding characteristics, and improved physical characteristics of the rubber. Hence, even the compounding of synthetic rubber *Denotes Trade Mark ., - . ; :. .- : . -~ ~ . .. .. . . . .
requiring no pre~astication will be enhanced by the use of these formulations.
The compositions of the prior invention are homogeneous mixtures of:
1) alkali salts of aromatic sulfonic acids having the general formula: ~
Xn ~ ~ OH
wherein X can be either hydrogen or a branched or straight chain alkyl group having from 4 to 14 carbon atoms, and preferably about 8 to 12 carbon atoms; and n has a value of from 1 to 5, and preferably l; and
The rubber is placed into a usual mixer, such as the Banbury*, and is subjected to heat and a plasticizer (peptizer), while being mixed for several minutes. The resulting mixture is then dumped, sheeted on a roll mill and cooled. The softened rubber then undergoes the mixing step.
The processing aids of United States Patent No.
3,787,341 were developed to eliminate the need for the mastica-tion step. These compositions are added directly to the crude rubber in the mixing cycle along with the other additives. In addition to facilitating the breaking of the polymer and the elimination of the need for both the mastication step and the peptizer, these compositions have other beneficial effects in rubber compounding. They reduce the mixing time required for rubber compounding and provide for better dispersal of additives than traditional methods. In addition, they enable'"~he use of ; lower mixing temperatures and provide for improved flow, improved physical properties, improved mixing and extruding characteristics, and improved physical characteristics of the rubber. Hence, even the compounding of synthetic rubber *Denotes Trade Mark ., - . ; :. .- : . -~ ~ . .. .. . . . .
requiring no pre~astication will be enhanced by the use of these formulations.
The compositions of the prior invention are homogeneous mixtures of:
1) alkali salts of aromatic sulfonic acids having the general formula: ~
Xn ~ ~ OH
wherein X can be either hydrogen or a branched or straight chain alkyl group having from 4 to 14 carbon atoms, and preferably about 8 to 12 carbon atoms; and n has a value of from 1 to 5, and preferably l; and
2) long chain fatty acids having a maximum of about 2Z
carbon atoms in the chain, such as, but not limited to, stearic acid, palmitic acid, oleic acid, neodecanolc acid and mixtures o~ such aci`ds. The ~atty acids should be present in amounts at least about equal to the amount o~ sulfonates but may be present in substantial excess if desired.
It has been found in accordance with the present invention that thioethers catalyze the action of the prior com-positions. In particular, they promote further reduction in the viscosity of the rubber compound. This results in a reduced energy input to effect compounding. In addition, it enables mixing of the rubber compound at lower temperatures, thereby minimizing the danger of scorching the rubber compound.
Thus according to this invention there is provided an -improved rubber processing aid comprising:
a) an alkali or amine salt of an aromatic sulfonic `~
ac1d h i g the : . ' '' ' '. ' ' . . ~ . : :.
.
wherein c~n be either hydrogen or ~ br~nched or str~ght chain alkyl group having from 4 to 14 carbon atoms, and n has a value of from 1 to 5; and b) a long chain fatty acid having a maximum of about 22 carbon atoms in the chain, wherein the amount by weight of said fatty acid present is at least equal to the amount by weight of said sulfonic acid salt, the improvement wherein said processing aid includes a thioether in an amount sufficient to catalyze the peptizing action of said salt.
This invention also provides improved rubber composi-tions containing the improved rubber processing aids of this invention.
Finally this invention provides an improved method for compounding rubber.
The thioethers which are employed in accordance with this invention are those of the formula:
`. ~ Rl _y_R2 wherein Y is sulfur or dithioalkylene, i.e. -SCXH2xS - wherein x has a value of from 1 to about 5, and preferably is 1; and each l and R2 is alkyl, aryl, alkaryl, aralkyl as well as sub-stituted alkyl, aryl, alkaryl and aralkyl. The precise nature of Rl and R is not highly critical, provided the thioether is sufficiently non-volatile to remain in the rubber compound for ¦a sufficient period of time to provide effective catalyzing ¦action. In general, thioethers having boiling points in excess ; of about 130C. are sufficiently non-volatile to be useful in accordance with the invention. In addition, the size of the compound should be such that sufficient catalytic activity can be imparted with relatively small amounts of thioether.
Accordingly, each of ~1 and R2 preferably contains no more than ~ ;
, .:
lOqS804 about 12 carbon atom3. Lastly, substituents, if any, should be inert and compatible with the compounds of this invention as well as with the ultimate rubber compound into which they will be incorporated. Suitable substituents include ether oxygen, carbonyl oxygen (i.e. keto, ester and carboxyl groups), cyano, amine nitrogen (primary, secondary or tertiary), amide groups and the like.
A preferred class of thioethers comprises thiodicarboxylic acids and their lower alkyl ethers of the formula:
Y~CzH2z_a (Co2R3)l~a~2 wherein Y is as defined above; z is a number having a value of from 1 to about 2; a is a number having a value of from about O
to about l; and R3 is hydrogen or lower alkyl of up to about 3 carbons. Typical thioethers include thio-diglycolic acid, thiodipropionic acid, methylene bis(thioacetic acid), dimethyl thiodipropionate, thiodisuccinic acid, thiodipropionitrile, and dibenzyl sulfide.
The thioether is believed to act as a catalyst. In particular, it is believed that the alkali metal sulfonate component of the prior composition is converted in part into the corresponding sulfonic acid which acts as a peptizer during the compounding process, and that the thioether catalyzes the peptizing action of the sulfonic acid. This theory is offered solely by way of explanation, however, and it is not intended to limit the invention to this theory.
Regardless of theory~ the amount of thioether suffi-cient to achieve a reduction in compound viscosity and mixing temperature is small. In general it will be from about 5 to about 10 per cent, based upon the weight of the sulfonate salt, "' . ., ' ~ .
1!)4~8~)4 or from about 1 to about 3 per cent based upon the combined weight of sulfonate salt and fatty acid.
The resulting composition is blended with the rubber at the beginning of the mixing cycle. The amount of the composition necessary to achieve improved compounding ordinarily is from about 0.5 to about 2 per cent, and preferably about 0.9 - to about 1.5 per cent, based upon the weight of the rubber in the compound. As a result, the thioether is present in the compound at levels of only 0.005 to about 0.06 per cent, based upon the rubber. Nonetheless, the incorporation of such small amounts of the thioether has a material effect on reducing com-pound viscosity and compounding temperatures.
The composition of this invention preferably is mixed with suitable materials to facilitate its introduction into the rubber. Such materials include esters and ethers of aromatic alcohols, acids, etc. These additional materials are preferably similar to the materials comprising the composition of the inven-tion of United States Patent No. 3,855,165, issued December 17, 1974. These generally are aromatic esters, compounds with alcoholic and glycolic hydroxyl groups, potassium or sodium soaps ~; of fats or fatty acids, metal soaps of zinc, magnesium, calcium or barium, and a paraffin. Specifically, these additional materials may comprise:
(a) From about 5% to about 15% aromatic esters selected from groups consisting of (1) di-aryl- and di-arylalkyl phthalates, (2) di-aryl- and arylalkyl mono-glycolether phthalates, (3) phthalates from polyglycol mono-ethers of aryl, aralkyl and alkaryl com-pounds wherein the polyglycol chain contains :
l 104S804 from 2 to 6 ethylene oxide groups in the chain, (1l) di-benzoates of glycol and propyleneglycol, and their di- and tri-mers; and (5) mixtures of the above.
From about 5% to about 30% of eompounds with alcoholie or glyeolie hydroxyl groups selected from ~1) straight or branehed chain aliphatie aleohols having -from about 8 to about 20 ear-bons in the ehain, (2) alkyl-phenoxy ethers of glyeols or polyglycols wherein the alkyl :.
group is limited to about 12 earbons in the :
ehain, and the polyglyeol grouping does not eontain more than about 6 (CH2-CH2-0-) groups, ~' ~ , ' .
.
-`` 1045804
carbon atoms in the chain, such as, but not limited to, stearic acid, palmitic acid, oleic acid, neodecanolc acid and mixtures o~ such aci`ds. The ~atty acids should be present in amounts at least about equal to the amount o~ sulfonates but may be present in substantial excess if desired.
It has been found in accordance with the present invention that thioethers catalyze the action of the prior com-positions. In particular, they promote further reduction in the viscosity of the rubber compound. This results in a reduced energy input to effect compounding. In addition, it enables mixing of the rubber compound at lower temperatures, thereby minimizing the danger of scorching the rubber compound.
Thus according to this invention there is provided an -improved rubber processing aid comprising:
a) an alkali or amine salt of an aromatic sulfonic `~
ac1d h i g the : . ' '' ' '. ' ' . . ~ . : :.
.
wherein c~n be either hydrogen or ~ br~nched or str~ght chain alkyl group having from 4 to 14 carbon atoms, and n has a value of from 1 to 5; and b) a long chain fatty acid having a maximum of about 22 carbon atoms in the chain, wherein the amount by weight of said fatty acid present is at least equal to the amount by weight of said sulfonic acid salt, the improvement wherein said processing aid includes a thioether in an amount sufficient to catalyze the peptizing action of said salt.
This invention also provides improved rubber composi-tions containing the improved rubber processing aids of this invention.
Finally this invention provides an improved method for compounding rubber.
The thioethers which are employed in accordance with this invention are those of the formula:
`. ~ Rl _y_R2 wherein Y is sulfur or dithioalkylene, i.e. -SCXH2xS - wherein x has a value of from 1 to about 5, and preferably is 1; and each l and R2 is alkyl, aryl, alkaryl, aralkyl as well as sub-stituted alkyl, aryl, alkaryl and aralkyl. The precise nature of Rl and R is not highly critical, provided the thioether is sufficiently non-volatile to remain in the rubber compound for ¦a sufficient period of time to provide effective catalyzing ¦action. In general, thioethers having boiling points in excess ; of about 130C. are sufficiently non-volatile to be useful in accordance with the invention. In addition, the size of the compound should be such that sufficient catalytic activity can be imparted with relatively small amounts of thioether.
Accordingly, each of ~1 and R2 preferably contains no more than ~ ;
, .:
lOqS804 about 12 carbon atom3. Lastly, substituents, if any, should be inert and compatible with the compounds of this invention as well as with the ultimate rubber compound into which they will be incorporated. Suitable substituents include ether oxygen, carbonyl oxygen (i.e. keto, ester and carboxyl groups), cyano, amine nitrogen (primary, secondary or tertiary), amide groups and the like.
A preferred class of thioethers comprises thiodicarboxylic acids and their lower alkyl ethers of the formula:
Y~CzH2z_a (Co2R3)l~a~2 wherein Y is as defined above; z is a number having a value of from 1 to about 2; a is a number having a value of from about O
to about l; and R3 is hydrogen or lower alkyl of up to about 3 carbons. Typical thioethers include thio-diglycolic acid, thiodipropionic acid, methylene bis(thioacetic acid), dimethyl thiodipropionate, thiodisuccinic acid, thiodipropionitrile, and dibenzyl sulfide.
The thioether is believed to act as a catalyst. In particular, it is believed that the alkali metal sulfonate component of the prior composition is converted in part into the corresponding sulfonic acid which acts as a peptizer during the compounding process, and that the thioether catalyzes the peptizing action of the sulfonic acid. This theory is offered solely by way of explanation, however, and it is not intended to limit the invention to this theory.
Regardless of theory~ the amount of thioether suffi-cient to achieve a reduction in compound viscosity and mixing temperature is small. In general it will be from about 5 to about 10 per cent, based upon the weight of the sulfonate salt, "' . ., ' ~ .
1!)4~8~)4 or from about 1 to about 3 per cent based upon the combined weight of sulfonate salt and fatty acid.
The resulting composition is blended with the rubber at the beginning of the mixing cycle. The amount of the composition necessary to achieve improved compounding ordinarily is from about 0.5 to about 2 per cent, and preferably about 0.9 - to about 1.5 per cent, based upon the weight of the rubber in the compound. As a result, the thioether is present in the compound at levels of only 0.005 to about 0.06 per cent, based upon the rubber. Nonetheless, the incorporation of such small amounts of the thioether has a material effect on reducing com-pound viscosity and compounding temperatures.
The composition of this invention preferably is mixed with suitable materials to facilitate its introduction into the rubber. Such materials include esters and ethers of aromatic alcohols, acids, etc. These additional materials are preferably similar to the materials comprising the composition of the inven-tion of United States Patent No. 3,855,165, issued December 17, 1974. These generally are aromatic esters, compounds with alcoholic and glycolic hydroxyl groups, potassium or sodium soaps ~; of fats or fatty acids, metal soaps of zinc, magnesium, calcium or barium, and a paraffin. Specifically, these additional materials may comprise:
(a) From about 5% to about 15% aromatic esters selected from groups consisting of (1) di-aryl- and di-arylalkyl phthalates, (2) di-aryl- and arylalkyl mono-glycolether phthalates, (3) phthalates from polyglycol mono-ethers of aryl, aralkyl and alkaryl com-pounds wherein the polyglycol chain contains :
l 104S804 from 2 to 6 ethylene oxide groups in the chain, (1l) di-benzoates of glycol and propyleneglycol, and their di- and tri-mers; and (5) mixtures of the above.
From about 5% to about 30% of eompounds with alcoholie or glyeolie hydroxyl groups selected from ~1) straight or branehed chain aliphatie aleohols having -from about 8 to about 20 ear-bons in the ehain, (2) alkyl-phenoxy ethers of glyeols or polyglycols wherein the alkyl :.
group is limited to about 12 earbons in the :
ehain, and the polyglyeol grouping does not eontain more than about 6 (CH2-CH2-0-) groups, ~' ~ , ' .
.
-`` 1045804
(3) polypropylene glycol of about three pro-pylene oxide groups in the molecule, and
(4) mixtures of the above.
(c) From about 5~ to about 15% of potassium or sodium soaps made from commercial mixtures of fats or fatty acids containing from about 12 to about 18 carbon atoms in the chain, said ~ -chains having only a small degree of unsatura-tion, with more than 50% of them having 18 carbon atoms in the chain.
(d) From about 10% to about 30% of fatty acids having from about 12 to about 18 carbon atoms in the chain, said chains having only a small degree of unsaturation, with more than 50% of them having 18 carbon atoms in the chain.
(e) From about 5% to about 10% of a metal soap where the metal is selected from the group consisting of zinc, magnesium, calcium, or barium; and the fatty acid part of the soap has from about 12 to about 18 carbon atoms in the chain and contains a high percentage of chains with a single double bond in the ; chain.
(f) From about 15% to about 60~ of hydrocarbons selected from the group consisting of mineral oil, mineral waxes, and petrolatum, or mix-tures of them.
Preferably the potassium or sodium soaps of (c) above or the fatty acids of (d) above are compounds which have iodine values in the range of from about 5 to about 15. The metal soaps of (e) above are more unsaturated and have iodine values in the :
: `
` 16)45804 range of about 80 to about 95.
Typical aromatic esters of (a) above which may be used in the compositions of this invention are dibenzyl phthalate;
diphenyl phthalate; bis(2-phenoxyethyl) phthalate; bis(nonyl-phenoxyethyl) phthalate; bis(nonylphenoxytetraethyleneglycol) phthalate; benzyl dodecylphenoxyhexaethyleneglycol phthalate;
bis(octylphenoxy) hexaethyleneglycol phthalate; diethyleneglycol dibenzoate; dipropyleneglycol dibenzoate; and triethyleneglycol dibenzoate.
Illustrative of the compounds with alcoholic or glycolic hydroxyl groups referred to in (b) above which may be employed are 2-ethylhexanol, cetyl alcohol, stearyl alcohol, nonyl-phenoxyglycol, nonylphenoxydiglycol, nonylphenoxytetraethylene-glycol, dodecylhexaethyleneglycol, dipropyleneglycol, tripropyleneglycol.
Among the potassium or sodium soaps referred to in (c) above are sodium and potassium soaps of hydrogenated tallow, hydrogenated oils of vegetable or marine origin, and soaps of potassium or sodium made with fractions prepared from oils and fats, such fractions having iodine values from about 5 to about :~
15. ~:
Typical fatty acids which may be employed are those derived from hydrogenated tallow and hydrogenated oils of vegetable or marine origin.
Illustrative of the fatty acids part of the metal soaps referred to in te) above are oils of vegetable origin or fractions ` :
of animal fatty acids such as red oil.
Among the petroleum jellies, mineral oils, and mineral waxes, which may be employed in the compositions of this inven- :- :
tion, are waxes having melting points of about 120 to 170F.
- : - . , . - " , .
1~458~4 However, compositions of this invention are not limited to use in combination with the above additional materials and any similar chemicals will suffice. All ingredients may be of technical grade and may contain varying amounts of related materials, by-products, etc. The novel rubber processing aids of this invention can be made by melting the ingredients together, mixing and cooling, forming a waxy solid. The additionalmaterials may be added together with the sulfonic acid salt, fatty acid and thioether and all components heated until a clear melt is obtained. The alkali soaps and soaps of the bivalent metals can also be made in situ as is well known in the art, from the oxide, hydroxide or carbonate of the metal and the desired acids or acid anhydrides, followed by the evaporation or boiling off of the resulting water.
A preferred formulation for balanced processing aids of this invention contains the following approximate percentages by weight of compounds which are typical of their class: -3% to 15% alkali salt of aromatic sulfonic acid
(c) From about 5~ to about 15% of potassium or sodium soaps made from commercial mixtures of fats or fatty acids containing from about 12 to about 18 carbon atoms in the chain, said ~ -chains having only a small degree of unsatura-tion, with more than 50% of them having 18 carbon atoms in the chain.
(d) From about 10% to about 30% of fatty acids having from about 12 to about 18 carbon atoms in the chain, said chains having only a small degree of unsaturation, with more than 50% of them having 18 carbon atoms in the chain.
(e) From about 5% to about 10% of a metal soap where the metal is selected from the group consisting of zinc, magnesium, calcium, or barium; and the fatty acid part of the soap has from about 12 to about 18 carbon atoms in the chain and contains a high percentage of chains with a single double bond in the ; chain.
(f) From about 15% to about 60~ of hydrocarbons selected from the group consisting of mineral oil, mineral waxes, and petrolatum, or mix-tures of them.
Preferably the potassium or sodium soaps of (c) above or the fatty acids of (d) above are compounds which have iodine values in the range of from about 5 to about 15. The metal soaps of (e) above are more unsaturated and have iodine values in the :
: `
` 16)45804 range of about 80 to about 95.
Typical aromatic esters of (a) above which may be used in the compositions of this invention are dibenzyl phthalate;
diphenyl phthalate; bis(2-phenoxyethyl) phthalate; bis(nonyl-phenoxyethyl) phthalate; bis(nonylphenoxytetraethyleneglycol) phthalate; benzyl dodecylphenoxyhexaethyleneglycol phthalate;
bis(octylphenoxy) hexaethyleneglycol phthalate; diethyleneglycol dibenzoate; dipropyleneglycol dibenzoate; and triethyleneglycol dibenzoate.
Illustrative of the compounds with alcoholic or glycolic hydroxyl groups referred to in (b) above which may be employed are 2-ethylhexanol, cetyl alcohol, stearyl alcohol, nonyl-phenoxyglycol, nonylphenoxydiglycol, nonylphenoxytetraethylene-glycol, dodecylhexaethyleneglycol, dipropyleneglycol, tripropyleneglycol.
Among the potassium or sodium soaps referred to in (c) above are sodium and potassium soaps of hydrogenated tallow, hydrogenated oils of vegetable or marine origin, and soaps of potassium or sodium made with fractions prepared from oils and fats, such fractions having iodine values from about 5 to about :~
15. ~:
Typical fatty acids which may be employed are those derived from hydrogenated tallow and hydrogenated oils of vegetable or marine origin.
Illustrative of the fatty acids part of the metal soaps referred to in te) above are oils of vegetable origin or fractions ` :
of animal fatty acids such as red oil.
Among the petroleum jellies, mineral oils, and mineral waxes, which may be employed in the compositions of this inven- :- :
tion, are waxes having melting points of about 120 to 170F.
- : - . , . - " , .
1~458~4 However, compositions of this invention are not limited to use in combination with the above additional materials and any similar chemicals will suffice. All ingredients may be of technical grade and may contain varying amounts of related materials, by-products, etc. The novel rubber processing aids of this invention can be made by melting the ingredients together, mixing and cooling, forming a waxy solid. The additionalmaterials may be added together with the sulfonic acid salt, fatty acid and thioether and all components heated until a clear melt is obtained. The alkali soaps and soaps of the bivalent metals can also be made in situ as is well known in the art, from the oxide, hydroxide or carbonate of the metal and the desired acids or acid anhydrides, followed by the evaporation or boiling off of the resulting water.
A preferred formulation for balanced processing aids of this invention contains the following approximate percentages by weight of compounds which are typical of their class: -3% to 15% alkali salt of aromatic sulfonic acid
5% to 25% fatty acid 0.5% to 1.5% thioether 7% to 15% diphenylphthalate 10% to 20% tetraethyleneglycol mono-nonylphenol ether 5% to 10% tripropyleneglycol 5% to 20~ potassium stearate 4% to 10% zinc oleate 0% to 5% cetyl alcohol 15% to 40% petrolatum In general, the above-described compositions are solids.
It is desirable that they be in liquid form to facilitate mixing ;
of the composition with the rubber compound. Such liquid com-_g_ ~C~45804 positions can be achieved by the use of amine salts of the aromatic sulfonic acids disclosed above. The salts are those of amines of the formula:
R R R N
and H tNHCH2CH2t NH2 Wherein R4 is alkyl or hydroxyalkyl, each of R5 or R6 is hydrogen, alkyl or hydroxyalkyl, and n is a number having a value of from 2 to 5. Preferred amines are those having a molecular weight of at least 149 which are themselves liquid and react with the aromatie sulfonic acid to form a liquid salt. ~
Preferred amines are tertiary amines, with triethanolamine being ~ -especially preferred.
The aromatic sulfonie aeid amine salt can be pre~
formed or it ean be formed in situ by adding the acid and the amine separately. In the latter case, the aromatic sulfonic acid ~-and the amine are added in approximately equivalent amounts.
The amine salt of the sulfonie acid, the carboxylie -aeid and the thioether ean be mixed with certain of the ingredients (a)-(f) discussed above and still afford a liquid formulation. In particular, the aromatic esters (a), the aleoholie eompounds (b), and the hydroearbon (f) can be employed.
However, the metal soaps (c) and (e) are to be avoided if a liquid formulation is desired. As a result, the proportions of the additional materials are appropriately ad~usted to refleet the omission of these eomponents as follows:
5.5% to 20% of ester (a) 5.5% to 38% of alcoholie eompound (b) - -5.5% to 38% of acid (d), and 16% to 75% of hydrocarbon (f) -10- " "
. . .
- , . , - .. : ~ ' ' ,. , - ., . -: . . :
Prefcrre~ liqui~ formulatlons contain:
20~ to 25~o amine salt of aroma~ic sulfonic acid 15% to 25% fatty acid 0.5~ to 1. 5~ thioether 5~ to 15~ dipropylene glycol dibenzoate 20% to 25~ tetraethyleneglycol mono-nonylphenol ether 5~ to 15% tripropyleneglycol 10% to 20% mineral oil As noted above, the compos~ions of this invention generally are added to the rubber at the beginning of the mixing cycle. The usual additives, such as pigments, fillers, vul- ~ -canizing agents, etc., can then be added and the entire com-pounding performed in one operation. They may be added to any type rubber, whether it is of a natural, synthetic or reclaimed type.
The following Examples are illustrative of the present invention. The processing aids employed in the Examples are as follows:
COMPOUND A
(illustrative of the composition of U.S. Patent No. 3,787,341 issued January 22, 1974) 10.0 Parts potassium n-dodecylbenzenesulfonate, techn. (mixed isomers) 22.0 " stearic acid, techn. rubber grade 10.0 " diphenylphthalate, techn.
15.0 " tetraethyleneglycol mono-nonylphenol ether, techn.
5.0 " tripropyleneglycol, techn.
18.0 " potassium stearate, techn.
4.0 " zinc oleate, techn.
2.0 " cetyl alcohol, techn.
14.0 " petrolatum, N.~.
. . ~' ' , ~ . ~, 1~)45~04 COMPOUND B
(Illustrative of this Invention) 10.0 Parts potassium n-dodecylbenzenesulfonate, tech. (mixed isomers) 22.0 " stearic acid, techn. rubber grade 10.0 " diphenylphthalate, techn.
15.0 " tetraethyleneglycol mono-nonylphenolether, techn. ;~-5.0 " tripropyleneglycol, techn.
18.0 " potassium stearate, techn.
4.0 " zinc oleate, techn.
2.0 " cetyl alcohol, techn.
14.0 " petrolatum, N. F.
0.6 " thiodiglycolic acid COMPOUND C
- (Illustrative of this Invention) 10.0 Parts potassium n-dodecylbenzenesulfonate, techn. (mixed isomers) ; 22.0 " stearic acid, techn. rubber grade 10.0 " diphenylphthalate, techn.
15.0 " tetraethyleneglycol mono-nonylphenolether, -techn.
5.0 " tripropyleneglycol, techn.
18.0 " potassium stearate, techn.
4.0 " zinc oleate, techn.
2.0 " cetyl alcohol, techn.
14.0 " petrolatum, N. F.
0.7 " thiodipropionic acid -Ah ...... ..
. ' . ., , :,. . .. .. : :.
1(~458U4 COMPOUND D
(Liquid formula of this Invention) 1.0 Parts thiodiglycolic acid 10.0 " tripropylene glycol 23.0 " tetraethyleneglycol mono-nonylphenoxyether 10.0 " dipropyleneglycol di-benzoate 14.0 " paraffinic mineral oil 100/100 20.0 " neodecanoic acid 15.0 " dodecylphenylsulfonic acid 7.0 " triethanolamine 99%
COMPOUND E
(Liquid formula of this Invention) 1.2 Parts thiodipropionic acid 9.8 " tripropylene glycol 23.0 " tetraethyleneglycol mono-nonylphenoxyether 10.0 " dipropyleneglycol di-benzoate 14.0 " paraffinic mineral oil 100/100 20.0 " neodecanoic acid 15.0 " dodecylphenylsulfonic acid 7.0 " triethanolamine 99%
COMPOUND F
1.3 Parts methylene bis(thioacetic acid) ~- 7 " tripropylene glycol 22 " tetraethyleneglycol mono-nonylphenol ether 13.4 " dipropyleneglycol dibenzoate 12 " paraffinic mineral oil 100/100 18 " neodecanoic acid 18 " dodecylphenylsulfonic acid 8.4 " triethanolamine 99 1~4S8~4 COMPOUND G
1.5 Parts dimethyl thiodipropionate 9 " tripropylene glycol 24 " tetraethyleneglycol mono-nonylphenol ether 14 " dipropyleneglycol dibenzoate 13.5 " paraffinic mineral oil 100/100 18 " neodecanoic acid 14 " dodecylphenylsulfonic acid
It is desirable that they be in liquid form to facilitate mixing ;
of the composition with the rubber compound. Such liquid com-_g_ ~C~45804 positions can be achieved by the use of amine salts of the aromatic sulfonic acids disclosed above. The salts are those of amines of the formula:
R R R N
and H tNHCH2CH2t NH2 Wherein R4 is alkyl or hydroxyalkyl, each of R5 or R6 is hydrogen, alkyl or hydroxyalkyl, and n is a number having a value of from 2 to 5. Preferred amines are those having a molecular weight of at least 149 which are themselves liquid and react with the aromatie sulfonic acid to form a liquid salt. ~
Preferred amines are tertiary amines, with triethanolamine being ~ -especially preferred.
The aromatic sulfonie aeid amine salt can be pre~
formed or it ean be formed in situ by adding the acid and the amine separately. In the latter case, the aromatic sulfonic acid ~-and the amine are added in approximately equivalent amounts.
The amine salt of the sulfonie acid, the carboxylie -aeid and the thioether ean be mixed with certain of the ingredients (a)-(f) discussed above and still afford a liquid formulation. In particular, the aromatic esters (a), the aleoholie eompounds (b), and the hydroearbon (f) can be employed.
However, the metal soaps (c) and (e) are to be avoided if a liquid formulation is desired. As a result, the proportions of the additional materials are appropriately ad~usted to refleet the omission of these eomponents as follows:
5.5% to 20% of ester (a) 5.5% to 38% of alcoholie eompound (b) - -5.5% to 38% of acid (d), and 16% to 75% of hydrocarbon (f) -10- " "
. . .
- , . , - .. : ~ ' ' ,. , - ., . -: . . :
Prefcrre~ liqui~ formulatlons contain:
20~ to 25~o amine salt of aroma~ic sulfonic acid 15% to 25% fatty acid 0.5~ to 1. 5~ thioether 5~ to 15~ dipropylene glycol dibenzoate 20% to 25~ tetraethyleneglycol mono-nonylphenol ether 5~ to 15% tripropyleneglycol 10% to 20% mineral oil As noted above, the compos~ions of this invention generally are added to the rubber at the beginning of the mixing cycle. The usual additives, such as pigments, fillers, vul- ~ -canizing agents, etc., can then be added and the entire com-pounding performed in one operation. They may be added to any type rubber, whether it is of a natural, synthetic or reclaimed type.
The following Examples are illustrative of the present invention. The processing aids employed in the Examples are as follows:
COMPOUND A
(illustrative of the composition of U.S. Patent No. 3,787,341 issued January 22, 1974) 10.0 Parts potassium n-dodecylbenzenesulfonate, techn. (mixed isomers) 22.0 " stearic acid, techn. rubber grade 10.0 " diphenylphthalate, techn.
15.0 " tetraethyleneglycol mono-nonylphenol ether, techn.
5.0 " tripropyleneglycol, techn.
18.0 " potassium stearate, techn.
4.0 " zinc oleate, techn.
2.0 " cetyl alcohol, techn.
14.0 " petrolatum, N.~.
. . ~' ' , ~ . ~, 1~)45~04 COMPOUND B
(Illustrative of this Invention) 10.0 Parts potassium n-dodecylbenzenesulfonate, tech. (mixed isomers) 22.0 " stearic acid, techn. rubber grade 10.0 " diphenylphthalate, techn.
15.0 " tetraethyleneglycol mono-nonylphenolether, techn. ;~-5.0 " tripropyleneglycol, techn.
18.0 " potassium stearate, techn.
4.0 " zinc oleate, techn.
2.0 " cetyl alcohol, techn.
14.0 " petrolatum, N. F.
0.6 " thiodiglycolic acid COMPOUND C
- (Illustrative of this Invention) 10.0 Parts potassium n-dodecylbenzenesulfonate, techn. (mixed isomers) ; 22.0 " stearic acid, techn. rubber grade 10.0 " diphenylphthalate, techn.
15.0 " tetraethyleneglycol mono-nonylphenolether, -techn.
5.0 " tripropyleneglycol, techn.
18.0 " potassium stearate, techn.
4.0 " zinc oleate, techn.
2.0 " cetyl alcohol, techn.
14.0 " petrolatum, N. F.
0.7 " thiodipropionic acid -Ah ...... ..
. ' . ., , :,. . .. .. : :.
1(~458U4 COMPOUND D
(Liquid formula of this Invention) 1.0 Parts thiodiglycolic acid 10.0 " tripropylene glycol 23.0 " tetraethyleneglycol mono-nonylphenoxyether 10.0 " dipropyleneglycol di-benzoate 14.0 " paraffinic mineral oil 100/100 20.0 " neodecanoic acid 15.0 " dodecylphenylsulfonic acid 7.0 " triethanolamine 99%
COMPOUND E
(Liquid formula of this Invention) 1.2 Parts thiodipropionic acid 9.8 " tripropylene glycol 23.0 " tetraethyleneglycol mono-nonylphenoxyether 10.0 " dipropyleneglycol di-benzoate 14.0 " paraffinic mineral oil 100/100 20.0 " neodecanoic acid 15.0 " dodecylphenylsulfonic acid 7.0 " triethanolamine 99%
COMPOUND F
1.3 Parts methylene bis(thioacetic acid) ~- 7 " tripropylene glycol 22 " tetraethyleneglycol mono-nonylphenol ether 13.4 " dipropyleneglycol dibenzoate 12 " paraffinic mineral oil 100/100 18 " neodecanoic acid 18 " dodecylphenylsulfonic acid 8.4 " triethanolamine 99 1~4S8~4 COMPOUND G
1.5 Parts dimethyl thiodipropionate 9 " tripropylene glycol 24 " tetraethyleneglycol mono-nonylphenol ether 14 " dipropyleneglycol dibenzoate 13.5 " paraffinic mineral oil 100/100 18 " neodecanoic acid 14 " dodecylphenylsulfonic acid
6 " triethanolamine 99%
COMPOUND H
2.0 Parts thiodisuccinic acid 9 " tripropylene glycol 24 " tetraethyleneglycol mono-nonylphenol ether 14 " dipropyleneglycol dibenzoate ;~
13. " paraffinic mineral oil 100/100 18 " neodecanoic acid : 14 " dodecylphenylsulfonic acid 6.6 " triethanolamine 99%
COMPOUND I
1.0 Parts thiodipropionitrile -9 " tripropylene glycol 25 " tetraethyleneglycol mono-nonylphenol ether 14.5 " dipropyleneglycol dibenzoate 14 " paraffinic mineral oil 100/100 18 " neodecanoic acid 14 " dodecylphenylsulfonic acid 6.5 " triethanolamine 99%
. , .
.
~04580~
COMPOUND J :
1.5 Parts d.ibenzyl sulfide 9 " tripropylene glycol " tetraethyleneglycol mono-nonylphenol ether 14 " dipropyleneglycol dibenzoate 14 " paraffinic mineral oil 100/100 18 " neodecanoic acid 14 " dodecylphenylsulfonic acid 6.5 " triethanolamine 99%
Example I
Three rubber compounds were prepared in a Banbury* mixer as follows. Crude natural rubber was added and subjected to mixing. After 1 minute Compound A, B or C was added with finely divided silica (Hi-Sil*). After continuing mixing for an addi-tional 5 minutes, carbon black (F T Black), mineral oil (Circo Light* Oil), poly(tetrafluoroethylene) plasticizer (Flexone 3C*) microcrystalline wax, zinc oxide and stearic acid were added.
After mixing for an additional 3 minutes, the ram was cleaned and after 2 more minutes the batch was dumped. Benzothiazyl disul-fide (MBTS) and sulfur accelerators were then added on the millin 3-1/2 minute's mixing.
Each of the resulting mixtures was inspected visually and was found to be a good dispersion without apparent difference.
However, the dump temperatures and the Mooney Viscosities for the two compositions made with the processing aids of this invention, Compounds B and C, were lower than those of the composition employing the processing aid of my prior application (Compound A).
The data for this Example is summarized as follows:
*Denotes Trade Mark -15- .:
. .: .
.
. - , .- ,, . . , , . :.
~0458~4 .
Compound No.
Compound Component _ 2 3_ Crude Natural Rubber 100 100 100 Compound A 3.10 - -Compound B - 3.10 Compound C - - 3.10 Hi-Sil* 10.00 10.00 10.00 F. T. Black 65.00 65.00 65.00 Circo Light* Oil15.00 15.00 15.00 :~
Flexone 3C* 2.00 2.00 2.00 Microcrystalline wax 2.00 2.00 2.00 ;-Zinc oxide 5.00 5.00 5.00 Stearic acid 2.00 2.00 2.00 MBTS 0.60 0.60 0.60 Sulfur 2.50 2.50 2.50 Dump Temperature, F. 270 260 260 Mooney Viscosity~4.0-44.~ ~41.~~1.5-42.
Example II
Employing procedures similar to those described in Example I, three crude rubber compounds were prepared employing Compounds B, D or E. The formulations were as follows: .
*Denotes Trade Mark .
, ' -16- -~
: '. ..... . ..... . . ' ... '' : ' ~ ': : . ' . ,.. , : . :
`` 15~45804 Compound No.
Compound Component 1 2 3 _ Natural Rubber (crude, #3 Rib Smoked Sheet) 100 100 100 Compound B 2.0 - -Compound D - 2.0 Compound E - - 2.0 Activated zinc salt of pentachlorothiophenol (ENDOR*) 0.80 0.80 0.80 Mercaptobenzothiazole (CAPTAX*) 1.46 1.46 1.46 Benzothiazyl-disulfide (ALTAX*) .66 .66 .66 Zinc dimethyldithiocarbamate (METHYL ZYMATE*) .025 .025 .025 Tetraethylthiuram disulfide `
(ETHYL TUADS*) .150 .150 .150 zinc oxide 5.00 5.00 5.00 Stearic acid 1.00 1.00 1.00 Petrolatum 2.00 2.00 2.00 Whiting 82.50 82.50 a2.50 Sulphur 2.00 2.00 2.00 For each formulation three measurements of Mooney viscosity were made after 10 minutes of mixing and the values were averaged. The average viscosity achieved with Compound B
was 26, while average viscosities of 8.5 and 9.5 were achieved employing Compounds D and E, respectively.
It has been found that the thiodicarboxylic acid also has an effect upon the accelerators employed in the rubber compound, causing increased curing. Accordingly, the amount of accelerator can be reduced by from about 10 to about 20 to : -avoid the risk of over-curing.
*Denotes Trade Mark , 4s8Q4 Example III
Employing procedures similar to those described in Example I, eight crepe rubber compounds were prepared employing Compounds B, D, E, E, G, H, I and J. The mixing time and dump temperatures were recorded and the Mooney viscosity and the radiograph dispersion rating for each of the resulting rubber compounds were determined. The data for these experiments are summarized as follows:
:~Q45804 o Lr U~ o U~ ~ ~ CO CO ~ ~, ~
~ ~ ~ er o u~ Lf) o ~ ~ ~ oo 1- o I~ ~
o U~ U~ o U~ ~ ~ CO o U~ U~
~D O
I o U~ o Z
o In U~ O In a~ ~ a~
er O
o Ln Lr~ o U~
~1 1 . ~o ~ L~ o n ~ ~ oo CO o ~ o ~1 ~I LO N I I I I I ~ ~
O 1/~ 1~') 0 1)~ ~ ~ 00 ~ O Ot~ CO
~1 O
' ~' z ~ ` ~ o ~ :
O ~ Ul N ` ` ` ` ` ` ` ` a) h t~
c~ ~ m ~ E~ C H 1~
U rl O O ~ ~ N ~ ~
O ~ Q ~ ~ ~ ~ O
' -19- ~:~
-:
COMPOUND H
2.0 Parts thiodisuccinic acid 9 " tripropylene glycol 24 " tetraethyleneglycol mono-nonylphenol ether 14 " dipropyleneglycol dibenzoate ;~
13. " paraffinic mineral oil 100/100 18 " neodecanoic acid : 14 " dodecylphenylsulfonic acid 6.6 " triethanolamine 99%
COMPOUND I
1.0 Parts thiodipropionitrile -9 " tripropylene glycol 25 " tetraethyleneglycol mono-nonylphenol ether 14.5 " dipropyleneglycol dibenzoate 14 " paraffinic mineral oil 100/100 18 " neodecanoic acid 14 " dodecylphenylsulfonic acid 6.5 " triethanolamine 99%
. , .
.
~04580~
COMPOUND J :
1.5 Parts d.ibenzyl sulfide 9 " tripropylene glycol " tetraethyleneglycol mono-nonylphenol ether 14 " dipropyleneglycol dibenzoate 14 " paraffinic mineral oil 100/100 18 " neodecanoic acid 14 " dodecylphenylsulfonic acid 6.5 " triethanolamine 99%
Example I
Three rubber compounds were prepared in a Banbury* mixer as follows. Crude natural rubber was added and subjected to mixing. After 1 minute Compound A, B or C was added with finely divided silica (Hi-Sil*). After continuing mixing for an addi-tional 5 minutes, carbon black (F T Black), mineral oil (Circo Light* Oil), poly(tetrafluoroethylene) plasticizer (Flexone 3C*) microcrystalline wax, zinc oxide and stearic acid were added.
After mixing for an additional 3 minutes, the ram was cleaned and after 2 more minutes the batch was dumped. Benzothiazyl disul-fide (MBTS) and sulfur accelerators were then added on the millin 3-1/2 minute's mixing.
Each of the resulting mixtures was inspected visually and was found to be a good dispersion without apparent difference.
However, the dump temperatures and the Mooney Viscosities for the two compositions made with the processing aids of this invention, Compounds B and C, were lower than those of the composition employing the processing aid of my prior application (Compound A).
The data for this Example is summarized as follows:
*Denotes Trade Mark -15- .:
. .: .
.
. - , .- ,, . . , , . :.
~0458~4 .
Compound No.
Compound Component _ 2 3_ Crude Natural Rubber 100 100 100 Compound A 3.10 - -Compound B - 3.10 Compound C - - 3.10 Hi-Sil* 10.00 10.00 10.00 F. T. Black 65.00 65.00 65.00 Circo Light* Oil15.00 15.00 15.00 :~
Flexone 3C* 2.00 2.00 2.00 Microcrystalline wax 2.00 2.00 2.00 ;-Zinc oxide 5.00 5.00 5.00 Stearic acid 2.00 2.00 2.00 MBTS 0.60 0.60 0.60 Sulfur 2.50 2.50 2.50 Dump Temperature, F. 270 260 260 Mooney Viscosity~4.0-44.~ ~41.~~1.5-42.
Example II
Employing procedures similar to those described in Example I, three crude rubber compounds were prepared employing Compounds B, D or E. The formulations were as follows: .
*Denotes Trade Mark .
, ' -16- -~
: '. ..... . ..... . . ' ... '' : ' ~ ': : . ' . ,.. , : . :
`` 15~45804 Compound No.
Compound Component 1 2 3 _ Natural Rubber (crude, #3 Rib Smoked Sheet) 100 100 100 Compound B 2.0 - -Compound D - 2.0 Compound E - - 2.0 Activated zinc salt of pentachlorothiophenol (ENDOR*) 0.80 0.80 0.80 Mercaptobenzothiazole (CAPTAX*) 1.46 1.46 1.46 Benzothiazyl-disulfide (ALTAX*) .66 .66 .66 Zinc dimethyldithiocarbamate (METHYL ZYMATE*) .025 .025 .025 Tetraethylthiuram disulfide `
(ETHYL TUADS*) .150 .150 .150 zinc oxide 5.00 5.00 5.00 Stearic acid 1.00 1.00 1.00 Petrolatum 2.00 2.00 2.00 Whiting 82.50 82.50 a2.50 Sulphur 2.00 2.00 2.00 For each formulation three measurements of Mooney viscosity were made after 10 minutes of mixing and the values were averaged. The average viscosity achieved with Compound B
was 26, while average viscosities of 8.5 and 9.5 were achieved employing Compounds D and E, respectively.
It has been found that the thiodicarboxylic acid also has an effect upon the accelerators employed in the rubber compound, causing increased curing. Accordingly, the amount of accelerator can be reduced by from about 10 to about 20 to : -avoid the risk of over-curing.
*Denotes Trade Mark , 4s8Q4 Example III
Employing procedures similar to those described in Example I, eight crepe rubber compounds were prepared employing Compounds B, D, E, E, G, H, I and J. The mixing time and dump temperatures were recorded and the Mooney viscosity and the radiograph dispersion rating for each of the resulting rubber compounds were determined. The data for these experiments are summarized as follows:
:~Q45804 o Lr U~ o U~ ~ ~ CO CO ~ ~, ~
~ ~ ~ er o u~ Lf) o ~ ~ ~ oo 1- o I~ ~
o U~ U~ o U~ ~ ~ CO o U~ U~
~D O
I o U~ o Z
o In U~ O In a~ ~ a~
er O
o Ln Lr~ o U~
~1 1 . ~o ~ L~ o n ~ ~ oo CO o ~ o ~1 ~I LO N I I I I I ~ ~
O 1/~ 1~') 0 1)~ ~ ~ 00 ~ O Ot~ CO
~1 O
' ~' z ~ ` ~ o ~ :
O ~ Ul N ` ` ` ` ` ` ` ` a) h t~
c~ ~ m ~ E~ C H 1~
U rl O O ~ ~ N ~ ~
O ~ Q ~ ~ ~ ~ O
' -19- ~:~
-:
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:-
1. An improved rubber processing aid comprising:
a) an alkali or amine salt of an aromatic sulfonic acid having the general formula:
wherein X can be either hydrogen or a branched or straight chain alkyl group having from 4 to 14 carbon atoms, and n has a value of from 1 to 5; and b) a long chain fatty acid having a maximum of about 22 carbon atoms in the chain, wherein the amount by weight of said fatty acid present is at least equal to the amount by weight of said sulfonic acid salt, the improvement wherein said processing aid includes a thioether in an amount sufficient to catalyze the peptizing action of said salt, said thioether having a boiling point in excess of 130°C and the formula:
wherein Y is S or -SCHxH2xS-; x has a value of from 1 to 5; and each of R1 and R2 is alkyl, aryl, alkaryl, aralkyl and substituted alkyl, aryl, alkaryl and aralkyl, said substituents being ether oxygen, carbonyl oxygen, cyano, amine nitrogen, and amide groups, each of said R1 and R2 containing no more than 12 carbon atoms.
a) an alkali or amine salt of an aromatic sulfonic acid having the general formula:
wherein X can be either hydrogen or a branched or straight chain alkyl group having from 4 to 14 carbon atoms, and n has a value of from 1 to 5; and b) a long chain fatty acid having a maximum of about 22 carbon atoms in the chain, wherein the amount by weight of said fatty acid present is at least equal to the amount by weight of said sulfonic acid salt, the improvement wherein said processing aid includes a thioether in an amount sufficient to catalyze the peptizing action of said salt, said thioether having a boiling point in excess of 130°C and the formula:
wherein Y is S or -SCHxH2xS-; x has a value of from 1 to 5; and each of R1 and R2 is alkyl, aryl, alkaryl, aralkyl and substituted alkyl, aryl, alkaryl and aralkyl, said substituents being ether oxygen, carbonyl oxygen, cyano, amine nitrogen, and amide groups, each of said R1 and R2 containing no more than 12 carbon atoms.
2. An improved rubber processing aid according to claim 1 wherein said thioether is a thiodicarboxylic acid or an ether thereof of the formula:
wherein Y is sulfur or -SCxH2xS-; x has a value of from 1 to 5; z has a value of from 1 to 2; a has a value of from 0 to 1; and R3 is hydrogen or lower alkyl.
wherein Y is sulfur or -SCxH2xS-; x has a value of from 1 to 5; z has a value of from 1 to 2; a has a value of from 0 to 1; and R3 is hydrogen or lower alkyl.
3. An improved rubber processing aid according to claim 1 wherein Y is -S-.
4. An improved rubber processing aid according to claim 1 wherein Y is -SCH2S-.
5. An improved rubber processing aid according to claims 1 or 2 wherein said thioether is thiodiglycolic acid.
6. An improved rubber processing aid according to claims 1 or 2 wherein said thioether is thiodipropionic acid.
7. An improved rubber processing aid according to claims 1 or 2 wherein said thioether is methylene bis(thioacetic acid).
8. An improved rubber processing aid according to claims 1 or 2 wherein said thioether is dimethyl thiodi-propionate.
9. An improved rubber processing aid according to claims 1 or 2 wherein said thioether is thiodisuccinic acid.
10. An improved rubber processing aid according to claim 1 wherein said thioether is thiodipropionitrile.
11. An improved rubber processing aid according to claim 1 wherein said thioether is dibenzyl sulfide.
12. An improved rubber processing aid according to claim 1 to which are added additional materials selected from aromatic esters, compounds with alcoholic and glycolic hydroxyl groups, potassium or sodium soaps of fats or fatty acids, a fatty acid, a metal soap of zinc, magnesium, calcium or barium, and a paraffin.
13. An improved rubber processing aid according to claim 12 comprising from about 3% to about 15% of the alkali salt of said aromatic sulfonic acid, about 5% to about 25% of said long chain fatty organic acid, about 0.5% to about 1.5%
thioether, about 7% to about 15% diphenylphthalate, about 10%
to about 20% tetraethyleneglycol mono-nonylphenol ether, about 5% to about 10% tripropyleneglycol, about 5% to about 20%
potassium stearate, about 4% to about 10% zinc oleate, up to 5% cetyl alcohol, and about 15% to about 20% petrolatum.
thioether, about 7% to about 15% diphenylphthalate, about 10%
to about 20% tetraethyleneglycol mono-nonylphenol ether, about 5% to about 10% tripropyleneglycol, about 5% to about 20%
potassium stearate, about 4% to about 10% zinc oleate, up to 5% cetyl alcohol, and about 15% to about 20% petrolatum.
14. An improved rubber processing aid according to claim 12 which comprises a liquid composition having from about 20% to about 25% of the amine salt of said aromatic sulfonic acid, about 15% to about 25% of said long chain fatty organic acid, about 0.5% to about 15% thioether, about 5%
to about 15% dipropyleneglycol dibenzoate, about 20% to about 25% tetraethyleneglycol mono-nonylphenyl ether, about 5% to about 15% tripropyleneglycol, and about 10% to about 20%
mineral oil.
to about 15% dipropyleneglycol dibenzoate, about 20% to about 25% tetraethyleneglycol mono-nonylphenyl ether, about 5% to about 15% tripropyleneglycol, and about 10% to about 20%
mineral oil.
15. An improved rubber composition comprising a rubber base and rubber additives, wherein the improvement comprises a small but effective amount of a composition according to claim 1 having from about 0.5% to about 2%, based upon the weight of the rubber in the compound.
16. An improved method for compounding rubber comprising admixing rubber with an additive of the class consisting of pigments, fillers and vulcanizing agents, wherein the improvement comprises admixing a composition according to claim 1 with rubber at the beginning of the mixing cycle prior to mastication of the rubber and no later than the time when said rubber is admixed with said additive.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41197573A | 1973-11-01 | 1973-11-01 | |
| US42168973A | 1973-12-04 | 1973-12-04 | |
| US430566A US3882062A (en) | 1973-12-04 | 1974-01-03 | Novel processing aids for natural and synthetic rubber compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1045804A true CA1045804A (en) | 1979-01-09 |
Family
ID=27410924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA212,200A Expired CA1045804A (en) | 1973-11-01 | 1974-10-24 | Processing aids for natural and synthetic rubber compounds |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS521930B2 (en) |
| CA (1) | CA1045804A (en) |
| FR (1) | FR2249921B1 (en) |
| GB (1) | GB1477371A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SK285498B6 (en) * | 2002-05-20 | 2007-03-01 | Matador Holding, A. S. | Vulcanizing agent and process for production thereof |
| BRPI0622084A2 (en) * | 2006-10-30 | 2014-06-17 | Pirelli | VEHICLE WHEEL TIRE, ELASTOMERIC ARTICLE, AND RETICULABLE ELASTOMERIC COMPOSITION |
-
1974
- 1974-10-24 CA CA212,200A patent/CA1045804A/en not_active Expired
- 1974-10-31 FR FR7436478A patent/FR2249921B1/fr not_active Expired
- 1974-10-31 GB GB4713874A patent/GB1477371A/en not_active Expired
- 1974-11-01 JP JP12559074A patent/JPS521930B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2451567B2 (en) | 1976-02-26 |
| JPS521930B2 (en) | 1977-01-19 |
| DE2451567A1 (en) | 1975-05-07 |
| GB1477371A (en) | 1977-06-22 |
| FR2249921B1 (en) | 1976-10-22 |
| FR2249921A1 (en) | 1975-05-30 |
| JPS5075235A (en) | 1975-06-20 |
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