As a quick after thought, you *may* need to access the product ID to get the data from the field, if so, try:
add_action( 'woocommerce_before_add_to_cart_form', 'my_pdf_field' );
function my_pdf_field() {
global $product;
$product_id = $product->get_id();
$pdf = get_field( 'pdf', $product_id );
#if we have data, show it
if( $pdf ){
echo '<a href="'.$pdf['url'].'">link</a>';
}
}