Colloids and Surfaces

A: Physiochemical and Engineering Aspects 153 1999. 321]323

Particle size control of PVC

Yusaku Suenagaa,U , Akira Akimotob

a
Department of Chemistry, Kinki Uni ersity, Kowakae, Higashi-Osaka, Osaka 577-8502, Japan
b
Yokkaichi Research Laboratory, Tosoh Corporation, Yokkaichi, Mie 510-8540, Japan

Abstract

We studied seeded emulsion polymerization which is one of the known particle-producing polymerization methods.
The colloidal stability of a polymer latex in the vinyl chloride polymerization was improved by addition of emulsifier.
When the emulsifier was added to the growing particles, without emulsifier excess in the water phase, the colloidal
stability of the polymer latex was excellent. This result means that the occurrence of new fine particles - 0.1 mm.
was prevented. Also, the viscosity properties of plastisols consisting of polyvinylchloride PVC. and dioctylphthalate
DOP. as plasticizer supported this result. Q 1999 Elsevier Science B.V. All rights reserved.

Keywords: Polyvinylchloride; Seeded emulsion polymerization; Emulsifier addition methods; Plastisol viscosity

1. Introduction coagulation or flocculation of destabilized latex

The seeded emulsion process consists of a two-
step polymerization w1,2x. The first step is the
preparation of 0.5 micron particles from vinyl
chloride, water and emulsifier which are dis-
persed using a mechanical homogenizer. In the
second step of the process, the produced particles
are used as seed particles. The process has sev-
eral distinct advantages. The particle size dis-
tribution is easy to control by the properties of
the seed particles. PVC particles produced by this
process have excellent properties for paste pro-
cessing. Moreover, the latex solution after po-
lymerization has a high solid content. This is an
important issue in the chemical industry to re-
duce the amounts of raw materials. However,
U
Corresponding author.
during the reaction sometimes occurs. In this
paper, we report the relation between the reac-
tion conditions and particle size and distribution.
2. Experimental
2.1. Materials
Vinyl chloride monomer was obtained from
Tosoh Corp. Emulsifier reagents were obtained
from Wako Chemical Co. Japan and organic per-
oxide from Nippon Oil Co.
2.2. Polymerization procedure
Polymerization was carried out in a 2-l stainless
steel reactor using a homogenizer. After the seed
polymer and water and emulsifier were added

0927-7757r99r$ - see front matter Q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 9 8 . 0 0 4 5 3 - 1
322 Y. Suenaga, A. Akimoto r Colloids Surfaces A: Physiochem. Eng. Aspects 153 (1999) 321]323

into the reactor tank, the reactor was sealed off

under high vacuum. The required amounts of
VCM were then charged. Polymerization was car-
ried out using a mechanical stirrer at a constant
temperature for a given time. After the polymer-
ization, the latex was dried under a steam spray
dryer.

2.3. Characterization of polymers

The particle size and distribution were de-

termined by laser diffraction measurements LA-
700, Horiba Co. Ltd.. and unimodal scattered
light measurements Model 370, NICOMP.. The
stability of the polymer latex was determined by Fig. 1. Particle size distribution for different monomer con-
the time until the latex viscosity increased at 608C versions.
under mechanical stirring. Plastisol properties
were characterized with a Brookfield viscosime- latex. The particle size distribution is shown in
ter. Fig. 2. This result indicates that the present site
of the initiators and the amount of the emulsifier
3. Results and discussion are important factors in preventing new fine par-
ticles.
3.1. Particle formation in the seeded emulsion
polymerization
3.2. Reaction conditions and occurrence of new fine
particles
In this process, the site of polymerization is the
seed polymer, because initiators are included in
the seed particles. However, the size of the final First, we studied how to add the emulsifier
particles is smaller than the considerable value during polymerization. Different addition meth-
from monomer conversion. Also, fine particles on ods are shown in Fig. 3. Method 3 seemed the
the surface of the final particles were discovered best for the stability of the polymer latex. This
with a scanning electron microscope SEM.. Po- means that the excess emulsifier concentration
lymerization was carried out by removing the
latex through the bottom of the reactor for a
period of time during polymerization. The results
showed that fine particles less than 0.1 mm size
increased during the initial polymerization period
Fig. 1.. The appearance of fine particles, which is
considered to occur in the continuous water phase,
is stabilized by the emulsifier. This suggests that
the origin of free radicals is in the water phase in
addition to that in the seed particles w1x.
Polymerization was studied using seed particles
having deactivated initiators and different initia-
tors in order to study the initiator effect in the
seed particles. In the former experiment, the ini- Fig. 2. Effect of the initiators with different water-solubility.
tiators were directly added before polymerization. Initiator 1: di-3,5,5-trimethylhexanoyl peroxide; initiator 2:
Many fine particles were found in the polymer t-butyl peroxypivalate.
 Y. Suenaga, A. Akimoto r Colloids Surfaces A: Physiochem. Eng. Aspects 153 (1999) 321]323 323

the application of coatings, the property of low

viscosity is an important factor. This result indi-
cates that formation of new fine particles is pre-
vented.

4. Summary

Based on this study, it is presumed that one of

the reasons for the coagulation or flocculation of
the destabilized latex is the occurrence of fine
particles. The origin of such particles is con-
Fig. 3. Different addition methods of the emulsifier.
sidered to be polymerization in the aqueous phase
outside the seed particles.
can lead to micelle formation in the water phase
causing a new polymerization site w2x. Second, we
References
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