I use Windows Live Mail to receive emails but because our ISP is not TalkTalk it won't allow outgoing emails from my account and I have to use their webmail to send out. I can do both no problem using Gmail on my phone (although cannot access Inbox subfolders even though can send email there) but much prefer the Outlooky feel of Live Mail on my desktop;
is there a way round it? we are with BT as ISP and I don't want to change my talktalk / tiscali personal email
Short answer no you can't.
The bit after the @ in your email address is the domain name part of the email address and if its TalkTalk then then when people try and send you an email the sending computer will look up the DNS MX record for talktalk.com (if your email is someone@talktalk.com) and get given the ip address of a talktalk mail server and send the email there. To read your email you either use the TalkTalk web email client or access it from a desktop client etc vi imap or pop3. TalkTalk are totally within their rights to restrict any of these access methods to IP addresses on their own network and since you arent with TalkTalk anymore .... In practice they usually allow access to the Web Based front end from anywhere due to people needing access from mobile phones whilst roaming or on other peoples WiFi.
When sending email it needs to go via the domains email server or it will be rejected by the receiving email server (or should be) to avoid people just spamming with email from that domain. ISPs usually prevent you from sending mail via their Email servers unless you are on their network.
Since you aren't paying TalkTalk for any service you dont really have any right or expectation to use their email service.
If you want email that's independent of ISP then you need either to run your own email server and buy your own domain or use an independent email service such as Google or Fastmail (my preferred option).