RUBBER COMPOSITIONS COMPRISING MIXTURES OF RUBBER AND SYNTHETIC POLYMERS

Abstract: Rubber compositions comprising a minor amount of natural rubber and a significant proportion of at least one synthetic triblock rubbery polymer and optionally a second synthetic rubbery polymer exhibit improved green strength and are useful in the fabrication of composite rubber articles, such as tires, hoses, belts, electrical products, toys, rollers, and the like. Specific examples of useful synthetic polymers include SBS triblock polymers and SBR copolymers.

Description: RUBBER COMPOSITIONS COMPRISING MIXTURES OF RUBBER AND SYNTHETIC POLYMERS Field of the Invention The invention relates to rubber compositions containing mixtures of synthetic polymer and natural rubber. More particularly, it relates to compositions containing a minor proportion of natural rubber (NR) in combination with a triblock synthetic rubbery polymer and, optionally, another synthetic rubbery polymer. It also relates to components for building rubber articles, such as tires, comprising these compositions as well as articles built from them. Background of the Invention Components used to build rubber articles such as tires must have sufficient green strength to prevent tearing and excessive sagging during building operations and to aid in dimensional stability of the uncured article. In addition, such green strength helps prevent tire cord movement during subsequent processing steps such as molding and curing. To satisfy these requirements, components such as tire body plies usually contain greater than 50% NR. Synthetic rubbery polymers such as random styrene butadiene rubbers (SBR) are generally deficient in these green strength properties and cannot be used without preliminary special treatment, such as irradiation and cement coatings, in article building operations. While such techniques are usually satisfactory, in certain instances it would be advantageous to avoid them and at the same time reduce the amount of NR required to provide satisfactory building component properties. In other words, it would be desirable to reduce or eliminate the NR content of such components and substitute therefor synthetic materials such as SBR to obtain components, such as tire body plies, having low NR content and, at the same time, high green strength properties comparable to those of plies currently in commercial use (which contain large amounts, such as up to 100%, NR). In addition, such synthetic rubber components should exhibit processing and cured physical properties required for their use. Prior Art SBR and triblock SBS (styrene-butadiene-styrene) synthetic rubbery polymers, as well as various blends of them with each other and with other types of polymers and/or NR, are known. See, for example, U.S. Patent Nos. 3,424,649 and 3,793,283 which disclose blends of SBS with certain polyolefin elastomers other than SBR. U.S. Patent No. 3,299,174 relates to blends of polypropylene with SBS. Other U.S. Patents disclosing similar blends include Nos. 3,572,721, 3,689,595, 3,830,767 and 3,850,474. U.S. Patents Nos. 4,343,918 and 4,340,684 both relate to thermoplastic elastomers comprising blends of crystalline 1 - olefin polymers, SBR and highly saturated elastomers. U.S. Patent No. 3,798,190 discloses compositions of high green strength comprising blends of SBR and hydrogenated random styrene-butadiene copolymers and, optionally, NR. U.S. Patent No. 4,254,013 discloses the combination of unsaturated acid monomers in polymers with NR and synthetic cis-1,4-polyisoprene rubber to allow the formation of ionic crosslinks. Even in these mixtures high (50-90%) proportions of NR were found necessary to give satisfactory green strength. Other techniques for improving the green strength of rubber components made from substantial amounts of synthetic rubber are known, such as irradiation with ionizing irradation and the application of cement coatings to enhance building tack. The preparation of SBR-type elastomers with improved green strengths by the incorporation of N-(alkoxy methyl) acrylamide monomers is described in commonly assigned U.S. Ser. No. 132,736. The above-described art, however, when taken individually or in any combination does not render obvious, much less anticipate, the present invention. Blends of synthetic rubbery polymers such as SBR and SBS, with low amounts of NR, having sufficient green strength, and cured performance properties to allow them to be used in high performance rubber articles such as tires, have not heretofore been available. Therefore, it is an object of this invention to provide rubber compositions made from low proportions of NR and high amounts of synthetic rubbers, such as SBR and SBS, having sufficient green strength to allow their use in fabricating rubber articles without the required intervention of irradiation and cement coating techniques. Other aspects of the invention will become apparent from careful study of this specification. Summary of the Invention According to the present invention, there is provided a rubber composition comprised of a minor proportion of NR in admixture with a triblock first synthetic rubbery polymer comprising vinyl aromatic and conjugated diene blocks wherein the vinyl aromatic regions constitute the end blocks. Such compositions can also contain significant proportions of a second synthetic rubbery polymer such as SBR. Also within the scope of the invention, are methods for improving the green strength of NR-containing compositions which comprises admixing therein a triblock first synthetic rubbery polymer and, optionally, a second synthetic rubbery polymer as described above. In addition, the invention includes tire body stocks comprised of a minor amount of NR in admixture with a triblock first synthetic rubber, optionally, a second synthetic rubber, and other ingredients conventionally incorporated in such stocks. Tire building components, such as plies, composed of such inventive stocks and optionally additional elements such as reinforcing cords, fabrics, webs, sheets, wires, etc., as well as rubber articles made of such stocks and components (such as tires, hoses, air springs, bumpers, engine mounts, etc.) are also within the scope of the invention. petails of the Invention and Preferred Embodiments The rubber compositions of the present invention contain a minor proportion of NR. Typically, the NR is a commercially available natural rubber, usually, Heava which is comprised principally of isoprene polymer. NR obtained from other natural sources, such as the guayule plant, as well as synthetic "natural" rubber, comprised of Cis-l, 4-polyisoprene can also be used in place of or in combination with the commercial available Heava. Typically, the inventive compositions contain about 1-49 percent by weight NR, usually about 20-40 weight percent NR (all percentages, parts and amounts set forth in this specification and the appended claims are by weight unless specifically indicated to the contrary). Typically, commercial grades of NR are used in the invention, particularly those that have been found useful in fabrication of tires and other built rubber articles, but other grades of NR can be used if convenience, economy or availability so indicate. The invention is not dependent on the use of a particular grade or source of NR. The triblock first synthetic rubbery polymers used in the compositions of this invention are typically polymers comprised of vinyl aromatic and conjugated diene blocks, wherein the vinyl aromatic region constitutes the end or outer blocks. Such triblock synthetic rubbers are prepared from a corresponding vinyl aromatic and conjugated diene monomers by techniques known to the art as indicated by the patents noted above. Generally, the first synthetic rubber is derived from vinyl aromatics such as styrene, alpha-methyl styrene, vinyl toluene and the like and a conjugated diene of 4 to about 20 carbon atoms such as butadiene, isoprene, 1, 3-pentadiene, chloroprene and the like. A readily available useful triblock first synthetic rubber is the above-mentioned styrene-butadiene-styrene (SBS) synthetic rubber. Such triblock rubbers are commercially available from, for example, the Shell Chemical Company under the trade name Kraton and from the Phillips Chemical Company under the trade name Solprene. Useful triblock synthetic rubbers have total average molecular weights of about 35,000-100,000 (Mn) and the respective blocks have average molecular weights of about 7000-20,000 and 20,000-60,000 (as measured by vapor pressure osmometry). The triblock first synthetic polymer helps provide high green strength to the inventive compositions of which it is a component as well as processability, as reflected by softness and low viscosity, particularly when warm, and high toughness when cool. Also blends containing it exhibit less shrinkage after calendering or extrusion. As an additional benefit, SBS containing compositions are also often found to be self-reinforcing and self-crosslinking. Such compositions do not require high loadings of carbon black for satisfactory reinforcement. The compositions of the present invention can optionally contain, in addition to NR and the first synthetic rubber, up to about 70% of a second synthetic rubbery polymer. Although many types of known synthetic rubbery polymer can be used in these compositions, a readily available and highly satisfactory second synthetic polymer is that prepared from vinyl aromatic and conjugated diene monomers. These monomers can each, or both, be the same, similar to or unrelated to the monomers from which the first synthetic polymer is prepared. Typical monomers include the aforementioned stryene, alpha methyl styrene, vinyl toluene, butadiene, isopropene, chloroprene, etc. Specific typical examples of the second synthetic polymers are random copolymers of styrene and butadiene (SBR) containing about 5-30 percent bound styrene, about 95-70 percent bound butadiene and having number average molecular weights of about 5000-500,000, typically 8000300,000. Such rubbers can be used in the compositions of this invention in amounts constituting about 15-35, say about 20-30 percent of the composition. Other synthetic rubbery polymers can be advantageously used as the second synthetic rubbery polymer, such as butyl, neoprene, ethylene-propylene, ethylene-propylene-diene monomer and nitrile rubbers. Mixtures of two or more rubbers of the same or different types can be used as the second rubbery polymer. Thus, it can be seen that typical compositions of the present invention comprise about 20-40 percent NR, about 10-50 percent triblock SBS rubber and about 15-35 percent SBR. As noted, conventional rubber compounding ingredients, fillers, preservatives, and adjuvants can be included in the compositions as desired to give the properties required for a particular end use. Conventional methods, techniques and equipment are used in blending and processing the compositions of the present invention and the results desired and obtained are not generally dependent on the particular methods used. Such methods include use of mixing and compounding equipment such as Brabender and Banbury mixers. The compositions can be further processed by calendering, hot and cold pressing and other procedures conventionally used in the art. Although the compositions of this invention generally exhibit sufficient building tack to be useful in many applications, it may, in certain instances, be advantageous to increase their tack to higher levels through the use of known tackifying resins in the stock. Many types of such agents are known to the art, such as aliphatic the phnol fcrmaldchyio tackifying agents sold commercially under the namePpiccopale. Proportions and techniques for using such tackifying agents are also known to the art. Typical stocks embodying the compositions of this invention which are useful for fabricating body plies to be used in construction of radial tires comprise: EMI8.1 TABLE A Component Parts NR 1-49 SBR 0-70 SBS 10-50 Carbon Black 50* Zinc Oxide 7 5* Stearic Acid 3.4* Aliphatic and Aromatic Resins 5-20** Processing Oil (e.g., extenders) Curatives 2-5 *Typical; amounts may be adjusted to provide the desired properties. **Conventional optional agents used as processing aids, plasticizers, softeners and tackifiers. Protective agents such as conventional awti-oxidants and - anti-ozonants can also be used in typical amounts if desired. SPECIFIC EMBODIMENTS OF THE INVENTION Five rubber compositions were prepared in a Brabender mixer using conventional techniques containing the components and proportions shown in Table I. EMI9.1 TABLE I Component/Blend: A B C D d (parts) NR 30 30 30 40 60 SBS a 10 20 30 10 d SBR b 60 50 40 50 20 HAF Carbon Black 30 30 30 30 30 FEF Carbon Black 20 20 20 20 20 Zinc Oxide 7.5 7.5 7.5 7.5 7.5 Stearic Acid 3.4 3.4 3.4 3.4 3.4 Tacki fi er c 5.2 5.2 5.2 5.2 5.2 Process Oil 5 5.1 5.1 5.1 1.1 a - A SBS Triblock copolymer (30%) styrene) sold by shell under the tradename Kraeton 1102 b - A cold emulsion SBR (23.5%) bound styrene) sold by Firestone under the designation S 1502. c - An aliphatic petroleum resin sold under the tradename Piccopale 100. d - Control sample, not of invention, containing 24 parts high green strength SBR (HX 567) in place of SBS (that is, a total of 44 parts SBR). The green strengths of these blends were measured in a strip stress-strain test. Tests were run after milling the samples with no pressing and with hot pressing. The results are shown in Tables II and III, respectively. Test conditions were 260C, cross head speed = 0.8467cm/s (20.0 in/min), sample width = 1.270 cm (0.500 in), intitial sample length = 2.54 cm (1.00 in). Blends A-D are according to the invention while Blend E, containing high green strength SBR in place of SBS is a control example included for comparative purposes. TABLE II (no pressing) Stress, MPa Elongation Blend 100 5 300% 500% Break that at Break, % A 0.412 0.389 0.414 0.485 1295 B 0.489 0.523 0.589 0.736 1194 C 0.628 0.726 0.856 1.271 1334 D 0.416 0.428 0.496 0.787 1604 E 0.351 0.402 0.530 1.065 1296 TABLE III (hot pressed) Stress, MPa Elongation Blend 100% 300% 500X Break at Break, X A 0.434 0.328 0.214 0.201 507 B 0.530 0.482 0.454 0,329 830 C 0.649 0.662 0.685 0.631 1234 D 0.427 0.365 0.353 0.300 1852 E 0.348 0.340 0.388 0.574 1669 The results presented in Tables II and III, particularly those of Blends A-D when compared to those of Blend E, demonstrate that rubber compositions embodying the invention exhibit green strengths that are satisfactory for many purposes. Thus, it is clear that there are many advantages in the use of the compositions of the present invention. Numerous other advantages will be apparent to those with skill in the art. while the present invention has been described above in terms of specific embodiments, certain modifications and equivalents will be apparent to those with skill in the art and are intended to be included within the scope of the present invention which is to be limited only by the appended claims.

Claims: What is claimed is: 1. A rubber composition comprising a minor portion of NR in admixture with a triblock first synthetic rubbery polymer comprising vinyl aromatic and conjugated diene blocks wherein the vinyl aromatic region constitutes the end blocks. 2. The composition of Claim 1 wherein the portion of NR is about 1-49 percent. 3. The composition of Claim 2 wherein there is also present up to about 70 percent of. second synthetic rubbery polymer. 4. The composition of Claim 3 wherein the vinyl aromatic in the first synthetic polymer is styrene, alpha methyl styrene, vinyl toluene and mixtures thereof and the conjugated diene is butadiene, isopropene, chloroprene and mixtures thereof. 5. The composition of Claim 4 wherein the second synthetic polymer is a random copolymer and a vinyl aromatic monomer and a conjugated diene monomer. 6. The composition of Claim 5 wherein the triblock first synthetic polymer is SBS. 7. The composition of Claim 6 wherein the second synthetic polymer is SBR. 8. The composition of Claim 7 wherein a tackifying resin is present. 9. The composition of Claim 7 comprising about 20-40 percent NR, about 10-50 percent triblock SBS rubber, and about 15-35 percent SBR. 10. A method of improving the green strength of NR-containing compositions which comprises mixing therein a triblock first synthetic rubbery polymer comprising vinyl aromatic and conjugated diene blocks wherein the vinyl aromatic region constitutes the end blocks. 11. The method of Claim 10 wherein the first synthetic polymer comprises about 10-50 percent of the composition. 12. The method of Claim 11 wherein the composition also contains about 15-35 percent of a second synthetic rubbery polymer and the percent of NR is les than about 50 percent. 13. The method of Claim 12 wherein the first synthetic polymer is SBS and the second synthetic polymer is SBR. 14. A tire body stock comprised of a minor proportion of NR in admixture with a triblock first synthetic rubbery polymer and a second synthetic rubbery polymer, said first and second synthetic polymers made from vinyl aromatic and conjugated diene monomers wherein the vinyl aromatic regions of the first synthetic polymer constitutes its end blocks. 15. The tire body stock of Claim 14 wherein there is about 20-40 percent NR, about 10-50 percent first synthetic polymer and about 10-50 percent second synthetic polymer. 16. The tire body stock of Claim 15 wherein the vinyl aromatic monomer is styrene and the conjugated diene monomer is butadiene. 17. A radial tire having a body made of the stock of Claim 15.

Inventors: HAMED, GARY R.
Applicants: THE FIRESTONE TIRE & RUBBER COMPANY
Application year: 1985
Main classification: C08L7
IPC codes: C08L33, C08L53, C08L7, C08L101, C08L51, C08L77, C08L23, B60C1, C08L9, C08L21