Progress in Organic Coatings 77 (2014) 913948

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Progress in Organic Coatings

j o ur na l ho me pa ge: www.elsev ier .com

Review

Recentcopoly

Piotr KrDepartment of

a r t i c l

Article history:Received 31 OReceived in reAccepted 29 JaAvailable onlin

Keywords:Polymer synthATRPCopolymer coaBiomaterialsBioactive surfa

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9132. The most important mechanisms of the growth of polymer chains used in ATRP methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9143. Controlled polymer structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9174. Applications of copolymers with particular emphasis on coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918

4.1. 4.2. 4.3. 4.4. 4.5. 4.6.

5. Come6. Summ

Refer

1. Introdu

Recent nnected withceramics anmaterials. Hronmental improving papplied suc

CorresponE-mail add

0300-9440/$ http://dx.doi.oProtective coatings with increased hydrophobicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 919Antifouling surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920Antibacterial surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 928Stimuli-responsive surface (micelles) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929Hydrogels (tissue engineering scaffolds) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 935Microgel-core star polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939

rcial applications of copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 940ary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941

ences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941

ction

eeds in a range of protective coatings permanently con- natural materials such as wood and paper or withd metal articles force the search for new polymericowever raw material limited possibilities and envi-

issues are directing the attention of researchers forolymerization methods of the well-known and widely

h as vinyl monomers, as well as raw materials useful for

ding author. Tel.: +48 661038877.ress: p chmiel@prz.edu.pl (P. Chmielarz).

producing condensation polymers and additive polymers e.g. PU. Inrecent years, these needs have been additionally enhanced by theneed to develop new synthetic biomaterials well cooperating withthe tissues of the human body. In our opinion, new polymeriza-tion methods discovered in recent years allow for the productionof polymers with controlled macromolecular structure and theyare outgoing opposite these very specic applications of polymercoatings. In addition less important is to use the new monomers,and much more important is obtaining during the polymerizationstep of even known vinyl monomers and acrylic new structures ofsuch macromolecules. Latest methods in this regard, already welldeveloped from the side of preparative and theoretical explainingkinetics and mechanism of their progress, but still poorly used in

see front matter 2014 Elsevier B.V. All rights reserved.rg/10.1016/j.porgcoat.2014.01.027 advances in ATRP methods in relation to the synthesis ofmer coating materials

l, Pawe Chmielarz

Polymer Science, Faculty of Chemistry, Rzeszw University of Technology, Al. Powstancw Warszawy 6, 35-959 Rzeszw, Poland

e i n f o

ctober 2013vised form 17 January 2014nuary 2014e 25 February 2014

esis

tings

ce

a b s t r a c t

Atom transfer radical polymerization (ATRP) is currently one of the most often used synthetic polymer-ization methods to prepare well-dened copolymers with complex architecture. This review covers somefundamentals of ATRP, presents new ATRP initiating processes with ppm amounts of copper catalysts andvarious reducing agents together with recent developed electrochemically controlled ATRP, as well asdiscusses ATRP enables to precise control over macromolecular structure, order, and functionality. More-over, this review briey describes some of the copolymer coating materials that can now be preparede.g., protective coatings with increased hydrophobicity, functional bioactive surfaces and functional bio-materials, as well as highlights some of the commercialization efforts currently underway. The researchactivities in the last decade indicate that ATRP has become an essential tool for the design and synthesisof advanced, noble and novel copolymer coatings.

2014 Elsevier B.V. All rights reserved./ locate /porgcoat

914 P. Krl, P. Chmielarz / Progress in Organic Coatings 77 (2014) 913948

Notations

AA acrylic acidAFM atomic force microscopyAGET ARGET ATRP BIBB Bpy CM CMU CRP CuBr CuBr2CuCl CuCl2DI DMAEMADMMSA

DMVSA

DP eATRP EBIB EGDMA GMA HEMA ICAR LCST LRP MDI ME Me6-TREMIP MPC MUBIB MW MWD NI NIP NIPAM OEG OEGMA PBA PDA PDMS PEG PMDETAPMMA PES PPCPA PPPGMAPS PSf PTMO PTX PU PVDF PVP RA SAM SEM SET-LRP

SI-ATRP surface-initiated ATRPSR reverse initiationSR&NI activators generated by electron transferactivators regenerated by electron transferatom transfer radical polymerization2-bromoisobutyryl bromide2,2-bipyridinecellulose membranesCarnegie Mellon Universitycontrolled radical polymerizationcopper (I) bromidecopper (II) bromidecopper (I) chloridecopper (II) chloridedispersity

2-dimethylaminoethyl methacrylate2-(methacryloyloxyethyl) ethyl-dimethyl-(3-sulfopropyl)-ammoniumN,N-dimethyl-N-(p-vinylbenyl)-N-(3-sulfopropyl)ammoniumdegree of polymerizationelectrochemically mediated ATRPethyl 2-bromoisobutyrateethylene glycol dimethacrylateglycidyl methacrylate2-hydroxyethyl methacrylateinitiation for continuous activators regenerationlower critical solution temperatureliving radical polymerization4,4-methylene diphenyl diisocyanate2-mercaptoethanolN hexamethylated tris(2-aminoethyl)aminemolecularly imprinted polymer2-methacryloyloxyethyl phosphorylcholine-mercaptoundecyl bromoisobutyratemolecular weightmolecular weight distributionnormal initiationnonimprinted polymerN-isopropylacrylamideoligo(ethylene glycol)oligo(ethylene glycol) methacrylatepoly(n-butylacrylate)poly(dopamine)poly(dimethylsiloxane)poly(ethylene glycol)

N,N,N,N,N-pentamethyldiethlyenetriaminepoly(methyl methacrylate)polyethersulfonepoly(pentachlorophenyl acrylate)

poly(poly(propylene glycol methacrylate))polystyrenepolysulfonepoly(oxytetramethylene) glycolpaclitaxelpolyurethanepoly(vinylidene uoride)poly(N-vinylpyrrolidone)reducing agentself-assembled monolayerscanning electron microscopesingle-electron transfer living radical polymeriza-tion

SS TEA QA VBA

materials eof atom trapresented pdevelopmetions of pola few years

This artcopolymer applicationmost of thelow surfacematerials aimprove ad

ATRP iscesses usewell-deneable sequefunctionalitmaterials teach indiviAs block leblock copoltant and th[5]. Most ofmers (synththeir abilitmorphologprimary drapplicationtive) syntheMWD blockapplicationsized by conin regular aintermolecutallization a

Recent focused onpletely newrespect to mental frieexperimentsynthesis oinvolves ating polymeoften Cu, asto ppm levregeneratio

2. The mopolymer ch

ATRP ismer sciencweights, nasimultaneous reverse and normal initiationstainless steeltriethylaminequaternary ammoniumvinylbenzoic acid

ngineering are methods known under the general namensfer radical polymerization (ATRP). Therefore in theublication we would like to draw attention to the latestnts in this eld and to indicate the directions of applica-ymers with a very specic structure, not known before

in the engineering of protective coatings.icle reviews recent advances in the preparation ofcoating materials using ATRP for biomedical and others. The modication of polymer surfaces, hydrophobic in

cases, is required for multiple applications. For instance, energy polymeric materials do not adhere well to othernd need of further modication/surface treatment tohesion.

one of the most powerful and versatile CRP pro-d for the synthesis of functional copolymers withd architectures, controlled molecular weights, and tun-nces. It enables precise control over MW, MWD, andy [14]. Block copolymers are an interesting class ofhat possess different properties compared to those ofdual homopolymer segments they are composed of.ngth is playing a major role on the properties of theymers, effective control of the block lengths is impor-is can easily be achieved using different CRP methods

the desirable properties of narrow MWD block copoly-esized by living polymerization or ATRP) originate from

y to form well-dened nanostructures with differenties of tunable periodicity or size, and this provides theiving force for the intensive interest in eld of coatings over the polydisperse copolymers (random or alterna-sized by conventional radical polymerization. Narrow

copolymers (controlled) are more useful for coating rather than polydisperse random copolymers synthe-ventional radical polymerization. It results from it, that

rrangements, in which arranging structures results fromlar interactions, exists a possibility of the simpler crys-s a result of stronger intermolecular interactions.advances in the synthesis of block copolymers have

techniques that either enable the preparation of com- materials or represent a substantial improvement withthe existing methods in terms of scalability, environ-ndliness, or scope. One observable trend is to designal setups which allow for the automated and optimizedf polymers and block copolymers. Another ongoing topictempts to reduce the environmental impact of exist-r syntheses. In ATRP reactions, the metal catalyst (most

well as Fe, Ru, Ni, etc.) loading could be decreased downels through the use of a suitable additive for catalystn, for example in ARGET process [6,7].st important mechanisms of the growth ofains used in ATRP methods

one of the most rapidly developing areas of poly-e, allowing to obtain effective control over molecularrrow molecular weight distributions, functionalities,

P. Krl, P. Chmielarz / Progress in Organic Coatings 77 (2014) 913948 915

architectures, and well-dened compositions [8,9]. ATRP processeshave evolved signicantly during the past 15 years and it hasstrongly inuenced the development of many elds of polymerscience, invigorating great interest in controlled polymerizations[10]. There are several reports on the synthesis of copolymers andthe study of their properties, as these copolymers are importantmaterials in the several elds of natural science, for example, col-loid science and biochemistry, as well as in industrial elds [11,12].Moreover, the interface of ATRP with biology has always been oneof the most attractive areas for applications due to ATRPs robustnature and ability to grow polymers from a variety of surfaces [10].

The essential feature of original normal (NI) ATRP is con-trolled by apropagatingdominatelyspecies (Rnis halogen acally react wmetal comprepresents tL is a ligandmittently fometal comphalide ligan

The deacreaction (kdtor. ATRP iredox-activintermediatrate constaoccur in ATation. Howeterminationcentration oof dormant is most compounds [21can also beActually, otemployed t[35,36], Re

Howeveused is senthis drawbgroup has d[9]. Subsequof the transas Cu(II)/L cCu(I)/L com(II), for exa(AIBN) [42

After deotion of Cu(Iof conventiassociated w

SR&NI Ause more a

CXR +n

M

I.

I I

R

M

.X Cu(II)/LCu(I)/LXR

RR

+

kpkt

+n n

n n

kact

kdeact

(2)

Scheme 2.

M

I.

I I

C+

P Initiator

amot of r

SR&gen-er wits cot of of bloNI AithouSR&Ns hasopol

fracr [15rdermer ocedentioompnic r

newNI eby var [47]. In a typical AGET ATRP system, the activator (Cu(I)

s) is rst rapidly oxidized by oxygen to the Cu(II) species, butter is quickly reduced to the Cu(I) state in the presence of aere is an induction period during which air is consumed, andally the polymerization starts. This process has been suc-ly used to prepare well-dened products in organic mediao in miniemulsion. Unfortunately, it is difcult to estimatect amount of RA needed [48].

R

M

.X Cu(II)/LCu(I)/L

RR

u(II)/L

+

kpkt

+ n

n n

kact

kdeact

(4)

Scheme 4.n equilibrium between a low concentration of active species and a larger number of dormant chains, pre-

in the form of initiating alkyl halides/macromolecularX, where Rn represents growing polymer chain and Xtom) [13,14] (Scheme 1). The dormant species periodi-ith the rate constant of activation (kact) with transitionlexes in their lower oxidation state (Cu(I)/L, where Cu(I)he transition metal species in lower oxidation state and). After which, these species acting as activators to inter-rm growing radicals (Rn), and deactivatorstransitionlexes in their higher oxidation state, coordinated withds Cu(II)/L (Scheme 1) [15].tivator reacts with the propagating radical in a reverseeact) to re-form the dormant species and the activa-s a catalytic process and can be mediated by manye transition metal complexes [1]. Upon addition of thee radicals to monomers, polymer chains grow with thent of propagation kp. Termination reactions (kt) alsoRP, mainly through radical coupling and disproportion-ver, a very small percentage of polymer chains undergo

in a well-controlled ATRP. This is due to the low con-f active propagating radicals and higher concentrationspecies, which minimizes termination. Although coppermonly used metal catalyst in ATRP [1620], iron com-28], which are generally considered to be less toxic,

used, especially for biomedical applications [29,30].her various metal complexes have been successfullyo mediate ATRP, including Ru [31,32], Ni [33,34], Ti[37], Mo [38], Co [39], and Os [40,41].r, NI ATRP has one notable limitation that is the catalystsitive to air and other oxidant. In order to overcomeack of normal ATRP, more recently, Matyjaszewskiseveloped an improved reverse (SR) ATRP techniqueently, SR ATRP was developed that started by additionition metal complex in its higher oxidation state, suchomplexes, which was then converted to the activatorplexes by reaction with a standard free radical initiatormple benzoyl peroxide (BP) or 2,2-azoisobutyronitrile44] (Scheme 2).xygenation, the polymerization is initiated by the reac-I) with radicals, generated by thermal decompositiononal thermal initiators. This circumvents the problemith oxidation of catalysts [45].

TRP was developed to take advantage of the ability toctive catalyst complexes with addition of a relatively

R

M

.X Cu(II )/Lu(I)/L

RR

kact

kdeact+

kpkt

n

n n (1)

Scheme 1.

XRn

ATR

larger amoun

In aor halotogethreagenamounthesis

SR&tion wWhile procesblock ca smallinitiato

In ocopolytion pra convCu(II) cof orgainitiate

SR&vated initiatospeciethe latRA. Theventucessfuland alsthe exa

XR

X C

n

RAR

M

.X Cu(II)/Lu(I)/L

RR

+

kpkt

n

n n

kact

kdeact

(3)

Scheme 3.

unt of alkyl halide initiator concurrently with a smalladical initiators [15].NI initiation procedure, ATRP initiators, alkyl halidesterminated macroinitiator, are added to the reactionth a conventional thermal initiator II (Scheme 3). Bothntribute to the ATRP equilibrium, so that the relativecatalysts can be dramatically decreased, and the syn-ck copolymers can be achieved [45].TRP provided a way to reduce the catalyst concentra-t sacricing the level of control over polymerization.I is a signicant improvement over SR ATRP, the SR&NI

an intrinsic deciency when it is used to synthesizeymers [45]. A limitation of SR&NI was the formation oftion of polymer chains initiated by the added free radical].

to overcome this limitation, and prepare a pure blockwithout contamination by homopolymers, an initia-ure named AGET was developed for ATRP. Instead ofnal radical initiator, a RA was used to react with thelex and to generate the activator without involvementadicals or formation of reaction products which could

chains (Scheme 4) [45,46].volved into AGET where the added deactivator was acti-rious RA including Mt0 species rather than a radical

916 P. Krl, P. Chmielarz / Progress in Organic Coatings 77 (2014) 913948

I.

R

M

.X Cu(II)/LCu(I)/LXR

RR

I II X

+

kpkt

+n n

n n

kact

kdeact

(5)

Scheme 5.

In addition to normal ATRP, the development of AGET ATRP,which enables polymerizations to be conducted without freeze-pump-thaw cycles, has poised AGET ATRP to be carried out bybiologists and other scientists in jars on the bench top [8].

In fact, based on the development of SR&NI and AGET techniquesdiscussed above, new initiation method, such as ICAR, were devel-oped at about 8 years ago [49]. In this system, a large excess of RA(free radicals from thermal initiator) were used for a continuousregeneration of very low levels of catalyst activators. By using ICARinitiation technique, the amount of Cu catalyst necessary for anATRP was lowered from several thousand ppm under normal con-ditions to 90%) by the

sulation and release of hydrophilic dyes of cation-condensed microgel in water [296].

940 P. Krl, P. Chmielarz / Progress in Organic Coatings 77 (2014) 913948

linking reaction of a PEG macroinitiator with a quaternary ammo-nium cation-carrying linking agent in ruthenium-catalyzed LRP.Owing to the locally high concentration of quaternary ammoniumcations in the core, the star polymers afforded efcient and versatileencapsulation of various dyes carrying sodium sulfonate in water.The efcient dye encapsulation is due to the high concentration ofquaternary ammonium cations in the core. Additionally, stimuli-responsive release of dyes from cation-condensed star polymerswas successfully achieved via ion exchange with NaCl aqueoussolution. Cation-condensed star polymers would be useful as ver-satile delivery vessels, contributing to a wide variety of biomedicalapplications [296].

5. Comercial applications of copolymers

In the early years of ATRP development, the expected fast andbroad devematerials wneeded to environmenin the matemers into thas been by

The proATRP ConsoMellon Uniyears (1996and licenseformed the that uses thby their cuATRP has bthe researcATRP Solutbegun com

With theprecisely ccially produand nd a[304], adhehydrogels [[304,309], ting agents[317319]. pounds, pri[320].

In this cship some include mistional branhigher DI oprovide acc[15].

(36)

CH3

OCHCH2

C O

O

n

R

C

O

CH CH2

OC

O

CHCH2

R = H or

Scheme 36.

(37)CH

3

SiCHCH2

C O

O

n

R

CH3

SiCH3

O

O

CH3

CH3

O

OCH3

CH3

R = H or

Scheme 37.

of ter pre sevoistuhesivre poor hela 37se pond-fucompt proeat, o

fromg ch

con build1a anrisonthermapplttinglantves, e foather

is PP, funcincluponeals tf the gs [3thermf surr the surface properties such as hydrophilicity/phobicity,

lass in different buildings [322].lopment of ATRP for the production of large volume ofas frustrated by the large amounts of catalyst complexcontrol the polymerization. For both economical andtal aspects, the level of potentially hazardous catalystrial had to be strongly decreased to bring ATRP poly-he marketplace. ATRP catalyzed by copper complexes

far the most studied and developed industrially [301].motion of ATRP towards industry began through thertium founded by Prof. K. Matyjaszewski at Carnegieversity (CMU) of Pittsburgh, PA, USA. It lasted for ve2000) and gave rise to several U. S. patents issueds signed with industrial partners [302]. In 2006, ATRPbasis for a CMU spin-off company called ATRP Solutionse technology to develop novel materials for evaluationstomers in their targeted markets [303]. Since 2003,een licensed to 8 of the over 40 corporations fundingh at CMU (Kaneka, PPG, Dionex, Ciba, Mitsubishi, WEP,ions, and Encapson). Licensees around the world havemercial production of specialty polymers [304].

aid of numerous reports in literature, copolymers withontrolled complex architectures have been commer-ced by ATRP in U. S., Japan, and Europe since 2002,

pplications among other as components of coatingssives [305], polar thermoplastic elastomers [306308],254,255,257,258,260262,264271], surface modierssealants [305], blend compatibilizers [310,311], wet-

[310], surfactants [312316] and pigment dispersantsIn the latter example, they were used for coating com-nts, images, inks or lacquers, and other disperse systems

ase, for optimization of the costperformance relation-structural imperfections can be tolerated. They maysing arms in star polymers, loss of functionality, addi-ching, and polymers with broader MWD. Sometimesf chains may not only facilitate processing but alsoess to materials with new nanostructured morphologies

Onepolymincludples mand admers aof UV (formu

Thehigh echain currenhigh haccruestaininsurfacerior of(Fig. 2compa

Furety of and poing seaadhesiexibl

Anoerage low DItures (as commateriglass obuildin

Furtion oto tailo

Fig. 21. Examples of glazing sealant for self cleaning ghe earliest industrial adopters of ATRP for large-scaleoduction was Kaneka. Kaneka XMAP range of productseral commercial reactive telechelic materials, for exam-re-curable and addition-curable PBA directed at sealante markets [301]. The most common Kaneka XMAP poly-lyacrylates type C (free-radical induced curing by meansat) (formula 36) and type S (moisture curable sealant)) (Schemes 36 and 37).lymers exhibit low MWD (1.11.3 for most grades) andnctionality. A range of molecular weights and mainositions is available [321]. The main advantages overducts are excellent performances in weatherability,il and ultraviolet resistance. One of the advantages that

use of environmentally stable materials is their non-aracteristics [305]. The benets are seen in the lack oftamination on articial marble attached to the exte-ings by sealants (Kaneka XMAP polyacrylates type C)d b) prepared using ATRP (a perfect example is the

of Fig. 22a with Fig. 22b and c) [321].ore these polymers have been developed for a vari-

ications such as sealants, adhesives, coatings, gasketss. Some examples of projected applications are glaz-s for TiO2-coated glasses, oil resistant gaskets, elasticliquid injection molding, coatings, oil resistant linings,ms as well as pressure sensitive adhesives [301].

active licensees corporation with a strong patent cov-G Industries. PPG explored ATRP as a means to designtional polymer additives of various controlled architec-ding block, gradient, graft, comb and star copolymers)nts for various coatings applications. ATRP copolymer

hat were evaluated include for example TiO2-treatedself-cleaning properties for use in ofces and residential04].ore, ATRP provides many advantages in modica-

faces with thin polymer lms, which can be used

P. Krl, P. Chmielarz / Progress in Organic Coatings 77 (2014) 913948 941

Fig. 22. Pictur sed seeffect of conta

(bio)-compfriction. Thecopolymersment affect[323].

Moreovecessfully uengineering

Thus, ATcan be expof the procpolymers.

6. Summa

As has bnew types onisms of poTherefore, work, howewere limiteissues.

This Revsentative reof functionaATRP metho

New ATpresence ofprocesses. technique utionality is monomer c

preor co. Thes of tiles attached with acrylate-based sealant prepared by ATRP (a), silicone-bamination after exposure for 4 years [322].

atibility, adhesion, adsorption, corrosion resistance, and surface properties can also be tuned by tethering block, where the composition and size of each polymer seg-

TheATRP fcations the morphology and behavior of the polymer brushes

r, copolymers prepared by ATRP were already suc-sed for drug delivery [107,324337] and for tissue

applications [107,338340].RP has already been employed in industry, and itected that in the near future it will surface as oneesses of choice for large-scale production of specialty

ry

een shown for use ATRP methods in the synthesis off polymer materials it is necessary to know the mecha-lymer chain growth process described in the literature.the major attention was paid to these issues in thisver extensively described in the literature kinetic issuesd here, and focused more to preparative and application

iew aims to provide an overview of selected but repre-cent developments, trends, and emerging applicationsl block copolymers obtained by using a wide range ofds.

RP procedures that utilize ppm amounts of Cu in the RA are more environmentally benign than earlier ATRPSignicant progress has been made in ARGET ATRPsing trace amounts of catalysts. If high chain end func-required, polymerization could be stopped at partialonversion and monomer recovered.

particularlyincreased hing antifousurfaces, thof stimuli-ralso been cter CRP tecapplicationruthenium-

It is posis returnedmers and cbiomaterialcreating detion of lineathe PU coatnew kinds o

ATRP haexpected thcesses of chsuch as therials with m

References

[1] F. di Lenpolyme

[2] V. Coestransfer

[3] G. Zhanmers froalant (b) and both KANEKA XMAP PBA and PDMS sealants showing

sent review summarizes recent research activities inpolymers with particular emphasis on coatings appli-e highly robust and exible ATRP techniques are suited for the preparation of protective coatings withydrophobicity, functional bioactive surfaces, includ-

ling and antibacterial surfaces. In addition to bioactivee preparation of functional biomaterials in the formsesponsive micelle delivery systems and hydrogels hasonveniently accomplished by ATRP and macroinifer-hniques. Besides the above coating applications, others such as microgel-core star polymers obtained bycatalyzed LRP, are also worth mentioning.sible to notice that the greater attention, up till now,

to the modication of acrylic polymers as homopoly-opolymers widely applied already in the production ofs. In our opinion new opportunities in this respect arescribed examples of using ATRP methods for modica-r PU among others to an increase in hydrophobicity ofings, what is creating great hopes for the synthesis off biomaterials.s already been employed in industry, and it can beat in the near future it will surface as one of the pro-oice for large-scale production of specialty polymers

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