Abstract
ABSTRACT
Resolving internal motion in hyperbranched chains under theta conditions is essential for separating branched connectivity from excluded‐volume screening, yet experimental benchmarks remain scarce. A model hyperbranched polystyrene (h‐PS;
f
= 3) assembled from a narrowly distributed V‐shaped macromonomer was fractionated and examined by static and dynamic light scattering. In toluene at 298.1 K, the selected fraction had
M
w
= 4.35 × 10
7
g/mol, ⟨Rg⟩ = 178 nm, and an apparent low‐angle ⟨Rh⟩ = 149 nm. In dilute cyclopentane from 312.1 to 299.1 K, the low‐angle distributions remained unimodal while apparent ⟨Rh⟩ decreased from 124.4 to 97.9 nm. For
qR
h
> 2,
D
app
/
D
0
scaled as (
qR
h
)
u
with
u
= 0.40–0.44, whereas
Γ
scaled as
q
v
with the algebraically coupled
v
= 2.40–2.44.
Γ
*(
q
) declined over
qR
h
qR
h
≈0.5 and ≈1.0, and their relative integrated area
A
f
/(
A
f
+
A
s
) increased overall with
qR
h
while the temperature series remained intermingled. Thus, the lower high‐q response is consistent with theta‐solvent conditions and branching while intrachain relaxation persists. Together, these analyses distinguish whole‐chain transport from internal relaxation.