Patent Application
20090215966
This invention relates to the field of sulfur vulcanization of rubber, especially to methods, compositions, and cured filled rubber articles wherein sulfur is the primary curing agent. In-situ formed complexes of zinc stearate from zinc oxide and stearic acid are known to improve the kinetics of unaccelerated sulfur vulcanization, and are particularly effective when used with thiazole accelerators. It is believed that soluble zinc can form complexes with accelerator fragments that, when reacted with sulfur, may form the active sulfurating agents.
Metal alcoholates and carboxylates have been shown to provide similar cure characteristics as to in-situ formed zinc stearate, with slight improvements in processing and filler dispersion, for example metal salts of synthetic and naturally occurring fatty acids such as zinc tallate, tallowate, laurate, stearate, naphthenates, and resonates. However, such metal salts provide adequate but not outstanding activating properties, resulting in modest improvements over the rate and state of cure realized in the absence of soluble zinc salts. In addition, such previously used salts typically provide improvements up to a certain loading in the compound formulation and beyond that amount provide no additional benefits.
There is a need in the art for an improved activator which would provide more efficient utilization of sulfur by providing a higher crosslink density and lower sulfur rank of the crosslinks, with the objective of reduced reversion, increased resilience, higher modulus, higher tensile strength, lower hysteresis, and increased scorch safety.
There have been several different prior art proposals concerning the use of unsaturated zinc salts or zinc salts of stearic acid or other saturated organic acids of 8 or more carbon atoms to improve the efficiency of accelerated sulfur vulcanization.
The use of unsaturated zinc salts of organic acids in sulfur curable natural rubber compounding is disclosed in U.S. Pat. Nos. 4,495,326; 3,823,122 4,192,790; 5,126,501; 5,962,593; 5,464,899: 5,494,091; and 5,769,980.
In one aspect the invention comprises a sulfur vulcanizable rubber composition comprising rubber, sulfur, at least one metal salt of a saturated organic acid having 1 to 7 carbon atoms. The vulcanizates derived thereof are another aspect of the invention. When the metal is polyvalent, as is the case with zinc, calcium, and magnesium, for example, the metal can be a mono-substituted basic adjuvant or a di-substituted salt. The metal can alternatively be monovalent.
In another aspect, the invention comprises a method of vulcanizing rubber comprising adding sulfur and, as an activator, at least one metal salt of a saturated organic acid having less than 1 to 7 carbon atoms.
A further aspect of the invention is an article prepared by curing the composition of the invention, the composition comprising a rubber, sulfur, and one or more metal salts of C1-C7 saturated organic acids.
The metal salts of C1-C7 saturated organic acids have activities in accelerated sulfur vulcanizations similar to those of corresponding metal salts of unsaturated organic acids, for example acrylic and methacrylic acids, but have improved cure characteristics and result in improved properties which were unexpected.
Among the improved properties, the metal salts of C1-C7 saturated organic acids provide higher crosslink density and improved state-of cure when compared to traditional zinc oxide/stearic acid systems or other commercially available materials such as zinc 2-ethylhexanoate and zinc stearate. In addition to the above benefits, the basic mono-substituted adjuvant metal salt also provides an exceptional level of scorch safety.
The uncrosslinked rubbers which may be used are natural rubber, synthetic cis-1,4-polyisoprene, polybutadiene, copolymers of isoprene and butadiene, copolymers of acrylonitrile and butadiene, copolymers of acrylonitrile and isoprene, terpolymers of styrene, butadiene and isoprene, copolymers of styrene and butadiene and blends thereof. The above synthetic rubbers may be emulsion polymerized or solution polymerized. The preferred rubbers are natural rubber, synthetic cis-1,4-polyisoprene, polybutadiene, copolymers of isoprene and butadiene, terpolymers of styrene, butadiene and isoprene, copolymers of styrene and butadiene and mixtures thereof.
The zinc salts of C1-C7 saturated acids are added to the sulfur-vulcanizable rubber. Therefore, one needs to have a sulfur-vulcanizing agent because the compound does not contain any peroxide curatives. Examples of suitable sulfur vulcanizing agents include elemental sulfur (free sulfur) or a sulfur-donating vulcanizing agent, for example, an amine disulfide, polymeric polysulfide or sulfur olefin adducts or mixtures thereof. Preferably, the sulfur vulcanizing agent is elemental sulfur. The amount of sulfur vulcanizing agent will vary depending on the components of the rubber stock and the particular type of sulfur vulcanizing agent that is used. The sulfur vulcanizing agent is generally present in an amount ranging from about 0.5 to about 6.0 phr. Preferably, the sulfur vulcanizing agent is present in an amount ranging from about 1.0 phr to about 4.0 phr.
Conventional rubber additives may be incorporated in the rubber stock of the present invention. The presence of these conventional rubber additives is not considered to be an aspect of the present invention. The additives commonly used in rubber stocks include fillers, plasticizers, waxes, processing oils, peptizers, retarders, antiozonants, antioxidants and the like. The total amount of filler that may be used may range from about 30 to about 150 phr, with a range of from about 45 to about 100 phr being preferred. Fillers include clays, calcium carbonate, calcium silicate, titanium dioxide, silica, and carbon black.
Plasticizers can be used in the compositions, preferably in amounts ranging from about 2 to about 50 phr with a range of about 5 to about 30 phr being preferred. The amount of plasticizer used will depend upon the softening effect desired. Examples of suitable plasticizers include aromatic extract oils, petroleum softeners including asphaltenes, pentachlorophenol, saturated and unsaturated hydrocarbons and nitrogen bases, coal tar products, cumarone-indene resins and esters such as dibutylphthalate and tricresol phosphate.
Common waxes such as paraffinic waxes and microcrystalline blends can be used in the rubber compositions, preferably in amounts ranging from about 0.5 to 5 phr.
Typical amounts of processing oils, when used, comprise from about 1 to 70 phr. Such processing oils can include, for example, aromatic, naphthenic and/or paraffinic processing oils.
Conventional accelerator-activators can be used in combination with the metal salts of saturated C1-C7 acids. For example, metal oxides such as zinc oxide and magnesium oxide which are used in conjunction with acidic materials such as for example, stearic acid, oleic acid, murastic acid, and the like, can be used to form such salts in-situ. The amount of the metal oxide to make such conventional salts in-situ may range from about 0 to about 10 phr with a range of from about 0 to about 5 phr being preferred. The amount of fatty acid which may be used may range from about 0 phr to about 5.0 phr with a range of from about 0 phr to about 3 phr being preferred. The preferred metal oxide is zinc oxide.
Accelerators are used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate. In one embodiment, a single accelerator system may be used, i.e., primary accelerator. The primary accelerator(s) may be used in total amounts ranging from about 0.5 to about 4, preferably about 0.8 to about 2.0, phr. In another embodiment, combinations of a primary and a secondary accelerator might be used with the secondary accelerator being used in a smaller, equal or greater amount to the primary accelerator. Combinations of these accelerators might be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by use of either accelerator alone. In addition, delayed action accelerators may be used which are not affected by normal processing temperatures but produce a satisfactory cure at ordinary vulcanization temperatures. Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a disulfide, guanidine, dithiocarbamate or thiuram compound.
Fillers may be included in the methods and curable compositions of the invention, preferably in finely divided form. Suitable fillers include, but are not limited to, the following: silica and silicates, thermal blacks (i.e., furnace, channel or lamp carbon black), clays, kaolin, diatomaceous earth, zinc oxide, cork, titania, cotton floc, cellulose floc, leather fiber, elastic fiber, plastic flour, leather flour, fibrous fillers such as glass and synthetic fibers, metal oxides and carbonates and talc. The amount of filler is dictated by its type and the intended end use of the composition and, in general, may be between 0 and 150 parts by weight of the elastomer and, more preferably, between 50 and 100 parts by weight.
Conventionally, antioxidants and sometimes antiozonants, hereinafter referred to as antidegradants, are added to rubber stocks. Representative antidegradants include monophenols, bisphenols, thiobisphenols, polyphenols, hydroquinone derivatives, phosphites, thioesters, naphthyl amines, diphenyl-p-phenylenediamines, diphenylamines and other diaryl amine derivatives, para-phenylenediamines, quinolines and mixtures thereof. Specific examples of such antidegradants are disclosed in The Vanderbilt Rubber Handbook (1990), pages 282-286. Antidegradants are generally used in amounts from about 0.25 to about 5.0 phr with a range of from about 1.0 to about 3.0 phr being preferred.
The sulfur vulcanizable rubber compound is sulfur-cured at a rubber temperature ranging from about 125° C. to 180° C. Preferably, the temperature ranges from about 135° C. to 160° C. The rubber compound is heated for a time sufficient to sulfur-vulcanize the rubber which may vary depending on the level of curatives and temperature selected. Generally speaking, the time may range from 3 to 60 minutes.
The mixing of the rubber compound can be accomplished by conventional methods. For example, the ingredients can be mixed in two or more stages, namely one non-productive stages followed by a productive mix stage. The final curatives are typically mixed in the final stage which is conventionally called the “productive” mix stage in which the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) of the preceding non-productive mix stage(s).
The above-described zinc salts of C1-C7 saturated acids may be added in a nonproductive stage or productive stage. Preferably, such zinc salt is added in a productive stage.
The method of mixing the various components of the rubber containing the zinc salts may be in a conventional manner. Examples of such methods include the use of Banburys, mills, extruders and the like to intimately disperse the zinc salt throughout the rubber and improve its effectiveness for subsequent reaction.
The sulfur-vulcanized rubber composition of this invention can be used for various purposes. The elastomeric compositions of the invention can be used in applications including, but not limited to, tire components, engineered rubber products such as belts and hoses, rubber gaskets and rings, engine mounts and vibration isolation mounts, rubber rollers, and rubber articles for other automotive and industrial applications.
Preferred amounts of metal salt of saturated organic acid having 1 to 7 carbon atoms are 0.5-40 parts per 100 parts by weight rubber.
The metal salt of C1-C7 saturated organic acid can be mono substituted or disubstituted neutral salts.
Examples of C1-C7 saturated organic acids having 1 to carbon atoms are formic acid, acetic acid, propionic acid, butanoic acid, 2-methyl propionic acid, pentanoic acid, 2-methyl butanoic acid, 2,2-dimethyl propionic acid, hexanoic acid, 2-ethyl butyric acid, 3,3-dimethyl butyric acid, 4-methyl butyric acid, 4-methyl pentanoic acid, cyclopentanecarboxylic acid, heptanoic acid, 2,2-dimethyl valeric acid, 2-methyl hexanoic acid, 4-methyl hexanoic acid, cyclohexanecarboxylic acid, cyclopentylacetic acid, structural isomers of the above acids. The preferred saturated acids have 3-6 carbon atoms. Isobutyric acid, having 4 carbon atoms, is especially preferred.
The following examples, in which all parts and percentages are by weight unless otherwise indicated, are presented to illustrate a few embodiments of the invention and comparisons with other compositions.
The compounded stock was prepared by mixing in a 450 cc Brabender prep mixer with the non-productive stage starting conditions of 100° C. and 100 rpm mixing for 4 minutes and the productive stage at 60° C., 60 rpm mixing for 2 minutes. Compounded stock was milled between stages and prior to testing. Table 1 outlines the basic formulation used for all subsequent Examples.
The elastomer used was synthetic polyisoprene (Natsyn® 2200, supplied by The Goodyear Tire and Rubber Company). The carbon black used was reinforcing N330-type (Cabot Vulcan® 1345), and the paraffinic process oil was Sunoco Sunpar® 2280 brand. Stearic acid was supplied by Aldrich. The antioxidant used was Uniroyal Chemical Naugard® Q. Flexsys Santocure® TBBS and rubbermaker's sulfur was used in addition to the zinc salts listed below as the curing agents.
The zinc oxide (ZnO), zinc dimethacrylate (ZDMA), zinc monomethacrylate (ZMMA), zinc 2-ethylhexanoate (ZEH) and zinc undecylenate (ZU) were commercially available grades. Zinc diisobutyrate (ZDIB), zinc monoisobutyrate (ZMIB), zinc dibenzoate (ZDB), and zinc dihexanoate (ZDH) were synthesized by reacting zinc oxide with the respective acids. In the case of the neutral salts, greater than two molar equivalents of organic acid were used. For the basic salts (mono functional), molar stoichiometry was used.
A TechPro rheoTech Oscillating Die Rheometer (ODR) was used to determine extent of cure and cure kinetics according to ASTM D 2084. The cure temperature used was 160° C., using an arc deflection of 3°. Physical testing was performed on samples cured in a press to optical cure times (t90). Scorch safety was characterized by the time to a two point rise in torque (ts2). Tensile data was acquired on a Thwing-Albert Materials Tester following ASTM D 412. Compression set was evaluated after heating at 100° C. for 22 hours (ASTM D 395).
Results are normalized in all Examples to the control formulation, which contains 5 phr of zinc oxide. Such a loading is equivalent to 0.063 mmols/100 grams rubber. The molar amounts of the zinc salts used in Examples 1-11 are set forth in Table 1.
Commercially available unsaturated zinc salts of methacrylic acid were compared to zinc stearate, prepared in-situ from stearic acid and zinc oxide in Examples 1-3. Table 2 provides the relevant cure kinetics and physical property testing data. Example 1 is the control (0.063 mmol ZnO/100 g rubber), while Examples 2 and 3 provide data for elevated levels of ZnO. Examples 4-7 contain zinc dimethacrylate (Sartomer SR708) and Examples 8-11 contain zinc monomethacrylate (Sartomer SR709) in increasing loadings.
At molar equivalent loading in the compound, both ZDMA and ZMMA provide significantly higher delta torque (indicative of high crosslink density) and modulus compared to the zinc stearate control (Ex. 1). Compression set is lower when employing ZDMA. In addition, the mono-basic adjuvant (ZMMA) provides significant improvements in scorch safety. It is noted that greater than equivalent loadings of zinc stearate does not provide the same benefits.
The fully saturated forms of ZDMA and ZMMA were prepared using isobutyric acid. Table 3 provides the cure kinetics and physical testing results when employing zinc diisobutyric acid (Examples 14-17) and zinc monoisobutyric acid (Examples 18-21) as the zinc species in the formulation (Table 1). Example 12 is used as the control (0.063 mmol ZnO/100 g rubber). Table 3 provides the results of cure kinetics and cured physical properties of the compounds derived using these materials as the zinc source.
Despite being completely saturated, both ZDIB and ZMIB provide similar improvements over the control formulation as ZDMA and ZMMA. In was unexpected that at molar equivalent loading in the compound, both ZDIB and ZMIB provide significantly higher delta torque (indicative of high crosslink density) and modulus compared to the control and the ZDMA and ZMMA. Compression set is lower when employing these saturated zinc salts, ZDIB and ZMIB. The modulus values and tensile strength of the vulcanizates prepared using the saturated zinc salts are higher than the unsaturated analogs.
Two alternative zinc salts were compared. Zinc 2-ethylhexanoate (Examples 24-27) is a fully saturated compound, while zinc undecylenate is unsaturated (Examples 28-31). Example 22 is used as the control (0.063 mmol ZnO/100 g rubber). Table 4 provides the results of cure kinetics and cured physical properties of the compounds derived using the above materials as zinc sources.
The zinc salts of the larger organic acids do not provide the same level of improvement as the zinc salts of diisobutyric acid. The addition of ZEH or ZU results in generally lower delta torque values and decreased modulus and tensile strength. These zinc salts differ from those tested in Examples 1-21 by virtue of having larger, sterically hindering organic groups.
Again, two alternate zinc salts were evaluated. Zinc dibenzoate (Examples 34-37) contains an unsaturated, aromatic organic structure. Zinc hexanoate (Examples 38-41) is a saturated, less sterically hindered form compared to zinc 2-ethylhexanoate. Table 5 compares the cure kinetics and cured physical properties of the compounds derived using these materials as the zinc source.
ZDB provides no advantage versus the control compound (Example 32) in terms of cure efficiency or tensile properties. Compression set are slightly improved. At equivalent molar loadings, ZDH provides an improvement over ZnO in both delta torque (crosslink density). Compression set is also significantly reduced. Tensile properties of ZDH compounds approach the control values at equal molar loading of zinc.
While the invention has been described and exemplified in detail, various alternative embodiments and improvements should become apparent to those skilled in this art without departing from the spirit and scope of the invention.
Benefit of provisional application Ser. No. 60/679,534, filed May 10, 2005, is claimed.
