Characterization of Phenol-Formaldehyde Prepolymer Resins by in Line FT-IR Spectros
Characterization of Phenol-Formaldehyde Prepolymer Resins by in Line FT-IR Spectros
Characterization of Phenol-Formaldehyde Prepolymer Resins by in Line FT-IR Spectros
Abstract
Different resol phenol-formaldehyde prepolymer resins have been synthesized with different formaldehyde / phenol
ratios. The phenolic resin composition depends on monomer ratio, catalyst, reaction conditions, and residual
free monomers. Temperature and pH conditions under which reactions of phenols with formaldehyde are carried
out have a profound effect on the characteristics of the resulting products. Three reaction sequences must be
considered: formaldehyde addition to phenol, chain growth or prepolymer formation and finally the crosslinking
or curing reaction. Two prepolymer types are obtained depending on pH, novolacs in an acidic pH region whereas
resols by alkaline reaction. Resol resins are synthesized with a molar excess of formaldehyde (1<F/P<3). These
are mono- or polynuclear hydroxymethylphenols which are stable at room temperatures, but are transformed
into three dimensional, cross linked, insoluble and infusible polymers by the application of heat.
An ATR-FTIR spectrometry technique (ReactIR 4000) with light conduit and diamond-composite sensor was
used to perform in-line monitoring of phenol-formaldehyde prepolymer synthesis. This technique was found to
be ideal for determining residual free phenol and formaldehyde, individual phenol and formaldehyde conversions
and prepolymer composition changes as a function of time when the condensation reaction was carried out.
The kinetics data obtained through the ReactIR 4000 in-line reaction analysis system agreed well with those
determined by the traditional titration method. ReactIR technology replaces time consuming and inaccurate
off-line methodology.
Table 1. Reaction conditions of phenol-formaldehyde resin synthesis, concentrations of phenol and formaldehyde at t=0 and free
formaldehyde in the resin at the end of reaction synthesis.
Synthesis Molar ratio Phenol:Formaldehyde CA0 Phenol mol/L CA0 Form. mol/L T*, °C t, h pH % Free Form.
Synthesis 1 1:1.6 4.05 6.22 61,5 3 8 3.35%
Synthesis 2 1:1.8 3.78 6.58 55 3 8 2.32%
Synthesis 3 1:1.8 3.78 6.58 21,3 3 7 8.86%
Synthesis 4 1:1.8 3.78 6.58 62 3 8 2.77%
Synthesis 5 1:1.9 3.68 6.5 65 3 8 5.77%
Synthesis 6 1:2 3.57 6.90 70 3 8 3.75%
* Temperature at which we started to collect mid FTIR spectra of the condensation components.
resins synthesis. Different resol prepolymer resins composite) insertion probe was used to collect mid-
have been synthesized with different F/P ratios. An FTIR spectra of the condensation components. IR
important structural factor determined quantitatively spectra were collected every three minutes in the
for resol prepolymer resins is the F/P ratio after the wavenumber range between 4000 and 650 cm–1 at
reaction. In order to evaluate the ability of the ATR- resolution 8 cm–1. These spectra were used to calculate
FTIR spectroscopic method, the kinetic data obtained the amounts of free phenol and free formaldehyde
through the IR in-line analysis were compared to results and to some extent the PF resin composition. At the
from the traditional titration method.14 end of the synthesis the traditional titration method
for determining free formaldehyde was carried out as
well as residual phenol content was determined by gas
Experimental chromatography. 15
Materials
Phenol (99+ %), 37% formaldehyde aqueous Results and discussion
solution and sodium hydroxide (98%) were used. All
the chemicals were supplied by Aldrich. ATR-FTIR spectrometry was utilized to monitor
the condensation reaction in real time. In-line
Resin synthesis data acquisition was performed by immersing the
Different resol prepolymer resins (Table 1) were transmission probe directly into the reactor. Assignment
prepared with the same amount of catalyst (NaOH) but of the characteristic peaks of phenol and formaldehyde
with different F/P ratios: R1, R2, R3 and R4 with F/P was done using the previously collected spectra of both
ratios of 1.6, 1.8, 1.9 and 2.0, respectively. PF resin was reactants in aqueous solution. The spectra of phenol and
synthesized in a 500 ml batch reactor fitted with a reflux formaldehyde solutions are presented in Figure 1 and
condenser, a mechanical stirrer, a digital thermometer collected in Table 2. The assignment of characteristic
and an IR probe. Several batch condensations of phenol peaks was done on the basis of relevant literature.16,17 In
and formaldehyde were conducted at 90 °C. Reaction Figure 1 a typical IR spectrum of a phenol-formaldehyde
vessels were heated to the same reaction temperature. resin (synthesis 2) is also represented.
The recipes used are shown in Table 1.
All resins were prepared by reacting the required
amounts of phenol (80% solution in water) with varying
amounts of formaldehyde (37% solution in water,
Merck) in the presence of the catalyst. The resulting
reaction mixture was stirred and heated to 90–95 °C
until the mixture became cloudy. Afterwards, the resin
is used as it is or it is neutralized. In the first set of
experiments the reproducibility of the resin synthesis
was investigated to determine the amounts of free
phenol and free formaldehyde.
FTIR spectroscopy Figure 1. FTIR specta at the wavelengths in the range of interest
A ReactIRTM 4000 reaction analysis system for phenol, formaldehyde and phenol-formaldehyde resin type
equipped with a light conduit and DiComp (diamond resol (synthesis 2, no.61).
Table 2. Functional groups and observed wavenumbers for Table 3. Functional groups and observed wavenumbers for
phenol and formaldehyde and their literature values. phenol-formaldehyde resin type resol and their literature values.
Literature data Observed Literature data Observed
of wavenumber, wavenumber, Functional group of wavenumber, wavenumber, Functional group
cm–1 cm–1 cm–1 cm–1
Phenol 3400 3389 OH
3400 3308 OH stretch 2925 in phase stretching vibration
2953
/ 3026 CH unsaturated stretch of -CH2- alkane
1605 1594 C = C aromatic ring 2850 out of phase stretching
2895
vibration of -CH2- alkane
1510 1498 C = C aromatic ring
1633 C = C aromatic ring
1485 1475 C = C aromatic ring
1610 1610* C = C aromatic ring
1380 1370 OH in-plane bend
1517 1552 C = C aromatic ring
1240 1224 C-C-O asymmetric stretch
1504 1513 C = C aromatic ring
1180 1170 CH aromatic, in-plane
1480 1478 C-H aliphatic
1160 1153 C-O stretch
1460 / -CH2- deformaton vibration
1060 1073 single bond C-O stretching
vibrations of -C-OH group 1450 C = C benzene ring obscured
1451*
by -CH2- methylene bridge
1020 1023 -C-OH
1390 1370 OH in plane
990 999.7 -C-H
1378
880 887.8 -C-H
1237 asymmetric stretch of
800 810.6 asymmetric stretch of 1235
phenolic C-C-OH
phenolic C-C-OH
1153 1154 C-O stretch
747 748.8 CH aromatic, out-of-plane
1100 asymmetric stretching
680 690.9 ring bend
1116 vibration of C – O-C
aliphatic ether
Formaldehyde 1045 single bond C-O stretching
1058*
3400 3350 OH stretch vibrations of -CH2OH group
2822 2980 CH stretch, general 1000 1019 aliphatic hydroxyl
2724 2914 CH bend overtone 976 1,2,4-substituted benzene
976*
1722 1644* C = O stretch (overlapped ring
with OH scissors of water) 885 887.8 CH out-of-plane, isolated H
1390 1447 C-H bend 835 CH out-of-plane, para-
826
/ 1158 C-O stretch substituted
/ 1108 -C-OH 760 CH out of plane, ortho-
756.6
/ 1023 -C-OH substituted
/ 992 C-H 694 694.8 adjacent 5H
/ 911 *observed IR spectral frequencies of 2,4,6-trihydroxymethyl
/ 671 phenol
Characteristic absorbances of the phenolic resin peaks at 1594 and 1498 cm–1 corresponded to the C=C
are assigned in Table 3 using the literature.18,19,20 These aromatic ring vibrations. The peaks at 1224 and 1170
signals were helpful in identifying the components of cm–1 corresponded to the C-C-O asymmetric stretch and
the condensation reaction of phenol and formaldehyde. C-H in plane deformations, respectively, while the 999.7,
We do have to emphasize that the literature assigned and 748.8 cm–1 peaks belonged to the C-H out of plane
absorption bands to the various chemical groups did vibrations. The peak at 1370 cm–1 which corresponded
vary, as might have been expected.19 to the phenol O-H in plane bend (Figures 1 and 2)
The normalized phenol-formaldehyde resin was also detected for phenol-formaldehyde resin. The
spectra at the wavelengths in the range of interest for width of the band at 1370 cm–1 indicates it is due to an
the PF resin synthesis are shown in Figure 2. The spectra O-H rather than C-H or C-C bond. The formaldehyde
were recorded at a resolution of 8 cm–1 with 128 scans for aqueous solution was added into the reactor at the
each spectrum. The reaction mixture spectra of PF resin beginning of the process, therefore the characteristic
run were collected every 3 minutes for a total of 180 peaks of methylene glycol C-O, O-H, and C-H bends
minutes at wavenumbers from 4000–650 cm–1. As shown at 1108 cm–1, 1023 cm–1, and 992 cm–1 were observed in
in Figure 2, the characteristic peaks of phenol at 1594, the first spectrum, respectively (Figure 2, Table 2). After
1498, 1224, 1170, 999.7, and 748.8 cm–1 diminished with the reactor content heated to preferred temperature a
increasing reaction time, while the absorbance band of sharp decrease of phenol and formaldehyde peaks was
hydroxymethyl and methylene groups increased. The observed as a result of the reaction.
The concentration profiles for phenol in the Figure 5. Concentration profile of formaldehyde in the syn-
synthesis of phenol-formaldehyde resin at different thesis of phenol-formaldehyde resin at different molar ratios
formaldehyde : phenol.
molar ratios formaldehyde : phenol agreed with the well
known theory that in the synthesis of PF resin the pH
value of the reaction mixture has a great influence as The concentration profiles for hydroxymethyl-
well as the temperature. For the synthesis of PF resin at phenols and for methylene bridges are shown in Figures
pH=7 the decrease of phenol is lower regarding to the 6 and 7, respectively. The profiles were generated by the
synthesis of PF resin at pH=8. At higher temperatures use of Conc IRTTM Opus I software. The concentration
the consumption of phenol is higher. profiles of hydroxymethylphenols in the synthesis of PF
The weight % of free formaldehyde in the synthesis resins for different molar ratios of F/P are shown in
3 and 5 are higher due to the lower temperature and Figure 6. The reaction rate of hydroxymethylphenols
lower pH value of the reaction mixture. The influence of increased with the increasing ratio between F/P. The
the pH value of the reaction mixture prevailed over the maximum of hydroxymethylphenol concentration was
influence of the reaction temperature. The lower rate of reached in 38 minutes for the molar ratio of 2/1 and
consumption of formaldehyde in the synthesis 5 (1 : 1.9) in 48 minutes for the molar ratio of 1.8/1 and then
can be ascribed to the lower pH value of the reaction started to decrease due to the formation of methylene
mixture due to the higher amount of formaldehyde at and methylene-ether bridges. For the synthesis 3 with
the start of the reaction and on the other hand due to the molar ratio of 1.8/1 it is obvious that the reaction
the lower starting temperature. The concentration of rate of hydroxymethylphenol is actually the same but
formaldehyde (Figure 5) in the synthesis of PF resin the reaction temperature was too low for the formation
with the F/P ratio 2/1 decreased for 35 minutes, when of methylene or methylene-ether bridges. The PF
it reached the minimum and started to increase due to resin synthesized under the conditions mentioned was
the formation of methylene bridges from the methylene- soluble in water which corresponds to the PF resins
ether bridges. In this reaction free formaldehyde is with a high concentration of hydroxymethyl groups. The
a side product. In order to observe the influence of polymerization of hydroxymethyl phenols was hindered
pH on the synthesis of PF resins the reaction was by lower pH values while the influence of lower starting
proceeded at pH=7 and pH=8. From the Figure 5 it temperatures was not so significant.
can be observed that the concentration of formaldehyde The concentration profiles of methylene bridges
for the reaction condition of pH=7 slowly decreased, in the synthesis of PF resins with different molar
regarding to the concentration of formaldehyde for the ratio between F/P are represented in Figure 7. The
synthesis at pH=8. The concentration of the catalyst is end concentration of methylene bridges increased as
very important for the reaction rate. For the synthesis the molar ratio between formaldehyde and phenol
of PF resin with a molar ratio of 1.8/1 at pH=8 the increased. The concentration of methylene bridges is
concentration of free formaldehyde decreased from the lowest in synthesis 3 with the molar ratio of 1.8/1
6.58 mol/L to 1.74 mol/L after the first hour and at because the temperature and pH value of the reaction
the end of the experiment the concentration of free mixture were too low.
Figure 6. Concentration profiles of hydroxymethylphenols in the Figure 7. Concentration profiles of methylene briges in the
synthesis of PF resins: synthesis 3 (molar ratio 1 : 1.8, pH=7); synthesis of PF resins: synthesis 6 (molar ratio 2 : 1); synthesis
synthesis 4 (molar ratio 1 : 1.8, pH=8); synthesis 6 (molar ratio 1 : 2). 2 (molar ratio 1.8 : 1);synthesis 3 (molar ratio 1.8 : 1, pH=7);
synthesis 1 (molar ratio 1.6:1).
Povzetek
Sintetizirali smo različne fenol-formaldehidne prepolimere s spreminjanjem razmerja med formaldehidom in
fenolom. Sestava fenolne smole je odvisna od začetnega razmerja monomerov, vrste katalizatorja, reakcijskih
pogojev in koncentracije prostih monomerov na koncu reakcije. Pomemben vpliv na značilnosti sintetizirane
smole imata tudi temperatura in pH vrednost pod katerimi poteka reakcija fenola s formaldehidom. Upoštevati
moramo tri zaporedne reakcije : adicijo formaldehida na fenol, rast verige ali tvorbo prepolimera in končno
zamreževanje ali reakcijo utrjevanja. Glede na pH vrednost dobimo dve vrsti prepolimera, novolak v kislem
območju pH vrednosti, medtem ko dobimo rezol pod alkalnimi reakcijskimi pogoji. Rezolno smolo sintetiziramo
z molarnim prebitkom formaldehida (1<F/P<3). Produkti so mono - ali poli - jedrski hidroksimetil fenoli, ki
so stabilni pri sobni temperaturi, vendar se pri povišani temperaturi zamrežijo v tridimenzionalen, netopen in
netaljiv polimer.
Potek sinteze fenol - formaldehidnega prepolimera smo spremljali s pomočjo "in-line" ATR-FTIR spektroskopske
analitske tehnike (ReactIR 4000), ki je opremljena z optičnim vodnikom in diamantnim kompozitnim senzorjem.
Ta tehnika se je izkazala kot idealna za določanje prostega fenola in formaldehida, kot tudi njunih konverzij,
prav tako pa tudi sprememb v sestavi prepolimera v odvisnosti od reakcijskega časa kondenzacije. Kinetični
podatki, ki smo jih dobili s pomočjo ReactIR 4000 "in-line" reakcijskega analiznega sistema se dobro ujemajo s
podatki določenimi s tradicionalnimi titracijskimi metodami. ReactIR tehnologija nadomešča časovno potratno
in nenatančno "off-line" metodologijo.