Synthesis of Reactive Comb Polymers and Their Applications as a

Subscriber access provided by Columbia Univ Libraries

Article

Synthesis of reactive comb polymers and their applications as a highly efficient compatibilizer in immiscible polymer blends Wenyong Dong, Hengti Wang, Meifeng He, Fanglu Ren, Tao Wu, Qianru Zheng, and Yongjin Li Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/ie503645a • Publication Date (Web): 26 Jan 2015 Downloaded from http://pubs.acs.org on February 3, 2015

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Industrial & Engineering Chemistry Research is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

Synthesis of reactive comb polymers and their applications as a highly efficient compatibilizer in immiscible polymer blends

Wenyong Dong, Hengti Wang, Meifeng He, Fanglu Ren, Tao Wu, Qianru Zheng， Yongjin Li*

College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, No.16 Xuelin Road, Hangzhou 310036, P.R. China

*Corresponding author. Email: [email protected] TEL: 86-571-2886-7206; FAX: 86-571-2886-7899

ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract Reactive comb (RC) polymers were synthesized by copolymerizing methyl methacrylate (MMA) with glycidyl methacrylate (GMA) and a kind of MMA macromer. The obtained molecules had both epoxide groups and long PMMA side chains distributed randomly along the PMMA backbone. The synthesized RC polymers were applied as compatibilizers in an immiscible poly(L-lactic acid)/poly(vinylidene fluoride) (PLLA/PVDF) system. Compared to their linear counterparts, only 1 wt% of RC polymers with appropriate length of side chains significantly reduced the size and enhanced the uniformity of the PVDF dispersed phase in PLLA matrix and the RC-compatibilized blends exhibited a significant improvement in fracture strain. The higher compatibilization efficiency of RC polymers was ascribed to the existence of PMMA side chains, which improved the stability of RC polymers at the interface of immiscible blend and this was demonstrated by TEM.

Keywords: Reactive comb polymer, Immiscible blends, Compatibilization efficiency, Interface


Page 2 of 26

Page 3 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1. Introduction Polymer blending is an efficient and economic pathway to develop novel polymer products with advantageous combination of useful properties.1,2 This technique is based on the addition of pre-made polymers (block, graft, etc) or in-situ formed reactive compatibilizers, in order to lower the interfacial tension of immiscible polymers, decrease the dispersed phase size, suppress the coalescence of the dispersed phase and improve the interfacial adhesion. Reactive compatibilization is attractive for industrial application; for the formation of block or graft polymers in this technique, the compatibilizers are required to have a backbone that is miscible with one phase and some functional groups, distributed along the backbone or at the chain end.3-8 During melt blending, the functional groups can react with the complementary groups of the other phase and the compatibilizers are in-situ formed at the interface. Although some authors have shown that the molecular structure had influences on the reaction kinetics and the stability of the reactively formed compatibilizers at the interface, which finally determined the microstructure morphology and compatibilization efficiency, only a limited number of theoretical and experimental works were devoted to this topic. Charoensirisomboon et al.9 found that the in-situ formed graft polymers were more stable at the interface than the in-situ formed block polymers under shear condition. Jeon et al.10 also indicated that graft polymers were more efficient than block ones in the reactive case, because graft polymers had a greater capacity to reduce interfacial tension. Kim et al.11 found that the chain architecture of the in situ formed graft or block copolymers significantly influenced the interfacial morphology. The aforementioned comparisons were all between in-situ formed block and graft polymers. In this work, we synthesized and compared the compatibilization efficiency of two kinds of polymers, reactive comb (RC) and reactive linear (RL) polymer. The former was synthesized by copolymerizing methyl methacrylate (MMA) with glycidyl methacrylate (GMA) and a kind of MMA macromer. Thus the obtained molecules had epoxide groups in the backbone and some PMMA side chains. It was a kind of comb structure and defined as RC polymer. The latter RL polymer was obtained by copolymerizing MMA with GMA. The compatibilization efficiency of these two kinds of compatibilizers was investigated in a model immiscible polymer blend, poly(L-lactic acid)/poly(vinylidene fluoride) (PLLA/PVDF), because PMMA was known to be thermodynamically miscible with PVDF and the epoxide groups in GMA were capable of reacting



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

with the end groups of PLLA.12-16 Hence the PLLA grafted RC polymers represented a bimodal system, where the PMMA side chains interacted with the PVDF phase and the PLLA grafted chains from the epoxide groups penetrated into the PLLA phase (see Figure 1); while the PLLA grafted RL polymers was a classic monodal system, where the PMMA backbones interacted with the PVDF phase and the grafted PLLA chains with the PLLA phase.17-22 By comparing and evaluating the compatibilization efficiency of the RL and RC polymers, we explored the effect of the side chains on the interfacial behavior of the reactive polymers.

Figure 1. Schematic illustration of the compatibilizing reaction between reactive comb polymer and PLLA.

2. Experimental section 2.1 Materials Methyl methacrylate (Shanghai Sinopharm) was washed twice with aqueous 5% NaOH and twice with water and distilled over CaH2

at reduced pressure just before use.

4,4’-azobis-(4-cyanovaleric acid) (ACVA) (98%, Acros) and 2,2’-Azoisobutyronitrile (AIBN) (99%, Shanghai Sinopharm) were recrystallized from methanol. Glycidyl methylacrylate (98%, ACROS) was passed through a basic alumina column to remove the inhibitor. Thioglycolic acid (TAC), hydroxyquinone and N,N’-dimethyllaurylamine were all from Shanghai Sinopharm and used as received. THF was dried by refluxed with the sodium-benzophenone complex under nitrogen gas and distilled just before use. Toluene were dried with CaH2 and distilled under reduced pressure before use. The PVDF and PLLA samples used were commercially available KF850 (Kureha Chemicals, Japan) and 3001D (Nature works, US), respectively.


Page 4 of 26

Page 5 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2.2 Instruments and Measurements 1

H Nuclear magnetic resonance (NMR) spectra were recorded with a Bruker Avance 500

spectrometer at room temperature, operating at a frequency of 500 MHz, with deuterated chloroform as the solvent. Fourier transformed infrared (FTIR) measurements were recorded on an FT-IR spectrometer (Bruker, VERTEX 70V). A minimum of 16 scans at a resolution of 2 cm-1 was used. The spectra of the synthesized PMMA-COOH, MMA macromer, RL and RC polymers were recorded by a KBr disc method, in which the samples were grinded with KBr. The spectra of the PLLA/PVDF blend were recorded by a solvent casting method and the samples were prepared as follows: the mixture of PLLA/PVDF/RC at a weight ratio of 50/50/10 was dissolved in DMF; the obtained solution was casted on KBr pellet; the DMF solvent was evaporated at room temperature in vacuum oven for at least a week and the obtained sample was denoted as the PLLA/PVDF blend before compatibilization. The sample of the PLLA/PVDF blend after compatibilization was obtained as follows: blending PLLA/PVDF/RC at a weight ratio of 50/50/10 in a batch mixer (Haake Polylab QC) with a twin screw at a rotation speed of 50 rpm at 190 °C for 10 min; the obtained blend was dissolved in DMF and then the following steps were the same as that of the sample denoted as the PLLA/PVDF blend before compatibilization. Gel permeation chromatography (GPC) was carried out to determine the number-average molecular weight (Mn) and dispersity (Ð) using two MZ-Gel SDplus 10.0 µm bead-size columns (10E5 and 10E3 Å) and Optilab T-rEX detector. THF was used as the mobile phase at a flow rate of 1 mL min-1 at 35 °C. The system was calibrated with both narrow molecular weight distribution polystyrene and poly(methyl methacrylate) standards from 2000 to 106 g mol-1. The elution diagrams were analyzed using the ASTRA 6 software from Wyatt Technology. Scanning electron microscopy (SEM) images were recorded using a field emission scanning electron microscope (Hitachi S-4800) at an accelerating voltage of 5.0 kV. All the samples were fractured by immersing in liquid nitrogen for about 10 min. The fracture surface was then sputtered with a thin layer of gold. Transmission electron microscopy (TEM) was performed using a Hitachi HT-7700 instrument operating at an accelerating voltage of 80 kV. The blend samples were firstly ultramicrotomed to obtain a section with a thickness of about 70~100 nm and then treated with



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Ruthenium tetroxide (RuO4) for 3 h in order to selectively stain the PVDF phase. Image analysis on SEM and TEM results was carried out using a semi-automatic method. The diameter of the dispersed particles di was calculated by di=2(Ai/π)1/2, assuming a spherical geometry and Ai was the area of an individual particle measured by NIH image software. The number-average particle size, dn was calculated according to the following equation:

∑N d = ∑N i

dn

i

i

i

i

where N was the number of particles with size d and more than 300 particles were counted.23-25 Differential scanning calorimetry (DSC) measurements were carried out from a DSC Q2000 (TA Instrument) in an inert atmosphere of nitrogen at a heating or cooling rate of 10 °C min-1 with a temperature range from -50 to 200 °C. Dynamic mechanical analysis (DMA) was carried out in tension mode using a DMA Q800 (TA Instrument) with sample dimensions of 8*6.30*0.50 mm. The samples were tested at a frequency of 5 Hz, an amplitude of 4 µm and a heating rate of 3 °C min-1 from -50 to 150 °C in a nitrogen atmosphere. Tensile tests were carried out using an Instron universal material testing system (model 5966) at 23 °C at a crosshead speed of 10 mm min-1. The specimens were punched out of the compression-molded films into dumbbell shape (18 mm gauge length, 0.5mm gauge thickness and 3 mm gauge width). 2.3 Synthesis of carboxyl-terminated PMMA (PMMA-COOH) A typical example was given for ACVA/TAC molar ratio of 1/5 (Code 6 in Table 1). As shown in Scheme 1, MMA (20g, 0.2mol), ACVA (0.56g, 0.002mol) and TAC (0.92g, 0.01mol) were dissolved in dry THF (20ml). The polymerization was conducted at 60 °C under a nitrogen atmosphere in septum-sealed glass bottle. After 4 h, the reaction was stopped by diluting with acetone and precipitated once in water and twice in petroleum ether. The product was dried in vacuum at 50°C over night.26-29 The number average molecular weight (Mn) of the products could not only be determined by GPC, but also by titrating with 0.02 mol L-1 KOH alcohol solution, using phenolphthalein as an indicator.


Page 6 of 26

Page 7 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2.4 Synthesis of MMA macromer The MMA macromer was synthesized by the reaction of the carboxyl-terminated PMMA with the epoxide groups of GMA (Scheme 1). A typical reaction was carried out as follows： PMMA-COOH (Mn = 2200 g mol-1, determined by titration) (30g, 0.015mol), GMA (3g, 0.02mol), hydroquinone (0.02g, 0.00018mol) and N,N’-dimethyl lauryl amine (0.03g, 0.00014mol) were dissolved in xylene (100ml) and reacted at 140 °C for 10 h. The product MMA macromer was purified by precipitating into petroleum ether for three times and dried in vacuum. 2.5 Synthesis of reactive comb (linear) polymers The RC polymers were synthesized by copolymerizing MMA macromer with MMA and GMA, initiated by AIBN; replacing the MMA macromer with MMA, RL polymers were obtained (Scheme 2). In a typical synthesis, MMA macromer (2g), GMA (4g), MMA (14g) and AIBN (0.7g) were dissolved in dry toluene (20 ml). The solution was degassed (three freeze-pump-thaw cycles) and sealed under vacuum. The polymerization was carried out at 60 °C for 5h to allow the almost complete conversion of the monomers (>95%). The reaction was stopped by diluting with acetone and the product thus obtained was precipitated twice in petroleum ether and dried in vacuum oven at 50 °C over night. 2.6 Preparation of PLLA/PVDF blends The PLLA/PVDF blends with various amounts of RC or RL polymers as synthesized above were prepared in a batch mixer (Haake Polylab QC) with a twin screw at a rotation speed of 50 rpm at 190 °C for 10 min. The weight ratio of PLLA/PVDF was fixed to 50/50 and the content of the RL or RC in the blends was 1, 3, 5 wt% with respect to the weight of the PLLA/PVDF blends. After blending, the samples were hot-pressed at 200 °C into sheets with a thickness of about 0.5 mm for 5 min under a pressure of 10MPa and then cooled to room temperature in another cold press under 10MPa. The obtained sheets were used directly in the subsequent characterization. 3. Results 3.1 Synthesis and characterization of reactive comb (linear) polymers As shown in Scheme 1, we chose a macromer method to synthesize reactive comb (RC) polymers and the first step was the telomerization of MMA with TAC as a chain transfer agent (TGA). Hatada et al30 indicated that the polymerization of MMA initiated by AIBN was mainly terminated by disproportionation and Tsukahara et al31 also indicated that in the presence of TGA,



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

the propagating radical was terminated by abstracting hydrogen from TGA. ACVA used in our experiment was also an azo-type initiator like AIBN, so we could conclude that disproportionation reaction predominated during the polymerization of MMA initiated by ACVA and mediated by TGA. As a typical example, for a feed molar ratio of 1/5 (Code 6 in Table 1), the gel-permeation chromatography exhibited a symmetric and monomodal distribution with number average molecular weight of 2200 g mol-1; the 1H-NMR spectrum, as illustrated in Figure 2 had a small peak at 3.2 ppm (the CH2 group in TAC) and this further proved that PMMA with a carboxyl group at one end (PMMA-COOH) was successfully synthesized. As shown in Table 1 and Figure 3, as the feed molar ratio increased from 1/5 to 1/1.1, the corresponding molecular weight determined by GPC increased linearly from 2200 to 8800 g mol-1; the number average molecular weight was also determined by a titration method by assuming every molecular chain was terminated by one carboxyl groups, and the results were close to that determined by GPC. In addition, our investigations showed that the GPC results calibrated by PS standards were almost the same as those by PMMA standards (Table S1), and so in the following, all the GPC results were based on the PS standards. All the results above demonstrated that the molecular weight of PMMA-COOH could be facilely tuned by varying the feed molar ratio of TAC to ACVA.

Scheme 1. Synthesis of PMMA-COOH and MMA macromer.


Page 8 of 26

Page 9 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Table 1. Molecular characterization of PMMA-COOH and MMA macromer. PMMA-COOH MMA macromer ACVA/TAC Mna Mnb Mw/Mnb Mnb Mw/Mnb (molar ratio) (g mol-1) (g mol-1) 1 1/1.1 8100±100 8800 2.0 2 1/1.5 6000±90 6400 2.3 3 1/1.75 5700±110 6000 2.2 6300 2.2 4 1/2.2 4200±120 4400 2.3 4800 2.3 5 1/2.5 3200±110 3500 2.2 6 1/5 2200±60 2200 2.3 2400 2.3 a Determined by titration; every titration experiment was repeated for three times and the results represented the arithmetic mean ± the standard error Code

b Determined by GPC

Figure 2. 1H-NMR spectrum and peak assignments for PMMA-COOH (Code 6 in Table 1) in CDCl3.

Figure 3. GPC curves of PMMA-COOH synthesized by different ACVA/TAC molar ratios.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

In the second step, the carboxyl groups in PMMA-COOH were esterified by reacting with the epoxide groups of GMA to produce MMA macromer (Scheme 1). The success of esterification was confirmed by both 1H NMR and FT-IR spectra. Compared to Figure 2, some new peaks appeared at 5.65 and 6.21ppm (peak h), which were characteristic of vinyl protons (Figure 4). Figure S1 showed the FT-IR spectra of PMMA-COOH and MMA macromer. Besides the absorption bands of PMMA-COOH, the weak absorption band at 1640 cm-1 was attributed to the vibration of the methacrylic double bond. The purity of the obtained MMA macromer was confirmed by GPC analysis. Figure S2 displayed the GPC curves of PMMA-COOH and its corresponding MMA macromer. The shapes of these two curves were almost identical, while the curve of MMA macromer shifted to short retention time side slightly. This result confirmed the nonexistence of side reactions, such as the polymerization of GMA and PMMA macromer with themselves or with each other during the esterification process.

Figure 4. 1H-NMR spectrum and peak assignments for MMA macromer (Code 6 in Table 1) in CDCl3.

As shown in Scheme 2, RC polymers were obtained by copolymerizing MMA, GMA with MMA macromer (path A)；RL polymers were obtained without using MMA macromer (path B). A typical 1H NMR spectrum of RC polymers was shown in Figure 5, besides the peaks of PMMA segments, the peak appeared at 3.22 ppm was assigned to CH group and the peaks at 2.85 and 2.64 ppm were assigned to CH2 group in the epoxide ring, respectively.32,33 Absorption at 910 cm-1 in the FT-IR spectrum corresponded to the vibration of the epoxide ring in GMA (Figure 6). MMA and GMA had appropriate reactivity ratios (rMMA=0.76, rGMA=0.88), so the epoxide groups were


Page 10 of 26

Page 11 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


considered to be randomly distributed along the backbone.34 As shown in Table 2, two kinds of RL and RC polymers with constant molecular weight and epoxide groups were synthesized; the Mn of the MMA macromer which constituted the side chains in RC polymers was 2400 g mol-1. In the following section, the obtained RC and RL polymers were applied as compatibilizers in the model PLLA/PVDF blend system.

Scheme 2. Synthesis of RC and RL polymers.

Figure 5. 1H-NMR spectrum and peak assignments for a representative RC polymer C-1-1-8(S-2400) in CDCl3.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 6. FT-IR spectrum of a representative RC polymer C-1-1-8(S-2400).

Table 2. Molecular characterization of RL and RC polymers. Composition (%) Mn Sample ID Mw/Mn (g mol-1) Macromer GMA MMA L-0-1-9 a 0 10 90 22000 2.0 b C-1-1-8(S-2400) 10 10 80 21000 1.9 a L was short for Linear and the numbers connected by dash was the weight ratio of Macromer/GMA/MMA b C was short for Comb, S in bracket was short for side chain and the number in bracket was the number average molecular weight of the MMA macromer 3.2 Morphology of PLLA/PVDF blends

Figure 7. SEM image of uncompatibilized PLLA/PVDF (50/50) blend. PVDF was more viscous than PLLA and the density of PVDF was higher than that of PLLA, so the volume fraction of PVDF was lower than that of PLLA at a weight ratio of 50/50. As shown


Page 12 of 26

Page 13 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


in Figure 7, these two points mentioned above drove the PVDF to form the dispersed phase in PLLA matrix and the PVDF particles displayed a very broad size distribution. TEM investigation showed a poor adhesion at the interface of black PVDF dispersed phase and white PLLA matrix (Figure S3). The obtained PMMA-type RC and RL polymers, miscible with PVDF and immiscible with PLLA, were applied as compatibilizers in the immiscible PLLA/PVDF system; the influence of the molecular structure and the amount of the compatibilizers on the morphology of PLLA/PVDF blends were investigated in detail. Figure 8 displayed the morphology and compared the size of PVDF dispersed particles in RL or RC compatibilized systems as a function of compatibilizer concentration. The addition of RL or RC polymers decreased both the size and the size distribution of the PVDF particles. It was found that the particles distributed more uniformly in RC-compatibilized blends as compared to those compatibilized by RL. It was noteworthy that the size of the PVDF particles reduced more sharply with the addition of only 1wt% of C-1-1-8 (S-2400) and the size decreasing was not remarkable with further increasing the concentration, which meant that the RC polymers at the interface of matrix and dispersed phase were close to saturation.35,36 It has been known that the domain size was determined by the equilibrium of break-up and coalescence of the dispersed phase during the blending and these results above implied that the RC polymers were prone to stay at the interface and thus inhibit the coalescence of the dispersed phase more efficiently.37



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 8. SEM images of (A) PLLA/PVDF/L-0-1-9 (50/50/1), (B) PLLA/PVDF/C-1-1-8(S-2400) (50/50/1), (C) PLLA/PVDF/L-0-1-9 (50/50/3), (D) PLLA/PVDF/C-1-1-8(S-2400) (50/50/3), (E) PLLA/PVDF/L-0-1-9 (50/50/5) and (F) PLLA/PVDF/C-1-1-8(S-2400) (50/50/5). Average particle size of PLLA/PVDF (50/50) blends versus wt% of L-0-1-9 or C-1-1-8(S-2400) was shown in (G) and (H), respectively.


Page 14 of 26

Page 15 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


3.3 Mechanical properties PLLA was a brittle polymer and PVDF was ductile. The stress-strain curves and the tensile properties of PLLA/PVDF blends uncompatibilized and compatibilized by RL or RC polymers were shown in Figure 9, Figure S4 and Table 3, respectively. As shown in Figure S4, the uncompatibilized blend fractured without yielding and with a fracture strain of only about 5.9%, even less than the neat components due to poor interfacial interaction between the phases (Figure S3). In Table 3, with the addition of the RL or RC polymers, the ductility of the PLLA/PVDF blends was significantly improved; at the same wt% addition, the fracture strain of the blends compatibilized by RC was at least three times higher than that by RL. For example, the fracture strain was 32% when the blends were compatibilized by 3 wt% of L-0-1-9 and 301% by 3 wt% of C-1-1-8 (S-2400), which was almost ten times higher than that by RL. Note that the modulus and the yield strength of the blend compatibilized by 3 wt% of C-1-1-8(S-2400) were 1.56 GPa and 67.7 MPa, respectively, which were close or identical to neat PLLA. The results above indicated that the blends compatibilized by RC polymers had a better balance of stiffness and toughness. An interesting difference between the blends compatibilized by RL or RC polymers was that the stress-strain curves showed a strain hardening when the strain was over 200% for the RC-compatibilized blends.

Figure 9. Stress-strain curves of PLLA/PVDF blends compatibilized by (A) RL or (B) RC polymers. The weight ratio of PLLA/PVDF/L-0-1-9 or C-1-1-8(S-2400) was (a) 50/50/1, (b) 50/50/3 and (c) 50/50/5.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Table 3. Mechanical properties of neat PLLA, neat PVDF and PLLA/PVDF (50/50) blends. Fracture Fracture Modulus Yield stress Sample stress strain (GPa) (MPa) (MPa) (%) PLLA 1.67 61.2 51.8 9.4 PVDF 1.25 47.9 35.3 254 PLLA/PVDF 1.56 61.2 5.9 (50/50)a PLLA/PVDF/L-0-1-9 1.3 55.8 33.8 17.6 (50/50/1)b PLLA/PVDF/L-0-1-9 1.19 61.7 35.7 32 (50/50/3) PLLA/PVDF/L-0-1-9 1.33 57.7 34.8 67 (50/50/5) PLLA/PVDF/C-1-1-8(S-2400) 1.33 60.1 36.4 111 (50/50/1) PLLA/PVDF/C-1-1-8(S-2400) 1.56 67.7 47.3 301 (50/50/3) PLLA/PVDF/C-1-1-8(S-2400) 1.41 62.2 36.7 220 (50/50/5) a The numbers in bracket was the weight ratio of PLLA/PVDF b The numbers in bracket was the weight ratio of PLLA/PVDF/compatibilizer

4. Discussion FT-IR spectra were applied to investigate the variation of the epoxide groups before and after reactive compatibilization. As shown in Figure S5, the epoxide groups, which was clearly observed at about 913 cm-1, was almost completely disappeared after reaction with the end groups of PLLA and these results demonstrated the successful formation of PLLA grafted RL or RC polymers. As shown in Figure 10 and Figure S6, both the DSC and DMA investigations indicated that reactive blending scarcely changed the Tg values of both the PLLA and the PVDF phase; the DSC thermograms exhibited a double melting behavior of PLLA and the lower peak (~163 °C) was ascribed to the melting of previously formed, imperfect small crystals and the higher peak (~169 °C) was ascribed to the melting of crystals formed from a melting and recrystallizing process.38,39 It was found that reactive compatibilization significantly increased the amount of imperfect crystals in PLLA, because some PLLA molecular chains were cracked after blending and a few of them were grafted onto PMMA backbones in this process; the grafted PLLA chains


Page 16 of 26

Page 17 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


penetrated into the PLLA matrix and disturbed the crystallization of PLLA.

Figure 10. DSC thermograms of neat PVDF, neat PLLA, uncompatibilized PLLA/PVDF (50/50) blend (A) and compatibilized PLLA/PVDF (50/50) blends (B).

TEM investigations on the microstructures of the blends compatibilized by RL or RC polymers were displayed in Figure 11 and Figure S7. The black region was PVDF dispersed phase, which was stained by RuO4. It was found that the PVDF particles did not exhibit spherical and deformed into ellipsoidal shape; the extent of deformation was a little greater when the PLLA/PVDF blends were compatibilized by RC than those by RL. This phenomenon was most obvious in Figure 11 A and B, when the blends were compatibilized by 3 wt% of RL or RC polymers. The reason for the formation of the ellipsoidal particles could be ascribed to the ratio of the shear stress and the interfacial tension, which was defined by the capillary number Ca：



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Ca =

ηγ& R σ

R is the radius of the particles, σ is the interfacial tension, η is the viscosity of the matrix and γ& is the shear rate.40-42 When the shear stress overruled, the particles deformed along the shear field and finally broke up into particles; on the contrary, no breakup occurred when the interfacial tension contracted the shear stress. The shear stress was constant in our experiment, while the interfacial tension was significantly reduced by the RL or RC compatibilizers, and so the morphology development indicated a variation of interfacial tension; the greater deformation implied a lower interfacial tension and furthermore a better emulsifying effect of the in-situ formed PLLA grafted RC polymers at the interface.43-48 As shown in Figure S8, the higher magnification TEM micrographs showed that many white particles (30~40 nm in diameter) existed in the PVDF phase when the blends were compatibilized by RL and these particles might be correlated with the PLLA grafted RL polymers, which were drawn from the interface under shear condition.49-52 It was noteworthy that such tiny particles were scarcely found in the PVDF phase of the blends compatibilized by RC. The PLLA phase was occasionally also occluded in the PVDF phase to form white domains with a diameter ranged from 200 to 500 nm, as shown in Figure 11 and Figure S7. The stability of the compatiblizers at the interface was determined by the balance of the reactivity of the epoxide groups with the PLLA phase and the miscibility of the PMMA with the PVDF phase; otherwise they were likely to escape from the interface. So the results above revealed that the better performance of the RC polymers on compatibilization were mainly due to their better interfacial stability.53


Page 18 of 26

Page 19 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 11. TEM images of (A) PLLA/PVDF/L-0-1-9 (50/50/3), (B) PLLA/PVDF/C-1-1-8(S-2400) (50/50/3), (C) PLLA/PVDF/L-0-1-9 (50/50/5) and (D) PLLA/PVDF/C-1-1-8(S-2400) (50/50/5). The scale bar was 1 µm. 5. Conclusion In this work, reactive comb (RC) and reactive linear (RL) polymers were successfully synthesized by copolymerizing MMA and GMA with or without a kind of MMA macromer. Compared to their linear counterparts, RC polymers exhibited a significant increase in compatibilization efficiency; the differentiation of the compatibilization efficiency between RC and RL polymers was more significant at the lower addition level. The fracture strain of the PLLA/PVDF blends compatibilized by RC polymers was at least three times higher than that by RL polymers and at the same time, the modulus was kept at a good level. These results indicated that the blends compatibilized by RC polymers displayed a better balance of stiffness and toughness. Morphology investigation on PLLA/PVDF blends showed that the size of the dispersed phase decreased significantly with the addition of only 1 wt% of RC polymers. The better



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

performance of RC polymers as compatibilizers was partly due to their better interfacial stability, so they were able to reduce the interfacial tension and inhibit the coalescence of the dispersed phase more efficiently and this had been convinced by TEM investigation. The molecular architecture, such as the length and number of the side chains also had influences on the compatibilization efficiency and we will report these results in the future.

ASSOCIATED CONTENT

SUPPORTING INFORMATION AVAILABLE FT-IR spetra and GPC curves of PMMA-COOH and MMA macromer, stress-strain curves, FT-IR spetra, TEM and DMA results of PLLA/PVDF blends. This information is available free of charge via the Internet at http://pubs.acs.org/.

AUTHOR INFORMATION Corresponding Authors *Email: [email protected]. TEL: 86-571-2886-7206; FAX: 86-571-2886-7899. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was financially supported by the National Natural Science Foundation of China (21244009, 21304026, 51173036, 21374027), PCSIRT (IRT 1231), and Program for New Century Excellent Talents in University. The authors wish to express their thanks to the reviewers for their valuable comments and corrections.

REFERENCES [1] Utracki, L. A. Commercial Polymer Blends, London: Chapman and Hall, 1998. [2] Paul, D. R.; Bucknal, C. B. Polymer Blends, 2nd ed. Wiley: New York, Vols 1 and 2, 2000. [3] Jeon, H. K.; Macosko, C. W.; Moon, B.; Hoye, T. R.; Yin, Z. H. Coupling Reactions of End- vs Mid-Functional Polymers. Macromolecules 2004, 37, 2563.


Page 20 of 26

Page 21 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


[4] Retsos, H.; Anastasiadis, S. H.; Pispa, S.; Mays, J. W.; Hadjichristidis, N. Interfacial Tension in Binary Polymer Blends in the Presence of Block Copolymers. 2. Effects of Additive Architecture and Composition. Macromolecules 2004, 37, 524. [5] Pernot, H.; Baumert, M.; Court, F.; Leibler, L. Design and Properties of Co-continuous Nanostructured Polymers by Reactive Blending. Nat. Mater. 2002, 1, 54. [6] Shi, H. C.; Shi, D. A.; Wang, X. Y.; Yin, L. G.; Yin, J. H.; Mai, Y. W. A Facile Route for Preparing Stable Co-continuous Morphology of LLDPE/PA6 Blends with Low PA6 Content. Polymer 2010, 51, 4958. [7] Sailer, C.; Handge, U. A. Melt Viscosity, Elasticity, and Morphology of Reactively Compatibilized Polyamide 6/Styrene−Acrylonitrile Blends in Shear and Elongation. Macromolecules 2007, 40, 2019. [8] Dedecker, K.; Groeninckx, G. Interfacial Graft Copolymer Formation during Reactive Melt Blending of Polyamide 6 and Styrene-Maleic Anhydride Copolymers. Macromolecules 1999, 32, 2472. [9] Charoensirisomboon, P.; Inoue, T.; Weber, M. Interfacial Behavior of Block Copolymers in Situ-formed in Reactive Blending of Dissimilar Polymers. Polymer 2000, 41, 4483. [10] Jeon, H. K.; Zhang, J.; Macosko, C. W. Premade vs. Reactively Formed Compatibilizers for PMMA/PS Melt Blends. Polymer 2005, 46, 12422. [11] Kim, H. Y.; Ryu, D. Y.; Jeong, U.; Kho, D. H.; Kim, J. K. The Effect of Chain Architecture of In Situ Formed Copolymers on Interfacial Morphology of Reactive Polymer Blends. Macromol. Rapid. Commun. 2005, 26, 1428. [12] Moussaif, N.; Jérôme, R. Compatibilization of Immiscible Polymer Blends (PC/PVDF) by the Addition of a Third Polymer (PMMA): Analysis of Phase Morphology and Mechanical Properties. Polymer 1999, 40, 3919. [13] Dong, W. Y.; Jiang, F. H.; Zhao, L. P.; You, J. C.; Cao, X. J. Li, Y. J. PLLA Microalloys Versus PLLA Nanoalloys: Preparation, Morphologies, and Properties. ACS Appl. Mater. Interfaces 2012, 4, 3667. [14] Macosko, C. W.; Jeon, H. K.; Hoye, T. R. Reactions at Polymer-polymer Interfaces for Blend Compatibilization. Prog. Polym. Sci. 2005, 30, 939. [15] Liu, G. C.; He, Y. S.; Zeng, J. B.; Xu, Y.; Wang, Y. Z. In Situ Formed Crosslinked



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Polyurethane Toughened Polylactide. Polym. Chem. 2014, 5, 2530. [16] Liu, H. Z.; Guo, X. J.; Song, W. J.; Zhang, J. W. Effects of Metal Ion Type on Ionomer-Assisted Reactive Toughening of Poly(lactic acid). Ind. Eng. Chem. Res. 2013, 52, 4787. [17] Xu, Y. W.; Thurber, C. M.; Lodge, T. P.; Hillmyer, M. A. Synthesis and Remarkable Efficacy of Model Polyethylene-graft-poly(methyl methacrylate) Copolymers as Compatibilizers in Polyethylene/Poly(methyl methacrylate) Blends. Macromolecules 2012, 45, 9604. [18] Zhang, C. L.; Feng, L. F.; Zhao, J.; Huang, H.; Hoppe, S.; Hu, G. H. Efficiency of Graft Copolymers at Stabilizing Co-continuous Polymer Blends During Quiescent Annealing. Polymer 2008, 49, 3462. [19] Zhang, C. L.; Feng, L. F.; Gu, X. P.; Hoppe, S.; Hu, G. H. Efficiency of Graft Copolymers as Compatibilizers for Immiscible Polymer Blends. Polymer 2007, 48, 5940. [20] Sailer, C.; Handge, U. A. Reactive Blending of Polyamide 6 and Styrene−Acrylonitrile Copolymer: Influence of Blend Composition and Compatibilizer Concentration on Morphology and Rheology. Macromolecules 2008, 41, 4258. [21] Bhadane, P. A.; Tsou, A. H.; Cheng, J. ; Favis, B. D. Morphology Development and Interfacial Erosion in Reactive Polymer Blending. Macromolecules, 2008, 41, 7549. [22] Koulic, C.; Francçois, G.; Jérôme, R. Formation of Polyamide 12-Polyisoprene Core-Shell Particles in Polystyrene by Reactive Blending. Macromolecules, 2004, 37, 5317. [23] Pan, L.; Chiba, T.; Inoue, T. Reactive Blending of Polyamide with Polyethylene: Pull-out of in Situ-formed Graft Copolymer. Polymer 2001, 42, 8825. [24] Oshinski, A. J.; Keskkula, H.; Paul, D. R. The Role of Matrix Molecular Weight in Rubber Toughened Nylon 6 Blends: 1. Morphology. Polymer, 1996, 37, 4891. [25] Feng, Y. L.; Zhao, G. Y.; Yin, J. H.; Jiang, W. Reactive Compatibilization of High-impact Poly(lactic acid)/Ethylene Copolymer Blends Catalyzed by N,N-dimethylstearylamine. Polym. In. 2014, 63, 1263. [26] Liu, P. G.; Ding, H. Y.; Liu, J. N.; Yi, X. S. Synthesis of Telechelic Methacrylate Oligomers with Carboxyl Ends Through Radical Polymerization-chemical Modification. Eur. Polym. J. 2002, 38, 1783. [27] McCord, E. F.; Anton, W. L.; Wilczek, L.; Ittel, S. D.; Nelson, L. T. J.; Raffell, K. D. Macromol. Symp. 1H and

13

C NMR of PMMA Macromonomers and Oligomers-end Groups and


Page 22 of 26

Page 23 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Tacticity. 1994, 86, 47. [28] Ito, K.; Usami, N.; Yamashita, Y. Syntheses of Methyl Methacrylate-Stearyl Methacrylate Graft Copolymers and Characterization by Inverse Gas Chromatography. Macromolecules 1980, 13, 216. [29] Ohtani, H.; Luo, Y. F.; Nakashima, Y.; Tsukahara, Y.; Tsuge, S. Determination of End Group Functionality in Poly(methyl methacrylate) Macromonomers by Pyrolysis Simultaneous Multidetection Gas Chromatography. Anal. Chem. 1994, 66, 1438. [30] Hatada, K.; Kitayama, T.; Masuda, E. Studies on the radical polymerization of methyl methacrylate in bulk and in benzene using totally deuterated monomer technique. Polymer J. 1986, 18, 395. [31] Tsukahara, Y.; Nakanishi, Y.; Yamashita, Y.; Ohtani, H.; Nakashima, Y.; Luo, Y. F.; Ando, T.; Tsuge, S. Investigation of the end groups of prepolymers/macromonomers prepared by radical chain transfer reaction. Macromolecules 1991, 24, 2493. [32] Hayek, A.; Xu, Y.; Okada, T.; Barlow, S.; Zhu, X.; Moon, J. H.; Marder S. R. ; Yang, S. Poly(glycidyl methacrylate)s with Controlled Molecular Weights as Low-shrinkage Resins for 3D Multibeam Interference Lithography. J. Mater. Chem. 2008, 18, 3316. [33] Moayeri, A.; Lessard, B.; Maric, M. Nitroxide Mediated Controlled Synthesis of Glycidyl Methacrylate-rich Copolymers Enabled by SG1-based Alkoxyamines Bearing Succinimidyl Ester Groups. Polym. Chem., 2011, 2, 2084. [34] Iwakura, Y.; Kurosaki, T.; Ariga, N.; Ito, T. Copolymerization of Methyl Methacrylate with Glycidyl Methacrylate and the Reaction of the Copolymer with Amines. Macromol. Chem. 1966, 97, 128. [35] Polizu, S.; Favis, B. D.; Vu-Khanh, T. Morphology-Interface-Property Relationships in Polystyrene/Ethylene-Propylene Rubber Blends. 2. Influence of Areal Density and Interfacial Saturation of Diblock and Triblock Copolymer Interfacial Modifiers. Macromolecules 1999, 32, 3448. [36] Lepers, J. C.; Favis, B. D. Interfacial Tension Reduction and Coalescence Suppression in Compatibilized Polymer Blends. AIChE J. 1999, 45, 887. [37] Sundararajs, U.; Macosko , C. W. Drop Breakup and Coalescence in Polymer Blends: The Effects of Concentration and Compatibilization. Macromolecules 1996, 28, 2647.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

[38] Yasuniwa, M.; Tsubakihara, S.; Sugimoto, Y.; Nakafuku, C. Thermal Analysis of the Double-melting Behavior of Poly(L-lactic acid). J. Polym. Sci., Part B: Polym. Phys. 2004, 42, 25. [39] Li, Y. H.; Venkateshan, K.; Sun, X. S. Mechanical and Thermal Properties, Morphology and Relaxation Characteristics of Poly(lactic acid) and Soy Flour/Wood Flour Blends. Polym. Int. 2010, 59, 1099. [40] Velankar, S.; Puyvelde, P. V.; Mewis, J.; Moldenaers, P. Effect of compatibilization on the breakup of polymeric drops in shear flow. J. Rheol. 2001, 45, 1007. [41] Asthana, H.; Jayaraman, K. Rheology of reactively compatibilized polymer blends with varying extent of interfacial reaction. Macromolecules 1999, 32, 3412. [42] Olbricht, W. L.; Kung, D. M. The deformation and breakup of liquid drops in low Reynolds number flow through a capillary. Phys. Fluids A 1992, 4, 1347. [43] Charoensirisomboon, P.; Inoue, T.; Weber, M. Pull-out of Copolymer in Situ-formed During Reactive Blending: Effect of the Copolymer Architecture. Polymer 2000, 41, 6907. [44] Lin, B.; Mighri, F.; Huneault, M. A.; Sundararaj, U. Effect of Premade Compatibilizer and Reactive Polymers on Polystyrene Drop Deformation and Breakup in Simple Shear. Macromolecules 2005, 38, 5609. [45] Xu, X.; Yan, X.; Zhu, T.; Zhang, C.; Sheng, J. Phase Morphology Development of Polypropylene/Ethylene-octene Copolymer Blends: Effects of Blend Composition and Processing Conditions. Polym. Bull. 2007, 58, 465. [46] Yin, B.; Zhao, Y.; Yu, R. Z.; An, H. N.; Yang, M. B. Morphology Development of PC/PE Blends During Compounding in a Twin-screw Extruder. Polym. Eng. Sci. 2007, 47, 14. [47] Macosko, C. W. Morphology Development and Control in Immiscible Polymer Blends. Macromol. Symp. 2000, 149, 171. [48] Li, J. M.; Ma, P. L.; Favis, B. D. The Role of the Blend Interface Type on Morphology in Cocontinuous Polymer Blends. Macromolecules 2002, 35, 2005. [49] Macosko, C. W.; Guégan, P.; Khandpur, A. K.; Nakayama, A.; Marechal, P.; Inoue, T. Compatibilizers for Melt Blending: Premade Block Copolymers. Macromolecules, 1996, 29, 5590. [50] Adedeji, A.; Lyu, S. P.; Macosko, C. W. Block Copolymers in Homopolymer Blends: Interface vs Micelles. Macromolecules 2001, 34, 8663. [51] Charoensirisomboon, P.; Chiba, T.; Solomko, S. I.; Inoue, T.; Weber, M. Reactive Blending of


Page 24 of 26

Page 25 of 26

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Polysulfone with Polyamide: a Difference in Interfacial Behavior Between in Situ Formed Block and Graft Copolymers. Polymer 1999, 40, 6803. [52] Dong, W. Y.; Cao, X. J.; Li, Y. J. High-performance Biosourced Poly(lactic acid)/Polyamide 11 Blends with Controlled Salami Structure. Polym. Int. 2014, 63, 1094. [53] Horiuchi, S.; Rodorogues, R. Morphological variations of polyamide 6/polycarbonate blends achieved by the incorporation of reactive graft copolymers. Kobunshi Ronbunshu 1999, 56, 651.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Table of Contents Use Only

Wenyong Dong, Hengti Wang, Meifeng He, Fanglu Ren, Tao Wu, Qianru Zheng， Yongjin Li*

College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, No.16 Xuelin Road, Hangzhou 310036, P.R. China


Page 26 of 26

Synthesis of Reactive Comb Polymers and Their Applications as a

Recommend Documents