Appendix D:

Procedures for acid and hydroxyl number

determination

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 Appendix D

D1 Acid Number Titrations

Procedure is adapted from ASTM D4662: Standard Methods for Polyurethane
Raw Materials: Determination of Acid and Alkalinity Number of Polyols, 2003. A
sample of poly(lactic acid) (PLA) oligomer (3 to 6 g) and phenolphthalein indicator
(~0.05 g) were dissolved in dichloromethane or tetrahydrofuran (20-30 mL). These
samples were titrated with 0.5 mol L -1 KOH solution in denatured ethanol. Purple
colour persisted for at least 15 seconds was taken as the end point. The acid number
was then calculated using:

(D1)

where:
AN = acid number, mg of KOH required to neutralise 1 g of sample (mg g-1)
V1 = volume of KOH solution required to neutralise sample solution (mL)
V2 = volume of KOH solution required to neutralise a blank solution (mL)
C = concentration of KOH (mol mL-1)
56.1g mol-1 is the molecular weight (MW) of KOH
m = mass of sample (g)

Titrations were repeated three times for each oligomer. Acid titrations were
also used to determCine the acid content of lactic acid (LA) solutions and pre-dried LA.
The first step was to ensure the commercial LA solution (~10 g) or pre-dried LA (~5 g)
is only present in its monomeric form. To do this a sample of LA solution was
dissolved in deionised water (~200 mL) and heated to a gentle reflux for 24 hours.
After reflux the apparatus was washed with deionised water (~40 mL). From this stock
solution were taken three aliquots of ~20 mL. All of these aliquots were titrated
individually via a 0.5 mol L -1 NaOH hydroxide solution in water to the purple endpoint.
The % of LA in the sample was calculated using:

(D2)

where:
wt%LA = weight percentage of lactic acid
V = volume of NaOH solution required to neutralise sample solution (mL)
C = Concentration of NaOH (mol mL-1)
90.08 g mol-1 is the MW of LA.
m = mass of the aliquot (g)

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 Appendix D

p = percentage of LA solution in the stock solution

Titrations were done for two different batches of L-LA solution, a batch of L-
LA which had been dried and DL-LA solution. Results of these titrations are shown in
table D1.

Table D1 - Acid content in LA solutions.

D2 Hydroxyl number titrations

Hydroxyl number titrations of poly(tetramethylene) PTMO oligomers were
conducted using a modified version of the procedure proposed in ASTM D4662:
Standard Test Methods for Testing Polyurethane Raw Materials, Determination of
Hydroxyl Numbers in Polyols, 1999. An outline of the chemistry involved in this
procedure is shown in figure B1. The day before the analysis a 500 mL phthalic
anhydride stock solution was made up containing phthalic anhydride (83.0 g, 0.560
mmol, 1.12 mol L-1) in pyridine. Samples solutions were prepared by adding together
the oligomer (3-13 g, higher weight for higher MW oligomer), phthalic anhydride stock
solution (10.0 mL) and pyridine (30 mL). This process converted hydroxyl groups to
terminal phthalic acid. Blank solutions were also produced by refluxing phthalic
anhydride stock solution (10.0 mL) and pyridine (30 mL) without oligomer. After one
hour refluxing at 115 °C these solutions were allowed to cool to room temperature and
titrated with aqueous sodium hydroxide (0.516 M). Phenolphthalein (~0.05 g) was used
as an indicator. Any free phthalic anhydride produces two acid groups upon a reaction
with water. The hydroxyl number was calculated using:

(D3)

Where:
HN = hydroxyl number, mg of KOH required to neutralise the acid formed
from 1g of sample (mg g-1)
V1 = volume of NaOH solution required to neutralise sample solution (mL)

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 Appendix D

V2 = volume of NaOH solution required to neutralise a blank solution (mL)

C = concentration of NaOH (mol mL-1)
m = mass of sample (g)

O O
pyridine, O O
ref lux R
R OH + O O OH + O

O (excess) O

H 2O/NaOH (cat.)
1 equiv. NaOH
O O

HO OH
O O
R
O O- Na+
2 equiv. NaOH

O O

Na+ -O O - Na+

Figure D1 - Chemical reactions occurring during the hydroxyl number titration

of oligomers.

Note that HN is defined in terms of mg KOH hence 56.1 g mol -1 (formula

weight of KOH). These titrations allow the MW of the PTMO to be calculated using:

(D4)

The factor of 2 in the equation accounts for the hydroxyl functionality of the
PTMO. The results of hydroxyl number titrations are shown in table D2. This
technique was ineffective for PLA oligomers as these conditions caused hydrolysis of
the PLA.

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 Appendix D

Table D2 - Hydroxyl numbers for PTMO oligomers.

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