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Modification of UF Resins Blocked Isocyanate


Byung-Dae Park1, M. Adly Rahandi Lubis1, Sang-Min Lee2, Sang-Bum Park2
1Department of Wood & Paper Sciences, Kyungpook National University, Daegu, Korea
2Department of Chemical Sciences, University of Padova, Padova, Italy
1. Introduction
In order to use available timber resources in an efficient manner, new types of adhesives which provide
improved performance of wood panel products with low formaldehyde emission have to be developed. Ureaformaldehyde (UF) resin is the most used resins for interior-grade plywood application. However, UF resin is low
water resistance, easy to aging, and releasing formaldehyde emission (FE) from the panels (Zhang et al., 2010).
Hence, there is a need to employ no added formaldehyde resin. This objective has been achieved by using
isocyanate based adhesive (Gopal, 2014). Isocyanate resins are formaldehyde free resins and highly reactive
compared to formaldehyde resins. Aliphatic isocyanates like HDI (Hexamethylene Diisocyanate) are hazardous
and are mainly used in coating formulation. Aromatic isocyanates are less hazardous than aliphatic isocyanates.
TDI (Toluene Diisocyanate) and MDI (Methylene-diphenyl Diisocyanate) are commonly used in aromatic
isocyanates. Due to lower toxicity, provide higher tensile strength, greater toughness, and heat resistance than
TDI, MDI resins are appropriate for bonding wood panel products (Petrie 2007).
Polymeric MDI resins easily react with the moisture present in the atmosphere, has a short pot life, and difficult
to operate. Blocked isocyanate is a solution to overcome these drawbacks (Lou and Di, 2013). The NCO groups
can be blocked with a compound containing active hydrogen atom. The isocyanate blocking technology is great
significance to further development and application of isocyanate adhesives (Zhang et al., 2011). Attention has
been focused on isocyanate adhesives and methods for using their properties in UF resin modification. Previous
study showed that 1-2% addition of pMDI to UF resin effectively reduces its susceptibility to hydrolysis and
accelerates cross-linking (Pizzi and Walton 1992), 3% addition of pMDI to UF resin give lower gel time, and high
viscosity (Yang et al., 2014), and also addition of pMDI to UF resin at 15% significantly improved resistance of glue
line to hot water (Mansouri et al., 2006). This research aims to investigate properties of UF/blocked pMDI (BPI)
hybrid resins on plywood and particle board.
2. Materials and Methods
2.1. Materials and instrument
Technical grade Urea, Formaldehyde, aqueous solutions of formic acid (HCOOH), and sodium hydroxide
(NaOH) were used for synthesis UF resins. Aqueous solutions of ammonium chloride (NH4Cl) was used as
hardener. Polymeric MDI was obtained from BASF Germany. Methyl Ethyl Ketoxime (MEKO) was used as blocking
agent of blocked pMDI (BPI), acetone as solvent, and sodium dedocyl sulphite (SDS) as surfactant. Meranti veneer
(Shorea spp) was used as plywood material. DSC thermal analyser and FTIR measurement were used to
investigate of the blocking and deblocking reaction of blocked pMDI. Wet analysis was used to measurement
liberated HCHO concentration. Properties of plywood and particle board were analyzed using KS F 301, and KS M
2.2. Methods
2.2.1. Preparation of UF/Blocked pMDI hybrid resin
UF resin used for this study was prepare use alkaline-acid two step reaction (Yang et al., 2014). Subsequently,
polymeric MDI was dissolved with acetone in four-necked glass reactor to obtain blocked pMDI. The mixture was
stirred under nitrogen atmosphere and under reflux condition. Subsequently, MEKO was added to the flask by
dropwise method. After that, SDS was added to the mixture to get MEKO blocked pMDI. Furthermore, blocked
pMDI at 1%, 3%, and 5% was introduced into UF resin on the basis of the non-volatile solid content of UF resin to
obtain UF/BPI hybrid resin.

2.2.2. Plywood and particle board manufacturing

Plywood (PW) made from Shorea spp. veneer, with 6 mm target of thickness, 3 ply, 170 g/m2 of glue spread,
3% of hardener. Furthermore, plywood pressed at cold pressed for 2 hours, and hot pressed at 120C for 4 min.
Particle board (PB) made with 3 layers, with 12 mm target of thickness, 750 kg/m3 of density, resin content 12% at
the surface, and 8% at the middle. Subsequently, particle board pressed with hot pressed at 160C for 4 min.
3. Result and Discussion
The FTIR spectra of pure and blocked pMDI (BPI) are shown that there is a characteristic peak of NCO around
2270 cm-1 for pure pMDI, which indicate presence of free isocyanate group. But then, there is no absorption peaks
appear between 2250-2270 cm-1 range for BPI, which indicates that NCO group of isocyanate molecules were
completely blocked by MEKO. The deblocking temperature was cearly observed by DSC measurement, which
deblocking temperature start from 157.96C. Some report showed that deblocking temperature for MEKO blocked
MDI start from 130C. Different monomer of isocyanate, and different blocking agent will give different deblocking
temperature of blocked isocyanate (Wicks and Wicks 1999).
Mechanical properties of PW and PB manufactured with UF/BPI hybrid resin showed that the higher amount of
blocked pMDI introduced to resin, the better improvement in the strength properties of PWs and PB. Thus already
with addition of 3% of blocked pMDI, Modulus Of Rupture (MOR) of PW and PB more higher than UF
manufactured boards, 57.0163 MPa and 57.1944 MPa, than 54.0895 MPa, respectively. The same results are also
shown on formaldehyde emissions from wood panels. The higher amount of blocked pMDI introduced to resin, the
lower FE liberated from PW and PB. FE from UF board has a higher value than the FE from UF/BPI hybrid of PW
and PB. 1% addition of blocked pMDI at UF/BPI hybrid resin can decrease FE from PW and PB than UF board,
32.4% and 25.9% from 0.352 mg/L, respectively. 5% addition of blocked pMDI can decrease FE from PW and PB
than UF board, 53.7% and 46.0% from 0.352 mg/L, respectively.
An addition of blocked pMDI to UF resin also improve resistance of glue line to water. In plywood case, with
addition of blocked pMDI to resin, resulting more higher water resistance to PW strength. The results showed that
the UF board has lower wet TS value than 1% of UF/BPI PW, but the result is higher than 1% of UF/BPI PB,
0.3693 MPa lower than 0.9623 MPa, but higher than 0.1596 MPa, respectively. Furthermore, with addition 5% of
blocked pMDI to UF resin, UF/BPI PB has higher wet TS value, but 0.4565 MPa still lower than UF board and
UF/BPI PW. PB manufacturing process using hot pressed at 160C for 4 min does not give good results, because
the deblocking process to release NCO groups from UF/BPI hybrid resin start from 157.96C, so the manufacturing
process of PB has not yet formed a perfect bond with raw materials. It would require further research on the
deblocking reaction of blocked pMDI and optimization of additional blocked pMDI to the UF resin.
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