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Contents
FunctionalHyperbranchedMacromoleculesConstructed
fromAcetylenicTriple-BondBuildingBlocks
M.Häußler·B.Z.Tang . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
PolymerMonolayerDynamics
A.R.Esker·C.Kim·H.Yu . . . . . . . . . . . . . . . . . . . . . . . . . 59
Silicone-BasedPolymerBlends:
AnOverviewoftheMaterialsandProcesses
P.Lucas·J.-J.Robin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
FunctionalMaterialsDerivedfromDNA
X.DongLiu·M.Yamada·M.Matsunaga·N.Nishi . . . . . . . . . . . 149
EngineeringBlood-ContactBiomaterials
by“H-BondGrafting”SurfaceModification
D.-A.Wang . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
AuthorIndexVolumes201–209 . . . . . . . . . . . . . . . . . . . . . . 229
SubjectIndex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
AdvPolymSci(2007)209:1–58
DOI10.1007/12_2007_112
© Springer-VerlagBerlinHeidelberg
Publishedonline:24March2007
FunctionalHyperbranchedMacromoleculesConstructed
fromAcetylenicTriple-BondBuildingBlocks
MatthiasHäußler·BenZhongTang((cid:1))
DepartmentofChemistry,TheHongKongUniversityofScience&Technology,
ClearWaterBay,Kowloon,HongKong,
andDepartmentofPolymerScienceandEngineering,ZhejiangUniversity,
310027Hangzhou,China
[email protected]
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1 Polycoupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.1 Palladium-CatalyzedPolycoupling . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.2 MechanisticConsiderations. . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.3 Copper-CatalyzedPolycoupling. . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2 Polyhydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2.1 Platinum-CatalyzedPolyhydrosilylation . . . . . . . . . . . . . . . . . . . . 13
2.2.2 Rhodium-andPalladium-CatalyzedPolyhydrosilylation . . . . . . . . . . . 13
2.3 Polycycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3.1 Diels–AlderPolycycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3.2 1,3-DipolarPolycycloaddition(ClickPolymerization) . . . . . . . . . . . . 15
2.4 Polycyclotrimerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.4.1 HyperbranchedPoly(alkylenephenylene)s . . . . . . . . . . . . . . . . . . . 20
2.4.2 HyperbranchedPolyarylenes . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.4.3 HyperbranchedPoly(aroylarylene)s . . . . . . . . . . . . . . . . . . . . . . 33
3 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1 ThermalandOpticalProperties . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2 PatterningandAssemblingBehaviors . . . . . . . . . . . . . . . . . . . . . 43
3.3 Photonic,MagneticandCatalyticProperties . . . . . . . . . . . . . . . . . 48
4 ConcludingRemarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Abstract Thisreviewarticlesummarizesthesynthetic effortsinconstructing functional
hyperbranchedmacromoleculesfromacetylenictriple-bondbuildingblocks.Polymeriza-
tionreactionsincludingpolycoupling,polyadditionandpolycyclotrimerizationhavebeen
developedforthesynthesis ofnewhyperbranched polymerssuchaspolyynes, polyenes,
polyarylenesandpolytriazoleswithnoveltopologicalstructuresandelectronicconjuga-
tions.Polymerswithhighmolecularweights(upto>1×106)havebeenobtainedinhigh
yields (up to 100%). Whilst their linear counterparts are often intractable, the hyper-
branched conjugated polymers are completely soluble in common organic solvents and
are hence readily processable by macroscopic techniques. The hyperbranched polymers
exhibit an array of functional properties including strong light emission, stable optical
2 M.Häußler·B.Z.Tang
nonlinearity and high photorefractivity. The polymers can generate fluorescent images,
assemble into supramolecular patterns,and formwell-alignednanotubes. The polyynes
canbepost-functionalizedthroughmetalcomplexation,whoserefractiveindexescanbe
manipulated to a great extent by photoirradiation. The hyperbranched polymer com-
plexescanserveasprecursorstosoftferromagneticceramicsandascatalystsforcarbon
nanotubefabrications.
Keywords Functionalmaterials·Hyperbranchedpolymers·Polyaddition·
Polycoupling·Polycyclotrimerization
Abbreviations
AAO anodicaluminumoxide
AFM atomicforcemicroscopy
Ar aromaticring
β molecularfirsthyperpolarizability
Bu butylgroup
c concentration
C coremolecule
CNT carbonnanotube
∗
Cp pentamethylcyclopentadienyl ligand
CVD chemicalvapordeposition
D dendriticunit
D0.5 doseneededforanFgvalueof0.5(or50%)
d33 macroscopicSHGcoefficient
DB degreeofbranching
DCM dichloromethane
De exposuredose
DMF N,N-dimethylformamide
DSC differentialscanningcalorimetry
EO electro-optical
Fg gelfraction
FOL opticallimitingthresholdfluence
FTIR Fourier-transferinfraredspectroscopy
Ft,m/Fi,m opticalsignalsuppressionratio
GPC gelpermeationchromatography
H strengthofmagneticfield
hb-PA hyperbranchedpolyarylene
hb-PAA hyperbranchedpoly(aroylarylene)
hb-PAE hyperbranchedpoly(aryleneethynylene)
hb-PAP hyperbranchedpoly(alkylenephenylene)
hb-PP hyperbranchedpolyphenylene
hb-PPE hyperbranchedpoly(phenyleneethynylene)
hb-PTA hyperbranchedpolytriazole
hb-PY hyperbranchedpolyyne
Hc coercivity
L ligand
L linearunit
l filmthickness
f
λ absorptionmaximum
ab
