METTLER TOLEDO Application M091-08

Hydroxyl Value in Polyols (DIN 53240-2:2007-11)

Method for the determination of the hydroxyl value of polyols.
The method is based on the recommendations of DIN 53240-2, November 2007

Sample 1,1,1-trimethylolpropane Preparation and Procedures

(2-Ethyl-2-(hydroxymethyl)-1,3-
Catalyst solution:
propandiol
10 g 4-N-Dimethylaminopyridine (DMAP) dissolved
in 1L N-Methylpyrrolidone (NMP)
Compound Hydroxyl groups
Acetylation mixture:
100 mL acetic anhydride in 1L N-Methylpyrrolidone

Preparing samples and blanks:

Chemicals Methyl ethyl ketone
1) Weigh 0.2-0.3 g of 1,1,1-trimethylolpropane in
Catalyst solution and
a glass titration beaker. For the blank value the
acetylation mixture:
same procedure is used without sample.
see preparation and procedures
2) Place a magnetic stirrer bar in the beaker, add
Titrant Potassium hydroxide in 30.0 mL catalyst solution and 10.0 mL
methanol acetylation mixture with a dosing unit.
c (KOH) = 0.5 mol/L 3) Cover the titration beaker with a watch glass or
similar. Continue stirring for 15 minutes.
4) Add 3.0 mL deionized water and stir again for
12 minutes.
Standard Benzoic acid 5) Rinse the cover and the walls of the beaker
with methyl ethyl ketone. The solution is now
ready for titration.
Indication DGi113-SC or
DGi116-SC Chemistry:
The acetylation reaction is catalysed by 4-dimethyl
aminopyridine. After completion of the reaction
Chemistry Acetylation: water is added to hydrolyze the excess of the
acetic anhydride. Acetic acid is formed then which
see chemical reaction in the is then back titrated with methanolic KOH solution.
comments section

Calculation Back value (Method m091a):

R2= Q1
B[Back Hydroxyl] = Mean[R2]
Remarks
Hydroxyl Value (Method m091b):
R2 = (B[Back Hydroxyl]-Q)*C/m The hydroxyl value is a reference number used to
C = M/z characterize resin, binders, primary alcohols,
glycols and fats. It is expressed as the amount of
KOH in mg to neutralize the consumed equivalent
amount of acetic acid used for the acetylation of 1 g
Waste Organic waste
of sample.
disposal
Literature:
DIN 53240-2; 2007-11
Author, Claudia Schreiner ISO 4629; 1996 (E)
Version MSG Anachem, March 2009 ASTM D4274-05

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 Instruments T50/T70/T90
XP205 Balance

Accessories 2 additional dosing units

Burettes DV1010
Glass beaker ME-101446
2 Peristaltic pumps (SP250) ME-5110016

Results
Method-ID m091a

Blank determination

1/5 Blank 1
R1 20.335 mmol
2/5 Blank 2
R1 20.307 mmol
3/5 Blank 3
R1 20.343 mmol
4/5 Blank 4
R1 20.358 mmol
5/5 Blank 5
R1 20.360 mmol

Statistics
R1 Blank (Consumption KOH mmol)
Samples 5
Mean 20.341 mmol
s 0.021
srel 0.10 %

Method-ID m091b

1/6 Trimethylolpropane 1/6 0.2601 g

R2 1237.4 g/100g

2/6 Trimethylolpropane 2/6 0.2670 g

R2 1236.2 g/100g

3/6 Trimethylolpropane 3/6 0.2015 g

R2 1231.2 g/100g

4/6 Trimethylolpropane 4/6 0.2383 g

R2 1235.8 g/100g

5/6 Trimethylolpropane 5/6 0.2246 g

R2 1234.4 g/100g

6/6 Trimethylolpropane 6/6 0.2777 g

R2 1245.6 g/100g

Statistics
R1 Hydroxyl value
Samples 5
Mean 1235.0 mg KOH/g
s 2.44
srel 0.2 %

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 Titration curve

Back value Hydroxyl

Sample Trimethylolpropan

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 Table of measured values

Volume Increment Signal Change 1st ٛ erive. Time Temperature

mL mL mV mV mV/mL s °C
0.00 NaN -126.80 NaN NaN 0.00 24.7
11.43 11.43 -52.40 74.40 NaN 34.00 28.2
17.14 5.71 -66.60 -14.20 NaN 42.00 28.6
20.00 2.86 -62.80 3.80 NaN 47.00 28.8
20.20 0.20 -67.80 -5.00 NaN 86.00 28.6
20.40 0.20 -64.80 3.00 1.03 90.00 28.6
20.60 0.20 -66.60 -1.80 -0.20 94.00 28.5
20.80 0.20 -66.60 0.00 -0.88 98.00 28.5
21.00 0.20 -64.40 2.20 1.72 101.00 28.5
21.20 0.20 -66.80 -2.40 -0.01 107.00 28.5
21.40 0.20 -65.50 1.30 0.11 113.00 28.4
32.10 0.10 -133.20 -3.50 -94.15 381.00 27.2
32.30 0.20 -152.30 -19.10 -213.30 385.00 27.2
32.34 0.04 -156.30 -4.00 -291.94 389.00 27.2
32.39 0.06 -171.50 -15.20 -501.47 392.00 27.1
32.41 0.01 -185.90 -14.40 -616.28 400.00 27.1
32.41 0.01 -195.30 -9.40 -719.11 408.00 27.1
32.42 0.01 -197.30 -2.00 -760.07 416.00 27.0
EQP1 32.43 NaN -202.60 NaN -873.05 NaN NaN
32.43 0.01 -203.70 -6.40 -871.87 419.00 27.0
32.44 0.01 -213.10 -9.40 -698.77 424.00 27.0
32.45 0.01 -221.90 -8.80 -681.44 432.00 26.9
32.45 0.01 -226.40 -4.50 -737.14 437.00 26.9
32.47 0.01 -232.60 -6.20 NaN 441.00 26.9
32.49 0.03 -248.00 -15.40 NaN 446.00 26.9
32.50 0.01 -263.40 -15.40 NaN 455.00 26.8
32.51 0.01 -266.40 -3.00 NaN 459.00 26.8
32.52 0.01 -273.80 -7.40 NaN 465.00 26.8

Comments
Acetylation
An excess of acetic anhydride is added for the acetylation of the hydroxyl groups in the polyols.

Hydrolysation
The excess of acetic anhydride which was not used for the reaction is hydrolyzed with water to acetic acid
and titrated with potassium hydroxide solution.

O
O
CH 3
H2O 2 KOH 2 C 2 H 2O
O
H3 C O K
CH 3

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 Method

001 Title 006 Calculation R2

Type General titration Result mmol Consumption KOH
Compatible with T50 / T70 / T90 Result unit mmol
ID m091a Formula R2=Q
Title Hydroxyl Value Back Constant C=1
Author C. Schreiner M M[None]
Date/Time 19.06.2008 13:40:35 z z[None]
Modified at 19.06.2008 13:40:35 Decimal places 3
Modified by schreiner Result limits No
Protect No Record statistics Yes
SOP None Extra statistical func. No
Send to buffer No
002 Sample Condition No
Number of IDs 1
ID 1 Blank 007 End of sample
Entry type Fixed Volume
Volume 40 mL 008 Blank
Density 1.0 g/mL Name Back Hydroxyl
Correction factor 1.0 Value B= Mean[R2]
Temperature 25.0°C Unit mmoL
Entry Arbitrary Limits No
Condition No
003 Titration stand
Type Manual Stand
Titration stand Manual Stand 1

004 Titration (EQP) [1]

Titrant
Titrant KOH
Concentration 0.5 mol/L ----------------------------------------------------------
Sensor
Type mV
Sensor DG113-SC
Unit mV
Temperature acquisition
Temperature acquisition No
Stir
Speed 35% Sample determination
Predispense
Mode Volume
Volume 35 mL
Waiting time 10 s
Control
Control User
Titrant addition Dynamic 001 Title
dE (set value) 8 mV Type General titration
dV (min) 0.005 mL Compatible with T50 / T70 / T90
dV (max) 0.2 mL ID m091b
Mode Equilibrium controlled Title Hydroxyl Value
dE 0.5 mV Author C. Schreiner
dt 1 s Date/Time 19.06.2008 13:41:41
t (min) 3 s Modified at 19.06.2008 13:41:41
t (max) 30 s Modified by schreiner
Evaluation and recognition Protect No
Procedure Standard SOP None
Threshold 500 mV/mL
Tendency Negative 002 Sample
Ranges 0 Number of IDs 1
Add. EQP criteria No ID 1 Trimethylolpropane
Termination Entry type Weight
At Vmax 60 Lower limit 0.0 g
At potential No Upper limit 0.5 g
At slope No Density 1.0 g/mL
After number of Correction factor 1.0
recognized EQPs Yes Temperature 25.0°C
Number of EQPs 1 Entry Arbitrary
Combined termination
criteria No 003 Titration stand
Type Manual Stand
005 Calculation R1 Titration stand Manual Stand 1
Result mL Consumption KOH
Result unit mL 004 Titration (EQP) [1]
Formula R1=VEQ Titrant
Constant C=1 Titrant KOH
M M[None] Concentration 0.5 mol/L
z z[None] Sensor
Decimal places 3 Type mV
Result limits No Sensor DG113-SC
Record statistics Yes Unit mV
Extra statistical func. No Temperature acquisition
Send to buffer No Temperature acquisition No
Condition No Stir
Speed 35%
Predispense
Mode Volume
Volume 20 mL
Waiting time 10 s

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 Control
Control User
Titrant addition Dynamic
dE (set value) 8 mV
dV (min) 0.005 mL
dV (max) 0.2 mL
Mode Equilibrium controlled
dE 0.5 mV
dt 1 s
t (min) 3 s
t (max) 30 s
Evaluation and recognition
Procedure Standard
Threshold 500 mV/mL
Tendency Negative
Ranges 0
Add. EQP criteria No
Termination
At Vmax 60
At potential No
At slope No
After number of
recognized EQPs Yes
Number of EQPs 1
Combined termination
criteria No

005 Calculation R1
Result mL Consumption KOH
Result unit mL
Formula R1=VEQ
Constant C=1
M M[None]
z z[None]
Decimal places 3
Result limits No
Record statistics Yes
Extra statistical func. No
Send to buffer No
Condition No

006 Calculation R2
Result mg KOH / g
Result unit mg KOH / g
Formula R2=(B[Back Hydroxyl]-Q)*C/m
Constant C=M/z
M M[Potassium hydroxide]
z z[Potassium hydroxide]
Decimal places 3
Result limits No
Record statistics Yes
Extra statistical func. No
Send to buffer No
Condition No

007 End of sample

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