Here is some info on CPVC connected to a water heater. Both Gas and Electric.
Nibco actually comes out and says why you need seperation. It is nothing to do with hot water melting any type of plastic. Its about the distance from the flue/draft diverter.
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Some plumbing codes contain detailed
requirements for connections to gas or electric
storage type water heaters. Determine whether
your code has such requirements and satisfy
them.
If no detailed requirements exist, use the
following information. On electric water heaters
CPVC can be piped directly to the heater with
special metal-to-CPVC transition fittings (photo
L). On high-efficiency, gas water heaters that
use plastic vent piping, CPVC can be connected
directly to the heater just like the electric
water heater connections (photo L). On all other
gas water heaters there should be at least 6
inches of clearance between the exhaust flue
and any CPVC piping (photo K). Twelve-inch
long metal nipples or appliance connectors
should be connected directly to the heater so
that the CPVC tubing cannot be damaged by
the build-up of excessive radiant heat from the
flue.
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Here is the PDF document,there is alot of useful information in it. I suggest everyone read it.
http://www.nibco.com/assets/cpvc_manual.pdf