Anionic alternating copolymerization of a bifunctional six‐membered lactone and glycidyl phenyl ether: Selective synthesis of a linear polyester having lactone moiety

An imidazole‐initiated copolymerization of an aromatic bislactone, 10‐methyl‐2H,8H‐benzo[1,2‐b:5,4‐b′]bipyran‐2,8‐dione ( 1 ), and glycidyl phenyl ether (GPE) was investigated. In spite of the bifunctional nature of 1 that would potentially permit formation of networked and thus insoluble polymers upon its copolymerization, only one of the two lactone moieties of 1 exclusively underwent the copolymerization to give a linear polyester. Spectroscopic analysis of the polyester and its reductive scission into the corresponding fragment revealed that the polyester was formed by a 1:1 alternating copolymerization of GPE and the lactone moiety of 1 . The other lactone in 1 that did not participate in the copolymerization was quantitatively incorporated into the side chain of the polyester as a reactive site, of which ring‐opening reactions by amine and alcohol as nucleophilic reagents allowed chemoselective polymer reactions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1661–1672, 2009     

Anionic alternating copolymerization of epoxide and six‐membered lactone bearing naphthyl moiety

This article describes the anionic copolymerization of glycidyl phenyl ether (GPE) and 1,2‐dihydro‐3H‐naphtho[2,1‐b]pyran‐3‐one (DHNP), a six‐membered aromatic lactone bearing naphthyl moiety. The copolymerization proceeded in a 1:1 alternating manner, to afford the corresponding polyester. The ester linkage in the main chain was cleavable by reduction with lithium aluminum hydride to give the corresponding diol that inherited the structure of the alternating sequence. The copolymerization ability of DHNP permitted its addition as a comonomer to an imidazole‐initiated polymerization of bisphenol A diglycidyl ether. The resulting networked polymer, of which main chain was endowed with the DHNP‐derived rigid naphthalene moieties, showed a higher glass transition temperature than that obtained similarly with using 3,4‐dihydrocoumarin (DHCM) as a comonomer, an analogous aromatic lactone bearing phenylene moiety instead of naphthalene moiety of DHNP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Anionic alternating copolymerization behavior of bifunctional six‐membered lactone and glycidyl phenyl ether

A copolymerization of 10‐methyl‐2H,8H‐benzo‐[1,2‐b:5,4‐b′]bipyran‐2,8‐dione ( 1 ) and glycidyl phenyl ether (GPE) was studied. 1 was a bislactone designed as a bifunctional analogue of 3,4‐dihydrocoumarin (DHCM), of which anionic 1:1 alternating copolymerization with GPE has been reported by us, previously. This alternating nature was inherited by the present copolymerization of 1 and GPE, leading to an intriguing copolymerization behavior in contrast to the ordinary statistical copolymerizations of monofunctional monomers and bifunctional monomers usually controlled by the proportional dependence of the crosslinking density on the monomer feed ratio: (1) When the feed ratio [GPE]₀/[ 1 ]₀ was 1, the two monomers underwent the 1:1 alternating copolymerization. In this case, 1 behaved as a monofunctional monomer, that is, only one of the two lactones in 1 participated in the copolymerization allowing the other lactone moiety to be introduced into the side chain almost quantitatively. (2) Increasing the feed ratio [GPE]₀/[1]₀ to larger than 4 allowed almost all of the lactone moieties to participate in the copolymerization system to give the corresponding networked polymers efficiently. The compositions of the copolymers [GPE unit]/[ 1 ‐derived acyclic ester unit] were always biased to smaller values than the feed ratios [GPE]₀/[lactone moiety in 1 ]₀ by the intrinsic 1:1 alternating nature of the copolymerization. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3662–3668, 2009     

Synthesis of bicyclic bis(γ‐butyrolactone) derivatives bearing sulfide moieties and their alternating copolymers with epoxide

A series of bicyclic bis(γ‐butyrolactone)s (BBL) bearing sulfide moiety 2 were readily synthesized from a precursor BBL bearing isopropenyl group 1. This efficient and versatile synthesis of 2 was achieved by a highly reliable radical addition reaction of thiols to the C‐C double bond in the isopropenyl group 2 underwent anionic copolymerization with glycidyl phenyl ether in a 1:1 alternating manner to give a series of the corresponding polyester 3, of which side chains inherited the sulfide group from 2. The glass transition temperatures (T_g) of 3 showed clear dependence on the flexibility of the sulfide side chains. The scope of this copolymerization system was further expanded by synthesizing a bifunctional BBL 4 from 1 with using hexanedithiol and performing its copolymerization with bisphenol A diglycidyl ether 5. The copolymerization gave the corresponding networked polymer in high yield. During the copolymerization, the volume expanding nature of the double ring‐opening reaction of 4 contributed to the efficient compensation of the intrinsic volume shrinkage of the ring‐opening of epoxide to achieve a shrinkage‐free curing system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ring‐opening polymerization of 6‐hydroxynon‐8‐enoic acid lactone: Novel biodegradable copolymers containing allyl pendent groups

This article reports the synthesis and copolymerization of 6‐hydroxynon‐8‐enoic acid lactone. The ring‐opening polymerization of this lactone‐type monomer bearing a pendant allyl group led to new homopolymers and random copolymers with ε‐caprolactone and L ,L ‐lactide. The copolymerizations were carried out at 110 °C with Sn(Oct)₂ as a catalyst. The introduction of unsaturations into the aliphatic polyester permitted us to carry out different chemical transformations on this family of polymers. For example, this article reports the bromination, epoxidation, and hydrosylilation of the allyl group in the new polyester copolymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 870–875, 2000     

Synthesis of a norbornene monomer having cyclic carbonate moiety based on CO2 fixation and its transition metal‐catalyzed polymerizations

A norbornene monomer bearing cyclic carbonate moiety ( NB‐CC ) was successfully synthesized from the corresponding precursor having epoxy moiety by its reaction with carbon dioxide under atmospheric pressure, which was efficiently catalyzed by lithium bromide. NB‐CC underwent the ring‐opening metathesis polymerization (ROMP) catalyzed by a ruthenium carbene complex to give the corresponding poly(norbornene), of which side chain inherited the cyclic carbonate moiety from the monomer without any deterioration. The same ROMP system was applicable to the copolymerization of NB‐CC and 5‐butyl‐2‐norbornene ( BNB ), which afforded the corresponding copolymer with a composition ratio same as a feed ratio. In addition, by using a catalytic system consisted of palladium (II) acetate/tricyclohexylphosphine/triphenylcarbenium tetrakis(pentafluorophenyl)borate, the copolymerization of NB‐CC and BNC proceeded successfully in a vinyl addition polymerization mode to give the corresponding poly(norbornene) having CC moiety in the side chain. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3896–3902, 2010     

Anionic alternating copolymerization of 3,4‐dihydrocoumarin and glycidyl ethers: A new approach to polyester synthesis

Anionic copolymerizations of 3,4‐dihydrocoumarin (DHCM) and a series of glycidyl ethers (n‐butyl glycidyl ether, tert‐butyl glycidyl ether, and allyl glycidyl ether) with 2‐ethyl‐4‐methylimidazole as an initiator proceeded in a 1:1 alternating manner to give the corresponding polyesters, whose structures were confirmed by spectroscopic analyses and reductive scission of the ester bonds in the main chain with lithium aluminum hydride, followed by detailed analyses of the resulting fragments. The polyester obtained by the copolymerization of DHCM and allyl glycidyl ether inherited the allyl groups in the side chain, whose applicability to chemical modifications of the polyester was successfully demonstrated by a platinum‐catalyzed hydrosilylation reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4092–4102, 2008     

Postfunctionalization of polyoxanorbornene via sequential Michael addition and radical thiol‐ene click reactions

We demonstrated the successful postfunctionalization of poly(oxanorbornene imide) (PONB) with two types of double bonds using sequential orthogonal reactions, nucleophilic thiol‐ene coupling via Michael addition and radical thiol‐ene click reactions. First, the synthesis of PONB with side chain acrylate groups is carried out via ring‐opening metathesis polymerization and nitroxide radical coupling reaction, respectively. Subsequently, the resulting polymer having two different orthogonal functionalities, main chain vinyl and side chain acrylate, is selectively modified via two sequential thiol‐ene click reactions, nucleophilic thiol‐ene coupling via Michael addition and photoinduced radical thiol‐ene. The orthogonal reactivity of two diverse double bonds, vinyl and acrylate functionalities, for the abovementioned consecutive thiol‐ene click reactions was first demonstrated on the model compound. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of reactive poly(norbornene): Ring‐opening metathesis polymerization of norbornene monomer bearing cyclic dithiocarbonate moiety

A norbornene monomer bearing cyclic dithiocarbonate moiety (NB‐DTC) was successfully synthesized from the corresponding precursor having epoxy moiety by its reaction with carbon disulfide. NB‐DTC underwent the ring‐opening metathesis polymerization (ROMP) catalyzed by a ruthenium carbene complex to give the corresponding poly(norbornene). The dithiocarbonate moiety incorporated into the side chain of the obtained poly(norbornene) reacted with amine to afford the corresponding thiourethane moiety with thiol group, which underwent oxidative S‐S coupling and/or addition reaction to the C‐C double bond in the main chain, leading to formation of a cross‐linked polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Alternating copolymers with degradability and quantitatively controlled thermosensitivity

To combine temperature responsivity and degradability, novel alternating copolymers with polyester backbone and oligo(ethylene glycol) side chain were designed and prepared by alternating ring‐opening copolymerization of succinic anhydride (SA) and functional epoxide monomer(s). The epoxide monomer containing one ethylene glycol unit, 2‐((2‐methoxyethoxy)methyl)oxirane (MEMO), has displayed similar copolymerization activity to that containing two ethylene glycol units, 2‐((2‐(2‐methoxyethoxy)ethoxy)methyl)oxirane (ME₂MO), when copolymerized with SA. This feature led to the formation of alternating copolymers with statistical random distribution of MEMO/ME₂MO units along the backbone when mixed MEMO/ME₂MO comonomers were fed. These polyesters possess degradability and quantitatively controlled lower critical solution temperature (LCST; 18–50 °C) and T_g (?40 to ?31 °C) both in linear relations with MEMO/ME₂MO feed ratio. Fine control of LCST near body temperature is thus realized for the reported degradable and thermoresponsive polyesters, which have promising applications in biomedical fields. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Asymmetric polymerization using C1 resources

Two examples of asymmetric alternating copolymerization, (1) the alternating copolymerization of α‐olefins (monosubstituted ethenes) with carbon monoxide and (2) the alternating copolymerization of meso‐epoxide with carbon dioxide, are described, and the meaning of chirality in polymer synthesis is emphasized. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 215–221, 2004     

Novel approach to well‐defined polyester by living anionic alternating copolymerization of ethylphenylketene with 4‐methoxybenzaldehyde

A living anionic alternating copolymerization of ethylphenylketene (EPK) with 4‐methoxybenzaldehyde (MBA) was achieved. When n‐butyllithium was added to a mixture of EPK and MBA in tetrahydrofuran at ?40 °C in the presence of an excess amount of lithium chloride, the copolymerization of these monomers proceeded via complete 1:1 alternating manner to afford the polymer with a narrow molecular weight distribution. A linear relationship was observed between the molecular weight and the monomer/initiator ratio, keeping a narrow molecular weight distribution. The structure of the obtained polymer was determined to be a polyester by IR spectroscopy together with the reductive degradation of the polymer by lithium aluminum hydride, which quantitatively afforded the corresponding diol to the repeating unit of the expected polyester structure. Both conversions of EPK and MBA agreed to a first‐order kinetic equation with linear evolution between the molecular weight and conversion. These observations along with the successful results in two‐stage polymerization indicate that the present copolymerization proceeded through a living mechanism. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2078–2084, 2001     

Synthesis and palladium‐catalyzed addition polymerization of norbornene carrying epoxy moiety

A norbornene monomer carrying epoxy moiety 1 was successfully synthesized from 5‐norbornene‐2‐carbardehyde by treating it with thioylide. With using a catalytic system consisted of palladium (II) acetate/tricyclohexylphosphine/triphenylcarbenium tetrakis(pentafluorophenyl)borate, homopolymerizations and copolymerization of 1 and 5‐butyl‐2‐norbornene (BNB) were examined. The homopolymerization of 1 was slower than that of BNB presumably due to coordination of the epoxy moiety to the palladium‐center in competition with the C? C double bond of norbornene. This deceleration became less significant in the copolymerizations with low initial feed ratios [ 1 ]₀/[BNB]₀, leading to successful formation of the corresponding copolymers having a rigid poly(norbornene) main chain and epoxy moiety in the side chains, of which composition ratios agreed with the feed ratios. Influence of the epoxy moiety of 1 on its Pd‐catalyzed addition polymerization was elucidated by studying the homopolymerization of BNB in the presence of 1,2‐epoxyhexane. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3982–3989, 2009     

Copolymerization of carbon dioxide and epoxide

An erratum has been published for this article in J Polym Sci Part A: Polym Chem (2005) 43(4) 916 . The alternating copolymerization of carbon dioxide and epoxide to produce polycarbonate has attracted the attention of many chemists because it is one of the most promising methodologies for the utilization of carbon dioxide as a safe, clean, and abundant raw material in synthetic chemistry. Recent development of catalysts for alternating copolymerization is based on the rational design of metal complexes, particularly complexes of transition metals with well‐defined structures. In this article, the history and recent successful examples of the alternating copolymerization of carbon dioxide and epoxide are described. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5561–5573, 2004     

Mechanistic insight into initiation and chain transfer reaction of CO2/cyclohexene oxide copolymerization catalyzed by zinc?cobalt double metal cyanide complex catalysts

Although zinc? cobalt (III) double metal cyanide complex (Zn? Co (III) DMCC) catalyst is a highly active and selective catalyst for carbon dioxide (CO₂)/cyclohexene oxide (CHO) copolymerization, the structure of the resultant copolymer is poorly understood and the catalytic mechanism is still unclear. Combining the results of kinetic study and electrospray ionization‐mass spectrometry (ESI‐MS) spectra for CO₂/CHO copolymerization catalyzed by Zn? Co (III) DMCC catalyst, we disclosed that (1) the short ether units were mainly generated at the early stage of the copolymerization, and were hence in the “head” of the copolymer and (2) all resultant PCHCs presented two end hydroxyl (? OH) groups. One end ? OH group came from the initiation of zinc? hydroxide (Zn? OH) bond and the other end ? OH group was produced by the chain transfer reaction of propagating chain to H₂O (or free copolymer). Adding t‐BuOH (CHO: t‐BuOH = 2:1, v/v) to the reaction system led to the production of fully alternating PCHCs and new active site of Zn? Ot‐Bu, which was proved by the observation of PCHCs with one end ? Ot‐Bu (and ? OCOOt‐Bu) group from ESI‐MS and ¹³C NMR spectra. Moreover, Zn?OH bond in Zn? Co (III) DMCC catalyst was also characterized by the combined results from FT‐IR, TGA and elemental analysis. This work provided new evidences that CO₂/CHO copolymerization was initiated by metal? OH bond. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and properties of polythiophenes with conjugated side‐chains containing carbon–carbon double and triple bonds

Two soluble side‐chain conjugated polythiophenes, poly{3‐[2‐(4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3OPVT) and poly{3‐(4‐octyloxy‐phenylethynyl)‐thiophene} (P3OPET) have been synthesized successfully. In P3OPVT and P3OPET, substituted benzene rings are connected with the polythiophene backbone through trans carbon–carbon double bond and carbon–carbon triple bond, respectively. Absorption spectra of the P3OPVT and P3OPET both show two absorption peaks located in UV and visible region, respectively. The results of optical and electrochemical measurements indicate that the conjugated side‐chains can reduce the bandgap effectively. This type of side‐chain conjugated polythiophenes may be promising for the applications in polymer photovoltaic cells and field effect transistors. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2206–2214, 2006     

Enantioselective Total Synthesis of (+)‐Plumisclerin A

The first and enantioselective total synthesis of (+)‐plumisclerin A, a novel unique complex cytotoxic marine diterpenoid, has been accomplished. Around the central cyclopentane anchorage, a sequential ring‐formation protocol was adopted to generate the characteristic tricycle[4.3.1.0^1,5]decane and trans‐fused dihyrdopyran moiety. Scalable enantioselective La^III‐catalyzed Michael reaction, palladium(0)‐catalyzed carbonylation and SmI₂‐mediated radical conjugate addition were successfully applied in the synthesis, affording multiple grams of the complex and rigid B/C/D‐ring system having six continuous stereogenic centers and two all‐carbon quaternary centers. The trans‐fused dihyrdopyran moiety with an exo side‐chain was furnished in final stage through sequential redox transformations from a lactone precursor, which overcome the largish steric strain of the dense multiring system. The reported total synthesis also confirms the absolute chemistries of natural (+)‐plumisclerin A.     

Molecular design of diene monomers containing an ester functional group for the synthesis of poly(diene sulfone)s by radical alternating copolymerization with sulfur dioxide

Functional poly(diene sulfone)s are prepared by the radical alternating copolymerization of 1,3‐diene monomers containing an ester substituent with sulfur dioxide. Methyl 3,5‐hexadienoate (MH) and methyl 5,7‐octadienoate (MO) with both an alkylene spacer and a terminal diene structure are suitable to produce a high‐molecular‐weight copolymer in a high yield, while the copolymerization of 5,7‐nonadienoic acid, ethyl 2,4‐pentadienoate, and ethyl 4‐methyl‐2,4‐pentadienoate including either an alkylene spacer or a terminal diene structure lead to unsuccessful results. The ¹³C NMR chemical shift values of MH and MO suggest a high electron density at their reacting α‐carbon for exhibiting a high copolymerization reactivity. Fluorene‐containing diene monomers, 9‐fluorenyl 3,5‐hexadienoate (FH) and 9‐fluorenyl 5,7‐octadienoate (FO), are also prepared and copolymerized with sulfur dioxide. The thermal and optical properties of the poly(diene sulfone)s containing the methyl and fluorenyl ester substituents in the side chain are investigated. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1000–1009     

A paradigm for the mechanisms and products of spontaneous polymerizations

In spontaneous vinyl and ring‐opening copolymerizations, polar and resonance effects on the intermediates from bond‐forming initiation offer a continuous spectrum of reactivities and polymer structures. In bond‐forming initiation, an electron‐rich donor monomer forms a bond to an acceptor monomer. The donor monomer may be a vinyl monomer with O, N, or aryl substituent or it may be an aza‐ or oxacycle. The acceptor monomer may be a vinyl monomer carrying CN, COOR, or SO₂R substituent or it may be a cyclic anhydride or maleimide. Beyond this, the donor may have a π‐like strained single bond, whereas the acceptor may be an electrophilic quinodimethane. Lewis acids may be used to enhance the electrophilicity of acceptor monomers. Reaction rates and polymer composition are determined by systematically varying the stability of the first intermediate, designated P (for polymethylene). The nature of the intermediate will vary from a highly reactive trans biradical, which initiates chain alternating copolymerization, to a cis/gauche zwitterion, which can initiate chain ionic homopolymerization, to an extremely stabilized zwitterion, which cannot add monomer, but builds up in concentration and terminates by combination, forming alternating copolymer. This model embraces the existing literature for a wide variety of monomers and possesses predictive power. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Stereocontrolled anionic alternating copolymerization of ethylphenylketene with benzaldehyde by a bisoxazoline ligand

Anionic copolymerization of ethylphenylketene with benzaldehyde with butyllithium or diethylzinc as the initiator proceeded in a perfect 1:1 alternating manner to produce the corresponding polyester, whose repeating unit had two adjacent chiral centers. The relative stereochemistry between these two chiral centers was successfully controlled by the addition of (S,S)‐(‐)‐2,2′‐isopropylidenebis(4‐tert‐butyl‐2‐oxazoline), producing the corresponding polyester that had excellent diastereoselectivity (erythro‐configuration : threo‐configuration = 4:96). The diastereomeric ratio was determined by high‐performance liquid chromatography analysis of the diol, which was obtained by reductive degradation of the polyester while maintaining the configuration of the repeating unit. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5384–5388, 2004