Polymerization of vinyl chloride with blends of peroxide initiators

Abstract

Process for the polymerization of vinyl chloride or the copolymerization of vinyl chloride and vinyl acetate at temperatures of less than about 70° C., in the presence of a polymerization initiator which is a blend of an acetyl alkylsulfonyl peroxide with (A) a peroxydicarbonate, (B) a diacyl peroxide and a tertiary-alkyl neoacid peroxyester or (C) a diacyl peroxide and a peroxydicarbonate. .Iadd.

What is claimed is: .[. 
     
       1.  In a proceess for the homopolymerization of vinyl chloride or the copolymerization of vinyl chloride and vinyl acetate, wherein the vinyl chloride constitutes at least 50% by weight of the comonomers, at a temperature of not more than 70° C. in the presence of an initiating amount of a peroxide polymerization initiator, the improvement which comprises using as said initiator a mixture of peroxides in the amount of 0.005% to 1.0% by weight of the monomer(s) being polymerized and being selected from the group consisting of: (A) a mixture of (1) an acetyl alkylsulfonyl peroxide having the formula ##STR5##  and (2) a peroxy dicarbonate having the formula ##STR6##  the weight proportions of component 1:component 2 being from 1:0.2 to 1:4,     (B) a mixture of (1) said acetyl alkylsulfonyl peroxide,   (2) a diacyl peroxide having the formula ##STR7##  and (3) a tertiary-alkyl neoacid peroxyester having the formula ##STR8##  the weight proportions of 1:2 being from 1:0.25 to 1:7 and of 1:3 being from 1:0.25 to 1:5, and     (C) a mixture of (1) said acetyl alkylsulfonyl peroxide,   (2) said diacyl peroxide, and   (3) said peroxy dicarbonate, the weight proportions of 1:2 being from 1:0.25 to 1:7 and of 1:3 being from 1:0.25 to 1:5; wherein R is alkyl of 4-12 carbon atoms, cycloalkyl of 3-12 carbon atoms, or 1-adamantyl; R 1  is alkyl of 2-18 carbon atoms, cycloalkyl of 3-12 carbon atoms, or benzyl; R 2  is primary alkyl of 2-17 carbon atoms; R 3  is tertiary alkyl of 4-8 carbon atoms; and R 4 , R 5  and R 6  are each of alkyl of 1-6 carbon atoms..]. .[.     
     
     
       2.  The process of claim 1 wherein the temperature is 30° C. to 70° C..]. .[.3. The process of claim 1 wherein said mixtures of peroxides is present in the amount of 0.01 to 0.5% by weight of the vinyl monomers to be polymerized..]. .[.4. The process of claim 3 wherein said 
     
     
        amount is 0.02 to 0.2%..]. 5. .[.The process of claim 1.]. .Iadd.In a process for the suspension homopolymerization of vinyl chloride or the suspension copolymerization of vinyl chloride and vinyl acetate, wherein the vinyl chloride constitutes at least 50% by weight of the comonomers, at a temperature of not more than 70° C. in the presence of an initiating amount of a peroxide polymerization initiator, the improvement which comprises using as said initiator a mixture of peroxides in the amount of 0.005% to 1.0% by weight of the monomer(s) being polymerized .Iaddend.wherein said mixture of peroxides is a mixture of (A) an acetyl alkylsulfonyl peroxide having the formula ##STR9##  and (B) a peroxy dicarbonate having the formula ##STR10## wherein R is alkyl of 4-12 carbon atoms, cycloalkyl of 3-12 carbon atoms, or 1-adamantyl; R 1  is alkyl of 2-18 carbon atoms, cycloalkyl of 3-12 carbon atoms, or benzyl.Iadd., provided, however, that when R 1  is an alkyl group of 3 carbon atoms it is n-propyl; .Iaddend.and the weight   
     
     
        proportions of component (A) to component (B) are from 1/0.2 to 1/4. 6. The process of claim 5 wherein said initiator is a mixture of one part by weight of acetyl cyclohexylsulfonyl peroxide and 0.7 part by weight of dibenzyl peroxydicarbonate. .[.7. The process of claim 5 wherein said initiator is a mixture of 1 part by weight of acetyl cyclohexylsulfonyl 
     
     
        peroxide and 0.4 part by weight of diisopropyl peroxydicarbonate..]. 8. The process of claim 5 wherein said initiator is a mixture of 1 part by weight of acetyl 1-methylclclohexylsulfonyl peroxide and 0.6 part by 
     
     
        weight of dicyclohexyl peroxydicarbonate. 9. The process of claim 5 wherein said initiator is a mixture of 1 part by weight of acetyl cyclohexylsulfonyl peroxide and 1.8 parts by weight of di(n-propyl) 
     
     
        peroxydicarbonate. 10. .[.The process of claim 1.]. .Iadd.In a process for the suspension homopolymerization of vinyl chloride or the suspension copolymerization of vinyl chloride and vinyl acetate, wherein the vinyl chloride constitutes at least 50% by weight of the comonomers, at a temperature of not more than 70° C. in the presence of an initiating amount of a peroxide polymerization initiator, the improvement which comprises using as said initiator a mixture of peroxides in the amount of 0.005% to 1.0% by weight of the monomer(s) being polymerized .Iaddend.wherein said mixture of peroxide is a mixture of (A) an acetyl alkylsulfonyl peroxide having the formula ##STR11## (B) a diacyl peroxide having the formula ##STR12##  and (C) a tertiary-alkyl neoacid peroxyester having the formula ##STR13## wherein R is alkyl of 4-12 carbon atoms, cycloalkyl of 3-12 carbon atoms, or 1-adamantyl; R 2  is primary alkyl of 2-17 carbon atoms; R 3  is tertiary alkyl of 4-8 carbon atoms; R 4 , R 5  and R 6  are each alkyl of 1-6 carbon atoms; and the weight proportions of component (A) to component (B) are from 1/0.25 to 1/7 and of component (A) to component (C)   
     
     
        are from 1/0.25 to 1/5. 11. The process of claim 10 wherein said initiator is a mixture of 1 part by weight of acetyl cyclohexylsulfonyl peroxide, 6.2 parts by weight of lauroyl peroxide, and 2.7 parts by weight of 
     
     
        t-butyl peroxypivalate. 12. The process of claim 10 wherein said initiator is a mixture of 1 part by weight of acetyl t-amylsulfonyl peroxide, 2.7 parts by weight of di(3,5,5-trimethylhexanoyl) peroxide, and 1.6 parts by 
     
     
        weight of t-butyl peroxyneodecanoate. 13. The process of claim 10 wherein said initiator is a mixture of 1 part by weight of acetyl sec-heptylsulfonyl peroxide, 0.4 part by weight of pelargonyl peroxide, 
     
     
        and 0.4 part by weight of 1,1,3,3-tertamethylbutyl peroxypivalate. 14. .[.The process of claim 1.]. .Iadd.In a process for the suspension homopolymerization of vinyl chloride or the suspension copolymerization of vinyl chloride and vinyl acetate, wherein the vinyl chloride constitutes at least 50% by weight of the comonomers, at a temperature of not more than 70° C. in the presence of an initiating amount of a peroxide polymerization initiator, the improvement which comprises using as said initiator a mixture of peroxides in the amount of 0.005% to 1.0% by weight of the monomer(s) being polymerized .Iaddend.wherein said mixture of peroxides is a mixture of (A) an acetyl alkylsulfonyl peroxide having the formula ##STR14## (B) a diacyl peroxide having the formula ##STR15##  and (C) a peroxy dicarbonate having the formula ##STR16## wherein R is alkyl of 4-12 carbon atoms, cycloalkyl of 3-12 carbon atoms, or 1-adamantyl; R 1  is alkyl of 2-18 carbon atoms, cycloalkyl of 3-12 carbon atoms, or benzyl; R 2  is primary alkyl of 2-17 carbon atoms; and the weight proportions of component (A) to component (B) are from 1/0.25 to 1/7 and of component (A) to component (C) are from 1/0.25 to   
     
     
        1/5. 15. The process of claim 14 wherein said initiator is a mixture of 1 part by weight of acetyl cyclohexylsulfonyl peroxide, 3.9 parts by weight of lauroyl peroxide, and 0.7 part by weight of di-sec-butyl 
     
     
        peroxydicarbonate. 16. .[.Claim 1.]. .Iadd.Claim 5 .Iaddend.wherein the 
     
     
        monomer(s) is vinyl chloride. 17. .[.Claim 1.]. .Iadd.Claim 5 .Iaddend.wherein the monomer(s) are by weight 85% vinyl chloride and 15% 
     
     
        vinyl acetate. 18. In a method for polymerizing vinyl chloride alone or in mixture with vinyl acetate in the presence of a medium which does not dissolve the product, the improvement which comprises using as the catalyst a mixture of acetyl cyclohexyl sulfonyl peroxide with .[.diisopropyl peroxydicarbonate or.]. di-2-ethylhexyl peroxydicarbonate. .Iadd. 19. Claim 10 wherein the monomer(s) is vinyl chloride. .Iaddend..Iadd. 20. Claim 14 wherein the monomer(s) is vinyl chloride. 
     
     
        .Iaddend..Iadd.21.  Claim 10 wherein the monomer(s) are by weight 85% vinyl chloride and 15% vinyl acetate. .Iaddend..Iadd. 22. Claim 14 wherein the monomer(s) are by weight 85% vinyl chloride and 15% vinyl acetate. .Iaddend.