Vinyl chloride-based copolymer resin and a method of preparing the same
The present invention relates to an inner-plasticized vinyl chloride-based copolymer resin not requiring plasticizers and a preparation method thereof. Specifically, the vinyl chloride-based copolymer resin is prepared by a suspension polymerization method of initiating the polymerization of vinyl chloride monomer, feeding a certain amount of butyl acrylate continuously or discontinuously thereinto and carrying out the additional polymerization at the temperature higher than the polymerization initiation temperature so as to prepare a core-shell type vinyl chloride-based random copolymer resin. The vinyl chloride-based copolymer resin of core-shell structure prepared by the present invention includes vinyl chloride-butyl acrylate copolymer, and it can provide a vinyl chloride-butyl acrylate copolymer product which can be processed without plasticizers positively necessary to produce a soft product.
1. A vinyl chloride-based copolymer resin of core-shell structure, characterized in that the core includes a vinyl chloride-butyl acrylate polymer, the shell includes a polyvinyl chloride, and the content of butyl acrylate in the copolymer is 10 to 50 wt % per the weight of the whole copolymer resin.
2. The vinyl chloride-based copolymer resin of core-shell structure according to claim 1 , including 85 to 95 wt % of vinyl chloride-butyl acrylate polymer which is the core, and 5 to 15 wt % of polyvinyl chloride which is the shell.
3. The vinyl chloride-based copolymer resin of core-shell structure according to claim 1 , which is a spherical particle having the average diameter of 50 to 250 μm and has the volumetric specific gravity of 0.3 to 0.7 g/cc and the shore hardness of 80 to 100.
4. A method of preparing the vinyl chloride-based copolymer resin of core-shell structure of claim 1 , including the steps of:
(a) mixing 0.09 to 0.6 parts by weight of a suspending agent and 0.05 to 0.15 parts by weight of an initiator with 100 parts by weight of the total sum of vinyl chloride monomer and butyl acrylate monomer, and initiating a reaction at the polymerization temperature of 40 to 60° C.; and
(b) partitively feeding 5 to 43 parts by weight of butyl acrylate monomer per 100 parts by weight of the total sum of vinyl chloride monomer and butyl acrylate monomer into the reaction product of step (a) continuously or discontinuously for 3 to 7 hrs and carrying out a suspension polymerization at the polymerization temperature of 45 to 70° C.
5. The method according to claim 4 , wherein the suspending agent includes a mixture of:
a first suspending agent selected from a polyvinyl alcohol-based compound having the degree of saponification of 60 to 80%, a cellulose-based compound, and a mixture thereof; and
a second suspending agent selected from a polyvinyl alcohol-based compound having the degree of saponification of 30 to 50%, a 20 to 40% hydroxylated cellulose-based compound, and a mixture thereof.
6. The method according to claim 4 , wherein the suspending agent includes a first suspending agent selected from a polyvinyl alcohol-based compound having the degree of saponification of 60 to 80%, a 20 to 40% hydroxylated cellulose-based compound, and a mixture thereof.
7. The method according to claim 5 , wherein the suspending agent includes the mixture of 0.2 to 0.39 parts by weight of the first suspending agent and 0.05 to 0.11 parts by weight of the second suspending agent per 100 parts by weight of the total sum of vinyl chloride monomer and butyl acrylate monomer.
8. The method according to claim 6 , wherein the suspending agent includes 0.09 to 0.6 parts by weight of the first suspending agent alone per 100 parts by weight of the total sum of vinyl chloride monomer and butyl acrylate monomer.
9. The method according to claim 4 , wherein the initiator is at least one compound selected from the group consisting of lauryl peroxide, acetyl cyclohexanol peroxide, 2,2,4-trimethylpentyl-2-peroxyneodecanoate, α-cumyl peroxyneodecanoate, di-butyl peroxydicarbonate, t-butyl hydroxyperoxide, bis(2-ethylhexyl)peroxydicarbonate, azoisobutyronitrile, and azobis(2,4-dimethyl)valeronitrile.
10. The method according to claim 9 , wherein the initiator includes a mixture of a lower temperature initiator of 10 hr HLT 60° C. or less, and a higher temperature initiator of 10 hr HLT 60° C. or more.
11. A particle form resin product, including 100 wt % of the vinyl chloride-based copolymer resin of core-shell structure of claim 1 .
12. A resin product, using the vinyl chloride-based copolymer resin of core-shell structure of claim 1 as a processing material or an impact modifier.