Synthesis of Branched Polymers by Means of Living Anionic Polymerization, 7. Synthesis of Well‐Defined Highly Branched Polymers and Graft Copolymers Having One Branch per Repeating Unit Using Poly(m‐halomethylstyrene)s as Backbone Polymers

Well‐defined poly(m‐chloromethylstyrene) and poly(m‐bromomethylstyrene) were prepared by the living anionic polymerization of m‐(tert‐butyldimethylsilyl)oxymethylstyrene and subsequent transformation reactions with BCl₃ and (CH₃)₃SiCl/LiBr. The reaction of poly(m‐chloromethylstyrene)s with 1,1‐diphenylethylene (DPE) end‐capped polystyryllithium proceeded very fast in the initial stage (76% of efficiency after 10 min) and reached quantitative reaction efficiency after 24 h at –40°C. The reaction of poly(m‐bromomethylstyrene) with DPE end‐capped polystyryllithium of molecular weight value of up to 68.8 kg/mol proceeded completely without steric hindrance of the polystyrene branch at –40°C for 168 h to afford a very high molecular weight branched polystyrene with one branch per repeating unit (M̄_w = 2.3 million). Well‐defined graft copolymers with the same architecture were also successfully synthesized by reacting poly(m‐halomethylstyrene)s with living anionic polymers of isoprene, 2‐vinylpyridine, and tert‐butyl methacrylate at –40°C for 168–336 h. The high compact structures of the branched polystyrenes synthesized here comparable to those of star‐branched polymers were confirmed by viscosity measurement performed in toluene at 35°C.     

Synthesis of Branched Polymers by Means of Living Anionic Polymerization, 5. Synthesis of Star Polymers by Reactions of End‐Functionalized Polystyrenes with Chloromethylphenyl Groups with Polymer Anions Consisting of Two Polymer Chains

Well‐defined five‐arm star polymers, having different arms in molecular weight or composition, were synthesized by linking reactions of end‐functionalized polystyrenes with two chloromethylphenyl (CMP) groups and polymer anions consisting of two identical or different polymer chains. The polymer anions were prepared by coupling living anionic polymers of styrene or isoprene with 1,1‐diphenylethylene (DPE)‐end‐functionalized polymers. They were then reacted in situ with the CMP‐end‐functionalized polystyrenes to afford heteroarm star polymers of the AA′₂A″₂, AA′₂B₂, and AB₂C₂ types where the A, B, and C segments were polystyrene, poly(a‐methylstyrene), and polyisoprene, respectively. ¹H NMR spectroscopy, SEC, vapor pressure osmometry (VPO), and static light scattering measurements evaluated the well‐defined architecture of these polymers.     

Synthesis of Functionalized Polymers by Means of Living Anionic Polymerization, 2. Synthesis of Well‐Defined Chain‐End and in‐Chain Functionalized Polymers with 1,3‐Butadienyl Groups

The synthesis of well‐defined functionalized polystyrenes and poly(methyl methacrylate)s with 1,3‐butadienyl groups has been described by the methodology based on the functionalization reactions of living anionic polymers of a new substituted 1,1‐diphenylethylene with a 1,3‐butadienyl group, 1‐[4‐(4‐methylene‐5‐hexenyl)phenyl]‐1‐phenylethylene ( 1 ). Both chain‐end and in‐chain functionalized polystyrenes with one or two 1,3‐butadienyl groups were synthesized by utilizing the addition reactions of living polystyrenes to 1 followed by methanol termination or treatment with appropriate electrophiles. On the other hand, chain‐end and in‐chain functionalized poly(methyl methacrylate)s with one or two 1,3‐butadienyl groups were obtained by the living anionic polymerization of methyl methacrylate with the adduct prepared from 1 and either s‐BuLi or lithium naphthalenide. The 1,3‐buadienyl groups thus introduced were quantitatively transformed into anhydride or epoxy functions without any side reactions by the (C₂H₅)₂AlCl‐catalyzed Diels‐Alder reaction or by treatment with 3‐chloroperoxybenzoic acid.     

Synthesis of Branched Polymers by Means of Living Anionic Polymerization, 8. Synthesis of Well‐Defined Star‐Branched Polymers by an Iterative Approach Based on Living Anionic Polymerization Using 1,1‐Diphenylethylene Derivatives

The synthesis of well‐defined four‐ and six‐arm star branched polymers in which arms differ either in molecular weight or composition has been achieved via a new iterative approach based on living anionic polymerization using 1,1‐diphenylethylene (DPE) derivatives. Each stage in the iteration involves two reactions: a living functionalization reaction of living anionic polymer with DPE derivatives and an in‐situ reaction of the resulting linked product having two anions with 1‐4‐(4‐bromobutyl)phenyl]‐1‐phenylethylene to introduce two DPE moieties into the polymer. In each living functionalization reaction, a 1.2‐fold excess or more of living anionic polymer relative to DPE moiety was employed to complete the reaction. Asymmetric A₂A′₂ and A₂A′₂A′′₂ star‐branched polystyrenes as well as A₂B₂ and A₂B₂C₂ heteroarm star‐branched polymers were synthesized by repeating the iteration synthetic sequence two and three times, respectively. Since the polymers obtained by each reaction stage were contaminated with their precursor polymers, they were isolated by SEC fractionation. Their high degrees of compositional, molecular weight and architectural homogeneity were confirmed by the analytical results of SEC, SLS, VPO, ¹H NMR and viscosity measurements.     

New Functionalized Anionic Initiators Prepared from Substituted 1,1‐Diphenylethylene Derivatives with Acetal‐Protected Monosaccharides and Their Application to Chain‐Multi‐Functionalized Polymers with Glucose and Galactose Molecules

Living anionic polymerizations of methyl methacrylate, tert‐butyl methacrylate, 2‐(perfluorobutyl)ethyl methacrylate, tert‐butyl acrylate, and ethylene oxide were carried out with functionalized initiators prepared from substituted 1,1‐diphenylethylene (DPE) derivatives with two and four acetal‐protected α‐D ‐glucofuranose and α‐D ‐galactopyranose residues and carbanionic species such as sec‐butyllithium (sec‐BuLi), cumylpotassium, lithium and potassium naphthalenides. In certain cases, either LiCl or diethylzinc was used as an additive to control the polymerization. Several new well‐defined chain‐end‐ and in‐chain‐functionalized polymers with two and four glucose and two galactose molecules were successfully synthesized by these living polymerizations followed by deprotection. We have proposed a promising iterative methodology based on a convergent approach, with which novel two dendritic substituted DPE derivatives with four and eight acetal‐protected D ‐glucofuranose residues can successively be synthesized. With use of the functionalized anionic initiators prepared from such dendritic DPE derivatives and sec‐BuLi in the polymerization of methyl methacrylate, well‐defined chain‐end‐functionalized poly(methyl methacrylate)s with four and eight glucose molecules were synthesized.

     

A Novel Synthetic Route Toward Amphiphilic Comb‐Like Polymers: Alternating Copolymerization of 4‐Alkyloxybenzylidenemalononitriles with Ethyl Vinyl Ether

Radical polymerization of 4‐alkyloxybenzylidenemalononitriles with ethyl vinyl ether yielded 1 : 1 alternating copolymers. The M̄_n and M̄_w/M̄_n of these polymers were in the range of 41 000–61 000 and 1.85–2.12, respectively. These polymers were thermally stable up to 300°C and the glass transition temperatures of these polymers were between 56–78°C. The copolymers layered structure originated from the microphase separation between the polar main chain and the nonpolar alkyl side chain. The layer spacing gradually increased with increasing alkyl chain length. This layered structure was maintained up to the thermal decomposition temperatures of the polymers. These polymers are covalent‐bonded analogs of polyelectrolyte/surfactant systems.     

Electrochemical Polymerization of 1,10‐Decanedithiol in CH3CN at Constant Current

Synthesis of polymers containing disulfide bonds in the main chain by electrochemical polymerization of 1,10‐decanedithiol (DEDT) in acetonitrile (CH₃CN) at constant current was investigated. The electrochemical polymerization of DEDT proceeded easily to give a polymer containing disulfide bonds in the main chain formed by intermolecular coupling reaction in good yields. The polymer yield was proportion to both Faradaic charge and DEDT concentration in the feed, but the M̄_n of the polymer remained almost constant during the reaction. On the addition of benzylthiol (BzSH) to the electrochemical polymerization of DEDT, the polymer yield decreased, whereas the polymer yield increased when dibenzyldisulfide (DBDS) was added to the polymerization of DEDT. The benzylthiyl anion derived from DBDS seems to promote the formation of an S—S bond. The content of benzylthiyl derived from DBDS at the chain end was proportion to the amount of DBDS added.     

Liquid‐Crystalline Polymethacrylates by Atom‐Transfer Radical Polymerization at Ambient Temperature

Side‐on and side‐end liquid‐crystalline (LC) polymethacrylates were synthesized by atom‐transfer radical polymerization at 20°C using monofunctional and difunctional initiators. The polymers have narrow molecular‐weight distributions (M̄_w /M̄_n = 1.15–1.45). The polymerization kinetics were determined for a side‐on LC methacrylate, and appear to be first‐order, whatever the initiator used. However, the measured molecular weight is much larger than expected, probably because the initiation step is slow. The thermotropic properties of the LC polymers were studied by thermal optical polarizing microscopy, differential scanning calorimetry, and X‐ray diffraction. For a side‐end LC polymethacrylate, two LC phases were detected although only one has been reported in the literature. The phase sequence was shown to be Cr–SmA–N–Iso.     

Chain‐Growth Polycondensation in Solid‐Liquid Phase with Ammonium Salts for Well‐Defined Polyesters

Polycondensation of a potassium 4‐bromomethylbenzoate derivative dispersed in organic solvent was carried out with tetrabutylammonium iodide as a phase transfer catalyst (PTC) and a reactive benzyl bromide as an initiator to yield polyesters having a defined molecular weight and a narrow molecular weight distribution (M̄_w/M̄_n < 1.3). Polymerization involves the transfer of monomer to organic solvent layer with the PTC and the reaction of monomer with the initiator and the polymer end benzyl bromide moiety in a chain polymerization manner, as evidenced by polymerization behavior; increase of the molecular weight in proportion to monomer conversion and equal amount of the initiator unit and the end group in polymer irrespective of monomer conversion. Furthermore, the molecular weight increased in proportion to feed ratio ([monomer]₀/[initiator]₀), and the polydispersity index M̄_w/M̄_n stayed less than 1.3 over the whole range of feed ratio.     

Neodymium(III) tert‐Butoxide‐Dialkylmagnesium,a New Initiator System for Syndiotactic Polymerization of Methyl Methacrylate

The polymerization of methyl methacrylate (MMA) in toluene at 0°C using combinations of dihexylmagnesium (Hex₂Mg) with various metal tert‐butoxides as initiators has been studied. Purely anionic initiator systems based on alkali metal salts allow complete conversion of MMA within 1 h to yield either highly isotactic PMMA (LiOt‐Bu/MgR₂ = 5, M̄_n = 61 000, M̄_w/M̄_n = 1.95, 84% mm) or narrow polydispersity atactic PMMA (NaOt‐Bu/MgR₂ = 20, M̄_n = 39 000 and M̄_w/M̄_n = 1.18). The combination of Hex₂Mg with Nd₃(Ot‐Bu)₉(THF)₂ (Nd/Mg = 5–10) affords a novel initiator system that gives in 40–63% yield syndiotactic‐rich PMMA (M̄_n = 50–90 000, M̄_w/M̄_n = 1.06–1.12, 76–79% rr) with low initiation efficiency. In this case, characteristics of the polymers and polymerization reactivity data are consistent with the in situ generation of an alkylneodymium species.     

Polyacetylenes with Ferrocenophane Pendant Groups: Synthesis by Rh‐Complex‐Catalyzed Polyaddition,Characterization and Properties

The Rh(I)‐complex‐catalyzed polymerization of N‐(4‐propynyloxyphenyl)‐2‐aza‐[3]‐ferrocenophane ( 1 ) and of N‐(4‐pentynyloxyphenyl)‐2‐aza‐[3]‐ferrocenophane ( 2 ) gives the corresponding polyacetylenes with ferrocenophane pendant groups; compounds 3 and 4 , respectively. Polymers 3 and 4 are soluble in organic solvents such as tetrahydrofuran and CHCl₃ , although polymer 3 contains a small portion of an insoluble fraction. The molecular weights of polymers 3 (soluble part) and 4 are determined to be M̄_n = 10 000 and M̄_w = 14 000, and M̄_n = 5 100 and M̄_w = 9 300, respectively. The copolymerization of 1 and 4‐ethynyltoluene yields copolymers containing the two monomer units in various ratios depending on the ratio of the monomers used in the polymerization. Molecular weights of the copolymers range from M̄_n = 8 800 and M̄_w = 13 200 to M̄_n = 23 800 and M̄_w = 36 900, and increase with a decreasing content of monomer units derived from 1 . The thermal decomposition temperature is also influenced linearly over a wide range by the monomer unit ratios. All these polymers are characterized by NMR and UV spectroscopies as well as by elemental analyses. The polymers undergo two electrochemical oxidations: quasi‐reversible oxidation of the Fe and irreversible oxidation of the nitrogen‐containing part of the ferrocenophane unit.     

cis‐Specific Living Polymerization of 1,3‐Butadiene with CoCl2 and Methylaluminoxane

The polymerization of 1,3‐butadiene was conducted by CoCl₂ combined with methylaluminoxane (MAO) as a cocatalyst at 0 and 18°C. The uni‐modal molecular weight distribution curves of the resulting polymers shifted toward higher molecular weight regions and became narrower when increasing the polymerization time. The number‐average molecular weight increased linearly with polymerization time, while the polymer yield increased exponentially in the initial stage. As a consequence, the number of polymer chains, calculated from the polymer yield and M̄_n, increased gradually with polymerization time to reach a plateau value. These phenomena was interpreted based on a slow initiation system without any termination and chain transfer reaction. The microstructure of the polymer was determined by ¹H NMR and ¹³C NMR spectroscopy to be a cis‐1,4 structure in a 98–99% purity.     

Synthesis and Characterization of PNIPAm Core Cross‐Linked Star Polymers and Their Functionalization with Cyclodextrin

Poly(N‐isopropylacrylamide) (PNIPAm) core cross‐linked star (CCS) polymers (s‐(PNIPAm)_n) are synthesized by arm‐first ATRP method. The related synthesis conditions are investigated and optimized. By varying cross‐linker N,N‐methylenebisacrylamide (BIS) concentration, PNIPAm CCS polymers with about 47, 86, and 211 arms are synthesized. Then, under ATRP condition, the “living” sites at the core of s‐(PNIPAm)_n reacting with a monovinyl β‐cyclodextrin (β‐CD) monomer afford β‐CD functionalized s‐(PNIPAm)_n (CDF‐SPNIPAm). The structures of the star polymers are characterized. The results indicate that in CDF‐SPNIPAm, the ratio of β‐CD units to PNIPAm arm numbers could be up to 0.6:1. The fluorescence spectra of star polymer/ANS (8‐­anilino‐1‐naphthalenesulfonic acid ammonium salt hydrate) systems prove that the β‐CD moieties of CDF‐SPNIPAm are available for including guest molecules. By using pH‐sensitive adamantyl (Ada)‐terminated poly(4‐vinylpyridine) (Ada‐P4VP) (synthesized by ATRP strategy) as a model guest macromolecule, the host–guest complexation between β‐CD units of CDF‐SPNIPAm and adamantyl groups of Ada‐P4VP is confirmed via 2D NOESY ¹H NMR and DLS measurements. The results indicate that the presence of the Ada‐P4VP arms provides temperature‐responsive star polymers with pH sensitivity. Therefore, the β‐CD‐functionalized star PNIPAm could provide host macromolecular platform for constructing novel miktoarm star polymers.

     

Linear Addition Polymers and Cyclic Oligomers of N,N‐Diglycidyl Aniline and Amines. Uncrosslinked Epoxide–Amine Addition Polymers, 46

The addition polymerization of N,N‐diglycidyl aniline (DGA) and disecondary diamines leads to linear addition polymers with molecular weights ranging from 2 500 to 9 100 Da respectively. Their relatively broad molecular weight distribution (M̄_w /M̄_n = 5.5 to 17) is caused by the formation of small amounts of cyclic oligomers. Surprisingly, the addition polymerization of primary monoamines and DGA results in the formation of oligomers only. These oligomers have molecular weights between 684 and 1 165 g·mol^–1. ¹³C NMR spectra proof that during addition reaction no side‐reaction took place and that the epoxide end groups were completely consumed. Obviously, the addition products mainly consist of cyclic oligomers. In the MALDI‐TOF mass spectra cyclic oligomers of repeat units between n = 1 and n = 7 were observed. The kinetics of the addition polymerization can be described by both a formal model and the smallest necessary set of elementary reactions. In order to find the optimum parameters, the set of differential equations was solved numerically by multivariate non‐linear regression. The perfect agreement between model calculations and experimental curves allows reliable predictions of the reaction behavior for arbitrary temperature–time profiles.     

Protection and Polymerization of Functional Monomers, 31. Living Anionic Polymerization of Styrene Derivatives m,m′‐Disubstituted with Acetal‐Protected Monosaccharide Residues

Two new styrene derivatives m,m′‐disubstituted with acetal‐protected monosaccharide residues, 3,5‐bis(1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose‐3‐oxymethyl)styrene ( 1 ) and 3,5‐bis(1,2:3,4‐di‐O‐isopropylidene‐α‐D ‐galactopyranose‐6‐oxymethyl)styrene ( 2 ) were synthesized viahigh yielding eight reaction steps starting from isophthalic acid. Their anionic polymerizations were carried out with sec‐BuLi in THF at –78°C for 30 min. Both monomers, 1 and 2 , were found to undergo living anionic polymerization to afford quantitatively the polymers of predictable molecular weights and narrow molecular weight distributions (M̄_w/M̄_n < 1.08). Novel AB and BA diblock copolymers of 1 and styrene were also successfully synthesized. Complete deprotection of the acetal protective groups by treatment with trifluoroacetic acid was achieved to quantitatively regenerate D ‐glucose and D ‐galactose. The resulting polymers were highly water‐soluble polymers as expected.     

Polymerization of Vinyl Acetate Initiated with Di‐tert‐butyl Perfumarate

The polymerization behavior of vinyl acetate ( 2 ) was studied in benzene using di‐tert‐butyl perfumarate ( 1 ) as an initiator. Low molecular weight polymer (M̄_n ≈ 3 000) is formed in the early stage of polymerization where 1 is substantially consumed by thermal decomposition, copolymerization with 2 , and chain transfer reactions through an addition‐substitution mechanism. As a result, the low molecular weight polymer formed in the early stage of polymerization contains five peroxy ester groups per polymer molecule. Then, the polymerization of 2 initiated with the low molecular weight polymer further proceeds to yield high molecular weight poly( 2 ) (M̄_n = 2.5–23×10⁴). Decomposition of the peroxy ester group of 1 in benzene was studied in the absence and in the presence of methyl methacrylate (MMA) or 2 . The activation energy of decomposition of the peroxy ester group of 1 is 118 kJ/mol in the absence of the monomers. The decomposition of the peroxy ester group of 1 is highly accelerated in the presence of MMA. The peroxy ester groups derived from 1 decompose in two stages in the presence of 2 . In the first stage, some of them are rapidly consumed mainly by the chain transfer reaction. In the second stage, the peroxy ester groups of copolymer from 1 and 2 decompose slowly.     

SmI2/SmI3 as a Convenient Bisinitiator for the Living Polymerization of Methacrylates

A combined initiator comprising SmI₂ and SmI₃ has proven to serve as an excellent and convenient bisinitiator for the living polymerization of methyl (MMA) and tert‐butyl methacrylates (TBMA). The polymerization of MMA or TBMA with SmI₂ in the presence of catalytic amounts of SmI₃ led to the quantitative formation of polymers with low polydispersity (M̄_w/M̄_n = 1.08–1.11). A linear relationship between the feed ratio of the monomers to SmI₂ and the M̄_n of the polymers was recognized, which implies the absence of chain transfer reactions. The absence of termination was confirmed by the post‐polymerization technique in which – after the complete consumption of the initially charged monomer – the second feed of MMA resulted in an increase in M̄_n of the polymer maintaining its narrow molecular weight distribution. The initiation efficiency of the living polymerization of MMA was as high as 98%. Functionalization of the end group of living poly(MMA) was also accomplished with various electrophiles to give telechelic polymers.     

Synthesis of Hyperbranched Polymers by Anionic Self‐Condensing Vinyl Polymerization

Anionic self‐condensing vinyl polymerization is achieved from an in situ creation of a vinyl monomer bearing an active anion by the reaction of equimolar amount of 1,3‐diisopropenylbenzene (DIPB) and butyllithium in THF at 30°C. Onset of the intermolecular‐equilibrium between isopropenyl groups (α‐methylstyrene) and isopropenyl‐α‐methylstyryllithium sites of the oligomer restricts the growth of hyperbranched poly‐(DIPB) in THF at –40°C. Addition of a small amount of styrene interrupts this equilibrium. Conversion of isopropenyl‐α‐methylstyryllithium into styryllithium sites quickly directs the consumption of styrene and concurrent intermolecular‐condensation into remaining α‐methylstyrene groups of the oligomers. Thus, the equilibrium is reestablished and it has been shifted to the right by one or more α‐methylstyrene units that increase the molecular weight of the hyperbranched living polymer. Repeated small additions of styrene are attended by impressive multiplications of molecular weights. Up to seven generations of hyperbranched polymers have been synthesized as reported in this paper; the polymers exhibit high molecular weight and broad molecular weight distributions (1.8 < M̄_w/M̄_n < 4). The Mark‐Houwink exponent, α, is found to be 0.38 indicating a densely packed three‐dimensional structure resulting from the hyperbranched topology.     

Thermally Stable and Well‐Defined Pentadiene‐Derived Copolymers Prepared by Anionic Alternating Copolymerization and Subsequent Controlled Postmodification

Thermally stable and well‐defined hydrocarbon polymers prepared via anionic alternating copolymerization of 1,3‐pentadiene (P monomer: trans (TP) and cis (CP) mixture) and styrene derivatives (S monomer: styrene (St) and 1,1‐diphenylethylene (DPE)) and subsequent hydrogenation and cationic cyclization modifications are reported. The TP/S/CP terpolymerization reveals that an incorporation of S‐alt‐CP sequence into the alternating chain is more favorable, while the S‐alt‐TP insertion is also possible especially under high temperature owing to their competitive energy barriers and thermodynamic properties. Then the resultant copolymers with equimolar amount of the two monomers and predominant linear units are intramolecularly cyclized with CF₃SO₃H, or hydrogenated with p‐toluenesulfonyl hydrazide, to afford soluble and thermally stable hydrocarbon polymers with controlled Mns and narrow ?_Ms. The T_g of cylized polymer increases dramatically (ΔT_g > 100 °C) on cyclization between the adjacent C?C bond in the P structure and the aromatic ring of S unit through the intramolecular Friedel–Crafts alkylation. On the other hand, the T_g of hydrogenated product slightly decreases (ΔT_g ≈ 10 °C) after 98% hydrogenation due to the increasing flexibility of the saturated main‐chain, while the Td increases about 60 °C due to the loss of C?C bonds under oxygen atmosphere.     

A New Series of Conjugated Platinum‐co‐Poly(p‐phenylenebutadiynylene)s Polymers: Syntheses and Photophysical Properties

An efficient route is developed to synthesize a series of platinum‐co‐poly(p‐phenylenebutadiynylene)s (Pt‐co‐PPBs) polymers by stoichiometric mixing of poly(p‐phenylenebutadiynylene)s (PPBs) and platinum bis‐phosphine dichlorides. This synthetic route involves two steps; first, oxidative coupling of diterminal phenyleneethynylenes (PEs) gives low‐molecular‐weight PPBs oligomers H? C?C? (Ph(OR)₂ ? C?C? C?C)_n ? Ph(OR)₂ ? C?CH (R = C₄H₉ 1 , R = C₈H₁₇ 2 , R = C₁₂H₂₅ 3 ) (M_n = 1000–3000, degrees of polymerization, P_n(M_n) = 4–6 ), which have bifunctional alkynyl end groups, and in the second step, these organic oligomers are allowed to react with trans‐[(PⁿBu₃)₂PtCl₂] to form newly designed Pt‐co‐PPBs (R = C₄H₉ 4 , R = C₈H₁₇ 5 , R = C₁₂H₂₅ 6 ) polymers. The yield of 4–6 varies from good (63%) to high (76%) with high molecular weights (M_n) ranging from 52 738 to 74 212, and this methodology tolerates different alkoxy substituted PPBs. These new organometallic polymers contain platinum to phenylenebutadiynylene (PB) ratio of 1:4 to 1:6 and are solution processable. Polymer 4 displays fluorescence at room temperature and fluorescence and phosphorescence at low temperature in thin film, which would be useful for studying the triplet emission in these polymers.