Surface mobility and diffusion at interfaces of polystyrene in the vicinity of the glass transition

Symmetric polydisperse (M_w = 23 × 10⁴, M_w/M_n = 2.84) and monodisperse (M_w = 21 × 10⁴, M_w/M_n < 1.05) polystyrene (PS), and asymmetric polydisperse PS/poly(2,6-dimethyl 1,4-phenylene oxide) (PPO) interfaces have been bonded in the vicinity of the glass transition temperature (T_g) of PS. In a lap-shear joint geometry, strength develops in all cases with time to the fourth power, which indicates that it is diffusion controlled. Strength developing at short times at the polydisperse PS/PS interface, at 90°C, is higher than that at the monodisperse interface, at 92°C (at T_g − 13°C in both cases), presumably due to the contribution of the low molecular weight species. The decrease of strength at the PS/PPO interface when the bonding temperature decreases from 113 to 70°C, i.e., from T_g + 10°C to T_g − 33°C of the bulk PS, indicates a high molecular mobility at the surface as compared to that in the bulk, and can be expressed by a classical diffusion equation, which is valid above T_g (of the surface layer). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 567–572, 1998     

Eight-arm star polystyrene in methylcyclohexane: Cloud-point curves,critical lines,and coexisting densities and viscosities

We measured the cloud-point curves of eight-arm star polystyrene (sPS) in methylcyclohexane (MCH) for polymer samples of three total molecular masses [weight-average molecular weight (M_w) × 10⁻³ = 77, 215, or 268]. We found a downward shift of 5–15 K in the critical temperature (T_c) of the star polymer solutions with respect to linear polystyrene (PS) solutions of the same M_w. The shift in T_c became smaller as M_w increased. The critical volume fraction for eight-arm sPS in MCH was equal within experimental uncertainty (10–40%) to that of linear PS in MCH. For sPS of M_w = 77,000 in MCH, we studied the mass density (ρ) as a function of temperature (T). As for linear polymers in solution, the difference in ρ between coexisting phases (Δρ) could be described over t = (T_c − T)/T_c for 1.1 × 10⁻⁴ < t < 4.7 × 10⁻³ with the Ising value of the exponent β in the expression Δρ = B t^β. Both ρ(T) above T_c and the average value of ρ below T_c were linear functions of temperature; no singular corrections were observed. The measurements of the shear viscosity (η) near T_c for sPS (M_w = 74,000) in MCH indicated a strong critical anomaly in η, but the data were not precise enough for a quantitative analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 129–145, 2004     

Relation between the adhesion strength and interfacial width for symmetric polystyrene bilayers

Polystyrene (PS) bilayers were prepared and were adhered at a temperature between the surface and bulk glass-transition temperatures for a given time. Then, the interfacial adhesion strength (G_L) was examined with a conventional lap-shear measurement. G_L first increased with increasing adhesion time and then reached a constant value. This result implied that the segments moved across the interface, to a certain depth, even at a temperature below the bulk glass-transition temperature. To confirm this, the interfacial evolution for the PS/deuterated PS bilayers was examined with dynamic secondary-ion mass spectrometry. The G_L value was linearly proportional to the thickness of the interfacial adhesion layer. Finally, we propose a strategy for regulating the adhesion strength based on the chain-end chemistry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3598–3604, 2006     

Dynamic light scattering studies of atactic and syndiotactic poly(methyl methacrylate)s in dilute theta solution

The present article considers the coil‐to‐globule transition behavior of atactic and syndiotactic poly(methyl methacrylates), (PMMA) in their theta solvent, n‐butyl chloride (nBuCl). Changes in Rh in these polymers with temperature in dilute theta solutions were investigated by dynamic light scattering. The hydrodynamic size of atactic PMMA (a‐PMMA‐1) in nBuCl (M_w: 2.55 × 10⁶ g/mol) decreases to 61% of that in the unperturbed state at 13.0°C. Atactic PMMA (a‐PMMA‐2) with higher molecular weight (M_w: 3.3 × 10⁶ g/mol) shows higher contraction in the same theta solvent (α_η = R_h(T)/R_h (θ) = 0.44) at a lower temperature, 7.25°C. Although syndiotactic PMMA (s‐PMMA) has lower molecular weight than that of atactic samples (M_w: 1.2 × 10⁶), a comparable chain collapse was observed (α_η = 0.63) at 9.0°C. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2253–2260, 1999     

Molecular relaxation in the blends of polystyrene/poly(2,6-dimethyl-1,4-phenylene oxide) at low temperature

Molecular relaxation behavior in terms of the α, β, and γ transitions of miscible PS/PPO blends has been studied by means of DMTA and preliminary work has been carried out using DSC. From DSC and DMTA (by tan δ), the observed α relaxation (T_α or T_g) of PS, PPO, and the blends, which are intermediate between the constituents, are in good agreement with earlier reports by others. In addition, the β transition (T_β) of PS at 0.03 Hz and 1 Hz is observed at −30 and 20°C, respectively, while the γ relaxation (T_γ) is not observed at either frequency. The T_β of PPO is 30°C at 0.03 Hz and is not observed at 1 Hz, while the T_γ is −85°C at 0.03 Hz and −70°C at 1 Hz. On the other hand, blend composition-independent β or γ relaxation observed in the blends may be a consequence of the absence of intra- or intermolecular interaction between the constituents at low temperature. Thus it is suggested that at low temperature, the β relaxation of PS be influenced solely by the local motion of the phenylene ring, and that the β or γ relaxation of PPO be predominated by the local cooperative motions of several monomer units or the rotational motion of the methyl group in PPO. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1981–1986, 1998     

Effect of nanoscale confinement on the glass transition temperature of free-standing polymer films: Novel,self-referencing fluorescence method

The effect of nanoscale confinement on the glass transition temperature, T_g, of freely standing polystyrene (PS) films was determined using the temperature dependence of a fluorescence intensity ratio associated with pyrene dye labeled to the polymer. The ratio of the intensity of the third fluorescence peak to that of the first fluorescence peak in 1-pyrenylmethyl methacrylate-labeled PS (MApyrene-labeled PS) decreased with decreasing temperature, and the intersection of the linear temperature dependences in the rubbery and glassy states yielded the measurement of T_g. The sensitivity of this method to T_g was also shown in bulk, supported PS and poly(isobutyl methacrylate) films. With free-standing PS films, a strong effect of confinement on T_g was evident at thicknesses less than 80–90 nm. For MApyrene-labeled PS with M_n = 701 kg mol⁻¹, a 41-nm-thick film exhibited a 47 K reduction in T_g relative to bulk PS. A strong molecular weight dependence of the T_g-confinement effect was also observed, with a 65-nm-thick free-standing film exhibiting a reduction in T_g relative to bulk PS of 19 K with M_n = 701 kg mol⁻¹ and 31 K with M_n = 1460 kg mol⁻¹. The data are in reasonable agreement with results of Forrest, Dalnoki-Veress, and Dutcher who performed the seminal studies on T_g-confinement effects in free-standing PS films. The utility of self-referencing fluorescence for novel studies of confinement effects in free-standing films is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2754–2764, 2008     

Unexpected Molecular Weight Dependence to the Physical Aging of Thin Polystyrene Films Present at Ultra‐High Molecular Weights

The physical aging behavior, time‐dependent densification, of thin polystyrene (PS) films supported on silicon are investigated using ellipsometry for a large range of molecular weights (MWs) from M_w = 97 to 10,100 kg mol^?1. We report an unexpected MW dependence to the physical aging rate of h < 80‐nm thick films not present in bulk films, where samples made from ultra‐high MWs ≥ 6500 kg mol^?1 exhibit on average a 45% faster aging response at an aging temperature of 40 °C compared with equivalent films made from (merely) high MWs ≤ 3500 kg mol^?1. This MW‐dependent difference in physical aging response indicates that the breadth of the gradient in dynamics originating from the free surface in these thin films is diminished for films of ultra‐high MW PS. In contrast, measures of the film‐average glass transition temperature T _g(h) and effective average film density (molecular packing) show no corresponding change for the same range of film thicknesses, suggesting physical aging may be more sensitive to differences in dynamical gradients. These results contribute to growing literature reports signaling that chain connectivity and entropy play a subtle, but important role in how glassy dynamics are propagated from interfaces. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1224–1238     

Laser light scattering of the molecular weight distribution of unfractionated phenolphthalein poly(aryl ether sulfone)

Two unfractionated samples of phenolphthalein poly(aryl ether sulfone) (PES-C) were characterized in CHCl₃ at 25°C by applying a recently developed laser light-scattering (LLS) procedure. The Laplace inversion of precisely measured intensity–intensity time correlation function lead us first to an estimate of the characteristic line-width distribution G(Λ) and then to the translational diffusion coefficient distribution G(D). A combination of static and dynamic LLS results enabled us to determine D = (2.69 × 10⁻⁴)M^−0.553, which agrees with the calibration of D = (2.45 × 10⁻⁴)M^−0.55 previously established by a set of narrowly distributed PES-C samples. Using this newly obtained scaling between D and M, we were able to convert G(D) into a differential weight distribution f_w(M) for the two PES-C samples. The weight-average molecular weights calculated from f_w(M) are comparable to that obtained directly from static LLS. Our results showed that using two broadly distributed samples instead of a set of narrowly distributed samples have provided not only similar final results, but also a more practical method for the PES-C characterization. © 1997 John Wiley & Sons, Inc.     

A polymer–solvent system with two homogeneous double critical points: Polystyrene (PS)/(n-heptane + methylcyclohexane)

Liquid–liquid (LL) critical demixing loci have been experimentally determined in the (T,P) projection for some polystyrene/solvent systems with nonspecific interaction for (∼ 270 K < T < ∼ 500 K) and (0 MPa < P < 200 MPa). A lower homogeneous double critical pressure and lower homogeneous double critical temperature have been located for a solution of PS (M_w = 2.0 × 10⁶) dissolved in an n-heptane/methylcyclohexane mixture [PS/n-C₇H₁₆/CH₃C₆H₁₁//0.029/0.194/0.777 (wt. fractions)]. That solution forms the first example of a polymer/solvent with nonspecific interaction that exhibits two double critical points. A symmetrical representation of the LL critical loci in the (P,T) plane is developed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2747–2753, 1999     

Effect of polystyrene‐b‐poly(ethylene oxide) on self‐assembly of polystyrene‐b‐poly(N‐isopropylacrylamide) in aqueous solution

Mixed micelles of polystyrene‐b‐poly(N‐isopropylacrylamide) (PS‐b‐PNIPAM) and two polystyrene‐b‐poly(ethylene oxide) diblock copolymers (PS‐b‐PEO) with different chain lengths of polystyrene in aqueous solution were prepared by adding the tetrahydrofuran solutions dropwise into an excess of water. The formation and stabilization of the resultant mixed micelles were characterized by using a combination of static and dynamic light scattering. Increasing the initial concentration of PS‐b‐PEO in THF led to a decrease in the size and the weight average molar mass (〈M_w〉) of the mixed micelles when the initial concentration of PS‐b‐ PNIPAM was kept as 1 × 10^?3 g/mL. The PS‐b‐PEO with shorter PS block has a more pronounced effect on the change of the size and 〈M_w〉 than that with longer PS block. The number of PS‐b‐PNIPAM in each mixed micelle decreased with the addition of PS‐b‐PEO. The average hydrodynamic radius 〈R_h〉 and average radius of gyration 〈R_g〉 of pure PS‐b‐PNIPAM and mixed micelles gradually decreased with the increase in the temperature. Both the pure micelles and mixed micelles were stable in the temperature range of 18 °C–39 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1168–1174, 2010     

Poly(styrene‐b‐isobutylene) multiarm star‐block copolymers

Multiarm star‐branched polymers based on poly(styrene‐b‐isobutylene) (PS‐PIB) block copolymer arms were synthesized under controlled/living cationic polymerization conditions using the 2‐chloro‐2‐propylbenzene (CCl)/TiCl₄/pyridine (Py) initiating system and divinylbenzene (DVB) as gel‐core‐forming comonomer. To optimize the timing of isobutylene (IB) addition to living PS⊕, the kinetics of styrene (St) polymerization at −80°C were measured in both 60 : 40 (v : v) methyl cyclohexane (MCHx) : MeCl and 60 : 40 hexane : MeCl cosolvents. For either cosolvent system, it was found that the polymerizations followed first‐order kinetics with respect to the monomer and the number of actively growing chains remained invariant. The rate of polymerization was slower in MCHx : MeCl (k_app = 2.5 × 10⁻³ s⁻¹) compared with hexane : MeCl (k_app = 5.6 × 10⁻³ s⁻¹) ([CCl]_o = [TiCl₄]/15 = 3.64 × 10⁻³M; [Py] = 4 × 10⁻³M; [St]_o = 0.35M). Intermolecular alkylation reactions were observed at [St]_o = 0.93M but could be suppressed by avoiding very high St conversion and by setting [St]_o ≤ 0.35M. For St polymerization, k_app = 1.1 × 10⁻³ s⁻¹ ([CCl]_o = [TiCl₄]/15 = 1.82 × 10⁻³M; [Py] = 4 × 10⁻³M; [St]_o = 0.35M); this was significantly higher than that observed for IB polymerization (k_app = 3.0 × 10⁻⁴ s⁻¹; [CCl]_o = [Py] = [TiCl₄]/15 = 1.86 × 10⁻³M; [IB]_o = 1.0M). Blocking efficiencies were higher in hexane : MeCl compared with MCHx : MeCl cosolvent system. Star formation was faster with PS‐PIB arms compared with PIB homopolymer arms under similar conditions. Using [DVB] = 5.6 × 10⁻²M = 10 times chain end concentration, 92% of PS‐PIB arms (M_n,PS = 2600 and M_n,PIB = 13,400 g/mol) were linked within 1 h at −80°C with negligible star–star coupling. It was difficult to achieve complete linking of all the arms prior to the onset of star–star coupling. Apparently, the presence of the St block allows the PS‐PIB block copolymer arms to be incorporated into growing star polymers by an additional mechanism, namely, electrophilic aromatic substitution (EAS), which leads to increased rates of star formation and greater tendency toward star–star coupling. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1629–1641, 1999     

Polyurethane elastomers based on amphiphilic poly(caprolactone)‐b‐poly(butadiene)‐b‐poly(caprolactone) triblockcopolyols

Hydroxyl‐terminated poly(butadiene) (HTPB; M_n = 2100 g mol⁻¹) was capped with 30 and 60 wt % of ɛ‐caprolactone to reach amphiphilic triblock copolymers in form of capped poly(butadiene) CPB. The former (CPB30; M_n = 3300 g/mol) is amorphous with a glass temperature of −56 °C. CPB60 (M_n = 4000 g mol⁻¹) is semi‐crystalline with a melting point of 50 °C and a glass transition at −47 °C. The CPBs, HTPB and polycaprolactone diol (M_n = 2000 g mol⁻¹) were used as soft segment components in the preparation of polyurethane elastomers (PUE), using a 1/1 mixture of an MDI prepolymer and uretonimine modified MDI, and hard phase components in form of 1,3‐propane diol, 1,4‐butane diol, and 1,5‐pentane diol. CPB‐based elastomers with 1,4 butane diol (8 wt %) show hard domains as fringed aggregates with a better connection to the continuous phase than the HTPB‐based PUE. The soft segment glass transition temperature (T_g) is at −28 °C for HTPB‐based PUE and at −43 °C for those of CPB. The tensile strength of the CPB30&60‐based PUE is found between 20 and 30 MPa at an elongation at break of 400% and 550%, respectively. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1162–1172     

Effect of Molecular Weight on Enthalpy Relaxation in Syndiotactic Poly(Methyl-Methacrylate)

The structural relaxation behaviour of narrow fractions (M_w/M_n < 1.1) of syndiotactic poly(methyl methacrylate) with molecular masses ranging from 2,000 to 200,000 Daltons have been studied by DSC with two classical procedures, namely: the rate of cooling and the isothermal approaches. The apparent activation energy (Δh*) of enthalpy relaxation was evaluated from the dependence of the glass transition temperature on the cooling rate while a comparison of the apparent relaxation rates was appraised from the enthalpy loss by annealing the different samples at the same level of undercooling (T_a = T_g − 10 °C). As expected, the increase of molecular weights gives rise to both a continuous increase of Δh* and a decrease of the apparent isothermal relaxation rate. More interestingly, both Δh* and the apparent isothermal relaxation rate showed abrupt changes around the syndiotactic PMMA entanglement mass (M_e ).     

Studies on Macromolecular Complexing Agents. II. Effects of Polypropylene Oxide on the Copolymerization Reaction between Butadiene and Styrene

ABSTRACT

Ultra-high-molecular-weight poly[(R)-3-hydroxybutyrate](P(3HB)) was biosynthesized from glucose by a recombinant Escherichia coli XL-1 Blue (pSYL105) harboring Alcaligenes eutrophus PHB biosynthesis phbCAB genes. Six kinds of P(3HB) samples with differ-ent weight-average molecular weight (M_w ) from 1.1 × 10⁶ to 11 × 10⁶ measured by multi-angle laser light scattering were respectively produced at pH values of 7.0 to 6.5 in culture media. Solvent-cast P(3HB) films of high-molecular-weights over M_w of 3.3 × 10⁶ were stretched easily and reproducibly at 160°C to a draw ratio of 400-650%. Mechanical properties of the stretched P(3HB) films were markedly improved relative to those of solvent-cast film. The elongation to break, Young's modulus, and tensile- strength of stretched film (M_w = 11 × 10⁶) were 58%, 1.1 GPa, and 62 MPa, respectively. X-ray diffraction patterns indicated that the stretched film was highly oriented and had a high crystallinity over 80%. When the stretched film was annealed at 160°C for 2 hours, the mechanical properties were further improved (elongation to break = 67%, Young's modulus = 1.8 GPa and tensile strength = 77 MPa). The mechanical properties of the stretched-annealed film remained almost unchanged for 6 months at room temperature, suggesting that a high crystallinity of the stretched-annealed film avoids a progress of secondary crystallization.

     

Phase separation temperatures in the ternary system polystyrene/poly(α-methyl styrene)/cyclopentane

Phase separation temperatures of the ternary system polystyrene (PS) (M_w = 1.67 × 10⁴)/poly(α-methyl styrene) (PαMS) (M_w = 9.0 × 10⁴)/cyclopentane with a blend ratio PS/PαMS = 55/45 have been determined over the polymer concentration range 0.02 ≤ ψ_{PS + PαMS} ≤ 0.52, where ψ _{PS + PαMS} is the segment fraction of polymer in ternary system. Phase separation temperatures for the upper critical separation in the ternary system decrease with increasing ψ _{PS + PαMS} over the range 0.1 ≤ ψ _{PS + PαMS} ≤ 0.52. The vapor—liquid equilibrium in this system with a blend ratio PS/PαMS=50/50 has been determined over the concentration range 0.925 ≤ ψ_{PS + PαMS} < 0.995 and the temperature range 60–100°C by the piezoelectric vapor sorption method. The polymer—polymer interaction parameters χ′₁₂ determined are positive except at 100°C and increase with increasing ψ _{PS + PαMS}. Values of χ′₁₂ extrapolated to zero solvent concentration are positive (0.0–1.3) over the temperature range measured. Phase separation behavior is discussed in terms of phase separation temperature in a ternary system and the polymer–polymer interaction parameter.     

Water-soluble silicon containing polymer resist

Poly(divinylsiloxyethylene glycol), which consists of alternating oligo(ethylene glycol)s (MW = 300) and divinylsiloxanes were prepared by a polycondensation reaction (M_n = 6500–9300, M_w/M_n = 2.01–2.27). The obtained polymer (PVSE300) showed a lower critical solution temperature (LCST) at 10.5°C, meaning that the polymer was soluble in water below the LCST. The glass transition temperature (T_g) and onset temperature of degradation (T_d) of the PVSE300 were −72.5 and +317.5°C, respectively. The hydrolytic stability of the PVSE300 in aqueous media was also examined and it was found that PVSE300 was fairly stable in cold water. The lithographic characteristics of PVSE300 were examined against UV and electron-beam (EB) exposure and it was found that the PVSE300 film showed a negative character when developed by cold water. The photosensitivity parameter, Dg⁵⁰, which denotes the dose at half remaining film thickness after development, against EB exposure was extremely high (1.0 μC/cm²) when a probe current and an accelerating voltage was 100 pA and 20 kV, respectively. A high durability for O₂ reactive ion etching (O₂ RIE) was also observed. The characteristics of PVSE300 against photoirradiation were also examined. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2827–2833, 1997     

Polymerization of styrene oxide catalyzed by a diethylzinc/α-pinene oxide system

Styrene oxide (SO) was polymerized with a diethylzinc/α-pinene oxide (ZnEt₂/α-PiO) catalyst system under various conditions. Polystyrene oxide (PSO) thus obtained had a regular head-to-tail and isotactic structure. The number-average molecular weight reached 4.07 × 10⁴, and the molecular weight distribution was 5.7 (M_w/M_n). The glass-transition temperature of PSO was about 47 to 50 °C, depending on the molecular weight. The molar ratio of ZnEt₂ to α-PiO, 2 : 1, led to a high molecular weight of PSO in an 89.2% yield within 72 h. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4640–4645, 1999     

Living anionic ring-opening polymerization of 1,1-dipropylsilacyclobutane

Synthesis and living anionic ring-opening polymerization of 1,1-dipropylsilacyclobutane are reported. High molecular weight poly(dipropylsilylenepropylene) up to M _n = 83900 g/mol (SEC/PS standards) with low polydispersity (M _w/M _n = 1.11 to 1.22) was obtained at −20°C. End functionalization of poly-(dipropylsilylenepropylene) with chlorodimethylvinylsilane and synthesis of block copolymers with styrene was achieved. The polymers were characterized with NMR, SEC, MALDI-TOF and DSC.     

Laser light-scattering investigation of the density of pauci-chain polystyrene microlatices

The average density (〈ρ〉) of the pauci-chain polystyrene microlatices (PCPS), which contains a few linear polystyrene chains, was investigated by laser light scattering (LLS) including both angular dependence of absolute integrated scattered intensity (static LLS) and of the line-width distribution G(Γ) (dynamic LLS). In static LLS, the weight-average particle mass (M_w) and the z-average radius of gyration (R_g) were measured; and simultaneously in dynamic LLS, the hydrodynamic radius distribution was obtained from Laplace inversion of very precisely measured intensity-intensity time correlation function. A combination of both the static and dynamic LLS results leads us to a value of 〈ρ〉. For comparison, we also determined 〈ρ〉 of conventional multichain polystyrene latex (MCPS) by following the same LLS procedure. It was found that 〈ρ〉_MCPS = 〈_bulk〉 = 1.05 g/cm^3, but 〈ρ〉_PCPS = 0.92 g/cm^3. This difference in density suggests that the intersegmental distance in MCPS or bulk polystyrene is smaller than that in PCPS, even the chains in PCPS are confined to a smaller volume. This might attribute to the fact, namely the intersegmental approaching inside PCPS is mainly the intrachain crossing which is more difficult in comparison with the interchain crossing inside MCPS or bulk polystyrene.     

Coil-globule transition: Self-assembly of a single polymer chain

The coil collapse problem is of interest not only because it represents the simplest model of protein folding, but also because of its fundamental importance as related to polymer nanostructures and fractionation. It is extremely difficult to observe the coil-to-globule transition experimentally because at finite concentrations in a poor solvent, the macromolecules tend to aggregate due to phase separation when the collapsed state is being achieved. In the mid-1980s, two-stage kinetics of a single-chain collapse was proposed theoretically.^1,2 The first successful experimental observation of a two-stage coil-to-globule transition was achieved by quenching a dilute solution of polystyrene (PS) in cyclohexane.³ By using a thinnest capillary tube cell with a wall thickness of 0.01 mm and a diameter of 5 mm for dynamic light scattering, two relaxation times, τ_crum for the crumpled globule state and τ_eq for the compact globule state, were determined⁴ for the first time. The relaxation times were much slower than expected. From the size of the crumpled globule and that of the compact globule and by assuming the intraglobular density to be uniform, the volume fraction of the PS chain in the crumpled globule state, ϕ_crum, and that in the compact globule state, ϕ_comp, can be estimated, with ϕ_crum = 0.02 and ϕ_comp ∼ 0.24-0.4 at 28°C for polystyrene in cyclohexane. The results imply that a single-chain globule contains a large amount of solvent. It should also be noted that ϕ_comp is temperature dependent, i.e., one would have to go to hypothetically low temperatures in order to squeeze out all the solvent (cyclohexane) in the compact PS globule. The single-chain coil collapse state could be achieved under equilibrium conditions by using a high molecular weight, M_w ∼ 1.08 × 10⁷ g/mol; M_w/M_n < 1.06) poly(N-isopropylacrylamide) (PNIPAM) in water,<⁵ even though the ten million molecular weight for PNIPAM was substantially lower than that for polystyrene (M_w ∼ 50 × 10⁶ g/mole).⁶ Under equilibrium conditions, it was feasible to determine both the hydrodynamic radius R_h and the radius of gyration R_g. The ratio of R_g/R_h changed from 1.45 to 0.77, clearly demonstrating the transition from the theta coil state to the compact globule state. At the maximum value of the scaled expansion factor α_s³ |τ| M_w^1/2, R_g/R_h = 1.33 where α_s = R_g/R_g (θ) and τ = |T-θ| / θ with θ being the theta temperature. In the compact globule, R_g/R_h was of the order of 0.7, implying that the PNIPAM compact globule in water still contained ∼80% water, of the same order of magnitude as the PS compact globule in cyclohexane at 7° below its theta temperature (35°C).