Poly(alkyl lactate acrylate)s having tunable hydrophilicity

Four alkyl lactates and alkyl lactate acrylates having methyl, ethyl, propyl, and butyl as alkyl moiety were synthesized by azeotropic distillation. Their formation was confirmed by Fourier transform infrared (FTIR), mass, ¹H nuclear magnetic resonance (NMR) and proton decoupled ¹³C NMR spectroscopic techniques. Solution polymerization was carried out for these alkyl lactate acrylates and the formed homopolymers were characterized by FTIR, ¹H NMR, proton decoupled ¹³C NMR spectroscopic, and gel permeation chromatographic techniques. Shear thinning behavior was observed for all the polymers. Wide angle X‐ray Diffraction studies showed that the polymers were amorphous in nature and also exhibited odd‐even effect among alkyl lactate groups with respect to average molecular interchain spacing. Depending on the length of the alkyl lactate groups, relative humidity and time, the hydrophilicity of the polymers decreased with increase in the length of the alkyl lactate group among the odd and even series. Among the studied polymers, poly(ethyl lactate acrylate) may have the potential for hydrogel applications, due to its highly hydrophilic nature. T_g decreased with increase in length of alkyl lactate groups. Trend observed on the thermal stabilities of poly(alkyl lactate acrylate)s could be explained on the basis of average molecular interchain spacing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40962.     

Synthesis and Characterization of Novel Azido Polymers: Hyperbranched Poly‐3‐azidomethyl‐3‐hydroxymethyl Oxetane

In the past thirty years, azido polymers have attracted wide attention in the field of energetic materials. Currently, the synthesized azido polymers have linear structure. In the present research, hyperbranched poly‐3‐azidomethyl‐3‐ hydroxymethyl oxetane (HBPAMHMO) was synthesized using an AB₂ monomer, and its physical and chemical properties were studied. The results showed that the molecular weight of HBPAMHMO increased along with the increasing ratio of r ([monomer]₀/[initiator]₀), together with very narrow PDI (from 1.12 to 1.34), and moreover, the degree of branching increased along with the increase in polymerization temperature. As compared to linear azido polymer with similar structure, it has lower glass transition temperature, sensitivity, higher combustion heat and mechanical properties, suggesting a great prospect for numerous applications.     

Characteristics of poly(vinyl pyrrolidone)/poly(acrylic acid) interpolymer complex prepared by template polymerization of acrylic acid: Effect of reaction solvent and molecular weight of template

Poly(vinyl pyrrolidone) (PVP)/poly(acrylic acid) (PAA) interpolymer complexes were prepared, in ethanol or dimethylformamide (DMF), by template polymerization of acrylic acid in the presence of PVP (MW: 42.5 or 1100 K) used as the template. FTIR analysis showed that the complexes were formed through hydrogen bonding between the carboxyl groups of the PAA and the carbonyl groups of the PVP. The glass‐transition temperature (T_g) of the complex, prepared in ethanol, was higher than that of the component polymers, whereas the T_g of the complex, prepared in DMF, was located between that of the component polymers. The dissolution rate of the complex was affected by the molecular weight of the PVP and the reaction solvent. The release rate of ketoprofen from the complexes showed a pH dependency, and was slower at a lower pH. The ketoprofen release rate from the complex was controlled mainly by the dissolution rate of the complex above the pK_a of PAA (4.75) and by the diffusion rate below the pK_a. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2390–2394, 2004     

Preparation and characterization of the molecular weight controllable poly(lactide-<Emphasis Type="Italic">co</Emphasis>-glycolide)

A series of poly(d,l-lactide-co-glycolide) (PLGA) polymers with various molecular weight were synthesized by a ring-opening polymerization method using stannous 2-ethyl hexanoate (Sn(Oct)₂) as the catalyst. The molecular weight of these polymers was controlled in a novel way, using t-butyldimethylsilanol (TBDS) or triphenylsilanol (TPS). The silicon-end group attached to the PLGA copolymer was removed at room temperature using either hydrochloric acid (HCl) or trifluoroacetic acid (TFA). The structures of these polymers before and after end group removal were characterized by ¹HNMR spectroscopy, while the molecular weight and polydispersity index (PDI) were determined by viscosity method and gel permeation chromatography (GPC). The residual amounts of stannum in PLGA and the glass transition temperature (T _g) of copolymer before and after end group removal were determined by the atomic absorption spectrum (AAS) and differential scanning calorimetry (DSC), respectively. The results showed that the removal method was effective. This study demonstrated that the molecular weight of PLGA could be easily controlled by altering the monomers/silanol molar ratio and the molecular weight and the purity of PLGA copolymer materials after silicon-end group removal could meet the demand of drug release.     

Hydrolytic degradation and crystallization behavior of linear 2‐armed and star‐shaped 4‐armed poly(l‐lactide)s: Effects of branching architecture and crystallinity

“Linear” aliphatic polyesters composed of two poly(l ‐lactide) arms attached to 1,3‐propanediol and “star‐shaped” ones composed of four poly(l ‐lactide) arms attached to pentaerythritol (2‐L and 4‐L polymers, respectively) with number‐average molecular weight (M_n) = 1.4–8.4 × 10⁴g/mol were hydrolytically degraded at 37°C and pH = 7.4. The effects of the branching architecture and crystallinity on the hydrolytic degradation and crystalline morphology change were investigated. The degradation mechanism of initially amorphous and crystallized 2‐L polymers changed from bulk degradation to surface degradation with decreasing initial M_n; in contrast, initially crystallized higher molecular weight 4‐L polymer degraded via bulk degradation, while the degradation mechanism of other 4‐L polymers could not be determined. The hydrolytic‐degradation rates monitored by molecular‐weight decreases decreased significantly with increasing branch architecture and/or higher number of hydroxyl groups per unit mass. The hydrolytic degradation rate determined from the molecular weight decrease was higher for initially crystallized samples than for initially amorphous samples; however, that of 2‐L polymers monitored by weight loss was larger for initially amorphous samples than for initially crystallized samples. Initially amorphous 2‐L polymers with an M_n below 3.5 × 10⁴g/mol crystallized during hydrolytic degradation. In contrast, the branching architecture disturbed crystallization of initially amorphous 4‐L polymers during hydrolytic degradation. All initially crystallized 2‐L and 4‐L polymers had δ‐form crystallites before hydrolytic degradation, which did not change during hydrolytic degradation. During hydrolytic degradation, the glass transition temperatures of initially amorphous and crystallized 2‐L and 4‐L polymers and the cold crystallization temperatures of initially amorphous 2‐L and 4‐L polymers showed similar changes to those reported for 1‐armed poly(l ‐lactide). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41983.     

New soluble cyano‐containing poly(arylene ether) copolymers bearing pendant xanthene groups

Homopolymers and copolymers of poly(arylene ether nitrile) (PAEN)‐bearing pendant xanthene groups were prepared by the nucleophilic substitution reaction of 2,6‐difluorobenzonitrile with 9,9‐bis(4‐hydroxyphenyl)xanthene (BHPX) and with various molar proportions of BHPX to hydroquinone (100/0 to 40/60) with N‐methyl‐2‐pyrrolidone (NMP) as a solvent in the presence of anhydrous potassium carbonate. These polymers had inherent viscosities between 0.61 and 1.08 dL/g, and their weight‐average molecular weights and number‐average molecular weights were in the ranges 34,200–40,800 and 17,800–20,200, respectively. All of the PAENs were amorphous and were soluble in dipolar aprotic solvents, including NMP, N,N‐dimethylformamide, and N,N‐dimethylacetamide and even in tetrahydrofuran and chloroform at room temperature. The resulting polymers showed glass‐transition temperatures (T_g's) between 220 and 257°C, and the T_g values of the copolymers were found to increase with increasing BHPX unit content in the polymer. Thermogravimetric studies showed that all of the polymers were stable up to 422°C with 10% weight loss temperatures ranging from 467 to 483°C and char yields of 54–64% at 700°C in nitrogen. All of the new PAENs could be cast into transparent, strong, and flexible films with tensile strengths of 106–123 MPa, elongations at break of 13–17%, and tensile moduli of 3.2–3.7 GPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of poly(ε-caprolactone)-containing amino acid-based poly(ether ester amide)s

A new family of biodegradable amino acid-based poly(ether ester amide)s (AA-PEEAs) consisting of three building blocks [poly(ε-caprolactone) (PCL), L -phenylalanine (Phe), and aliphatic acid dichloride] were synthesized by a solution polycondensation. Using DMA as the solvent, these PCL-containing Phe-PEEA polymers were obtained with fair to very good yields with weight average molecular weight (M_w) ranging from 6.9 kg/mol to 31.0 kg/mol, depending on the original molecular weight of PCL. The chemical structures of the PCL-containing Phe-PEEA polymers were confirmed by IR and NMR spectra. These PCL-containing Phe-PEEAs had lower T_g than most of the oligoethylene glycol (OEG) based AA-PEEAs due to the more molecular flexibility of the PCL block in the backbones, but had higher T_g than non-amino acid based PEEA. The solubility of the PCL-containing Phe-PEEA polymers in a wide range of common organic solvents, such as THF and chloroform, was significantly improved when comparing with aliphatic diol based poly(ester amide)s and OEG based AA-PEEAs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dynamic mechanical behavior of chlorosubstituted derivatives of poly(ethyl methacrylate) and poly(ethyl acrylate)

A freely oscillating torsional pendulum was used in the investigation of the influence of trichloroethyl, tetrachloroethyl, trichloromethoxyethyl, and trichloroethoxyethyl side groups on the molecular mobility in the glassy state and on the glass transition temperature of poly(meth)acrylates. All the polymers under study, which may be used as fire retardants, exhibit a simple relaxation behavior. While the parameters of the low-temperature and secondary relaxation process in the glassy state are not noticeably affected by the substituents used, the glass transition temperature T_g, increases with rising polarity and volume of side chains. The increase is larger in the series of polyacrylates, so that differences in the softening temperatures of polymethacrylates and polyacrylates having the same side chains decrease considerably with growing substitution.     

Ionic naphthalene thermotropic copolyesters with para-linked ion-containing units

Novel ionic naphthalene thermotropic polymers (NTPs) based on wholly aromatic copolyesters were synthesized, in which ionic monomer was introduced in the form of para-linked metal hydroquinone disulfonate (HQDS). These ionic NTPs contained ionic groups of up to 4 mol%, with counterions of either monovalent K or divalent Ca, and exhibited thermotropic liquid crystallinity. The K-salts exhibited the crystalline and liquid crystalline behaviors, typically observed for a non-ionic NTP; and they developed excellent thermal and mechanical properties. Testing was made as a function of ionic content under similar processing and testing conditions. The value of glass transition temperature rose as the average molecular weight increased. Both the melting temperature, T_m, and the crystallization temperature, T_c, remained nearly constant over the composition range studied. All the K-salt ionic NTPs showed enhanced tensile properties over a non-ionic NTP. The strength increased significantly as the ionic content increased despite the decrease in the molecular weight, reflecting the dominant effect of ionic interactions over the effect of molecular weight. Enhanced tensile properties arise from enhanced interchain interactions via ionic bonds (cross-links) between highly aligned NTP chains. The incorporation of HQDS-type ‘straight’ ionic units into a NTP copolyester can provide useful information about the effect of ionic interactions on the thermal/mechanical properties of NTPs.     

Influence of melt stability on the crystallization of bis(4-aminophenoxy)benzene-oxydiphthalic anhydride based polyimides

Novel high performance semicrystalline polyimides, based on controlled molecular weight phthalic anhydride (PA) endcapped 1,4-bis(4-aminophenoxy)benzene (TPEQ diamine) and oxydiphthalic dianhydride (ODPA), were synthesized. They exhibited excellent thermal stability in nitrogen and air atmospheres as determined by thermogravimetric analysis (TGA). The glass transition temperatures (T_g) for these polymers ranged from 225°C for the 10,000 M_n (10K) polymer, to 238°C for the 30,000 (30K) M_n material. The observed melting temperatures for all the polymers were ∼420°C. The crystallization behavior of these polymers showed a strong molecular weight dependence, as illustrated by the observation that the 10K and 12.5K polymers crystallized with relative ease, whereas the 15K, 20K, and 30K polymers showed little or no ability to undergo thermal recrystallization. The thermal stability of these polymers above T_m was investigated by studying the effect of time and temperature in the melt on the cold crystallization and melting of these polymers. Increased time and temperature in the melt resulted in lower crystallinity because of melt state degradation, such as crosslinking and branching, as evidenced by an increase in melt viscosity, which was more prominent for the higher molecular weight polymers.     

Synthesis of nitrile and benzoyl substituted poly(biphenylene oxide)s via nitro displacement reaction

A series of substituted poly(biphenylene oxide)s (PBPOs) was synthesized via nucleophilic nitro displacement reactions. High molecular weight PBPO's with nitrile groups were effectively synthesized from the polymerization of A-B type monomers with K₂CO₃ as a base in N-methyl-2-pyrrolidinone (NMP) at 140 °C. The polymers are completely amorphous, soluble in polar aprotic solvents, and formed flexible films on solution casting. Para-linked PBPO with nitrile groups showed excellent thermal properties such as high 5% weight loss temperature above 530 °C and T_g at 241 °C which is higher than those of commercially available PPO™ (T_g=210 °C). The pendent nitrile groups of PBPO were easily transformed to carboxylic acid groups by acidic hydrolysis.     

Thermal response of low molecular weight poly-(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) polymers in aqueous solution

Temperature-induced phase transition of three low-molecular-weight samples (M _w  < 1.2 × 10⁴) of poly(N-isopropylacrylamide) was studied with the aid of turbidimetry, dynamic light scattering, and rheology. We have demonstrated that the lower critical solution temperature depends on the length of the chain and the concentration of the polymer in the low molecular weight range. The turbidity results show a transition peak in the turbidity curve at intermediate temperatures. This peak, as well as the cloud point, is shifted toward lower temperatures when the molecular weight and the concentration of the polymer increase. The DLS measurements disclose a fast and a slow relaxation mode, which in both cases are found to be diffusive. The fast mode is linked to the diffusion of small species in the solution, and the slow mode is associated with the formation of large aggregates. The formation of these aggregates is less pronounced in solutions of polymers with low molecular weight and the incipient aggregation is shifted to higher temperatures. The shear viscosity measurements show the formation of weak aggregates, which are easily broken in solutions of short polymers. This effect is less pronounced when the molecular weight of the sample is increased. At certain shear rates, temperature-induced transition peaks of the viscosity are observed.     

Poly(arylene ether)s with trifluoromethyl groups via meta-activated nitro displacement reaction

New poly(arylene ether)s with pendent trifluoromethyl groups were synthesized from 2,2′-bis(trifluoromethyl)-4,4′-dinitro-1,1′-biphenyl with several bisphenols. The nitro leaving group activated by the trifluoromethyl group at meta position was quantitatively displaced with phenolate ions, resulting in high molecular weight polymers. The quantum mechanical calculation of the energy state suggested that the nitro displacement reaction activated by the trifluoromethyl group at meta position is an energetically favorable process. The polymers having weight average molecular weight of 42,100-95,000 g/mol and molecular weight distribution of 2.65-2.95 were obtained. The polymers were amorphous and dissolved in a wide range of organic solvents. Transparent and flexible films were obtained by solution casting. The resulting polymers are thermally stable, and T_gs of the polymers are in the range of 176-199 °C depending on their molecular structure. All of the synthesized polymers show refractive indices in the range of 1.592-1.624 with low birefringence below 0.006.     

Synthesis and characterization of liquid crystalline polymers containing aromatic ester mesogen and a nonmesogenic ferrocene unit in the spacer

A new series of liquid crystalline polymers containing aromatic triad ester mesogen and 1,1′‐disubstituted ferrocene as a nonmesogenic unit along with polymethylene spacer was synthesized. The polymer was synthesized by a room temperature polycondensation reaction between bis(4‐chloroformyl phenyloxy alkyl ferrocene dicarboxylate) and quinol. The alkyl groups have been varied by an even number of methylene groups with a range from two to ten groups. All the polymers were found to possess liquid crystalline properties. The identification of the mesophase is more transparent with an increase in the spacer. The thermal characteristics were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results reveal that the thermal stability of the polymers was decreased with increasing spacer length. The T_g, T_m, and T_i of the polymers decreased with increasing methylene groups. The incorporation of the ferrocene moiety also has a considerable effect on the glass transition temperature. The char yield of the polymer decreases with an increasing methylene chain length. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3494–3501, 2002     

Facile synthesis of dendronized polyamides with chloromethyl groups in the periphery and some properties

A novel dendronized aromatic polyamide with a polyamide backbone and chloromethylene‐end‐functionalized polyamide dendrons is reported for the first time. An attempt at a one‐pot synthesis of end‐functionalized dendronized polymers with a macromonomer strategy without protection and deprotection procedures is also reported for the first time. The results from Fourier transform infrared and NMR spectral analysis indicated that perfect coverage of the chloromethyl groups in the periphery of the resulting polymers was obtained. Data from gel permeation chromatography analysis showed a typical weight‐average molecular weight (M_w) of 76,678 and a polydispersity of 2.44 for the first‐generation polymers and an M_w of 41,554 and a polydispersity of 2.74 for the second‐generation polymers. The solubility in solvents for the resulting polymers was improved remarkably because of the introduction of the dendritic fragments and the existence of the periphery functional groups. Both the glass‐transition temperature and onset decomposition temperature decreased versus those of the linear aromatic polyamides, but the 50% weight loss temperature was still up to 723°C. The X‐ray diffractograms indicated only an amorphous peak in the wide‐angle region of 24–25°. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and properties of novel poly(coumarin‐amide)s

A novel monomer diacid, 6,6′‐methylenebis(2‐oxo‐2H‐chromene‐3‐carboxylic acid), was synthesized and used in a direct polycondensation reaction with various aromatic diamines in N‐methyl‐2‐pyrrolidone solution containing dissolved LiCl and CaCl₂, using triphenyl phosphite and pyridine as condensing agents to give a series of novel heteroaromatic polyamides containing photosensitive coumarin groups in the main chain. Polyamide properties were investigated by DSC, TGA, GPC, wide‐angle X‐ray scattering, viscosity, and solubility measurements. The copolymers were soluble in aprotic polar solvents, and their inherent viscosities varied between 0.49 and 0.78 dL g^?1. The weight‐average and number‐average molecular weights, measured by gel permeation chromatography, were 27,500–43,900 g mol^?1 and 46,500–66,300 g mol^?1, respectively, and polydispersities in the range of 1.48–1.69. The aromatic polyamides showed glass‐transition temperatures (T_g) ranging from 283 to 329°C and good thermal properties evidenced by no significant weight loss up to 380°C and 10% weight loss recorded above 425°C in air. All the polyamides exhibited an amorphous nature as evidenced by wide‐angle X‐ray diffraction and demonstrated a film forming capability. Water uptake values up to 3.35% were observed at 65% relative humidity. These polymers exhibited strong UV‐vis absorption maxima at 357–369 nm in DMSO solution, and no discernible photoluminescence maxima were detected by exciting with 365 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Tailoring the molecular and thermo–mechanical properties of kraft lignin by ultrafiltration

This study has shown that ultrafiltration allows the selective extraction from industrial black liquors of lignin fraction with specific thermo‐mechanical properties, which can be matched to the intended end uses. Ultrafiltration resulted in the efficient fractionation of kraft lignin according to its molecular weight, with an accumulation of sulfur‐containing compounds in the low‐molecular weight fractions. The obtained lignin samples had a varying quantities of functional groups, which correlated with their molecular weight with decreased molecular size, the lignin fractions had a higher amount of phenolic hydroxyl groups and fewer aliphatic hydroxyl groups. Depending on the molecular weight, glass‐transition temperatures (T_g) between 70 and 170°C were obtained for lignin samples isolated from the same batch of black liquor, a tendency confirmed by two independent methods, DSC, and dynamic rheology (DMA). The Fox–Flory equation adequately described the relationship between the number average molecular masses (M_n) and T_g's‐irrespective of the method applied. DMA showed that low‐molecular‐weight lignin exhibits a good flow behavior as well as high‐temperature crosslinking capability. Unfractionated and high molecular weight lignin (M_w >5 kDa), on the other hand, do not soften sufficiently and may require additional modifications for use in thermal processings where melt‐flow is required as the first step. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40799.     

Dynamic mechanical properties of polyurethane block polymers

The dynamic mechanical properties of polyester and polyether urethane block polymers have been investigated at four frequencies (3.5, 11, 35 and 110 Hz) in the temperature range of — 150 to 200°C. The existence of a two phase structure was demonstrated in these systems by the observation of two major transition regions corresponding to (1) the glass transition temperature (T_g) of the ester or ether soft segments, and to (2) the softening temperature of the aromatic-urethane hard segments. Several secondary relaxations were observed in addition to the two major relaxations. It was possible to assign molecular mechanisms to each of these relaxations. All relaxation phenomena were greatly influenced by the molecular weight of the prepolymer, weight percent of hard segments, and thermal history. An increase in the molecular weight of the prepolymer above 1,000 at constant hard segment content resulted in a semi-crystalline material, which possessed a lower T_g for the macroglycol segments. Annealing to enhance crystallinity increased the T_g of the soft segments, consistent with the usual observation in semicrystalline homopolymers. These findings suggest that the relaxation mechanisms of polyurethane block polymers are not only influenced by the degree of crystallinity, but also by the nature of the domain structure.     

Development of polyurethanes with azo‐type chromophores for second‐order nonlinear optical applications

Active nonlinear optical nitro‐substituted thiazole, benzothiazole, and thiadiazole chromophores were prepared and condensed with tolylene‐2,4‐diisocyanate (TDI) and 4,4′‐methylenedi(phenyl isocyanate) (MDI) to yield a series of polyurethanes. The resulting polyurethanes were characterized with Fourier transform infrared, proton nuclear magnetic resonance, and ultraviolet–visible spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The weight‐average molecular weights of the polyurethanes ranged between 19,500 and 28,000 (weight‐average molecular weight/number‐average molecular weight = 1.71–2.15). All the polyurethanes exhibited excellent solubility in most common organic solvents, and this indicated that these polyurethanes offered good processability. The glass‐transition temperatures (T_g's) of the polyurethanes were in the range of 166–204°C. Among the polyurethanes, chromophores containing the nitrothiazole moiety exhibited lower T_g values in comparison with those of chromophores containing nitrobenzothiazole and nitrothiadiazole moieties. This was attributed to the small size of the nitrothiazole moiety in the polyurethane matrix. The polyurethanes containing a TDI backbone demonstrated relatively high T_g values in comparison with those of the polyurethanes containing an MDI backbone. This was a result of an enhancement of the rigidity caused by the incorporation of a toluene ring into the polyurethane backbone. The second harmonic generation (SHG) coefficients of the poled polyurethane films ranged from 67.29 to 105.45 pm/V at 1064 nm. High thermal endurance of the poled dipoles was observed for all the polyurethanes. This was attributed to the formation of extensive hydrogen bonds between urethane linkages. Furthermore, none of the developed polyurethanes showed SHG decay below 150°C, and this signified their acceptability for nonlinear optical devices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of glycopolypeptides bearing mannose moieties and biphenyl pendants and their upper‐critical‐solution‐temperature‐type thermoresponsive properties in alcohol/water solvent mixtures

A series of glycopolypeptides with constant main‐chain lengths and various compositions of mannose moieties and biphenyl pendants were synthesized by copper‐mediated 1,3‐dipolar cycloadditions. ¹H NMR and Fourier transform IR (FTIR) analysis confirmed the molecular structures of the resulting polypeptides. FTIR analysis characterized the molar contents of the mannose pendants and α‐helical conformations in the solid state. Glycopolypeptides conjugated with tetra‐O‐acetyl‐d ‐(+)‐mannopyranoside showed a reversible upper‐critical‐solution‐temperature‐type (UCST‐type) phase behavior both in MeOH/H₂O and EtOH/H₂O binary solvent mixtures depending on the weight percentage of alcohols (f_w). Incorporation of a low content of biphenyl pendants (≤0.20) can broaden the range of f_w at which polymers showed UCST‐type phase behaviors. The UCST‐type transition temperature (T_pt) was highly related to the incorporation of biphenyl pendants, polymer concentrations, and the nature and weight percentage of alcohols. It decreased as the polymer concentration decreased and increased on incorporation of biphenyl groups. © 2016 Society of Chemical Industry