Preparation of hydrocarbon resins using zirconium tetrachloride

Abstract

Styrene is homopolymerized or copolymerized with alpha methyl styrene, preferably in the presence of limonene, with or without t-butyl styrene, using zirconium tetrachloride as the catalyst. The light colored resins formed are useful as .[.drying.]. .Iadd.dry .Iaddend.cleaning sizing agents and in hot melt adhesives.

What is claimed is: .[. 
     
       1.  A process of preparing a light colored aromatic vinyl resin comprising polymerizing a member of the group consisting of (1) as the sole monomer styrene, alpha-methyl styrene, alpha-pinene, beta-pinene, di-pentene limonene or p-t-butyl stryene; (2) a mixture of (a) styrene and (b) alpha-methyl styrene; or (3) a mixture of (a) styrene, (b) alpha-methyl styrene and (c) as a third monomer a member of the group consisting of alpha-pinene, beta-pinene, dipentene limonene p-t-butyl styrene and vinyl toluene; or (4) a mixture of (a) styrene, (b) alpha-methyl styrene, (c) polymerizable terpene selected from the group consisting of alpha-pinene, beta-pinene, dipentene and limonene and (d) p-t-butyl styrene, in the presence of zirconium tetrachloride as a catalyst..]. .[.2. The product prepared by the process of claim 1..]. .[.3. A process according to claim 1 wherein the catalyst consists essentially of zirconium tetrachloride in 
     
     
        an amount of 0.1 to 8% of the total monomers..]. 4. A process according to claim .[.3.]. .Iadd.35 .Iaddend.wherein there is employed 10 to 40% 
     
     
        styrene and 90 to 60% alpha-methyl styrene. 5. The product prepared by the 
     
     
        process of claim 4. 6. A process according to claim 4 wherein there is 
     
     
        employed 25% styrene and 75% alpha-methyl styrene. 7. The product prepared 
     
     
        by the process of claim 6. 8. A process according to claim 6 wherein the zirconium tetrachloride is used in an amount of 2% based on the total 
     
     
        monomers. 9. A process according to claim 3 wherein there is employed 5 to 50% styrene, 5 to 80% alpha-methyl styrene and 5 to 50% of said third monomer, .[.alpha-pinene, beta-pinene, dipentene,.]. limonene, p-t-butyl 
     
     
        styrene or vinyl toluene. 10. The product prepared by the process of claim 9. .[.11. A process according to claim 9 wherein said third monomer is 
     
     
        alpha-pinene, beta-pinene, dipentene or limonene..]. 12. A process according to claim .[.11.]. .Iadd.9 .Iaddend.wherein said third monomer is 
     
     
        d-limonene. 13. The product prepared by the process of claim 12. 14. A process according to claim 12 wherein there is employed 331/3 to 38% d-limonene, 331/3 to 38 alpha-methyl styrene and 331/3 to 24% styrene. 
     
     
            The product prepared by the process of claim 14. 16. A process according to claim 14 wherein there is employed 2% of zirconium 
     
     
        tetrachloride based on the total monomers. 17. A process according to claim 14 wherein there is employed equal parts of d-limonene, alpha-methyl 
     
     
        styrene and styrene. 18. The product prepared by the process of claim 17. 
     
     
         9. A process according to claim 17 wherein there is employed 2% of 
     
     
        zirconium tetrachloride based on the total monomers. 20. A process according to claim .[.3.]. .Iadd.35 .Iaddend.carried out in a hydrocarbon 
     
     
        solvent. 21. A process according to claim 20 wherein the monomers are dissolved in the solvent and then the zirconium tetrachloride is added. 
     
     
            A process according to claim .[.3.]. .Iadd.35 .Iaddend.wherein there is polymerized a mixture of (a) styrene, (b) alpha-methyl styrene, .[.(c) a polymerizable terpene selected from the group consisting of alpha-pinene, beta-pinene, dipentene and.]. limonene, and (d) p-t-butyl 
     
     
        styrene. 23. The product prepared by the process of claim 22. 24. A process according to claim .[.3.]. .Iadd.35 .Iaddend.wherein there is 
     
     
        polymerized styrene or alpha-methyl styrene. 25. The product prepared by 
     
     
        the process of claim 24. 26. A process according to claim 24 wherein there 
     
     
        is prepared a homopolymer of styrene. 27. A process according to claim 24 wherein there is prepared a homopolymer of t-butyl styrene. .[.28. A process according to claim 1 wherein the polymerization is carried out at a temperature of 20° to 55° C..]. .[.29. A process according to claim 28 which is carried out in a aromatic hydrocarbon solvent..]. .[.30. A process according to claim 28 which is carried out in xylene, benzene, toluene, heptane and mineral spirits as a solvent..]. .[.31. A process according to claim 1 wherein the polymerization is carried out in an aromatic hydrocarbon solvent..]. .[.32. A process according to claim 1 wherein the polymerization is carried out in xylene, benzene, toluene, heptane or mineral spirits as a solvent..]. .[.33. A process according to claim 1 wherein the catalyst consists essentially of zirconium tetrachloride in an amount of 0.1 to 8% of the total monomers, and there is polymerized a mixture of (a) styrene, (b) alpha-methyl styrene, (c) a polymerizable terpene selected from the group consisting of alpha-pinene, beta-pinene, dipentene and limonene and (d) p-t-butyl styrene..]. .[.34. A process according to claim 33 wherein the terpene is limonene..]. .Iadd. 35. A process of preparing a light colored aromatic vinyl resin comprising polymerizing a member of the group consisting of (1) as the sole monomer styrene, alpha-methyl styrene or p-t-butyl styrene; (2) a mixture of (a) styrene and (b) alpha-methyl styrene; or (3) a mixture of (a) styrene, (b) alpha-methyl styrene and (c) as a third monomer a member of the group consisting of limonene, p-t-butyl styrene and vinyl toluene, and (4) a mixture of (a) styrene, (b) alpha-methyl styrene, (c) limonene and (d) p-t-butyl strene, in the presence of a catalyst consisting essentially of zirconium tetrachloride in an amount of 0.1 to 8% of the total monomer. .Iaddend..Iadd. 36. A process of preparing a light colored aromatic vinyl resin comprising polymerizing a member of the group consisting of (1) as the sole monomer styrene, alpha-methyl styrene or p-t-butyl styrene; (2) a mixture of (a) styrene and (b) alpha-methyl styrene; or (3) a mixture of 5 to 50% of (a) styrene, 5 to 80% of (b) alpha-methyl styrene, and 5 to 50% of (c) as a third monomer a member of the group consisting of limonene, alpha-pinene, beta pinene, dipentene, p-t-butyl styrene and vinyl toluene; or (4) a mixture of (a) styrene, (b) alpha-methyl styrene, (c) limonene and (d) p-t-butyl styrene, in the presence of a catalyst consisting essentially of zirconium tetrachloride in an amount of 0.1 to 8% of the total monomer. .Iaddend.