Libyan Desert Glass
Like obsidian, it was knapped and used to make tools during the Pleistocene. (It has a sleek, honey yellow colour.)
From the Wikipedia article:
The glass is nearly pure silica which requires temperatures above 1,600 °C to form – hotter than any igneous rock on Earth. However, few mineral relics survived from whatever caused the melting, including a form of quartz called cristobalite, a rarely occurring high-temperature mineral; and grains of the mineral zircon, although most have reacted to form a higher-temperature mineral called zirconia. Ideas about how the glass formed include melting during meteorite impact, or melting caused by an airburst from an asteroid or other object burning up high in Earth's atmosphere.
Moldavite
From the Wikipedia article:
Moldavites were discovered by prehistoric peoples in the Czech Republic and Austria and were used to make flaked tools. Some of the worked moldavites date to the Aurignacian period of the Upper Paleolithic, approximately 43,000 to 26,000 years before the present.
In the modern world, moldavites are often used, rough or cut, as semi-precious stones in jewelry. They have purported metaphysical qualities and are often used in crystal healing.
The chemical formula of moldavite is SiO2(+Al2O3).
This means it's a silica glass. (It has a gorgeous array of green colours, from forest green, olive green to a unique blue greenish).
If this glass was in high use, and rare (cause, you know, meteors strike Earth everyday.. ;P) AND a highly influential family/group found it.. Glassworking practices may take a step for that world, due to the "prestige" of owning the only (functional) "Glass" Weapons of the planet. Eventually, other deposits would be found on Earth, then other cultures would attempt to copy the glassblowing techniques, either succeeding, failing, or inventing entirely new methods to glassworking.
Would it be useful?
Depends on the technological standards of your world, and WHY certain practices may have been focused on. If a high quality glass based on the above two real life glasses could be worked into a more solid and secure molecular form so that it wasn't as easy to break, chip, or damage after the weapon/tool/item was shaped and created, then possibly.
BUT. How did that happen?
That's the big Sci-Fi question.