The key to accomplishing this is using a <Pane HBox.hgrow="ALWAYS" /> between the edges to create space (see code below). Enjoy!!
This project has been uploaded to github. For the most recent updates please visit : https://github.com/dtbell99/JavaFXToolbar
FXML Code:
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<?xml version="1.0" encoding="UTF-8"?>
<?import javafx.geometry.*?>
<?import javafx.scene.text.*?>
<?import java.lang.*?>
<?import java.util.*?>
<?import javafx.scene.*?>
<?import javafx.scene.control.*?>
<?import javafx.scene.layout.*?>
<AnchorPane id="AnchorPane" prefHeight="364.0" prefWidth="727.0" xmlns="http://javafx.com/javafx/8" xmlns:fx="http://javafx.com/fxml/1" fx:controller="com.broadlyapplicable.javafxexamples.toolbar.ToolbarExampleController">
<children>
<VBox prefHeight="577.0" prefWidth="727.0" AnchorPane.bottomAnchor="0.0" AnchorPane.leftAnchor="0.0" AnchorPane.rightAnchor="0.0" AnchorPane.topAnchor="0.0">
<children>
<Pane>
<children>
<Label prefHeight="24.0" prefWidth="356.0" text="Left Aligned Buttons (Default)">
<font>
<Font size="19.0" />
</font>
<padding>
<Insets bottom="15.0" left="15.0" right="15.0" top="15.0" />
</padding>
</Label>
</children>
</Pane>
<ToolBar>
<items>
<Button mnemonicParsing="false" text="Left Button 1" />
<Button mnemonicParsing="false" text="Left Button 2" />
</items>
</ToolBar>
<Pane>
<children>
<Label prefHeight="24.0" prefWidth="356.0" text="Center Aligned Buttons">
<font>
<Font size="19.0" />
</font>
<padding>
<Insets bottom="15.0" left="15.0" right="15.0" top="15.0" />
</padding>
</Label>
</children>
</Pane>
<ToolBar>
<items>
<Pane HBox.hgrow="ALWAYS" />
<Button mnemonicParsing="false" text="Center Button 1" />
<Button mnemonicParsing="false" text="Center Button 2" />
<Pane HBox.hgrow="ALWAYS" />
</items>
</ToolBar>
<Pane>
<children>
<Label prefHeight="24.0" prefWidth="356.0" text="Right Aligned Buttons">
<font>
<Font size="19.0" />
</font>
<padding>
<Insets bottom="15.0" left="15.0" right="15.0" top="15.0" />
</padding>
</Label>
</children>
</Pane>
<ToolBar>
<items>
<Pane HBox.hgrow="ALWAYS" />
<Button mnemonicParsing="false" text="Right Button 1" />
<Button mnemonicParsing="false" text="Right Button 2" />
</items>
</ToolBar>
<Pane>
<children>
<Label prefHeight="24.0" prefWidth="356.0" text="Left Center Right Align Buttons">
<font>
<Font size="19.0" />
</font>
<padding>
<Insets bottom="15.0" left="15.0" right="15.0" top="15.0" />
</padding>
</Label>
</children>
</Pane>
<ToolBar>
<items>
<Button mnemonicParsing="false" text="Left Button 1" />
<Button mnemonicParsing="false" text="Left Button 2" />
<Pane HBox.hgrow="ALWAYS" />
<Button mnemonicParsing="false" text="Left Button 1" />
<Button mnemonicParsing="false" text="Left Button 2" />
<Pane HBox.hgrow="ALWAYS" />
<Button mnemonicParsing="false" text="Left Button 1" />
<Button mnemonicParsing="false" text="Left Button 2" />
</items>
</ToolBar>
</children>
</VBox>
</children>
</AnchorPane>