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Syntheses and properties of low‐level melamine‐modified urea–melamine–

formaldehyde resins

Article in Journal of Applied Polymer Science · July 2004

DOI: 10.1002/app.20778

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Syntheses and Properties of Low-Level Melamine-Modified
Urea–Melamine–Formaldehyde Resins

B. Young No, Moon G. Kim

Department of Forest Products, College of Forest Resources, Mississippi State University, Mississippi State,
Mississippi 39762-9820

Received 5 January 2004; accepted 19 March 2004

DOI 10.1002/app.20778
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Syntheses of urea–melamine–formaldehyde lymerization. The overpolymerization of MF components

(UMF) resins were studied using 2–12% melamine levels resulted in increasingly more opaque resins, with viscosity
and UF base resins that were preadvanced to various differ- remaining stable for more than a month. As the preadvance-
ent extents. The melamine reaction was carried out at pH 6.3 ment of UF base resin was increased, the extent of advance-
with F/(U ⫹ M) mole ratio of 2.1 until a target viscosity of ment of MF components decreased, to give clearer resins,
V was reached (Gardener–Holdt) and then the second urea with viscosity slowly increasing at room temperature. Over-
added at pH 8.0 to give a final F/(U ⫹ M) mole ratio of 1.15. all, preadvancing the UF base resin components to an ap-
Analyses with 13C-NMR and viscosity measurements propriate extent was found to be a key to synthesizing
showed that MF components react fast and the UF compo- various low-level melamine-modified UMF resins. © 2004
nents very slowly in the melamine reaction. Therefore, as the Wiley Periodicals, Inc. J Appl Polym Sci 93: 2559 –2569, 2004
extent of preadvancement of UF base resin was decreased,
the reaction time to reach the target viscosity became longer Key words: polycondensation; resins; thermosets; 13C-NMR
and the MF resin components showed high degrees of po- spectra of UMF resins; synthesis

INTRODUCTION urea–melamine–formaldehyde (UMF) resins have

1– 8 been claimed to enhance the water resistance and
Urea–formaldehyde (UF) resins (Fig. 1) are the ma-
physical strength and also reduce the formaldehyde
jor binders for interior-grade wood composite boards,
emission of boards.15–21 However, as will be described
such as particleboard, medium density fiberboard,
below, past research results on UMF resins failed to
and hardwood plywood,9 and the drawbacks are low
show a positive relationship, apparently because of
water resistance and emission of formaldehyde from
the wood composite boards.10 –13 The overall formal- the varying resin synthesis procedures used without
dehyde/urea (F/U) mole ratio used in manufacturing recognizing the different chemistries for urea and mel-
of UF resins, currently at a low value of about 1.15, has amine components. Current commercial melamine–
been the key parameter used to lower the formalde- urea–formaldehyde (MUF) resins, which are quite dif-
hyde emission. Lowering the F/U mole ratio would ferent from UMF resins, are normally synthesized
further decrease the formaldehyde emission but the with far higher levels of melamine (⬎50%), and used
bond strength and water resistance of boards would in different wood-bonding applications.14
also decrease. The low F/U mole ratio of UF resins is The melamine–formaldehyde (MF) resin–forming
necessitated by the low functionality of urea (ⱗ2.3) reaction, often carried out at pH between 6 and 9,
that also limits the extent of crosslinking in curing of initially results in various hydroxymethylmelamines
UF polymers. and then in dimers, trimers, and so forth, which pre-
Melamine, with a functionality of 3 or higher,14 has cipitate out from the aqueous phase (Fig. 2). The resins
been used as a low-level copolymer component of are often spray-dried. The MF reaction is too fast at pH
particleboard binder-type UF resins by some North ⬍ 6. Somewhat stable, clear-liquid MF resins are ob-
American manufacturers. With the rigid ring structure tained at pH 8.3– 8.614 because the formation of dimers
and reaction chemistry, similar to that of urea, these and trimers is very slow at this pH range. Because UF
components polymerize at a reasonable speed only at
pH 4 –5 or below, coreaction of MF and UF compo-
Journal article No. FP-267 of the Forest and Wildlife Re- nents in the usual manner would be impractical. Also,
search Center, Mississippi State University. UF components can be polymerized to higher degrees
Correspondence to: M. Kim (mkim@cfr.msstate.edu).
without a phase separation because of their better
Journal of Applied Polymer Science, Vol. 93, 2559 –2569 (2004) compatibility with water. In past research on UMF
© 2004 Wiley Periodicals, Inc. resins, these differences in reactivity and solubility
2560 NO AND KIM

Figure 1 Synthesis steps of urea–formaldehyde resins.

between UF and MF components have been only used in synthesis of UF resins and then melamine was
slightly recognized. Often, melamine (M) and first added with some more formaldehyde (F2) and further
urea (U1) were simultaneously reacted with formalde- reacted.15,21 In this method, MF components would
hyde (F1) from the beginning at pH 8 –9 and then the advance only minimally or to varied extents. In both
reaction mixture’s pH was allowed to decrease to procedures, the (F1 ⫹ F2)/(U1 ⫹ M) mole ratio is
about 6.2 to speed up the reaction.15,17 In this method, normally kept at 2–3 and the polymerization reaction
the UF components would advance very minimally carried out until a predetermined water dilutability is
because of the high pH and mainly the MF compo- obtained. The water dilutability is determined mostly
nents would advance in obtaining the target extents of by the MF components. The second urea is then added
polymerization. In another method, the UF compo- to lower the (F1 ⫹ F2)/(U1 ⫹ M ⫹ U2) mole ratio to
nents are first advanced to the high degree commonly 0.7–1.3, which is another variable that affects the

13
Figure 2 Melamine–formaldehyde resin system and their C-NMR chemical shift values.
LOW-LEVEL MELAMINE-MODIFIED UMF RESINS 2561

discussed above, resulted in lower formaldehyde

emission of boards but the internal bond and water-
soak thickness (TS) values sometimes deteriorated as
the melamine level was increased from 9.5 to 34.4%.30
Thus, either procedure failed to clearly show the ad-
vantages of incorporating melamine in UF resins, ap-
parently because of the lack of controls for advance-
ments of UF and MF components. It is also known that
the curing of MF resins requires stronger catalysts and
Figure 3 Copolymer formation of urea and melamine in higher press temperatures, or longer press times, com-
UMF resins. pared to UF resins because of the lower reactivity of
the hydroxymethyl groups.14 Another possibility for
the varying board performances of UMF resins ob-
bonding and formaldehyde emission performances of served could be the migration of hydroxymethyl
boards. groups of the polymeric UMF resin components to the
In our recent research, the synthesis chemistry of UF second urea during the cooling and storage periods, as
resins has been well clarified.22–27 In manufacturing in UF resins.22–27 Overall, although showing the bond-
UF resins, the urea is added in two parts, the first urea ing and formaldehyde emission improvements that
(U1) and the second urea (U2) (Fig. 1). The first urea parallel the melamine levels of UMF resins would be a
and formaldehyde are reacted at about 90°C in a weak rather complex thesis, the extents of polymerization of
alkaline pH at F/U1 mole ratio of about 2.10 to form UF and MF components appeared to be the key pa-
hydroxymethylureas. Then, the reaction mixture is rameter. Therefore, various UMF resins were synthe-
acidified to pH 4 –5 and maintained at about 95°C to sized using UF base resins preadvanced to D, K, and S
form methylene and methylene– ether bonds to result viscosity as well as A2 and V, the latter two corre-
in UF polymers. In this second reaction step, some sponding to the two typical procedures discussed
hydroxymethyl groups split off as formaldehyde, by above. The melamine level was varied over 2–12%
the reverse reaction, attributed to the decreasing num- based on the liquid resin weight, and the F/(U ⫹ M)
ber of urea amide groups available within the resin mole ratio kept at 2.1 during the polymerization and at
system. The urea functionality attained under this typ- 1.15 after the second urea addition. Other parameters
ical UF resin synthesis condition is only about 2.3–2.5 were kept constant. The reaction times taken in resin
and the freed formaldehyde amounts to about 0.28 syntheses were measured. Selected resin intermedi-
mol/mol of first urea. Once the target viscosity is ates and finished resins were analyzed by 13C-NMR
obtained, V–X (Gardener–Holdt) at resin solids level and finished resins examined for storage stability and
of 60 – 65% for particleboard binder-type resins, in- other resin characteristics. Results of examining fin-
creasing the pH to 8.0 ends the reaction. Then, the ished resins for their curing properties and particle-
reaction mixture is cooled to about 60 –70°C, the sec- board bonding and formaldehyde emission perfor-
ond urea is added and mixed, and the mixture is mances will be published in sequel articles.
cooled to room temperature with a final F/(U1 ⫹ U2)
ratio of about 1.15. During the cooling and storage
EXPERIMENTAL
period, the second urea reacts with the free formalde-
hyde present in the reaction mixture to form mono- Reagent-grade 98% urea and 99% melamine, and a
meric hydroxymethylureas (Fig. 1). fresh industrial-grade 50% aqueous formaldehyde so-
In past research, a reaction product of urea, mel- lution from the Georgia–Pacific Corp. resin plant
amine, and formaldehyde at pH 6.5 was shown to (Louisville, MS), kept at 60°C in the laboratory, were
contain, by 13C-NMR analyses, methylene groups used. The pH adjustments were made using 8% sul-
formed between urea and melamine, a result of copo- furic acid and 25% sodium hydroxide solutions, and
lymerization (Fig. 3).28 In general, copolymers have Brookfield or Gardner-Holt viscometers used to mea-
been assumed to be formed in UMF and MUF resins. sure the viscosity. A convection oven, gel timer, and
MUF resins are generally difficult to analyze because specific gravity meter (Troemner Co., Philadelphia,
of insolubility. UMF resins synthesized with a F/(U PA) were used to measure other resin properties.
⫹ M) mole ratio of 3.0, using the first procedure dis-
cussed above, showed a cloudiness in 30 min of cook-
Synthesis of control UF resin
ing at pH 6.5.29 The resultant resins, at 4 – 8% mel-
amine levels, showed lower formaldehyde emission Following the known procedure,23 a 50% aqueous
than that of control UF resin but the internal bond formaldehyde solution (F) (1697 g) was charged to a
strength of particleboard remained about the same.17 stirred reactor, the pH was adjusted to 7.0 – 8.0, and
UMF resins synthesized, using the second procedure the solution was heated to 70°C. Then, first urea (807
2562 NO AND KIM

g) was added slowly while the reaction temperature to 7.0 – 8.0, and the solution was heated to 75– 80°C.
was maintained at below 90°C (F/U1 ⫽ 2.1). The tem- Then, first urea (710.0 g) and melamine (484.0 g; 12%
perature was increased to 90°C in 20 min and held for based on finished resin weight) were added slowly
30 min, after which the reaction mixture was adjusted while the reaction temperature was maintained at
to pH 4.6 to begin the polymerization. When the re- about 80°C [F/(U1 ⫹ M) ⫽ 2.1]. After the urea and
action mixture reached X viscosity in about 120 min, it melamine had completely dissolved, the temperature
was adjusted to pH 8.0, cooled to about 60°C, and was increased in 20 min to 85°C and maintained for 30
second urea (668 g) was added and cooled further to min. The pH was then adjusted to 6.7 and allowed to
room temperature, resulting in Resin UFA for control decrease by itself. The viscosity of the reaction mixture
[F/(U1 ⫹ U2) ⫽ 1.15]. began at about A2 and reached the target viscosity “V”
in 65 min with the pH decreasing to 6.3. The pH was
adjusted to 8.3 and the cooling began, after which a
Synthesis of a UF resin intermediate at pH 6.3 for small sample was taken for NMR analysis, Resin
NMR comparison
UMF12A2V. When the temperature reached 60°C, sec-
Into a stirred reactor, a 50% aqueous formaldehyde ond urea (775.0 g) was added and the reaction mixture
solution (126 g) was charged, the pH was adjusted to was mixed and cooled to room temperature, to obtain
8.0, and the solution was heated to 70°C. Then, urea Resin UMF12A2VU2 [F/(U1 ⫹ U2 ⫹ M) ⫽ 1.15].
(60.0 g) was added slowly while the reaction temper-
ature was maintained at ⬍90°C (F/U1 ⫽ 2.1). Then,
the temperature was increased to 90°C in 20 min and Synthesis of a UMF resin with 12% melamine with
held for 30 min (viscosity ⬃ A2). Then, the pH was base UF resin preadvanced to V viscosity
adjusted to 6.3 and the reaction mixture maintained at A batch of the control UF resin described above was
90°C for 6 h. The reaction mixture became cloudy in made until the polymerization reaction advanced to
1 h and reached B viscosity only at the end of the “V” viscosity, using 50% formaldehyde solution (1450
reaction period. The reaction mixture was cooled to g) and first urea (690 g). To this UF base resin at pH
60°C, the pH was adjusted to 8.0, second urea (49.6 g) 8.0, a 50% formaldehyde solution (F2) (524 g), pread-
was added and mixed well, and the mixture was justed pH to 8.0, and melamine (484 g; 12% based on
cooled to room temperature to obtain Resin UFA2BU2 finished resin weight) were added and reacted for 20
[F/(U1 ⫹ U2) ⫽ 1.15]. min at 85°C [(F1 ⫹ F2)/(U1 ⫹ M) ⫽ 2.1]. The viscosity
of the reaction mixture was J. Then, the pH was ad-
justed to 6.7 and allowed to decrease while maintain-
Synthesis of MF resin intermediates for NMR ing the temperature at 85°C until the viscosity reached
comparison
V, which took about 20 min. Then, the reaction mix-
Into a stirred reactor, 50% aqueous formaldehyde ture was adjusted to pH 8.0, cooled to 60°C, and an
(150.0 g) and water (20.0 g) were charged, the pH was NMR sample was taken, Resin UMF12VV. Then, sec-
adjusted to 7.0 – 8.0, and the mixture was heated to ond urea (795.0 g) was added and the reaction mixture
80°C. Then, melamine (150.0 g) was added slowly was mixed and cooled to room temperature, to obtain
while the reaction temperature was maintained at 80 – Resin UMF12VVU2 [(F1 ⫹ F2)/(U1 ⫹ U2 ⫹ M) ⫽ 1.15].
90°C (F/M ⫽ 2.1). After the melamine had completely
dissolved, the temperature was increased to 90°C in 20
min and held, while the pH was kept at 8.3– 8.6. The Syntheses of UMF resins with 6% melamine with
water dilutability of the reaction mixture reached a UF base resins preadvanced to two intermediate
extents
value of 1 : 2, resin to water, in 70 min. The reaction
product was cooled to 60°C and adjusted to pH 8.5 to Using a similar procedure used for control UF resin,
give sample Resin MFa (F/M ⫽ 2.1) with O viscosity. 50% aqueous formaldehyde (1697 g) and first urea
A small sample taken was clear but gelled in 2 days at (807 g) were reacted (F/U1 ⫽ 2.1) until the reaction
room temperature. Then, urea (59.0 g) was added and mixture reached D viscosity. Then, the reaction mix-
the reaction mixture mixed at pH 8.5 and then cooled ture was adjusted to pH 8.0, 50% formaldehyde solu-
to room temperature to give Resin MFU2 [F/(U ⫹ M) tion (F2) (272 g), preadjusted to pH 8.0, and melamine
⫽ 1.15] with G viscosity, which was clear and stable at (227 g; 6% based on finished resin weight) were added
room temperature for about 10 days. [(F1 ⫹ F2)/(U1 ⫹ M) ⫽ 2.1]. The reaction mixture was
heated at 85°C, while allowing the pH to decrease,
until VW viscosity, adjusted to 8.0, and cooled to 60°C;
Synthesis of a UMF resin with 12% melamine urea (789 g) was then added and mixed, and the
added in the beginning
reaction product cooled to room temperature, to ob-
First, a 50% aqueous formaldehyde solution (1974 g) tain Resin UMF6DVU2 [(F1 ⫹ F2)/(U1 ⫹ U2 ⫹ M)
was charged to a stirred reactor, the pH was adjusted ⫽ 1.15].
LOW-LEVEL MELAMINE-MODIFIED UMF RESINS 2563

13
Another batch of resin was made using the same C-NMR spectroscopy
formulation and procedure except that the extent of
NMR resin samples were prepared by mixing liquid
reaction for the base UF resin was K viscosity, result-
resins (2.0 g) and D2O (1.0 g). Carbon spectra were
ing in Resin UMF6KVU2 [(F1 ⫹ F2)/(U1 ⫹ U2 ⫹ M)
obtained on a Techmag 360-MHz NMR spectrometer
⫽ 1.15].
(Spectral Data Services, Inc., Champaign, IL) using a
12-␮s pulse width and a 10-s pulse delay for quanti-
Syntheses of UMF resins with 12% melamine with tative results of methylenic groups, which showed T1
UF base resins preadvanced to two intermediate values of 0.16 s or smaller by the inversion–recovery
extents method.23 About 400 scans were accumulated for each
The synthesis procedures similar to those described run. Peak integration values of urea carbonyls, mel-
above for 6% melamine level resins were used. Thus, amine carbons, and methylenic carbons were sepa-
50% aqueous formaldehyde solution (F1) (1365 g) and rately summed and percentages calculated according
first urea (649 g) (F/U1 ⫽ 2.1), additional 50% form- to group types and substitution patterns.
aldehyde solution (540 g), melamine (458 g; 12% based
on the finished resin), and second urea (785 g) were RESULTS AND DISCUSSION
used. Resin UMF12DVU2 was obtained from the UF 13
base resin viscosity D and Resin UMF12KVU2 from General characteristics of C-NMR of UMF resins
the UF base resin viscosity K, both with (F1 ⫹ F2)/(U1 13
C-NMR analysis of UF resins has been well estab-
⫹ U2 ⫹ M) ⫽ 1.15. Several samples were also taken lished.21–26,32–36 13C-NMR results of UMF resins and
during syntheses for NMR analysis: UF base resin at D intermediates indicated the typical characteristics of
viscosity, Resin UFD; after the melamine reaction mix- UF resin components as shown by the various meth-
ture reached N viscosity, Resin UMF12DN; after the ylenic carbon and urea carbonyl group percentage
melamine reaction reached V viscosity, Resin values (Table I). The methylenic groups of UF resins
UMF12DV. NMR samples were adjusted to pH 8.0 have been classified as free and oligomeric formalde-
and cooled to room temperature. hyde; Types I, II, and III methylene– ether groups;
Types I and II hydroxymethyl groups; and Types I, II,
and III methylene groups (Fig. 4 and Table I). The
Syntheses of UMF resins with various levels of intergal values of these groups would define the poly-
melamine and UF base resins preadvanced to three
intermediate extents mer structures as described in previous reports.21,22 In
general, the extent of polymerization, or the (methyl-
Using the resin synthesis procedures described above, ene ⫹ 1/2 methylene– ether) bond content, increases
UMF resins within the matrix of melamine levels and as the resin system is advanced and the total free and
D, K, and S viscosity values of UF base resin were oligomeric formaldehyde content decreases drasti-
synthesized. The melamine levels were 2, 4, 8, and cally after the addition of second urea. For the MF
10%, based on the liquid resin weight. The F/(U ⫹ M) components, new peaks at 65.6 and 71.6 ppm ap-
mole ratio of the reaction mixture during the polymer- peared in UMF resins, the former assigned to Type I
ization step was kept at 2.1 and the second urea added hydroxymethyl groups and the latter to Type II hy-
to obtain the finished resins with mole ratio of 1.15. droxymethyl groups, from the similarity with those on
Viscosity measurements were made during the resin UF resin components at 65.2 and 71.9 ppm, respec-
syntheses and all resins were evaluated for storage tively. They were very close together and calculated
stability by measuring the viscosity changes for 50 together in this study. The methylene (48.3 ppm) and
days at room-temperature storage. methylene– ether (68.8 ppm) groups on MF compo-
nents [Figs. 2 and 5(a)] were broad and not differen-
tiated from broad Type I methylene (47.4 ppm) and
Resin property tests
methylene– ether groups (69.5 ppm) on UF compo-
Nonvolatile resin solids contents were measured by nents. Therefore, it was difficult to form a conclusion
heating 1.0 g of liquid resins at 110°C for 3 h in an whether any copolymerization occurred between urea
oven. Gel times were measured at 100°C (boiling wa- and melamine units. Melamine ring carbons occurred
ter) using a Sunshine gel timer. The catalyst was 0.5% at 167.1–168.1 ppm.37
ammonium sulfate (25%) solution in water for both
nonvolatile solids content and gel time measurements.
UF resin intermediate UFA2BU2
Specific gravity was measured using a specific gravity
meter (Troemner Co.). The stability of resins was eval- This UF resin intermediate, made by polymerizing at
uated by storing resins (⬃ 400 g) in a plastic container pH 6.3 and 90°C for 6 h of reaction at F/U1 mole ratio
at room temperature and measuring the viscosity of 2.1, became cloudy in the first hour of reaction and
daily. reached B viscosity only at the end of the reaction.
2564 NO AND KIM

TABLE I
Percentage Values for Various Methylenic and Carbonyl Carbons of Urea Portions of UF and UMF
Resin Samples Determined by 13C-NMR Spectroscopic Methoda
Synthesized UF and UMF resin samples
Groups UMF12 UMF12 UMF12 UMF12 UMF12 UMF12 UF
(ppm) A2V A2VU2 UFD* DN DV DVU2 VVU2 A2BU2 MFaU2

Free and 91.0 0.59 0.41 0.56 0.61 0.42 0.34 0.33 0.65 0
oligomeric 87.0 1.04 0 2.72 1.56 1.72 0.15 0.10 0 0.33
formaldehyde 83.1 1.56 0 2.98 2.74 3.52 0.17 0.19 0 0.25
Total 3.19 0.41 6.26 4.91 5.66 0.66 0.62 0.65 0.58
Methylene–ether 79.1 (III) 0.93 0 1.02 1.56 1.99 1.24 1.85 2.64 0
groups 75.1 (II);
74.8* 4.26 3.93 5.04 7.03 7.63 5.66 4.43 6.62 3.43
69.5 (I);
68.8* 19.15 20.50 8.39 12.14 12.10 11.85 9.76 18.20 16.14
Total 24.34 24.43 14.45 20.73 21.72 18.25 16.04 27.46 19.57
Hydroxymethyl 71.9 (II);
groups 71.6* 16.60 12.53 14.20 26.40 24.69 19.83 16.18 16.03 10.05
65.2 (I);
65.6* 44.75 51.62 13.13 22.90 22.48 34.87 38.90 35.10 64.78
Total 61.35 64.15 27.33 49.30 47.17 54.70 55.08 51.13 74.83
Methylene 60.1 (III) 0 0 3.13 2.19 2.84 1.82 0.94 2.03 0
groups 53.9 (II);
55.0* 7.17 6.66 14.64 16.02 15.69 15.79 17.16 10.48 1.87
47.4 (I);
48.3* 3.96 4.35 5.83 6.86 6.87 8.29 10.16 8.25 5.02
Total 11.13 11.01 23.60 25.07 25.40 25.90 28.26 20.76 6.89
Urea carbonyl 164.0 2.86 38.80 0 0 0 34.74 34.59 38.11 46.84
groups 162.2 30.02 30.21 6.07 9.67 11.03 21.36 23.06 19.84 44.59
160.7 65.68 30.75 91.85 87.72 84.81 42.06 39.64 39.21 8.57
158.0 1.45 0.24 2.08 2.60 4.16 1.84 2.70 2.84 0
a
Sample numbers were defined in the text and the chemical shift values are related to the chemical structures shown in
Figure 4. The amount of formaldehyde in Resin UFD is smaller than that in others and its methylenic group percentage values
were proportioned to make them comparable. For Resin UMF12 series, to convert the values into moles based on the first urea,
multiply by 2.935. Chemical shift values of methyleneic groups bonded to melamine are marked with asterisks. Melamine
ring carbon peaks appeared at 167.1–168.1 ppm and are not included in this table.

After the addition of the second urea [F/(U1 ⫹ U2) 8.4, the reaction mixture remained clear and its water
⫽ 1.15], the viscosity decreased to A1. The 13C-NMR dilutability decreased slowly to 1 : 2 (resin : water) in
results (Table I) showed a (methylene ⫹ 1/2 methyl- 70 min of reaction. The sample taken before the addi-
ene– ether) bond content of 0.722, corresponding to an tion of the second urea, Resin MFa (F/M ⫽ 2.1) with O
extent of polymerization 3.6, on average 0.12 group viscosity, gelled overnight to indicate an appreciable
being formed per hour of reaction. The methylene : reactivity of hydroxymethyl groups at pH 8.4. Resin
methylene– ether group ratio was 60 : 40, a higher MFaU2, obtained by adding the second urea to Resin
ether group value compared to the ratio of 77 : 23 MFa [F/(M ⫹ U) ⫽ 1.15], showed G viscosity and
found for Resin UFD synthesized at pH 4.6 in about 30 remained clear at room temperature for at least 10
min. These results indicate that the polymerization of days, with the ending viscosity increased to P. The
13
UF components is very slow and more ether groups C-NMR results of Resin MFaU2 [Table I, Fig. 5(a)]
are formed at pH 6.3, both of which will apply for UF indicated an overall (methylene ⫹ 1/2 methylene–
resin components in syntheses of UMF resins at or ether) bond content of 0.415, mostly of Type I bonds.
near pH 6.3. The role of methylene– ether bonds in UF Because little polymerization would have occurred for
resins is not well understood, but such a bond has the second urea components, the bond content value
been assumed to break and emit a mole of formalde- indicates that the melamine components have an ex-
hyde on curing. tent of polymerization 1.71. This low extent of ad-
vancement appears necessary for MF components to
remain in solution. Furthermore, the methylene : m-
Resin MFaU2
ethylene– ether group ratio of Resin MFU2 was 41 : 59,
MF resins synthesized with an F/M ratio of 2.5 at pH a high ether group content compared to that of UF
6.3 in preliminary experiments quickly became cloudy resins. These reaction characteristics would apply for
and insoluble. In the synthesis of Resin MFaU2 at pH MF components in syntheses of UMF resins. The NMR
LOW-LEVEL MELAMINE-MODIFIED UMF RESINS 2565

13
Figure 4 Chemical structures of UF resins and their C-NMR chemical shift values.

results further indicated that the second urea added using the base resin UFD: adding 12% melamine and
had reacted to form mono- and dihydroxymethylu- reacting to N viscosity and V viscosity, respectively,
reas, consuming about 0.8 out of 2.5 mol of formalde- and then adding the second urea. The 13C-NMR spec-
hyde used in resin synthesis, leaving the balance 1.7 tra [Fig. 5(b)] and data (Table I) indicate the various
mol to be bonded to melamine molecules. Although a reaction characteristics. The methylene/methylene–
direct comparison was not made because of the pre- ether group content, adjusted for the second formal-
mature gelation of Resin MFa, the results indicate that dehyde added with the melamine, gradually in-
some of the hydroxymethyl groups, bonded to mel- creased by 0.146 groups from Resin UFD to Resin
amine molecules, migrated to the second urea [Fig. MUF12DVU2 per mole of the first urea. This increase
6(a)] as in UF resins. This reversibility of hydroxy- constitutes 18.8% of the total methylene/methylene–
methyl groups of MF resin components has been little ether group content 0.774/mol per mole of the first
known, although it has been assumed to occur in urea. Because polymerization of UF resin components
curing of MF resins at elevated temperatures, espe- would have progressed little in this stage, the meth-
cially for resins made with higher F/M ratios.14 The ylene/methylene– ether group content increase would
melamine ring carbons appeared at 167.15, 167.24, and be mostly of the MF components, which translate into
168.06 ppm, the first two peaks for di- and trisubsti- in an extent of polymerization 1.58 for MF compo-
tuted melamines and not well separated and the last nents. This value is comparable to that of Resin
peak for monosubstituted melamine. Overall, the MFaU2, discussed above, and indicates that the MF
Resin MFaU2 synthesis experiment indicates that the components remain soluble and translucent and
reaction of MF components goes relatively fast even at would continue to polymerize to increase the resin
pH 8.4 and will thus go faster at lower pH 6 –7, where viscosity at room temperature.
most UMF resin syntheses have been carried out in the The free formaldehyde level was relatively high
past. until the second urea addition (Table I), indicating that
the formaldehyde ratio used, (F1 ⫹ F2)/(U1 ⫹ M)
⫽ 2.1, was in excess with the melamine components
Resin UMF12D series intermediates
having not fully reacted in this reaction period. Type I
Samples UFD, UMF12DN, UMF12DV, and UMF12DVU2 hydroxymethyl groups (⬃ 65.5 ppm) increased from
were obtained in synthesis of the last resin sample 13 to 23% when the second formaldehyde and mel-
2566 NO AND KIM

Figure 5 (a) 13C-NMR spectrum of Resin MFaU2 with chemical shifts indicated for various carbons shown in Figure 2. (b)
13
C-NMR spectra of Resin samples UFD(1), UMF12DV(2), and UMF12DVU2(3) with chemical shifts indicated for various
carbons shown in Figures 2 and 4.

amine were added and then further increased to 35% and first urea with formaldehyde at pH 6.3 reached
with the addition of the second urea [(F1 ⫹ F2)/(U1 the target viscosity VW in about 60 min. The finished
⫹ M ⫹ U2) ⫽ 1.15] as a result of reaction with form- resin was cloudy. The reaction time, the longest com-
aldehyde. Type II hydroxymethyl groups of both UF pared with that of UMF resins synthesized with UF
and MF components (⬃ 72.0 ppm) similarly increased, base resins, preadvanced to D, K, or S viscosity values,
but decreased after the second urea addition because but was relatively short compared with UF resins,
of dissociation into formaldehyde and reaction with about 120 min at pH 4.6 (Fig. 8). 13C-NMR results of
the second urea, as observed with Resin MFU2 [Fig. the final resin and the sample taken before the addi-
6(a)] discussed above. This migration of hydroxy- tion of second urea (UMF12A2V) (Table I) indicated a
methyl groups also resulted in decreasing Type II and (methylene ⫹ 1/2 methylene– ether) bond content of
Type III methylene and methylene– ether groups with 0.465 groups per mole of combined first urea and
addition of the second urea, similar to UF resins. melamine, a DP value of 1.87. This synthesis proce-
dure thus resulted in resins having a very low average
molecular weight compared to the common DP value
Resin UMF12A2VU2 made without 10 for finished UF resins. On the other hand, because
preadvancement of UF base resin
the UF components would have experienced only a
With this UMF resin synthesis procedure, often used small increase in the methylene/methylene– ether
in previous research, the reaction with 12% melamine bond content (0.12 group) as discussed above, the
LOW-LEVEL MELAMINE-MODIFIED UMF RESINS 2567

Figure 6 (a)–(c) Reaction schemes of melamine and formaldehyde resins.

balance of about 0.345 bond/0.336 mol of melamine nents, which was prepolymerized to V viscosity. The
for the MF components indicates a very high degree of reaction time to the target viscosity V was short, about
polymerization value [Fig. 6(b)]. This overpolymeriza- 20 min (Fig. 8), and resulted in a clear resin as ex-
tion of MF components in Resin UMF12A2VU2 is sup-
ported by the cloudy appearance. The resin’s apparent
viscosity showed a good stability for more than 30
days at room temperature. For the UMF resin synthe-
sized with 2% melamine and no advancement of UF
base resin, the final resin did not even reach the target
viscosity in 5.5 h of reaction, apparently because of the
lack of reactive, dissolved MF components. This res-
in’s apparent viscosity similarly remained low and
stable for more than 30 days (Fig. 7). With these UMF
resins, the MF components polymerized to a point
where they are no longer soluble and formed small
particles that remain suspended in the low molecular
weight UF components.

Resin UMF12VVU2, made with UF base resin,

advanced to full extent
With this second typical UMF resin synthesis proce-
dure used in previous research, 12% melamine and the Figure 7 Viscosity changes of UMF resins and control UF
second formaldehyde were added to the UF compo- resin in storing at room temperature.
2568 NO AND KIM

selected resins are reported in Table II. The reaction

time taken after the melamine addition until the target
viscosity of V became shorter as the melamine level
was increased, from 5.5 h to 40 min (Fig. 8), indicating
that the major reacting components in this stage are
the MF components. The reaction time also became
slightly shorter as the UF base resin viscosity in-
creased from D to S, as expected. The UF base resin
components would have incurred only a small extent
of polymerization during the melamine reaction. The
cloudiness of UMF resins made with 12% melamine
was typical, changing gradually from the opaque to
translucent and to clear as the UF base resin viscosity
increased from A2 to V in preadvancement, reflecting
the MF components’ decreasing extents of polymer-
ization. On the other hand, for a given UF base resin
the resultant resins’ cloudiness tended to be greater
for lower melamine levels because of the higher ex-
tents of polymerization incurred. Similarly, the viscos-
ity increases in the room-temperature storage experi-
Figure 8 Reaction times taken in syntheses of UMF resins ment were faster for resins made with more advanced
depending on the starting UF base resin viscosity values and UF base resins (Fig. 7).
melamine levels.

General resin properties

pected. The resin sample taken before the addition of
second urea gelled overnight at pH 8.0, indicating that The UMF resins generally showed longer gel times
the MF components were low molecular weight, reac- than that of the control UF resin with ammonium
tive compounds. The 13C-NMR results of Resin sulfate catalyst (Table II) and the higher melamine
UMF12VVU2, compared with those of typical UF res- level resins showed longer gel times than those of
ins24 (Table I), showed that the extent of polymeriza- lower melamine level resins. These gel time trends
tion attained by the melamine components was very agree with the generally known fact that MF resins
low. The resin remained clear for several days without cure slower than UF resins. Detailed differences based
clouding, and the viscosity of the resin increased the on the different synthesis procedures used were not
fastest during room-temperature storage (Fig. 7). apparent in gel time results. In a companion article,38
Thus, MF components in this UMF resin appear to be the UMF resins were compared for curing properties
almost monomeric and remain dissolved and reactive using the dynamic mechanical analysis (DMA)
[Fig. 6(c)]. method at 120 –175°C. The DMA curing speeds of
resins showed trends similar to those of gel time mea-
surements and also showed differences for different
UMF resins made with UF base resins advanced to melamine addition points used in resin syntheses. One
intermediate extents and at various melamine important question in synthesizing UMF resins will be
levels
the efficiency of the MF resin components in curing of
In these experiments the UF base resin was polymer- resins as adhesives. MF components need to cure co-
ized at pH 4.6 to D, K, and S viscosities and then operatively with UF resin components in the final
reacted at pH 6.3 with 2–12% levels of melamine at curing of boards. MF components that are too highly
[(F1 ⫹ F2)/(U1 ⫹ M) ⫽ 2.1]. Resin property data of advanced in the resin stage could lose such capacity.

TABLE II
Properties of UF and UMF Resins Synthesized with F/(U ⴙ M) ⴝ 1.15
Gel time Specific Viscosity Solids
Resin pH (s) gravity (G-H scale) content (%)

UF Control 8.5 88 1.26 N 61.3

UMF6DVU2 8.5 135 1.27 JK 62.5
UMF12DVU2 8.5 129 1.29 J 64.5
UMF12KVU2 8.6 126 1.29 KL 64.4
 LOW-LEVEL MELAMINE-MODIFIED UMF RESINS 2569

CONCLUSIONS 10. Myers, G. E. Wood Sci 1982, 15, 127.

11. Myers, G. E. Forest Prod J 1984, 34, 35.
UMF resins synthesized with low levels of melamine 12. Myers, G. E. Holzforschung 1990, 44, 117.
were shown to have various important resin charac- 13. Go, A. T. In: Proceedings of the 25th International Particleboard
teristics that reflected the UF base resin’s extent of and Composite Materials Symposium, Washington State Uni-
preadvancement as well as the melamine level. It be- versity, Pullman, WA, 1991.
14. Wirpsza; Z.; Brezezinski, J. Aminoplasty; Kimya (Chemistry):
came apparent that the varying and sometimes incon- Moscow, 1973; pp 71–76.
sistent bonding and formaldehyde emission results of 15. Shiau; D. W.; Smith, E. U.S. Pat. 4,536,245 (1985).
UMF resins reported in previous research would be 16. Graves, G. In: Proceedings of the 27th International Particle-
traced to the advancement imbalances between the UF board and Composite Materials Symposium, Washington State
and MF components in resins. The melamine compo- University, Pullman, WA, 1993.
nents need to be reacted at pH 6 or higher and the UF 17. Maylor, R. In: Proceedings of Wood Adhesives 1995, Forest
Products Society, Madison, WI, 1995; pp 115–121.
base resin components can be advanced only at pH
18. Breyer; R. A.; Hollis; S. G.; Jural, J. J. U.S. Pat. 5,681,917 (1997).
4 –5 in syntheses of UMF resins. The UF base resin 19. Rammon, R. M. In: Proceedings of the 31st International Particle-
components therefore need to be first advanced to an board/Composite Materials Symposium; Maloney, T. M., Ed.;
appropriate extent, followed by the melamine addi- Washington State University, Pullman, WA, 1997; pp 177–181.
tion and an appropriate further advancement. Fur- 20. Parker; R.; Crews, G. M. In: Proceedings of the 33rd Interna-
thermore, to have balanced advancements of UF and tional Particleboard/Composite Materials Symposium; Ma-
loney, T. M., Ed.; Washington State University, Pullman, WA,
MF components the extent of advancement of UF base
1999; pp 57– 66.
resin components needs to be adjusted to the mel- 21. Druet; B.; Hopin, D. U.S. Pat. 4,997,905, 1988.
amine use levels, less for higher melamine levels, and 22. Kim; M. G.; Amos, L. W. Ind Eng Chem Res 1990, 29, 208.
more for lower melamine levels, to avoid an overpo- 23. Kim, M. G. J Polym Sci Part A: Polym Chem 1999, 37, 995.
lymerization of the MF components. The storage sta- 24. Kim, M. G. J Appl Polym Sci 2000, 75, 1243.
bility of the cloudy UMF resins made by highly ad- 25. Kim, M. G. J Appl Polym Sci 2001, 80, 2800.
vancing the MF components was generally good and 26. Kim; M. G.; Wan; H.; No; B. Y.; Nieh, W. L. J Appl Polym Sci
2001, 82, 1155.
the storage stability of the clear UMF resins made by 27. Kim; M. G.; No; B. Y.; Lee; S. M.; Nieh, W. L. J Appl Polym Sci
minimally advancing the MF components was some- 2003, 89, 1896.
what shorter. Overall, preadvancing the UF base resin 28. Tomita; B.; Hse, C. Y. Mokuzai Gakkaishi 1995, 41, 349.
components to an appropriate extent was found to be 29. Tomita; B.; Hse, C. Y. Mokuzai Gakkaishi 1995, 41, 490.
a key parameter in synthesizing various low-level 30. Hse; C. Y.; He, Z. In: Proceedings Wood Adhesives 1990, Forest
melamine-modified UMF resins. Products Society, Madison, WI, 1990; pp 155–159.
31. Levy; G. C.; Nelson, G. L. Carbon-13 NMR for Organic Chem-
ists; Wiley–Interscience: New York, 1972.
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