5-7 OCTOBERISFR2011

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TOLEDO (SPAIN)CHEMICAL REACTION OF PHENOL RESIN FOAM POWDER AND PREPOLYMER IN
HIGH㸫TEMPERATURE FLUIDS
T. Sugeno, H. Tagaya
Yamagata university, Graduate School of Science and Engineering
e-mail: tne75618@st.yamagata-u.ac.jp

Abstract
In this study waste plastics such as phenol resin foam powder were decomposed into their monomer and oligomer
compounds in sub- and supercritical fluids. Solvents play important roles as stable physical medium at high temperature andreactive chemical reagents to accelerate decomposition reaction of the thermosetting resin. In the decomposition reaction atrelatively high temperature, methylene bonds of plastics were cleaved selectively via the ionic reaction by solvents. Thesolvent participating mechanism of decomposition was confirmed to make clear the decomposition products of phenol resin
foam. The methylated reaction also occurred in the reaction in methanol, and cresol and dimethylphenol were found as main
components.

Keywords: High Temperature Water, High Temperature Methanol, Phenol Resin, Thermosetting Resin,
Chemical Recycling

1. Introduction
The chemical recycling of waste plastics has beengaining greater attention in recent years as a means ofobtaining valuable products from wastes. Thermal
cracking of thermosetting resin is a well-known techniqueand fluidized-bed pyrolysis technology has been underdevelopment. It is well known that water under
supercritical conditions is much less polar and canhomogenize substantial amounts of non-polar organiccompounds. Furthermore, it is pointed out that thesupercritical water is emerging as a medium, which could
provide the optimum conditions for a variety of chemical
reactions, among them the destruction of hazardous
waste. We have already confirmed that waste plastics
such as phenol resin decompose into their monomericcompounds in sub- and supercritical water (Fig.1) [1], [2].

(Fig.2). In the thermal analysis the temperature
increasing rate was 10 ºC/min.
10 mL tubing bomb reactor
or2L autoclave reactor
Heating
Filtration

LiquidproductResidue

Ether extraction

Ether-soluble part

Water-soluble partHigh temperature
water

GC,GC-MS

Fig.2. Experiment method.
Fig.1. Decomposition reaction of foamed phenol resin.

3. Results and Discussion

2. Materials and Methods

3.1 Decomposition reaction in high temperature water.
Foamed phenol resin was decomposed into theirmonomers by reactions at 350ºC under an Ar
atmosphere in high temperature water with Na2CO3 for
2h. According to GC/MS analysis, phenol and cresol
were found as main components in the liquid phase(Fig.3). The decomposition was accelerated by thequantity of Na2CO3 addition increasing. In addition, theFoamed phenol resin was reacted after pulverizing. A 10mL tubing bomb reactor and 2L autoclave reactor wereused as the reactor. The typical reaction was carried outfor 0.1g of foamed phenol resin in 1 mL water with
Na2CO3 or methanol. After the reaction, products wereextracted by ether and measured by GC/MS and GC

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6th International Symposium on Feedstock Recycling of Polymeric Materials

yield of their monomers was higher at longer reaction
time and higher temperature (Fig.4). However,carbonization reaction occurred at the high reaction
temperature.

Intensity [ arb.units ](a)References[1] T. Sugeno and H. Tagaya. Recycling of PolymericWaste Materials. FSRJ Symposium proceedings 13th,Chiba, (2010) 39–40.
[2] T. Sugeno and H. Tagaya. Treatment of phenol resin
foam powder and prepolymer in high-temperature fluids.
PACIFICHEM 2010, Honolulu, (2011); Abstract 587.

(b)

5101520
Time [min]25Yield㻌 [wt%]Fig.3. GC/MS chromatogram of the products in thereaction of foamed phenol resin (a) in water 400mL with
Na2CO3 at 350 ºC for 1h and (b) in methanol 400mL at
280 ºC for 1h by using 2L reactor.

704603(a)⣔ิ㻝502(b)⣔ิ㻞

401(c)⣔ิ㻟300(d)⣔ิ㻠(e)⣔ิ㻡20(f)⣔ิ㻢100phenolo-cresolp-cresol

2,4dimethylphenol

Residue

Fig.4. Decomposition reaction of foamed phenol resin inwater 1.0 mL with Na2CO3 for 2h (a) at 280 ºC ,(b) at
300 ºC ,(c) at 320 ºC ,(d) at 350 ºC ,(e) at 400 ºC ,(f) at430 ºC.
3.2 Decomposition reaction in high temperature methanol.
Foamed phenol resin was decomposed by reactions at280ºC in high temperature methanol without the additionof additive. Foamed phenol resin decomposed mainly
into dimethylphenol and xylene in high temperature
methanol shown in Fig.3. It is considered that xylene wasproduced from the plasticizer.

4. Conclusions
Decomposition reaction of phenol resin foam could be
carried out using methanol at around 300ºC. Indicatingthat the decomposition reaction proceeded at lower
temperature when methanol was used as the solvent.
The reaction products depended on the solvent used.

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