Shi et al.

/ J Zhejiang Univ SC1 2004 5(6):709-713 709

Journal of Zhejiang University SCIENCE

ISSN 1009-3095
http://www.zju.edu.cn/jzus
E-mail: [email protected]

Preparation of poly (methyl methacrylate)/nanometer calcium

r162
carbonate composite by in-situ emulsion polymerization

SHI Jian-ming (..~[[ fl~j)t, BAO Yong-zhong (/~_~TJ(,~,),

HUANG Zhi-ming ( ~ B~), WENG Zhi-xue ( f i ~ )
(Institute of Polymer Reaction Engineering, Zhejiang University, Hangzhou 310027, China)
*E-mail: shijianming 1@ 163.com
Received July 4, 2003; revision accepted Oct. 28, 2003

Abstract: Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate
(nano-CaCO3) surface modified with y-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly
(methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting
of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on
nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting
ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of
PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ
emulsion polymerization.

Key words: Methyl methacrylate, Nanometer calcium carbonate, Emulsion polymerization, y-methacryloxypropyltrimeth-
oxysilane, Grafting
Document code: A CLC number: TQ316.334

INTRODUCTION compatibility with polymer matrix and the disper-

sion homogeneity, and thus to improve the proper-
In recent decades, extensive research efforts ties of the polymer/inorganic particles nanocom-
have been directed towards the preparation and posite.
characterization of polymer/inorganic nanometer Emulsion polymerization has been widely used
particles composite (Siegel, 1994). Nanometer in- to modify inorganic particles with polymer. Sur-
organic particles easily agglomerate because of factant-free emulsion polymerizations of vinyl
their high surface energy, so it is difficult to achieve monomers in the presence of various inorganic
the homogeneous dispersion of nanoparticles in particles were carried out by Hasegawa et al. (1987a;
polymer matrix. Surface modification of an inor- 1987b), Hergeth et al.(1988; 1989) and Caris et
ganic particle with an organic substance is a useful al.(1989). In most cases, the surface of particles is
way to reduce its surface energy, to increase its partially or totally covered with polymer mainly
through static electric forces. The remarkable im-
provement in properties of nanocomposite can be
* Project (No. 01101619) supported by the Science and Technol- achieved when some polymer chains are covalently
ogy Project of Zhejiang Province, China bonded to inorganic nanoparticles (Baraton et al.,
710 Shi et aL /JZhejiang Univ SCI 2004 5(6):709-713

1997; Espiard and Guyot, 1995; Espiard et al., 1995; The slurry was left standing in the flask for 2 days.
Hayashi et al., 1999; Liu et al., 1998). The solvent was removed under vacuum at 60 ~
Although encapsulation of silica with polymer The modified nano-CaCO3 was dried and ground,
has been extensively studied, only few studies con- then stored at room temperature for 3 days before
cern calcium carbonate. Janssen et a/.(1993) em- use.
ployed emulsion polymerization to encapsulate
CaCO3 pretreated with titanate, and found that less Emulsion polymerization
than 10% of polystyrene produced was chemically
Polymerizations were carried out using a 500
bonded at the surface of CaCO3. Yang et a/.(1999) ml jacketed glass reactor fitted with a stirrer, reflux
obtained composites of CaCO3 encapsulated by po-
condenser, thermometer and N2 inlet. The pre-
lystyrene using soapless emulsion polymerization.
treated nano-CaCO3, 200 ml distilled water and
The encapsulating ratio was 60%, but only 6.4%
SDS were put into the reactor after ultrasonic
remained after Soxhlet extraction with toluene.
treatment for 10 rain. The concentration of SDS
In this work, in-situ emulsion polymerizations
was 1.0 g/L to water, which was much lower than
of methyl methacrylate in the presence of nano- its critical micelle concentration (CMC). After the
meter CaCO3 pretreated with g-methacryloxypropy- addition of initiator solution and monomer, the
ltrimethoxysilane were carried out to prepare poly mixture was raised to 60 ~ and maintained at this
(methyl methacrylate)/nanometer CaCO3 compos-
temperature for 5 h under N2 atmosphere.
ite.
The reaction mixture was then centrifuged at
4000 rev/min for 10 min, and the sediment was dis-
persed in deionized water again using mechanical
EXPERIMENTAL DETAILS
agitation and ultrasonic bath, this centrifugation-
Material dispersion cycle was repeated two to five times.
Methyl methacrylate (MMA), purchased from Finally, the composite was collected, dried and
Yuhang Co., China, was distilled under reduced ground into powder.
pressure. Nanometer CaCO3 (nano-CaCO3) was do-
nated by ACCR Co. Ltd, Hangzhou, and had avera- Characterization
ge particle diameter of about 50 nm. Nano-CaCO3 A drop of a diluted dispersion was put on a
modified with stearic acid was also donated by carbon film supported by a copper grid and dried in
ACCR Co. Ltd. y-methacryloxypropyltrimethoxy- the vacuum chamber of a JEM-1200EX electron
silane (MPTMS) from Shuguang Company was of microscope. The morphology ofnano-CaCO3 parti-
chemical purity. 2,2'-Azoisobutyronitrile (AIBN) cles and PMMA/nano-CaCO3 composite particles
and sodium dodecyl sulfate (SDS) were of ana- was observed by using TEM.
lytical purity and used as received. The product was extracted with toluene for
more than 20 h to remove the ungrafted PMMA
Surface modification of nano-CaCO3 completely. The weight loss of the original nano-
Nano-CaCO3 was dried under vacuum (2 kPa) CaCO3, silane modified nano-CaCO3 and PMMA/
at 100 ~ for 20 h to remove physically adsorbed nano-CaCO3 composite was determined by using a
species before modification. The introduction of re- Perkin Elmer TGA thermogravimetric instrument
active groups onto CaCO3 surface was achieved by under N2 atmosphere. The heating rate was 10 ~
the reaction of MPTMS with the hydroxyl groups of min.
CaCO3. A typical process was as follows: 30 g The conversion of MMA monomer to polymer
CaCO3 and 200 ml pure toluene were placed into a was determined gravimetrically. The grafting ratio
flask equipped with a stirrer. MPTMS (5 wt% to (fr) and efficiency of PMMA (fe) were calculated
CaCO3) was added dropwisely under rapid stirring. as follows:
 Shi et al. /JZhejiang Univ SC1 2004 5(6):709-713 711

PMMA unremoved by extraction (g) x 100% vimetric analysis (TGA) showed that 52.2% (2.61
=

CaCO 3 added (g) wt% to CaCO3) of MPTMS remained after extrac-

tion. The IR spectrum of the extracted sample (2 in
PMMA unremoved by extraction (g) x 100%
L PMMA formed (g)
Fig.2) showed adsorptions at 2931.1 cm -1 (v-CH3),
1124.5 cm -l (v-COOR) and 812.7 cm -1 (vC(CH3) =
CH2). This clearly indicated the existence of
chemically bonded MPTMS on the CaCO3 surface.
Thus, the inert CaCO3 surface can become active
RESULTS AND DISCUSION
part and act with MMA like a comonomer in the
polymerization.
Modification of n a n o - C a C O 3
The introduction of C=C group onto CaCO3
Influence of surface modification of nano-
surface was achieved by the reaction described in
CaCO3 on the grafting of P M M A
Fig. 1.
Emulsion polymerization of MMA was carried
The existence of free - O H group on the sur-
out in the presence of modified CaCO3 with dif-
face of CaCO3 was confirmed by its infrared (IR)
ferent weight ratios between CaCO3 and MMA. The
spectrum shown in Fig.2, in which an obvious ad-
formation of PMMA grafted to CaCO3 particles is
sorption at 3432 cm -t is shown. The content o f - O H
confirmed by the IR spectrum shown in Fig.3, in
group of CaCO3 was determined to be 0.42 mmol/g
which absorptions at 750.5 cm -1 (v=CH2), 1147.7
by measuring volumetrically the amount of hy- -1

drogen evolved by reaction with triethylaluminum. cm (v-C-O), 1732.1 cm -~ (v-C=O) and 2951.8
-I

Nano-CaCO3 pretreated with MPTMS was cm (v-CH3) indicate existence of PMMA.

Soxhlet-extracted with toluene for 24 h. Thermogra- The applied SDS concentration in the present
emulsion polymerization system was much lower
than its CMC, so few latex particles without CaCO3
OCH3 0 particles would be formed. During the polymeriza-
I II
CaCO3~--OH+(HsCO)3--~i--O--C--~= CH2 tion process, the oligomers formed at the early
OCH 3 CHs stage of emulsion polymerization behaved like
OCH~ O surface-active agents and were adsorbed on the
"~ I II CaCO3 surface, then the monomer molecules and
~, CaCO~-- O--~i-- O--C--~= CH2 + CH,OH
radicals in the water phase were also be adsorbed
OCH~ CH~
onto the surface layer formed by the oligomers. As
Fig.1 Introduction of MPTMS onto CaCO3 particle a result, the polymerization locus transferred from

1
1
2

=CH:

i . i . i . i . i , i . i ,

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 5 0
Wave numbers (cm ') Wave numbers (cm ~)
Fig.2 IR spectrum of original nano-CaCO3 (1) and Fig.3 IR spectrum of original CaCO3 (1) and PMMA/
nauo-CaCO3 modified with MPTMS (2) CaCO3 composite (2)
712 Shi et al. /JZhejiang Univ SC1 2004 5(6).'709-713

the aqueous phase to the powder surface at the early

100 --1
stage of the reaction, and C=C bond of MPTMS
would react with MMA to form grafted PMMA. 80
Influence of the modifier type and the weight
v 60
ratio between CaCO3 and MMA on the polymeri-
zation conversion, fr andf~ of the resulted compos- "~ 40
ite is shown in Table 1, showing that the existence 20
of nano-CaCO3 in the polymerization system af-
;',;o""
fects the final conversion of MMA (the conversion 200 300. 400
. . . 2 ,
500' 600'700' 800
of MMA is 96% for polymerization with no nano- Temperature (~
CaCO3). The conversion of MMA decreased as
more CaCO3 was added. When nano-CaCO3 pre- Fig.4 TGA plot of original CaCO3 (curve 1), pure
PMMA (curve 2) and PMMA/CaCO3 composite after
treated with stearic acid was used in the polymeri-
extraction (curve 3, 4, 5 and 6 correspond to the sample
zation, most of the formed PMMA could be easily 1, 2, 3, 4 in Table I)
removed by Soxhlet extraction, and grafting ratio of
PMMA was much lower. However, relatively Electron microscopy
higher grafting ratio was achieved when MPTMS Fig.5 shows TEM photographs of original
pretreated CaCO3 was used in the in-situ emulsion nano-CaCO3 (a) and PMMA/CaCO3 composite (b)
polymerization. It can also be seen that the grafting taken from the emulsion system after the poly-
efficiency decreased as more MMA was added. merization. The average size of primary particles of
original nano-CaCO3 was about 50 nm. TEM pho-
Thermogravimetric analysis tograph of PMMA/CaCO3 composite shows the
Fig.4 shows TGA plots of original CaCO3 encapsulation of PMMA on CaCO3 with each com-
(curve 1), pure PMMA (curve 2) and different ex- posite particle encapsulating more than one CaCO3
tracted PMMA/CaCO3 composites. The original primary particle. This was caused by the agglom-
CaCO3 did not decompose below 550 ~ and the eration of the original CaCO3 particles.
weight loss was 1.2% above 550 ~ Curve 2 shows
that pure PMMA decomposes completely above
550 ~ and that the remained weight was 4.63%. CONCLUSIONS
For PMMA/CaCO3 composite, the weight loss
between 250 ~ to 550 ~ was attributed to the PMMA/nano-CaCO3 composite with higher
existence of encapsulating PMMA. TGA of ex- grafting efficiency of PMMA was successfully
tracted PMMA/CaCO3 composites revealed weight prepared by emulsion polymerization of MMA in
loss of 94.05%, 78.13%, 80.18%, 84.57% for the presence of nano-CaCO3 pretreated with
sample 1 to sample 4 in Table l, respectively. From MPTMS. The coupling of MPTMS and grafting of
the conversions of MMA and the weight loss of PMMA onto CaCO3 were confirmed by IR spec-
extracted PMMA/CaCO3 composites, the grafting trum. The grafting efficiency of PMMA was much
ratio and grafting efficiency of PMMA can be higher in case of using MPTMS pretreated CaCO3
calculated as shown in Table 1. than in case of using stearic acid pretreated CaCO3.

Table 1 Influence of the modifier type and CaCO3/MMA ratio on the polymerization conversion,fr andfe
Sample Modifier type CaCO3/MMA Conversion(%) f~ (%) )re (%)
1 Stearic acid 2/3 85 2.86 2.38
2 MPTMS 2/3 81 14.25 12.42
3 MPTMS 1/2 89 18.69 11.12
4 MPTMS 1/3 93 22.46 8.53
 Shi et al. /JZhejiang UnivSC1 20045(6):709-713 713

(a) (b)

Fig.5 TEM micrographs of original CaCO3 (a) and PMMA/CaCO3 (b) composite prepared by emul-
sion polymerization

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