Polymer Degradation and Stability 93 (2008) 2025–2031

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Preparation, thermal properties and flame retardancy of phosphorus- and

silicon-containing epoxy resins
M. Spontón, L.A. Mercado, J.C. Ronda, M. Galià*, V. Cádiz
Departament de Quı́mica Analı́tica i Quı́mica Orgànica, Universitat Rovira i Virgili, Campus Sescelades, Marcel.lı́ Domingo s/n, 43007 Tarragona, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Phosphorus- and silicon-containing epoxy resins were prepared from (2,5-dihydroxyphenyl)diphenyl
Received 1 February 2008 phosphine oxide (Gly-HPO), diglycidyloxy methylphenyl silane (DGMPS) and 1,4-bis(glycidyloxydimethyl
Received in revised form 12 February 2008 silyl)-benzene (BGDMSB) as epoxy monomers and diaminodiphenylmethane (DDM), bis(3-amino-
Accepted 21 February 2008
phenyl)methyl phosphine oxide (BAMPO) and bis(4-aminophenoxy)dimethyl silane (APDS) as curing
Available online 23 July 2008
agents. Epoxy resins with different phosphorus and silicon content were obtained. Their thermal,
dynamic mechanical and flame retardant properties were evaluated. The high LOI values confirmed that
Keywords:
epoxy resins containing hetero-atoms are effective flame retardants, but a synergistic efficiency of
Flame retardance
Epoxy phosphorus and silicon on flame retardation was not observed.
Phosphorus-containing resins Ó 2008 Elsevier Ltd. All rights reserved.
Silicon-containing resins

1. Introduction developing novel compounds with specific reactive functional

groups, as flame retardant oxirane and diamine compounds for
Epoxy resins are used worldwide on a large scale for adhesive, epoxy resins. Among non-halogenated flame retardants, phos-
lamination, coating applications, so forth. They have excellent phorus-containing compounds are attractive owing to their low
moisture, solvent and chemical resistances, toughness, low generation of smoke and toxic gases and the high flame retardant
shrinkage on cure, high adhesion to many substrates and superior efficiency [6]. Phosphorus-containing polymers confer fire resis-
electrical and mechanical resistance properties [1,2]. To extend the tance mainly by modifying the thermal decomposition of the
applications of epoxy resins as electronic materials and in the polymers, in favour of reactions yielding carbonaceous char rather
aerospace industry, it is crucial to improve their thermal and flame than CO and CO2. They form a surface layer of protective char
resistance. Several approaches have been reported in the literature during fire before the unburned material begins to decompose. The
for the improvement of flame resistance. Halogenated compounds char acts as a barrier to inhibit gaseous products from diffusing to
have been widely used as flame retardant in the past. The major the pyrolysis zone and to shield the polymer surface from heat and
problem encountered with these systems is the fire hazards air [7]. The efficiency of flame retardation of phosphorus basically
resulting from the formation of highly toxic and corrosive products depends on the amount of char formation, thus, by improving the
during combustion. With safety and environmental concerns in thermal stability of phosphorus char at high temperatures the
mind, epoxy resins that are flame resistant and halogen-free have flame retardant efficiency could be improved. Silicon-containing
been the focus of attention by researchers in recent years [3,4]. polymers are described that can degrade forming thermally stable
A traditional technique of preparing flame retardant epoxy silica, which have the tendency to migrate to the char surface
resins is to blend the flame retardant additive with the polymer. As serving as a protection layer to prevent further degradation of char
there is no chemical bonding between the flame retardant additive at high temperatures [8].
and the polymer, some shortcomings, such as low efficiency of Moreover, enhancement of flame retardancy of epoxy resins has
flame retardance, leaking out during processing and usage, and been achieved by incorporation of phosphorus and silicon into
detrimental effects on polymer’s thermal and mechanical proper- epoxy resins with bringing a P–Si synergistic effect of flame retar-
ties accompany the introduction of flame retardant into the poly- dation [9–13]. While under flame exposure, phosphorus provides
mer. Therefore, the present trend is moving towards using reactive a tendency for char formation, silicon provides an enhancement of
type flame retardants, which are permanently bonded to the the thermal stability of the char and introducing both elements
polymer [5]. Preparing a reactive type flame retardant requires may successfully combine these two factors in a strong flame
retardation mechanism.
* Corresponding author. In our search for new flame retardant epoxy monomers and curing
E-mail address: [email protected] (M. Galià). agents, we considered phosphine oxides. In a previous work, we

0141-3910/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2008.02.014
2026 M. Spontón et al. / Polymer Degradation and Stability 93 (2008) 2025–2031

synthesized the diglycidyl ether of (2,5-dihydroxyphenyl)diphenyl under positive argon pressure during the entire course of the
phosphine oxide (Gly-HPO) and investigated its thermal behaviour reaction in order to flush the H2 gas from the reaction mixture. The
and reactivity. Systems containing different amounts of Gly-HPO solution was stirred at 60  C for 1 h to ensure complete conversion
and DGEBA cured with primary amines were also described and and was allowed to cool down to ambient temperature overnight.
their thermal, mechanical and flame retardant properties were The reaction mixture was washed with water and phosphate buffer
discussed [14]. We also investigated silicon-containing compounds and the organic layer was dried over MgSO4, filtered and then the
as flame retardants: silicon-containing glycidyl monomers and pre- solvent was evaporated at reduced pressure. The product obtained
polymers have been cured with primary amines and the thermal was dissolved in hexane/ethyl acetate (8:2) mixture and filtered
stability and flame retardant properties have been reported [15]. through a short column of silica gel to remove traces of catalyst
We described a new silicon-containing monomer, diglycidyloxy and other polar impurities. The obtained colourless solution was
methylphenyl silane (DGMPS) and we examined the incorporation concentrated under vacuum to give a clear oil (74% yield) essen-
of different amounts of silicon into the epoxy resin by the curing of tially pure by 1H NMR.
1
DGMPS/DGEBA system [16]. In the present work, phosphorus and H NMR (CDCl3/TMS, d (ppm)): 7.65 (2H, m); 7.42 (3H, m); 4.03
silicon were introduced into the epoxy resins by curing phosphorus (2H, dd, 12.0, 3.2 Hz); 3.75 (2H, dd, 12.0, 5.2 Hz); 3.15 (2H, m); 2.78
and silicon epoxy monomers with diaminodiphenylmethane (2H, dd, 4.4, 2.8 Hz); 2.65 (2H, dd, 4.4, 2.8 Hz); 0.42 (3H, s).
13
(DDM) or a phosphorus- or silicon-containing diamines. In this way, C NMR (CDCl3/TMS, d (ppm)): 134.0 (d); 132.2 (s); 130.4 (d);
the phosphorus and silicon contents of the resins were altered. 127.9 (d); 63.6 (t); 52.0 (d); 44.5 (t); 4.4 (q).
The degradation behaviours and flame retardant properties were
investigated to examine the possibility of phosphorus–silicon 2.1.3. Synthesis of 1,4-bis(glycidyloxydimethyl silyl)-benzene
synergistic effect. (BGDMSB)
20 ml (22.4 g, 0.3 mol) of glycidol dissolved in 40 ml of anhy-
2. Experimental drous toluene and 0.3 g (0.5 mol% per Si–H) of copper hydride
hexamer catalyst were introduced into a 250 ml Schlenk flask
2.1. Materials containing a magnetic stirrer and sealed with a rubber septum. The
mixture was degassed and infused with argon. 19.5 g (22.4 ml,
Methylphenyl silane (Aldrich), 1,4-bis(hydroxydimethyl silyl) 0.1 mol) of 1,4-bis(dimethylsilyl benzene) was introduced dropwise
benzene (ABCR), bis(dimethylamino)dimethyl silane (ABCR), 4,40 into the reaction flask via dropping funnel for 10 min. At this time
diaminodiphenylmethane (DDM) (Aldrich), triphenylphosphine the reaction solution became red in colour and gas evolution was
(Aldrich), copper(II) chloride (Probus), sodium sulfite (Baker), observed. The reaction mixture was kept at room temperature and
potassium tert-butoxide (Fluka) and Wilkinson catalyst (Aldrich) after 5 h the reaction was complete. After washing with 5% of NH3
were used as received. Glycidol (Aldrich) was vacuum distilled over and water three times and drying with MgSO4, the resulting clear
CaH2 prior to use. p-Aminophenol (Fluka) was recrystallised from oil was dissolved in hexane/ethyl acetate (9:1) mixture and filtered
ethanol. Copper(I) chloride was prepared by the reduction of cop- through a short column of silica gel to remove polar impurities.
per(II) chloride with sodium sulfite. All solvents were purified by By concentration under vacuum a colourless oil (78% yield), pure by
1
standard procedures. H NMR, was obtained.
1
Diglycidyl ether of (2,5-dihydroxyphenyl)diphenyl phosphine H NMR (CDCl3/TMS, d (ppm)): 7.58 (4H, s); 3.82 (2H, dd, 12.0,
oxide (Gly-HPO) was obtained from (2,5-dihydroxyphenyl)diphenyl 3.3 Hz); 3.60 (2H, dd, 12.0, 5.4 Hz); 3.09 (2H, m); 2.76 (2H, dd, 5.2,
phosphine oxide by reaction with epichlorohydrin and BTMA as 4.1 Hz); 2.59 (2H, dd, 5.2, 2.9 Hz); 0.42 (12H, s).
13
catalyst as has been previously described [14]. Bis(3-amino- C NMR (CDCl3/TMS, d (ppm)): 139.7 (s); 132.8 (d); 63.8 (t); 52.1
phenyl)methyl phosphine oxide (BAMPO) was prepared by nitration (d); 44.6 (t); 1.9 (q).
of diphenylmethyl phosphine oxide and subsequent reduction with
HCl and SnCl2 [17]. 2.1.4. Synthesis of bis(4-aminophenoxy)dimethyl silane (APDS)
Into a three-necked round bottom flask equipped with
2.1.1. Synthesis of [(Ph3P)CuH]6 a magnetic stirrer, a dropping funnel and a reflux condenser, 37.3 g
Triphenylphosphine (31.0 g, 0.12 mol), copper(I) chloride (4.6 g, (0.34 mol) of p-aminophenol and 100 ml of anhydrous toluene
0.045 mol) and toluene (200 ml) were added to a dry, septum- were placed. The mixture reaction was vigorously stirred under
capped 500 ml Schlenk flask and placed under argon. The resultant argon and heated to 110  C. Bis(dimethylamino)dimethyl silane
solution was stirred and potassium tert-butoxide (5.1 g, 0.45 mol) (25 g, 0.17 mol) was added dropwise for 60 min. The reaction was
was added. The yellow mixture was placed under positive pressure kept at this temperature for 36 h until no dimethylamine evolution
of hydrogen and stirred overnight. During this period the solution was observed. The dark yellow suspension was filtered to obtain
turned red, then dark red, and some brown material precipitated. a yellow solution that was concentrated under vacuum to obtain
The reaction mixture was transferred under argon pressure to 40 g of a yellow oil that solidifies on standing overnight. The
a 500 ml flask and 250 ml of pentane was added. The solution was product was purified by recrystallisation from hexane/ethyl acetate
cooled promoting crystallization of the product, which was filtered (9:1), and obtained as a yellow solid with a 62% yield.
1
and washed several times with pentane and toluene and dried H NMR (CDCl3/TMS, d (ppm)): 6.75 (4H, d); 6.55 (4H, d); 3.43
under vacuum to give 10.5 g (75% yield) of dark red crystals. (4H, s); 0.30 (6H, s).
13
C NMR (CDCl3/TMS, d (ppm)): 146.7 (s); 140.0 (s); 120.3 (d);
2.1.2. Synthesis of diglycidyloxy methylphenyl silane (DGMPS) 116.2 (d); 2.5 (q).
Into a three-necked round bottom flask equipped with
a magnetic stirrer, a dropping funnel and a reflux condenser, 30 ml 2.2. Curing reactions
of anhydrous toluene, 12.0 g (0.162 mol) of freshly distilled glycidol
and 6.7  102 g (7.2  102 mol, 0.05 mol% per Si–H) of Wilkinson The curing conditions were established by Differential Scanning
catalyst were placed. The red solution was degassed with argon and Calorimetry. Samples (Table 1) were prepared by the dissolution of
heated at 60  C for 30 min, after which 8.8 g (0.072 mol) of meth- epoxy monomers and curing agent in CH3OH or CH2Cl2. Then this
ylphenyl silane was added dropwise over 1 h. Vigorous H2 evolu- solution was evaporated at room temperature in vacuum. About
tion was observed immediately and the reaction mixture was kept 5 mg of a known weight of the mixture was put into the aluminium
 M. Spontón et al. / Polymer Degradation and Stability 93 (2008) 2025–2031 2027

Table 1 Mechanical properties were measured using a dynamic mechanical

Compositions, phosphorus and silicon content and curing data of the epoxy resins thermal analysis (DMTA) apparatus (TA DMA 2928). Specimens
Sample Epoxy monomera Curing P Si Tonsetc Tmaxd DH0e (3  6  10 mm3) were tested in a three point bending configura-
agentb (%) (%) ( C) ( C) (Kj/ee) tion. The thermal transitions were studied in the 100–250  C
1 Gly-HPO DDM 5.9 – 120 150 82 range at a heating rate of 5  C/min and at a fixed frequency of 1 Hz.
2 Gly-HPO BAMPO 8.5 – 137 168 95 LOI values were measured on a Stanton Redcroft, provided with an
3 Gly-HPO APDS 5.5 2.5 112 143 82
oxygen analyser, on bars of the polymers (100  6  3 mm3).
4 DGMPS DDM – 7.7 120 157 83
5 DGMPS BAMPO 4.0 7.2 132 172 –
6 DGMPS APDS – 10.4 117 145 84
7 BGDMSB DDM – 12.8 111 168 83 3. Results and discussion
8 BGDMSB BAMPO 3.4 12.2 148 196 –
9 BGDMSB APDS – 14.7 129 162 83
10 Gly-HPO/DGMPS DDM 3.5 3.2 119 159 88
By using phosphorus- or silicon-containing epoxy compounds
11 Gly-HPO/DGMPS BAMPO 6.6 3.0 136 170 – or phosphorus- or silicon-containing diamine compounds as curing
12 Gly-HPO/DGMPS APDS 3.2 5.8 111 142 82 agents, epoxy resins with different phosphorus or silicon contents
13 Gly-HPO/BGDMSB DDM 3.2 5.8 117 163 91 are obtained. Based on the above, phosphorus-containing epoxy,
14 Gly-HPO/BGDMSB BAMPO 6.2 5.5 123 170 97
Gly-HPO [14], and phosphorus-containing amine, BAMPO, previ-
15 Gly-HPO/BGDMSB APDS 3.0 8.1 114 156 81
ously described [17] are used (Scheme 1). Silicon-containing diep-
a
For the mixtures of epoxy monomers, a 1:1 mol ratio was used. oxides, DGMPS [16] and BGDMSB [15] (Scheme 1) were previously
b
Stoichiometric amounts were used in all cases.
c
Initial temperature of the crosslinking exotherm (10  C/min).
synthesized by catalysed transetherification of the dimethox-
d
Temperature of the maximum heat release rate (10  C/min). ymethylphenyl silane with allylic alcohol and by condensation of
e
Reaction enthalpy values per epoxy equivalent. 1,4-bis(hydroxydimethyl silyl)benzene with allylic alcohol respec-
tively, followed by the epoxidation of the intermediate compounds
pan, and the polymerization was monitored in a dynamic DSC in both cases. These synthetic approaches in two steps, led to
experiment using a heating rate of 10  C/min. The curing conditions a products with moderate yields.
are shown in Table 2. Moulded epoxy resins for DMTA and LOI Alkoxysilanes are usually prepared by reaction of chlorosilanes
measurements were obtained by moulding about 1.5 g of a known with either alcohols or alkoxides. Since these reactions either
weight of the mixture obtained as described above. involve acidic (evolution of HCl) or basic conditions (alkoxide, or
base as HCl acceptor), alternative methods are advantageous. A
particularly mild method is the alcoholysis of hydrogen-substituted
2.3. Instrumentation
silanes, because only H2 is formed as a byproduct. However, alco-
1 hols normally do not attack silanes in the absence of a catalyst and
H (300 MHz) and 13C (75.4 MHz) NMR spectra were obtained
most silanes undergo alcoholysis only in the presence of either
with a Varian Gemini 300 spectrometer with Fourier Transform,
strongly nucleophilic or electrophilic catalysts. A limited number of
with CDCl3 as a solvent, and with TMS as an internal standard. The
transition metal complexes have been reported as homogeneous
IR spectra were obtained with a ATR-FTIR JASCO 680.
catalyst for the alcoholysis of hydrosilanes. The Wilkinson catalyst,
Calorimetric studies were carried out on a Mettler DSC821e
one of the more active catalysts has been used in the present work
thermal analyser using N2 as a purge gas (20 ml/min). Thermal
in the synthesis of DGMPS. The reaction took place at 60  C for 1 h.
stability studies were carried out on a Mettler TGA/SDTA851e/LF/
The Wilkinson catalyst, like most of the transition metal complexes
1100 with N2 and air as a purge gas at scan rates of 10  C/min.
is not active to catalyze the alcoholysis of trialkylsilanes. On the
other hand, the copper hydride complex [(Ph3P)CuH]6 is a very
Table 2
Curing and post-curing conditions and Tg data of the epoxy resins
reactive catalyst for the alcoholysis of hydrosilanes under mild
reaction conditions [18]. It provides silyl ethers in generally high
Sample Epoxy Curing Curing Post-curing Tg ( C)
yields. In this case the tertiary silane, 1,4-bis(dimethyl silyl)benzene,
monomera agentb c
½ D Cp E00 maxd tan dmaxe reacts with glycidol at room temperature for 5 h to give the corre-
1 Gly-HPO DDM 
120 C, 2 h 
200 C, 3 h 193 181 193 sponding silylglycidylether.
2 Gly-HPO BAMPO 140  C, 2 h 200  C, 2 h 198 154 194 Epoxy resins have been prepared by curing with stoichiometric
3 Gly-HPO APDS 120  C, 2 h 180  C, 2 h 167 158 167
amounts of diamine with the compositions, phosphorus and silicon
4 DGMPS DDM 105  C, 2 h 165  C, 2 h 77 72 87
5 DGMPS BAMPO 150  C, 2 h 180  C, 1 h 75 76 84 contents that are shown in Table 1. The reactions were monitored
6 DGMPS APDS 120  C, 3 h 160  C, 3 h 70 63 70 by DSC and showed exotherms with crosslinking enthalpy values
7 BGDMSB DDM 120  C, 2 h 180  C, 2 h 60 62 64 and onset and maximum heat release rate temperatures collected
8 BGDMSB BAMPO 145  C, 2 h 195  C, 2 h 80 90 105 in Table 1. Fig. 1 depicts the crosslinking exotherms for GLY-HPO
9 BGDMSB APDS 120  C, 3 h 180  C, 2 h 59 53 68
10 Gly-HPO/ DDM 120  C, 2 h 180  C, 2 h 125 123 139
with different amines (a), for the APDS amine with different epoxy
DGMPS compounds (b) and for the system Gly-HPO/DGMPS with different
11 Gly-HPO/ BAMPO 145  C, 3 h 195  C, 2 h 146 136 148 amines (c). The diamine curing agent with the lowest peak exo-
DGMPS therm temperature under the same curing conditions was more
12 Gly-HPO/ APDS 120  C, 3 h 160  C, 3 h 120 100 118
reactive towards the epoxy resin. The APDS amine showed the
DGMPS
13 Gly-HPO/ DDM  
120 C, 2 h 180 C, 2 h 123 119 138 highest reactivity and the BAMPO the lowest, either when reacts
BGDMSB with pure epoxy monomer, Gly-HPO, or with a mixture of epoxy
14 Gly-HPO/ BAMPO 145  C, 3 h 195  C, 3 h 145 130 148 monomers, Gly-HPO/DGMPS. The reactivity may vary because of
BGDMSB the electronic effects. An electron-donating group by resonance in
15 Gly-HPO/ APDS 120  C, 3 h 160  C, 3 h 100 84 99
the amine compound, e.g. the oxygen atom in APDS, increased
BGDMSB
a
the electron density of the amine groups towards oxirane ring.
For the mixtures of epoxy monomers, a 1:1 mol ratio was used.
b This effect is lower for DDM because methylene group is an elec-
Stoichiometric amounts were used in all cases.
c
From DSC measurements (10  C/min). tron-donating group by inductive effect. Incorporating electron-
d
Maximum of the loss modulus from DMTA measurements. withdrawing groups such as –P]O groups in BAMPO, reduced the
e
a relaxation peak of the loss factor. activity in curing epoxides.
2028 M. Spontón et al. / Polymer Degradation and Stability 93 (2008) 2025–2031

H2N CH2 NH2

CH2 CH CH2 O O CH2 CH CH2

O O
DDM
Gly-HPO

H2N NH2
CH3
O
CH2 CH CH2 O Si O CH2 CH CH2 P

O O CH3

BAMPO
DGMPS

CH3 CH3 CH3

CH2 CH CH2 O Si Si O CH2 CH CH2 H2N O Si O NH2

O CH3 CH3 O CH3

BGDMSB APDS

Scheme 1.

In addition, the epoxy resins with the lowest peak exothermic The dynamic mechanical behaviour of the phosphorus- and
temperature under the same curing conditions were more reactive silicon-containing epoxy resins was studied as a function of the
towards the curing agent. As can be seen in Fig. 1b Gly-HPO and temperature beginning in the glassy state of each composition to
DGMPS showed the highest reactivity. We previously reported the rubbery plateau of each material. Fig. 2 shows the obtained
[16,19] that silicon-containing oxiranes have higher reactivity due plots for Gly-HPO (a), for the APDS amine (b) and for the system
to electronic effects. The silicon atom acts as a p acceptor, with- Gly-HPO/DGMPS (c). The crosslinking density of a polymer can be
drawing the electron density of the oxygen atom and increasing its estimated from the plateau of the elastic modulus in the rubbery
electron-withdrawing character. Therefore, the electrophilic state [21]. This theory is strictly valid for lightly crosslinked mate-
character of the oxirane carbons increases. The high reactivity of rials, and was therefore used to make qualitative comparisons of
Gly-HPO may be also explained due to an increase in the electron- the crosslinking density among the various polymers. As can be
withdrawing character of the oxygen, because the resonance effect seen in Fig. 2 for the crosslinking of Gly-HPO, the lower crosslinking
of P]O group in the ortho position to the glycidyl moiety. BGDMSB density is obtained when APDS is used as a curing agent. As far as
showed the lowest reactivity because the p acceptor character of the chemical structures of these networks are concerned, this
the silicon atom towards oxygen atom diminishes due to the behaviour is to be expected since longer Si–O and Si–C bonds
adjacent aromatic ring. Even for the systems Gly-HPO/BGDMSB should provide flexibility to the backbone. A similar trend can be
which show the higher reactivity difference between epoxy observed for the systems Gly-HPO/DGMPS. When comparing the
monomers only an exotherm appears, thus indicating that cross- crosslinking density of the epoxy monomers cured with APDS
linking takes place homogeneously. (Fig. 2b), it can be seen that the lower crosslinking density is ach-
According to DSC data epoxy networks were prepared at the ieved for DGMPS, which contains additional Si–O and Si–C units
curing and post-curing conditions shown in Table 2. FTIR spec- that confer flexibility to the network.
troscopy showed the disappearance of the absorption at 910 cm1 The plots of loss factor versus temperature show the a relaxa-
of the oxirane ring, thus confirming that the curing reaction takes tion peak, which is associated with the Tg of the materials and
place to completion. follows the trend mentioned earlier. Moreover, the analysis of the
Table 2 also summarizes the Tgs of the crosslinked materials that height and width of the a relaxation peak shows trends in the
can be detected as an endothermic step in the heat flow by DSC, as crosslinking densities and network homogeneities. The height of
the maximum of the loss modulus (E00 ) and as the a relaxation peak the tan d peak decreases for the APDS crosslinked systems. Because
of the loss factor by DMTA. As can be seen the most decisive tan d is the ratio of viscous component to elastic component, it can
parameter that affects the Tg value is the epoxy monomer. Higher Tg be assumed that the decreasing height is associated with lower
values were obtained for Gly-HPO, which contains a strong polar segmental mobility and fewer relaxing species, and is therefore
P]O group and a bulky pendant moiety that causes restriction in the indicative that networks for the APDS containing systems show
segmental mobility. The Tg values decrease for the DGMPS epoxy higher flexibility. The peak width at half height broadens as the
thermosets, what can be explained by the presence of Si–O and Si–C number of branching modes increases, which produces a wider
units and the lower proportion of aromatic moieties in the backbone. distribution of structures. The range of temperatures at which the
The Tg of thermosets from BGDMSB has the lowest Tg values that different network segments gain mobility therefore increases.
must be related to a larger volume fraction of Si–O and Si–C units in There were no significant differences among the different samples,
the backbone. thus showing similar branching distribution for all samples.
The mixed epoxy systems exhibit a single Tg between the Tgs To examine the effect of phosphorus and silicon content on
of pure epoxy monomers, indicating a homogeneous morphology thermal stability and the decomposition behaviour, TGA data under
for these systems, in accordance with the observations of other nitrogen and air atmospheres were determined and analyzed. Fig. 3
authors [20]. shows the weight loss with the temperature for some of the epoxy
 M. Spontón et al. / Polymer Degradation and Stability 93 (2008) 2025–2031 2029

a ^exo 3 a 10000
1
2
1000

Storage Modulus (MPa)

100
1

10 2

1 3
40 60 80 100 120 140 160 180 200 220 240 °C

6 0.1
b 40 90 140 190 240
Temperature (°C)
9
10000
3 b

1000

Storage Modulus (MPa) 100

9
40 60 80 100 120 140 160 180 200 220 240 °C 3
10

12
c 10
6
1

0.1
11 40 90 140 190 240
Temperature (°C)

c 10000

1000
Storage Modulus (MPa)

40 60 80 100 120 140 160 180 200 220 240 °C

100
Fig. 1. DSC plots of systems (a) 1 (Gly-HPO/DDM), 2 (Gly-HPO/BAMPO) and 3
(Gly-HPO/APDS); (b) 3 (Gly-HPO/APDS), 6 (DGMPS/APDS) and 9 (BGDMSB/APDS); (c)
10 (Gly-HPO/DGMPS/DDM), 11 (Gly-HPO/DGMPS/BAMPO) and 12 (Gly-HPO/DGMPS/ 11
APDS). 10

10
compositions. Table 3 summarizes the thermogravimetric data. 1
Decomposition temperatures (T5%) for the phosphorus-containing 12
resins are lower than for the conventional epoxy resins due to the
decomposition of P–C bonds which have lower thermal stability 0.1
than C–C bonds [22]. Moreover, decomposition temperatures for 40 90 140 190 240
the silicon-containing resins are also expected to be lower than Temperature (°C)
conventional epoxy resins. The Si–O unit can decompose at lower
Fig. 2. Storage modulus for (a) 1 (Gly-HPO/DDM), 2 (Gly-HPO/BAMPO) and 3
temperatures leading to the formation of the silicone-containing (Gly-HPO/APDS); (b) 3 (Gly-HPO/APDS), 6 (DGMPS/APDS) and 9 (BGDMSB/APDS); (c)
group [16]. In our case, independent of the atmosphere, all the 10 (Gly-HPO/DGMPS/DDM), 11 (Gly-HPO/DGMPS/BAMPO) and 12 (Gly-HPO/DGMPS/
thermosets start the degradation at similar temperatures, being APDS).
slightly lower in air. No relationships between decomposition
temperatures and phosphorus or/and silicon contents can be
established. Again, no relationships can be established. In air a third stage in the
In nitrogen, two different behaviours can be observed. Some decomposition process is observed at temperatures above 500  C.
samples exhibit a single major break in their decomposition curve Under an air atmosphere, the weight loss of a polymeric material
before their major weight losses level off. This behaviour is indic- at these temperatures came from the oxidation of the formed
ative of a single mechanism of decomposition which is similar for char. According to the mechanism of improved fire performance
these resins. The others show a two step break in the decomposi- via phosphorus incorporation, the phosphorus groups form an
tion curves, suggesting a more complex decomposition pathway. insulating protective layer which prevents the volatiles from
2030 M. Spontón et al. / Polymer Degradation and Stability 93 (2008) 2025–2031

a 100 N2 100
90 90 air
80 80
70 70
60 60
%

%
50 50
2
40 40
2
30 30
20 20
10 3 10 3 1
1
0 0
50

0
0
0
0
0
0
0
0
0
0
0
0
0
0
°C

50

0
0
0
0
0
0
0
0
0
0
0
0
0
0
°C
10
15
20
25
30
35
40
45
50
55
60
65
70
75

10
15
20
25
30
35
40
45
50
55
60
65
70
75
b 100 100
90 N2 90 air
80 80
70 70
60 60
6

%
%

50 50
40 6 40
30 30
3 3
20 20
9
10 9 10
0 0
50

0
0
0
0
0
0
0
0
0
0
0
0
0
0
°C

50

0
0
0
0
0
0
0
0
0
0
0
0
0
0
°C
10
15
20
25
30
35
40
45
50
55
60
65
70
75

10
15
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25
30
35
40
45
50
55
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65
70
75
c 100 100
90 N2 90 air
80 11 80
70 10 70
60 60
12
%

50 50
40 40 11
30 30 12
20 20
10 10 10
0 0
50

0
0
0
0
0
0
0
0
0
0
0

°C
0
0
0

50

0
0
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°C
0
0
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0
0
0
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10
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55
60
65
70
75

10
15
20
25
30
35
40
45
50
55
60
65
70
75

Fig. 3. TGA plots in nitrogen and air for (a) 1 (Gly-HPO/DDM), 2 (Gly-HPO/BAMPO) and 3 (Gly-HPO/APDS); (b) 3 (Gly-HPO/APDS), 6 (DGMPS/APDS) and 9 (BGDMSB/APDS); (c) 10
(Gly-HPO/DGMPS/DDM), 11 (Gly-HPO/DGMPS/BAMPO) and 12 (Gly-HPO/DGMPS/APDS).

Table 3
Thermogravimetric data of epoxy resins

Sample P (%) Si (%) Nitrogen Air LOI %O2 (V/V)

T5%a ( C) Tm1b ( C) Tm2b ( C) Charc (%) T5%a ( C) Tm1b ( C) Tm2b ( C) Tm3b ( C) Charc (%)
1 5.9 – 345 390 430 23 338 383 456 550 22 31.0
2 8.5 – 352 410 450 25 352 393 458 560 29 32.0
3 5.5 2.5 335 350 435 20 328 342 460 630 27 31.0
4 – 7.7 318 – 415 34 302 325 412 580 16 36.0
5 4.0 7.2 308 – 430 33 312 380 470 750 31 38.0
6 – 10.4 320 350 – 35 306 356 – 745 22 37.0
7 – 12.8 362 – 439 21 348 419 – 690 12 33.5
8 3.4 12.2 358 – 420 15 307 416 – 680 11 33.9
9 – 14.7 329 362 420 18 320 430 – 700 9 33.0
10 3.5 3.2 336 – 400 23 338 380 470 595 13 36.5
11 6.6 3.0 341 – 406 24 332 385 460 560 31 34.0
12 3.2 5.8 327 340 390 25 319 350 478 575 22 34.6
13 3.2 5.8 330 – 400 19 302 390 470 600 9 34.0
14 6.2 5.5 331 395 447 16 323 380 475 564 24 33.5
15 3.0 8.1 317 355 – 17 304 420 480 605 16 33.6
a
Temperature of 5% weight loss.
b
Temperature of the maximum weight loss rate.
c
Char yield at 800  C.
 M. Spontón et al. / Polymer Degradation and Stability 93 (2008) 2025–2031 2031

40

38
37 34
35
33 34
34 36
36 34 37 34
35
34
32
LOI

30
3133
31
30 29
25 31
31
31 30
29 31
27
28
20 26

15 25
24 10
10 8
6
%Si 5 4
%P
2
0 0

Fig. 4. Plot of LOI values for phosphorus-, silicon- and phosphorus–silicon-containing epoxy resins.

transferring to the surface of the materials and increases the properties that could bring some benefits to the epoxy resins in
thermal stability of the char at higher temperatures. Silicon-con- applications. A synergistic effect cannot be observed for phos-
taining polymers are described that can degrade forming thermally phorus–silicon-containing resins.
stable silica, which have the tendency to migrate to the char surface
serving as a protection layer to prevent further degradation of char Acknowledgements
at high temperatures [8]. For the P–Si synergistic effect of flame
retardation, it has been described that phosphorus provides The authors express their thanks to CICYT (Comisión Inter-
a tendency for char formation and silicon favorably provides an ministerial de Ciencia y Tecnologı́a) (MAT2005-01593) for
enhancement of the thermal stability of the char, resulting in a high providing financial support for this work.
efficiency of char formation which exhibits extremely high thermal
stability and antioxidant properties. In our case, no increase in the
amount of char yield in air at 800  C with the P þ Si content was References
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[3] Hamerton I, Lu SY. Prog Polym Sci 2002;27:1661.
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[19] Mercado LA, Galià M, Reina JA, Garrido M, Larrechi MS, Rius FX. J Polym Sci
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was DGMPS and the most reactive curing agent was APDS because [20] Wang WJ, Perng LH, Hsiue GH, Chang FC. Polymer 2000;41:6113.
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[22] Quittmann U, Lecamp L, El Khatib W, Youssef B, Bunel C. Macromol Chem Phys
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obtained, with the corresponding excellent flame retardant [23] Ribera G, Mercado LA, Galià M, Cádiz V. J Appl Polym Sci 2006;99:1367.