Synthesis and characterization of poly(n‐butyl methacrylate)‐b‐polystyrene diblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate) (PBMA)‐b‐polystyrene (PSt) diblock copolymers were synthesized by emulsion atom transfer radical polymerization (ATRP). PBMA macroinitiators that contained alkyl bromide end groups were obtained by the emulsion ATRP of n‐butyl methacrylate with BrCH₃CHCOOC₂H₅ as the initiator; these were used to initiate the ATRP of styrene (St). The latter procedure was carried out at 85°C with CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as the catalyst and polyoxyethylene(23) lauryl ether as the surfactant. With this technique, PBMA‐b‐PSt diblock copolymers were synthesized. The polymerization was nearly controlled; the ATRP of St from the macroinitiators showed linear increases in number‐average molecular weight with conversion. The block copolymers were characterized with IR spectroscopy, ¹H‐NMR, and differential scanning calorimetry. The effects of the molecular weight of the macroinitiators, macroinitiator concentration, catalyst concentration, surfactant concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2123–2129, 2005     

Synthesis and characterization of Pst‐b‐PDMS‐b‐PSt copolymers by atom transfer radical polymerization

Polystyrene‐b‐poly(dimethylsiloxane)‐b‐polystyrene (Pst‐b‐PDMS‐b‐PSt) triblock copolymers were synthesized by atom transfer radical polymerization (ATRP). Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide, resulting in the PDMS macroinitiators for the ATRP of styrene (St). The latter procedure was carried out at 130°C in a phenyl ether solution with CuCl and 4, 4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as the catalyzing system. By using this technique, triblock copolymers consisting of a PDMS center block and polystyrene terminal blocks were synthesized. The polymerization was controllable; ATRP of St from those macroinitiators showed linear increases in M_n with conversion. The block copolymers were characterized with IR and ¹H‐NMR. The effects of molecular weight of macroinitiators, macroinitiator concentration, catalyst concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3764–3770, 2004     

Synthesis and characterization of PBMA‐b‐PDMS‐b‐PBMA copolymers by atom transfer radical polymerization

Poly(butyl methylacrylate)–b–poly(dimethylsiloxane)–b–poly(butyl methylacrylate) (PBMA–b–PDMS–b–PBMA) triblock copolymers were synthesized by atom transfer radical polymerization (ATRP). The reaction of α,ω‐dichloride PDMS with 2′‐hydroxyethyl‐2‐bromo‐2‐methylpropanoate gave suitable macroinitiators for the ATRP of BMA. The latter procedure was carried out at 110°C in a phenyl ether solution with CuCl and 4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as the catalyzing system. The polymerization was controllable, with the increase of the monomer conversion, there was a nearly linear increase of molecular weight and a decrease of polydispersity in the process of the polymerization, and the rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with IR and ¹H‐NMR and differential scanning calorimetry. The effects of macroinitiator concentration, catalyst concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP were reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 532–538, 2004     

Synthesis of block copolymers from PDMS macroinitiators

The synthesis of polystyrene‐b‐polydimethylsiloxane‐b‐polystyrene (PSt‐b‐PDMS‐b‐PSt) copolymers is described. Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide resulting in the PDMS macroinitiators. The terminal alkyl bromide groups were then used as initiators for atom transfer radical polymerization (ATRP) to produce block copolymers. Using this technique, triblock copolymers consisting of a PDMS centre block and polystyrene terminal blocks were synthesized. ATRP of St from those macroinitiators showed linear increases in M_n with conversion, demonstrating the effectiveness of ATRP to synthesize a variety of inorganic/organic polymer hybrids. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers by atom‐transfer radical polymerization

Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl₃ as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000     

Synthesis of poly(octadecyl acrylate‐b‐styrene‐b‐octadecyl acrylate) triblock copolymer by atom transfer radical polymerization

The synthesis of triblock copolymer poly(octadecyl acrylate‐b‐styrene‐b‐octadecyl acrylate), using atom transfer radical polymerization (ATRP), is reported. The copolymers were prepared in two steps. First, polystyrene was synthesized by ATRP using α,α′‐dichloro‐p‐xylene/CuBr/bpy as the initiating system; Second, polystyrene was further used as macroinitiator for the ATRP of octadecyl acrylate to prepare ABA triblock copolymers in the presence of FeCl₂·4H₂O/PPh₃ in toluene. Polymers with controlled molecular weight (M_n = 17,000–23,400) and low polydispersity index value (1.33–1.44) were obtained. The relationship between molecular weight versus conversion showed a straight line. The effect of reaction temperature on polymerization was also investigated, showing a faster polymerization rate under higher temperature. The copolymers were characterized by FTIR, ¹H‐NMR, DSC, and GPC and the crystallization behavior of the copolymers was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1539–1545, 2004     

Synthesis of poly[(decanoic acid)‐block‐styrene] diblock copolymers and their self‐assembly behavior in aqueous medium

Diblock copolymers, poly[(10‐hydroxydecanoic acid)‐block‐styrene] (PHDA‐b‐PSt), were synthesized by combining enzymatic condensation polymerization of HDA and atom transfer radical polymerization (ATRP) as of St PHDA was first obtained via enzymatic condensation polymerization catalyzed by Novozyme‐435. Subsequently, one terminus of the PHDA chains was modified by reaction with α‐bromopropionyl bromide and the other terminus was protected by chlorotrimethylsilane. The resulting monofunctional macroinitiator was used subsequently in ATRP of St using CuCl/2,2′‐bipyridine as the catalyst system to afford diblock copolymers including biodegradable PHDA blocks and well‐defined PSt blocks. Polymeric nanospheres were prepared by self‐assembly of the PHDA‐b‐PSt diblock copolymers in aqueous medium. Copyright © 2008 Society of Chemical Industry     

Synthesis and characterization of PS‐b‐PDMS‐b‐PS triblock copolymer

A series of polystyrene‐b‐poly(dimethylsiloxane)‐b‐polystyrene (PS/PDMS/PS) triblock copolymers had been synthesized by atom transfer radical polymerization (ATRP). The products had been characterized by Fourier transform infrared, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, contact angle, and scanning electron microscope. The results indicate that the PS chains have been successfully blocked onto the PDMS back bone, and the PS‐b‐PDMS‐b‐PS triblock copolymers have low‐surface tension, good thermal stability, and microphase separation configuration. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface microphase separation in PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films

Well‐defined poly(dimethylsiloxane)‐block‐poly(methyl methacrylate)‐block‐poly(2,2,3,3,4,4,4‐heptafluorobutyl methacrylate) (PDMS‐b‐PMMA‐b‐PHFBMA) triblock copolymers were synthesized via atom transfer radical polymerization (ATRP). Surface microphase separation in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films was investigated. The microstructure of the block copolymers was investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Surface composition was studied by X‐ray photoelectron spectroscopy (XPS). The chemical composition at the surface was determined by the surface microphase separation in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films. The increase of the PHFBMA content could strengthen the microphase separation behavior in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films and reduce their surface tension. Comparison between the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymers and the PDMS‐b‐PHFBMA diblock copolymers showed that the introduction of the PMMA segments promote the fluorine segregation onto the surface and decrease the fluorine content in the copolymers with low surface energy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of novel polystyrene‐block‐polyurethane‐block‐polystyrene tri‐block copolymers through atom transfer radical polymerization

Background: Radical polymerization is used widely to polymerize more than 70% of vinyl monomers in industry, but the control over molecular weight and end group of the resulting polymers is always a challenging task with this method. To prepare polymers with desired molecular weight and end groups, many controlled radical polymerization (CRP) ideas have been proposed over the last decade. Atom transfer radical polymerization (ATRP) is one of the successful CRP techniques. Using ATRP, there is no report on the synthesis of polystyrene‐block‐polyurethane‐block‐polystyrene (PSt‐b‐PU‐b‐PSt) tri‐block copolymers. Hence this paper describes the method of synthesizing these tri‐block copolymers. To accomplish this, first telechelic bromo‐terminated polyurethane was synthesized and used further to synthesize PSt‐b‐PU‐b‐PSt tri‐block copolymers using CuBr as a catalyst and N,N,N,N″,N″‐pentamethyldiethylenetriamine as a complexing agent. Results: The ‘living’ nature of the initiating system was confirmed by linear increase of number‐average molecular weight and conversion with time. A semi‐logarithmic kinetics plot shows that the concentration of propagating radical is steady. The results from nuclear magnetic resonance spectroscopy, gel permeation chromatography and differential scanning calorimetry show that the novel PSt‐b‐PU‐b‐PSt tri‐block copolymers were formed through the ATRP mechanism. Conclusion: For the first time, PSt‐b‐PU‐b‐PSt tri‐block copolymers were synthesized through ATRP. The advantage of this method is that the controlled incorporation of polystyrene block in polyurethane can be achieved by simply changing the polymerization time. Copyright © 2007 Society of Chemical Industry     

Preparation and characterization of PSt‐b‐PHEMA metal hybrids

The block copolymer polystyrene‐b‐poly[2‐(trimethylsilyloxy)ethylene methacrylate] (PSt‐b‐PTMSEMA) was synthesized using atom‐transfer radical polymerization (ATRP). The hydrolysis of PSt‐b‐PTMSEMA led to the formation of an amphiphilic block copolymer, polystyrene‐b‐poly(2‐hydroxylethyl methacrylate) (PSt‐b‐PHEMA), which was characterized by GPC and ¹H‐NMR. TEM showed that the PSt‐b‐PHEMA formed a micelle, which is PSt as the core and PHEMA as the shell. Under appropriate conditions, the nickel or cobalt ion cause chemical reactions in these micelles and could be reduced easily. ESCA analysis showed that before reduction the metal existed as a hydroxide; after reduction, the metal existed as an oxide, and the metal content of these materials on the surface is more than that on the surface of the copolymer metal ion. XRD analysis showed that the metal existed as a hydroxide before reduction and existed as a metal after reduction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2883–2891, 2002; DOI 10.1002/app.10278     

Synthesis of PMMA‐PTHF‐PMMA and PMMA‐PTHF‐PST linear and star block copolymers

Combination of cationic, redox free radical, and thermal free radical polymerizations was performed to obtain linear and star polytetramethylene oxide (poly‐THF)‐polymethyl methacrylate (PMMA)/polystyrene (PSt) multiblock copolymers. Cationic polymerization of THF was initiated by the mixture of AgSbF₆ and bis(4,4′ bromo‐methyl benzoyl) peroxide (BBP) or bis (3,5,3′,5′ dibromomethyl benzoyl) peroxide (BDBP) at 20°C to obtain linear and star poly‐THF initiators with M_w varying from 7,500 to 59,000 Da. Poly‐THF samples with hydroxyl ends were used in the methyl methacrylate (MMA) polymerization in the presence of Ce(IV) salt at 40°C to obtain poly(THF‐b‐MMA) block copolymers containing the peroxide group in the middle. Poly(MMA‐b‐THF) linear and star block copolymers having the peroxide group in the chain were used in the polymerization of methyl methacrylate (MMA) and styrene (St) at 80°C to obtain PMMA‐b‐PTHF‐b‐PMMA and PMMA‐b‐PTHF‐b‐PSt linear and star multiblock copolymers. Polymers obtained were characterizated by GPC, FT‐IR, DSC, TGA, ¹H‐NMR, and ¹³C‐NMR techniques and the fractional precipitation method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 219–226, 2004     

Synthesis of defined polyhedral oligosilsesquioxane‐containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

Defined diblock and triblock copolymers composed of methyl methacrylate‐co‐glycidyl methacrylate block and 3‐{3,5,7,9,11,13,15‐hepta(2‐methylpropyl)‐pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]‐octasiloxan‐1‐yl}propyl methacrylate block(s), i.e., P(MMA‐co‐GMA)‐b‐PiBuPOSSMA and PiBuPOSSMA‐b‐P(MMA‐co‐GMA)‐b‐PiBuPOSSMA, were synthesized by atom transfer radical polymerization (ATRP). First, monofunctional and bifunctional P(MMA‐co‐GMA) copolymers were synthesized by ATRP. Subsequently, these copolymers were successfully used as macroinitiators for ATRP of POSS‐containing methacrylate monomer. The process showed high initiation efficiency of macroinitiators and led to products with low dispersity. The synthesized block copolymers were characterized by size exclusion chromatography, ¹H‐NMR spectroscopy and their glass transition temperatures were determined by differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The potential of Cu(I)Cl/2,2′‐bipyridine catalysis in a triblock copolymer preparation by atom transfer radical polymerization

The ability of atom transfer radical polymerization (ATRP) in the sequential synthesis of triblock copolymers was examined using Cu(I)Cl/2,2′‐bipyridine catalysis at 110°C in toluene, starting from PMMA macroinitiators terminated with the C‐Br group. The PMMAs were prepared by living anionic or group transfer polymerization (GTP), followed by bromination of the respective active site with Br₂ or N‐bromosuccinimide (NBS). The yield of the terminal bromination in the products of both living polymerizations was 60–64% at best, compared with the yield of the bromination of 1‐methoxy‐(1‐trimethylsilyloxy)prop‐1‐ene (a model of the GTP active site) with NBS, as found by ¹H‐NMR. The PMMA macroinitiators prepared were utilized to start the sequential ATRP, finally affording PMMA‐b‐PBuA‐b‐PSt (M_n 69,100), PMMA‐b‐PSt‐b‐PBuA (M_n 21,300) and PMMA‐b‐PSt‐b‐PMMA (M_n 35,200), which have not yet been synthesized by ATRP. After the second block has been formed, the Br‐unterminated part of PMMA macroinitiator was removed by extraction or repeated precipitation. In the third (last) sequence polymerization, induction periods were observed. The first two triblock copolymers were free of precursors and have M_w/M_n values 1.5–1.6 (SEC). In the course of the last step of PMMA‐b‐PSt‐b‐PMMA synthesis, the content of the PMMA‐b‐PSt precursor slowly decreased with increasing MMA conversion. Still, at ≈90% MMA conversion, about 10–15% of the precursor remained in the product. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3514–3522, 2001     

The effects of acrylate monomers and polystyrene addition on the morphology of DOP‐plasticized styrene–acrylate polymer particles prepared by SPG emulsification and suspension polymerization

Fairly uniform copolymer particles of methyl acrylate (MA), butyl acrylate (BA), or butyl methacrylate (BMA) were synthesized via Shirasu porous glass (SPG) membrane and followed by suspension polymerization. After a single‐step SPG emulsification, the emulsion composed mainly of the monomers. Hydrophobic additives of dioctyl phthalate (DOP), polystyrene molecules, and an oil‐soluble initiator, suspended in an aqueous phase containing poly(vinyl alcohol) (PVA) stabilizer and sodium nitrite inhibitor (NaNO₂), were subsequently subjected to suspension polymerization. Two‐phase copolymers with a soft phase and a hard phase were obtained. The composite particles of poly(St‐co‐MA)/PSt were prepared by varying the St/PSt ratios or the DOP amount. The addition of PSt induced a high viscosity at the dispersion phase. The molecular weight slightly increased with increasing St/PSt concentration. The multiple‐phase separation of the St‐rich phase and PMA domains, observed by transmission electron microscopy, was caused by composition drift because the MA reactivity ratio is greater than that of St. The addition of DOP revealed the greater compatibility between the hard‐St and soft‐MA moieties than that without DOP. The phase morphologies of poly(St‐co‐MA), poly(St‐co‐BMA), and their composites with PSt were revealed under the influence of DOP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1195–1206, 2006     

Synthesis of diblock and triblock copolymers containing dendrons via ‘living’ controlled radical polymerization

The dendritic Fréchet‐type polyarylether 2‐bromoisobutyrates (Gn‐Br, n = 1–3) as macroinitiators for the ‘living’/controlled radical polymerization of styrene (St) and methyl methacrylate (MMA) were investigated. The atom transfer radical polymerization of St and MMA carried out with CuBr/bpy (2,2′‐bipyridine) catalyst in bulk yielded well‐defined dendritic–linear diblock copolymers (Gn–PSt and Gn–PMMA). The use of G3–PSt for the block copolymerization of MMA and G3–PMMA for the chain extension polymerization of MMA in the presence of CuBr/bpy catalyst is also described. The triblock copolymers obtained were of predetermined molecular weights and relatively low polydispersities, which indicates the living nature of the reaction system. © 2002 Society of Chemical Industry     

Atom transfer radical polymerization of styrene and methyl (meth)acrylates initiated with poly(dimethylsiloxane) macroinitiator: Synthesis and characterization of triblock copolymers

Poly(dimethylsiloxane)(PDMS)‐based triblock copolymers were successfully synthesized via atom transfer radical polymerization (ATRP) initiated with bis(bromoalkyl)‐terminated PDMS macroinitiator (Br‐PDMS‐Br). First, Br‐PDMS‐Br was prepared by reaction between the bis(hydroxyalkyl)‐terminated PDMS and 2‐bromo‐2‐methylpropionyl bromide. PSt‐b‐PDMS‐b‐PSt, PMMA‐b‐PDMS‐b‐PMMA and PMA‐b‐PDMS‐b‐PMA triblock copolymers were then synthesized via ATRP of styrene (St), methyl methacrylate (MMA) and methyl acrylate (MA), respectively, in the presence of Br‐PDMS‐Br as a macroinitiator and CuCl/PMDETA as a catalyst system at 80 ^oC. Triblock copolymers were characterized by FTIR, ¹H‐NMR and GPC techniques. GPC results showed linear dependence of the number‐average molecular weight on the conversion as well as the narrow polydispersity indicies (PDI < 1.57) for the synthesized triblock copolymers which was lower than that of Br‐PDMS‐Br macroinitiator (PDI = 1.90), indicating the living/controlled characteristic of the reaction. Also, there was a very good agreement between the number‐average molecular weight calculated from ¹HNMR spectra and that calculated theoretically. Results showed that resulting copolymers have two glass transition temperatures, indicating that triblock copolymers have microphase separated morphology. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of double‐hydrophilic poly(methylacrylic acid)–poly(ethylene glycol)–poly(methylacrylic acid) triblock copolymers and their micelle formation

The aim of the work reported was to synthesize a series of double‐hydrophilic poly(methacrylic acid)‐block‐poly(ethylene glycol)‐block‐poly(methacrylic acid) (PMAA‐b‐PEG‐b‐PMAA) triblock copolymers and to study their self‐assembly behavior. These copolymeric self‐assembly systems are expected to be potential candidates for applications as carriers of hydrophilic drugs. Bromo‐terminated difunctional PEG macroinitiators were used to synthesize well‐defined triblock copolymers of poly(tert‐butyl methacrylate)‐block‐poly(ethylene glycol)‐block‐poly(tert‐butyl methacrylate) via reversible‐deactivation radical polymerization. After the removal of the tert‐butyl group by hydrolysis, double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers were obtained. pH‐sensitive spherical micelles with a core–corona structure were fabricated by self‐assembly of the double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers at lower solution pH. Transmission electron microscopy and laser light scattering studies showed the micelles were of nanometric scale with narrow size distribution. Solution pH and micelle concentration strongly influenced the hydrodynamic radius of the spherical micelles (48–310 nm). A possible reason for the formation of the micelles is proposed. Copyright © 2010 Society of Chemical Industry     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Synthesis and characterization of PMMA‐b‐PBMA block copolymers by atom transfer radical polymerization

The synthesis of diblock copolymers using atom transfer radical polymerization, ATRP, of n‐butyl methacrylate, BMA, and methyl methacrylate, MMA, is reported. These copolymers were prepared from 2‐bromoisobutyryl‐terminated macroinitiators of poly(MMA) and poly(BMA), using copper chloride, CuCl,/N,N,N′,N″,N″‐pentamethyldiethylenetretramine, PMDETA, as the catalyst system, at 100°C in bulk and in benzonitrile solution. The block copolymers were characterized by means of size‐exclusion chromatography, SEC, and ¹H‐NMR spectroscopy. The SEC analysis of the synthesized diblock copolymers confirmed important differences in the molecular weight control depending on the reaction medium (solvent effect) and the chemical structure of the macroinitiator used. In addition, differential scanning calorimetry, (DSC) measurements were performed, showing for all the copolymers a phase separation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2683–2691, 2002