It's really a lot more complicated than just thowing polyfill in because you don't want to waste it. I assume you've accepted the premise that a raw speaker (no box) radiates sound from the back as well as the front. So if a speaker is placed in a sealed box, a lot of useful radiation from the speaker is lost inside the cabinet. By placing a vent or port in the cabinet, the acoustic energy from the rear of the speaker is allowed to escape and reinforce the front energy.
If the sound emerges out of phase with the forward radiation, there will be cancellation rather than reinforcement. But the box interior has "capacitance," or the capacity to store the flow of acoustic energy, much the same as an electrical capacitor in an electrical circuit. The box must "fill up" with sound from the back of the speaker before it is released into the port. By the time the rear acoustic energy exits the port, it is in phase with the front-radiated energy, but only between box tuning and about one octave above.
Acoustic energy (sound waves) have difficulty negotiating a small opening, especially through a tube so the capacity of the box to store and delay sound waves is aided by the "inertance" of a tube or duct at the port. By adding the tube with it's inertia effect to the port opening, the box size may be diminished while maintaining the same "filling up" capacity. For various reasons, the port only reinforces low frequencies. In effect, the capacitance and inertance of the box and port tube tend to "filter" out the hight frequencies from exiting the port.
The acoustic capacitance of the box and acoustic inertance of the port tube are variable and therefore become a tunable circuit. Because a speaker moves back and forth, the volume of air inside a box and how easily it exits the port tube has a direct effect on the acoustic resistance seen by the speaker. By controlling the size of the box (acoustic capacitance) and the length and diameter of the port tube (acoustic inertance), we can choose the frequency at which the speaker moves most freely, or it's resonance frequency. By adjusting the variable "capacitance" and "inertance", we control the compliance of air in the box and the mass of air in the port. So the enclosure becomes part of a system, tuned to resonate with the loudspeaker with which it is to work. In fact, one can think of the mass of air as a "piston" or "diaphram of air" which resonates along with the speaker, thereby enhancing output.
If the resonance frequency of the cabinet is tuned closely to that of the loudspeaker, resonant peaks and "boominess" are reduced and smooth tight sounding bass is the result. Futhermore, when the box is tuned to the speaker's free-air resonance (fs), the damping action of the port permits the use of a more highly efficient woofer and also improves the transient response of the bass because of the reduced cone excursion. Increasing the duct length increases the mass of vibrating air which permits lower frequency tuning. Remember that the larger the port area, the longer the duct must be for a given frequency.
Now you've got me rambling on.......... You can half-fill your box with polyfill, and see if you like the extra "boominess" caused by the woofer believing you have increased your box size.