Synthesis of novel copolymers obtained from acceptor/donor radical copolymerization of phosphonated allyl monomers and maleic anhydride

Article abstract of DOI:10.1002/pola.24827

A series of four phosphonated-bearing allyl monomers, that is, diethyl-1-allylphosphonate (AP), dimethyl-1-allyloxymethylphosphonate (AOP), 5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (AEDPH), and 2-benzyl-5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (AEDPBn) were synthesized. These monomers were then copolymerized by free radical polymerization in the presence of maleic anhydride, thus leading to alternated copolymers with phosphonate moieties. It was shown that both monomer conversion and reaction rate were dependent on the phosphonate moieties carried out by the allyl monomer: the bulkier the phosphonate group, the higher the polymerization rate. Thermogravimetric analysis of the copolymers revealed a high content of residue, also varying with the nature of the phosphonate moieties.

Full text of DOI:10.1002/pola.24827

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ARTICLE
Synthesis of Novel Copolymers Obtained from Acceptor/Donor
Radical Copolymerization of Phosphonated Allyl Monomers and
Maleic Anhydride
C. Negrell-Guirao, G. David, B. Boutevin, K. Chougrani
Institut Charles Gerhardt UMR 5253, Universite´ de Montpellier II, Universite´ de Montpellier I, Centre National de Recherche
Scientifique and Ecole Nationale Supe´rieure de Chimie de Montpellie, IAM, Rue de l’e´cole normale,
34296 Montpellier cedex 5, France
Correspondence to: G. David (E-mail: ghislain.david@enscm.fr)
Received 21 April 2011; accepted 8 June 2011; published online 29 June 2011
DOI: 10.1002/pola.24827
ABSTRACT: A series of four phosphonated-bearing allyl
monomers, that is, diethyl-1-allylphosphonate (AP), dimethyl-1-
allyloxymethylphosphonate (AOP), 5-ethyl-5-(allyloxymethyl)-2-
oxo-1,3,2-dioxaphosphorinane (AEDPH), and 2-benzyl-5-ethyl-5-
(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane (AEDPBn) were
synthesized. These monomers were then copolymerized by free
radical polymerization in the presence of maleic anhydride, thus
leading to alternated copolymers with phosphonate moieties. It
was shown that both monomer conversion and reaction rate
were dependent on the phosphonate moieties carried out by the
allyl monomer: the bulkier the phosphonate group, the higher the
polymerization rate. Thermogravimetric analysis of the copoly-
mers revealed a high content of residue, also varying with the na-
C
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ture of the phosphonate moieties. 2011 Wiley Periodicals, Inc.
J Polym Sci Part A: Polym Chem 49: 3905–3910, 2011
KEYWORDS: AD copolymerization; allyl monomer; copolymer-
ization; dioxaphosphorinane; flame retardance; heteroatom-
containing polymers; kinetics (polym.); maleic anhydride;
radical polymerization; thermogravimetric analysis
INTRODUCTION Flame retardants (FR) for textiles1,2 have
never had so much interest as the recent introduction of a
strict legislation, especially focusing on halogenated com-
pounds. Then, phosphorus atoms containing FR progressively
came to replace halogenated ones.3–7 These phosphorus-
based flame retardants additives are generally incorporated
into polymeric materials as additives in melted polymers.
These FR additives usually have low molecular weight, which
may undergo migration to the surface of polymeric materials,
in time and uses. This exudation sometimes creates a change
in the mechanical properties as well as in the FR behavior of
the material. Hence FR additives having higher Mw should
allow reducing this phenomenon. A wide range of phospho-
rus-containing polymers were synthesized and used as FR
additives of polymeric materials.8–10 Phosphorus-containing
allyl monomers have also attracted much interest. We have
recently developed11,12 the synthesis of polymers from radi-
cal polymerization of 2-R-5-ethyl-5-(allyloxymethyl)-2-oxo-
1,3,2-dioxaphosphorinane (Scheme 1).
mers usually results in low Mw oligomers, mainly due to
degradative chain transfer.13–15 The weakness of the allyl
CAH bond arises from the high resonance stability of the
allyl radical, which is too stable to reinitiate polymerization
and undergoes termination by reaction with a propagating
radical.11
However, if allyl monomers poorly homopolymerized, they
are good candidates in radical copolymerizations. Indeed,
allyl monomers, as electron-donating monomers, are able to
efficiently copolymerize with high electron-accepting mono-
mers, leading to high Mw copolymers. As an example, Nippon
Oils and Fats Corporation16 performed the radical copoly-
merization of allyl ether, containing (oxyalkylenes) side
groups of Mw ranging from 400 to 5000 g molꢀ1, with ma-
leic anhydride (Scheme 2). The resulting copolymer was sold
R
under the MALIALIMV trademark.
Furthermore, the radical copolymerizations of vinyl mono-
mers can be carried out either by heating or under UV light,
with or without photoinitiator.17
We also showed that, depending on both the reaction condi-
tions and of the R substituent, the resulting polymeric spe-
cies could have either hyperbranched (with high Mw values)
or linear structure (with low Mw values). Indeed, it is well-
known that the radical homopolymerization of allyl mono-
To our knowledge, no study was achieved, so far, on the radi-
cal copolymerization of phosphonated-containing allyl mono-
mers with electron-accepting monomers. The purpose of this
work is first to prepare a series of phosphonated allyl
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SCHEME 1 Polymerization of 2-R-5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphorinane by radical solution procedure (CTA
stands for Chain Transfer Agent).
monomers, which then will be used as electron-donating
monomers in radical copolymerizations with electron-accept-
ing monomers (such as maleic anhydride). Kinetics of radical
copolymerizations were investigated as well as the thermal
properties of the resulting copolymers.
firmed by 1H NMR (Fig. 1), especially by considering the
peak centered at 2.34 ppm, characterizing the methylene ad-
jacent to the phosphonate group. 31P NMR showed only one
peak at 26.8 ppm for the phosphonate group.
To the author’s knowledge, the synthesis of AOP has never
so far been described. AOP was obtained by nucleophilic
substitution of allyl bromide by a primary alcohol bearing a
phosphonate group (Scheme 4).
RESULTS AND DISCUSSION
Synthesis of Phosphonate-Bearing Allyl Monomers
Four phosphonated-bearing allyl monomers were selected for this
study. Scheme 3 gathers the structures of the monomers: diethyl-
1-allylphosphonate (AP), dimethyl-1-allyloxymethylphosphonate
This reaction requires an equimolar amount of allyl bromide
and primary alcohol. The functional alcohol, that is, dimethyl
hydroxymethylphosphonate, was previously synthesized
from reaction of dimethylhydrogenophosphonate with para-
formaldehyde using anhydrous potassium carbonate, as
described elsewhere.22,23 Following this procedure, AOP was
obtained in quantitative yield. The high purity of AOP
was evidenced from 31P NMR as a single peak in 24 ppm
was observed (Fig. 2). 1H NMR (Fig. 2) also allows to per-
fectly characterizing AOP: allyl protons signal is shown at d
¼ 5.8-5.2 ppm, the signal of CH2 in a-position is centered at
d ¼ 4.03 ppm and the 8 others protons show a broad signal
centered at d ¼ 3.75 ppm.
(AOP),
5-ethyl-5-(allyloxymethyl)-2-oxo-1,3,2-dioxaphosphori-
nane (AEDPH) and 2-benzyl-5-ethyl-5-(allyloxymethyl)-2-oxo-
1,3,2-dioxaphosphorinane (AEDPBn).
We can note that AOP, AEDPH, and AEDPBn are allyl-oxy
monomers. Both AP and AOP contain a dialkylphosphonate
group, whereas both AEDPH and AEDPBn have a dioxaphos-
phorinane group. None of them is commercially available
and, hence, need to be synthesized. AEDPH and AEDPBn
syntheses, described in a recently published paper,12 consist
on a direct transesterification of a diol with hydrogen or
arylphosphonate.
Free Radical Copolymerization
As mentioned in the literature, diethyl-1-allylphosphonate
(AP) monomer was obtained by reaction of allyl bromide
(Scheme 4) with triethylphosphite, according to Arbusov
rearrangement,18–21 that is, isomerization of P(OR)3 into
(RO)2P(¼¼O)R0 (where R0 corresponds to allyl group). The
Arbuzov reaction of triethyl phosphite with commercial allyl
bromide afforded AP with 95% yield. The structure was con-
It is widely recognized that conventional radical homopoly-
merization of allyl monomers usually leads to low molecular
weights oligomers (DPn less than 50 units); this behavior is
generally ascribed to chain transfer process occurring onto
the methylene group of allyl monomers, then limiting the
SCHEME 2 MALIALIM structures obtained by radical copoly-
SCHEME 3 Structures of phosphonated-bearing allyl mono-
merization of maleic anhydride with allyl ether.
mers AP, AOP, AEDPH, and AEDPBn.
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SCHEME 4 Synthesis of dimethyl-1-allyloxymethylphosphonate
(AOP) and of diethyl-1-allylphosphonate (AP).
propagation reaction.14,15,24 As already mentioned in the
introduction part, allyl monomers are good electron-donating
monomers, and their radical copolymerizations with elec-
tron-accepting monomers mainly afford alternated copoly-
mers. The capability of monomers to efficiently copolymerize
is connected to both their polarizing effect and their ability to
accept/give electrons. These Alfrey-Price parameters, noted Q
(for polarizing effect) and e (for the ability to give/accept elec-
trons), must be known in order to estimate the copolymer
structures, that is, statistical or alternated structures. If the
polarizing effects are similar for both monomers (i.e., values of
Q very close), then the polymerization will turn into alternated
radical copolymerization. Besides, if two monomers show op-
posite values for e parameter, then expected alternated copoly-
mer should be also obtained. According to the literature, allyl
monomers usually exhibit negative values for e parameter,
which enhances the electron-donating character of allyl mono-
mers. For instance, allyl butyl ether and allyl alcohol show e val-
ues of ꢀ2.53 and ꢀ1.48, respectively. When involved in radical
copolymerizations with maleic anhydride, maleimides or mal-
eates (showing e values of 3.69, 3.3, and 1, respectively), it
turned to alternated structures.25 Some others papers also
described the radical copolymerization between alkyl allyl
ethers and monomers such as vinyl acetate,26 maleic anhydride
(MA),27 maleates,28,29 maleimides or fluorinated olefins.30–32
In all cases, alternated copolymers were obtained. Noteworthy,
if the radical copolymerization of allyl ethers usually leads to
alternated copolymers, the final conversion is lowered by using
FIGURE 2 1H and 31P NMR spectrum of dimethyl-1-allyloxyme-
thylphosphonate (AOP).
different electron-accepting monomers, that is, butyl acrylate,
dialkyl maleate or fumarate. Among all electron-accepting
monomers, maleic anhydride (MA) appears to be the most effi-
cient to obtain alternated copolymers by radical copolymeriza-
tions with allyl monomers, according to its Q and e parameters
(0.86 and 3.69, respectively).33 As mentioned earlier, the radi-
cal copolymerization of allyl ether, containing (oxyalkylenes)
side groups, with MA afforded alternated copolymer produced
R
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and sold under the MALIALIM trademark.
Hence, in this study, the radical copolymerizations of phospho-
nate-bearing allyl monomers (AP, AOP, AEDPH, and AEDPBn)
were investigated with MA as electron-accepting monomer. For
each radical copolymerization involving phosphonate-bearing
allyl ether/MA, the reaction conditions were the following: ace-
tonitrile as solvent with a molar ratio concentration S0 of 4 (S0
¼ [solvent]0/[monomers]0), AIBN as initiator with a molar ra-
tio concentration C0 of 0.05 (C0 ¼ [initiator]0/[monomers]0).
All radical copolymerizations were carried out at 70 ꢁC with a
MA/allyl monomer molar ratio of 1/1 (Scheme 5).
SCHEME 5 Radical copolymerizations of maleic anhydride with
phosphonate-bearing allyl monomers. MA/ABE (allyl butyl
ether) radical copolymerization was used as model reaction.
FIGURE 1 1H and 31P NMR spectrum of dimethyl-1-allylphos-
phonate (AP).
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TABLE 1 Monomer Conversions, Molecular Weight, and
Polydispersity Index Obtained for the Radical
Copolymerizations of Phosphonate-Bearing Allyl Monomers
with MA Carried Out at 70 8C in Acetonitrile in the Presence of
AIBN and Stopped after 24 h
Mn (g/mol)b
PDIb
a
a
Copolymer
aAllyl
aMA
MA/ABE
MA/AP
0.99
0.49
0.45
0.80
0.98
0.68
0.78
0.97
2.500
1.700
1.600
8.300
1.9
2.3
2.9
1.8
MA/AOP
MA/AEDPBn
Results for radical copolymerization of MA with allyl butyl ether are
also given for comparison.
a
Monomer conversions obtained from 1H NMR after 24 hrs of reaction.
Calculated from SEC analysis in DMF by using PMMA standards.
FIGURE 3 Kinetic plots of allyl monomer conversion vs reac-
tion time for the radical copolymerizations of MA with a series
of phosphonate-bearing allyl monomers (AP, AOP and
AEDPBn) carried out at 70 ꢁC in acetonitrile in the presence of
AIBN. Radical copolymerization of MA with allyl butyl ether
(ABE) is also given for comparison.
b
This behavior is ascribed to predominant radical transfer
onto ABE, referred to as ‘‘degradative monomer chain trans-
fer.’’ Inoue et al.14 have therefore estimated the chain transfer
constant Cm of allyl acetate of about 3.7 ꢂ 10ꢀ2 at 80 ꢁC.
The MA/phosphonate allyl monomers free radical copoly-
merizations show different trend, as compared to MA/ABE
copolymerization. First the polymerization rates are lowered,
according to monomers conversion, which highlights the
decrease of the electron-donating character for phosphonate-
bearing allyl monomers. Such decrease was already observed
by Skwarski and Wodka34,35 during the free radical copoly-
merization of acrylonitrile with phosphonate-bearing allyl
monomer. This decrease was indeed denoted by the Q and e
values of 0.02 and ꢀ0.15, respectively for the phosphonate-
bearing allyl monomer. Nevertheless, we can note distinct
behaviors between phosphonate-allyl type monomers. Con-
cerning MA/AEDPBn free radical copolymerization, after 24
hrs of reaction 1H NMR of the crude reaction mixture gave
allyl conversions (aAEDPBn) of 80%, the maleic anhydride
conversion (aAM) increased further up to 97%. AEDPBn con-
version shows a two-step kinetic; a first-order kinetic is
observed with a sharp increase until 60% of conversion after
1 hr, followed by a slow-down of the monomer conversion.
The sharp increase may be explained by the affinity of ma-
leic anhydride radical towards allyloxy monomer, that is,
acceptor-donor (AD) free radical copolymerization. This also
demonstrates that the electron-donating character of
AEDPBn is not lowered by the phosphonate moities, situated
far from the allyl double bond. The slowdown of the poly-
merization may be explained either by the benzyl-dioxaphos-
phorinane group or by occurrence of termination reaction
(contribution of both phenomena is not excluded). MA/
AEDPH free radical copolymerization was also performed in
the same experimental conditions but a gelification of the
reaction mixture was observed. This gel was insoluble in
conventional organic solvents such as THF, dichloromethane,
acetone or even in DMF… Despite the presence of MA, hyper-
branched species were indeed growing due to the reactivity
of the P-H bond, as already mentioned in a previous arti-
cle.11 MA/AP and MA/AOP free radical copolymerizations
proceed similarly (Fig. 3). Indeed, the conversion profiles of
Allyl butyl ether (ABE)/MA radical copolymerization was
carried out as a model reaction by using the aforementioned
reaction conditions. Kinetic plots of allyl monomer conver-
sion were reported (Fig. 3) against reaction time for each
radical copolymerization.
Kinetic plots of allyl monomer conversion vs reaction time
for the radical copolymerizations of MA with a series of
phosphonate-bearing allyl monomers (AP, AOP, and AEDPBn)
carried out at 70 ꢁC in acetonitrile in the presence of AIBN.
Radical copolymerization of MA with allyl butyl ether (ABE)
is also given for comparison.
We can note that, expectedly, reaction completion was
observed after only few hours for MA/ABE radical copolymer-
ization. The copolymers were precipitated into methanol and
molecular weights were evaluated by means of SEC. Monomer
conversions obtained after 24 hr of reaction as well as molec-
ular weight values and PDI are also given (Table 1).
Free radical copolymerization of MA/ABE affords low molec-
ular weights oligomers with rather low polydispersity values.
FIGURE 4 TGA thermograms of MA/ADEPBn, MA/AOP and MA/
AP copolymers recorded in nitrogen atmosphere 10 ꢁCꢃmin-1.
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TABLE 2 Thermal Stability of Copolymers
Copolymer
P Content (%)a
T Onset (ꢁC)b
T10% (ꢁC)c
T50% (ꢁC)c
Residue at 600 ꢁC (%)
Tg (ꢁC)d
MA/ABE
MA/AEDPBn
MA/AOP
MA/AP
a
/
285
180
150
140
303
260
240
165
d
399
440
430
310
13
23
41
36
79
118
85
7.5
10.5
10.5
105
P content is the phosphorus content in the copolymer.
Glass transition temperature obtained from DSC analysis.
b
c
T onset corresponds to the temperature of the decomposition onset.
T10% and T50% are the temperatures at 10% and 50% weight loss,
respectively.
both AP and AOP are identical, that is, denoting a very slow
polymerization rate. The resulting copolymers show low mo-
lecular weight values (ca. 1600 g/mol) for high PDI (Table
1). This behavior can be explained by the close proximity of
the phosphonate moieties to the allyl double bond, thus low-
ering the electron-donating effect of the allyl group. The high
polydispersity associated to the low molecular weights val-
ues is probably the result of either occurrence of termination
process or radical transfer.
groups, MA/AP and MA/AOP copolymers easily form P-O-P
anhydride bonds highly thermally stable.20 In the other way,
MA/AEDPBn copolymer has a lower phosphorous content,
which explains the lower content of residue. Finally, we can
note that MA/AOP copolymer, having the same phosphorous
content and the same Mw value than MA/AP, gives both a
better stability and a higher content of residue. MA/ABE co-
ꢁ
polymer shows a starting thermal degradation at 250 C but
low residue content (ca. 13%) was obtained at 600 ꢁC,
which enhances the contribution of phosphonate groups in
the condensed phase. Finally, MA/AOP copolymer is probably
a good candidate as flame retardant additive; this will be
studied in a forthcoming paper.
Thermal Behavior
DSC curves of copolymers were operated at 20 ꢁC/min heating
rate. As shown in Table 2, only one glass transition was
observed for each copolymer. The Tg value increases with the
steric hindrance of the lateral group (i.e., phosphonate or diox-
aphosphorinane). Recently, organo-phosphorus compounds
have demonstrated good ability in imparting flame retardancy
to polymers and some researchers reported that they work ei-
ther in both condensed and gas phase.36 They degrade at a rel-
atively low temperature and form a protective layer of char
rather than yielding to radicals capturing volatiles during
decomposition. Thermogravimetric analyses (TGA) of copoly-
mers were performed under nitrogen atmosphere at a heating
rate of 10 ꢁC/min, from 50 to 600 ꢁC. Detailed TGA data
including initial decomposition temperature (Tonset), the tem-
peratures at 10 and 50% weight loss (T10 and T50) and the
fraction of residue at 600 ꢁC, are summarized in Table 2.
EXPERIMENTAL
All the solvents and reagents (Sigma-Aldrich, Fluka or Acros)
were used with a purity of 98–99%. 1,3-propanediol, diethyl
hydrogenophosphonate, dimethyl hydrogenophosphonate,
allyl butyl ether, 2-(allyloxymethyl)-2-ethyl-1,3-propanediol,
allyl bromide, benzyl bromide, sodium hydride (60% in oil),
triethyl phosphite, potassium tert-butoxide were used without
purification. 2,2’-azobis(isobutyronitrile) (AIBN) was purified
by recristallization from methanol and dried under vacuum.
1H and 31P NMR spectra were recorded in CDCl3 solutions on a
Bruker Avance 400 MHz spectrometer. 1H and 31P chemical
shifts are expressed in ppm/TMS and ppm/H3PO4 external
standard, respectively. Size exclusion chromatography (SEC)
was performed on a Varian apparatus equipped with a RI Sho-
dex refractive index detector. Two PL-gel mix D columns were
used at 70 ꢁC with a 0.8 mL minꢀ1 flow rate of DMF, calibrated
using poly(methyl methacrylate) or PMMA standards. TGA
experiments were conducted on a Pyris 1 TGA by Perkin–Elmer.
They were performed on 2–10 mg samples under nitrogen at a
First, the initial decomposition temperature was rather low
for the three copolymers, according to the progressive loss
of solvent (i.e., water). Then, MA/AEDPBn copolymer shows
a better thermal behavior until about 450 ꢁC. The benzyl
group attached to the phosphonate moieties enhances the
thermal stability of MA/AEDPBn copolymer, as compared to
alkyl ester groups. The better resistance of benzyl groups
was already mentioned in the literature.3,4,37,38 Furthermore,
Hoang et al.3,4 showed that the thermal degradation behavior
of phosphonate-bearing (co)polymers is mainly dependant
on the nature of pendant groups directly linked to the phos-
phorus atom. The sharp decrease of the thermal stability
until about 350 ꢁC for both MA/AP and MA/AOP, corre-
sponding to about 35% weight loss, was attributed to the
cleavage of ester group from phosphonate moieties. Never-
theless, the content of residue for both MA/AP and MA/AOP
is rather high (ca. 36–40%) and more important than for
MA/AEDPBn copolymer. Indeed, after the loss of alkyl
heating rate of 10 C minꢀ1. Differential scanning calorimeter
ꢁ
analyses were recorded with a Netzsch 200 Maı¨a DSC at a heat-
ing rate of 20 ꢁC/min under nitrogen atmosphere.
Synthesis of Dimethyl-1-allyloxymethylphosphonate
(AOP)
To a solution of NaH (0.99 g, 4 ꢂ 10ꢀ2 mol) in dry THF (40
ꢁ
mL), under inert gas at 0 C, was added dropwise a mixture
of 4.2 ꢂ 10ꢀ2 mol (5.0 g) of allyl bromide and 4.2 ꢂ 10ꢀ2
mol (4.6 g) of dimethyl hydroxymethylphosphonate. The
reaction mixture was stirred at room temperature during 24
hrs. The precipitated NaBr was removed by filtration and the
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6 Liu, Y.-L.; Hsiue, G. H.; Chiu, Y. S.; Jeng, R. J.; Perng, L. H.
J Appl Polym Sci 1996, 61, 613–621.
solvent was evaporated. The dimethyl allyloxymethylphosph-
onate was obtained in quantitative yield.
7 Levchik, S. V.; Weil, E. D. Adv Fire Retard Mater 2008, 41–66.
1H NMR (400 MHz, CDCl3, d): 3.72 (s, H5); 3.75 (d, H7); 4.03
(s, H3); 5.18-5.27 (dd, H1) and 5.82 (m, H2). 31P NMR (400
MHz, CDCl3, d): 24.03 (P-C).
8 Quittmann, U.; Lecamp, L.; El Khatib, W.; Youssef, B.; Bunel,
C. Macromol Chem Phys 2001, 202, 628–635.
9 Wang, Q.; Shi, W. Eur Polym J 2006, 42, 2261–2269.
10 Youssef, B.; Lecamp, L.; El Khatib, W.; Bunel, C.; Mortaigne,
B. Macromol Chem Phys 2003, 204, 1842–1850.
Synthesis of Diethyl-1-allylphosphonate (AP)
Into a flask equipped with a dean-starck, 6 ꢂ 10ꢀ2 mol (9.95
g) of triethyl phosphite was added to 9 ꢂ 10ꢀ2 mol (10.8 g)
of allyl bromide under nitrogen. The resulting solution was
stirred for 14 hrs at 80 ꢁC. The product was distilled under
reduced pressure (5 mmHg) with a yield of 95%.
11 Negrell-Guirao, C.; Boutevin, B. Macromolecules 2009, 42,
2446–2454.
12 Negrell-Guirao, C.; Boutevin, B.; David, G.; Fruchier, A.; Son-
nier, R.; Lopez-Cuesta, J. M. Polym Chem 2011, 2, 236–243.
13 Inoue, S.; Tamezawa, H.; Aota, H.; Matsumoto, A.;
Yokoyama, K.; Matoba, Y.; Shibano, M. Macromolecules 2011,
44, 3169–3173.
1H NMR (400 MHz, CDCl3, d): 1.05 (m, H7); 2.34 (m, H3);
3.83 (m, H6); 4.94 (m, H1) and 5.53 (m, H2). 31P NMR (400
39
ꢁ
MHz, CDCl3, d): 26.76 (P-C). Bp ¼ 102 C (11 mmHg).
14 Inoue, S.; Kumagai, T.; Tamezawa, H.; Aota, H.; Matsumoto,
A.; Yokoyama, K.; Matoba. Y.; Shibano, M. J Polym Sci Part A:
Polym Chem 2011, 49, 156–163.
Radical Copolymerization of Phosphonated-Bearing Allyl
Monomer with Maleic Anhydride or Dimethyl Maleate
Allyl monomer (3 ꢂ 10ꢀ3 mol) and 3 ꢂ 10ꢀ3 mol of
acceptor monomer (maleic anhydride or dimethyl maleate)
was added in acetonitrile (2.4 ꢂ 10ꢀ2 mol). The reaction
mixture was stirred at 70 ꢁC under nitrogen for 20 min.
Then, 5 mol % of AIBN initiator was added in several shots
(3 times, every 24 hrs). After 24 hrs, the product was pre-
cipitated in water to obtain a powder.
15 Inoue, S.; Kumagai, T.; Tamezawa, H.; Aota, H.; Matsumoto, A.;
Yokoyama, K.; Matoba, Y.; Shibano, M. Polym J 2011, 42, 716–721.
16 Kihara, K. Jpn Kokai Tokkyo Koho 05,301,939 (1993).
17 Decker, C.; Bianchi, C. Polym Int 2003, 52, 722.
18 Arbuzov, A. J. Russ Phys Chem 1906, 38, 687.
19 Boutevin, B.; Hervaud, Y.; Pietrasanta, Y. Phosphorus Sulfur
Relat Elem 1981, 11, 373–381.
20 Tayouo, R.; David, G.; Ameduri, B.; Roziere, J.; Roualdes, S.
Macromolecules 2010, 43, 5269–5276.
CONCLUSIONS
21 Yu, Z.; Zhu, W. X.; Cabasso, I. J Polym Sci Part A: Polym
Chem 1990, 28, 227–230.
The free radical copolymerization of maleic anhydride was
successfully carried out in the presence of allyl monomers
carrying phosphonate moieties, that is, diethyl phosphonate
or dioxaphosphorinane group. The free radical copolymeriza-
tion resulted in alternated copolymers with rather low mo-
lecular weights values. Interestingly, the kinetics of copoly-
merization were influenced by the phosphonate group of the
allyl monomers: the bulkier the phosphonate moieties, the
faster the polymerization rate and the higher the monomer
conversion. Furthermore, the close proximity between the
phosphonate moieties and the allyl double bond led to a
decrease of the electron-donating character of allyl monomer.
We also showed the occurrence of allyl transfer, by compari-
son with model free radical copolymerization, thus explain-
ing the low molecular weight values. Finally, the high content
of residue obtained from thermo gravimetric analysis proves
the potential efficiency of such copolymers as flame retard-
ant additives.
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