Hydroxyl Number 3251s

LUBRIZOL TEST PROCEDURE TP-AATM-111A-02 Edition: October 17, 2006 Previous Edition: May 1, 2000

Hydroxyl Value DEFINITION

DESCRIPTION OF METHOD

This method determines the number of hydroxyl groups present which can be acetylated under the conditions of this test.

APPARATUS

Hydroxyl value (or acetyl value) is defined as the number of milligrams of potassium hydroxide necessary to neutralize the acetic acid which combines on acetylation of 1 gram of sample. SCOPE

1. 2. 3. 4. 5. 6.

This method is applicable to Lubrizol Advanced Materials products with the following exceptions: 1. Samples which contain hindered (secondary or tertiary) hydroxyl groups will give low values because there will be incomplete reaction under these conditions. An alternate method (Lubrizol Test Procedure TP-AATM-111C-02) should be used in these cases. 2. Significant amounts of water interfere with the analysis by hydrolyzing the reagent before the acetylation reaction can take place. Samples which contain amounts of water in excess of 5% may be dried under vacuum prior to analysis. Excess acetic anhydride is required to drive the reaction to completion. Therefore special attention must be paid to the ratio of sample size to reagent as set forth in the table shown in the procedure.

7. 8.

250 ml ground neck Erlenmeyer flask. Controlled oil bath regulated to maintain the temperature at 95-100°C. Cooling water bath. Class A volumetric pipette calibrated to deliver 5 (±0.03) ml. Balance capable of weighing to the nearest 0.1 mg. Burette (50 ml) Class A with a tolerance of ±0.05 ml. Assorted Mohr pipettes, graduated cylinders, droppers. Magnetic stirrer, stirring bars.

REAGENTS The acetic anhydride and pyridine used should be pure and dry (analytical reagent grade) and have as little color as possible. 1.

2.

3. 4. 5. 6.

Acetic anhydride -pyridine reagent - 1 volume Acetic Anhydride plus 4 volumes pyridine Reagent 1 (Note: greater dilution than AOAC to keep titration < 50 ml as specified) Neutralized Ethanol - neutralize Reagent Ethanol to a faint Phenolphthalein pink color with 0.1N Methanolic Potassium Hydroxide Methanolic potassium hydroxide 0.5N commercially available Phenolphthalein Indicator - commercially available Deionized Water Pyridine, reagent grade

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Lubrizol Test Procedure TP-AATM-111A-02 Hydroxyl Value Page 2 of 2 PROCEDURE All blanks and samples are to be run in duplicate. In-Process samples are to be run in triplicate.

1. Accurately weigh the specified amount of sample into a 250 ml Erlenmeyer flask according to the following table and record weight to the nearest 0.1 mg. Sample Hydroxyl value 0 -20 20 - 50** 50 - 100 100 - 200 200 - 250 250 - 300 300 - 350 350 - 450 450 - 600 600 - 700

ml Size 10g (±0.1) 5g (±0.1) 3g (±0.1) 2g (±0.05) 1g (±0.05) 0.5g (±0.05) 0.5g (±0.05) 0.5g (±0.05) 0.5g (±0.05) 0.5g (±0.05)

Reagent 1 5 + 5 ml pyridine* 5 5 5 5 5 5 5 5 5

* the 5 ml pyridine is added only for samples with Value of 0 - 20 ** for DOE-120 use 5 g Exceptions: Vilvanolin CAB, Vilvanolin LFA LO, Vilvanolin P, Modulan, MP-142: use 2 g

7. Return the flasks to the oil bath for 10 minutes to complete the hydrolysis of the excess acetic anhydride reagent. Swirl at frequent intervals. 8. Cool in the water bath to room temperature for at least ten minutes. 9. To each flask, add a stirring bar and add by cylinder 25 ml neutralized alcohol (around half through the air condenser), remove the condenser and use the rest to wash down the sides of the flask. Using a dropper, add 1 ml of phenolphthalein solution. 10. Fill burette and titrate the samples and the blanks using methanolic potassium hydroxide to a faint pink color. Stir thoroughly during the titration. Read the burette to two decimal places. 11. In the case of samples which are solid at room temperature place in the ultrasonic bath until the pink color remains. At that point the flask may be heated under hot water to release any remaining occluded traces of acid and the titration may be completed. NOTE: Early application of heat during the titration may drive off some of the acetic acid and an incorrect titration will result. 12. Determine the acid value of the sample (Lubrizol Test Procedure TP-AATM-109-01). CALCULATIONS Hydroxyl value = (ml KOH blank - ml KOH sample) X N KOH X 56.1 + Acid Value g sample

2. Into each flask, using Class A volumetric pipette, accurately pipette the specified amount of acetic anhydride- pyridine reagent and attach an air condenser. At the same time set up reagent blanks, containing no sample but the corresponding volume of reagent. 3. Place the flasks in the 95-100°C oil bath, immersing to the liquid level. Swirl vigorously until all the solid material is melted and is thoroughly mixed into the solution. 4. Continue heating at 95-100°C for one hour, swirling the flasks frequently to insure uniform reaction. 5. Remove the flasks from the oil bath and cool for at least ten minutes in a room temperature shallow water bath. 6. To each flask, add by Mohr pipette through the air condenser 10 ml of water. Swirl vigorously to mix thoroughly.

REFERENCE AOAC Method 965.32 First Action 1965, Final Action 19