5.

Practice of step growth polymerization

44

5.1.6.

Preparation of a Phenol-Formaldehyde Resin and Fabrication of a Moulding

OH OH

OH

+
H

C O

OH

OH

a) Preparation of the Novolak: Reagents:

phenol 37% aqueous formaldehyde solution oxalic acid water three necked flask, 250 ml mechanical stirrer, reflux condenser oil bath, Mini Claisen still head

65 g (0.69 mol) 46 g (0.57 mol) 1g 7.5 ml

Equipment:

Procedure:

Phenol, the formaldehyde solution and oxalic acid are placed into the flask and heated under reflux for 1.5 h. 150 ml of water are added, stirred briefly and allowed to cool, in the course of which the condensation polymer settles out. The aqueous layer is separated and the residual water distilled off at 50-100 torr while slowly raising the temperature to 150C.This temperature is maintained (at most for 1 h) until test samples solidify on cooling. The resin is poured out while still warm and solidifies to a colourless, brittle mass, soluble in alcohol.
b) Fabrication of a moulding: Reagents:

novolak sawdust hexamethylenetetramine magnesium oxide magnesium stearate

12.5 g 12.5 g 1.75 g 0.5 g 0.25 g

5. Practice of step growth polymerization

Procedure:

45

The finely ground novolak, dry sawdust, hexamethylene tetramine, magnesium oxide (to trap residual acid from the condensation) and magnesium stearate (as lubricant) are thoroughly mixed in a ball mill and then heated in a mould at 140 bar for 5 min at 160C. The resulting moulding is infusible and insoluble.
c) Preparation of a cation exchanger by sulfonation of the novolak Reagents:

novolak 20 g 95% sulfuric acid 60 g 37% aqueous formaldehyde solution 18.5 ml round-bottomed flask, 250 ml oil bath, reflux condenser porcelain dish

Equipment:

The novolak is gradually warmed to 140C in the acid till its completely dissolved. The solution is cooled to room temperature, poured into the porcelain dish and the formaldehyde solution is stirred in with a spatula as quickly as possible. The dish is placed in an oven and heated to 110C for 2 h. The cooled product is washed with water, broken up with a hammer and ground by means of a mortar. The particles are then washed with water until the washings are clear.
d) Determination of the ion-exchange capacity

The sulfonated polymer is washed into a chromatographic column and 100 ml of 2 M NaCl solution are allowed to run through, followed by 100 ml of 2 M HCl. Finally the column is washed with distilled water, the runnings being collected in 10 ml portions and titrated with 0.1 M NaOH using phenolphthalein as indicator. When the concentration has fallen below 0.001 M the washing is stopped. The water remaining in the column is allowed to run off and the damp ion exchanger is poured into a beaker. Three samples, each of 2 g are weighed into tared 100 ml conical flasks as quickly as possible. One is heated to constant weight in an oven at 110C in order to determine the water content of the sample. 50 ml of 0.1 M NaOH are added to each of the other two flasks and vigorously shaken. After 30 min the mixtures are filtered, the resin washed with a little water and the filtrates back-titrated with 0.1 M HCl. The ion-exchange capacity is expressed in milliequivalents per g of dry exchanger.
Analysis:Yield (Novolak, sulfonated) [g]; water content [%]; exchange capacity [mVal/g]