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1.
The design of a semicontinuous emulsion polymerization process, primarily based on theoretical calculations, has been carried out with the objective of achieving overall independent control over the latex particle size, the monodispersity in the particle size distribution, the homogeneous copolymer composition, the concentration of functional groups (e.g., carboxyl groups), and the glass‐transition temperature with n‐butyl methacrylate/n‐butyl acrylate/methacrylic acid as a model system. The surfactant coverage on the latex particles is very important for maintaining a constant particle number throughout the feed process, and this results in the formation of monodisperse latex particles. A model has been set up to calculate the surfactant coverage from the monomer feed rate, surfactant feed rate, desired solid content, and particle size. This model also leads to an equation correlating the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture. This equation can be used to determine the maximum polymerization rate, only below or at which monomer‐starved conditions can be achieved. The maximum polymerization rate provides guidance for selecting the monomer feed rate in the semicontinuous emulsion polymerization process. The glass‐transition temperature of the resulting carboxylated poly(n‐butyl methacrylate‐con‐butyl acrylate) copolymer can be adjusted through variations in the compositions of the copolymers with the linear Pochan equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 30–41, 2003  相似文献   

2.
BA‐MMA‐POMA copolymer latex was successfully prepared by soap‐free emulsion polymerization of 2‐(perfluoro‐(1,1‐bisisopropyl)‐2‐propenyl)oxyethyl methacrylate(POMA) with butyl acrylate(BA), methyl methacrylate (MMA) initiated by K2S2O8 in the water. POMA was synthesized from the intermediate perfluoro nonene and 2‐hydroxyethyl methacrylate as the staring reactants. The structure of BA‐MMA‐POMA copolymer latex was investigated by Fourier transform infrared (FTIR). The characteristics of the film such as hydrophobicity and glass transition temperature were characterized with the contact angle and differential scanning calorimetry respectively. The influences of the amount of the fluorinated monomer and the initiator on the soap‐free emulsion polymerization and performance of the latex were studied. In addition, comparison with the latex prepared by the conventional emulsifier SDBS is investigated. Results show that the hydrophobicity and glass transition temperature (Tg) of the latex are increased when the fluorinated monomer is introduced to copolymerize with other monomers. The hydrophobicity can be improved further with heating. Compared with the latices prepared by using SDBS emulsifier, the latices prepared by using HMPS emulsifier have larger particle size, higher surface tension. However, the difference of their Tg is extremely minute. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

3.
A modified emulsifier‐free emulsion polymerization of butyl methacrylate (BMA) with ionic or/and nonionic comonomers was successfully used to prepare nanosized poly(butyl methacrylate) (PBMA) latices with high polymer contents. After seeding particles were generated in an initial emulsion system, consisting of a portion of BMA, water, ionic comonomer [sodium styrenesulfonate (NaSS)] or nonionic comonomer [2‐hydroxyethyl methacrylate (HEMA)] and potassium persulfate, most of the BMA monomer or the mixture of BMA and HEMA was added dropwise to the polymerizing emulsion over a period of 6–12 h. Stable latices with high PBMA contents up to 27% were obtained. It was found that the latex particle sizes (2Rh) were largely reduced (34 nm) by the continuous addition of monomer(s) compared to those (107 nm) obtained by the batch polymerization method. The effect of comonomer concentration on the particle size, the number of PBMA particles/mL of latex (Nd), and the molar mass (Mw) of copolymer during the polymerization were discussed. The surface compositions of latex particles were analyzed by X‐ray photoelectron spectroscopy, indicating that the surface of latex particles was significantly enriched in NaSS or/and HEMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3080–3087, 2004  相似文献   

4.
Two latices—the poly(dimethylsiloxane) (PDMS)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) system (PA latex) and the PDMS/poly(vinyl acetate‐co‐butyl acrylate) system (PB latex)—were prepared by seeded emulsion polymerization, and PA/PB complex latices were obtained through the interparticle complexation of the PA latex with the PB latex. In addition, for the further study of the interparticle complexation of the PA latex with the PB latex, copolymer latices [PDMS/methyl methacrylate‐co‐butyl acrylate‐co‐vinyl acetate‐co‐methacrylic acid) (PC)] were prepared according to the monomer recipe of the complex latices and the polymerization process of the component latices. The properties of the obtained polymer latices and complex latices were investigated with surface‐tension, contact‐angle, and viscosity measurements. The mechanical properties of the coatings obtained from the latices were investigated with tensile‐strength measurements. The results showed that, in comparison with the two component latices (PA latex and PB latex) and the corresponding copolymer latices (PC latices), the PA/PB complex latices had lower surface tension, lower viscosities, and better wettability to different substrates. The tensile strengths of the coatings obtained from the complex latices were higher than the tensile strengths of the coatings from the two component latices and copolymer latices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2522–2527, 2004  相似文献   

5.
In this research, the thermoresponsive composite latex particles were prepared via W/O miniemulsion polymerization. Fe3O4 nanoparticles were homogeneously dispersed inside the poly(NIPAAm‐co‐MAA) latex particles. In the first step, PAA oligomers were used as stabilizers to produce a stable water‐based Fe3O4 ferrofluid, which could mix well with the water‐soluble monomers. In the second step, the Fe3O4/poly(NIPAAm‐co‐MAA) composite latex particles were synthesized via W/O miniemulsion polymerization. This polymerization proceeded in cyclohexane at room temperature, with Span80 as the emulsifier, NIPAAm as the thermoresponsive monomer, MAA as a comonomer with ? COOH functional groups, and APS/SMBS as the redox initiator system. The distribution of Fe3O4 nanoparticles inside the composite latex particles was expected to be homogeneous. The nucleation and morphology of the composite latex particles were mainly controlled by the concentration of the surfactant, Span80, in cyclohexane. The properties of the composite latex were examined with several instruments such as DSC and TGA. Finally, the superparamagnetic and thermoresponsive characteristics of this functional composite latex were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3987–3996, 2006  相似文献   

6.
中空聚合物微球的制备——种子及核乳胶粒的制备   总被引:3,自引:0,他引:3  
为了制得具有中空结构的聚合物微球,首先以十二烷基苯磺酸钠(SDBS)为乳化剂,在其用量低于CMC的条件下,进行甲基丙烯酸甲酯(MMA)、甲基丙烯酸(MAA)和丙烯酸丁酯(BA)的乳液聚合,制备了带羧基的种子乳胶粒.然后采用MMA、MAA和二乙烯基苯为单体进行种子乳液聚合,制备了轻度交联的带羧基的核乳胶粒.该核乳胶粒经过核-壳乳液聚合和适当的碱处理工艺就可成为具有中空结构的聚合物微球.采用粒度仪测定了乳胶粒的直径及其分布,采用TEM对乳胶粒结构形态进行了表征.研究了种子及核乳胶粒制备过程中单体加料方式、乳化剂用量及羧基单体种类等因素对聚合稳定性、乳胶粒直径及其分布以及最终的中空聚合物微球结构形态的影响,确定了制备种子及核乳胶粒的最佳工艺条件.在制备种子阶段,SDBS用量为单体总量的0.5%,采用一次性加入单体的进料工艺;在核乳胶粒制备阶段,以MAA为羧基单体,所有单体采用"饥饿式"加料,半连续补加乳化剂并使乳化剂用量为核单体总量的0.15%时可保持聚合稳定性并保证无新乳胶粒生成.  相似文献   

7.
3‐Allyloxy‐2‐hydroxyl‐propanesulfonic (AHPS) salt was synthesized and used as a hydrophilic comonomer for the methyl methacrylate (MMA) and n‐butyl acrylate (BA) emulsifier‐free emulsion copolymerization system to obtain latices of stable and high‐solid content. Properties of the latices, such as flow behavior, stability, and final diameter of the latex particles were studied. In addition, physical properties of the obtained copolymers, such as glass transition temperature (Tg), stress–strain behavior, and water resistance were investigated. With the addition of AHPS, the latices of stable and high‐solid content (as high as 60%) were prepared. Flow of the latices follows the law of the Bingham body. The final diameter of the latex particles is 0.3–0.5 μm in diameter, which is larger than that of the conventional latex particles and decreases with the increase of AHPS and potassium persulfate (KPS) concentration. All the copolymers are atactic polymers, showed as single Tg on dynamic mechanical analysis spectrum. Compared with the copolymers that were prepared by surfactant emulsion polymerization, tensile strength, as well as water resistance is greatly improved. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 21–28, 2001  相似文献   

8.
Heterogeneous film‐forming latexes were prepared using two‐stage, seeded emulsion polymerization. The polymerization was performed in a calorimetric reactor with a control unit that monitored the reaction rate and controlled the charging rate of the monomers. Three types of styrene seed latexes were prepared at 70°C. The first was an unmodified polystyrene (PS) latex. The second had the molecular weight lowered by the use of carbon tetrachloride (CCl4) as a chain‐transfer agent, added at the start of the polymerization. For the third one, divinylbenzene (DVB) was used as a comonomer. DVB was added under starved conditions near the end of the polymerization to achieve crosslinked particle shells and to introduce double bonds as possible grafting sites. The second polymerization step was performed at 80°C as a batch operation in a 200‐mL calorimeter reactor. The second‐stage polymer was poly(styrene‐co‐butadiene‐co‐methacrylic acid) (S/B/MAA). A fixed S/B ratio was used together with varying small amounts of MAA. Particle morphology and particle‐size distributions were examined after the second stage using TEM after staining with osmium tetroxide. The particle morphology was found to depend on both the seed composition and the amount of MAA used in the second stage. Molecular weight and crosslinking of the DVB‐containing seed influenced the internal particle viscosity, which gave differences in the polymerization rate and the particle morphology. Crosslinking of the second‐stage polymer decreased the monomer concentration in the particles, which could be detected as a change in the slope the pressure/conversion curve. This phenomenon was used to indicate the critical conversion for crosslinking of the second‐stage polymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 297–311, 2000  相似文献   

9.
The zinc ion self-crosslinkable polyacrylate latexes (PAs) cured at room temperature were synthesized by seeded semi-continuous emulsion polymerization with zinc oxide (ZnO) as crosslinker. The ZnO and methacrylic acid (MAA) mass contents, method of ZnO introduction in relation to the degree of crosslinking, and the properties of self-crosslinkable latices are examined and discussed. The characterization techniques such as Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA) have been used to determine the structure and properties of PAs. The experimental results show that in a certain range, the average particle size decreases with an increase in the content of MAA, while the latex stability is undoubtedly improved. The optimum mass content of MAA is 12?% of the total monomers. The optimum amount of ZnO needed is 25?% (mole fraction) of MAA, and the optimum temperature of ZnO introduction is 60?°C. TEM analyses show that the latex particles are coarse spherical particles with surface enriched with comprising abundant carboxyl groups, and zinc ions are dissociated as zinc ammine complex in the aqueous phase. FTIR analyses confirm that the chelate crosslinking occurs between zinc ions and carboxylic acid during the film-forming process. The DSC results indicate that the glass transition temperature (T g) of PAs increases as a function of the formation of a coordinate structure, and the obtained film exhibits excellent initial hardness and sandability. TGA analyses demonstrate that the introduction of ZnO evidently enhances the thermal stability of self-crosslinkable PAs.  相似文献   

10.
Several carboxylated poly(butyl acrylate) latices prepared by a semibatch emulsion poly-merization process were characterized in this study. A significant amount of polyelectrolyte was found in the latex product containing 10% AA, designated as AA10. On the other hand, latices containing 0.1% AA (AA0.1), 0.1% MAA (MAAC.1), and 10% MAA (MAA10) showed very low levels of polyelectrolyte in water. Based on the critical flocculation concentration data, it can be concluded that incorporation of 10% AA or 10% MAA into the emulsion polymers can greatly improve the chemical stability of the latex products, especially at higher pH. The data of the pH and conductometric titration experiments show that the MAA unit can be distributed more uniformly in the latex particles in comparision with the AA unit. This result is further confirmed by determination of the Tg's of the emulsion polymers by means of thermally stimulated current (TSC). © 1996 John Wiley & Sons, Inc.  相似文献   

11.
Self crosslinkable core‐shell polyacrylate latices (PAs) cured at ambient temperature were synthesized by semicontinuous‐seeded emulsion polymerization with diacetone acrylamide (DAAM) and adipic dihydrazide (ADH) as crosslinkable monomers. The influences of DAAM monomer mass content, neutralizer, and curing temperature on the properties of self crosslinkable core‐shell latices and the keto‐hydrazide crosslinking were discussed. The spectroscopic techniques such as Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), atomic force microscopy (AFM), transmission electron microscopy (TEM), and contact angle instruments were used to determine the structure and properties of PAs. The water evaporating rate during the film‐forming process of self crosslinkable core‐shell latices was also investigated. FTIR analyses demonstrate that the keto‐hydrazide crosslinking reaction does not occur in the latex environment but occurs at ambient temperature with the evaporation of water during the film‐forming process. The results of DSC show that the core‐shell crosslinkable PAs have two glass transition temperatures (Tg), and Tgs of crosslinked film are higher than that of non crosslinked fim. Moreover, the keto‐hydrazide reaction is found to be acid catalyzed and favored by the loss of water and the simultaneous decrease in pH arising from the evaporation of ammonia or amines during film‐forming process. Hence, in the volatile ammonia or amines neutralized latices, the latex pH value adjusted to 7–8, which not only ensure the crosslinkable latex with good storage stability but also obtain a coating film with excellent performances by introducing the keto‐hydrazine crosslinking reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

12.
In a low emulsifier system, the MMA‐BA‐MAA copolymer emulsions were prepared as seed latices and the seeded emulsion polymerization of MMA‐MAA‐DVB was consequently carried out to prepare carboxylated core particles. The hydrophobic shell was then synthesized onto the core using styrene, acrylonitrile, and divinylbenzene as comonomers. The hollow latex particles were obtained by alkalization treatment of the core‐shell latex particles. The effects of the feeding rate of monomer mixture, contents of emulsifier SDBS and crosslinking agent DVB, and ratio of the monomers during the core stage and shell stage on the morphology and volume expansion of the latex particles were investigated. The results show that the monodispersed hollow latex particles with large size can be obtained when the feeding rate is 0.1 g/min, SDBS content is 0.15 and 0.2 wt % during the core stage and shell stage, respectively, DVB contents are 1% during the preparation of shell copolymers, and the monomer ratio of the core particle to shell layer is 1 : 8. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1505–1510, 2005  相似文献   

13.
In the absence of emulsifier, we prepared stable emulsifier‐free polymethylmethacrylate/polystyrene (PMMA/PSt) copolymer latex by batch method with comonomer N,N‐dimethyl, N‐butyl, N‐methacryloloxylethyl ammonium bromide (DBMEA) by using A1BN as initiator. The size distribution of the latex particles was very narrow and the copolymer particles were spherical and very uniform. Under the same recipe and polymerization conditions, PMMA/PSt and PSt/PMMA composite polymer particle latices were prepared by a semicontinuous emulsifier‐free seeded emulsion polymerization method. The sizes and size distributions of composite latex particles were determined both by quasi‐elastic light scattering and transmission electron microscopy (TEM). The effects of feeding manner and staining agents on the morphologies of the composite particles were studied. The results were as follows: the latex particles were dyed with pH 2.0 phosphotungestic acid solution and with uranyl acetate solution, respectively, revealing that the morphologies of the composite latex particles were obviously core–shell structures. The core–shell polymer structure of PMMA/PSt was also studied by 1H, 13C, 2D NMR, and distortionless enhancement by polarization transfer, or DEPT, spectroscopy. Results showed that PMMA/PSt polymers are composed of PSt homopolymer, PMMA homopolymer, and PMMA‐g‐PSt graft copolymers; results by NMR are consistent with TEM results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1681–1687, 2005  相似文献   

14.
The emulsion polymerization of the monomers methyl methacrylate (MMA) and 2‐ethylhexyl acrylate (EHA) was studied to investigate the effect of the crosslinkable monomer poly(propylene glycol diacrylate) (PPGDA). IR spectroscopy, NMR, differential scanning calorimetry, gel permeation chromatography, and scanning electron microscopy were used to characterize the synthesized polymers. These polymers were coated on glass panels and cured at appropriate temperatures to study the physical properties, swelling behavior, surface tension, and contact angle of these polymer latices. The results show that as the concentration of EHA monomer increased, the surface tension of the latices decreased. The copolymers were characterized by 1H‐NMR spectroscopy to ensure the absence of unreacted monomer, and the results confirm the incorporation of EHA units in the copolymer. The contact angle of the latices on the glass substrate was smaller than that on the metal. The swelling mechanism of the film showed that the Fickian diffusion coefficient with 10 wt % PPGDA was at a minimum value and was the most highly crosslinked polymer among the samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

15.
Poly(styrene‐co‐butyl methacrylate) and poly(styrene‐co‐butyl acrylate) latices were prepared by emulsion polymerization with alkali‐hydrolyzable and nonhydrolyzable cationic emulsifiers and were used as a dispersant and binder for waterborne carbon black (CB) paint. CB was dispersed in the latex solutions and then coated on filter paper pretreated with dilute aqueous Na2CO3 under mild conditions. The styrene (St)‐rich rigid copolymer latices easily dispersed the CB but fixed a little amount of the pigment on the paper surface. In contrast, the methacrylate‐ and acrylate‐rich soft latices tended to increase the adhesibility on it. We also demonstrated that the hydrolyzable‐emulsifier‐containing latices always had a higher adhesibility than the nonhydrolyzable‐emulsifier‐containing ones. Thus, the hydrolyzable‐emulsifier‐containing latices with an appropriate St content had the highest paintability, rapid adhesion, quick drying, reduced fading, superior fastness, and so on. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3869–3873, 2013  相似文献   

16.
A novel emulsion polymerization technique referred to as emulsifier‐minor emulsion polymerization was achieved by the copolymerization of methyl methacrylate, butyl acrylate, and styrene (MMA‐BA‐St) with a combination of water‐soluble ionic monomers [methacrylic acid (MAA) or acrylic acid (AA)] and nonionic monomers (N‐methylol acrylamide). In the technique, water‐soluble monomers play a crucial role in the stabilization of the latex particles as they can be bound to the particle surface and form a hydrate protective layer, which exhibits steric and/or electrostatic effects to prevent particle coagulation. The minor but over its critical micelle concentration emulsifier sodium alkylated diphenyl ether disulfonate (DSB) results in the nucleation of particles mainly by the micelle nucleation mechanism and thus determines the polymerization rate, the particle size, and the number. The film water resistance of the latices can be improved, and the foaming capacity of can be lowered by using technique instead of conventional emulsion polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2923–2929, 2004  相似文献   

17.
The adsorbability of bovine serum albumin (BSA) onto poly(styrene‐co‐itaconic acid) (PS–IA), poly(styrene‐co‐hydroxyethyl methacrylate) (PS–HEMA), poly(styrene‐co‐acrylic acid) (PS–AA), and poly(styrene‐co‐methacrylic acid) (PS–MAA) latices were investigated with a quartz crystal microbalance. The amount adsorbed onto the functionalized latices, except for PS–MAA, was greater than that adsorbed onto polystyrene (PS) latex. To explain this result, two kinds of interaction forces were considered, hydrogen bonding and hydrophobic interactions, whereas electrostatic interaction was assumed to be small. When comparing the two extremes of hydrophobic interaction and hydrogen bonding, the latter was stronger. The corrected adsorption mass suggested that the BSA molecules were adsorbed onto the PS–MAA latex in a side‐on mode. However, in the case of the PS, PS–IA, PS–HEMA, and PS–AA latices, the BSA molecules were probably adsorbed in multiple layers. The presence of the BSA in the latex particle surface was verified by attenuated total reflectance/Fourier transform infrared spectroscopy and atomic force microscopy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42055.  相似文献   

18.
A simple synthetic method for preparing the core‐shell latex particles containing fluorinated shell was presented. Polymerization was achieved by a low‐sheer monomer‐starved emulsion polymerization process, thus facilitating mobility and subsequent polymerization of perfluoroacrylate (FA) along with methyl methacrylate (MMA) and n‐butyl acrylate (nBA) monomers. The structure and thermal behavior of the resulting perfluoroacrylate copolymer were investigated by FTIR, NMR, and DSC. Furthermore, PCS, TEM as well as SFM, were carried out to characterize the surface morphology of the particles. These studies illustrated that the incorporation of FA into MMA/nBA particle morphologies facilitated surface phase separation during coalescence, resulted in F‐containing film‐air interfaces. Thus, surface properties with a significant increase in the contact angles could be produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

19.
Poly(n‐butyl methacylate‐co‐n‐butyl acylate) [P(BMA/BA)] soft latexes (carboxylated and noncarboxylated) were synthesized using a semicontinuous emulsion polymerization process that was designed on the basis of a theoretical calculation to determine the suitable surfactant [i.e., sodium dodecyl sulfate (SDS)], monomer, and water feed rates to maintain a constant particle number throughout the polymerization (guaranteeing monodispersity in the particle size), to obtain a homogeneous copolymer composition, and to independently control the particle size and carboxyl group concentration. The experimental results support the theoretical calculation. The surface coverage of the carboxyl groups present on the soft latex particles ranges from 7.6 to 21.9% for a series of latexes with particle sizes around 120 nm. In another series of latexes, the particle size was varied over a range from 120 to 450 nm. Monodisperse carboxylated polystyrene hard latexes were synthesized by shot growth (batch) and semicontinuous processes. The shot growth method is somewhat inflexible in providing more choices in surfactant, particle size, and surface carboxyl coverage. A semicontinuous process designed using a similar method used for the synthesis of P(BMA/BA) latexes successfully eliminated the drawbacks of the shot growth process. In this way, the changes in the surface carboxyl coverage (varies from 0 to 77.2%) was independent of the particle size, which was precisely controlled by the amount of styrene fed under suitable styrene and SDS feed rates. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 644–659, 2000  相似文献   

20.
In this study, water‐based polymer coating materials used for the surface coating of substrates with lower surface energies were prepared by the complexation of two‐component polymer latices containing polydimethylsiloxane (PDMS) and having chemically complementary structures. The film‐forming performance of the polymer latices and the surface structures and properties of the coatings formed by the polymer latices were studied by means of scanning electron microscopy and by the measurement of mechanical strength, thermal performance, water absorbability, and contact angle. When the two‐component polymer latices [the poly(methyl methacrylate‐co‐butyl acrylate‐co‐methyl acrylic acid)/polydimethylsiloxane system (PA latex) and the poly(methyl methacrylate‐co‐butyl acrylate‐co‐pyrrolidone)/polydimethylsiloxane system (PB latex)] were compared, the complex polymer latex formed by the complexation of the PA latex with the PB latex had the best film‐forming performance, with formed coatings that were more smooth and had fewer less cracks. Also, compared to the two coatings formed by the two‐component polymer latices, the coatings formed by the complex polymer latex had a unique structure, a higher mechanical strength and elongation, a higher decomposing temperature, and better water resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1748–1754, 2003  相似文献   

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