Here is what I did recently in PHP on one of my bigger systems:
User inputs newsletter text and selects the recipients (which generates a query to retrieve the email addresses for later).
Add the newsletter text and recipients query to a row in mysql table called *email_queue*
I created another script, which runs every minute as a cron job. It uses the SwiftMailer class. This script simply:
during business hours, sends all email with priority == 0
after hours, send other emails by priority
Depending on the hosts settings, I can now have it throttle using standard swiftmailers plugins like antiflood and throttle...
$mailer->registerPlugin(new Swift_Plugins_AntiFloodPlugin(50, 30));
and
$mailer->registerPlugin(new Swift_Plugins_ThrottlerPlugin( 100, Swift_Plugins_ThrottlerPlugin::MESSAGES_PER_MINUTE ));
etc, etc..
I have expanded it way beyond this pseudocode, with attachments, and many other configurable settings, but it works very well as long as your server is setup correctly to send email. (Probably wont work on shared hosting, but in theory it should...) Swiftmailer even has a setting
$message->setReturnPath
Which I now use to track bounces...
Happy Trails! (Happy Emails?)