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1.
Molecular weights and grafting frequencies of graft copolymers prepared with ferrous ammonium sulfate-hydrogen peroxide initiation showed a dependence on granule swelling similar to that found with ceric ammonium nitrate (increased swelling of starch granules decreased the number of grafted polyacrylonitrile chains and increased their average molecular weight). As with unswollen starch, the composition of the copolymer prepared from swollen starch was not influenced by granule size. Molecular weights of polyacrylonitrile branches grafted to swollen and unswollen starch were independent of reaction time; however, grafting frequencies with swollen and unswollen starch tended to converge toward a common value with increased reaction time and increased dilution. Data suggest that the influence of granule swelling on copolymer composition is due to a faster termination rate for growing polyacrylonitrile chains in unswollen starch.  相似文献   

2.
Polymerization of vinyltoluene (VT) in quaternary microemulsions containing cetyltrimethylammonium bromide (CTAB) as the cationic surfactant is studied using laser Raman spectroscopy (LRS) and dilatometry. The influences of water soluble (potassium peroxodisulphate, ammonium peroxodisulphate) and oil soluble (azobisisobutyronitrile, benzoyl peroxide) initiators, monomer, surfactant, cosurfactants (n-alcohol and bifunctional alcohols) and temperature on the rates of polymerization (R p), energy of activation (Ea), particle diameter (D), number of polymer particles (N p), molecular weight of polyvinyltoluene (M v) and number of polymer chains per latex particle (N pc) are investigated. The dependencies of the kinetic and latex size parameters on the initiators and cosurfactants are discussed in terms of the efficiency of the initiators in initiating the polymerization and on the interfacial partitioning behavior of various cosurfactants. The polymerization mechanism seems to follow Smith Ewart Case II hypothesis with two distinct rate regions. Final polymer microlatexes are found to lie within 10–50 nm as observed by transmission electron microscopy (TEM). Molecular weights are in the range of (1 to 5)×106. Each latex particle contains one to three polymer chains.  相似文献   

3.
Summary Thin poly(vinylidene fluoride/hexafluoropropylene) (P(VDF/HFP)) films ahve been irradiated with gammarays to induce the initiation of styrene grafting by the indirect method. To obtain a better understanding of the radiation-grafting process we have used size exclusion chromatography (SEC) to study the effect of irradiation of this polymer and the evolution of the molecular weights of the polystyrene (PS) grafted chains as a function of the grafting time. Pristine, irradiated and PS radiation-grafted samples have been compared. We present evidence that the gamma irradiation induces both scission and crosslinking of the P(VDF/HFP) chains. We show that the average molecular weights of the PS grafted chains increase with grafting time and that the asymmetry of the chromatographic peak increases also. These grafted chains have molecular weights much higher than those of pristine P(VDF/HFP) and they cannot be confused with PS homopolymer chains, which have higher molecular weights as both, pristine and radiation-grafted P (VDF/HFP). Reversed-phase high-performance liquid chromatography (RPHPLC) has shown the absence of additives in pristine P(VDF/HFP) and has provided evidence of the presence of oligomers.  相似文献   

4.
The grafting of methyl methacrylate (MMA) onto polybutadiene rubber latex by the direct radiation method was carried out. The effects of monomer concentration, absorbed dose and dose rate of gamma rays on the grafting yield were investigated. The graft copolymers were characterized by transmission electron microscopy (TEM), FTIR spectroscopy, and differential scanning calorimetry. TEM photographs revealed that the core–shell structures of latex particles are formed at low MMA content, and with the increasing of MMA content, the semi-IPN-like structure with core–shell could be developed due to the high gel fraction of polybutadiene (PBD) seed particles. In addition, infrared analysis confirmed that MMA could be grafted onto PBD molecular chains effectively under appropriate irradiation conditions. The interfacial adhesion between PBD rubber (core) and PMMA (shell) phases could be enhanced with the increase of MMA concentration.  相似文献   

5.
We previously reported that grafted polystyrene (PS) chains on silica nanoparticles at a low grafting density show similar conformations to free PS chains in the same solvent, THF (diameter ?50 nm, Colloid.poly.Sci. (2013), 291, 9, 2087–2099). As an extension of our previous study we choose an organic nanoparticle (deuterated polystyrene, dPS) instead of inorganic nanoparticle to see the impact of the substrate material on chain conformation. Additionally, a wider range of molecular weights were prepared to investigate the conformation feature of grafted PS chains more in detail. Small angle neutron scattering (SANS) experiments were performed to characterize PS grafted dPS particles in good solvent condition, with deuterated toluene and deuterated THF as solvent. To get insight into the conformation of the grafted PS layer we apply a scaling law describing the dimension of free PS polymer in good solvent condition to the obtained thickness of the grafted PS layer. We find an overall agreement with the scaling law where the thickness of the grafted PS layer is slightly larger than 2Rg of the free polymer chains in the respective solvent giving hint for semi dilute polymer brush (SDPB) situation.  相似文献   

6.
In efforts to produce polymeric materials with tailored physical properties, significant interest has grown around the ability to control the spatial organization of nanoparticles in polymer nanocomposites. One way to achieve controlled particle arrangement is by grafting the nanoparticle surface with polymers that are compatible with the matrix, thus manipulating the interfacial interactions between the nanoparticles and the polymer matrix. Previous work has shown that the molecular weight of the grafted polymer, both at high grafting density and low grafting density, plays a key role in dictating the effective inter-particle interactions in a polymer matrix. At high grafting density nanoparticles disperse (aggregate) if the graft molecular weight is higher (lower) than the matrix molecular weight. At low grafting density the longer grafts can better shield the nanoparticle surface from direct particle-particle contacts than the shorter grafts and lead to the dispersion of the grafted particles in the matrix. Despite the importance of graft molecular weight, and evidence of non-trivial effects of polydispersity of chains grafted on flat surfaces, most theoretical work on polymer grafted nanoparticles has only focused on monodisperse grafted chains. In this paper, we focus on how bidispersity in grafted chain lengths affects the grafted chain conformations and inter-particle interactions in an implicit solvent and in a dense homopolymer polymer matrix. We first present the effects of bidispersity on grafted chain conformations in a single polymer grafted particle using purely Monte Carlo (MC) simulations. This is followed by calculations of the potential of mean force (PMF) between two grafted particles in a polymer matrix using a self-consistent Polymer Reference Interaction Site Model theory-Monte Carlo simulation approach. Monte Carlo simulations of a single polymer grafted particle in an implicit solvent show that in the bidisperse polymer grafted particles with an equal number of short and long grafts at low to medium grafting density, the short grafts are in a more coiled up conformation (lower radius of gyration) than their monodisperse counterparts to provide a larger free volume to the longer grafts so they can gain conformational entropy. The longer grafts do not show much difference in conformation from their monodisperse counterparts at low grafting density, but at medium grafting density the longer grafts exhibit less stretched conformations (lower radius of gyration) as compared to their monodisperse counterparts. In the presence of an explicit homopolymer matrix, the longer grafts are more compressed by the matrix homopolymer chains than the short grafts. We observe that the potential of mean force between bidisperse grafted particles has features of the PMF of monodisperse grafted particles with short grafts and monodisperse grafted particles with long grafts. The value of the PMF at contact is governed by the short grafts and values at large inter-particle distances are governed by the longer grafts. Further comparison of the PMF for bidisperse and monodisperse polymer grafted particles in a homopolymer matrix at varying parameters shows that the effects of matrix chain length, matrix packing fraction, grafting density, and particle curvature on the PMF between bidisperse polymer grafted particles are similar to those seen between monodisperse polymer grafted particles.  相似文献   

7.
Sha-Ni Hu  Yu Lin  Guo-Zhang Wu 《高分子科学》2020,(1):100-108,I0008
How to control the spatial distribution of nanoparticles to meet different performance requirements is a constant challenge in the field of polymer nanocomposites.Current studies have been focused on the flexible polymer chain systems.In this study,the rigid polyimide(PI) chain grafted silica particles with different grafting chain lengths and grafting densities were prepared by "grafting to" method,and the influence of polymerization degree of grafted chains(N),matrix chains(P),and grafting density(a) on the spatial distribution of nanoparticles in the PI matrix was explored.The glass transition temperature(Tg) of PI composites was systematically investigated as well.The results show that silica particles are well dispersed in polyamic acid composite systems,while aggregation and small clusters appear in PI nanocomposites after thermal imidization.Besides,the particle size has no impact on the spatial distribution of nanoparticles.When σ·N0.5<<(N/P)2,the grafted and matrix chains interpenetrate,and the frictional resistance of the segment increases,resulting in restricted relaxation kinetics and Tg increase of the PI composite system.In addition,smaller particle size and longer grafted chains are beneficial to improving Tg of composites These results are all propitious to complete the microstructure control theory of nanocomposites and make a theoretical foundation for the high performance and multi-function of PI nanocomposites.  相似文献   

8.
RAFT mediated grafting of poly(t‐butyl acrylate) onto the surface of a commercial poly(ethylene‐co‐propylene), Elpro, has been carried out using initiation by 60Co γ‐radiation at 298 and 273 K. The polymerizations were in bulk monomer and using the RAFT agent 1‐phenylethyl phenyldithioacetate. The rates of homopolymerization and grafting were found to decrease with increasing RAFT agent concentration, indicating that both polymerization processes involve participation of the RAFT agent. There was good agreement between the predicted and experimental molecular weights of the homopolymer that had a narrow polydispersity. The poly(t‐butyl acrylate) grafts were hydrolyzed by trifluoroacetic acid to form poly(acrylic acid) grafts, which could either be further functionalized or used to control the surface polarity of the Elpro. ATR‐FTIR spectroscopy was used to characterize the grafts and Raman spectroscopy was used to assess the depth of the grafts. The water contact angle for the Elpro surface grafted with poly(acrylic acid) was found to be linearly dependent on the amount of the graft present. The living nature of the grafted chains was demonstrated by the addition of a second block of polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1074–1083, 2007  相似文献   

9.
The role of grafting in particle nucleation during the emulsion polymerization of vinyl acetate with partially hydrolyzed poly(vinyl alcohol) (PVA) as an emulsifier and potassium persulfate as an initiator was investigated. The polymerizations were carried out in batch with a low solids (10%) recipe. An automated reaction calorimeter (Mettler RC1) was used for the direct monitoring of the kinetics of emulsion polymerizations with three medium molecular weight PVAs differing in their degrees of blockiness (Poval 217EE > 217E > 217). Smith–Ewart case 1 kinetics (average number of free radicals per particle < 0.5) were followed in all cases, and no constant rate in interval II was observed. Contrary to what was expected, a nonlinear relationship was observed between the rate of polymerization (Rp) and the number of particles (Np). At Rp max, Np (217E) > Np (217EE) > Np (217), and the final Np was independent of the degree of blockiness of PVA. The particle size distributions were broad (particle diameter = 20–100 nm) and bimodal. On the basis of these data, we concluded that particle nucleation was continuous and was accompanied by extensive limited aggregation during the particle growth stages. The evolution of the amounts of grafted PVA and poly(vinyl acetate) (PVAc) were determined in polymerizations employing the two PVAs differing the most in blockiness (Poval 217EE and 217). The grafted PVAc followed similar profiles, increasing with conversion, particularly near the end of the two reactions. The amounts of grafted PVAc were about the same in the final latexes (37–39%). In contrast, the grafting of PVA was nearly complete by the time monomer droplets had disappeared in each reaction (25% conversion). However, the extent of grafting differed significantly, with the blockier PVA having about one‐third the grafting of the more random PVA (~10% vs ~30%). In these low solids recipes, grafting appeared to be primarily a solution event, occurring predominantly in the aqueous phase and not at the particle/water interface, as was previously speculated. The PVAc grafts grew until the molecules became water‐insoluble and precipitated, forming polymer particles. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3633–3654, 2001  相似文献   

10.
This study aimed at the synthesis of silica particles grafted with better-defined homopolymers and block copolymers by tandem approach. Z-functionalized S-benzyl S′-(3-trimethoxysilyl)propyltrithiocarbonate (BTPT) was used as a couplable RAFT agent to synthesize the target inorganic-organic hybrids. Simultaneous coupling reaction and RAFT process using silica particles and BTPT as raw materials efficiently afforded homopolymers grafted silica, and RAFT-synthesized macro chain transfer agents with ω-terminal trimethoxysilane moiety were utilized to mediate graft reaction to prepare silica particles grafted with di-, tri- and tetrablock copolymers comprised of polymer segments such as polystyrene, polyacrylamides and polyacrylates. When the grafted chains had molecular weights ranging between 3920 and 24800 g/mol, the molar grafting ratios, which were dependent on reaction conditions and types and compositions of grafted chains, were estimated to be in the range of 15.2–101 μmol/g, and grafted polymers usually had polydispersity indices lower than 1.3, revealing that the grafting process was almost controllable. To the best of our knowledge, this versatile tandem approach is one of the most facile techniques to prepare silica particles grafted with polymeric chains with controlled molecular weight, low polydispersity and precise composition due to its minimal reaction steps, mild conditions, straightforward synthesis and satisfactory controllability.  相似文献   

11.
Dispersion polymerization of styrene in polar solvents in the presence of hydroxypropyl cellulose (HPC) produces latex particles from ca. 1 to 26 μm depending on reaction parameters. Increasing the initiator concentration or temperature decreases the molecular weight, but increases the particle size and breadth of the size distribution. The decrease in molecular weight with increasing Ri, caused by larger initiator concentration or higher temperature, is expected based of fundamental kinetic relationships. The inverse correlation between size and rate of initiation is rationalized by polarity (stabilizing ability) of the grafted HPC-polystyrene formed in situ. High polar HPC-g-PS, which contains shorter graft polystyrene chain, stabilizes particles less effectively and this leads to larger particles. The primary influence of initial styrene concentration is a solvent effect: larger particles are obtained at high styrene concentration due to high solubility of polystyrene during the initial part of the reaction. The influence of the molecular weight of HPC is to change the polarity of the HPC-g-PS stabilizer. Comparison of particle growth of three critical polymerization systems suggests that the favorable continuous-phase solubility parameter for dispersion polymerization of styrene is around 11.6 (cal/mL)1/2. Too high or too low polarity generates particles with broad size distribution because large particles are formed during the initial stage and nucleation continues as the polymerization proceeds. © 1992 John Wiley & Sons, Inc.  相似文献   

12.
In this study we modified the surface of silica nanoparticles with methyl methacrylate by UV-induced graft polymerization. It is a surface-initiated polymerization reaction induced by ultraviolet irradiation. The resulting organic-inorganic nanocomposites were near-monodisperse and fabricated without homopolymerization of the monomer. Substantial increase in mean particle size was observed by SEM image analysis after UV-induced grafting of methyl methacrylate onto pure silica particles. FT-Raman spectroscopy and X-ray photoelectron spectroscopy studies of these materials revealed the successful grafting of methyl methacrylate onto the silica surface. The formation of a covalent bond between the grafted PMMA chains and silica surface was indicated by FT-Raman spectra. Thermogravimetric analysis of the PMMA-grafted silica particles indicated the polymer contents in good agreement with SEM photographs.  相似文献   

13.
In the final product of a bimodal bigraft ABS, consisting of crosslinked polybutadiene particles (diameter 100 nm) with grafted and ungrafted poly (styrene-co-acrylonitrile) (=SAN) with an acrylonitrile (=AN) content of 28 weight %, crosslinked polybutadiene particles (diameter 300 nm) with grafted and ungrafted SAN with an AN content of 12 weight % and an added SAN with an AN content of 28 weight % the following parameters can be determined: degree of grafting of the small polybutadiene particles, degree of grafting of the large polybutadiene particles, acrylonitrile content of the grafted chains of the small polybutadiene particles, acrylonitrile content of the grafted chains of the large polybutadiene particles, grafting efficiency of the large particles, average particle diameter and particle diameter distribution of the small particles, average particle diameter and particle diameter distribution of the big particles, molar mass distribution of the ungrafted chains of the large particles, chemical distribution of the ungraftd chains of the large particles, molar mass distribution of the SAN resin added, chemical distribution of the SAN resin added.Preparative differential ultracentrifugation in acetone/-butyrolacrone (volume ratio 0.550.45), FTIR spectrometry and electron microscopy of the floating and sedimentating fraction yield the degree of grafting and AN content of the graft chains of the large particles and the degree of grafting and AN content of the graft chains of the small particles.Preparative differential centrifugation, FTIR spectrometry and electron microscopy of the fractions give nearly equivalent results. Fractional demixing with the demixing solvents ethylene carbonate/tetraline of the acetone-soluble part yields the SAN with 12 weight % AN in the upper-phase and the SAN with 28 weight % AN in the lower phase.Size exclusion chromatography (SEC) and high-performance precipitation liquid chromatography (HPPLC) of the fractions yield the molecular distribution and chemical distribution of the different SAN resins. SEC, coupled with turbidimetric titration of the acetone-soluble fractions withn-hexane as precipirant, indicates SAN resin with lower AN content in addition to the SAN resin with 28 weight % AN.Dedicated to Prof. Dr. Dr. h.c. mult. Karl Heinz Büchel on the occasion of his 60th birthday  相似文献   

14.
Initiation of polymerization in styrene oil-in-water microemulsions by water-soluble potassium persulfate of oil-soluble 2,2′-azobis-(2-methyl butyronitrile) at 70°C gave stable latexes which were bluish and less translucent than the original microemulsions. The effects of initiator concentration, polymerization temperature, and monomer concentration on the kinetics, particle size distributions, and molecular weight distributions were investigated. The kinetics of polymerization were measured by dilatometry. In all cases, the polymerization rate shows only two intervals, which increased to a maximum and then decreased. There was no apparent constant rate period and no gel effect. A longer nucleation period was found for polymerizations initiated by potassium persulfate as compared to 2,2′-azobis-(2-methyl butyronitrile). The small latex particle size (20–30 nm) and high polymer molecular weight (1–2 × 106) implies that each latex particle consists of two or three polystyrene molecules. The maximum polymerization rate and number of particles varied with the 0.47 and 0.40 powers of potassium persulfate concentration, and the 0.39 and 0.38 powers of 2,2′-azobis-(2-methyl butyronitrile) concentration, respectively. This is consistent with the 0.4 power predicted by Smith–Ewart Case 2 kinetics. Microemulsion polymerizations of styrene–toluene mixtures at the same oil-water phase ratio gave lower polymerization rates and lower molecular weights, but the same latex particle size as with styrene alone. A mechanism is proposed, which comprised initiation and polymerization in the microemulsion droplets, by comparing the kinetics of microemulsion polymerization with conventional emulsion and miniemulsion polymerization systems.  相似文献   

15.
Previous studies have shown a two-peak molecular weight distribution of the grafted polystyrene side chains from preirradiation-grafted cellulose acetate. ESR has been used to investigate this grafting system in further detail. It was found that the rate of decay of the trapped radicals on adding the monomer solution was quite slow and a substantial proportion remained after 3 days at 25°C. The G value for radicals lost was, however, in good agreement with the G (grafted side chains) produced during the same period. The ESR spectrum does not change on addition of the monomer solution. The explanation offered is that the side chains grow and terminate rapidly compared with the slow overall rate of decay. The grafting yield and the molecular weight of the grafted side chains continue to grow until the reaction is terminated, leading perhaps to the high molecular weight narrow distribution fraction.  相似文献   

16.
 Radical dispersion polymerization of styrene in aqueous ethanol solutions was performed in the presence of a new reactive polyethylene oxide stabilizer with thiol end groups. This reactive stabilizer was compared to the more conventional poly (N-vinyl pyrrolidone). Particles size distribution, molecular weights and kinetics were investigated. Monodispersed polymer particles with diameter in the range 200–2000 nm were obtained depending on the amount of stabilizer used. In all cases, the polyethylene oxide (PEO) sequence of the dispersant was partly incorporated at the surface of the latex particles, but the grafting yield of polyethylene oxide chains was always limited and did not exceed 15%. Part of the stabilizer being unreacted or reacted with low molecular weight polystyrene remained in the continuous phase. Received: 26 September 1996 Accepted: 4 March 1997  相似文献   

17.
Nanosized copolymer latex of hydroxypropylmethylcellulose (HPMC) grafted with ethyl acrylate (EA) and dimethylaminoethyl methacrylate (DMAEMA) has been prepared by acidifying submicron-sized latex particles synthesized by soap-free emulsion graft copolymerization using potassium persulfate (KPS) as initiator. The effects on the diameter of the latex particles of different conditions, for example concentration of DMAEMA, amount of HPMC, and ratio of HCl to DMAEMA for acidification, were investigated. It was found that increasing the mole ratio of HCl to DMAEMA to 1.0 and increasing the DMAEMA content both resulted in a decrease in particle diameter, whereas increasing the amount of HPMC resulted in larger particle sizes. Measurement by dynamic light scattering (DLS) revealed the diameter of the latex particles was >200 nm before acidification and <100 nm after acidification. Evidence of grafting was obtained by use of Fourier transform infrared (FTIR) spectroscopy. Transmission electron microscopy (TEM) was used to characterize the morphology of the copolymer particles before and after acidification.  相似文献   

18.
An investigation of the grafting efficiency of methacrylamide during graft polymerization in natural rubber latex has shown that the efficiency is independent of the initiator and rubber concentrations but increases markedly with temperature. The overall activation energy of the graft polymerization was found to be 25 ± 2 kcal mole?1 greater than that for the corresponding homopolymerization. The molecular weight of the free homopolymer isolated from the graft copolymerization was very close to that of polymer isolated from the analogous homopolymerization, thus demonstrating that chain transfer with rubber hydrocarbon was unimportant. Electron micrographs of grafted and control latex particles confirm earlier conclusions that grafting occurs on the surface rather than the interior of the rubber particles.  相似文献   

19.
Abstract

A method of radiation graft copolymerization of n-butyl acrylate (NBA) on natural rubber (NR) latex has been studied. The rate of conversion increases with the increase of NBA in latex. An irradiation dose of about 12 kGy is needed to obtain 90% conversion with 40 phr of NBA in latex. Tensile strength, tear strength, and elongation at break of grafted NR are found to decrease with increasing degree of grafting. The physical strength of a vulcanizate prepared from a mixture of NR and ply-NBA was found to be better than that of NBA-NR graft copolymer vulcanizate. The graft copolymerization reaction takes place in the outer layer of NR particles, and because the secondary bonds between poly-NBA molecules may be weaker than those between NR molecules, the existence of a poly-NBA layer in NR particles will decrease its physical strength.  相似文献   

20.
A series of five near-monodisperse sterically stabilized polystyrene (PS) latexes were synthesized using three well-defined poly(glycerol monomethacrylate) (PGMA) macromonomers with mean degrees of polymerization (DP) of 30, 50, or 70. The surface coverage and grafting density of the PGMA chains on the particle surface were determined using XPS and (1)H NMR spectroscopy, respectively. The wettability of individual latex particles adsorbed at the air-water and n-dodecane-water interfaces was studied using both the gel trapping technique and the film calliper method. The particle equilibrium contact angle at both interfaces is relatively insensitive to the mean DP of the PGMA stabilizer chains. For a fixed stabilizer DP of 30, particle contact angles were only weakly dependent on the particle size. The results are consistent with a model of compact hydrated layers of PGMA stabilizer chains at the particle surface over a wide range of grafting densities. Our approach could be utilized for studying the adsorption behavior of a broader range of sterically stabilized inorganic and polymeric particles of practical importance.  相似文献   

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