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Semicontinuous Emulsion Copolymerization of Vinyl Acetate and Butyl Acrylate Using A New Protective Colloid Part 1. Effect of Different Emulsifiers A. Sarac, H. Yldrm
Yildiz Technical University, Davutpasa Campus, Chemistry Departmant, 34210 Esenler, IstanbulTURKIYE

1. Introduction Emulsion copolymers of vinyl acetate are generally water based, milky-white liquids containing 48-55 % solids, the balance being water and small amounts of emulsifiers or emulsifier mixture, protective colloids or free and other additives. Vinyl acetate (VAc) can be copolymerized with many monomers especially butyl acrylate (BuA), 2-ethyl hexyl acrylate, Veova 10, methyl metacrylate etc. by applying different monomer compositions and using bulk, suspension and emulsion polymerization methods [1-3]. Among them, the most preferred is VAc-BuA monomer couple (due to their superior product properties) and the commonly used method for copolymerization is emulsion polymerization. VAc-acrylic copolymer latexes and polyvinyl acetate (PVAc) are generally used as binders in water-based interior and exterior architectural paints, coatings, and adhesives, since they have higher mechanical and water resistance properties than the homopolymers of both monomers. In general, particle stabilization is achieved by the use of either nonionic or the combination of nonionic and anionic emulsifiers, which are widely employed in emulsion polymerization systems. The properties of copolymer latexes primarily depend on the copolymer composition, polymer morphology, and colloidal characteristics of polymer particles. Controlling copolymer composition has long been of prime interest in polymer reaction engineering. Because of possible differences in reactivity ratios, the copolymer composition distribution may be broad, and only the average copolymer composition need be at the ratio of monomer feeds [4]. In the present study, a new protective colloid (Nmethylol acrylamide) was employed beside different type of emulsifiers (either nonionic or the mixture of anionic+nonionic) for the particle stabilization of waterborne VAc-co-BuA latexes. The main goal of this study was to investigate the effect of various emulsifiers on the molecular weights of final latexes, and viscosity under this polymerization conditions. 2. Materials and Methods VAc-co-BuA latexes were synthesized in the presence of nonionic emulsifiers which with different chain length, or anionic+nonionic emulsifier mixtures, thermal initiator (ammonium persulfate), protective colloid. Nonyl phenol ethoxylates (NP-n) (where n designates the average chain length of the ethoxylate chain) were used as nonionic emulsifier, and sodium dodecyl benzene sulfonate (SDBS) was used as anionic emulsifier. VAc/BuA monomer ratio was determined as 85/15 based on previous studies [5-7]. The effects of emulsifiers type on the the physicochemical properties of emulsion copolymers obtained were investigated. The conversions of the copolymer latexes were pointed out by gravimetric method, original viscosities with Brookfield viscometer, viscosity average molecular weights by viscometric method, number and weight average molecular weights of copolymers and molecular weight distributions of copolymers were measured by GPC. A sample of copolymerization recipe was given in Table 1. Table1. A sample recipe used in copolymerization experiments Substance VAc BuA Protective Colloid Emulsifier APS NaHCO3 Nopco Deionized Water Total 3. Results and Discussion The viscosities of the final latexes were determined by Brookfield Programmable DV-II model viscometer with spindle number 4 at 26C after diluting 40% (wt.) solids content of all samples. Viscosity average molecular weight (Mv) values of the polymers were determined using a Ubbelohde-type viscometer in a acetone solvent at 25C. MarkHouwink constant values of a= 0.75 and k= 6.85x10-5 (dL/g) were used in calculations [8]. Number average molecular weights (Mn) and weight average molecular weights (Mw) of copolymers were determined by the GPC Agilent model 1100 type instrument with a refractive index detector and Weight % 37.15 6.56 1.88 3.69 0.24 0.12 0.10 50.26 100.00

Proceeding of the 8th Polymers for Advanced Technologies International Symposium Budapest, Hungary, 13-16 September 2005

PROCEEDING FORM (1-3 pages with the given font types) calibrated with polystyrene standarts consist of three Waters styragel columns (HR 4, HR 3, and HR 2). THF was diluent solvent at a flow rate of 0.3 mL/min at 30C. For this purpose copolymer latexes were fractioned according to related literatures Chujo et al. [5] and us [6, 7, 9].
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4a. 4b. Figure 4a-b. Change of Brookfield viscosity and Mv of copolymers versus chain length of emulsifier for nonionic+anionic emulsifiers, respectively. It was seen that Mv, Mn and Mw increased by increasing the ethoxylation number of the participating emulsifiers increased (Figure 3 and Figure 4). Moreover either Mn or Mw of copolymers increased with increasing ethoxylation degree of emulsifier, and monodisperse copolymers (HI=1.64-8.14) obtained by using nonionic and nonionic+anionic emulsifiers. El-Aasser et. al [2] found the similar results for molecular weighs of copolymers having 85/15 monomer ratio for batch process, but obtained copolymers in this work has highly smaller polydispersity value than El-Aasser et al. 4. Conclusion Emulsion copolymers of VAc and BuA were synthesized in the presence of different emulsifiers. It was found that anionic+nonionic emulsifier mixture give higher molecular weight than nonionic emulsifier. Nonionic emulsifier gives more regular Brookfield viscosities increased than the emulsifier mixture the aspects of original viscosities of final latexes. References
10 10+30 30 40

Figure 1. Change of Brookfield viscosity with the ethoxylation number for nonionic emulsifiers.
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B rookfiel viscosity (cP)d

13 12 11 10 9 8 S+10 S+10+30 S+30 Emulsifier S+40

Figure 2. Change of Brookfield viscosity with the emulsifier for emulsifier mixture. Increasing poly(EO) block length caused to increase in the viscosities of copolymer latexes (Figure 1 and 2).
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3a. 3b. Figure 3a-b. Change of Brookfield viscosity and Mv of copolymers versus chain length of emulsifier for nonionic emulsifiers, respectively.

Latexes usually show Newtonian fluid behaviour and surface layers can significantly increase the effective volume of latex particles [1]. The smaller the particle size, the greater will be the contribution of a surface layer of given thickness to the effective volume of the particle. the viscosity depends on an effective particle volume which increases with increasing poly(EO) block length. In addition, it is thought that VAc-co-BuA latexes show that core-shell structure, so core-shell type structure can cause to increase the viscosities of VAcco-BuA latex.

[1] Lovell P.A. El-Aasser M.S.: Emulsion Polymerization and Emulsion Polymers; John Wiley and Sons: Chichester, (1997). [2] El-Aasser M.S. Vanderhoff J.W.: Emulsion Polymerization of Vinyl Acetate; Applied Science Publication: London and New Jersey, (1981). [3] Erbil H.Y.: Vinyl Acetate Emulsion Polymerization and Copolymerization with Acrylic Monomers; CRC Press: Boca Raton, (2000). [4] M.S. El-Aasser, T. Makgawinata, S. Misra, J.W. Vanderhoff, C. Pichot, M.F. Llauro, in: Emulsion Polymerization of Vinyl Acetate, M.S. El-Aasser, J.W. Vanderhoff, Eds., Applied Science Publishers, London: 215-252 (1981). [5] Chujo, K. Harada, Y. Tokuhara, S. Tanaka, K.: J. Polym. Sci. Part C, 321-327 (1969). [6] Sarac, A., Yildirim, H., J. Appl. Polym. Sci., 90(2), 537-543 (2003). [7] Sarac A.: Macromol. Symp. 217: 161-167 (2004) [8] Erbil H.Y.: Polymer 37(24): 5483-5487 (1995). [9] Sarac A. Erbil HY. Yildirim H.: J. Appl. Polym. Sci., 86(4):844-857 (2002).

Proceeding of the 8th Polymers for Advanced Technologies International Symposium Budapest, Hungary, 13-16 September 2005