Preparation of Calcium Carbonate@Methyl ... - ACS Publications

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Industrial & Engineering Chemistry Research

Preparation of Calcium Carbonate@Methyl Methacrylate Nanoparticles by Seeded-Dispersion Polymerization for High Performance Polyvinyl Chloride Nanocomposites Wenqiong Ye, Ling Zhang*, Guowei Feng, Jing Ye, Chunzhong Li* Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China *Corresponding author: Tel.: +86-21-64250949, Fax: +86-21-64250624 E-mail: [email protected] (L. Zhang), [email protected] (C. Z. Li)

ACS Paragon Plus Environment


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ABSTRACT Calcium carbonate@methyl methacrylate-polyvinyl chloride (CaCO3@PMMA-PVC) nanocomposites with outstanding mechanical performance have been successfully prepared. The precisely control over CaCO3 surface modification via a green, facile and reproducible seed dispersion polymerization, not only efficiently avoid agglomeration of the incorporated nanofillers, but also ensure enhanced interfacial adhesion between components, endowing the resultant composite with high performance. Specifically, the maximum tensile strength of PVC composites was achieved when the addition of CaCO3@PMMA NPs is 4 wt% and the grafting content is 25%. Compared to pure PVC (P-PVC), the composite shows robust mechanical properties with a 116.7 % increase in modulus and a 57.0% improvement in hardness. KEYWORD PVC, PMMA, CaCO3, Nanocomposite, Mechanical properties


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1. INTRODUCTION Hybrid inorganic-organic nanocomposites are advanced functional materials, which combine high mechanical strength and thermal stability of inorganic nanoparticles with the flexibility and processability of organic macromolecules. 1,2 In addition to different kinds of inorganic nanoparticles (NPs), such as montmorillonite, aluminum oxide

5,6

3,4

and silica, 7,8 CaCO3 plays an important role in reinforcement

components due to very low cost, chemical resistance and nanoscale effects.

9,10

CaCO3 based-nanocomposites are usually created by melt mixing CaCO3 NPs with polymers. However, the high surface energy of NPs, especially under melt fabrication processes with high viscosity, makes them difficult to disperse individually in matrices11-13and instead deteriorate the original performance of polymer matrix. Zaman et al. 14 put forward that the poor adhesion between CaCO3 and polypropylene (PP) leads to the decreasing of the tensile yield stress with increasing CaCO3 addition fraction. Thus, the modification of CaCO3 NPs to control their dispersion state in polymeric matrix and interfacial compatibility within components is well understood to be the prerequisite for developing new materials with synergic performance. 15, 16 A large number of studies are targeted to this goal in the past few decades. 17-20 Sun et al21 studied the influence of titanate coupling agents on the dispersion of CaCO3 in PVC matrix. Although simple surface treatment with coupling agents led to the reduction of agglomerates, substantial small, strongly bonded aggregates still remain in the composite. Another attractive and efficient method to improve the distribution and dispersion of NPs in polymer matrix is grafting or dispersion polymerization.



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Bourgeat-Lami et al. 22 have prepared micron-sized polystyrene (PS)/silica core-shell nanostructures with well-defined morphology. CNT grafted with styrene-maleic anhydride copolymers (SMA) was used to enhance the interaction with PVC matrix. 23 Nevertheless, this method is almost carried out on nanofillers such as silicas, carbon nanotubes (CNTs) and clays, seldom was done on CaCO3 NPs. It is still a challenge for the dispersion of CaCO3 NPs, which is very critical for the preparation of polymer nanocomposites with low costs. Herein, we have explored the use of CaCO3@PMMA NPs as reinforcing filler for PVC via a green, facile and reproducible seed dispersion polymerization and solution blending method. The CaCO3@PMMA NPs with high uniform coating not only effectively prevents the aggregation of CaCO3 nanoparticles but also simultaneously enhances the interfacial adhesion between the fillers and the PVC matrix, endowing the resultant composite with outstanding mechanical performance. 2. Material and methods Materials. Methyl methacrylate (MMA, 99%, vacuum-distilled), oleic acid, ammonia (NH3·H2O) were obtained from Shanghai Lingfeng Chemical Reagent Co., Ltd.. Pure CaCO3 NPs were homemade through the batch bubbling carbonation method. 2,2’-Azobis(isobutyramidine)

dihydrochloride

(AIBA),

2,2'-Azobis(2-methylpropionitrile) (AIBN) and poly(N-vinylpyrrolidone) (PVP) were purchased from Aladdin Chemistry Co., Ltd., Shanghai, China. PVC powders were kindly afforded by Huazhijie Plastic Building Material Co.,Ltd.. Deionized water was applied for all polymerization and treatment processes. CaCO3 treated with stearic


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acid (CaCO3-st) were purchased from Shanghai Zhuoyue nano New Material Co., Ltd .. Synthesis of CaCO3@PMMA NPs. CaCO3 NPs were previously modified by oleic acid to enhance favorable interactions with the growing polymer chains. 24 In a typical synthesis, 15g CaCO3 NPs, 50ml H2O and 1 ml oleic acid were vigorously agitated for 2 h at 25°C. Then, 4 ml NH3·H2O was added to the above solution and it was continued to stir at 70°C for another 4 h. The reaction product was centrifuged and redispersed several times to purify in a 3:1 ethanol/water mixture and before freeze drying. 1g oleic acid-CaCO3 NPs, 1.5 g PVP and aqueous ethanol solution were introduced into 250 ml three-neck round flask fitted with evacuation-nitrogen(N2) system and ultrasonically dispersed for 2 h. The reaction medium was then degassed by several cycles of evacuation-N2, and MMA and initiator (0.5 wt % relative to monomer) were subsequently added into the suspension when the system was heated to 70 °C in an oil bath. The resulting products were collected by centrifugation (7000 rpm, 20 min) before drying in the vacuum freeze dryer. Fabrication

of

the

CaCO3@PMMA/PVC

composite

Film.

All

the

CaCO3@PMMA/PVC composite film were made by the liquid phase blending method. CaCO3@PMMA NPs and PVC powders were dispersed in DMF separately. And then two solutions mixed together and stirred for 4h at 70°C. The mixtures were drop casted on polytetrafluoroethylene plate and dried under 110°C to obtain CaCO3@PMMA/PVC composite films.



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Characterizations. The morphology of as-produced materials were characterized by transmission electron microscope (TEM, Oxford JEM-2100) and scanning electron microscopy (SEM, Hitachi S-4800).The corresponding mechanical properties of nanocomposite films have been analysed by nanoindentation tests (Hysitron TRIBOINDENTER) with Berkovich tips, dynamic mechanical analysis (DMA, TA 2980) and tensile test (H10KL Tinius Olsen) with cross-head speed of 5 mm/min. 3. RESULTS AND DISCUSSION

Fig. 1 TEM and SEM images of CaCO3@PMMA NPs obtained in an ethanol (100 x)/water (x) % medium in the presence of CaCO3 seeds: (a, d) x =80, (b, e) x =66, and (c, f) x = 50. T=70°C, [MMA] =5 g/L The morphology of CaCO3@PMMA NPs is determined by various factors, especially the nature of the dispersing medium and monomer concentration. In order to investigate the influence of the medium on the morphology of CaCO3@PMMA NPs, polymerization reactions were performed in series of different ethanol/water medium. Considering that PMMA was much more solvable in ethanol than in water, increasing the water portion would be efficient to decrease the solubility of polymer chains and


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shorten the critical chain length at which the PMMA nuclei are formed. Fig. 1 shows the resulting SEM and TEM images of the CaCO3@PMMA NPs by adjusting the ratio of ethanol/water from 1:4 to 1:1. As shown in Fig.1, both the size and number of pure PMMA particles decreased when decreasing the water portion in medium. When the portion of water is high (1:4), the trend of forming individual large pure PMMA particles is obvious and uncoated CaCO3 particle appeared on the surfaces of PMMA particles. When the water portion in medium decreases to 50%, CaCO3 particles with high coating efficiency are obtained, which reveals that decreasing the water portion results in increasing the critical chain length at which the PMMA precipitates from the solution and afford sufficient time for reaction between MMA radical chain segments with CaCO3 surface oleic double bond to form PMMA polymer layer on the surfaces of CaCO3. Hence, we conclude that the uniform coating was obtained at an ethanol: water volume ratio of 1(Figure 1f) and this ratio was applied for the following research. Fig. 2 shows the effect of the monomer concentration on the morphology of CaCO3@PMMA NPs. When the concentration of MMA was 11 g /L, the PMMA particles showed a great tendency to coagulate with CaCO3 NPS merely attaching at their surfaces. In order to achieve the well-designed hybrids, we varied the MMA concentration from 9 g/L to 3 g/L in a train of experiments. The SEM images revealed a strong influence of the MMA concentration on the particle distribution and coating efficiency of PMMA on the surfaces of CaCO3 NPs. As lowering the MMA concentration, the hybrids gradually changed from large clusters to chain-like



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aggregation. When MMA concentration was 3 g/L, CaCO3 showed a well distribution and the PMMA shells are about 3 nm in thickness (Figure 2e and 2f), which is beneficial for CaCO3 dispersion. Thus, by adjusting the reaction medium and the MMA concentration, the CaCO3@PMMA NPs with high uniform coating and well dispersion can be achieved.

Fig. 2 Typical TEM images of the CaCO3@PMMA NPS morphology as a function of MMA concentration: a) 11 g/L, b) 9 g/L, c) 7 g/L, d) 5 g/L and e) 3 g/L; f) is the FE-TEM image of the CaCO3@PMMA NPs


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Fig. 3 TGA curves of CaCO3@PMMA hybrids synthesized with different MMA content To investigate the amount of PMMA grafted on the surfaces of CaCO3, thermogravimetric analysis was performed. During the warming process, the weight loss of CaCO3@PMMA around 200-600 ℃ corresponds to the oxidative degradation of PMMA. As can be seen in the Fig.3, the PMMA layer outside the CaCO3 cores became thinner and thinner when decreasing the MMA concentration. And in order to classify,

each

obtained

hybrid

was

named

as

CaCO3@45%PMMA,

CaCO3@32%PMMA, CaCO3@25%PMMA and CaCO3@14%PMMA, respectively. CaCO3@PMMA NPs with different PMMA concentration were incorporated in PVC through solution blending method. The effect of the grafted PMMA concentration on the resultant mechanical properties of CaCO3@PMMA NPs reinforced PVC composites were investigated. In order to investigate the structure-property relationship, we make further morphological analysis. Fig. 4 demonstrated the cross-sectional SEM images of as-produced films after tensile test. As can been seen, the untreated CaCO3 exhibited severe nanoparticle aggregation within the matrix due



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to their high surface energy. While the uniform coating of PMMA on the surfaces of CaCO3 NPs by seed dispersion polymerization can effectively avoid the fillers aggregation (Figure 4b-d) as well as afford enhanced interaction between the fillers and the matrix, which can effectively accelerates load transfer from the matrix to CaCO3 NPs.

Fig. 4 The cross-sectional SEM images of (a) untreated CaCO3/PVC composites, surface PMMA grafting content of CaCO3 filler: (b) 14%, (c) 25%, (d) 32%, (e) 45%, all the scale bars are 1µm

Fig. 5 The tensile properties of as-produced nanocomposites The

corresponding

tensile

properties

of CaCO3@PMMA


reinforced

PVC

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nanocomposites have been tested as shown in Fig. 5 along with those for untreated CaCO3 filled PVC film for comparison. It is obvious that the untreated CaCO3 filled composite showed declining trend with the increasing CaCO3 content due to the poor dispersion of CaCO3 NPs and the weak interfacial adhesion between the CaCO3 NPs and the matrix (Fig.4a). However, it’s worth noting that the grafted PMMA on the CaCO3 surface has great influence on the tensile properties of CaCO3@PMMA NPs reinforced PVC composites. The importance of optimizing the grafted PMMA concentration in CaCO3 modification is immediately apparent. Too low PMMA concentration (14%) leads to inefficient interface interaction, whereas too high PMMA concentration (45%) leads to form severe CaCO3 aggregation embedded in PMMA layers (Fig. 2b and Fig. 4e). Only when treated with suitable PMMA grafting mass percent (25% and 32%), the CaCO3 showed great compatibility with PVC and thus increased the tensile stress of the polymer matrix. In a word, we can make a conclusion that CaCO3@25%PMMA with 4% addition can achieve optimal performance, and this condition was used in the following study.

Fig. 6. Thermomechanical properties of as-produced films: (a) storage modulus (E’), (b) tan δ as function of temperature



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Figure 6 shows the dynamic mechanical properties of as-produced films. As for all nanocomposite films, the incorporation of CaCO3 NPs suppresses the mobility of the segments of PVC chains and thus increases the modulus of pure PVC film (p-PVC). The PVC nanocomposite with CaCO3@25%PMMA showed the highest E’ values due to the homogeneously dispersion of CaCO3 within the polymer matrix (Fig.4c) and the interfacial grafted PMMA layer, which entangled with the PVC chains and enhanced the interaction between components. Fig. 6b showed loss factor (tanδ) examined as a function of temperature. The tanδ curves show peaks, which are corresponding to the glass transition temperature (Tg). The Tg of pure PVC is about 101°C, whereas the Tg for CaCO3@25%PMMA-PVC nanocomposites shifted to higher value (approximately 106°C). The increased Tg for CaCO3@25%PMMA-PVC can also be ascribed to the improved interfacial interaction between PVC chain and the PMMA chains grafted on CaCO3 surfaces.

Fig. 7 (a) typical indentation load-displacement curves of the films. (b) The corresponding modulus (E) and hardness values of the films In addition to the tensile and dynamic mechanical properties, the typical nanoindentation test was also carried out with the maximum load setting as 4 mN. As


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shown in the Fig. 7a, the CaCO3@25%PMMA-PVC composite film only consists of 5% CaCO3 fillers, but exhibited the minimum deformation, indicating it was excellent for withstanding

the

external

force.

What’s

more,

the

incorporation

of

CaCO3@25%PMMA increased the hardness and modulus of the nanocomposites to 0.26 GPa and 5.48 GPa, respectively, which is about 116.7 % and 57.0% higher than those of pure PVC. However, the CaCO3/PVC film with untreated CaCO3 only showed a relatively low increase trend due to the formation of severe nanoparticle aggregates (Fig.4a). Therefore, both well-dispersed load-bearing CaCO3@PMMA NPs and the strong adhesion between the components are responsible for the relatively higher hardness and modulus of the composite. 4. CONCLUSION In this work, we have successfully prepared the CaCO3@PMMA-PVC composite via a green and facile seed dispersion polymerization and the liquid phase blending method. The resultant film possesses outstanding mechanical properties due to the well-dispersed CaCO3@PMMA NPs and the strong adhesion between the components, which closely relates to the precisely controlled structure of CaCO3@PMMA NPs by changing the synthesis conditions. This work sets up a facile and successful method for the design of a nanocomposite with excellent properties and are promising to be used for further research.

Acknowledgements This work was supported by the National Natural Science Foundation of China



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TOC

The precisely control over CaCO3 surface modification has efficiently ensured enhanced interfacial adhesion between components, endowing the resultant composite with high performance.


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Preparation of Calcium Carbonate@Methyl ... - ACS Publications

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