首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
PVC/PS blends are obtained through a reactive extrusion–polymerization method by the absorption of a solution of styrene monomer, initiator, and a crosslinking agent in commercial suspension‐type porous polyvinyl chloride (PVC) particles, forming a dry‐blend with a relatively high monomer content. These PVC/styrene dry‐blends are reactively polymerized in a twin‐screw extruder in the melt state. They do not contain monomer residues as detected by GC. The transparency, fracture surface morphology, thermal stability, rheology and static and dynamic mechanical properties of these blends are compared to physical PVC/PS blends at similar compositions. Owing to the high polymerization temperature (180°C), short PS chains are formed in the reactive extrusion process. These short chains are dispersed both as a separate phase of ~2 μm particles (recognized by SEM) and also as molecularly dispersed chains enhancing plasticization and compatibilization. The molecularly dispersed short PS chains tend to plasticize the PVC phase, reducing its melt viscosity and glass transition temperature. The content of the short PS chains forming the dispersed separate PS particles is too low for DMTA to detect a separate Tg. Thus, reactively extruded PVC/PS blends exhibit single Tg transitions at lower temperatures compared with the neat PVC. Migration of the PVC's low‐molecular‐weight additives (lubricants and thermal stabilizer) to the PS phase is observed in the physical PVC/PS blends, causing antiplasticization of the PS phase. This results in both reduction of the Tg and an increase in the thermal stability of the PS phase in the physical PVC/PS blends. Comparing TGA thermograms of reactively extruded and physical PVC/PS indicates that the PS formed in the extruder is different from the commercial PS. This can stem from various chemical reactions that can take place in the studied reactive polymerization process. Polym. Eng. Sci. 44:1473–1483, 2004. © 2004 Society of Plastics Engineers.  相似文献   

2.
The modification of porous PVC particles by an insitu stabilizer‐free polymerization/crosslinking of a monomer/crosslinker/peroxide solution absorbed within the PVC particles is presented. The modifying crosslinked polymers are polystyrene (PS) crosslinked with DVB (divinyl benzene), polymethyl methacrylate (PMMA) crosslinked with ethylene glycol dimethacrylate (EGDMA), and styrene‐MMA copolymer crosslinked with DVB. The modified PVC particles characterization includes polymerization yield, non‐extractables, 13C solid‐state CPMAS NMR, porosity measurements and also morphology and dynamic mechanical behavior (DMTA). The levels of nonextractable fractions found and 13C solid‐state CPMAS NMR results are indicative of low chemical interaction in the semi‐IPN PVC particles. Particle porosity levels and SEM observations indicate that styrene and MMA mainly polymerize within the PVC particles' bulk and just small amounts in the pores. MMA polymerization in the PVC pores is as crusts covering the PVC pore surfaces, whereas styrene polymerization in the PVC pores is by filling the pores. Dynamic mechanical studies show that tanδ and the storage modulus curves are influenced by the incorporation of PS and XPS but not by the incorporation of PMMA and XPMMA.  相似文献   

3.
Small‐angle X‐ray scattering (SAXS) was applied to investigate the microstructure of unmodified and modified porous commercial suspension‐type poly(vinyl chloride) (PVC) particles. The modified PVC particles were prepared by an in situ stabilizer‐free polymerization/crosslinking of particles absorbed with a monomer/crosslinker/peroxide solution. The modifying polymers include styrene with or without divinyl benzene (DVB) as a crosslinker and methyl methacrylate (MMA) with or without ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The SAXS method was used to highlight the effect of polystyrene (PS) on the microstructure of PVC particles and to evaluate the characteristic lengths, both in the PVC/PS and the PVC/XPS (PS crosslinked with 0 and 5% DVB, respectively) systems. A model is suggested, where during the synthesis modification process, swelling of PVC by styrene and styrene polymerization occur simultaneously. PVC swelling by styrene causes destruction of the PVC subprimary particles, whereas styrene polymerization leads to phase separation resulting from incompatibility of the polymers. It was further suggested that because of PVC swelling by styrene, structure of the subprimary particles is lost. Therefore the characteristic lengths of PVC/PS and PVC/XPS, as calculated from the SAXS measurements, were attributed to the size of the phase‐separated PS and XPS inclusions, respectively. The SAXS method also shows that PMMA and XPMMA do not influence the PVC microstructure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1024–1031, 2005  相似文献   

4.
Monodisperse polymer particles were prepared via conventional microsuspension polymerization or one‐step seeded polymerization, using 1,6‐hexanedioldiacrylate or its mixture with ethylene glycol dimethacrylate (EGDMA) as crosslinking monomer and poly(methyl methacrylate) synthesized by soap‐free polymerization as seed particles. For the study, the effects of the ratio of the absorbed monomer or monomer mixture to the seed polymer particles (swelling ratio), the ratio of EGDMA in absorbed monomer mixture, the dosage of initiator, polymer particle structure, and the electroless Ni plating on the mechanical properties of polymer particles, such as recovery rate, K‐values, breaking strength, and breaking displacement were investigated using micro compression test. It was observed that monomer swelling ratio influenced only on breaking strength, whereas EGDMA ratio in monomer mixture, dosage of initiator, polymer structure and electroless Ni plating did on both K‐values and breaking strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

5.
以聚丙烯酸丁酯(PBA)为内核,通过种子乳液聚合制备了分别以聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、PMMA/PVC为壳层的纯丙烯酸酯(ACR)和PVC改性ACR乳液.扫描电镜观察发现,纯ACR乳胶粒子具有明显的核-壳结构,进一步包覆PVC后形成疏松外层.考察了不同结构ACR与PVC共混物的相态结构、抗冲性能和断面形貌,发现用PVC部分或完全替代PMMA壳层的改性ACR在PVC基体分散良好,具有与纯ACR相当的增韧PVC作用,冲击断面呈现典型的韧性断裂特征.  相似文献   

6.
Monodispersed soap‐free poly(methyl methacrylate/ethyl acrylate/methacrylic acid) latex particles were synthesized by the seeded emulsion polymerization of methyl methacrylate, ethyl acrylate, and methacrylic acid (MAA), and particles with a porous morphology were obtained after an alkali posttreatment. The effects of the unsaturated acid and crosslinking agent on the properties and morphology of the latex particles were investigated. The results showed that the particle size decreased and its distribution widened when the concentration of MAA was greater than 10.0 mol % or the concentration of ethylene glycol dimethacrylate (EGDMA) was greater than 1.5%. When more than 4.0 mol % MAA was used, a porous structure could be detected clearly under a transmission electron microscope, and the particle volume and pore size first gradually increased to a maximum and then decreased rapidly with an increase in the MAA concentration. The porous morphology disappeared completely as the MAA concentration reached 16.0 mol %. A multihollow morphology was generated when the EGDMA concentration exceeded 1.0%, and the particle volume decreased monotonously with the concentration of EGDMA increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1934–1939, 2006  相似文献   

7.
Summary PB-g-MMA core-shell impact modifiers were synthesized by seed emulsion polymerization and impact-modified PMMA/PVC blends were prepared by melt blending PMMA, PVC and PB-g-MMA at 160 °C. The PB-g-MMA particles were dispersed uniformly in the PMMA/PVC matrix. PMMA/PVC blends were prepared in the blend ratio from 100/0 to 0/100 and the rubber content was kept 16% in all the compositions. The effects of matrix composition on the mechanical properties and morphology of the blends were studied. It was found that when the matrix was a PMMA-rich system, the sample broke in a brittle mode and crazing of the matrix was the main mechanisms of deformation. When the matrix was a PVC-rich system, the sample broke in a ductile mode and the main deformation mechanisms were cavitation of the particle and shear yielding of the matrix. There existed a transition from crazing to shear yielding in the rubber-modified PMMA/PVC blend as the matrix composition varied.  相似文献   

8.
A facile and environment friendly process, called water‐solid phase suspension grafting polymerization, was developed to prepare polypropylene‐g‐poly(methyl methacrylate) (PP‐g‐PMMA) copolymer with a submicrometer microdomain. In this approach, graft polymerization was elaborately regulated to occur within micropores of polypropylene particles prepared by reactor granule technology. FTIR spectra of the samples after extraction demonstrated that PMMA was successfully grafted onto the PP. The results showed grafting percentage (GP) of PMMA increased with the increasing monomer ratios to PP and that could reach 13.6%. Whereas the grafting efficiency decreased as the monomer ratio increased. The addition of second monomer styrene improved GP up to 24.5%. Differential Scanning Calorimetry tests showed that the grafting of PMMA have a slight effect on the melting point and the relative crystallinity of PP. TEM micrographs demonstrated PMMA domains distributed in PP matrix with sizes ranging from about 100 to 300 nm. In addition, Shear viscosity increased with the growing GP indicated by rheological measurement. The preliminary evaluation showed PP‐g‐PMMA was effective in improving the compatibility of PP/acrylonitrile‐styrene‐acrylate blends. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

9.
通过种子乳液聚合方法,采用丙烯酸丁酯(BA)、丙烯酸2-乙基己酯(EHA)为核层单体,与少量有机锡单体共聚制备了含有机锡的P(BA-EHA)胶乳,与氯乙烯(VC)乳液接枝共聚合成了P(BA-EHA)/PVC复合改性剂。通过透射电子显微镜(TEM)、动态力学分析仪(DMA)、扫描电子显微镜(SEM)等测试手段,考察了复合乳胶粒子和共混材料的形态结构、复合改性剂中有机锡含量对其共混改性PVC材料的力学性能及复合粒子热稳定性的影响。DMA和TEM分析结果表明:复合粒子的加入显著改善了橡胶相与PVC之间的相容性,P(BA-EHA)在PVC基体中具有很好的分散性和均匀度,SEM照片显示共混材料缺口断面表现为优异的基体屈服型断裂韧性。  相似文献   

10.
This paper reports about the polymerization of ε‐caprolactam monomer in the presence of low molecular weight hydroxyl or isocyanate end‐capped ethylene‐butylene elastomer (EB) elastomers as a new concept for the development of a submicron phase morphology in polyamide 6 (PA6)/EB blends. The phase morphology, viscoelastic behavior, and impact strength of the polymerization‐designed blends are compared to those of similar blends prepared via melt‐extrusion of PA6 homopolymer and EB elastomer. Polyamide 6 and EB elastomer were compatibilized using a premade triblock copolymer PA6‐b‐EB‐b‐PA6 or a pure EB‐b‐PA6 diblock reactively generated during melt‐blending (extrusion‐prepared blends) or built‐up via anionic polymerization of ε‐caprolactam on initiating ? NCO groups attached to EB chain ends (polymerization‐prepared blends). Two compatibilization approaches were considered for the polymerization‐prepared blends: (i) the addition of a premade PA6‐b‐EB‐b‐PA6 triblock copolymer to the ε‐caprolactam monomer containing nonreactive EB? OH elastomer and (ii) generation in situ of a PA6‐b‐EB diblock using EB? NCO precursor on which polyamide 6 blocks are built‐up via anionic polymerization of ε‐caprolactam. The noncompatibilized blends exhibit a coarse phase morphology, either in the extruded or the polymerization prepared blends. Addition of premade triblock copolymer (PA6‐b‐EB‐b‐PA6) to a EB? OH /ε‐caprolactam dispersion led to a fine EB phase (0.14 μm) in the PA6 matrix after ε‐caprolactam polymerization. The average particle size of the in situ reactively compatibilized polymerization‐prepared blend is about 1 μm. The notched Izod impact strength of the blend compatibilized with premade triblock copolymer was much higher than that of the neat PA6, the noncompatibilized, and the in situ reactively compatibilized polymerization blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2538–2544, 2004  相似文献   

11.
Problems related to the formation and stability of primary particles in VCM suspension and bulk polymerization were theoretically analyzed, based on the DLVO (Deryaguin-Landau-Verway-Overbeek) and HVO (Hesselink-Vrij-Overbeek) theories of stability of colloidal systems. In the absence of secondary stabilizers, PVC primary particles were solely stabilized by negative electric charges, as a result of the presence of HCl formed by a chain transfer reaction of chloride redicals to PVC polymer chains. The dependence of the stability of primary particles on the ionic strength of the medium, temperature, and total particle charge was quantitatively investigated in terms of the stability ratio and the particle coalescence rate constant. The steric stabilization of primary particles, arising from the addition of surfactants or polymers to the monomer phase, was examined, using the HVO theory. It was shown that PMMA improved the stability of primary particles and, thus, could alter the particle agglomeration kinetics. The effects of molar mass and the amount of the absorbed PMMA, as well as the influence of solvent quality on the steric stabilization of primary particles, were also investigated. The experimental results, published on the electrostatic and steric stabilization of PVC primary particles, were in good agreement with the theoretical predictions obtained in this study. © 1993 John Wiley & Sons, Inc.  相似文献   

12.
The dumbbell‐like/egglike microspheres of poly(4‐vinylpyridine/n‐butyl acrylate)/polystyrene [P(4VP/nBA)/PS] were prepared by soap‐free seed emulsion polymerization. The effects of various polymerization parameters, such as the amount of ethyl acetate (EA) in the continuous phase, swelling time, degree of crosslinking of seed polymer, polymerization temperature, and compatibility of seed polymer and the secondary polymer, and so forth, on the formation of dumbbell‐like/egglike morphology were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that secondary particles could be eliminated either by drastically increasing the number of seed particles or by stripping EA from the seed latex by dialysis and evaporation under a vacuum. Swelling the seed particle with the secondary monomer was essential for the preparation of egglike microspheres. For the localization of PS domains on one side of the egglike particle, the most effective factors were to elevate the polymerization temperature up to 90°C and simultaneously to lower the compatibility of the polymer on the seed particle surface with the phase of PS, while using the uncrosslinked seed latex. Crosslinking the seed latex was not suitable for localizing the PS domains in the seed particle, especially when the degree of crosslinking exceeded 0.5 wt % of EGDMA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2002–2017, 2001  相似文献   

13.
Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

14.
Seeded suspension copolymerization or a one‐stage copolymerization was used to synthesize acrylate core/shell imbiber beads. A two‐stage polymerization technique was used for seeded suspension polymerization. The seed particles for poly(methyl acrylate) or poly(2‐ethylhexyl acrylate) were synthesized first in a mixed solvent of toluene/isooctane containing the ethylene glycol dimethacrylate (EGDMA) crosslinking agent. These beads were swollen in styrene‐EGDMA‐BPO (benzoyl peroxide) and then polymerized in the aqueous phase to produce the polystyrene (PS) shell. The one‐stage copolymerization was carried out in toluene/isooctane containing methyl methacrylate (MMA), styrene (St), EGDMA, and BPO at 75°C for 10 h to give a core/shell copolymer of St‐MMA morphology. The appearance of core/shell imbiber beads prepared from these two techniques varied from monomer to monomer. This article describes the preparation, characterization, and application of the core/shell beads for organic solvent absorption/desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 670–682, 2002  相似文献   

15.
The heterogeneous polymerization of vinyl chloride monomer (VCM), with n‐butane as the reaction medium, was used to prepare poly(vinyl chloride) (PVC) resins. The particle features of the resulting resins and the particle formation mechanism of the polymerization process were investigated. The PVC resins prepared by the new polymerization process had a volume‐average particle size comparable to that of suspension PVC resins and a lower number‐average particle size. From scanning electron micrographs, it could be seen that the new PVC resins had a regular particle shape and a smooth surface with no obvious skin. They also had a high porosity. The new PVC resins were composed of individual and loosely aggregated primary particles. The diameter of the primary particles in the top layer of the grains was smaller than that of the primary particles in the center part of the grains. On the basis of the particle features of these PVC resins, a particle formation mechanism for the new polymerization process was proposed. PVC chains precipitate from a VCM/n‐butane mixed medium to form primary aggregates at a very low conversion, and the primary aggregates of the PVC chains aggregate to form primary particles, which further aggregate to form grains. The primary particles and grains grow by the capture of newly formed PVC chains and their primary aggregates and by polymerization occurring inside the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 954–958, 2003  相似文献   

16.
The properties and morphology of nano‐calcium carbonate (nano‐CaCO3) modified with the titanate coupling agent isopropyl trioleoyl titanate (IPTT) were characterized by Fourier transform infrared, thermogravimetric analyses, surface tension, and transmission electron microscopy. The results showed that the grafting ratio of IPTT on the surface of nano‐CaCO3 (IPTT‐Ca) increased with IPTT content. IPTT‐Ca/PBA/PMMA (IPTT‐Ca/ACR, PBA/PMMA core‐shell polymer, referred to ACR) latexes were prepared by seeded emulsion polymerization. They were then used to mix with PVC resin. The outer layer (PMMA) enhanced the dispensability of IPTT‐Ca/ACR in the PVC matrix by increasing the interfacial interaction of these composite particles with PVC. The notched impact strengths of the blends were influenced by the weight ratio of IPTT‐Ca to BA/MMA monomers, the weight ratio of BA/MMA. The relationships between the mechanical properties and the core‐shell composite structures were elaborated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

17.
Continuous dosing of a fast initiator during the suspension polymerization of vinyl chloride has been carried out in a pilot‐scale reactor. The kinetics course of this polymerization and the particle features of the resulting grains were discussed and compared to the conventional polymerization with the same conversion and maximum reaction rate. It was found for the system used that a suitable dosage trajectory allows the reaction rate to remain constant during polymerization. This decreases the polymerization time up to 53% compared with the conventional suspension polymerization, while the molecular weight distribution and molecular weight of the final grains remained almost unchanged. SEM micrographs revealed that PVC grains prepared using this polymerization process had irregularly shaped, uneven particle surfaces and larger particle sizes. The grains also featured high porosity with loosely aggregated smaller primary particles that led to low levels of residual unreacted monomer. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44079.  相似文献   

18.
Uniform macroporous particles carrying hydroxyl groups have been obtained in the size range 3–11.5 µm by seeded polymerization. For this purpose, uniform polystyrene particles in the size range 1.9–6.2 µm were used as seeds. The seed particles were successively swollen by dibutyl phthalate (DBP) and a monomer mixture comprising styrene, 2‐hydroxyethylmethacrylate (HEMA) and a crosslinker. Two different crosslinkers, divinylbenzene (DVB) and ethylene glycol dimethacrylate (EGDMA), were tested. Size distribution properties together with bulk and surface structures of the particles have been characterized by both scanning and transmission electron microscopy. While EGDMA provides uniform particles with a non‐porous surface, DVB produces uniform particles having a highly porous surface and interior. The comparison of FTIR and FTIR‐DRS spectra shows that the HEMA concentration is higher on the particle surface than within the particle interior. Seed latex size and monomer/seed latex ratios are identified as the most important variables affecting the final particles. Different seed latexes have been tried; the result is that highly macroporous particles with a sponge‐like pore structure both on the surface and in the particle interior have been obtained by use of the seed latex with the largest particles and the lowest molecular weight. An increase in the HEMA feed concentration leads to final particles with a non‐porous surface and a crater‐like porosity in the particle interior. The average pore size significantly decreases with increasing DBP/seed latex and monomer/seed latex ratios. © 2001 Society of Chemical Industry  相似文献   

19.
The properties and morphology of nanosilica modified with silane coupling agent, methacryloxypropyltrimethoxysilane (MPS), were characterized by fourier transform infrared, zeta potentials, thermogravimetric analysis, and transmission electron microscopy. The results showed that the grafting ratio of MPS on the surface of nanosilica increased with the MPS content. MPS‐silica/PBA/PMMA core‐shell latexes (MPS‐Si/ACR) were prepared by seeded emulsion polymerization. Then they were used to mix with PVC resin. The outer layer (PMMA) enhanced the dispersibility of MPS‐Si/ACR in the PVC matrix by increasing the interfacial interaction of these composite particles with PVC. The notched impact strengths of the blends were influenced by the weight ratio of MPS to silica, the concentration of emulsifier (SDS), and the MPS‐Si/ACR content. The relationships between the mechanical properties and the core‐shell composite structures were elaborated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008  相似文献   

20.
In this study, polymethyl methacrylate (PMMA)‐coated talc was produced by the in situ polymerization of methyl methacrylate on the talc surface. The polymerization reaction was performed by both batch and semicontinuous emulsion processes. The polymerization kinetics, particle size and distribution, grafting efficiency, and coated‐talc morphology were systematically investigated. It was found that the talc particles have no effect on the polymerization of PMMA. The PMMA produced was found to cover the talc surface well. However, only a small amount can be grafted onto the talc. The size distribution of talc particles treated by semicontinuous emulsion polymerization is more uniform than by batch polymerization. The treated talc was subsequently used as filler in a poly(vinyl chloride) (PVC) matrix, and mechanical properties of the PMMA‐coated‐talc/PVC composites were studied. Morphological structure of PVC‐matrix composites revealed that the PMMA coating on talc improved the dispersion of talc in the PVC matrix and enhanced the interfacial adhesion between the talc and PVC. The mechanical properties of the composites, especially the impact strength, were found to be improved. There appears to be a critical covering thickness of PMMA on the talc surface for optimum toughening. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2105–2112, 2001  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号