Excellent Compatibilization Effect of a Dual Reactive Compatibilizer on the Immiscible MVQ/PP Blends

Han-Bin Wang; Hong-Chi Tian; Shi-Jia Zhang; Bing Yu; Nan-Ying Ning; Ming Tian; Li-Qun Zhang

doi:10.1007/s10118-023-2945-z

Your Location：

Home >

Browse articles >

Excellent Compatibilization Effect of a Dual Reactive Compatibilizer on the Immiscible MVQ/PP Blends

RESEARCH ARTICLE | Updated：2023-06-14

- Excellent Compatibilization Effect of a Dual Reactive Compatibilizer on the Immiscible MVQ/PP Blends
- role： First author , 第一作者 ,
  
  Affiliation：
  Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
  
  Email：
  
  No information about the author is available
  Wang Han-Bin
  ,
  role：
  
  Affiliation：
  Shandong Dawn Polymer Material Co., Ltd., Longkou 265700, China
  
  Email：
  
  No information about the author is available
  Tian Hong-Chi
  ,
  role：
  
  Affiliation：
  Shandong Dawn Polymer Material Co., Ltd., Longkou 265700, China
  
  Email：
  
  No information about the author is available
  Zhang Shi-Jia
  ,
  role：
  
  Affiliation：
  Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
  Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  
  Email：
  
  No information about the author is available
  Yu Bing
  ,
  role： Corresponding author , 通讯作者 ,
  
  Affiliation：
  Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
  Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  
  Email： ningny@mail.buct.edu.cn
  
  Introduction： ningny@mail.buct.edu.cn (N.Y.N.)
  
  No information about the author is available
  Ning Nan-Ying
  ,
  role： Corresponding author , 通讯作者 ,
  
  Affiliation：
  Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
  Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  
  Email： tianm@mail.buct.edu.cn
  
  Introduction： tianm@mail.buct.edu.cn (M.T.)
  
  No information about the author is available
  Tian Ming
  ,
  role：
  
  Affiliation：
  Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
  Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  
  Email：
  
  No information about the author is available
  Zhang Li-Qun
  ,
- Chinese Journal of Polymer Science Vol. 41, Issue 7, Pages: 1133-1141(2023)
- Affiliations：
  
  a.Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
  b.Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  c.Shandong Dawn Polymer Material Co., Ltd., Longkou 265700, China
- Author bio：
  
  ningny@mail.buct.edu.cn (N.Y.N.)
  tianm@mail.buct.edu.cn (M.T.)
- Funds：
- DOI：10.1007/s10118-023-2945-z
  CLC：
Scan for full text
Cite this article
Han-Bin Wang, Hong-Chi Tian, Shi-Jia Zhang, et al. Excellent Compatibilization Effect of a Dual Reactive Compatibilizer on the Immiscible MVQ/PP Blends. [J]. Chinese Journal of Polymer Science 41(7):1133-1141(2023)
DOI：

Han-Bin Wang, Hong-Chi Tian, Shi-Jia Zhang, et al. Excellent Compatibilization Effect of a Dual Reactive Compatibilizer on the Immiscible MVQ/PP Blends. [J]. Chinese Journal of Polymer Science 41(7):1133-1141(2023) DOI： 10.1007/s10118-023-2945-z.

Excellent Compatibilization Effect of a Dual Reactive Compatibilizer on the Immiscible MVQ/PP Blends

Wang Han-Bin ; Tian Hong-Chi ; Zhang Shi-Jia ; Yu Bing ; Ning Nan-Ying ; Tian Ming ; Zhang Li-Qun ;

PDF Download

Sections

Abstract

Methyl vinyl silicone rubber (MVQ)/polypropylene (PP) thermoplastic vulcanizate (TPV) combines the good melt processability, recyclability and sealing performance as well as biosafety, stain and fluid resistance, and thus it is especially suitable in bio-safety areas and wearable electronic devices, etc. Nevertheless, the compatibility between MVQ and PP phases is poor. A big challenge on the compatibilization of MVQ/PP blends is that neither MVQ nor PP contains any reactive groups. In this study, a dual reactive compatibilizer composed of ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-co-GMA) and maleic anhydride grafted polypropylene (PP-g-MAH) was designed for the compatibilization of MVQ/PP blends. During melt blending, a copolymer compatibilizer at the MVQ/PP interface can be formed because of the in situ reaction between EMA-co-GMA and PP-g-MAH. The thermodynamic predict of its compatibilization effect through calculating the spreading coefficient of the in situ formed copolymer indicates that it can well compatibilize MVQ/PP blends. The experimental results show that under the GMA/MAH molar ratio of 0.5/1, the interface thickness largely increase from 102 nm for non-compatibilized blend to 406 nm, and the average size of MVQ dispersed phase largely decreases from 2.3 μm to 0.36 μm, the T_g of the two phases shifts toward each other, the mixing torque and mechanical properties of the blend are increased, all indicating its good compatibilization effect. This study provides a good compatibilizing method for immiscible MVQ/PP blends with no reactive groups in both components for the preparation of high performance MVQ/PP TPVs.

译

Keywords

Methyl vinyl silicone rubber (MVQ); Polypropylene (PP); Immiscible polymer blends; Reactive compatibilization

译

INTRODUCTION

Thermoplastic vulcanizate (TPV), as a special kind of thermoplastic elastomer, exhibits the high elasticity of traditional cross-linked rubbers and the good melt processability and recyclability of thermoplastics.^[

1−6] Nowadays, because of the requirements of energy saving and protection of environmental, TPV as a kind of “green” polymer has attracted more and more attention in industry to replace the unrecyclable thermoset rubbers.^{[Reference 1

1,Reference 3

3,Reference 7

7,Reference 8

8]} MVQ/PP TPV combines these good properties of TPV as well as the biosafety, high chemical barrier, stain and fluid resistance, and thus finds application in sealing parts for bio-safety areas, wearable electronic devices and so on.^{[Reference 9

9]}

译

To simultaneously achieve good mechanical strength and high elasticity of TPVs, a smaller size of rubber phase dispersed in plastic phase is required.^[

4,10,11] Therefore, a good compatibility between the two phases is a key. Nevertheless, MVQ/PP blend is thermodynamically immiscible because of the difference of their backbone molecular chain structure and surface tension. Thus, the compatibilization of MVQ/PP blend is highly required for producing MVQ/PP TPVs with high-performance. A classical method to compatibilize them is by adding a pre-made compatibilizer such as a graft/block copolymer,^{[Reference 12−15

12−15]} or a reactive compatibilizer.^{[Reference 16−21

16−21]} The latter allows in situ formation of a graft/block copolymer at the interfaces during melt blending.^{[Reference 22

22,Reference 23

23]} A pre-made compatibilizer may not always be technically possible or economically viable, whereas a reactive compatibilizer (reactive compatibilization) requires the presence of adequate reactive groups in the blend systems. Nevertheless, neither MVQ nor PP contains any reactive groups in their molecular chains. Thus, there are few reports on the compatibilization of MVQ/PP blends. The maleic anhydride grafted polypropylene (PP-g-MAH) was used as a compatibilizer for MVQ/PP blend, but its compatibilization effect was limited.^{[Reference 24

24]} This is because the interaction between PP-g-MAH and MVQ is not strong enough. For unreactive blends, a new one-pot reactive compatibilization strategy was proposed by Li and Wang et al.^{[Reference 25

25]} through simultaneously introducing two reactive polymers for the in situ formation of an effective copolymer compatibilizer. This strategy provides greater possibility for the reactive compatibilization of immiscible polymer blends with all components containing no reactive groups.

译

In this study, a dual reactive compatibilizer composed of ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-co-GMA) and PP-g-MAH was designed for the compatibilization of MVQ/PP blends, and their compatibilization mechanism is shown in Scheme 1. During melt blend, the entanglement of molecular chains between PP-g-MAH and PP occurs because of the high content of polypropylene units in PP-g-MAH (98.8%), while EMA-co-GMA terpolymer can graft onto the MVQ chains by the reaction between α-carbon atom from MA segments of EMA-co-GMA and the vinyl groups from MVQ chains at high temperature and high shearing stress.^[

26] Meanwhile, the in situ reaction between the epoxy groups from EMA-co-GMA terpolymer and the anhydride groups from PP-g-MAH can occur,^{[Reference 27

27]} and thus can lead to the formation of a copolymer compatibilizer at the MVQ/PP interface during melt blending. The thermodynamic predict of compatibilization effect of such dual reactive compatibilizer with different molar ratios of epoxy group from EMA-co-GMA terpolymer and anhydride group from PP-g-MAH on MVQ/PP blends was conducted through calculating the interfacial tensions and spreading coefficient of in situ formed copolymer. The effect of such dual reactive compatibilizers on the interfacial thickness, the size of MVQ dispersed phase in blends, T_g of MVQ and PP phases, mixing torque, the crystallinity of PP phase, and mechanical properties of the blends were studied. This study provides a good compatibilizing method for immiscible MVQ/PP blends with no reactive groups in both components for the preparation of high performance MVQ/PP TPVs.

译

Fig 1 Schematic diagram of in situ compatibilization of MVQ/PP blends by EMA-g-GMA and PP-g-MAH.

Download: Full-size image | High-res image | Low-res image

EXPERIMENTAL

Materials

Methyl vinyl silicone rubber (MVQ), polypropylene (PP) and dual reactive compatibilizers were commercialized products. The methyl vinyl silicone rubber containing 0.21% vinyl groups (MVQ, M_w=60×10⁴, trademark: 110-3s) was purchased from Nanjing Dongjue Silicon Industry Co., Ltd., (China). PP (Trademark: Hifax@CA60A) was supplied by LyondellBasell Industries. The ethylene-methyl acrylate-glycidyl methacrylate terpolymer containing 0.35 mmol/g glycidyl methacrylate (EMA-co-GMA, Trademark: EPA-810) was purchased from Hyer Polymer Material Co., Ltd., (Hangzhou, China). Maleic anhydride grafted polypropylene (PP-g-MAH, Trademark: MD353D, maleic anhydride conent: containing 0.12 mmol maleic anhydride/g of PP-g-MAH) was purchased from DuPont Co., Ltd., (USA). Pentaerythritol tetrakys 3-(3,5-ditert-butyl-4-hydroxyphenyl) propionate (1010) as an antioxidant, chloroform as a solvent and Ethylene glycol as test liquid for contact angle were purchased from Beijing Chemical Reagents Co., Ltd., (China). Ultra-pure water (H₂O) as test liquid was made by an ultra-pure water machine (Clever-Q, Zhi Ang Instrument (Shanghai) Co., Ltd.).

译

Preparation of MVQ/PP Blends

Table 1 shows the recipes of the MVQ/PP blends. The MVQ/PP weight ratio was kept constant (30/70). The total mass of MVQ, PP and compatibilizers is 49.5 g. The MVQ/PP blends were prepared in a Haake Rheomix 600 OS internal mixer (Thermo Fisher Scientific, USA) equipped with two counter-rotating rotors at 180 °C with a rotation speed of 80 r/min. Specifically, PP, EMA-co-GMA, PP-g-MAH and the antioxidant were simultaneously mixed till the torque leveled off. Then the MVQ was added to the internal mixer and was mixed till the torque leveled off again. The blends were quickly taken out and quenched into liquid nitrogen to freeze in the morphology. They were pressed at into films at 180 °C under 0, 7.5 and 15 MPa for 5, 5 and 3 min, respectively, and then were pressed at 25 °C under 15 MPa for 5 min. Finally, the MVQ/PP films were conditioned at room temperature for 24 h before any subsequent characterization.

译

Table 1 The formulation of preparing MVQ/PP blends.

With or without compatibilizer	MVQ (phr)	PP (phr)	Antioxidant 1010 (phr)	EMA-co-GMA (phr)	PP-g-MAH (phr)	GMA/MAH (Molar ratio)
Blends-G/M-0/0	30	70	0.14	0	0	0/0
Blends-G/M-0.5/1	30	70	0.14	1.4	8.6	0.5/1
Blends-G/M-0.75/1	30	70	0.14	2	8	0.75/1

Download: Export CSV

Preparation of Model Copolymer Compatibilizer

In order to research the thermodynamics of copolymer compatibilizer in situ formed by a dual reactive compatibilizer, a model copolymer compatibilizer were synthesized in the above internal mixer under the same conditions as described above using two different recipes (two different GMA/MAH molar ratios). Table 2 shows the recipes of model copolymer compatibilizers.

译

Table 2 Recipes used for the synthesis of model copolymer compatibilizers.

Model compatibilizers	EMA-co-GMA (phr)	PP-g-MAH (phr)	GMA/MAH (molar ratio)
Model-G/M-0.5/1	14	86	0.5/1
Model-G/M-0.75/1	20	80	0.75/1

Download: Export CSV

Characterization Methods

An optical contact angle measuring device (SL200KS, USA KINO Industry Co., Ltd.) was used to measure the contact angles of ultra-pure water (H₂O) and ethylene glycol ((CH₂OH)₂) on the surfaces of the MVQ, PP, and premade copolymer compatibilizers at room temperature. The films of 2 mm thick were made and washed with ethanol before the contact angle measurements. Cuboid-shaped samples (length × width × thickness: 6 mm × 4 mm × 2 mm) were placed on the sample table of optical contact angle measuring device and control the liquid volume (5 μL). After the liquid droplet is stable, fine tune the sample table to make the droplet contact the solid. At this time, click the snap button to obtain the photograph of the liquid on the sample surface. The contact angles were then used to calculate the spreading coefficient (λ) in order to predict the location of the premade model copolymers in the MVQ/PP blends and the effect of the epoxy (GMA)/anhydride (MAH) molar ratio on the compatibilization efficiency.

译

Scanning electron microscopy (SEM, S-4800) was used to characterize the morphology of the MVQ/PP blends with an accelerated electron energy of 5.0 kV. Cuboid-shaped samples of MVQ/PP blends were fractured after immersing in liquid nitrogen for 3 min and were then etched with chloroform solution under room temperature for 72 h to remove the MVQ phase, during which the chloroform solution was replaced every 24 h. The fractured surface of samples was sputtered with gold. The diameter distribution of the MVQ phase domains was determined by Image-Pro Plus 7. For counting the size of not uniform dispersed regions, its mechanism is that “reports the average length of the diameters measured at two-degree intervals joining two outline points and passing through the centroid.”

译

The morphologies of samples were observed using a Nanoscope V peak force tapping atom force microscope (PF-AFM) (Bruker, Germany) with RTESPA-150 probe (spring coefficient: 1.5−10 N/m, Bruker, Germany) under room temperature. The actual spring constant was measured by the thermal tuning method. The samples were first polished using a cryo-ultramicrotome (Leica EMUC7, Germany) equipped with a glass knife at −130 °C. The darker and lighter region regions corresponded to the MVQ and PP phases, respectively. The interfacial thicknesses between the MVQ and PP phases were measured based on the AFM images using the NanoScope Analysis 1.9 software.

译

X-ray Diffraction (DX-1000 X-ray diffractometer) was used to determine the crystallinity of the PP in the MVQ/PP blends. The Cu Kα (wavelength = 0.15406 nm) irradiation source was operated at 40 kV and 40 mA. The scanning was conducted at a 2θ range from 5° to 30° and a scanning speed of 3 (°)/min. The crystallinity (X_C) was calculated by Eq. (1):

译

${X}_{\rm{C}}=\frac{{A}_{\rm{c}}/({A}_{\rm{c}}+{A}_{\rm{a}})}{{\emptyset}_{\rm{P}\rm{P}}}$

where

${A}_{\rm{c}}$ and

${A}_{\rm{a}}$ are the fitted areas of the crystalline and amorphous phases, respectively,

${\emptyset}_{\rm{P}\rm{P}}$ is the weight fraction of PP in MVQ/PP blends.

Tensile testing of the MVQ/PP blends at room temperature was conducted on dumbbell-shaped specimens (25 mm × 6 mm × 2 mm) using Instron 5567, USA) with a tensile rate of 50 mm/min.

译

Dynamic mechanical properties of the MVQ/PP blends were measured by dynamic mechanical analysis (DMA 1 with SRARA system) under nitrogen. The tests were performed from −150 °C to 80 °C at a frequency of 1 Hz with an amplitude of 10 μm and a scanning rate of 10 °C/min.

译

RESULTS AND DISCUSSION

Thermodynamic Predicts of Compatibilization Effect of Dual Reactive Compatibilizer on MVQ/PP Blends

A copolymer can compatibilize an immiscible polymer blends when it is located at the interfaces between the polymer components instead of being located in one of their phases.^[

23] According to previous studies, it is common to stabilize the morphology of an immiscible binary polymer blend using a third-component polymer (usually called compatibilizer) and it should prefer to lie at the interface rather than form micelles or a separate phase.^{[Reference 28

28,Reference 29

29]} In this work, the position of the model copolymer compatibilizers premade by the dual reactive compatibilizers in the MVQ/PP blends is predicted by the spreading coefficient which is defined by Eq. (2). A larger spreading coefficient indicates the more stable of the third-component copolymer on the interface and the better compatibilization effect.^{[Reference 30

30]}

译

${\lambda }_{\rm{C}\rm{o}/\rm{M}\rm{V}\rm{Q}}={\sigma }_{\rm{M}\rm{V}\rm{Q}/\rm{P}\rm{P}}-({\sigma }_{\rm{C}\rm{o}/\rm{p}\rm{p}}+{\sigma }_{\rm{M}\rm{V}\rm{Q}/\rm{C}\rm{o}})$

where

${\lambda }_{\rm{C}\rm{o}/\rm{M}\rm{V}\rm{Q}}$ is commonly called spreading coefficient which in fact is not a coefficient (dimensionless) but an interfacial tension difference,

${\sigma }_{\rm{M}\rm{V}\rm{Q}/\rm{P}\rm{P}}$ ,

${\sigma }_{\rm{C}\rm{o}/\rm{p}\rm{p}}$ and

${\sigma }_{\rm{M}\rm{V}\rm{Q}/\rm{C}\rm{o}}$ denote the interfacial tensions for MVQ/PP, premade model copolymer /PP and MVQ/premade model copolymer pairs, respectively. The copolymer is located at the MVQ and PP interfaces when

${\lambda }_{\rm{C}\rm{o}/\rm{M}\rm{V}\rm{Q}}$ >0, indicating that the interfacial tension between them is reduced by the presence of the copolymer at the interface.^{[Reference 30

30]}

The interfacial tensions are calculated from the surface tensions of each of the components at room temperature by the harmonic mean equation:^[

31]

译

${\sigma }_{12}={\sigma }_{1}+{\sigma }_{2}-4\left(\frac{{\sigma }_{1}^{\rm{d}}{\sigma }_{2}^{\rm{d}}}{{\sigma }_{1}^{\rm{d}}+{\sigma }_{2}^{\rm{d}}}+\frac{{\sigma }_{1}^{\rm{p}}{\sigma }_{2}^{\rm{p}}}{{\sigma }_{1}^{\rm{p}}+{\sigma }_{2}^{\rm{p}}}\right)$

where subscripts 1 and 2 denote any two of the MVQ, PP and premade model copolymer compatibilizer, and

${\sigma }_{i}$ (i denotes 1 or 2) is the surface tension of polymer i (MVQ, PP or the premade model copolymer compatibilizer) which is calculated by Owens-Wendt equation:^{[Reference 32

32]}

${\sigma}_{{i}}={\sigma}_{{i}}^{\rm{d}}+{\sigma}_{{i}}^{\rm{p}}$

where indexes d and p are the dispersive and polar surface tension components of i, respectively.

译

The values of

${\sigma}_{{i}}^{\rm{d}}$ and

${\sigma}_{{i}}^{\rm{p}}$ for the MVQ, copolymer and PP at 25 °C are calculated by solving Eqs. 5(a) and 5(b):

$\tag{5a}\left({1+{\rm{cos}}}{\theta}_{{\rm{H}}_{\rm{2}}\rm{O}}\right){\sigma}_{{\rm{H}}_{\rm{2}}\rm{O}}{=2}\left(\sqrt{{\sigma}_{{\rm{H}}_{\rm{2}}\rm{O}}^{\rm{d}}{\sigma }_{{i}}^{\rm{d}}}+\sqrt{{\sigma}_{{\rm{H}}_{\rm{2}}\rm{O}}^{\rm{p}}{\sigma}_{{i}}^{\rm{p}}}\right)$

$\tag{5b}\left(\rm{1+cos}{\theta}_{{\left({\rm{C}\rm{H}}_{2}\rm{O}\rm{H}\right)}_{2}}\right){\sigma}_{{\left({\rm{C}\rm{H}}_{2}\rm{O}\rm{H}\right)}_{2}}{=2}\left(\sqrt{\sigma_{{\left({\rm{C}\rm{H}}_{2}\rm{O}\rm{H}\right)}_{2}}^{\rm{d}}{\sigma}_{{i}}^{\rm{d}}}+\sqrt{\sigma_{{\left({\rm{C}\rm{H}}_{2}\rm{O}\rm{H}\right)}_{2}}^{\rm{p}}\sigma_{{i}}^{\rm{p}}}\right)$

where

${\sigma}_{{\rm{H}}_{\rm{2}}\rm{O}}^{\rm{d}}$ and

${\sigma}_{{\rm{H}}_{\rm{2}}\rm{O}}^{\rm{p}}$ are the dispersive and polar surface tension components of H₂O, which are 23.9 and 48.8 mN·m⁻¹ at 25 °C, respectively;

${\sigma}_{{\left({\rm{C}\rm{H}}_{2}\rm{O}\rm{H}\right)}_{2}}^{\rm{d}}$ and

${\sigma}_{{\left({\rm{C}\rm{H}}_{2}\rm{O}\rm{H}\right)}_{2}}^{\rm{p}}$ are the dispersive and polar components of (CH₂OH)₂ which are 31.0 and 17.2 mN·m⁻¹ at 25 °C, respectively;^{[Reference 33

33]} and

${\theta}_{{\rm{H}}_{\rm{2}}\rm{O}}$ and

${\theta}_{{\left({\rm{C}\rm{H}}_{2}\rm{O}\rm{H}\right)}_{2}}$ are the contact angles of H₂O and (CH₂OH)₂ on polymer i (MVQ, PP and premade model copolymer compatibilizer) at 25 °C, respectively. The surface tension of above polymer or model compatibilizers at the blending temperature (180 °C) are extrapolated from those at room temperature using the relationship −dσ_i/dT ≈ 0.05 mN·m⁻¹·°C⁻¹ (T is temperature), as reported in previous studies.^{[Reference 34

34]} Table 3 gathers the experimentally measured contact angles and calculated surface tensions at 25 °C as well as the surface tensions extrapolated from 25 °C to 180 °C. Table 4 shows that the values of the calculated spreading coefficient

$({{ \lambda }}_{\rm{C}\rm{o}/\rm{M}\rm{V}\rm{Q}})$ for two premade model copolymers compatibilizers with the GMA/MAH molar ratios of 0.5/1 and 0.75/1 are 1.19 and 0.24, respectively. The results indicate that the copolymers formed under the GMA/MAH molar ratio of 0.5/1 reduce the interfacial tension of the blends more greatly and can stay at the interfaces between the MVQ and PP more stable than that formed under the GMA/MAH molar ratio of 0.75/1. Thus, the copolymer compatibilizer formed under the GMA/MAH molar ratio of both 0.5/1 and 0.75/1 can effectively compatibilize MVQ/PP blends, and the compatibilization effect of the former is theoretically better than that of the latter.

Table 3 Surface tensions of neat polymers and compatibilizers.

Polymer	Contact angle (°) at 25 °C			Surface tension at 25 °C (mN·m⁻¹)			Surface tension at 180 °C (mN·m⁻¹)
Polymer	H₂O		(CH₂OH)₂	${\sigma }_{{i} }^{\text{d} }$	${\sigma }_{{i} }^{\text{p} }$	${\sigma}_{{i} }^{}$	${\sigma }_{{i} }^{\text{d} }$	${\sigma }_{{i} }^{\text{p} }$	${\sigma}_{{i} }^{}$
PP		105.1±0.8	74.5±1.1	29.91	0	29.91	22.15	0	22.15
MVQ		104.1±0.6	80.2±1.0	19.72	0.70	20.42	12.22	0.43	12.65
Model-G/M-0.5/1		99.1±0.7	73.0±0.8	23.71	0.91	24.62	16.23	0.62	16.85
Model-G/M-0.75/1		105.0±0.8	80.9±0.6	20.01	0.50	20.51	12.44	0.31	12.75

Download: Export CSV

Table 4 Interfacial tensions and

${\lambda }_{\rm{C}\rm{o}/\rm{MVQ}}$ for compatibilizers.

Copolymer prepared by two compatibilizers	Interfacial tension (mN·m⁻¹)		Interfacial tension of MVQ/PP, σ_MVQ/PP (mN·m⁻¹)	Spreading coefficient ${ { \lambda } }_{\rm{C}\rm{o}/\rm{M}\rm{V}\rm{Q} }$
Copolymer prepared by two compatibilizers	σ_Co/PP	σ_MVQ/Co	Interfacial tension of MVQ/PP, σ_MVQ/PP (mN·m⁻¹)
Model-G/M-0.5/1	1.53	0.58	3.30	1.19
Model-G/M-0.75/1	3.04	0.02	3.30	0.24

Download: Export CSV

Effect of Dual Reactive Compatibilizer on Interfacial Thickness of MVQ/PP Blends

To evaluate the compatibilization effect of the dual reactive compatibilizer (EMA-co-GMA and PP-g-MAH) on the as-prepared MVQ/PP blends, QNM-AFM was used to determine the interfacial thickness between MVQ and PP phases. Fig. 1 shows the AFM images of the MVQ/PP blends and their interfacial thicknesses. Without the dual reactive compatibilizer, the interfacial thickness between MVQ and PP is 102 nm. With the dual reactive compatibilizer, the interfacial thickness largely increases to 406 and 298 nm when the GMA/MAH molar ratio is 0.5/1 and 0.75/1, respectively. This indicates that the copolymers formed under GMA/MAH molar ratio of both 0.5/1 and 0.75/1 can significantly improve the interfacial interaction between MVQ and PP component. This further confirms that the dual reactive compatibilizer is efficient on compatibilizing the MVQ/PP blend and the compatibilization effect is better at the GMA/MAH molar ratio of 0.5/1. This could be due to the formation of the more suitable architecture and/or amount of copolymer compatibilizers. In addition, the in situ formed copolymer compatibilizer reacted under the molar ratio of 0.5/1 is more stable at the interface. This result is in agreement with the spreading coefficients in Table 4.

译

Fig 1 Height and logDMT Modulus images and the corresponding logDMT Modulus-horizontal distance curve of MVQ/PP blends of (a, a’, a”) GMA/MAH-0/0, (b, b’, b”) GMA/MAH-0.5/1 and (c, c’, c”) GMA/MAH-0.75/1.

Download: Full-size image | High-res image | Low-res image

Effect of Dual Reactive Compatibilizer on the Size of MVQ Dispersed Phase in MVQ/PP Blends

To further evaluate the compatibilization effect of the dual reactive compatibilizer (EMA-co-GMA and PP-g-MAH), SEM micrographs were employed to study the MVQ dispersed phase structure in MVQ/PP blends. Figs. 2(a)−2(c) show the SEM micrographs of the MVQ/PP blends without and with the dual reactive compatibilizer. Figs. 2(a’)−2(c’) show the equivalent diameter distributions of the MVQ domains. For MVQ/PP blend without compatibilizer, the average size of the dispersed phase is the biggest (2.32 μm), and their size distribution is in the range of 1−5 μm, which is due to their poor interfacial interaction between MVQ and PP. After compatibilized by dual reactive compatibilizer at the GMA/MAH molar ratio of 0.5/1, the average size of MVQ phases largely decreases to 0.36 μm, and their size distribution is in the range of 0.2−0.6 μm. With further increasing the molar ratio of GMA/MAH to 0.75/1, the average size of MVQ phase increases to 0.8 μm, and the size distribution is in the range of 0.5−1.2 μm. This result is in agreement with the spreading coefficients in Table 4 and the interfacial thicknesses in section Effect of Dual Reactive Compatibilizer on Interfacial Thickness of MVQ/PP Blends. A higher spreading coefficient facilitates the achievement of a higher interfacial thickness, and thus a smaller size of MVQ dispersed phase.

译

Fig 2 SEM micrographs of MVQ/PP blends and the equivalent diameter distributions of MVQ domain (a, a’) Blends-G/M-0/0, (b, b’) Blends-G/M-0.5/1 and (c, c’) Blends-G/M-0.75/1 (The MVQ phase has been removed by etching in chloroform solvent).

Download: Full-size image | High-res image | Low-res image

Effect of Dual Reactive Compatibilizer on Glass Transition Temperature (T_g)

The shift of glass transition temperature (T_g) is often used as a criterion to determine the compatibilization effect of a compatibilizer on incompatible polymer blends.^[

35] Fig. 3 shows the tanδ versus temperature curves of the MVQ/PP blends without and with the dual reactive compatibilizer (EMA-co-GMA and PP-g-MAH). Two relaxation peaks are observed for all blends, indicating that the phase separation structure exists in all these samples, consistent with the AFM and SEM results mentioned above. One located at around −125 °C represents the T_g of MVQ phase, and the other located at 5−8 °C represents the T_g of PP phase. Without the dual reactive compatibilizer, the T_g of MVQ and PP is −126 and 8 °C, respectively. With the dual reactive compatibilizer, the T_g of PP phase shifts toward lower temperature, whereas that of MVQ phase shifts toward higher temperature, again indicating the compatibilization effect of dual reactive compatibilizer under both GMA/MAH molar ratios. Under the GMA/MAH molar ratio of 0.5/1, the shift of T_g of both PP and MVQ phases is more significant than that under the GMA/MAH molar ratio of 0.75/1, again indicating the better compatibilization effect of the former.

译

Fig 3 Temperature dependence of loss factor (tanδ) of MVQ/PP blends without compatibilizer, GMA/MAH-0.5/1 and GMA/MAH-0.75/1.

Download: Full-size image | High-res image | Low-res image

Effect of Dual Reactive Compatibilizer on Mixing Torque and Rheological Properties

Fig. 4 shows the torque versus time curves of the MVQ/PP blends without and with the dual reactive compatibilizer (EMA-co-GMA and PP-g-MAH). Here, it should be noted that the total weight of these blends is the same. The equilibrium mixing torque of the blend without compatibilizer is approximately 4.3 Nm, and it significantly increases to 6.6 Nm for the blend compatibilized by the dual reactive compatibilizer at the GMA/MAH molar ratio of 0.5/1, and it decrease to approximately 5.6 Nm under the GMA/MAH molar ratio of 0.75/1, still higher than that without the compatibilizer. Because the composition ratio of rubber/plastic is the same in all these blends, the enhancement of torque is mainly ascribed to the enhancement of interfacial interaction between MVQ and PP caused by the compatibilization reaction between the epoxy functional groups of EMA-g-GMA and anhydride group of the PP-g-MAH at the MVQ/PP interface. The stronger interfacial interaction of the blend results in the higher equilibrium mixing torque.

译

Fig 4 Variations of torque and temperature with time of MVQ/PP blends during melt blending.

Download: Full-size image | High-res image | Low-res image

Effect of Dual Reactive Compatibilizer on Crystallinity of PP Phase

Fig. 5 shows the crystallinity of neat PP, and PP in the MVQ/PP blends. The crystallinity of neat PP is 59%, whereas that of PP in all the blends significantly decreases, which is mainly due to the introduction of MVQ. The crystallinity of PP in the blends without the dual reactive compatibilizers is 45.3%, and that of the blend with the dual reactive compatibilizer further decreases to 31.3% and 35.4% under the GMA/MAH molar ratio of 0.5/1 and 0.75/1, respectively. The lower crystallinity of PP in the blend under the GMA/MAH molar ratio of 0.5/1 than that under the GMA/MAH molar ratio of 0.75/1 is mainly attributed to the smaller diameter of MVQ phase and the larger interfacial thickness between MVQ and PP of the former (see section Effect of Dual Reactive Compatibilizer on Glass Transition Temperature (T_g)).

译

Fig 5 (a) XRD patterns and (b) crystallinity of neat PP, PP phase in the non-compatibilized MVQ/PP blend, and PP phase in the MVQ/PP blend compatibilized with GMA/MAH-0.5/1 and 0.75/1.

Download: Full-size image | High-res image | Low-res image

Effect of Dual Reactive Compatibilizer on Mechanical properties

Fig. 6(a) shows the stress-strain curves of the MVQ/PP blends without and with the dual reactive compatibilizer (EMA-co-GMA and PP-g-MAH). The corresponding tensile strength and tensile stress at 300% strain, and elongation at break are summarized in Figs. 6(b) and 6(c), respectively. MVQ/PP blend without the dual compatibilizer shows the tensile strength of 5 MPa, stress at 300% strain of 3.8 MPa and elongation at break of 632%. In the presence of the dual reactive compatibilizer with the GMA/MAH molar ratio of 0.5/1, the tensile strength, stress at 300% strain and elongation at break increases to 6.2 MPa, 4.7 MPa and 679%, respectively, which is mainly attributed to the stronger interfacial interaction (Fig. 1) and the smaller size of MVQ domains (Fig. 2). But the decrease in crystallinity of PP phase in such blend has an adverse effect on the increase in mechanical properties. Thus, the increase in these mechanical properties is not very significant at the GMA/MAH molar ratio of 0.5/1. As the GMA/MAH molar ratio increases to 0.75/1, the stress at 300% strain (5.5 MPa) is higher than that of the other blends, but the tensile strength (6.3 MPa) remains almost unchanged, and this is owing to the decrease in elongation at break to 523%, which is even lower than that of the blend without the compatibilizer. This can be explained by the combined effect of the moderate interfacial interaction, the moderate size of MVQ dispersed phase, and the higher crystallinity of PP phase in such blend.

译

Fig 6 (a) The stress-strain curves, (b) the tensile strength and stress at 300% strain and (c) elongation at break of the MVQ/PP blends.

Download: Full-size image | High-res image | Low-res image

CONCLUSIONS

In summary, the compatibility between MVQ and PP phases in the MVQ/PP blends with no reactive groups in both components is largely improved by using a dual reactive compatibilizer composed of EMA-co-GMA and PP-g-MAH. Theoretical calculation of the spreading coefficient of the in situ formed copolymer indicates that it can well compatibilize MVQ/PP blends. The effect of the copolymer compatibilizer on the interfacial thickness, the size of MVQ dispersed phase in blends, T_g of MVQ and PP phases, mixing torque and mechanical properties of the blends was studied. Under the GMA/MAH molar ratio of 0.5/1, the interface thickness largely increases, and the average size of MVQ dispersed phase largely decreases, the T_g of both PP and MVQ phases shifts toward each other, the mixing torque of blends increases, and the mechanical properties are improved, indicating the good compatibilization effect of the dual reactive compatibilizer. This study provides a good compatibilizing method for immiscible MVQ/PP blends with no reactive groups in both components for the preparation of high performance MVQ/PP TPVs.

译

References

Ning,N.;Li,S.;Wu,H.;Tian,H.;Yao,P.;Hu,G.H.;Tian,M.;Zhang,L.Preparation,microstructure,andmicrostructure-propertiesrelationshipofthermoplasticvulcanizates(TPVs):areview.Prog. Polym. Sci.2018,79,61−97..

Wang,H.S.;Zhang,X.H.;Zhu,Y.L.;Song,Z.H.;Qiao,J.L.One-stepprocesstomakeelectricallyconductivethermoplasticvulcanizatesfilledwithMWCNTs.Chinese J. Polym. Sci.2012,30,138−142..

Fan,J.;Huang,J.;Cao,L.;Yin,S.;Chen,Y.Mechanicallyrobust,reprocessableshapememoryfluorosiliconmaterialsusingβ-Heliminationreactionandin situinterfacialcompatibilization.Indust. Eng. Chem. Res.2020,59,12745−12754..

Wu,H.;Tian,M.;Zhang,L.;Tian,H.;Wu,Y.;Ning,N.;Chan,T.W.Newunderstandingofmorphologyevolutionofthermoplasticvulcanizate(TPV)duringDynamicVulcanization.ACS Sustain. Chem. Eng.2015,3,26−32..

Shen,Y.;Tian,H.;Pan,W.;Feng,J.;Wang,D.;Ning,N.;Tian,M.;Zhang,L.UnexpectedimprovementofbothmechanicalstrengthandelasticityofEPDM/PPthermoplasticvulcanizatesbyintroducingβ-nucleatingagents.Macromolecules2021,54,2835−2843..

Hu,X.;Kang,H.;Li,Y.;Geng,Y.;Wang,R.;Zhang,L.Preparation,morphologyandsuperiorperformancesofbiobasedthermoplasticelastomerbyin situdynamicalvulcanizationfor3D-printedmaterials.Polymer2017,108,11−20..

Yao,P.;Wu,H.;Ning,N.;Zhang,L.;Tian,H.;Wu,Y.;Hu,G.H.;Chan,T.W.;Tian,M.Microstructureandpropertiesofbromo-isobutylene-isoprenerubber/polyamide12thermoplasticvulcanizatetowardrecyclableinnerlinersforgreentires.RSC Adv.2016,6,30004−30013..

Matchawet,S.;Kaesaman,A.;Vennemann,N.;Kummerlöwe,C.;Nakason,C.Optimizationofelectricalconductivity,dielectricproperties,andstressrelaxationbehaviorofconductivethermoplasticvulcanizatesbasedonENR/COPAblendsbyadjustingmixingmethodandionicliquidloading.Indust. Eng. Chem. Res.2017,56,3629−3639..

Garois,N.;Sonntag,P.;Hong,S.;Martin,G.;Galpin,D.2011,U.S.Pat.,0281984A1.

Li,S.Q.;Tian,H.C.;Hu,G.H.;Ning,N.Y.;Tian,M.;Zhang,L.Q.EffectsofshearduringinjectionmoldingontheanisotropicmicrostructureandpropertiesofEPDM/PPTPVcontainingrubbernanoparticleagglomerates.Polymer2021,229,124008..

Fan,J.;Yan,M.;Huang,J.;Cao,L.;Chen,Y.Fabricationofsmartshapememoryfluorosiliconthermoplasticvulcanizates:theeffectofinterfacialcompatibilityandtinycrystals.Indust. Eng. Chem. Res.2019,58,15199−15208..

Gong,K.;Tian,H.;Liu,H.;Liu,X.;Hu,G.H.;Yu,B.;Ning,N.;Tian,M.;Zhang,L.Graftingofisobutylene-isoprenerubberwithglycidylmethacrylateanditsreactivecompatibilizationeffectonisobutylene-isoprenerubber/polyamides12blends.Indust. Eng. Chem. Res.2021,60,16258−16266..

Dong,W.;Wang,H.;He,M.;Ren,F.;Wu,T.;Zheng,Q.;Li,Y.Synthesisofreactivecombpolymersandtheirapplicationsasahighlyefficientcompatibilizerinimmisciblepolymerblends.Indust. Eng. Chem. Res.2015,54,2081−2089..

Li,H.;Hu,G.H.Theearlystageofthemorphologydevelopmentofimmisciblepolymerblendsduringmeltblending:compatibilizedvs.uncompatibilizedblends.J. Polym. Sci., Part B: Polym. Phys.2001,39,601−610..

Yu,C.;Shi,D.;Wang,J.;Shi,H.;Jiang,T.;Yang,Y.;Hu,G.H.;Li,R.K.Y.Effectofadualcompatibilizerontheformationofco-continuousmorphologyofimmisciblepolymerblends.Materials & Design2016,107,171−177..

Rong,C.;Chen,Y.;Chen,C.;Hu,L.;Wang,H.;Li,Y.Towardsimultaneouscompatibilizationandnucleationoffullybiodegradabenanocomposites:effectofnanorod-assistedinterfacialstereocomplexcrystalsinimmisciblepolymerblends.Compos. Part B: Eng.2022,234,109708..

Wang,H.;Chen,J.;Li,Y.Arrestedelongatedinterfacewithsmallcurvaturebythesimultaneousreactivecompatibilizationandstereocomplexation.Macromolecules2020,53,10664−10674..

Li,Q.;Lin,G.;Chen,S.;Zhang,L.;Song,Y.;Geng,C.;Qu,S.;Jing,Y.;Liu,F.;Liang,Z.Enhancingmechanicalperformanceandwet-skidresistanceofemulsionstyrenebutadienerubber/naturalrubberlatexcompositesvia in-situhybridizationofsilanizedgrapheneoxideandsilica.J. Appl. Polym. Sci.2022,139,52083..

Liu,X.-x.;Wang,Y.-f.;Zhang,N.-z.;Shanks,R.A.;Liu,H.S.;Tong,Z.;Chen,L.;Yu,L.Morphologyandphasecompositionofgelatin-starchblends.Chinese J. Polym. Sci.2014,32,108−114..

Wang,X.;Peng,S.;Chen,H.;Yu,X.;Zhao,X.Mechanicalproperties,rheologicalbehaviors,andphasemorphologiesofhigh-toughnessPLA/PBATblendsbyin situreactivecompatibilization.Compos. Part B: Eng.2019,173,107028..

Ji,W.Y.;Feng,L.F.;Zhang,C.L.;Hoppe,S.;Hu,G.H.;Dumas,D.Aconceptofreactivecompatibilizer-tracerforstudyingreactivepolymerblendingprocesses.Aiche J.2016,62,359−366..

Deng,S.H.;Bai,H.W.;Liu,Z.W.;Zhang,Q.;Fu,Q.Towardsupertoughandheat-resistantstereocomplex-typepolylactide/elastomerblendswithimpressivemeltstabilityvia in situformationofgraftcopolymerduringone-potreactivemeltblending.Macromolecules2019,52,1718−1730..

Wei,B.;Lin,Q.;Zheng,X.;Gu,X.;Zhao,L.;Li,J.;Li,Y.Reactivesplicingcompatibilizationofimmisciblepolymerblends:compatibilizersynthesisinthemeltstateandcompatibilizerarchitectureeffects.Polymer2019,185,121952..

Prakashan,K.;Gupta,A.K.;Maiti,S.N.EffectofcompatibilizeronmicromehanicaldeformationsandmorphologyofdispersioninPP/PDMSblend.J. Appl. Polym. Sci.2007,105,2858−2867..

Wei,B.;Chen,D.;Wang,H.;You,J.;Wang,L.;Li,Y.;Zhang,M.In-situgraftingofcarboxylicacidterminatedpoly(methylmethacrylate)ontoethylene-glycidylmethacrylatecopolymers:one-potstrategytocompatibilizeimmisciblepoly(vinylidenefluoride)/lowdensitypolyethyleneblends.Polymer2019,160,162−169..

Rajan,K.P.;Al-Ghamdi,A.;Ramesh,P.;Nando,G.B.Blendsofthermoplasticpolyurethane(TPU)andpolydimethylsiloxanerubber(PDMS),part-I:assessmentofcompatibilityfromtorquerheometryandmechanicalproperties.J. Polym. Res.2012,19,9872..

Robert,C.;deMontigny,F.;Thomas,C.M.Tandemsynthesisofalternatingpolyestersfromrenewableresources.Nat. Commun.2011,2,586..

Wang,H.;Fu,Z.;Dong,W.;Li,Y.;Li,J.Formationofinterfacialjanusnanomicellesbyreactiveblendingandtheircompatibilizationeffectsonimmisciblepolymerblends.J. Phys. Chem. B2016,120,9240−9252..

Wang,H.;Fu,Z.;Zhao,X.;Li,Y.;Li,J.Reactivenanoparticlescompatibilizedimmisciblepolymerblends:synthesisofreactiveSiO₂withlongpoly(methylmethacrylate)chainsandtheinsituformationofjanusSiO₂nanoparticlesanchoredexclusivelyattheinterface.ACS Appl. Mater. Interfaces2017,9,14358−14370..

Zolali,A.M.;Favis,B.D.Tougheningofcocontinuouspolylactide/polyethyleneblendsviaaninterfaciallypercolatedintermediatephase.Macromolecules2018,51,3572−3581..

Yao,N.;Wang,H.;Zhang,L.;Yue,D.;Tian,M.One-potsolvothermalsynthesisofsilane-functionalizedcarbonnanodotsascompatibilizersfortheimmiscibleTPU/MVQblends.Appl. Surf. Sci.2020,530,147124..

Mahmud,M.B.;Anstey,A.;Shaayegan,V.;Lee,P.C.;Park,C.B.EnhancingthemechanicalperformanceofPA6basedcompositesbyalteringtheircrystallizationandrheologicalbehaviorvia in-situgeneratedPPSnanofibrils.Compos. Part B: Eng.2020,195,108067..

Jańczuk,B.;Wójcik,W.;Zdziennicka,A.Determinationofthecomponentsofthesurfacetensionofsomeliquidsfrominterfacialliquid-liquidtensionmeasurements.J. Colloid Interface Sci.1993,157,384−393..

Yu,F.;Huang,H.X.Simultaneouslytougheningandreinforcingpoly(lacticacid)/thermoplasticpolyurethaneblendviaenhancinginterfacialadhesionbyhydrophobicsilicananoparticles.Polym. Test.2015,45,107−113..

Fu,Z.;Wang,H.;Zhao,X.;Li,X.;Gu,X.;Li,Y.Flame-retardingnanoparticlesasthecompatibilizersforimmisciblepolymerblends:simultaneouslyenhancedmechanicalperformanceandflameretardancy.J. Mater. Chem. A2019,7,4903−4912..

摘要

A dual reactive compatibilizer was designed to compatibilize MVQ/PP blends. Under the GMA/MAH molar ratio of 0.5/1, the interface thickness largely increases, the average size of MVQ dispersed phase largely decreases, and the mechanical properties of the blend are increased, all indicating its good compatibilization effect.

Abstract

Methyl vinyl silicone rubber (MVQ)/polypropylene (PP) thermoplastic vulcanizate (TPV) combines the good melt processability, recyclability and sealing performance as well as biosafety, stain and fluid resistance, and thus it is especially suitable in bio-safety areas and wearable electronic devices,etc,. Nevertheless, the compatibility between MVQ and PP phases is poor. A big challenge on the compatibilization of MVQ/PP blends is that neither MVQ nor PP contains any reactive groups. In this study, a dual reactive compatibilizer composed of ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-,co,-GMA) and maleic anhydride grafted polypropylene (PP-,g,-MAH) was designed for the compatibilization of MVQ/PP blends. During melt blending, a copolymer compatibilizer at the MVQ/PP interface can be formed because of the ,in situ, reaction between EMA-,co,-GMA and PP-,g,-MAH. The thermodynamic predict of its compatibilization effect through calculating the spreading coefficient of the ,in situ, formed copolymer indicates that it can well compatibilize MVQ/PP blends. The experimental results show that under the GMA/MAH molar ratio of 0.5/1, the interface thickness largely increase from 102 nm for non-compatibilized blend to 406 nm, and the average size of MVQ dispersed phase largely decreases from 2.3 μm to 0.36 μm, the ,T,g, of the two phases shifts toward each other, the mixing torque and mechanical properties of the blend are increased, all indicating its good compatibilization effect. This study provides a good compatibilizing method for immiscible MVQ/PP blends with no reactive groups in both components for the preparation of high performance MVQ/PP TPVs.

关键词

Keywords

Methyl vinyl silicone rubber (MVQ)Polypropylene (PP)Immiscible polymer blendsReactive compatibilization

references

Wang,H.S.;Zhang,X.H.;Zhu,Y.L.;Song,Z.H.;Qiao,J.L.One-stepprocesstomakeelectricallyconductivethermoplasticvulcanizatesfilledwithMWCNTs.Chinese J. Polym. Sci.2012,30,138−142..

Wu,H.;Tian,M.;Zhang,L.;Tian,H.;Wu,Y.;Ning,N.;Chan,T.W.Newunderstandingofmorphologyevolutionofthermoplasticvulcanizate(TPV)duringDynamicVulcanization.ACS Sustain. Chem. Eng.2015,3,26−32..

Garois,N.;Sonntag,P.;Hong,S.;Martin,G.;Galpin,D.2011,U.S.Pat.,0281984A1.

Li,H.;Hu,G.H.Theearlystageofthemorphologydevelopmentofimmisciblepolymerblendsduringmeltblending:compatibilizedvs.uncompatibilizedblends.J. Polym. Sci., Part B: Polym. Phys.2001,39,601−610..

Yu,C.;Shi,D.;Wang,J.;Shi,H.;Jiang,T.;Yang,Y.;Hu,G.H.;Li,R.K.Y.Effectofadualcompatibilizerontheformationofco-continuousmorphologyofimmisciblepolymerblends.Materials & Design2016,107,171−177..

Wang,H.;Chen,J.;Li,Y.Arrestedelongatedinterfacewithsmallcurvaturebythesimultaneousreactivecompatibilizationandstereocomplexation.Macromolecules2020,53,10664−10674..

Liu,X.-x.;Wang,Y.-f.;Zhang,N.-z.;Shanks,R.A.;Liu,H.S.;Tong,Z.;Chen,L.;Yu,L.Morphologyandphasecompositionofgelatin-starchblends.Chinese J. Polym. Sci.2014,32,108−114..

Ji,W.Y.;Feng,L.F.;Zhang,C.L.;Hoppe,S.;Hu,G.H.;Dumas,D.Aconceptofreactivecompatibilizer-tracerforstudyingreactivepolymerblendingprocesses.Aiche J.2016,62,359−366..

Prakashan,K.;Gupta,A.K.;Maiti,S.N.EffectofcompatibilizeronmicromehanicaldeformationsandmorphologyofdispersioninPP/PDMSblend.J. Appl. Polym. Sci.2007,105,2858−2867..

Robert,C.;deMontigny,F.;Thomas,C.M.Tandemsynthesisofalternatingpolyestersfromrenewableresources.Nat. Commun.2011,2,586..

Wang,H.;Fu,Z.;Dong,W.;Li,Y.;Li,J.Formationofinterfacialjanusnanomicellesbyreactiveblendingandtheircompatibilizationeffectsonimmisciblepolymerblends.J. Phys. Chem. B2016,120,9240−9252..

Wang,H.;Fu,Z.;Zhao,X.;Li,Y.;Li,J.Reactivenanoparticlescompatibilizedimmisciblepolymerblends:synthesisofreactiveSiO2withlongpoly(methylmethacrylate)chainsandtheinsituformationofjanusSiO2nanoparticlesanchoredexclusivelyattheinterface.ACS Appl. Mater. Interfaces2017,9,14358−14370..

Zolali,A.M.;Favis,B.D.Tougheningofcocontinuouspolylactide/polyethyleneblendsviaaninterfaciallypercolatedintermediatephase.Macromolecules2018,51,3572−3581..

Yao,N.;Wang,H.;Zhang,L.;Yue,D.;Tian,M.One-potsolvothermalsynthesisofsilane-functionalizedcarbonnanodotsascompatibilizersfortheimmiscibleTPU/MVQblends.Appl. Surf. Sci.2020,530,147124..

Jańczuk,B.;Wójcik,W.;Zdziennicka,A.Determinationofthecomponentsofthesurfacetensionofsomeliquidsfrominterfacialliquid-liquidtensionmeasurements.J. Colloid Interface Sci.1993,157,384−393..

Yu,F.;Huang,H.X.Simultaneouslytougheningandreinforcingpoly(lacticacid)/thermoplasticpolyurethaneblendviaenhancinginterfacialadhesionbyhydrophobicsilicananoparticles.Polym. Test.2015,45,107−113..

Views

125

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Structural Evolution in Flowing Immiscible Blends in the Presence of Rough Particles: Dependence of Shear Rate and Blend Ratio

Coalescence Suppression in Flowing Polymer Blends Using Silica Rods with Different Surface Chemistries

A New Evaluation Criterion for Optimizing the Mechanical Properties of Toughened Polypropylene/Silica Nanocomposites

Improvement in Toughness of Poly(ethylene 2,5-furandicarboxylate) by Melt Blending with Bio-based Polyamide11 in the Presence of a Reactive Compatibilizer

Related Author

No data

Related Institution

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering of China, Sichuan University

Group of Energy Materials, École Polytechnique Fédérale de Lausanne, Sion

School of Chemical, Petroleum and Gas Engineering, Iran University of Science and Technology, Tehran 4

School of Mechanical Engineering, Braunschweig university of technology, Braunschweig

Key Laboratory of Bio-based Polymeric Materials Technology and Application of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences

⁰