Process for production of styrene polymers

Abstract

A process for production of styrene polymers of high syndiotactic configuration is disclosed, comprising polymerizing styrene or styrene derivatives by the use of a catalyst comprising: (A) a titanium compound, e.g., at least one compound selected from those represented by the formulae: TiR 1 a R 2 b R 3 c X 1 4 -(a+b+c) and TiR 1 d R 2 e X 1 3- (d+e) (all the symbols are as defined in the appended claims); and (B) a contact product of an organoaluminum compound and a condensation agent, e.g., a product resulting from modification of trimethylaluminum with water. Because of such high syndiotactic configuration, the styrene polymers are greater in thermal resistance and solvent resistance than conventional atactic polystyrene.

What is claimed is: 
     
       1. A process for producing .Iadd.syndiotactic .Iaddend.styrene polymers which comprises polmerizing styrene or styrene derivatives .Iadd.at a polymerization temperature of from 0° C. to 90° C. .Iaddend.by the use of a catalyst comprising: (A) a titanium compound, and   (B) .[.a contact product of an organoaluminum compound and a condensation agent.]. .Iadd.an alkyl aluminoxane compound represented by the formula: .Iaddend. ##STR3## .Iadd.wherein n is 2 to 50 and R 6  is an alkyl group having 1 to 8 carbon atoms, wherein said titanium compound is at least one compound selected from titanium compounds and titanium chelate compounds represented by the general formulae:   TiR.sup.1.sub.a R.sup.2.sub.b R.sup.3.sub.c X.sup.1.sub.4-(a+b+c) and       TiR.sup.1.sub.d R.sup.2.sub.e X.sup.1.sub.3-(d+e)     wherein R 1 , R 2  and R 3  each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, a cyclopentadienyl group, a substituted cyclopentadienyl group or an indenyl group, X 1  represents a halogen atom, a, b and c each represent an integer of 0 to 4, and d and e each represent an integer of 0 to 3; provided that said titanium compound is not absorbed or deposited on a magnesium compound. .Iaddend.     
     
     
       2. .[.The process as claimed in claim 1, wherein the titanium compound is at least one compound selected from titanium compounds and titanium chelate compounds represented by the general formulae:   TiR.sup.1.sub.a R.sup.2.sub.b R.sup.3.sub.c X.sup.1.sub.4-(a+b+c) and       TiR.sup.1.sub.d R.sup.2.sub.e X.sup.1.sub.3-(d+e)     (wherein R 1 , R 2  and R 3  each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, a cyclopentadienyl group, a substituted cyclopentadienyl group or an indenyl group, X 1  represents a halogen atom, a, b and c each represent an integer of 0 to 4, and d and e each represent an integer of 0 to 3)..]..Iadd.2. The process as claimed in claim 1, wherein the styrene derivative is selected from the group consisting of para- or meta-alkylstyrene and para- or meta-halogenated styrene. .Iaddend.   
     
     
       3. The process as claimed in claim 1, wherein the component (B) is a product resulting from modification of trimethylaluminum with water. .Iadd.4. The process as claimed in claim 1, wherein the styrene or styrene derivative is selected from the group consisting of styrene, alkylstyrene and halogenated styrene. .Iaddend. .Iadd.5. The process as claimed in claim 1, wherein the styrene or styrene derivative is methylstyrene, ethylstyrene, butylstyrene, p-tert-butylstryene, or dimethylstyrene. .Iaddend. .Iadd.6. The process as claimed in claim 1, wherein the styrene or styrene derivative is chlorostyrene, bromostyrene or fluorostyrene. .Iaddend. .Iadd.7. The process of claim 1, wherein the titanium compound comprises titanium tetrahalide. .Iaddend. .Iadd.8. The process of claim 1, wherein the titanium compound comprises titanium tetrachloride. .Iaddend. .Iadd.9. The process of claim 1, wherein the titanium compound comprises titanium tetrabromide. .Iaddend. .Iadd.10. The process of claim 1, wherein the titanium compound comprises titanium tetraalkoxide. .Iaddend. .Iadd.11. The process of claim 1, wherein the titanium compound comprises 
     
     
        titanium tetramethoxide. .Iaddend. .Iadd.12.  The process of claim 1, wherein the titanium compound comprises titanium tetraethoxide. .Iaddend. .Iadd.13. The process of claim 1, wherein the titanium compound comprises titanium tetraisopropoxide. .Iaddend. .Iadd.14. The process of claim 1, wherein the titanium compound comprises titanium tetra-n-butoxide. .Iaddend. .Iadd.15. The process of claim 1, wherein the titanium compound is titanium trihalide. .Iaddend. .Iadd.16. The process of claim 1, wherein the titanium compound is titanium trichloride. .Iaddend. .Iadd.17. The process of claim 1, wherein the titanium compound comprises tetra(octradecyloxy)titanium. .Iaddend. .Iadd.18. The process of claim 1, wherein the titanium compound comprises tetra(2-ethylhexyloxy)titanium. .Iaddend. .Iadd.19. The process of claim 1, wherein the titanium compound comprises titanium monoisopropoxy trichloride. .Iaddend. .Iadd.20. The process of claim 1, wherein the titanium compound comprises titanium 
     
     
        diisopropoxy dichloride. .Iaddend. .Iadd.21.  The process of claim 1, wherein the titanium compound comprises titanium trisopropoxy monochloride. .Iaddend. .Iadd.22. The process of claim 1, wherein the titanium compound comprises bis(2,4-pentanedionate) titanium dibutoxide. .Iaddend. .Iadd.23. The process of claim 1, wherein the titanium compound comprises isopropoxytitanium tristearate. .Iaddend. .Iadd.24. The process of claim 1, wherein the titanium compound comprises methyltitanium trichloride. .Iaddend. .Iadd.25. The process of claim 1, wherein the titanium compound comprises biscyclopentadienyltitanium dichloride. .Iaddend. .Iadd.26. The process of claim 1, wherein the titanium compound comprises cyclopentadienyltitanium trichloride. .Iaddend. .Iadd.27. The process of claim 1, wherein the titanium compound comprises titanium tetrachloride/ethyl benzoate complex. .Iaddend. .Iadd.28. The process of claim 1, wherein the titanium compound is adsorbed or deposited on a carrier. .Iaddend. .Iadd.29. The process of claim 23, wherein the carrier 
     
     
        is silica or alumina. .Iaddend. .Iadd.30.  The process of claim 29, wherein the carrier is silica. .Iaddend. .Iadd.31. The process of claim 
     
     
        29, wherein the carrier is alumina. .Iaddend. .Iadd.32.  The process of claim 1, wherein the component (B) further comprises an aluminum containing compound having the formula AlR 3  wherein R is C 1  to C 8  alkyl. .Iaddend. .Iadd.33. The process of claim 32, wherein said aluminum containing compound is trimethylaluminum. .Iaddend. .Iadd.34. The process of claim 32, wherein said aluminum containing compound is 
     
     
        triisobutylaluminum. .Iaddend. .Iadd.35.  The process of claim 1, wherein the titanium compound is selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, tetra(octadecyloxy) titanium, tetra(2-ethyl hexyloxy) titanium, titanium monoisopropoxy trichloride, titanium diisopropoxy dichloride, titanium trisopropoxy monochloride, bis(2,4-pentanedionate) titanium dibutoxide, isopropoxytitanium tristearate, methyltitanium trichloride, biscyclopentadienyl titanium dichloride, cyclopentadienyl titanium trichloride, and titanium tetrachloride (ethyl benzoate complex). .Iaddend. .Iadd.36. The process of claim 1, wherein the aluminoxane compound is formed by reacting an organoaluminum compound selected from the group consisting of trimethyl aluminum, triethylaluminum and 
     
     
        triisobutyl aluminum and water. .Iaddend. .Iadd.37.  The process of claim 36, wherein said water is water of crystallization contained in metal salts. .Iaddend.