Polymerization for Advanced Applications - Material Matters v1n1

8/14/2019 Polymerization for Advanced Applications - Material Matters v1n1

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Polymerizationfor Advanced Applications

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Initiator/Stabilizer FA

Polymer Analysis by N

Fluorinated HyperbraPolymers

Etch-Resistant BlockCopolymers

Bioactive Hydrogels

Anionic Polymerizatio

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Vol. 1 No.

Introduction

Introduction

Welcome to the premiere issue of Material Matters, a technical guide from Sigma-Aldrichdedicated to addressing research needs in materials science and technology. The themefor this issue is polymerization. Innovative polymers are helping advance almost every fieldof materials science, from alternate energy to organic electronics. Included in this guideare reviews from researchers in relevant technical fields that discuss a subset of some ofthe tools available to scientists and engineers.

Our mission at Sigma-Aldrich is to inspire and advance your research. I hope that byhighlighting the innovations and products featured in this technical guide, we will helpgenerate the next ideas to significantly impact research in polymerization.

Sincerely,

Luke Grocholl, Ph.D.Materials Science TeamSigma-Aldrich Corporation

About Our Cover

Central to advances in science and engineering are the dedicated researchers whose ideasdrive tomorrows technologies. This premiere issue of Material Matters features advancedand unique Sigma-Aldrich materials for polymerization such as monomers, cross-linkers,and functional polymers. The cover depicts how our products combine with your ideasto yield the next generation of nanolithography, fiber optics, flexible LEDs and bioactivepolymers for drug delivery. Material MattersChemistry Driving Performance.

Comments on this technical guide

Suggested topics for future technical guides

New product suggestions

Spectral and other data to facilitate your research

Questions for inclusion in a FAQ

Subscriptions to future issues of Material Matters

The MatSci eMailboxContact us at [email protected] for:

The Polymerization Tools Web SiteVisit us atsigma-aldrich.com/polyfor:

Over 1000 monomers for applications from drug delivery to PLEDs

Guide to thermal initiators with solvent-specific half-life temperature values

Absorbance spectra of over 250 photoinitiators

Functional polymers for the synthesis of advanced copolymers

Comprehensive list of surfactants organized by HLB value

Cross-linkers, chain transfer agents, plasticizers, and stablizers for polymermodification
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For questions, product data, or new product suggestions,please contact the Materials Science team at [email protected].

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Sigma-Aldrich Quality Control Team

One of the challenges polymer scientists face is molecular weight(average chain length) determination of their materials. Whilemembrane osmometry, gel permeation chromatography, viscosityanalysis and mass spectrometry are typically used for molecularweight determination, the techniques can be time consuming,

inaccurate for the molecular weight ranges involved, or requirespecialized instrumentation. End-group analysis by NMR offers aneasy alternative method using an instrument commonly found inmany analytical labs. In addition, NMR analysis can also be usedto accurately determine monomer ratios for various copolymer.

Scientists at Sigma-Aldrich routinely determine number-average molecular weight (Mn) by

1H NMR end-group analysisfor polymers having Mn values under 3000. Sensitivity of theinstrument to detect end-group protons will determine the upperlimit that can be measured. In order to use this method, thefollowing criteria must be met:

Identifiable end-group protons distinguishable from repeatingmonomer-group protons by NMR

Accurate integration of both end-group and monomer protons

Knowledge of monomer formula weights

Once the ratio of protons on the end-groups to protons on thepolymer chain is determined, using the NMR, simple math canbe applied to generate the Mn value.

This example illustrates this method:

437441 Poly(ethylene glycol) diacrylate

H2CC(H)CO-(OCH2CH2)n-OC(O)C(H)CH2

FW= 55.06 (44.05)n 71.06

1) Calculation, integral per proton:

Locate the end-group proton signals (ca. 5.8, 6.2 & 6.4 ppm)

integral per proton = sum of vinyl proton integrals# of protons in the two vinyl end groups

10.00 + 9.66 + 10.17 4.97 per proton6

2) Calculation, number of repeating monomer units, n:

Locate the OCH2CH2 proton signals (ca. 3.6, 3.7 & 4.3 ppm)

(sum of CH2 proton integrals)/# of CH2 protons{integral per proton value}

(20.79 + 151.87)/4 8.69 repeating units, n4.97

3) Calculation, Mn:

Mn = (FW end groups) + (FW repeating unit)(n)

= (55.06 + 71.60) + (44.05)(8.69) = 509

Therefore, the Mn of this polymer is approx. 509

Polymer Analysis by NMR

End-Group(Vinyl) Protons

Repeating Unit(Methylene) Protons

Dr. S. S. NewazPolyorganix Inc.Houston, TX

Q. How does one choose anappropriate initiator?In a free-radical addition polymerization, the

choice of polymerization initiator dependsmainly on two factors: a) its solubility and

b) its decomposition temperature. If the polymerization is performedin an organic solvent, then the initiator should be soluble in thatsolvent, and the decomposition temperature of the initiator mustbe at or below the boiling point of the solvent. Commonly, AIBN(2,29-Azobis(2-methylpropionitrile)) (441090, dec.102104C) andBPO (2-(4-Biphenyl)-5-phenyloxazole) (216984, mp 115119C) suitthese requirements. If the desired polymerization occurs at or below20 C, then special, low-temperature free-radical initiators needto be used. Various azo-type initiators can be chosen to satisfy thedecomposition temperature requirement.

For emulsion polymerization or polymerization in an aqueoussystem, a water-soluble initiator like K2S2O8 (379824) or an organic,water-soluble initiator (4,49-Azobis(4-cyanovaleric acid)) (118168,dec.118125 C) would be suitable.

Q. How does one determine the reactivity of a monomer?Determination of monomer reactivity is not always obvious orstraightforward. Researchers rely on their experience and publisheddata on individual monomers. In general, extent of conjugation inthe molecular structure can be viewed as indicative of its tendencyto form the initial free radical required for propagating a free-radical polymerization. Usually, a more conjugated system is morelikely to undergo free-radical polymerization.

Q. When is it necessary to remove a stabilizer prior topolymerization and how does one do so?To inhibit polymerization during storage, many monomers areprovided with a stabilizer as indicated by the label. Usually, it is not

necessary to remove stabilizers. They are typically present in ppmlevel, and the use of a free radical initiator at the polymerizationtemperature will overwhelm the effect of the stabilizer. In worst-case scenarios, one may need to add extra amounts of initiator tosustain an acceptable polymerization rate. In most cases, once apolymerization initiates, the rate can be sustained without muchdifficulty. If, however, it is absolutely necessary to remove thestabilizer, column chromatography is the preferred method (forinhibitor removal columns, see products 306312, 311332, 306320).

Q. How does one remove residual initiator, stabilizer, and/orunreacted monomer after polymerization?It is a common practice to dissolve the polymers in a solvent priorto end use, followed by precipitating the polymer using a cosolvent.Usually, the residual initiators and stabilizers will remain in solutionand the polymers will separate out as a solid (powder, gum, or

fibers). This process may be repeated until desirable polymercharacteristics are obtained. This fractional precipitation is alsoeffective in removing lower molecular weight polymers, resulting innarrower molecular weight distributionof course accompaniedwith a loss of yield. Typical solvent/cosolvent pairs could betoluene/hexane, toluene/methanol, THF/water, etc., determined bythe relative solubilities of the polymer versus the small-moleculecomponent.

For initiator solubilities and decomposition temperatures, visitour Web site at sigma-aldrich.com/poly.

Initiator/Stabilizer FAQs

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yp

y

,6-Difluorophthalic anhydride, 97%

C8H2F2O3

O

F

F

O

O

MW: 184.1MP: 218221 C (lit.)

381128-100MG 100 mg 28.20

381128-500MG 500 mg 94.60

-Fluorostyrene, 98%C8H7FMW: 122.14BP: 2930 C (4 mm Hg) (lit.)

290505-1G 1 g 30.90

290505-5G 5 g 98.40

4-Fluorostyrene, 99%

C8H7F

CH2

FMW: 122.14BP: 67 C (50 mm Hg) (lit.)

155799-1G 1 g 18.90

155799-10G 10 g 81.30

Glycidyl ,,,-tetrafluoropropyl ether, 97%C6H8F4O2

OO

F

FF

F

HMW: 188.12BP: 50 C (4 mm Hg) (lit.)

474150-5ML 5 mL 49.50

474150-25ML 25 mL 164.50

Hexafluoroglutaric acid, 97%

C5H2F6O4MW: 240.06MP: 88-91 C (lit.)BP: 134138 C (3 mm Hg) (lit.)

196908-5G 5 g 43.30

196908-25G 25 g 171.00

4,4-(Hexafluoroisopropylidene)dianiline, 98%

C15H12F6N2MW: 334.26MP: 195198 C (lit.)

368148-1G 1 g 26.50

368148-5G 5 g 104.00

4,4-(Hexafluoroisopropylidene)diphenol, 97%C15H10F6O2

OH

CF3F3C

336.23MP: 160163 C (lit.)

257591-5G 5 g 30.80

257591-25G 25 g 98.00

257591-100G 100 g 336.50

,,4,5,6-Pentafluorostyrene, 99%

C8H3F5

F

FF

F

F

CH2MW: 194.1BP: 6263 C (50 mm Hg) (lit.)

196916-5G 5 g 42.20

196916-25G 25 g 140.50

Tetrafluorophthalic anhydride, 97%C8F4O3

O

F

F

F

F O

O

MW: 220.08MP: 9496 C (lit.)

339016-1G 1 g 37.70

339016-5G 5 g 126.50

Tetrafluoroterephthalic acid, 97%

C8H2F4O4MW: 238.09MP: 275277 C (dec.) (lit.)

104418-1G 1 g 62.70

104418-5G 5 g 241.00

-(Trifluoromethyl)styrene, 99%

C9H7F3MW: 172.15BP: 64.5 C (40 mm Hg) (lit.)

366692-1G 1 g 79.00

Fluorinated Monomers

Monomer R R9 Quantity

2,2,3,3,3-Pentafluoropropyl acrylate, 98% H CF2CF2CF3 470961-5ML

470961-25ML

74.00

246.50

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl acrylate, 97%

H CH2CH2(CF2)7CF3 474487-5ML474487-25ML

77.90258.00

Heneicosafluorododecyl acrylate, 96% H CH2CH2(CF2)9CF3 474355-5G 111.50

2,2,2-Trifluoroethyl methacrylate, 99% CH3 CH2CF3 373761-5G373761-25G

16.2053.60

2-(Trifluoromethyl)acrylic acid, 98% CF3 H 369144-1G369144-5G

38.10126.00

Zonyl TM fluoromonomer (CF2)nCF3, n ~ 78 CH2CH3 421480-10ML421480-50ML

20.1055.40

H2C

R

O

O R'

Fluorinated Acrylates

For halogenated monomers that result in high and low refractiveindex polymers, see theAdvanced Polymers for Electronic/OpticalDevices technical guide. Request your free copy at [email protected];reference code GGE.
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6

Etch-Resistant

BlockCopolymers

Prof. Padma GopalanDepartment of Materials Science and Engineering,University of Wisconsin, Madison, WI

Prof. Shu YangDepartment of Materials Science and EngineeringUniversity of Pennsylvania, Philadelphia, PA

Introduction

Block copolymers offer a means of combining the desirablecharacteristics of different polymers in a new hybrid material.Polymers consisting of hydrophobic and hydrophilic blocks, for

example, can be used to encapsulate organic molecules anddeliver them into aqueous media. There has been tremendousinterest in the self-assembly of block copolymers in nanoscaledimensions, especially in thin-film configuration.

Conventional lithography has its limitations when features ofless than 30 nm are desired. Accessibility to a wide range ofperiodic structures with feature sizes less than 30 nm makeblock copolymers attractive as templates for nanopatterning.13Most of the literature approaches use selective ozonolysis orpreferential staining of one block with heavy metals to increaseetch selectivity between the blocks. Often, an intermediatesilicon nitride (SiN) layer and selective etching of one blockover another is required for successful pattern transfer. Ingeneral, the use of organic block copolymers is limited at hightemperatures because of low thermal/mechanical stabilities.Thus, direct patterning of semiconductors that requires highgrowth temperature (>500 C) using organic block copolymersas templates is nearly impossible.

It has been well established that incorporation of silicon (atleast 10 wt %) in resist polymers provides improved oxygenRIE(reactive ion etching) etch resistance. When exposed to oxygenplasma, the silicon-containing polymers are oxidized to siliconoxide that is stable in an O2 environment. The high etchresistance to oxygen plasma compared to organic polymersmakes silicon-containing polymers favorable as bilayer resists topattern high-aspect ratio structures and to create nanoporousceramic thin films in a variety of morphologies.48 In addition,silicon oxide has high thermal and mechanical stability ata temperature greater than 500 C, making it a long-time

dielectric in microchip fabrication. Thus, the possibility ofcombining acid labile groups and silicon-containing groupsin block copolymers offers a new route to directly patternnanostructured semiconductors.

As the synthesis of silicon-containing block copolymers is quitechallenging using traditional living anionic polymerization, postfunctionalization of polymers is often used to incorporate silicon.Recent advances in controlled living free-radical polymerization(LFRP),911 including nitroxide-mediated radical polymerization(NMRP), atom transfer radical polymerization (ATRP), andreversible addition fragmentation chain transfer (RAFT), make it

possible to design and synthesize a variety of block copolymers

with novel functionalities. The LFRP procedures in generalare easier to carry out as they are tolerant to a variety offunctionalities and do not require stringent purification of thestarting materials, unlike living anionic or cationic polymerizatioWe had recently applied NMRP towards, (i) the synthesis ofnarrow dispersed silicon-containing homopolymers from threekinds of silicon-containing styrenic monomers, including4-(pentamethyldisilyl)-styrene (Si2St), 4-(bis(trimethylsilyl)-methyl)styrene (Si2-CSt), and 4-(pentamethyldisiloxymethyl)styrene (OSi2-St) (Scheme 1), each containing two siliconatoms to enhance the etch selectivity, and (ii) the synthesis ofblock copolymers from silicon-containing styrenic monomerswith styrene and acid labile acetoxystyrene by sequentialmonomer addition using an nitroxide unimer initiator. Byoptimizing conditions such as solvent polarity, temperature ofpolymerization, and the monomer addition sequence, well-defined narrow dispersed silicon-containing block copolymerswere synthesized from the above monomers. Both TEM(transmission electron microscopy) and SAXS (small angle X-rayscattering) data showed that these polymers formed cylindricallamellae, or disordered structures depending on the volumeratio between the blocks and their molecular weights. When thsilicon-containing block was the major phase and silicon contenwas greater than 12 wt %, block copolymer morphology andits domain size were well maintained under exposure to oxygenplasma12 (Figure 1).

Etch-Resistant Block Copolymers

Scheme 1. Synthesis of macroinitiators and SiBCPs by LFRP at 100 C.

X

ON O

X

100 Cacetic anhydride

n

X

100 C

O

X

nm

N

N

Y

-H unimer

Macroinitiator

SiBCP

X,Y = HSi(CH3)2Si(CH3)3CH(Si(CH3)3)2CH2Si(CH3)2oSi(CH3)OC=OCH3

Figure 1. Transmission electron micrograph (TEM) images of PAcOSt-PSi2St(21/79 v/v) before and after O2 plasma for 10 minutes, showing intactcylindrical morphology.

Before After
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Synthetic access to novel silicon-containing block copolymersvia LFRP enables potential applications such as (1) growth ofnanostructured semiconductor crystals at high temperatures,(2) formation of nanoporous ceramic films, or (3) creationof hierarchical hybrid nanostructures by combiningphotolithography and self-assembly of photosensitive silicon-containing block copolymers.

References: (1) Park, M. et al. Science1997, 276, 1401. (2) Black, C. T. etal.Appl. Phys. Lett.001, 79, 409. (3) Kim, H. C. et al.Adv. Mater.001,13, 795. (4) Gabor, A. H. et al.Chem. Mater.1994, 6, 927. (5) Zharov, I. etal. Chem. Mater.00, 14, 656. (6) Bowden, M. et al. J. Photopolym. Sci.Technol.00, 16, 629. (7) Avgeropoulos, A. et al. Chem. Mater.1998, 10,2109. (8) Chan, V. Z.-H. et al.L. Science1999, 286, 1716. (9) Matyjaszewski,K.Advances in Controlled/Living Radical Polymerization; American ChemicalSociety: Washington, DC, 2003; Vol. 854, p 2. (10) Hawker, C. J.J.Am. Chem.Soc.1994, 116, 1185. (11) Benoit, D. et al.J. Am.Chem. Soc.1999, 121,3904. (12) Fukukawa, K. et al.Macromolecules005,38, 263.

Allyltriethoxysilane, 97%

C9H20O3Si

H3C O CH2O

O CH3

H3C

MW: 204.34BP: 78 C (21 mm Hg) (lit.)

A36301-5G 5 g 37.20

A36301-25G 25 g 123.00

Diphenylsilanediol, 95%C12H12O2SiMW: 216.31

D213705-25G 25 g 18.30

D213705-100G 100 g 49.20

Octadecyltrichlorosilane, 90+%

C18H37Cl3SiMW: 387.93BP: 223 C (10 mm Hg) (lit.)

104817-25G 25 g 20.10

104817-100G 100 g 53.00104817-500G 500 g 169.50

Poly(dimethylsiloxane), vinyl terminated,viscosity 1,000 centistokesBP: >93 C (lit.)

433012-100ML 100 mL 23.50433012-500ML 500 mL 76.30

Trichlorovinylsilane, 97%C2H3Cl3Si

SiCl

Cl

ClCH2

MW: 161.49MP: 95 C (lit.)BP: 90 C (lit.)

104876-5G 5 g 13.50

104876-100G 100 g 15.60104876-500G 500 g 60.00

Trimethylsilyl methacrylate, 98%

C7H14O2Si

H3C SiO

O

CH3

CH2H3C

H3C

MW: 158.27BP: 5151.5 C (20 mm Hg) (lit.)

347493-25G 25 g 81.50

347493-100G 100 g 226.50

Vinyltrimethoxysilane, 98%C5H12O3Si

H3C Si

H3C

H3C

CH2MW: 148.23BP: 123 C (lit.)

235768-5ML 5 mL 19.30

235768-100ML 100 mL 31.40235768-500ML 500 mL 82.10

1,4-bis(dimethyl(-(5-norbornen--yl)ethyl)silyl)benzene,mixture of endo and exo

C28H42Si2

SiSi

CH3

CH3

CH3

CH3

MW: 434.8BP: 314 C (lit.)

523607-5ML 5 mL 168.00

Hexamethyl-1,5-bis(-(5-norbornen--yl)ethyl)trisiloxane,mixture of endo and exo

C24H44O2Si3

OSi

CH3

CH3

Si

CH3

CH3

O Si

CH3

CH3

MW: 448.86

523593-1ML 1 mL 41.70

523593-5ML 5 mL 139.00

Silicone-Containing Monomers

Monomer R Quantity

Styrene, reagentplus,99+%

H 240869-5ML240869-100ML

17.6019.50

4-Bromostyrene, 98% Br 124141-1G124141-10G124141-25G

17.7060.10

128.00

Monomer R Quantity

4-Chlorostyrene, 97% Cl C71203-10GC71203-50G

40.80158.00

4-Acetoxystyrene, 96%OCH3C

O 380547-5ML380547-25ML

21.5050.30

R

Styrene Monomers

For an up-to-date list of silsesquioxane monomers, visit ournanomaterials Web site at sigma-aldrich.com/nano.

For styrenic and other vinyl monomers, use our advanced sub-structure search: sigma-aldrich.com.
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8

Bioactive

Hydrogels

Bioactive Hydrogels

Anthony Guiseppi-ElieABTECH Scientific, Inc.Richmond, VA

The first report of the synthesis ofcomposite materials comprising conductingpolymers and hydrogels was in 1994by Wallace et al.1 Their objective was toenhance the porosity and ion-transportproperties of hydrogels for controlled drug

delivery through electrochemically stimulated release of analytes.Since then, the electrochemical and oxidative polymerizationof pyrrole, aniline, and thiophene and their derivatives withinhydrogel hosts, such as polyacrylamide, poly(acrylic acid), chitosan,and poly(HEMA) have been routinely accomplished for biosensorapplications and to achieve voltage-stimulated or controlled release.There have also been several studies conducted on the fabricationof polymer blends of hydrogels, such as poly(methyl methacrylate)(PMMA), poly(vinyl methyl ether) (PVME), poly(4-vinylpyridine),2and poly(2-hydroxyethyl methacrylate) (p(HEMA)), primarily for theconstruction of artificial muscles.3,4 With hydrogels, high degreesof hydration (ca. 90 %) could be reversibly achieved along withbiocompatibility, good refractive index matching with water, andrelative ease of molecular engineering. In general, the conductingpolymer component of these composites retains their electroactiveproperties.

Brahim et al.5 have fabricated bioactive polypyrrole-p(HEMA)composites to function as sensing membranes for clinicallyimportant amperometric biosensors. A monomer cocktailcontaining, among other components, the relevant methacrylatemonomers, pyrrole or aniline, and photoinitiator was spin-castonto microfabricated electrodes and first irradiated by UV toeffect polymerization of the hydrogel components. This wasimmediately followed by potentiostatic electropolymerization ofthe pyrrole/aniline monomer in a phosphate-buffered potassiumchloride solution saturated with further monomer. Amperometric

enzyme biosensors for the detection of glucose, cholesterol, andgalactose were demonstrated, each possessing extensive lineardynamic response ranges, high sensitivities, and prolonged storagestabilities.6

Of particular recent interest is the development of bioactive(containing biologically active moieties such as bioactive peptides,growth factors, enzymes and the like) and biosmart (responsiveto biologically derived external stimuli) electroconductive hydrogelsfor implant biocompatibility. A novel polymer composite materialconsisting of a water-dispersed complex of polypyrrole dopedwith polystyrenesulfonate and embedded in polyacrylamidehydrogel was prepared and evaluated as a matrix for enzymeimmobilization.7 The enzyme glucose oxidase was physicallyentrapped in the polymer by inclusion in the aqueous phase duringemulsion polymerization. The resulting bioactive microparticles

(3.57.0 m diameter) were cast onto platinum electrodes andthe polymer-modified electrodes used as amperometric glucosebiosensors. This configuration displayed rapid response times andefficient screening of interferents.

For implantable biosensing applications, the synthesis of hydrogelcomposite polymers consisting of cross-linked p(HEMA) withincorporated polypyrrole and/or polyaniline chains are renderedbioactive by the covalent immobilization of oxidoreductaseenzymes. Enzymes were first monomerized by hetero-bifunctional coupling of the amines of the lysine residues of

the enzyme (typically 1:2) with acryloyl (polyethylene glycol)110N-hydroxy succinamide ester (Acryl-PEG-NHS). This allowed thecovalent immobilization of the tethered oxidoreductase enzymewithin the hydrogel milieu. To provide for stabilization of theimmobilized enzymes, poly(ethylene glycol)200 monomethacrylate(PEGMA) was also included in the monomer cocktail at 0.5 mol %Together these components allowed photolithographically

defined, spin-cast membranes formed on microlithographicallydefined electrodes to recognize and amperometrically respondto the enzymes substrate and achieve approximately one year ofretained enzyme activity (ca. 80%). For implant biocompatibility,the synthesis of the monomer 2-methacryloyloxyethylphosphorylcholine (MPC) (Figure 1) was accomplished by thecoupling of HEMA with 2-chloro-2-oxo-1,3,2-dioxaphospholane(COP).8 When incorporated into the hydrogels at the level ofca. 510 mol %, this monomer conferred nonthrombogenicity,reduced protein adsorption, and supported cell viability. Mimickinthe zwitterionic head group of the outer leaflet of cell membranephosphotidyl choline, the phosphorylcholine moiety confersthe molecular equivalent of stelt to the polymer when thebiosensor is implanted. When cultured with muscle fibroblastsand endothelial cells, these highly porous hydrogel composites

support the migration and mobility of cells within its 3-D networka property that will render these materials appropriate for thefabrication of nerve electrodes and cellular interfaces as thepolymer mimics the biological structures that enable cells to grow

One challenge faced by the use of electroactive polymers ascomponents of hydrogels for mammalian implantation is thepotential toxicity. Early work has established polypyrrole as bio-benign. However, to address this issue, bi-functional monomersof pyrrole such as 2-methacrylooyloxyethyl pyrrolylbutyrate (MPB)(Figure ) and aniline that may be UV-polymerized, and hence,covalently coupled into the hydrogel network and also oxidativelypolymerized with imbibed free pyrrole or aniline monomer to formthe electroactive polymer component were developed. In this wayan interpenetrating network of the electroactive polymer is formewithin the preformed hydrogels network that serves as the reactoStudies are ongoing to evaluate the potential cytotoxicity andbiocompatibility of these polymers.

References: (1) Small, C. J. et al.Polymer Gels and Networks1997, 5, 251.(2) Asberg, P.; Ingana, O.Biosens. Bioelectron.00, 19, 199. (3) Pich, A. et alPolymer00, 43, 5723. (4) Douglass, P. M, et al.Soc. Automotive Eng. 000,1. (5) Brahim, S. et al. Biosens. Bioelectron.00, 17, 53. (6) Brahim, S. et al.Electroanalysis.00, 14(9), 627. (7) Rubio Retama, J. et al.Biosens. Bioelectron004, 20, 1111. (8) Brahim, S. et al.Microchimica Acta00, 143, 123. (9)Abraham, S et al. Biomaterials005, 26(23), 4767. (10) Abraham, S.; GuiseppElie, A. Biomaterials006, submitted for publication.

Figure 1. Strucutre of 2-methacryloyloxyethyl phosphorylcholine

N+CH3

CH3

H3C

OP

OO

O-

O

O

CH2

H3C

Figure . Structure of 2-methacrylooyloxyethyl pyrrolylbutyrate

O

O

O

O

CH2

H3C

N H
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US $ 9

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Cross-linking is the formation of chemical links between molecular chains to form a three-dimensionalnetwork of connected molecules. The strategy of covalent cross-linking is key to the formation of hydrogels.It is also used in several other technologies of commercial and scientific interest to control and enhance theproperties of the resulting polymer system or interface, such as thermosets and coatings.

For a complete list of cross-linkers, visit us at sigma-aldrich.com/biocomp and scroll down tocross-linkers.

Benzyl -ethyl acrylate, 99% 8C12H14O2

H2CCH3

O

OMW: 190.24

589136-250MG 250 mg 189.50

Benzyl -propylacrylate, 99% 8C13H16O2H2C

O

O

CH3

MW: 204.26

590126-250MG 250 mg 207.00

1,6-Bis(p-acetoxycarbonylphenoxy) 8hexane, 97%

C24H26O8MW: 442.46

657174-1G 1 g 204.50

1,-Bis(4-carboxyphenoxy)propane, 897%

C17H16O6

O O

O

HO

O

OH

MW: 316.31MP: 310 C(lit.)

655538-5G 5 g 205.50

1,6-Bis(p-carboxyphenoxy)hexane, 890%C20H22O6MW: 358.39

655546-5G 5 g 195.00

-Chloro-1,,-dioxaphospholane--oxideC2H4ClO3P

OP

O

Cl

OMW: 142.48MP: 1214 C (lit.)BP: 8991 at 0.8 mm Hg (lit.)

377953-1G 1 g 18.10

377953-5G 5 g 59.50

-Ethylacrylic acid, 98% 8C5H8O2

H2C

CH3

OH

O

MW: 100.12BP: 176 C (lit.)

589128-250MG 250 mg 138.50

Ethyl -propyl acrylate, 99%

C8H14O2MW: 142.2BP: 141 C (lit.)

590118-250MG 250 mg 140.50

Glycosyloxyethyl methacrylate, 85% (w/v) solution in ethanol

C12H20O8

OO

OO

CH2

CH3

HO

HO

HO OH

MW: 292.28

659576-25ML 25 mL 150.00

-Propylacrylic acid, 99% 8C6H10O2

H2C

CH2CH3

OH

O

114.14165-188 C (lit.)

591009-100MG 100 mg 75.80

591009-1G 1 g 413.50

Pyrrole, 98%C4H5N

NH

MW: 67.09MP: 23 C (lit.)BP: 131 C (lit.)

131709-25ML 25 mL 17.10

131709-100ML 100 mL 46.70131709-500ML 500 mL 163.00

-Vinylpyridine, 97%

C7H7N

NCH2

MW: 105.14BP: 7982 C (29 mm Hg) (lit.)

132292-5ML 5 mL 16.10

132292-100ML 100 mL 19.00132292-500ML 500 mL 65.80

4-Vinylpyridine, 95%C7H7N

N

CH2

MW: 105.14BP: 6265 C (15 mm Hg) (lit.)

V3204-5ML 5 mL 18.80

V3204-100ML 100 mL 30.30

V3204-500ML 500 mL 68.10

1-Vinyl--pyrrolidinone, 99+%C6H9NO

N

CH2

O

MW: 111.14BP: 9295 C (11 mm Hg) (lit.)

V3409-5G 5 g 23.60

V3409-250G 250 g 26.50V3409-1KG 1 kg 60.90V3409-18KG 18 kg 817.00

Monomers for Bioactive Polymers

DVB, 85% (5558)

Cross-linkers

Three grades of HEMA (2-hydroxyethyl

methacrylate) are available: 97%(128635), 98% (525464), 99+%(477028).

For a comprehensive list of hydrogel hosts such as polyacrylamide, poly(acrylic acid), chitosan and poly(HEMA), as wellas functionalized PEGs (linear, 4-arm and 6-arm), visit sigma-aldrich.com/biocomp.
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10

Anionic

Polymerization

DiffusionPump

Connection toMechanical

Pump

LiquidN2 Trap

Inert GasInlet

High VacuumTeflon

Stopcocks

Connection toPolymerization

Reactor

Prof. Roderic P. QuirkandMs. Manuela OcampoMaurice MortonInstitute ofPolymer Science

The University ofAkron, Akron, OH

Living anionic polymerization, especially using alkyllithium initiators,has been demonstrated to be a convenient and useful method tomake well-defined polymers with low degrees of compositionalheterogeneity and with control of the major structural variablesthat affect polymer properties.1,2 Living polymerizations are chain-reaction polymerizations that proceed in the absence of thekinetic steps of chain termination and chain transfer. For a livingpolymerization, one initiator molecule generates one polymermolecule; thus, it is possible to calculate and control the numberaverage molecular weight (Mn) of the final polymer via thestoichiometry of the reaction using the following relationship.

Mn = g of monomer consumed/moles of initiator

Given a comparable or faster rate of initiation relative topropagation, it is possible to obtain narrow molecular weightdistribution polymers, i.e., Mw/Mn 1.1.

3 Due to the absenceof termination and transfer steps, the product after completemonomer consumption is a reactive, polymeric organolithiumcompound. The living nature of alkyllithium-initiated anionicpolymerizations using suitable monomers provides versatilemethods for the preparation of well-defined block copolymersby sequential addition of monomers,4 chain-end functionalizedpolymers by reaction of the living chain ends with appropriatemonomers and/or electrophilic terminating agents5,6 and branchedpolymers by linking reactions with multi-functional linking agents.7

The monomers that can be polymerized anionically are classified

into two categories: (a) unsaturated monomers with one ormore double bonds, such as vinyl (e.g., styrenes, vinylpyridines,alkyl methacrylates), dienes (e.g., isoprene, 1,3-butadiene) andcarbonyl-type monomers (e.g., formaldehyde); and (b) heterocyclicmonomers (e.g., epoxides, thiiranes, lactones, lactams, andsiloxanes). In the case of vinyl monomers, the presence of electron-withdrawing substituents (e.g., X, Y) in the double bond isgenerally required to stabilize the negative charge that develops inthe transition state as shown below.

R- H2CX

YH2C C

X

YR

- -

H2C C

X

Y

R

Organolithium Initiators

Of all alkali metals, lithium is unique in that it exhibits the highestelectronegativity, the smallest covalent and ionic bond radii, alongwith low-lying, unoccupied p-orbitals available for bonding.8,9Organolithium compounds are unique among organoalkalicompounds in exhibiting properties characteristic of both covalentand ionic compounds. Thus, they are aggregated in solution,in the solid state and in the gas phase, and they are generallysoluble in hydrocarbon solution. In general, the initiation of anionicpolymerization of styrene and diene monomers is effected withalkyllithium compounds such assec-butyllithium (195596) and

Anionic Polymerization

Figure 1. The typical construction of a glass high vacuum line for anionicpolymerization.1517

Figure . Aldrich products a) Z544787 b) Z173053 c) Z174254 d) Z174432e) Z220418

Figure . General set-up for a glass polymerization reactor.

A

B

C

D

EF

G

n-butyllithium (186171, 0707, 0715, 0104, and 010)in hydrocarbon solution. Under these conditions, the unique abilitof organolithium compounds to effect 1,4-enchainment of 1,3-

dienes is achieved.1,10

The concentrations of solutions of activeorganolithium compounds can be determined using the Gilmandouble titration method.11

Experimental Methods

Due to the reactivity of organolithium compounds and othercarbanionic species toward impurities such as oxygen, moistureor carbon dioxide,12 it is necessary to exclude these contaminantsfrom the reaction environment by the use of an inert gasatmosphere13,14 or high vacuum techniques.1517

a)

b)

c)

d)

e)

Typical Inert Gas System
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High Vacuum Techniques The use of high vacuum techniquesprovides the most effective experimental method to excludeimpurities from the reaction system.1517 In order to attain highvacuum, the combination of a mechanical pump and an oildiffusion pump (Z0418) is used in conjunction with a two-stageglass manifold as shown in Figure 1.

In order to achieve the desired levels of purity for controlled anionicpolymerization, all monomers, reactants, and solvents should

be purified, dried, and degassed, preferably on the vacuum line.Solvents are distilled directly into the requisite glass reactors(Figure ) via D followed by flame sealing from the vacuumline. Ampules B, E, and F contain monomers or functionalizingagents. Ampule C contains a terminating agent such as degassedmethanol. Ampule A is equipped with a degassed methanol tube,and it is used to remove a base sample of the living polymer.

Schlenk Line and Glove Box Techniques are often suitablefor carrying out many living anionic polymerization procedures.Alkyllithithium-initiated polymerizations are somewhat forgivingin the sense that one can add a calculated excess of initiator toclean the reactor/solvent/monomer system of reactive impurities.See Figure for representative Schlek Line Glassware. Forrepresentative and the Sigma-Aldrich glass center, visit sigma-aldrich.com/glass.

Safety Considerations

Vacuum traps should be vented while warming because of thepossibility of trapped, liquefied gases. Hydrocarbon solutions ofalkyllithium compounds are air- and moisture-sensitive; they shouldbe either handled under an inert atmosphere or using syringes andrecommended procedures for handling air-sensitive compounds.13Carbon dioxide extinguishers should not be used because RLi

compounds and many other organometallic compounds react withcarbon dioxide exothermically. An all-purpose fire extinguisher,or one designed specifically for combustible metals, should beavailable when working with these organometallic compounds andalkali metals.18

References: (1) Hsieh, H. L.; Quirk, R. P.Anionic Polymerization: Principlesand Practical Applications; Dekker: New York, 1996. (2) Quirk, R.P. AnionicPolymerization. In Encyclopedia of Polymer Science and TechnologyKroschwitz,J. I., Ed.; 3rd ed.; Wiley-Interscience: New York, 2003; Vol. 5, p 111. (3) Fetters,

L. J. Monodisperse Polymers. In Encyclopedia of Polymer Science and EngineeringKroschwitz, J. I., Ed.; 2nd ed.; Wiley-Interscience: New York, 1985; Vol. 2, p478. (4) Hadjichristidis, N.; Pispas, S.; Flouds, G. A.Block Copolymers: SyntheticStrategies, Physical Properties, and Applications; Wiley-Interscience: New York,2003. (5) Quirk, R. P. Anionic Synthesis of Polymers with Functional Groups.In Comprehensive Polymer Science, First Supplement; Aggarwal, S. L., Russo,S., Eds.; Pergamon Press: Oxford, 1992; p 83. (6) Hirao, A.; Hayashi, M.ActaPolym.1999, 50, 219. (7) Hadjichristidis, N. et al.Chem. Rev.001, 101,3747.(8) Wardell, J. L. Alkali Metals. InComprehensive Organometallic Chemistry: TheSynthesis, Reactions and Structures of Organometallic Compounds; Wilkinson,G., Gordon, F., Stone, A. Abel, E. W., Eds.; Pergamon Press: Oxford; 1982; Vol.1, p 43. (9) Sanderson, R. T.Chemical Periodicity; Reinhold: New York; 1960. (10)Bywater, S. In Comprehensive Polymer Science; Eastmond, G. C., Ledwith, A.,Russo, S., Sigwalt, P., Eds.; Chain Polymerization I; Pergamon Press: Elmsford, NewYork, 1989, Vol. 3, p. 433. (11) Gilman, H.; Cartledge, F. K.J. Organomet.Chem.1964, 2, 447. (12) Wakefield, B. J.The Chemistry of Organolithium Compounds;Pergamon Press: New York; 1974. (13) Shriver, D. F.; Drezdzon, M. A.Themanipulation of Air-Sensitive Compounds; Wiley: New York, 1986. (Cat. No.

Z558486) (14) Ndoni, S.; et al.Rev. Sci. Instrum.1995, 66, 1090. (15) Morton, M;Fetters, L. J. Rubber Chem. Technol.1975, 48, 359. (16) Hadjichristidis, N. et al.J. Polym. Sci., Part A: Polym. Chem.000,38, 3211. (17) Uhrig, D; Mays, J. W.J.Polym. Sci., Part A: Polym. Chem.005, 43, 6179. (18) Wietelmann, U.; Bauer, R.J. In Ullmanns Encyclopedia. Industrial Inorganic Chemicals and Products; Wiley-VCH Verlag: Weinheim, Germany; 1998; Vol. 4, p. 2899.

H2C

X

Y

X Y

Vinylidene chloride, 99%163023-100G163023-500G

25.5035.40

H

Cl

Acrylic acid, 99%147230-5G147230-100G147230-500G

19.7024.0029.20

H CO

OH

Methyl acrylate, 99%M27301-5MLM27301-250ML

19.5020.40

H CO

OCH3

Ethyl acrylate, 99%E9706-5MLE9706-100ML

21.7022.50

H CO

O CH3

Butyl acrylate, 99+%234923-5ML234923-100ML

23.3024.50

H CO

O CH3

-Hydroxyethyl acrylate, 96%292818-5ML292818-250ML

22.3033.70

HC

O

O

OH

-Hydroxy--phenoxypropylacrylate407364-100ML407364-500ML

31.10101.50

H CO

O O

OH

N,N-Dimethylacrylamide, 99%274135-5ML274135-100ML274135-500ML

29.1030.70

102.50

H CO

NCH3

CH3

N-Isopropylacrylamide, 97%415324-10G415324-50G

21.6070.60

H CO

OHN

CH3

CH3

X Y

Methacrylic acid, 99%155721-5G155721-100G155721-500G

20.7021.9025.90

CH3 CO

OH

Methyl methacrylate, 99%M55909-25MLM55909-500ML

20.1021.70

CH3 CO

OCH3

Ethyl methacrylate, 99%234893-5ML234893-100ML234893-500ML

26.2031.1040.30

CH3 CO

O CH3

-Hydroxyethyl methacrylate,99+%128635-5G

6.30CH3 C

O

O OH

Glycidyl methacrylate, 97%151238-5G151238-100G151238-500G

20.7022.8073.70

CH3 CO

O

O

-Isocyanatoethylmethacrylate, 98%477060-5ML477060-50ML

59.80316.50

CH3 CO

O N C O

Methyl -(bromomethyl)-acrylate, 97%302546-250MG302546-1G302546-5G

29.1093.90

306.00

C

O

OCH3

Monomers for Anionic Polymerization

CH2 Br

For the manipulation of air-sensitive compounds, see also AldrichTechnical Bulletins AL-134, AL-136, AL-164, and AL-166.

For a comprehensive list of acrylete-methacryletemonomers visit sigma-aldrich.com/polymer.
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Polymerization for Advanced Applications - Material Matters v1n1

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