$re = '/^([^,]*),|,(?=[^,]*$)/m';
$str = '101, "Name1", "Designation1", "blah1", "Blah1", 20200914001
102, "Name2", "Designation2", "blah2", "Blah2", 20200914002
103, "Name3", "Designation3", "blah3", "Blah3", 20200914003
104, "Name4", "Designation4", "blah4", "Blah4", 20200914004
105, "Name5", "Designation5", "blah5", "Blah5", 20200914005';
$subst = "\1||";
$result = preg_replace($re, $subst, $str);
echo "The result of the substitution is ".$result;
Please keep in mind that these code samples are automatically generated and are not guaranteed to work. If you find any syntax errors, feel free to submit a bug report. For a full regex reference for PHP, please visit: http://php.net/manual/en/ref.pcre.php