Modification of Porous Suspension-PVC Particles by Stabilizer-Free Aqueous Dispersion Polymerization of Absorbed Monomers

M. SHACH-CAPW a n d M . NARKIS*

Department o f Chemical Engineering

M. S . SILVERSTEIN

Department o f Materials Engineering Technion-LIT, Haiii Israel

The modification of porous W C particles by an in-situ stabilizer-free polymerization/crosslinking of a monomer/crosslinker/peroxide solution absorbed within the W C particles is presented. The modifying crosslinked polymers are polystyrene (PS) crosslinked with DVB (divinylbenzene), polymethyl methacrylate (PMMA)crosslinked with ethylene glycol dimethacrylate (EGDMA), and styrene-MMA copolymer crosslinked with DVB. The modified PVC particles characterization includes polymerization yield, non-extractables, 13C solid-state CPMAS NMR, porosity measurements and also morphology and dynamic mechanical behavior (DmA). The levels of nonextractable fractions found and solid-state CPMAS NMR results are indicative of low chemical interaction in the semi-IPN WC particles. Particle porosity levels and SEM observations indicate that styrene and MMA mainly polymerize within the W C particles' bulk and just small amounts in the pores. MMA polymerization in the W C pores is as crusts covering the W C pore surfaces, whereas styrene polymerization in the PVC pores is by filling the pores. Dynamic mechanical studies show that t a n 6 and the storage modulus curves are influenced by the incorporation of PS and XPS but not by the incorporation of PMMA and XPMMA.

INTRODUCTION

he focal point of polymer science and technology tends to shift from wholly new polymers toward modification of existing ones. There are several methods for the preparation of polymer blends, such as mechanical mixing, casting from a common solvent and in-situ polymerization. In-situ polymerization is the polymerization of one monomer in the presence of another polymer (l), which can be performed by reactions in the melt, in solution, or in the solid phase (2). In-situ polymerization in the solid state (usually powder or granular material) is advantageous because of its low cost and large variety of possible modifications, compared to polymerization in solution or in the melt ( 3 ) .
~

*Correspondingauthor. email: narkis@tx.technion.ac.il

A prominent type of in-situ polymerization in the solid state is the Two-Stage Latex W L )polymerization method. Different morphologies generated in the twostage latexes are reported in the literature (4-8). Seed emulsion polymerized particles without emulsifiers have received much attention (9-11). as thyy provide important advantages for production of pure 1ate.Kes (12, 1 3 ) . In-situ polymerization in large-scale particles is infrequent in the literature. The authors recently reported the in-situ stabilizer-free polymerization/crosslinkiig of butyl acrylate and ethylhexyl acrylate crosslidred with ethylene glycol dimethacxylate (EGDMA) within porous commercial suspension type W C particles (14). Wtzsch et aL (2, 3, 15, 1 6 )investigated the absorption and polymerization of styrene and methyl methacrylate in porous reactor polypropylene particles. The control on miscibility has been demonstrated. using

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M. Shach-Caplan, M . Narkis. and M . S . Silverstein

knowledge of the PVC-PBA-monomer phase diagram, in the in-situpolymerization of butyl acrylate imbibed in suspension type polyvinyl chloride (PVC) particles using carboxymethyl cellulose as a stabilizing agent (I), contrary to the present work, where stabilizer-free systems are used. In a polymerization reaction described by Walker ( 1 7 ) , irregularly shaped polyolefrn particles, with sizes in the range of 1 to 5 mm, are grafted with a polymerizable monomer to form a grafted polymer. Polymerization of a monomer absorbed in a fim of a host polymer is another type of in-situ polymerization in the solid state (18-21). In-situ polymerization/crosslinking of a given monomer within an uncrosslinked polymer leads to the formation of semi-IPNs (22).With two inherently miscible polymers the interpenetration occurs on a molecular level. A major parameter making the networks in IPNs more miscible appears to be the presence of the crossl i n k swhich hinders phase separation (23,24). The semi-IPN of W C may serve as interesting absorbents of halogenated organic compounds from water, currently under investigation in the authors laboratories. In this study, porous semi-IPN of PVC particles are prepared by an in-situ stabilizer-free polymerization/ crosslinking of a monomer/crosslinker mixture absorbed within the porous commercial suspension type W C particles. The concept of this method has some similarity to a two-stage latex polymerization, though in the former no stabilizer is being used. The character of the semi-IPN WC particles obtained can be adjusted by selection of suitable monomer/crosslinker pairs, such as styrene crosslinked with DVB (divinyl benzene), methyl methacrylate (MMA) crosslinked with ethylene glycol dimethacrylate (EGDMA),and styreneMMA copolymer crosslinked with DVB. The influence of composition, process parameters and nature of the polymerizing/crosslinking constituents upon the structure, porosity, dynamic mechanical properties, level of grafting and non-extractable fraction of the modified W C particles, is investigated. EXPERIMENTAL
MtBtWialB

Concentrations in this paper are given as weight percent, excluding pore contents expressed as volume percent.

Preparation o f the Modified PVC

PVC particles were modified by XPS (polystyrene crosslinked with 0, 0.5, 5% DVB solution), XPMMA (polymethyl methacrylate crosslinked with 0, 0.5, 5% EGDMA) and XP(St-co-MMA) (styrene/methylmethacrylate 50/50 copolymer crosslinked with 5% DVB solution), using benzoyl peroxide as an initiator (0.5%). The WC/modifymg monomer mass ratio was 75/25. The following two polymerization procedures were used: Method (a)-The polymerization/crosslinking step took place in a glass reactor, immersed in a water bath at a constant temperature. The reactor was fitted with a teflon blade agitator, nitrogen bleed, dropping funnel and condenser. Distilled water (800g) and the PVC particles (75 g) were placed into the reactor and stirred. Monomer, crosslinker and benzoyl peroxide solution (25 g) was placed in a dropping funnel and continuously added to the reactor during 30 minutes, at room temperature, while stirring. After the monomer solution was added, the temperature was elevated to the polymerization temperature, 8OoC,which was subsequently maintained for four hours. The resulting modified WC particles were filtered and dried. M e t h o d 0-The polymerization/crosslinking took place in a glass reaction vessel. The dry PVC particles (75 g) were placed into the vessel and the monomer, crosslinker and benzoyl peroxide solution (25 gl was gradually added to the reactor, at room temperature, while stirring the W C particles (a process similar to dry-blending of WC particles with plasticizers). After 90 minutes, distilled water (800g) at 8OoCwas added to the reactor, and polymerization proceeded for four hours. The resulting modified PVC particles were filtered and dried. The yield, for both methods, is calculated from the weight gain after filtration and drying, divided by the weight of the added monomer solution (monomer, crosslinker and initiator). The yield of very fine particles present in the filtered water is calculated from the weight of a dried filtrate divided by the weight of the monomer solution.

Suspension PVC (Epivyl40, kutarom, Israel), porous particles, 100-150 p,m diameter, was used as received. THF (tetrahydrofuran, analytical grade, Frutarom, Israel) and MEK (methyl ethyl ketone, chemically pure, Frutarom, Israel) were used as received. DVB solution containing 50% ethylvinylbenzene (Riedel de Haen, Germany) and EGDMA (practical grade, F l h , Switzerland), the crosslinking agents, were used as received. Styrene (Riedel de Haen, Germany) and MMA (Merck, Germany) monomers were washed with a 5% sodium hydroxide aqueous solution for removal of the inhibitor, followed by water rinsing for neutralization. Benzoyl peroxide (BP) (Merck, Germany), the initiator, was purified by re-crystahation from hot ethanol. Water was deionized and distilled.
912

Characterization

Non-extractablea. Samples of 0.3 g enclosed in sealed extraction thimbles were placed in boiling cyclohexanone (solvent for WC, PS and PMMA) for 24 hours, and subsequently dried in a vacuum oven at 120C for 3-4 hours, ASTM D 2765. The insoluble fraction in cyclohexanone, i.e., non-extractables, is the ratio of the weight of the insoluble residue to the weight gained by the PVC modification. lac!%did State NMR. 13C solid-state CPMAS NMR was used to probe and actually to deny possible phase miscibility and molecular level interaction within the modified WC, since such effects are not very probable
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Modtication o f Porous Suspension-WC Particles

at the polymerization conditions used. The measurements were carried out on a 300 MHz (Chemagnetics/ Varian) CMX-infinity triple-resonance spectrometer, Double-resonance measurements were performed using a Chemagnetics probe with a 7.5 mm spinning module with high performance Zirconia rotors. For cross polarization (CP) the radio frequency level of the Hartman-Hahn match was set at 50 kHz for a duration of 2 ms to allow optimal transferred polarization to carbon. Proton decoupling power was kept at levels corresponding to 80 kHz. All experiments employed magic angle spinning [MAS) with spinning speeds of 5000 t 2 Hz. In addition, interrupted decoupling (ID) experiments were performed. The interrupted decoupling (ID) technique results in a substantial intensity attenuation of peaks belonging to nuclei with strong dipolar coupling to protons, leaving intact peaks from quaternary nuclei and from nuclei with motionally averaged dipolar interactions (e.g. methyl groups with fast C, rotations). Porosity characterization. The total open pore volume in the W C particles was determined by the quantity of DOP plasticizer [di-2-ethylhexyl phthalate) absorbed by the particles, and also with a mercury porosimeter (Aminco, American Instrument Co., Inc.) according to ASTM D 3367 and ASTM D 2873, respectively. The apparent pore size (diameter) distribution was calculated using the mercury porosimeter method. Electron microscopy. A Jeol J S M 5400 Scanning Electron Microscope (SEM), at an accelerating voltage of 10 kV, was employed to observe the modified PVC particles' external surfaces and freeze fractured

surfaces. The latter were produced by embedding W C particles in an epoxy matrix and fracturing at liquid1 nitrogen temperature. PS is soluble in THF imd PMMA is soluble in MEK. PVC is soluble in both (25). To increase the contrast between the phases within a particle a gentle exposure to THF (tetrahydrofuram)or M E K (methyl ethyl ketone) [for 15 sec and 80 sec, respectively) was employed. By employing the SEM-EDS technique it was possible to i d e n m accumulation zones of the chlorine atoms and thus to discern the XPS or XPMMA location in the PVC particles. All samples were gold sputtered prior to observation. High Resolution Scanning Electron Microscopy (HRSEM)of the particles' surface was perfonmed using a Leo Gemini-982 machine, at an accelerating voltage of 1 kV utilizing the SE IN-LENStechnique. Dynamic Mechanical Properties.The dynamic mechanical properties of compression molded specimens (at 150C) made of the modified PVC particles were measured by dynamic mechanical thermal analysis system (Rheometric Scientific-ARES system), i~n a torsion mode. The frequency used was 1 Hz,and heating was carried out at a rate of 3"C/min.
RESULTS AND DISCUSSION

Yield and Non-ExLractablee The polymerization yields within the moclified IVC particles are shown in Table 1 . The yields for PVC/XPS and WC/PS, by Method (a),were 100% and 80.7940, respectively. Yields for PVC/XPMMA and W C / PMMA were sigmficantly lower. MMA has a large sollubility in

Table 1. Yield, Non-Extractable Content and Pore Volume Fraction From Mercury Penetration and DOP Absorption. No. Ref.
1

___-

System PVC PVCIPS = 75/25 Method (a) PVCIXPS = 75/25, 0.5% DVB Method (a) PVCIXPS = 75/25, 5% DVB Method (a) PVClPMMA = 75/25 Method (a) PVCMPMMA = 75/25,0.5%EGDMA Method (a) PVCIXPMMA = 75/25,5%EGDMA Method (a) PVCIXPMMA = 75/25,5%EGDMA Method (b) PVCMPMMA = 75/25,5%EGDMA, 0.2%Co Method (a) PVCIXP(St-Co-MMA 50/50) = 75/25, 5% DVB Method (a) PVCIXP(St-co-MMA 50150) = 75/25, 5% DVB Method (b)

Yield (wt%.)*

Non-Extractable (wt%)"
0

Pore volume, Y o [Mercury penetration]

Pore volume, Yo [DOP albsorption]

80.7 100 100 39.8 44.6 53.0 69.6

64.0

30.0 26.0 25.5 27.5 26.6 27.8 26.2 22.6

29.5

25.5 23.1 24.1

;!4.0

2 3 4 5
6
7

64.8 86.0
0

111.2 98.9 109.1 83.8 90.8 91.6

i!5.6 2!7.4

8 9 10

72.2 82.2

24.3 22.0

913

'Yield is calculatedfrom the weight gained divided by the weight of the monomer solution (monomer, crosslinker and initiator). ""Non-extractable" is the ratio of the weight of the insoluble residue to the weight gained by the PVC modification.

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M. Shuch-Caplan, M. Narkis, and M. S . Silverstein

water at 20C compared with styrene: 15.9 g MMA/Kg water (26) and 0.6 g styrene/& water (27). respectively. Thus, MMA that did not polymerize within the PVC particles has presumably partially polymerized in the water phase and some has partially escaped the reaction vessel. MMA is more volatile than styrene: boiling points of MMA and styrene are 101 and 145C (28),respectively. A bimodal particle size distribution resulted by p o l y m e r i z i n g / c r o s s l g MMA in the presence of the PVC particles. The overwhelming majority of the resulting solid, 95%, was the 150 pm in diameter modified PVC particles and 5% submicron particles, presumably PMMA particles, generated by an aqueous solution-precipitation polymerization of MMA. Higher yields (69.6V0, Tabk 1 ) were obtained by increasing the crosslinker concentration, adding a cobalt naphthenate accelerator and using Method (b) . Copolymerization, namely synthesis of XP(St-co-MMA),has also increased the yield value ( T a b l e1). The styrene modified PVC with 5% DVB has a higher non-extractable fraction than with 0.5% DVB. The PS is not fully crosslinked and there is 14% extractable fraction even with 5% DVB. It is assumed that most of the non-extractable material is XPS, since under the mild polymerization crosslinking conditions used grafting reactions are not expected. WC/XPMMA and WC/xP(St-co-MMA) contain higher non-extractable fractions than the PVC/XPS parti1 ) and are thus more fully crosslinked. cles (Table The non-extractable fractions (> loo%, experiments 5 and 7) are greater than the possible XPMMA content in these experiments: [WC/XPMMA/0.5% EGDMA, Method (a)]and [WC/XPMMA/5% EGDMA, Method @)I. Thus, although PVC is not expected to undergo crosslinking or grafting reactions under the present polymerization conditions, perhaps some PVC has been entrapped within the XPMMA network. This assumption is supported by EDS analysis, that showed traces (3%) of chlorine within the non-extractable fraction of [PVC/XPMMA/5% EGDMA, Method (b)],but not supported by the following solid NMR experiments.
lSC Solid-State CPMAS

NWR Analysis

13C solid-state CPMAS NMR was used to probe possible phase miscibility and molecular level interactions between XPMMA and W C in [PVC/XPMMA/5% EGDMA, Method (b)].The 13C solid-state CPMAS NMR spectra of WC, a commercial PMMA reference, [PVC/ XF'MMA/.?%o EGDMA, Method (b)], and the non-extractable fraction of [ P V c / X P m / 5 % EGDMA, Method (b)] are presented in Flg. 1 . The spectrum of PVC, spectrum (a),exhibits two major peaks for the different PVC carbons (-CHC1- at 55 ppm, -CH,- at 46 ppm). The spectrum of PMMA, spectrum (el, shows five major peaks (Me at 16.8 ppm, - C-

at 45.6 ppm, OMe at 52.3

ppm. CH, at 56.8 ppm and C=O at 178.3 ppm). The spectrum of [WC/XPMMA/5% EGDMA, Method @)I, spectrum (b),has peaks seen in both the WC and PMMA spectra. Employing an interrupted decoupling scheme further simplifies the CPMAS spectra by sorting out individual contributions (PMMA vs. PVC) within the overlapping peaks. The interrupted decoupling emphasizes the presence of the XPMMA in [WC/XPMMA/ 5% EGDMA Method (b)], spectrum (c).In particular,the quaternary carbon peak of PMMA (45.6 ppm), which overlaps the -CH,- peak of PVC (46 ppm), stands out using interrupted decoupling.

c=o

[PV CIX P M M A , 5% E G D M A

[PV C / X P M M A , 5% E G D M A M e t h o d (b)]

200

160

4 0

Rg. I . I3C CPMAS N M R spectra o f PVC,P M M A and WC/XPMMA = 75/25, 5% EGDMA,m e t h o d [b)]before and after extraction (*SpinningsidebadsJ
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ModiJicQtwn o f Porous Si*spension-PVC Particles The spectra of the non-extractable fraction of [PVC/ PMMA/5% EGDMA, Method @)I, spectrum (d).and the neat PMMA, spectrum (e), are almost identical, within the accuracy of the solid-state NMR measurements, with several small cyclohexanone residual peaks, in the non-extractable fraction of [WC/PMMA/5% EGDMA, Method (b)].The presence of cyclohexanone residual peaks can imply that the 10%additional non-extractables beyond that expected for fully crosslinked PMMA, found in the non-extractable fraction results, is cyclohexanone entrapped by the XPMMA. The spectrum o f the non-extractable fraction of [PVC/PMMA/5% EGDMA, Method (b)] is devoid of the typical PVC peaks that are so prominent in the [wc/xPMMA/5% EGDMA, Method (b)] spectrum. Thus, within the accuracy of the CPMAS NMR measurements, one can conclude, that there is no W C in the non-extractable fraction and thus no indication of grafting of PMMA to W C. The pore volume fractions in the modified W C par. ticles are 1 0 Y o to 20% less than those within the neal W C particles (Table 1 ) . The pore size distributions i n the unmodified and modified PVC particles are g$venl in Fig. 2. The location of the Hg penetratiion curves along the vertical penetration volume axis depends on1 the samples packing level in the glass penetrometer and therefore has no physical meaning. A dematrcation between the voids among the particles and t h e internal particles' open pores occurs at about 8.1 KPa (ASTM D 2873). The pore size within the W C particles lies in the range of 0.17 to 1 km. The pore ,size distribution is only slightly altered by the polymerizationmodification process. Thus, styrene, MMA and St-coMMA polymerize mainly within the PVC bulk with only small fractions polymerized on the pores surface or within the pores. The porosity data, Table 1 , show that W C parbicles modified with PS or PMMA (polymerizedby IMethotrl (a) with different levels of crosslinker) have similar open porosity values. However, Table 1 shows, based on "yield" values, that the amount of PS polymerized within the W C particles is about twice the i U n O U n t of PMMA. Dissolution experiments of W C particles (0.5%) in styrene as a solvent have shown that the PVC has almost completely dissolved after 90 min, whereas PVC particles in MMA as a solvent hardly dissolve after 90 min. The solubility of the monomers in water at 20C is significantly different: styrene-0.6 g/kg 127), NIMA -15.9 g/kg (26). Prior to the polymerization course,

Particle Porosity The inner particle porosity volume fraction of PVC and the modified PVCs, as determined by mercury porosimetry and DOP absorption, are summarized in T a b l e 1. The two measurements of open porosity follow a similar trend. The porosity volume fractions from mercury porosimetry are somewhat larger, since high pressures are employed in the test, whereas the DOP absorption test is performed at atmospheric pressure.

Diameter [microns1 1.2

1

17.5

1.7

0.17

2
I

LI

OV8

* U
.m

0.6
0.4

E *

0 PVCIXPsISo/DVB

CI PVC/XPMMA/S%EGDMA, Method (a)

0
0.1 1

10 Pressure [ma]

100

1000

l?g. 2. Mercury porosimetry curvesfor determination o f modifiedPVC pore sue and volume.
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M . Shach-Caplan, M. Narkis, and M. S. Silverstein

in Method (a),the monomers are added at room temperature to an aqueous dispersion of the PVC particles. Styrene is then absorbed mainly within the PVC particles' bulk and affects their pore size owing to the PVC bulk swelling. In addition to the styrene polymerized in the PVC bulk, a small amount of styrene may polymerize in the PVC pores, filling the pores. In a typical MMA polymerization experiment, by Method (a),25 g MMA are added to the reactor of which 12.7 g MMA dissolve in the 800 g water used and the remaining MMA, 12.3 g, are absorbed in the PVC particles' bulk and coat the PVC pore walls (based on solubility and yield results, Table 1 ) . Polymerization of the "adsorbed" MMA forms a thin coating on the WC pore walls, which reduces the pore size in addition to the reduction caused by MMA polymerization within the PVC particles bulk. PMMA modified PVC particles produced by Method (a),experiment 6, exhibit a slightly higher porosity

(26.2%) than the porosity obtained by Method (b) (22.6%), experiment 7. T a b l e I shows that 53.0% and 69.6% of PMMA are incorporated within the PVC particles by Methods (a) and @), respectively. The larger amount of PMMA incorporated within the PVC particles by Method (b) results from "dry-blending" MMA with PVC prior to contact with water and thus partially hindering MMA dissolution in the water, which eventually leads to lower porosity levels by Method (b).

Particle Structure The inner structure of the modified WC particles is seen in Figs. 3-6, by SEM micrographs of cryogenically fractured particles. Figure 3a shows the porous f the original PVC particle and its interior structure o which is reminiscent of clusters of grapes, a structure typical of suspension-type PVC (29).A second phase, presumably the XPS phase, is visible among the PVC clusters in the styrene-modified PVC particles, Figs.

Rs.3. SEM microgmphs offreezefracture s w f w e s Method (4): (4-lPVC1, DvB1, I@--JpVC/XPS = ?5/25,5%DVE].
916

cbl-lWC/PS = 75/25]. (c)-pvC/xps

75/25, 0.5%

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Modificationo f Porous Suspension-PVC Particles

F7g. 4. SEM micrographs o f freeze fracture swfaces [Method ( 4 foliowing ) THF etching for 15 s: [&-[PVCJ,(b)-[PVC/PS,[clN C / X P S = 75/25,0.5%DVB], [d)--[PVC/xpS = 75/25, 5% DVB].

3b-d, i.e., a certain amount of styrene is polymerized in the W C pores. The second phase is more noticeable for [WC/XPS/S% DVB], Fig. 3d, than for [PVC/PS] and [PVC/XPS/O.5% DVB], Figs. 3b,c, respectively. In Figs. 4a,b the porous PVC and [PVC/PS] clustered morphologies are collapsed owing to solvent etching by THF for 15 s. A distinct network of crosslinked PS, XPS, is seen for [PVC/XPS/O.5% DVS] and [PVC/ xPS/5% DVB] in Figs. 4c,d,respectively, following the THF etching. EDS analysis shows a reduction in chlorine concentration (- 500/0) following etching, supporting that the network structure observed is principally XPS. The XPS network becomes thicker (Fig.4d)and the non-extractable content increases (TableI) at the higher DVB concentration. The exposed XPS network (Figs. 4c,d) may be XPS polymerized within the PVC bulk, in agreement with porosity results which indicate that most of styrene is polymerized within the PVC bulk (TableI).
POLYMER ENGINEERING AND SCIENCE, MAY 2002, Vol. 42, No. 5

The fracture surface of [PVC/PMMA, Method (a)], Fig. 5a, shows some submicron fibrils connecting the W C clusters (marked with arrows). The fracture surfaces of [WC/XPMMA/0.5% EGDMA, Method (a)]and [Pvc/xPMMA/5% EGDMA, Method (a)] in 1"igs. 5,b,c, respectively, are similar to the unmodified PVC (Rg. 3a). The fracture surface of PVC modified with MMA by Method (b)[WC/XPMMA/%o EGDMA] (not shown) is also similar to the unmodified PVC. This suggests that MMA is polymerized mainly within the PVC bulk and just a small amount of MMA is polymerized as crusts on the surface of the PVC pares, in agreement with the porosity results (SEM does not distinguish between W C surfaces and PVC surfaces co,ated with PMMA layer). Etching of neat PVC fracture surfaces with MEK (in which PVC is soluble) shows some collapse of the clustered structure (Rg. 6 4 . The clustered structure is presemed, however, on etching the PMMA and 2PMMA
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M . Shach-Caplan, M . Narkis, and M . S . Silverstein

%. 5. SEM micrographs o f freeze fracture s d - s

EGDMAI,(c)-[WC/X?'MMA
=

(Method (a)):(a)-[PVC/PMIMA = 75/25], IbJ--[WC/xpMMA = 75/25, 0.5%

75/25,5%EGDMA].

modified PVC particles (Figs. 6b-d).In addition, submicron fibrils connecting the W C clusters (marked with arrows) are seen (Figs.6b-d). These fibrils are seen for both PMMA and XPMMA modifications and for Methods (a) and (b).This indicates that there are PMMA and XPMMA coatings on the surface of the W C clusters, which prevent their dissolution in MEK by etching. The original W C clustered morphology is retained for the M E K etched WC/PMMA (without crosslinker) particles, despite the fact that PMMA is known to dissolve in MEK (Fig.6b) or in THF (not shown). The "crosslinked-like"behavior of PMMA may be a result of the tendency of MMA for autoaccelerated polymerization, leading to higher molecular weights, in addition to reduction of termination reactions while dissolved in the W C bulk (3, 16, 30).The inherent viscosity data,
918

T a b l e 2, indeed show that [WC/PMMA] has a signific a n t l y higher inherent viscosity than that of W C and [WC/PS], which supports the finding of high resistance to solvent etching of the P M M A phase. The P M M A and XPMMA present within the W C particles' bulk and also as crusts on the surface of the W C clusters are demonstrated by a schematic model describing the structure of the modified W C particles, shown in Figs. 7c,e, where the neat W C structure is shown in Rg. 8a.Owing to the hydrophilicity difference of P M M A and PS and between their respective monomers, the styrene and MMA polymerization within the PVC particles generates different morphologies (Figs. 7b,c,de). The solubility parameters of styrene and WC, 19.0 and 19.2 [MPa1/21,respectively (25). are close and styrene also has a low solubility in water, 0.6 g/kg (27). Therefore, the styrene is mainly absorbed within
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Modifiatwn o f Porous Suspenswn-PVC Particles

m. 6. SEM micrographs of freQefracture surfaces Method (a))following MEK etching for 80 s: (a)-[PVC],
75/25l, (c)-fWC/xpMMA = 75/25,0.5% EGDMA], (d)-[WC/XFMMA = 75/25,5% EGDMAI.

(b)-[PVC/PMMA

the W C bulk, swell the W C clusters and polymerizes there and just small amount of styrene is polymerized in the WC pores (%s. 7b,d). The solubility parameter values of MMA and WC, 18.0 and 19.2 [Mpa/2], respectively (25), are slightly different. MMA also has a much higher solubility in water, 15.9 g/kg (26), than styrene. Hence, the MMA is absorbed mainly within the WC bulk and some MMA also coats the W C clusters surface. Owing to WC/PS and WC/PMMA incompatibility, the polymerization of the modifying monomers
Table 2. Inherent Viscosity of PS and PMMA Modified PVC (Polymer Concentration in THF = 0.33 dl00 ml).
qinh

PVC PVCIPS PVCIPMMA

0.88

0.83
1.17

leads to the formation of intra-particle modifying piolymer microdomains within the W C bulk (Figs.7b,c)(i31). The presence of crosslinks (XPS and XPMhM) foims a semi-IPN structure that includes the intra-particle modifylng polymer phase as separated microdomatins inter-connected by the modifylng polymer phwe ( F i g s . 7de) (31). The fracture surfaces of [PVC/XP(St-co-ldMA)/5% DVB] (not shown) are similar to those of the XPMMA modified WC particles (Rg. 5c) for both Methods (a) and (b).Styrene/= copolymerization reactivity ratios (rl = k,,/k,, = 0.52 and r, = k,,/k,,, = 0.46, where styrene is monomer 1) are comparable (32) and indicate a similar tendency towards copolymerization. The SEM micrographs of MEK etched fracture surfaces of [WC/XP(St-co-MMA)/5% DVB] (not shown) and [WC/XPMMA/5% EGDMAI (Rg. 6 d ) are s i r m i and show that MMA in both systems produces a crust
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M. Shach-Caplan, M.Ncukis, and M.S. Silverstein

2Clm

I
d i @ d W C . (cI-PMMA modified

Fig. 7 . A schematic model describing the obserued rnimotorned structure of: (al-PVC, (b)-PS W C , W-XPS d $ e d W C , (eJ-XPMMA m o d i i PVC.

920

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Modifiation o f Porous Suspension-PVCParticles

Temperature ["C]
8 . Dynamic behavior: [d-bss modulus (bl--tanS o f compression molded PVC,PVC/PS and W C / X P S , 5% DVB. 'Werirnent No. 1 , Table 1 . **JCcperiment No. 3, Table I .

m.

upon the PVC cluster surfaces. The non-extractable contents (Table1 ) of [PVC/XP(St-co-MMA)/5Yo DVB] and lPVC/XPMMA/5% EGDMA] are similar and support that MMA's presence increases the degree of crosslinking in the [PVC/XP(St-co-MMA)/5Vo DVB] particles. The outer surface of the modified W C particles was observed by SEM and also by HRSEM (not shown).No difference between the unmodified and the XPS and XPMMA modified PVC particles external surface was observed. Outer surface etching and EDS analysis, indicated that there is no XPS or XPMMA crust upon the modified PVC particles. A further support stems from the observation that the modified particles did not stick to each other, indicating that the polymerization/crosslinking process took place within the PVC particles.

Dynamic Mechanical Analysis The dynamic mechanical properties o f the XPS and XPMMA modified PVC particles were studied. The Tgs were taken at the loss modulus maxima. The neat W C has a Tgof 83.9"C. [PVC/PSl and [PVC/XPS/S% DVBl have T e of 82.9"C and 83.9"C, respectively, indicating insignificant differences. Fcgure 8 depicts tans curves where the t a n S curve o f [WC/PS] has a broader peak than of the neat W C , with a barely discernable shoulder that may be ascribed to the ps's transition. The shoulder is not discemable for [Wc/xPs/5% DVB], indicating that there is a smaller degree o f phase separation when the styrene is crosslinked (23). [PVC/XPS/5% DVB] has a broader peak than [PVC/pS], indicating a broad range of compositions in the semi-IPN (33,34). The tans peak
POLYMER ENGINEERING AND SCIENCE, MAY 2002, Vol. 42, No. 5

heights for both [PVC/PSl and [PVC/XPS/'5% DVB] are lower than of the W C t a n S peak height and are a partial reflection of the reduction in W C content [see Table 1). In addition, the peak height for [FVC/XPS/ 5% DVB] is lower than that of [PVC/PS] and thus also reflects the increase in restriction imposed by the presence of a crosslinked network in the semi-IPN morphology, which limits segmental motion and phase separation, in accordance with Nielsen and Lander description (33). The loss modulus curves (not shown) of neat PVC, [PVC/PMMA] and [Wc/XPMMA/5% EGDMA] depict similar glass transitions: 83.9"C, 84.0"C and 83.EiC, respectively. The tan6 curves of neat WC, [WC/PMIM] and [PVC/XEWMA/5% EGDMA] are shown in FQ. 9. The presence of PMMA yields a slight increase in the t a n 6 peak height (contrary to PS presence, F'ig. 9) imd breadth. The storage modulus curves of PVC, [PVC/PS] and WC/XFS/5Vo DVB] are shown in Fcg. 10. The decrease in the storage modulus with temperature within the glass transition region is more rapid for PVC: than for [PVC/PS] and [PVC/XPS/5% DVB]. [PVC/PS] and [Wc/XPs/5% DVB] also exhibit a longer rubbery plateau, which reaches 125C for PVC, 137C for [WC/PS] and 145C for [ w c / x P S / 5 % DVB] typical o f preseince of a network. The thermal mechanical stability is thus slightly enhanced on incorporation of PS and even further enhanced on incorporation of XPS. Tfie storaage modulus curves of PVC, [PVC/PMMAl arid [PVC/ XPMMA/5% EGDMA] are shown in Fig. 1 1 , where practically no change in the storage modulus behavior
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M.Shach-Caplan, M.Narkis, and M. S . Silverstein

Temperature ["C]
Fig. 9. Dynamic behavior: (a)--Loss modulus (b)-tanS o f compression molded PVC,[PVC/PMIMA] and *ExperimentNo. 4. Table I . *' t No. 6, Table 1.

lPVC/XpMMA/B%E G D M ] .

Temperature ["C]
Fig. 10. Storage modulus o f compression molded PVC,[pvC/PS] and mC/XPS/5% DVB]. *Eqeriment No. 1, Table 1. ***Experiment No. 3, Table 1.

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Modification o f Porous Suspension-PVCP a r t i c l e s

loooo
1000

T-

100

10
-

-PVC/XPMMA,

S%EGDMA**

1
100 120
140

20

40

60

Temperature["CI
Fig. 1 1 . Storage modulus o f compression molded PVC, [WC/PMMA] and [PVC/XF'MMA/B% E G D M ] . *Experiment No. 4, Table 1. **ExperimentNo. 6, Table 1 .

within the glass transition region is noted and only a small extension of the rubbery plateau is seen on incorporation of XPMMA. The lack of influence of PMMA on the loss and storage modulus is a reflection of the smaller amounts of MMA incorporated within the W C particles. Also, a more compatible blend seems to result for the PS modified W C particles.
SURlMLARY

ACKNOWLEDGMENT

This paper describes a novel modification method of in-situ stabilizer-free polymerization/crosslinking of a monomer/crosslinker/peroxide solution absorbed within porous commercial suspension type PVC particles. The modifying crosslinked polymers chosen are based on styrene crosslinked with DVB, MMA crosslinked with EGDMA a n d styrene-MMA copolymer crosslinked with DVB. The conversions of styrene and MMA are affected by their solubility level in water and the polymerization method used. The non-extractable fr-actionand 13C solid-state CPMAS NMR results do not provide a n indication of chemical interaction between the modifying polymers and WC. Porosity variation studies are useful to identify the modifying polymer's location in the porous particles. Tans and storage modulus curves are only slightly influenced by incorporation of PS and XPS. The lack of influence of PMMA on the loss and storage modulus is a reflection of the smaller amounts of MMA incorporated within the PVC particles compared to styrene and perhaps since a more compatible blend results for the PS modified W C particles.
POLYMER ENGINEERiNG AND SCIENCE, MAY 2002, Voi. 42, No. 5

The support of the Water Research Institute, Technion-IIT, is gratefully acknowledged. The authors wish to thank Drs. A Schmidt and S . Kababya, Departmlent of Chemistry, Technion, for the solid-state IVMR studies and Dr. F. Lerner, Electrochemical Industries, Frutarom Israel, for the DOP absorption tests. M. Shach-Caplan acknowledges the generous financial support of the Levi Eshkol scholarship from the Israel Ministry of Science and Culture to support her PhD studies.

REFERENCES
1. D. J. Walsh and G. L. Cheng, Polymer,25,1 0 1 2 3( 1 9 1 3 4 ) . 2.M. Riitzsch, H. Bucka, A. Hesse, and M. Amold, lzVe AppL Chem, A33(7), 913 (1996a). 3 . M.Riitzsch, H. Bucka, A. Hesse, and E. Boraig, AhTEC

'97, 2022 (1997). 4. M. Narkis, Y. Talmon, and M. Silverstein. Polymer, 20, 1359 (1985). 5. S.-A. Chen and S.-T. Lee, polymer. 33,1437 (1992). 6. W. He, C. Cao, and C. Pan, J. AppL P o l y m Sci, 01,383 (1996). 7 . M. Silverstein and M. Narkis, J. AppL Polyn~Sci, S S , 2529 (1987). 8.N. Nemirovsky, M. Silverstein, and M. Narkcis. Polym Adv. Tech, 7, 247 (1996). 9.M. Okubo, Y. Katsuta, and T. Matsumoto, J. Poolyn !W: Polym Mt. Ed, 18,481 (1980). 1 0 .D.ZQU, L . Sun, J. J. Aklonis, and R. Salovey, J. Polym sci: PartA: m4m C h e m Ed,50, 1463 ( 1 9 9 2 , ) . 11. S.Shim,Y. Cha, and S. Chne, P o h ~ m Reprints, S 8 ( 1 ) , 434 (1997). 1 2 .Z . Song and G. W. Poehlein, J. Colloid Intebrface Sci., 138(2),486 (1989).

923

M. Shach-Caplan, M.Narkis, and M. S . Silverstein

13. A. Eshuis, H. J. Leendertse, and D. Thoenes, Colloid Polyrn Sci, 269, 1086 (1991). 14. M. Shach-Caplan, M. Narkis. and M. S . Silverstein, PoZyrn Ado. Tech, to appear. 15. M. Mtzsch, H. Bucka, and C. Wohlfahrt, Angewandte MaJwomoL Chern,229, 145 (1995). 16. M.Mtzsch, H. Bucka, A. Hesse, M. Arnold, and E. Borsig, AN773C '96, 1616 (1996b). 17. L. E. Walker, Graft polymers of polymerizable monomers and olefh polymers, U.S Patent 4,661,549 (1987). 18. G.Akovali, K.Biliyar, and M. Shen, J.AppL Polym Sci, 20, 2419 (1976). 19. L. Lapcik, V. Chrastova, J. Polavka, and J. Panak. Colloid &PoZyrn Sci, 267, 1128 (1979). 20. M. Kryszewski, PoZym. Ado. Tech., 9, 244 (1998). . 21. A. Slumy, M.Silverstein, A. Schmidt, and M. Narkis. J Polym Sci., Chem. Ed, 39, 8 (2001). 22. L . H. Sperling, Interpenetrating PoZyrner Networks and Related Materials,Plenum Press, New York (1981). 23. J. K . Yeo. L. H. Sperling, and D. A. Thomas, Polym Eng. Sci,22, 190 (1982). 24. L. H. Sperling and J. M. Widmaier. Polyrn Eng. Sci, 23, 693 (1983). 25. J. Brandrup and E. H. Immergut, Polymer Handbook, John Wiley & Sons Inc. (1989). 26. W. Gerhartz. Lnlman's Encyclopedia o f Industrial Chemi s t r y ,A l e , 442, VCH, Weinhartz (1985). 27. R. H.Boundy and R F. Boyer, Styrene, Reinhold, New York (1952). f Chemistry and Physics, 67th Edition, 28. CRC Handbook o CRC Press, Inc., Boca Raton, Florida (1986). 29. P. V. Smallwood, PoZymer, 27, 1609 (1986). 30. P. J. Flory, Polymer Chemistry, 15th Ed., Cornell University Press,Ithaca, N.Y. (1992). 31. M. Silverstein and M. Narkis. PoZyrn Eng. Sci. 29, 824 ( 1989). f Polymer Sci32. D.W. Fox and R. B. Allen, Encyclopedia o ence & Technology, 16, p. 37, John Wiley & Sons Inc. (1989). 33. L. E. Nielsen and R. F. Lander, Mechanical properties o f Polymers and Composites, Marcel Dekker, Inc. (1994). i t a n i ,and Y. Mizutani, J . Appl. 34. T. Hayashi, J. Ito, K. M PoZyrn Sci, 2 8 , 2867 (1983).

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