Stereospecific and asymmetric polymerization of 1-phenyldibenzosuberyl methacrylate with radical and anionic initiators

Stereospecific and asymmetric (helix-sense-selective) polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA) was performed with radical and anionic initiators. A highly isotactic polymer having triad isotacticity greater than 97% was obtained by radical polymerization with (i-PrOCOO)₂ at 40°C. The radical polymerization of PDBSMA in (+)- and (-)-menthol gave (-)-and (+)-polymers, respectively, whose optical activity is ascribed to the prevailing one-handed helical conformation of a polymer chain. The radical copolymerization of PDBSMA with a small amount of an optically active monomer, (+)-phenyl-2-pyridyl-o-tolylmethyl methacrylate, afforded an optically active copolymer with the prevailing one-handed helical structure of PDBSMA sequences. Asymmetric anionic polymerization of PDBSMA was carried out with the complex of N, N′-diphenylethylenediamine monolithium amide and a chiral ligand, (+)-1-(2-pyrrolidinylmethyl)pyrrolidine in toluene at −78°C. The obtained polymer was highly isotactic and optically active due to nearly 100% one-handed helical structure.     

(−)-Sparteine: The compound that most significantly influenced my research

A chiral diamine alkaloid, (−)-sparteine (Sp), has been found to be very effective as a ligand for Grignard reagents when used for the enantiomer-selective polymerization of racemic RS-1-phenylethyl methacrylate. The enantiomeric excess of the initially polymerized monomer is 93%, and at about a 60% conversion, nearly optically pure R-monomer is recovered. This enantiomer selectivity is today the highest in polymer chemistry. Triphenylmethyl methacrylate (TrMA) is a unique monomer that gives a highly isotactic polymer even during radical polymerization. When TrMA is polymerized with the Sp complex with n-butyllithium in toluene at −78 °C, an optically active, isotactic polymer [poly(triphenylmethyl methacrylate) (PTrMA)] with a one-handed helical conformation is obtained. The helical structure is maintained even at room temperature in solution. Analogous helical polymethacrylates that show various conformational changes have also been found. One-handed helical PTrMA exhibits high chiral recognition to a variety of racemates as a chiral stationary phase (CSP) for high-performance liquid chromatography. This finding has led to the development of very powerful CSPs based on polysaccharides, such as cellulose and amylose. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4480–4491, 2004     

Stereospecific polymerization of 9-fluorenyl methacrylate: Tacticity effects on the thermal and photophysical properties of the polymers

Poly(9-fluoreneyl methacrylate) was obtained through anionic polymerization with t-BuLi and t-BuMgBr and through radical polymerization with α,α′-azobisisobutyronitrile. Anionic polymerization with t-BuLi in tetrahydrofuran and radical polymerization afforded syndiotactic polymers (rr ∼ 90%), whereas anionic polymerization with Li and Mg initiators in toluene and CH₂Cl₂ led to isotactic polymers. The thermal and photophysical properties of the polymers were examined. A syndiotactic polymer tended to show higher glass transition and decomposition temperatures than an isotactic polymer. However, polymers with different tacticities were not likely to assume specific, distinctive conformations such as a helix or a π-stacked conformation in solution. An isotactic polymer showed stronger interactions in a CH₂Cl₂ solution with 2,4,7-trinitro-9-fluorenylidenemalononitrile, an electron-acceptor molecule, than a syndiotactic polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4656–4665, 2004     

Helix‐sense‐selective copolymerization of triphenylmethyl methacrylate with chiral 2‐isopropenyl‐4‐phenyl‐2‐oxazoline

The asymmetric induction leading to a one‐handed helix was investigated in the anionic and radical copolymerization of triphenylmethyl methacrylate (TrMA) and (S)‐2‐isopropenyl‐4‐phenyl‐2‐oxazoline ((S)‐IPO), and highly isotactic copolymers with a reasonable optical activity were obtained. In the anionic copolymerization, the optical activity of the obtained copolymers depended on the polarity of solvents, and a highly optically active copolymer was produced in the copolymerization in toluene. The chiral oxazoline monomer functioned not only as a comonomer but also as a chiral ligand to endow the polymer with large negative optical rotation in the copolymerization with TrMA. The copolymers with small positive optical rotation were obtained in THF, indicating that IPO unit may work only as the chiral monomer that dictates the helical sense via copolymerization with TrMA. The isotacticity of the obtained copolymers depended on the contents of TrMA units in the copolymers, but was almost independent of the solvent for copolymerization. In the radical copolymerization, the obtained copolymers exhibited small optical activities. It seemed that the chiral monomer cannot induce one‐handed helical structure of TrMA sequences even if the sequences probably have a high isotacticity. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 441–447     

Synthesis and characterization of L‐leucine containing chiral vinyl monomer and its polymer,poly(2‐(methacryloyloxyamino)‐4‐methyl pentanoic acid)

A chiral monomer containing L ‐leucine as a pendant group was synthesized from methacryloyl chloride and L ‐leucine in presence of sodium hydroxide at 4 °C. The monomer was polymerized by free radical polymerization in propan‐2‐ol at 60 °C using 2,2′‐azobis isobutyronitrile (AIBN) as an initiator under nitrogen atmosphere. The polymer, poly(2‐(Methacryloyloxyamino)‐4‐methyl pentanoic acid) is thus obtained. The molecular weight of the polymer was determined to be: M_w is 6.9 × 10³ and M_n is 5.6 × 10³. The optical rotation of both chiral monomer and its polymer varies with the solvent polarity. The amplification of optical rotation due to transformation of monomer to polymer is associated with the ordered conformation of chiral monomer unit in the polymeric chain due to some secondary interactions like H‐bonding. The synthesized monomer and polymer exhibit intense Cotton effect at 220 nm. The conformation of the chain segments is sensitive to external stimuli, particularly the pH of the medium. In alkaline medium, the ordered chain conformation is destroyed resulting disordered random coils. The ordered coiling conformation is more firmly present on addition of HCl. The polymer exhibits swelling‐deswelling characteristics with the change of pH of the medium, which is reversible. The Cotton effect decreases linearly with the increase of temperature which is reversible on cooling. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2228–2242, 2009     

Control of thermal properties and hydrolytic degradation in poly(lactic acid) polymer stars through control of isospecificity of polymer arms

The synthesis of a family of polymer stars with arms of varied tacticities is discussed. The effect of polymer tacticity on the physical properties of these polymer stars is dramatic. Dipentaerythritol cores support six poly(lactic acid) arms. Lewis acidic tin and/or aluminum catalysts control the polymerization to afford polymer stars of variable tacticity. Analysis of these polymers by ¹H NMR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and differential scanning calorimetry reveals the effects of tacticity control on the physical properties of the polymer stars. Hydrolytic decomposition studies suggest that the degradation profile of a polymer star may also be tuned by stereochemical control. Differences between isotactic samples derived from rac‐lactide and L ‐lactide are heightened by longer arms of 50 and 100 monomer units. Control of polymer isospecificity shows that a ～70% isotacticity bias is necessary to induce crystallinity and alter the thermal and degradation properties of the material. Above 70% isotacticity, the degradation properties and thermal transitions can be further tuned across a relatively wide range. This technique allows for significant tunability to the physical properties of aliphatic polyester polymer stars. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and radical polymerization of styrene‐based monomer having a five‐membered cyclic dithiocarbonate structure

A styrene‐based monomer having a five‐membered cyclic dithiocarbonate structure, 4‐vinylbenzyl 1,3‐oxathiolane‐2‐thione‐5‐ylmethyl ether (VBTE), was synthesized from 4‐vinylbenzyl glycidyl ether (VBGE) and carbon disulfide in the presence of lithium bromide in 86% yield. Radical polymerization of VBTE in dimethyl sulfoxide by 2,2′‐azobisisobutyronitrile was carried out at 60 °C to afford the corresponding the polymer, polyVBTE, in 64% yield. PolyVBTE with number‐averaged molecular weight higher than 31,000 was obtained. The glass transition temperature (T_g) and 5 wt % decomposition temperature (T_d5) of the polyVBTE were evaluated to be 66 and 264 °C under nitrogen atmosphere by differential scanning calorimetry and thermal gravimetry analysis, respectively. It was confirmed that a polymer consisting of the same VBTE repeating unit could also be obtained via polymer reaction, that is, a lithium bromide‐catalyzed addition of carbon disulfide to a polyVBGE prepared from a radical polymerization of VBGE. Copolymerization of VBTE and styrene with various compositions efficiently gave copolymers of VBTE and styrene. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Stereospecific Radical Polymerization of a Side-Chain Transformable Bulky Acrylamide Monomer and Subsequent Post-Polymerization Modification for Syntheses of Isotactic Polyacrylate and Polyacrylamide

We report syntheses of isotactic polyacrylate and polyacrylamide via a stereospecific radical polymerization of a pendant-transformable monomer, acrylamide carrying isopropyl-substituted ureidosulfonamide ( 1 ), followed by post-polymerization modification (PPM). The study in the alcoholysis and aminolysis reactions of the model compound ( 2 ) for evaluation of the transformation ability of the electron-withdrawing pendant group on the repeating unit 1 revealed the following points: the pendant of the polymer became more reactive than that of monomer; the pendant was active enough for aminolysis reaction affording the amide compound quantitatively without additive/catalyst; the addition of a lithium triflate [Li(OTf)] and triethylamine (Et₃N) was effective as for promotion of the alcoholysis reaction. Poly(methyl acrylate) (PMA) was quantitatively obtained via the radical polymerization of 1 in the presence of Li(OTf) at 60 °C and the subsequent addition of methanol along with Et₃N. Thus-obtained PMA showed higher isotacticity [m=74 %] than that directly obtained via radical polymerization of methyl acrylate (MA) (m=51 %). The isotacticity was further increased as the temperature and monomer concentration were lower, and eventually m was increased up to 93 %. The aminolysis PPM after the iso-specific radical polymerization of 1 gave various isotactic polyacrylamides carrying different alkyl pendant groups, including poly(N-isopropylacrylamide) (PNIPAM).     

Editorial

Abstract

Asymmetric syntheses of optically active polymethacrylate, polyacrylate, polyacrylamide, and polyisocyanate with helical conformation and their chiral recognition abilities are described. 1-Phenyldibenzosuberyl methacrylate (PDBSMA) gave a purely onehanded-helical, optically active polymer ([α]₃₆₅ +1670 ～ +1780º) with almost perfectly isotactic structure by anionic polymerization using optically active initiators. Radical polymerizations of PDBSMA using chiral initiators, chain transfer agents, and additives also afforded optically active polymers with a prevailing onehanded helicity. Triphenylmethyl acrylate yielded an optically active, helical polymer ([α]₃₆₅ +102º) having a dyad isotacticity of 70% using an optically active anionic initiator. Although the polyacrylate demonstrated chiral recognition ability as a chiral stationary phase for HPLC, the ability was low mainly because of the low degree of one-handedness. N-(3-Chlorophenyl)-N-phenylacrylamide gave an optically active, helical polymer ([α]_365–343º) in the asymmetric anionic polymerization; the polymer had a dyad tacticity of 77%. Optically active polyisocyanates with a predominantly one-handed helical conformation were prepared in homo-and co-polymerization of optically active phenyl isocyanate derivative. These polyisocyanates showed the ability to discriminate enantiomers in solution.     

Organocatalytic synthesis of novel renewable non‐isocyanate polyhydroxyurethanes

Novel fully renewable AA‐BB type non‐isocyanate polyhydroxyurethanes were synthesized by the classical reaction between a diamine and a dicyclocarbonate. Sebacic acid was first reacted with an excess of glycerol carbonate, in presence of DCC and DMPA, leading to a renewable dicyclocarbonate monomer. Then, this monomer was reacted with several renewable diamines, in presence of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), as organocatalyst, to afford linear and branched polymers. The obtained materials exhibited T_g values varied from ?27 to ?8 °C, T_m values varying from 100 to 165 °C, and thermal stabilities above 200 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 758–764     

Synthesis,characterization, and application of helical polymers

This review mainly describes the asymmetric synthesis of optically active polymers with helical conformation. Bulky methacrylates such as triphenylmethyl methacrylate and 1-phenyldibenzosuberyl methacrylate give one-handed helical and optically active polymers with almost perfectly isotactic main chain conformation by polymerization with chiral anionic initiators. The radical polymerization and copolymerization of these monomers under chiral conditions also afford optically active polymers with prevailing one-handed helicity. N, N-Disubstituted acrylamides also give optically active, helical polymers in the asymmetric anionic polymerization. Optically active polyisocyanates with a prevailing one-handed helical structure have been prepared in the copolymerization of an achiral isocyanate with a small amount of an optically active isocyanate and also in the polymerization of alkyl and aromatic isocyanates with optically active lithium alkoxide or amide compounds. The existence of a stable helical structure for polychloral has been successfully proved with the helical oligomers of chloral. One-handed helical polyisocyanides have been prepared by helix-sense-selective polymerization of bulky isocyanides and also by the cyclopolymerization of a 1, 2-diisocyanobenzene derivative with the Pd complex of a one-handed helical oligomer.     

Polymerizability of Exo‐methylene‐lactide toward vinyl addition and ring opening

This work examines the stereochemical control and polymerizability of exo‐methylene‐lactide (MLA) or (6S)‐3‐methylene‐6‐methyl‐1,4‐dioxane‐2,5‐dione, a chiral monomer derived from l ‐lactide, toward vinyl‐addition and ring‐opening polymerization (ROP) pathways, respectively. Currently, no information on the stereochemistry of the vinyl‐addition polymerization of MLA is known, and the possible ROP pathway is unexplored. Accordingly, this work first investigated the stereochemical control and other characteristics of the radical polymerization of MLA and its copolymerization with an analogous exo‐methylene‐lactone, γ‐methyl‐α‐methylene‐γ‐butyrolactone (MMBL), and di‐methylene‐lactide (DMLA) or 3,6‐dimethylene‐1,4‐dioxane‐2,5‐dione. The MLA homopolymerization produced optically active, but atactic, vinyl‐type polymers having a specific rotation of [α]²³_D = ?42 ± 4°, a high T_g from 229 to 254 °C, and a medium (M_w = 76.3 kg/mol, ? = 1.16) to high (M_w = 358 kg/mol, ? = 2.83) molecular weight, depending on the solvent. The copolymerization of MLA with MMBL afforded copolymers exhibiting enhanced thermal stability, while its copolymerization with DMLA led to cross‐linked polymers. The results obtained from the model reactions designed to probe the possible ROP indicate that the nonpolymerizability of MLA by initiators or catalysts comprising acidic, protic, and/or nucleophilic reagents is due to the high sensitivity of MLA toward such common ROP reagents that trigger decomposition or other types of transformations of MLA forming nonpolymerizable derivatives. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015 , 53, 1523–1532     

Iron‐catalyzed radical polymerization of acrylamides in the presence of Lewis acid for simultaneous control of molecular weight and tacticity

This work is directed to the stereospecific living radical polymerization of acrylamides such as N,N‐dimethylacrylamide and N‐isopropylacrylamide with an iron complex and a Lewis acid. DMAM was polymerized with [FeCp(CO)₂]₂ in conjunction with an alkyl iodide [(CH₃)₂C(CO₂Et)I] as an initiator in the presence of Y(OTf)₃ in toluene/methanol (1/1) at 60 °C to be converted almost quantitatively to the polymers with controlled molecular weights and high isotacticity (m > 80%), wherein the Fe‐complex generates radical species from a covalent C? I bond of the dormant species and the Lewis acid controls the stereochemistry of the polymerization via coordination with the amide groups of the polymer terminal and the monomer. A series of Lewis acids were also used for the iron(I)‐catalyzed DMAM polymerization, and Yb(OTf)₃ and Yb(NTf₂)₃ proved effective in giving isotactic polymers without deteriorating the molecular weight control similar to Y(OTf)₃. Furthermore, a slight enhancement of isospecificity was observed for the iron‐catalyzed system in comparison with the α,α‐Azobisisobutyronitrile‐initiated, when coupled with Y(OTf)₃. Stereoblock polymerization of DMAM via a one‐pot reaction was also achieved by just adding the Y(OTf)₃ methanol solution in the course of the polymerization to give atactic‐b‐isotactic poly(DMAM). A similar but slightly lower control in the molecular weight and tacticity was achieved in the polymerization of NIPAM with [FeCp(CO)₂]₂/Y(OTf)₃. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2086–2098, 2006     

Stereoregulation in the polymerization of methyl α-ethylacrylate by n-BuLi in toluene

The polymerization of methyl α-ethylacrylate was carried out in toluene by n-BuLi at various temperatures. The yield of the polymer decreased with increase in the polymerization temperature and at 30°C and above no polymer was obtained, indicating that the ceiling temperature of this monomer lay between 0 and 30°C. The isotacticity increased with an increase in the polymerization temperature and at 0°C a highly isotactic polymer was obtained. The fractionation of the polymer obtained at ?78°C showed that the polymer was a mixture of isotactic and syndiotactic ones. Upon the addition of a small amount of methanol or water in the polymerization mixture the isotacticity of the polymer increased while the yield decreased. Syndiotactic polymer was obtained in the polymerization by n-BuLi in tetrahydrofuran as well as by diisobutyl aluminum diphenylamide in toluene.     

Synthesis and radical polymerization of methacrylate endowed with bicyclobis(γ‐butyrolactone) moiety through methylene linker

A series of methacrylates bearing bicyclobis(γ‐butyrolactone) (BBL) moiety were synthesized and radically polymerized to afford the corresponding poly(methacrylate)s bearing BBL moiety in the side chain, with expecting that the high polarity and rigidity of BBL would be inherited by the polymers. The resulting polymers were soluble in polar aprotic solvents such as dimethyl sulfoxide and N,N‐dimethylformamide because of the high polarity of the BBL moiety. The glass transition temperatures (T_g) of the polymers depended on the length of methylene linker that tethered the methacrylate and BBL moieties, making the use of shorter linkers lead to higher T_gs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2462–2468     

Synthesis of isotactic,syndiotactic, and heterotactic poly(tributyltin methacrylate) and poly(tributyltin methacrylate-co-styrene)

Pure isotactic and enriched syndiotactic poly(tributyltin methacrylate) were synthesized by the reaction of the respective poly(methacrylic acid) with tributyltin oxide. The heterotactic polymer was prepared in a similar manner and from free radical initiated (AIBN or BPO) polymerization of tributyltin methacrylate. In each case, polymer configuration was confirmed by ¹H-NMR of the hydrolyzed/esterfied product. The relatively large ¹¹⁹Sn-NMR linewidth of the isotactic tributyltin containing polymer suggests an intra-molecular exchange of the pendant tin groups. T_g, T_d, and M _v data are also reported. Poly(tributyltinmethacrylate-co-styrene) was prepared by free radical polymerization and reactivity ratios [r(styrene) = 0.51, r(TBTM) = 0.49] and Q-e values for TBTM (0.78, 0.38) were determined.     

Synthesis of polypropylene graft copolymers by the combination of a polypropylene copolymer containing pendant vinylbenzene groups and atom transfer radical polymerization

This article discusses a facile and inexpensive reaction process for preparing polypropylene‐based graft copolymers containing an isotactic polypropylene (i‐PP) main chain and several functional polymer side chains. The chemistry involves an i‐PP polymer precursor containing several pendant vinylbenzene groups, which is prepared through the Ziegler–Natta copolymerization of propylene and 1,4‐divinylbenzene mediated by an isospecific MgCl₂‐supported TiCl₄ catalyst. The selective monoenchainment of 1,4‐divinylbenzene comonomers results in pendant vinylbenzene groups quantitatively transformed into benzyl halides by hydrochlorination. In the presence of CuCl/pentamethyldiethylenetriamine, the in situ formed, multifunctional, polymeric atom transfer radical polymerization initiators carry out graft‐from polymerization through controlled radical polymerization. Some i‐PP‐based graft copolymers, including poly(propylene‐g‐methyl methacrylate) and poly(propylene‐g‐styrene), have been prepared with controlled compositions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 429–437, 2005     

Polar,functionalized diene‐based material. III. Free‐radical polymerization of 2‐[(N,N‐dialkylamino)methyl]‐1,3‐butadienes

The bulk free‐radical polymerization of 2‐[(N,N‐dialkylamino)methyl]‐1,3‐butadiene with methyl, ethyl, and n‐propyl substituents was studied. The monomers were synthesized via substitution reactions of 2‐bromomethyl‐1,3‐butadiene with the corresponding dialkylamines. For each monomer the effects of the polymerization initiator, initiator concentration, and reaction temperature on the final polymer structure, molecular weight, and glass‐transition temperature (T_g) were examined. Using 2,2′‐azobisisobutyronitrile as the initiator at 75 °C, the resulting polymers displayed a majority of 1,4 microstructures. As the temperature was increased to 100 and 125 °C using t‐butylperacetate and t‐butylhydroperoxide, the percentage of the 3,4 microstructure increased. Differential scanning calorimetry indicated that all of the T_g values were lower than room temperature. The T_g values were higher when the majority of the polymer structure was 1,4 and decreased as the percentage of the 3,4 microstructure increased. The Diels–Alder side products found in the polymer samples were characterized using NMR and gas chromatography‐mass spectrometry methods. The polymerization temperature and initiator concentration were identified as the key factors that influenced the Diels–Alder dimer yield. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4070–4080, 2000     

Synthesis and chiral recognition ability of optically active poly{N‐[(R)‐α‐methoxycarbonylbenzyl]methacrylamide} with various tacticities by radical polymerization using Lewis acids

The radical polymerization of an optically active methacrylamide, N‐[(R)‐α‐methoxycarbonylbenzyl]methacrylamide, was carried out in the absence and presence of Lewis acids such as yittribium trifluoromethanesulfonate [Yb(OTf)₃] and scandium trifluoromethanesulfonate [Sc(OTf)₃]. Catalytic amounts of the Lewis acids significantly affected the stereoregularity of the obtained polymers. The polymerization with Yb(OTf)₃ in tetrahydrofuran afforded isotactic polymers (up to mm = 87%), whereas the conventional radical method without the Lewis acid produced polymers rich in syndiotacticity (up to rr = 88%). The radical polymerization in the presence of MgBr₂ proceeded in a heterotactic‐selective manner (mr = 63%). Thus, the isotactic, syndiotactic, and heterotactic poly(methacrylamide)s were synthesized by the radical processes. The chiral recognition abilities of the obtained optically active poly(methacrylamide)s were affected by the stereoregularity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3354–3360, 2003     

A–B–A stereoblock copolymers of N‐isopropylacrylamide

A–B–A stereoblock polymers with atactic poly(N‐isopropylacrylamide) (PNIPAM) as a hydrophilic block (either A or B) and a non‐water‐soluble block consisting of isotactic PNIPAM were synthesized using reversible addition fragmentation chain transfer (RAFT) polymerizations. Yttrium trifluoromethanesulfonate was used in the tacticity control, and bifunctional S,S′‐bis(α,α′‐dimethyl‐α″‐acetic acid)‐trithiocarbonate (BDAT) was utilized as a RAFT agent. Chain structures of the A–B–A stereoblock copolymers were determined using ¹H NMR, SEC, and MALDI‐TOF mass spectrometry. BDAT proved to be an efficient RAFT agent in the controlled synthesis of stereoregular PNIPAM, and both atactic and isotactic PNIPAM were successfully used as macro RAFT agents. The glass transition temperatures (T_g) of the resulting polymers were measured by differential scanning calorimetry. We found that the T_g of isotactic PNIPAM is molecular weight dependent and varies in the present case between 115 and 158 °C. Stereoblock copolymers show only one T_g, indicating the miscibility of the blocks. Correspondingly, the T_g may be varied by varying the mutual lengths of the A and B blocks. The phase separation of aqueous solutions upon increasing temperature is strongly affected by the isotactic blocks. At a fixed concentration (5 mg/mL), an increase of the isotacticity of the stereoblock copolymers decreases the demixing temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 38–46, 2008