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40 Current Green Chemistry, 2014, 1, 40-50
Green Methods in Phosphorus-Containing Polymers Synthesis
Smaranda Iliescu
1
and Gheorghe Ilia
1,
*
1
Institute of Chemistry, Romanian Academy, 24 Mihai Viteazul Bvd. 300223 Timisoara, Romania
Abstract: The purpose of this review is to provide appropriate details concerning the application of green methods in
polymers synthesis. Phosphorus-containing polymers were synthesized by a simple and green synthetic method, namely
vapor-liquid polycondensation. Solvent and catalysts were not required in this technique. Another green method for the
polyphosphonate synthesis is the solid-phase polycondensation using ultrasound. Solid-liquid phase transfer catalysis also
was used as eco-friendly and economical procedure for phosphorus-containing polymers, by using potassium phosphate in
order to suppress the side reactions. In order to increase segmental motion and to aid the ion transport and ionic conduc-
tivity at ambient temperatures of polymer membranes for batteries, linear polymers composed of phosphonate (4-
chlorophenyldichlorophosphonate) as a linking agent with poly(ethylene glycol) were synthesized using green condi-
tions. An important area in the development of green chemical technology is the control of chemical reactions by the tun-
ing of the reaction medium. The influence of the structure and the nature of ionic liquids on the efficiency of polymeriza-
tion of white phosphorus is presented. Phosphorus-containing styrene derivatives (dimethyl-p-vinylbenzylphosphonate
and diphenyl styryl phosphine oxide) were used as comonomers in the cationic copolymerization of soybean oil, styrene
and divinylbenzene. Poly(oxyethylene hydrogen phosphonate) with an average molecular weight of 3100 Da was synthe-
sized under microwaves method for 55 min.
Keywords: Green synthesis, phase transfer catalysis, phosphorus-containing polymers.
INTRODUCTION
Organic synthesis on a large scale, compared to the labo-
ratory scale, involves the use of energy, basic chemical in-
gredients from the petrochemical sector, catalysts and after
the end of the reaction, separation, purification, storage,
packaging, distribution, etc. During these processes, there are
many problems of health and safety for workers, in addition
to the environmental problems caused by their use and dis-
posal as waste. Green Chemistry with its 12 principles would
like to see changes in the conventional ways that were used
for decades to make synthetic organic chemical substances
and the use of less toxic starting materials [1, 2]. Green
Chemistry seeks to increase the efficiency of synthetic meth-
ods, using less toxic solvents, reducing the stages of the syn-
thetic routes and minimizing waste as far as practically pos-
sible. In this way, organic synthesis will be part of the effort
for sustainable development [3]. Green chemistry is the de-
sign of chemical products and processes that reduce or
eliminate the use and generation of hazardous substances [4,
5].
Designing polymers and developing safe polymerization
processes, prevent pollution, and improve the use of materi-
als and energy is very important for these processes.
The main challenges of Green Chemistry and Engineer-
ing can be summarized as: utilizing renewable instead of
scarce resources; avoiding toxic/dangerous chemicals in

*Address correspondence to this author at the Institute of Chemistry,
Romanian Academy, 24 Mihai Viteazul Bvd. 300223 Timisoara, Romania;
Tel: +40256491818; Fax: +40256491824;
E-mail: ilia@acad-icht.tm.edu.ro; gheilia@yahoo.com
safer processes to obtain safer products; minimizing energy
use; minimizing waste and use natural resources, re-using
products, recovering and recycling materials thus making
processes globally more efficient.
Green chemistry techniques can be applied in organic
chemistry, inorganic chemistry, biochemistry, analytical
chemistry, and even physical chemistry. There is an increas-
ing interest in green polymer chemistry. This paper evaluates
the progress in green polymerization methods of phosphorus-
containing polymers.
In the early 60s, the discovery that the incorporation of
phosphorus into a polymer backbone confers to its flame-
retardant properties sparked great interest in phosphorus
polymer chemistry. However, because of the high cost of
synthesizing these polymers in comparison to the carbon
analogs, their low molecular weight, and their perceived hy-
drolytic instability, research interests have faded since the
70s. Polyphosphates and polyphosphonates are known as
very interesting fire retardant candidates [6, 7]. During the
past decade, the development of degradable polymers for
biomedical applications has been the focus of intensive re-
search. In particular, these polymers might possess potential
as a new class of degradable biomaterials whose properties
can be modified to match a specific application. These
polymers are biodegradable because of the hydrolyzable
phosphate ester in the backbone. Polymeric phosphorus ma-
terials have the potential to simulate the mechanical behavior
of biological tissues better than metals or ceramics. Further,
biodegradable phosphorus-containing polymers may elimi-
nate the need for surgical removal of implants used for bone
fixation or controlled drug delivery. Recently, a relatively
2213-347X/14 $58.00+.00 2014 Bentham Science Publishers
Green Methods in Phosphorus-Containing Polymers Synthesis Current Green Chemistry, 2014, Vol. 1, No. 1 41
new class of biodegradable polymers belonging to polyphos-
phoesters was evaluated as a potential carrier for bioactive
molecules [8, 9].
Structurally versatile polyphosphoesters contain repeated
P-O bonds in the backbone and are biocompatible, and bio-
degradable through hydrolysis. Taking into account the side
groups connected to the phosphorus atom, the polymers can
be divided into polyphosphates, polyphosphonates, or poly-
phosphites, as shown in (Scheme 1) [10].
As a response to the need of developing phosphorus-
containing polymers as biodegradable and retardant materi-
als, studies on these polymer syntheses have been performed.
The special interest shown in phosphorus-containing poly-
mers synthesis, as well as with biopolymers has caused the
development of other methods among which polycondensa-
tion in biphasic systems is worth mentioning [11-13].
The disadvantages of classical methods (corrosion, many
noxious secondary products) are avoided using multiphase
reaction systems. The phase transfer catalysis (PTC) method
gained much interest by the simplicity of the operations and
technological devices, reduced reaction time, avoidance of
secondary reactions, economy of energy and raw materials
and, in particular, as modern and new perspectives of the
modern organic synthesis. This method follows the trend of
green chemistry resulting in the reduction of environmental
pollution and steady development of chemistry [14]. The
development of cleaner technologies is a major emphasis on
green chemistry. The goal of chemists is to continue to de-
velop novel green chemistry and use such technology to de-
velop environmentally friendly processes to produce novel
materials. This paper evaluates the latest developments in
green methods of phosphorus-containing polymers. The aim
of this review is to summarize the recent developments in
this field mainly based on the literature during the last pe-
riod.
1. GREEN METHODS IN POLYPHOSPHONATE
SYNTHESIS
1.1. Solvent and Catalyst Free Synthesis of Polyphospho-
nates
One of the longest known classes of phosphorus-
containing polymers is polyphosphonates. It is know that the
best solvent is no solvent but if a solvent is needed, the water
is recommended, and catalysis in aqueous biphasic systems
is an industrially attractive methodology which has found
broad application [15]. Organic reactions in aqueous media
are a significant branch of green chemistry.
This system utilizes pairs of highly reactive reagents with
one of the reagents (alkyl(aryl)phosphonic dichloride) in the
vapor state and the other one (diphenol) in solution. The con-
tact of the reagents in the vapor-liquid reaction is readily
performed by bubbling the vapor (gaseous) reagents through
the aqueous solution of the partner reagent. The use of the
organic solvent is not required. The polymer separates from
the aqueous phase and does not need complicated purifica-
tion. This simple and green synthetic methodology method
was applied to the polycondensation of various phosphonic
dichlorides (PD) with bisphenols (B)(Scheme 2).
A series of polyphosphonates was synthesized: R=CPD,
R
1
=BA [16]; R=CH
3
;C
6
H
11
, C
6
H
5
; R
1
=HQ, BA, BP, ND
[17]; R=PPD and R
1
=SD [18]; R=PPD and R
1
=bisphenol
M [19]. Yields in the range of 20-80% were obtained. Inher-
ent viscosity measurements showed variations from 0.20
2.50 dl/g. Polymers were characterized by infrared (IR), pro-
ton magnetic resonance (
1
H-NMR) spectroscopy, molar mass
determination, solubility, and thermal analysis.
The infrared (IR) spectrum (film) exhibited absorptions
(cm
-1
) at: P
1
:(CPD +HQ) 930-945(P-O-C
phenyl
); 1282(P=O,
P-O-C
phenyl
), 1294-1320(P-C
alkyl
); P
2
: (CPD +BA) 940, 1377
(P-O-C
phenyl
); 1285(P=O); 1320- 1290 (P-C
alkyl
); P
3
:
(CPD+BP) 1290(P=O), 1195, 920(P-O-C
phenyl
); 1280-1265
(P-C
alkyl
);P
4
(CPD+ND) 910-922((P-O-C
phenyl
); 1240(P=O,
P-O-C
phenyl
); 1250-1280(P-C
alkyl
); P
5
(CPD +SD) 1300-1320
(P-C
alkyl
); 1280(SO
2
, P=O); 1150-1185(SO
2
, P-O-C
phenyl
);
920-940(P-O-C
phenyl
); P
6
:(PPD+HQ) 1465, 10012, 720(P-
C
phenyl
); 1275(P=O); 920, 1250(P-O-C
phenyl
); P
7
(PPD+BA)
1440, 1005, 715 and 686 P-C
phenyl
); 1275(P=O); 1250,
980(P-O-C
phenyl
); P8 (PPD+BP) 1454, 1002, 609 (P-C
phenyl
);
1290(P=O); 1255, 910 (P-O-C
phenyl
); P
9
(PPD+ND) 1410,
1018, 702(P-C
phenyl
), 1260-1275(P=O, P-O-C
phenyl
); 920-
940(P-O-C
phenyl
); P
10
(PPD+SD) 1475, 1018, 723(P-C
phenyl
);
1280-1300(SO
2
,P=O);1140(SO
2
); 1260, 980(P-O-C
phenyl
)
The nuclear magnetic resonance (
1
H-NMR) spectrum in
CDCl
3
, showed signals (, ppm) at: P
1
: 6.2(s, 4H, phenyl),
POLYPHOSPHOESTER
P
O
O
R'
R O
P
O
O
H
R O P
O
O
CR
1
R
2
R
3
R O P
O
O
OR
1
R O
POLYPHOSPHITE POLYPHOSPHONATE
POLYPHOSPHATE


(Scheme 1). Classes of polyphosphoesters.
42 Current Green Chemistry, 2014, Vol. 1, No. 1 Iliescu and Ilia
1.1-2.4(m, 11H, cyclohexyl); P
2
: 1.5-2.8(m,11H,cyclohexyl);
1.55(s, 6H, methyl); 7.06-7.12(m, 8H, phenyl); P
3
: 1.5-
2(m,11H, cyclohexyl); 7-7.5(m, 8H, phenyl); P
4
: 1-2(m,
11H, cyclohexyl); 7.1-8.2(m, 6H, phenyl); P
5
: 1.6-1.9(m,
11H, cyclohexyl); 6.9-7.1 and 7.4-7.8(m, 8H, phenyl); P
6
:
6.1-6.5(m, 4H, phenyl); 8.2(s, 5H, phenyl); P
7
: 7.20-8.15(m,
5H, phenyl); 7.01-7.24(m, 8H, phenyl); 1.68(s, 6H, methyl);
P
8
: 7.8-8.0(m, 5H, phenyl); 7.1-7.3(m, 8H, phenyl); P
9
: 7.7-
8.3(m, 5H, phenyl); 6.9-7.3(m, 6H, phenyl); P
10
: 8.1-
8.3(m,5H, phenyl); 7.5-7.9(m, 8H, phenyl).
The molecular weights M
n
values fall into the range of
8500-35000. A maximum molecular weight M
n
of 35000
was obtained [17] which is better compared to those reported
by other techniques. DSC measurements show Tg in the
range 95
o
-148
o
C. These polymers are soluble in solvents
such as N,N-dimethylformamide, tetrahydrofuran and chloro-
form. Polyphosphonates were stable upto 240
o
-300
o
C in air
atmosphere.
1.2. Solid Phase Polyphosphonate Synthesis Mediated by
Ultrasound
Another green method for the polyphosphonate synthesis
is the solid phase polycondensation, using ultrasound, [20]
and without solvent, [21] of phenylphosphonic dichloride
(PPD) with bisphenol A (BA) (Scheme 3) [22].
P
O
Cl Cl + C HO
CH
3
CH
3
OH
-(2n-1)HCl
P
O
O C
CH
3
CH
3
O
n


(Scheme3). Polyphosphonate synthesis mediated by ultrasound.
Ultrasound-assisted organic synthesis is another green
methodology which is applied in many organic synthetic
routes with great advantages for high efficiency, low waste,
and low energy [23, 24]. BA, PPD and the potassium salt of
BA were introduced in a flask. The ultrasonic immersion
horn (10 mm o.d.) was poured into the reaction mixture and
a fixed acoustic frequency of 25 MHz (Branson 250 equip-
ment) was applied. The obtained polymer was precipitated
into hexane. Polyphosphonate with high molecular weight
was obtained using this method, in order to increase the in-
teractions between the reactive sites.
Polyphosphonate was characterized by inherent viscosity.
A maximum inherent viscosity of 2.63 dl/g was obtained.
The FT-IR spectrum showed the typical signals at 1460 cm
-1

and 1377 cm
-1
for P-C (phenyl) and P-O-C(phenyl) respec-
tively. The
1
H-NMR spectrum showed peaks at 7.2 (m,
C
6
H
5
) and 1.5 (s, CH
3
) ppm.
1.3. Polyphosphonates Obtained by SolidLiquid Interfa-
cial Polycondensation
Phase transfer catalysis (PTC) polycondensation has
drawbacks for systems when the presence of water can lead
to side reactions such as hydrolysis of the phosphoryl chlo-
ride groups of the reagent or of the end-groups of the poly-
mer. New polymer structures were synthesized by a new
method, respectively PTC in solid-liquid system, when po-
tassium phosphate was used as a unique base. This method
was applied in order to prevent the degradation of polymer,
terminating competing reactions and to get data for preparing
thermally stable heteroatom polymers with high molecular
weights [25].
It was shown that potassium phosphate is a selective
solid base in phase-transfer catalyzed alkylation reactions
[26]. Potassium phosphate as a high performance base is
used for the first time in the polymers synthesis. The conver-
sion of liquid-liquid PTC into solid-liquid PTC proves to be
advantageous for suppression of side reactions, and phase
transfer catalysis in solid-liquid system was applied for the
first time in polymer synthesis, as eco-friendly and economi-
cal procedure. New polyphosphonates were obtained by
solid-liquid PTC polycondensation of phenylphosphonic
dichloride (PPD) or 4-chlorophenydichlorophosphate (4-
ClDPP) with bisphenols: 4,4'-cyclohexylidenebisphenol
(bisphenol Z, BZ), (P
1
) 4,4'-(9-fluorenylidene)diphenol
(FDP) (P
2
) and 4,4'-(hexafluoroisopropylidene) (bisphenol
AF, BAF) (P
3
) (Scheme 4) [25].
P
O
Cl + HO Cl
R
R
1
OH
-(2n-1)HCl
P
O
O
R
R
1
O
n
R=CH
3
(methylphosphonic dichloride (MPD)); C
6
H
11
(cyclohexylphosphonic dichloride (CPD));
C
6
H
5
(phenylphosphonic dichloride PPD)); CH
2
Cl (chloromethylphosphonic dichloride (CMPD))
R
1
=C
6
H
4
(hydroquinone (HQ)); C
6
H
4
-C(CH
3
)
2
-C
6
H
4
(bisphenol A (BA));
C
6
H
4
-C
6
H
4
(4,4'-biphenol (BP)); C
6
H
4
-
SO
2
-C
6
H
4
(4,4'-sulphonyldiphenol (SD));
C
10
H
8
(1,5 naphtalenediol (ND));
C
6
H
4
C(CH
3
)
2
-C
6
H
4
-C(CH
3
)
2
-C
6
H
4
(1,3-phenylenediisopropylidene)bisphenol (bisphenol M))


(Scheme2). Synthesis of polyphosphonates by solvent and catalyst free method.
Green Methods in Phosphorus-Containing Polymers Synthesis Current Green Chemistry, 2014, Vol. 1, No. 1 43
P
O
Cl Cl +
R
2 K
2
HPO
4
+2KCl +2K
3
PO
4
HO R
1
OH O R
1
O P
O
n
+
R
1
=
CF
3
CF
3
R=
P
1 ,
P
2 R= , R
1
=
P
3 R= O Cl, R
1
=
R


(Scheme4). Preparation of polyphosphonates and fluorinated poly-
phosphates using solid-liquid PTC technique.
Yields in the range of 80.2% - 86.5%, and inherent vis-
cosities in the range of 1.48 - 2.5 dl/g were obtained. High
molecular weight polymers (Mn of 11800-21600) have
been successfully prepared. The polymers are self-
extinguishing and begin to lose weight at around 280
o
-
380
o
C. The glass transition temperatures of the polymers
were detected in the range of 85
o
-180
o
C.The flammability
was investigated by measuring limiting oxygen index values.
The polymers were characterized by IR (KBr, cm
-1
),
1
H and
31
P-NMR (400 MHz, CDCl
3
, TMS):
P
1
: IR: 1247 (P=O), 1142;939 (P-O-C
phenyl
), 1497 (P-
C
phenyl
), 3028;1608;1380 (Ph);
1
H-NMR: 7.2-8.5(m,C
6
H
5
;
2.4(s, , 'CH
2
); 1.6(s, , ' and CH
2
);
31
P-NMR: 15.6(P at
chain end), 12.0(P in the repeat unit); P
2
: IR: 1225 (P=O),
1171; 939 (P-O-C
phenyl
), 1444 (P-C
phenyl
), 3057;1607;1377
(Ph);
1
H-NMR: 6.7-7.9 (m, C
6
H
5
);
31
P-NMR: 16.7(P at chain
end), 12.5 (P in the repeat unit); P
3
: IR: 1256 (P=O), 1175;
969 (P-O-C
phenyl
), 1467 (P-C
phenyl
), 1175-1215(-C(CF
3
)
2
);
3054; 1615; 1448 (Ph);
1
H-NMR : 7.2-8.0(m, C
6
H
5
);
31
P-
NMR: -17.0(P at chain end), -12.0 (P in the repeat unit)
Also a polyphosphonate was synthesized from PPD and
bisphenol M when potassium phosphate was used as base
and 2-methyltetrahydrofuran (2-MeTHF) as a green solvent.
2-MeTHF is derived from renewable resources such as corn-
cobs and bagasse (Scheme 5) [19]. The polymers were char-
acterized by gel permeation chromatography (GPC), FT-IR
(KBr, cm-1),
1
H and
31
P-NMR spectroscopy: IR: 1237
(P=O), 1145;960 (P-O-C
phenyl
), 1490 (P-C
phenyl
), 3028; 1606;
1380 (Ph);
1
H-NMR: 7.2-8.5(m, C
6
H
5
);1.8 (s, isopro-
pylidene);
31
P-NMR: 15.2 (P at chain end), 12.3 (P in the
repeat unit).
Yields in the range of 88.0%90.0%, and inherent vis-
cosities in the range of 2.23.2 dl/g were obtained. High mo-
lecular weight polymers (57600-114400) have been success-
fully prepared. The polymers are self-extinguishing and be-
gin to lose weight at around 300
o
C. The flammability was
investigated by measuring limiting oxygen index values
(LOI). LOI was determined on the powdered sample accord-
ing to modified ASTM D2863-70 and was 40.
P
O
Cl Cl
+HO OH
CH
3
H
3
C
CH
3
H
3
C
O O
CH
3
H
3
C
CH
3
H
3
C
P
O
n
(3)


(Scheme5). Polyphosphonate obtained from PPD and bisphenol M.
It is an alternative to dichloromethane or tetrahydrofuran
for biphasic reactions having the next advantages: low heat
of vaporization; saves energy during distillation and recov-
ery; lower peroxide formation than THF [27]. These meth-
odologies offer improvements for the synthesis of polymers
with regard to: elimination of catalysts and organic solvents
or use of green solvents; elimination of dangerous, inconven-
ient, and expensive reactants (the use of NaOH, KOH,
K
3
PO4, etc. instead of NaH, NaNH
2
, t-BuOK, R
2
NLi, etc.);
increased reactivity and selectivity of the active species;
higher yields; higher molecular weights; simplicity of the
procedure. Due to the specific features of this method and its
advantages presented above it should be considered as the
most efficient and general green technology.
Recently, organophosphorus polymers have regained
researchers interest as polymer electrolytes. Solid polymer
electrolytes are promising materials for electrochemical de-
vice applications, namely, high energy density rechargeable
batteries, fuel cells, supercapacitors, electrochromic displays,
etc. [28].
Iliescu et al. [29] obtained for the first time phosphorus-
containing (co)polyester electrolytes by phase transfer ca-
talysis. PTC (liquid-liquid or gas-liquid polycondensation)
has drawbacks in obtaining polymers with high molar
masses, because the presence of water can lead to side reac-
tions such as hydrolysis of the phosphoryl chloride groups of
the reagent or of the chain end-groups of the polymer [25].
The presence of water in the membranes for lithium re-
chargeable batteries leads to the decrease of electrochemical
windows[30].


The potassium phosphate acts as acid scavenger without
water formation (HCl +K
3
PO
4
=KCl +K
2
HPO
4
) [31]. The
conversion of liquid-liquid or gas-liquid PTC into solid-
liquid PTC proves to be advantageous for suppression of
side reactions in order to obtain a polymer candidate for
solid polymer electrolytes, without impurity and moisture.
Linear phosphorus-containing (co)polyesters were ob-
tained by solid-liquid phase transfer catalysis polycondensa-
tion of phenylphosphonic dichloride (PPD) with poly (ethyl-
44 Current Green Chemistry, 2014, Vol. 1, No. 1 Iliescu and Ilia
ene glycol) (PEG 12000) with and without bisphenol A (BA)
(Scheme 6).
Yields in the range of 85.0-88.0, and inherent viscosities
in the range of 0.32-0.58 dl/g were obtained. The polymers
were characterized by gel permeation chromatography, FT-
IR (KBr, cm
-1
),
1
H and
31
P-NMR spectroscopy(400 MHz,
CDCl
3
, TMS): 4a. IR: 1239.04 (P=O), 1100.19; 841.77 (P-
O-C
aliph
), 1462.74 (P-C
phenyl
); 2878.24(aliph-CH
2
-); 3048.3;
1343.18; 1620.91; 755.95 (Ph);
1
H-NMR: 7.3-7.9 (m, C
6
H
5
);
3.72 (s, -CH
2
-O-CH
2
-);
31
P-NMR: 14.7(P at chain end),
13.7(P in the repeat unit); 4b. IR: 1240.97(P=O); 1097.30;
840.812(P-O-C
aliph
), 1463.71(P-C
phenyl
), 2877.27(aliph-CH
2
-
), 3736.4; 1343.18; 1620.91; 755.95 (Ph);
1
H-NMR: 7.30-
7.90 (m,C
6
H
5
); 3.59-3.75 (m,-CH
2
-O-CH
2
-); 1.20-1.80 (m,
C(CH
3
)
2
);
31
P-NMR: 14.7(P at chain end), 13.7 and 14.0 (P
in the repeat unit); 4c: IR (KBr, cm
-1
): 1480 (P-C
phenyl
); 1280
(P=O); 940, 1200 (P(O)-O-C
phenyl
);
1
H-NMR: 6.6-7.3 (m,
C
6
H
5
); 1.2-1.6 (m, C(CH
3
)
2
);
31
P-NMR: 15.7 (P at chain
end), 12.0 (P in the repeat unit). The GPC measurements
show the average molecular weight is in the range of 5400-
26300. The polymers are flame retardants and begin to lose
weight in the range 190
o
-231
o
C. These (co)polymers showed
good LOI values (in the range 28-38). Solid phosphorus con-
taining (co)polyesters were complexed with lithium triflate
and ionic conductivity was determined. Conductivities in the
range of 10
7
-10
-8
S cm
1
have been obtained for
(co)polyphosphonates.
The properties of the (co)polymers such thermal stability
and flammability have been investigated. For all synthesized
(co)polyphosphonates ionic conductivity was determined.
1.4. Polymer Containing Phosphorus Groups and Poly-
ethers Synthesized Using a Green Media
Linear phosphonate-PEG polymers composed of 4-
chlorophenyldichlorophosphonate (CPPD) as a linking agent
and poly(ethylene glycol) (PEG) with different molecular
weights (MW of 200 and 2000) as soft segment increasing
chain flexibility) were synthesized in order to increase seg-
mental motion, to aid the ion transport and ionic conductivity
at ambient temperatures [32] (Scheme 7).
1-methylimidazole (MeI) was used as an acid scavenger,
when is obtained as an ionic liquid: 1-methyl-imidazolium
chloride, which has a melting point of about 75
o
C, in order to
improve the parameters of process, increase the molar
weight, and reduce the corrosion (Scheme 8).
The polymer can be retrieved by a simple layer separa-
tion and solvent evaporation, where the upper phase mainly
contains the polymer product and the lower layer mostly
consists of 1-methylimidazolium chloride, which could be
converted to 1-methylimidazole by treating it with NaOH
aqueous solution at room temperature.
Best results (yield 88%, inherent viscosities 0.48 dl/g and
Mn 2.6) were obtained with 1-methylimidazole as an acid
scavenger and PEG 2000. The polymers begin to lose weight
in the range 330
o
-412
o
C. The flammability was investigated
by measuring limiting oxygen index (LOI) values. These
polymers and membrane based on these polymers showed
good LOI values (in the range 23-29, 30). The polymers
were characterized by FT-IR (KBr, cm
-1
) ,
1
H and
31
P-NMR
spectroscopy(400 MHz, CDCl
3
, TMS) : P1=CPPD+PEG200
+MeI; P2=CPPD +PEG2000 +MeI
P1: IR: 1240.80 (P=O), 1099.26; 840.52 (P-O-C
aliph
),
1463.71(P-C
phenyl
); 2878.24(aliph-CH
2
-); 3048.3; 1343.18;
1620.91;755.95 (Ph); 1742.25 (P
arom
-Cl);
1
H-NMR: 7.0-7.6 (m,
C
6
H
5
); 3.4-3.7 (m, -CH
2
-O-CH
2
-);
31
P-NMR: 12.0(P at chain
end) and 15.7 (P in the repeat unit); P2: IR: 1242.61 (P=O),
1120.29; 842.51 (P-O-C
aliph
), 1460.25 (P-C
phenyl
); 2878.24(aliph-
CH
2
-)3048.3;1343.18; 1620.91; 755.95 (Ph); 1746.23 (C
phenyl
-
Cl);
1
H-NMR :7.2-7.8 (m, C
6
H
5
); 3.5-3.7 (m, -CH
2
-O-CH
2
-).
Best results (yield 88%, inherent viscosities 0.48 dl/g and Mn
2.6) were obtained with 1-methylimidazole as an acid scavenger
and PEG 2000. These polymers and membranes based on these
polymers showed good LOI values (in the range 23-29, 30) and
indicate an improvement of the safety of lithium batteries.
Recently, the process was improved in a greener or more
environmentally acceptable media. 1,3-dioxolane was used as
green solvent in order to provide a better mixing and higher
heat transfer of the exothermal reaction. Due to its strong sol-
vency, low odor, superior toxicological profile, and improved
safety in handling 1,3-dioxolane has successful green applica-
tions [33].
P
O
Cl Cl
C
6
H
5
P
O
C
6
H
5 x
+dK
3
PO
4
-dK
2
HPO
4
+dKCl
b HO(CH
2
CH
2
O)
n
H a
+c
C
CH
3
CH
3
HO OH
CH
3
CH
3
O P
1 3
2
4a: a=1; b=1; c=0; d=2
4b: a=1 ; b=0.5; c=0.5; d=2
4c: a=1; b=0; c=1; d=2
4
O
C
6
H
5
O
y
+
( (O OC CH H
2 2
C CH H
2 2
) )
n n O O


(Scheme6). Preparation of random phosphorus-containing (co)polyesters.
Green Methods in Phosphorus-Containing Polymers Synthesis Current Green Chemistry, 2014, Vol. 1, No. 1 45
P
O
Cl Cl
Cl
+ HO
O
H P
O
O
O
P
O
O
Cl
Cl
n
n
O
-HCl


(Scheme7). Synthesis of phosphonate-PEG polymers.
2. SOLVENT AND CATALYST FREE SYNTHESIS OF
POLYPHOSPHATES
In recent years, an increased interest was given to other
category of phosphorus-containing polymers, as polyphos-
phates, essentially because they are used in the synthesis of
poly(alchylenephosphate) biopolymers. Polymers with phos-
phate groups in the main chain are often proposed as biode-
gradable materials since the phosphate esters are readily
cleaved by hydrolysis [34, 35]. Biodegradable polymers have
become increasingly important for many applications in the
areas of agriculture, biomedical implants and drug release
[36-38]. For this reason, research workers have developed
several methods for industrial uses.
Polyphosphate structures were successfully prepared by a
simple and green method, respectively by solvent and cata-
lyst-free vaporliquid interfacial polycondensation of pheny-
phosphoric dichloride (FPD) with different diphenols:
bisphenol A(BA) (P
1
), 4,4-sulfonyldiphenol (P
2
) and 4,4-
biphenol (P
3
) [39]. (Scheme 9) This system utilizes pairs of
highly reactive reagents with one of the reagents (PPD) in
the vapor state and the other (i.e. diphenol) in solution. The
use of the organic solvent and catalyst is not required and for
that reason the auxiliary procedures in vapor-liquid interfa-
cial polycondensation are simplified considerably: only ionic
impurities (i.e. NaCl) need to be washed from the polymer.
The IR spectra confirmed the structure of the polyphosphates
synthesized. The absorptions around 1250-1300 cm
-1
and
2900 cm
-1
correspond for P=O stretching and for the charac-
teristic aromatics C-H for all three polyphosphates. Also, for
all polyphosphates the polymeric structures were supported
by P-O-C (aromatic) stretch at 1200 and 940 cm
-1
and the
disappearance of the broad O-H stretch of diphenols. For
polyphosphates P
2
the absorptions for SO
2
appear at 1470
cm
-1
. The
1
H-NMR spectra of the polyphosphate P
1
present a
singlet around 7.05 ppm for the aromatic protons of the main
chain and for the side chain phenyl presents a singlet at 7.3
ppm. The isopropylidene protons present a singlet at 1.58
ppm. In polyphosphates P
2
and P
3
the main chain phenyl
appears as multiplet around 7.2-7.7 ppm whereas the side
chain phenyl appears as a singlet at 7.2 ppm. All polyphos-
phates synthesized were stable in air below 240
o
C and had
reasonable molecular weight.
Iliescu et al. [40] applied the vapor-liquid methodology,
as eco-friendly and economical procedures for Green Chem-
istry for the synthesis of polyphosphate polycondensation of
phenylphosphoric dichloride with phenolphthalein. (Scheme
10) The IR spectrum confirmed the structure of the poly-
phosphate synthesized. The absorption band at 1780 cm
-1

corresponds to C=O of the lactone ring; at 1180 and 950 cm
-1

corresponds to P-O-C (phenyl) stretching, and at 1280 cm
-1

corresponds to P=O stretching, which is characteristic of
phosphate ester compound. The
1
H-NMR spectrum of the
polyphosphate presents a multiplet around 7.0-8-0 ppm for
the aromatic protons of the main chain and the pendent
phenyl groups. The introduction of the phenolphthalein
structure enhances thermal stability in the polymer.
New phosphorus polymers, structurally related to the
biopolymers with polyphosphates in the main chain were
synthesized in order to apply the vapor-liquid methodology,
as eco-friendly and economical procedures for Green Chem-
istry [41]. In this paper, the synthesis of polyphosphate by
the vapor-liquid polycondensation of alkylphosphoric dichlo-
rides (PD): methylphosphoric dichloride (MPD), ethylphos-
phoric dichloride (EPD), propylphosphoric dichloride
(PrPD), cyclohexylphosphoric dichloride (CDP) and the
arylphosphoric dichlorides: phenylphosphoric dichloride
(FPD) with the diols (D): bisphenol A (BA), 4,4-biphenol
(BP), tetrachlorobisphenol A (ClBA) was reported (Scheme
11).
The method does not require an organic solvent or cata-
lyst, reaction taking place in water and for that reason the
auxiliary procedures in vapor-liquid interfacial polyconden-
sation are simplified considerably. Organic reactions in
aqueous media are known to be a significant branch of green
chemistry. The polymers obtained by vapor-liquid technique
contain strongly adsorbed water which should be removed
prior to further polymer characterization of processing. This
can be achieved by means of effective drying, for example,
under vacuum. The simplification of reaction protocols is an
important concept in designing new clean methodology. The
most appropriate conditions for the synthesis of these poly-
mers by this method are as follows: reaction temperature
40
o
C, molar ratio PD: D =2.5:1; 1M NaOH. Yields in the
range 75-90% and inherent viscosities in the range 0.24-0.45
dl/g were obtained. Polyphosphates were stable up to 170-
250
o
C, function on phosphoric dichloride. For all polyphos-
P
O
Cl C Cl l
R
O OH H
R
1
OH
O R
1
O P
O
R
n
R=C
6
H
4
Cl
N
N
N
N
+ + +
H
+
Cl
-
2
2
R
1
= H
2
C CH
2
O CH
2
CH
2
O CH
2
CH
2
m


(Scheme8). 1-Methylimidazole as acid scavenger.
46 Current Green Chemistry, 2014, Vol. 1, No. 1 Iliescu and Ilia
phates the disappearance of the broad O-H stretch of diol
was observed. The
(P-OH)
band at 2700-2500 cm
-1
which
indicates the presence of a phosphonate linkage and the band
at 2400 cm
-1
for
(P-H)
are both absent and this confirms the
existence of the polyphosphate.
P
O
Cl Cl
O
+
P
O
O
O
-(2n-1)HCl
HO R OH
R O
R=C(CH
3
)
2
(BA); 0(BP); SO
2
(SDP)
n


(Scheme9). Polymers containing phosphate groups.

C
HO + P Cl
O
Cl
-(2n-1)HCl
O
OH
O P
O
O n
C
O
O
C
O O
C
O
O


(Scheme 10). Polycondensation of phenylphosphoric dichloride
with phenolphthalein.

P
O
Cl Cl
OR
+HO R
1
OH
base
-(2n-1)HCl
P
O
O
OR
R
1
O
n
R=CH
3
(MPD);C
2
H
5
(EPD); C
3
H
7
(PrPD); C
6
H
11
(CDP); C
6
H
5
(FDP)
R
1
=C
6
H
4
-C(CH
3
)
2
-C
6
H
4
(BA); C
6
Cl
4
-C(CH
3
)
2
-C
6
Cl
4
(ClBA); C
6
H
4
-C
6
H
4
(BP)


(Scheme11). Phosphorus polymers, structurally related to the bio-
polymers.
The
1
H-NMR spectra for all polyphosphates showed no
signals at higher 12 ppm values which indicate the presence
of phosphate [P(O)-OH] and no peaks for phosphonates (P-
H). This suggests that there was no significant cleavage of
the ester bond of the polyphosphates during reaction.
Direct, efficient, solvent and catalyst-free synthesis of a
series of polyphosphates was accomplished in a new paper
[42]. A series of new polyphosphates were synthesized by
vapor-liquid interfacial polycondensation of arylphosphoric
dichlorides (PD) with bisphenol A (BA) (Scheme 12). Reac-
tion conditions: 0.10 moles PD, 0.040 moles BA, 0.090
moles NaOH 1M, 50 minutes, reaction temperature 60
o
C;
temperature of phosphoric dichloride maintained by an oil
bath at 80-90
o
C;yields in the range 70-90% and inherent vis-
cosities in the range 0.30-0.40 dl/g were obtained. The struc-
ture of the polyphosphates synthesized was elucidated by IR,
and
1
H-NMR spectroscopy. A complex set of P=O at 1250-
1300 cm
-1
and characteristic aromatic C-H stretches at 2900
cm
-1
were seen for all polymers. Polymeric structure was
supported by P-O-C stretch at 925 cm
-1
and the disappear-
ance of the broad O-H stretch of bisphenol A. The polymers
showed strong absorptions around 1180 and 960 cm
-1
which
correspond to P-O-C(aromatic) stretching. All the polyphos-
phates are stable between 250 and 300
o
C.
P
O
Cl Cl +
b
a
s
e
-
(
2
n
-
1
)
H
C
l
C
CH
3
CH
3
HO OH
Cl P
O
O
O C
CH
3
CH
3
O P
O
O
X X
Cl
n
P
O
O
O C
CH
3
CH
3
O P
O
O
X X
OCH
3
n
CH
3
OH
H
3
CO
X=H (FPD), CH
3
(CPD), OCH
3
(MePD), Br, (BrPD), NO
2
(NPD)
O


(Scheme 12). Vapor-liquid interfacial polycondensation method.
Avoiding a solvent reduces the number of components in
a reaction, stops any solvent emission problems, and gets
around any solvent recycling requirements. Because of the
use of aqueous medium in organic synthesis and the absence
of the solvent and catalyst, a strong development in the fu-
ture is expected.
Green Methods in Phosphorus-Containing Polymers Synthesis Current Green Chemistry, 2014, Vol. 1, No. 1 47
3. PHOSPHORUS-CONTAINING SOYBEAN OIL CO-
POLYMERS
One of the biggest challenges of green chemistry and
engineering in polymer science is to utilize renewable in-
stead of scarce resources. Polymers from renewable re-
sources will play an increasing role because of economical
and environmental benefits and the new property profiles
that renewable resource polymers can exhibit, such as bio-
compatibility and biodegradability [43, 44]. Vegetable oils
are among the cheapest and most abundant annually renew-
able natural resources.
The soybean oil is one of the most studied oils. They are
available in large quantities from various oilseeds and are
now being used in an increasing number of industrial appli-
cations. Recently, there have been many attempts to convert
vegetable oils and fatty acids to useful polymers [45, 46].
One of the most stimulating facets of this field is the
search for new applications of vegetable oils, based on en-
hancing their specific reactivity in a given type of polymeri-
zation process. A factor limiting the use of oil-based poly-
mers is their flammability. For this reason, the search is now
on new environmentally friendly flame-retardant polymeric
materials. Phosphorus- and silicon-containing polymers are
well recognized for their flame retardant properties [47] and
they are increasingly becoming more popular than their
halogen counterparts as they generally give off nontoxic
combustion products.
To extend the application possibilities of vegetable oil-
based thermosets by improving their flame retardancy and
preserving the environmentally friendly character of these
materials, by using a phosphorus-based system, instead of a
halogen-based system two different approaches to phospho-
rus-containing soybean oil copolymers were investigated
[48]. Thus, two phosphorus-containing styrene derivatives
(dimethyl-p-vinylbenzylphosphonate (DMVBP) and
diphenyl styryl phosphine oxide (DPSPO)) where used as
comonomers in the cationic copolymerization of soybean oil,
styrene and divinylbenzene. Phosphine oxides were consid-
ered comonomers with high thermal and chemical stability.
In this way, styrene and diphenyl styryl phosphineoxide
(DPSPO) as major co-monomer and divinylbenzene as
crosslinking agent for the cationic initiated polymerization of
soybean oil were used. (Scheme 13).
A new reactive phosphorus-containing plant oil deriva-
tive was incorporated to the soybean oil, styrene and di-
vinylbenzene system. The cationic copolymerization was
investigated and the structure, thermal stability and mechani-
cal and flame retardant properties of the resulting copoly-
mers were studied. Flame retardance measurements showed
that the phosphorus-containing copolymers no longer burn in
ambient air without complementary oxygen.
4. PHOSPHORUS-CONTAINING POLYMERS SYN-
THESIZED USING A GREEN RADIATION-
INDUCED REACTION
Currently available technologies for the synthesis of
phosphorus-containing polymers with various dopants have a
considerable impact on the environment. The radiation-
induced synthesis of phosphorus-containing polymers in the
presence of ionic liquids to develop a process that meets the
principles of green chemistry was studied [3]. Tarasova et al.
[49] synthesized phosphorus-containing polymers using a
green radiation-induced reaction at room temperature in
the presence of ionic liquids. The influence of the structure
and the nature of ionic liquids on the efficiency of polymeri-
zation of white phosphorus was studied. The control by
means of varying media properties may be realized by dif-
ferent approaches: variation of the solvent nature (limitation
on solubility of phosphorus in different solvents) and varia-
tion of media polarity and the structural organization of the
solution (incorporation of ionic liquids [ILs] into the reaction
media).
Also, Tarasova et al. [50] synthesized phosphorus-
containing polymers (PCP) by polymerization in solution in
the presence of phosphonium ionic liquids [Et
3
OcP]NTf
2
-
triethyloctylphosphonium bis(trifluoromethylsulfonyl)imide
[(C
8
H
17
)(C
2
H
5
)3P]+[N(SO
2
CF
3
)
2
]
_
under radiation-induced
reaction at room temperature and characterized by a number
of physicochemical techniques. The use of ionic liquids in
polymerization processes makes it possible to enhance the
activity of catalysts, to increase selectivity, and to simplify
the separation of pure products with the repeated use of the
P
Ph Ph
O
P
OCH
3
CH
3
O
O
P
OCH
3
CH
3
O
O
ST DVB DPSPO DMVBP DMBP
O
O
O
O
O
O
SOY


(Scheme13). Structure of the monomers.
48 Current Green Chemistry, 2014, Vol. 1, No. 1 Iliescu and Ilia
ionic liquid and the catalyst. The polymers synthesized in
ionic liquids can be easily separated and isolated in a maxi-
mally pure state. The reaction products were characterized
by elemental analysis, XPS data, IR spectroscopy, X-ray
diffraction analysis, and NMR (
31
P,
1
H)-spectroscopy. Ac-
cording to elemental analysis data, the synthesized PCP
mainly consisted of phosphorus (56%), carbon (6%), hydro-
gen (3%), and oxygen (35%). According to XPS data, the
surface composition of the PCP particles was as follows: E,
68%; O, 22%; and P, 11%. The IR spectra of the PCP exhib-
ited absorption bands due to PP stretching vibrations (490-
520 cm
_1
). Absorption bands at 1400 and 1010 cm
_1
suggest
the chemical binding of organic fragments (benzene) to the
phosphorus atoms of the resulting polymer. The
1
H - NMR
spectra of PCP exhibited the presence of several types of
protons: the singlet (7.7 ppm) attributed to CPh-H; 5.1 ppm,
attributed to P-H;the singlet (4.8 ppm), attributed to the pro-
ton of the phosphinic group P(O)-H. The
31
P-NMR spectra
of PCP exhibited the presence of five types of phosphorus
nuclei: singlet at 0 ppm ( attributed to P-Ph group);doublet at
7 ppm (attributed to P-H group); triplet at 16 ppm (attributed
to O=P-H or HO-P-H groups); wide multiplet (1500 Hz)
with the centre at 30 ppm, which corresponds to PP polym-
eric group; wide singlet at 450 (460) ppm, attributed to the
absorption of the P-P group in the white phosphorus.
This reduces operational costs and is an important advan-
tage of ionic liquids in terms of green chemistry [51]. The
influence of phosphonium ionic liquids on the radiation-
initiated polymerization of white phosphorus was studied.
The effects of various factors on the efficiency of the synthe-
sis of phosphorus-containing polymers are discussed. Such a
control of chemical reactions by the tuning of the reaction
medium is an important area in the development of green
chemical technology. Red phosphorus modifications are of
considerable interest because these inorganic polymers can
be widely used [52].
5. MICROWAVE-ASSISTED SYNTHESIS OF POLY-
PHOSPHITE (H-POLYPHOSPHONATE)
Organic reactions under the microwave irradiation have
many advantages compared to the conventional reactions
which need very high temperatures. Microwave-assisted
reactions are cleaner, last only very few minutes, have
high yield and produce minimum waste [53].
Poly(alkylene hydrogen phosphonate)s are a relatively
new family of biodegradable polymers [54, 38]. Bezdushna
et al. [55] reported the synthesis of poly(alkylene hydrogen
phosphonate)s by transesterification of dimethyl hydrogen
phosphonate with poly(ethylene glycol) (PEG 400) under
microwave irradiation with a very short reaction time (55
min) relative to that of classical thermal heating (9 h)
(Scheme 14). Using conventional conditions, poly(alkylene
hydrogen phosphonate) with molecular weight of 4 900 Da is
obtained after 9.5 h heating.
The structure of the polymer was confirmed by
1
H,
31
P,
and
13
C NMR spectroscopy (CDCl
3
):
1
H- NMR: 3.59-3.68
(m, 4H, OCH
2
CH
2
); 3.68 (d, 3H, POCH
3
), 4.09-4.16 (m, 4H,
POCH
2
CH
2
); 6.85 (d, 1H, P-H); 6.76 (d, 1H, P-H); 6.74 (d,
1H, P-H).
13
C{H}- NMR: 52.8 (d, POCH
3
), 65.03 (d,
POCH
2
), 68.50 (d, POCH
2
CH
2
), 70.22 (CH
2
OCH
2
CH
2
).
31
P -
NMR: 10.46 (phosphorus atom in the repeating unit);
11.18(phosphorus atom in the end group, bonded with OCH
3

and OCH
2
groups); 8.31 (phosphorus atom bonded with OH
and OCH
2
groups).
Microwave technique avoids the undesirable thermal
degradation of reagents, especially phosphite, and polymers
because of the short reaction time at higher temperatures.
P
O
H O
O CH
3
CH
3
m +
O
H OH
a
x
O
H
3
C P
O
H
O
O
P
O
O
H
CH
3
z
140
o
C
-nCH
3
OH
160-180
o
C/vacum
-(CH
3
O)
2
P(O)H
P
O
O H
O
CH
3
O
P
O
H
O
O
P
O
H
O
CH
3
x x
n
P
O
O H
O
CH
3
O
P
O
H
O
O
P
O
OH
O
CH
3
x
x
n
+H
2
O
HO
P
O
H
O
OH
x
(n-p)
P
O
H
+
HO O
O
P
O
OH
H
x
p
x


(Scheme 14). The synthesis of poly(oxyethylene hydrogen phos-
phonate).
CONCLUSIONS
The development of cleaner technologies is a major em-
phasis in green chemistry. This article is a short comprehen-
sive review describing green phosphorus-containing poly-
mers synthesis. Synthetic methods have been developed that
are: efficient (fewer reaction steps, fewer resources required,
less wastage); simple (the catalysts are stable in air, at nor-
mal temperatures and pressures); environmentally friendly
(work under bulk conditions or in noninjurious solvents, less
hazardous waste products). Phosphorus-containing polymers
were synthesized through green chemistry routes: solvent
and catalyst-free synthesis which is a fast and environmen-
tally friendly route for the preparation of polyphosphonates
and polyphosphates; solid phase polyphosphonates synthesis
mediated by ultrasound; polyphosphonates and polyphos-
phates obtained by solid-liquid interfacial polycondensation,
an eco-friendly and economical procedures, using potassium
phosphate in order to suppress the side reactions; phospho-
rus-containing polymers synthesized using a green radia-
tion-induced reaction; polymers containing phosphorus
groups and polyethers synthesized using a green media.
So-called green solvents were used. The advantages are:
an ionic liquid is formed and the products can be easily re-
covered by a simple layer separation; the enhancing of
polymer yield; reducing of the corrosion problem. In order to
Green Methods in Phosphorus-Containing Polymers Synthesis Current Green Chemistry, 2014, Vol. 1, No. 1 49
extend the application possibilities of vegetable oil-based
thermosets by improving their flame retardance and to pre-
serve the environmental friendly character of these materials
by using a phosphorus based system instead of a halogen
based system, two different approaches to phosphorus-
containing soybean oil copolymers were investigated. Mi-
crowave irradiation is a promising green method for the syn-
thesis of phosphorus-containing polymers by transesterifica-
tion.
CONFLICT OF INTEREST
The authors confirm that this article content has no con-
flicts of interest.
ACKNOWLEDGEMENTS
Declared none.
REFERENCES
[1] Anastas, P.T.; Eghbali, N. Green chemistry: Principles and prac-
tice. Chem. Soc. Rev., 2010, 39(1), 301-312.
[2] Anastas, P. T.; Zimmerman, J . B. Peer reviewed: design through
the 12 principles of green engineering. Environ. Sci. Technol.,
2003, 37(5), 94A-101A.
[3] Anastas, P. T.; Warner J . C. Green Chemistry: Theory and Prac-
tice, Oxford University Press: New York, 1998.
[4] Brennecke, J .F; Allen D.T. Green chemistry and engineering: pref-
ace. Ind. Eng. Chem. Res., 2002, 41(18), 4439-14439.
[5] Pokhodenko, V.D.; Pavlishchuk V.V. Green chemistry and modern
technology. Theor. Exp. Chem., 2002, 38(2) 69-87.
[6] Dixon, B.G.; Moris R.; Dallek S. Non-flammable polyphosphonate
electrolytes. J. Power Sources, 2004, 138(1-2), 274-276.
[7] Ranganathan, T.; Zilberman, J .; Farris, R.J .; Coughlin, E.B.; Em-
rick, T. Synthesis and characterization of halogen-free antiflamma-
ble polyphosphonates containing 4,4'-bishydroxydeoxybenzoin.
Macromolecules, 2006, 39, 5974-5975.
[8] Lenz, R.W.; Marchessault, R.H. Polyesters: Biosynthesis, biode-
gradable plastics and biotechnology. Biomacromolecules, 2005,
6(1), 1-8.
[9] J asuhiko, I.; Kazunari, A. Design of biodegradable polyphosphates.
J. Am. Chem. Soc., 2006, 1, 26-30.
[10] Kaczorowska, M.A.; Cooper, H.J . Characterization of polyphos-
phoesters by Fourier Transform Ion Cyclotron Resonance Mass
Spectrometry. J. Am. Soc. Mass Spectrom., 2009, 20(12), 2238-
2247.
[11] Roy, S.; Maiti, S. Synthesis and characterization of unsaturated
polyphosphonates. J. Polym. Mater., 2001, 17(9), 267-282.
[12] Narendran, N.; Kishore, K. Hydrolytic degradation studies on
poly(phosphate ester)s, J. Appl. Polym. Sci., 2003, 87(4), 626-631.
[13] Senthil, S.; Kannan, P. Synthesis and characterization of liqud-
liquid-chrystaline polyphosphonates containing disubstituted fer-
rocene esters as mesogenes. J. Polym. Sci. Part A-Polym. Chem.,
2002, 40(14), 2256-2263.
[14] Makosza, M. Phase-transfer catalysis. A general green methodol-
ogy in organic synthesis. Pure Appl. Chem., 2000, 72(7), 1399-
1403.
[15] Scheldon, R.A. Green solvents for sustainable organic synthesis:
state of the art. Green Chem., 2005, 7(5), 267-278.
[16] Iliescu, S.; Ilia, G.; Popa, A.; Dehelean, G.; Macarie, L.; Pacure-
anu, L. The study of the vapor-liquid interfacial polycondensation
of the cyclohexylphosphonic dichloride with bisphenol A. The in-
fluence of temperature, reaction time, base concentration and molar
ratio on yield inherent viscosity and molecular weight. Polym.
Bull., 2001, 46, 165-174.
[17] Iliescu, S.; Ilia, G.; Dehelean, G.; Popa, A. New polyphosphonates
obtained by vapor-liquid interfacial polycondensation. Polym.
Bull., 2002, 48451-458.
[18] Iliescu, S.; Ilia, G.; Popa, A. Phase transfer catalysis in phosphorus
-containing polymers synthesis. J. Serb. Chem. Soc., 2005, 70(7),
951-956.
[19] Iliescu, S.; Plesu, N.; Popa, A.; Macarie, L.; Ilia, G. Green synthesis
of polymers containing phosphorus in the main chain. Compt.
Rend. Chim., 2011, 14(7-8), 647-651.
[20] Allen, J .; Bevinngthon, J .C. Comprehensive polymer science: the
synthesis, characterization, reactions & applications of polymers.
Pegamon Press; New York, 1988; Vol. II, p. 20.
[21] Lindley, J .; Mason, T.M. Sonochemistry. Part 2- Synthetic applica-
tions. Chem. Soc. Rev., 1987, 16, 275-311.
[22] Elizalde, L.E.; Torres, N. P.; Ciqua, R. J .G. Macromolecular Rep.,
1993, A30 (Suppls. 3&4), 295-299.
[23] Cintas, P.; Luche, J -L. Green Chemistry: The sonochemical ap-
proach. Green Chem., 1999, 1(3), 115-125.
[24] Mason, T.J . Ultrasound in synthetic organic chemistry. Review.
Chem Soc. Rev., 1997, 26, 443-451.
[25] Iliescu, S.; Avram, E.; Pascariu, A.; Plesu,; N.; Popa, A.; Ilia, G.
New technique for the synthesis of polyphosphoesters, Macromol.
Res., 2011, 19(11), 1186-1191.
[26] Qafisheh, N.; Mukhopadhyay, S.; J oshi, A.V.; Sasson, Y.; Chuah,
G.K.; J aenicke, S. Potassium phosphate as a high-performance
solid base in phase-transfer-catalyzed alkylation reactions. Ind.
Eng. Chem. Res., 2007, 46(10), 3016 3023.
[27] Aycock, D.F. Solvent applications of 2-methyltetrahydrofuran in
organometallic and biphasic reactions. Org. Process Res. Rev.,
2007, 11(1), 156-159.
[28] Gray, F.M. Solid Polymer Electrolytes:Fundamentals and Techno-
logical Applications, Wiley& Sons; New York, 1991.
[29] Iliescu, S.; Augusti, M.-G.; Fagadar-Cosma, E.; Plesu, N. ; Fa-
gadar-Cosma, G.; Macarie, L.; Popa, A.; Ilia, G.; Synthesis of new
phosphorus-containing (co)polyesters using solid-liquid phase
transfer catalysis and product characterization. Molecules, 2012,
17(8), 9090-9103.
[30] Itoh, T.; Ikeda, M.; Hirata, N.; Moriya, Y.; Wen, Z.; Ichikawa, Y.;
Kubo, M.; Yamamoto O. Electrochemical and thermal properties of
hyperbranched polymer electrolytes for batteries. Ionics, 2002, 8(1-
2), 44-52.
[31] Ilia, G.; Iliescu, S.; Macarie, L.; Popa, A. Synthesis of tervalent
phosphorus esters in biphasic system using potassiumphosphate as
unique solid base. Heteroat. Chem., 2008, 19(4), 360-364.
[32] Iliescu, S.; Zubizarreta, L.; Plesu, N.; Macarie, L.; Popa, A.; Ilia, G.
Polymers containing phosphorus groups and polyethers: From syn-
thesis to application. Chem. Cent. J., 2012, 6, art. no.132.
[33] Novolyte tecnologies: http://www.novolyte.com/performance-
materials/high-performance solvents/green-solvents.aspx
[34] Li, Q.; Wang, J .; Shahani, S.; Sun, D.D.N.; Sharma, B.; Elisseeff,
J .H.; Leong, K.W. Biodegradable and photocrosslinkable poly-
phosphoester hydrogel. Biomaterials, 2006, 27(7), 1027-1034.
[35] Chen, D.-P.; Wang, J . Synthesis and characterization of block
copolymer of polyphosphoester and poly(-caprolactone). Macro-
molecules, 2006, 39(2), 473-475.
[36] Dahiyat, B.I.; Richards, M.; Leong, K.W. Controlled release from
poly(phosphoester) matrices. J. Control. Release, 1995, 33(1), 13-
21.
[37] Richards, M.; Dahiyat, B.I.; Arm, D.M.; Brown, P.R.; Leong, K.W.
Evaluation of polyphosphates and polyphosphonates as degradable
biomaterials. J. Biomed. Mater. Res., 1991, 25(9), 1151-1167.
[38] Zhao, Z.; Wanh, J .; Mao, H.Q.; Leong, K.W. Polyphosphoesters in
drug and gene delivery. Adv. Drug Deliv. Rev., 2003, 55(4), 483-
499.
[39] Iliescu, S.; Popa, A.; Ilia, G.; Plesu, N. The synthesis of
biodegradable poly(phosphate esters) by vapor-liquid interfacial
polycondensation. Rev. Roum. Chim., 2005, 50 (7-8), 609-613.
[40] IIiescu, S.; Ilia, G.; Popa, A.; Macarie L. Polyphosphates obtained
by the gas-liquid technique. Mater. Plast., 2006, 43(2), 83-85
[41] Iliescu, S.; Ilia, G.; Plesu, N.; Popa, A.; Pascariu, A. Solvent and
catalyst-free synthesis of polyphosphates. Green Chem., 2006, 8(8),
727-730.
[42] Iliescu, S.; Ilia, G.; Pascariu, A.; Popa, A.; Plesu, N. Solvent-free
synthesis of phosphorus-containing polymers. Pure and Appl.
Chem., 2007, 79(11), 1879-1884.
[43] Belgacem, M.N.; Gandini, A. Monomers, Polymers and Compos-
ites from Renewable Resources, Elsevier; Oxford, 2008.
[44] Yu, L.; Dean, K.; Li, L. Polymer blends and composites from
renewable resources. Prog. Polym. Sci., 2006, 31(6), 576-602.
[45] Meier, M.A.R.; Metzger, J .O.; Schubert, U.S. Plant oil renewable
resources as green alternatives in polymer science. Chem. Soc.
Rev., 2007, 36(11), 1788-1802.
50 Current Green Chemistry, 2014, Vol. 1, No. 1 Iliescu and Ilia
[46] Sharma, V.; Kundu, P. Addition polymers from natural oils-A
review Prog. Polym. Sci., 2006, 31(11), 983-1008.
[47] J ain, P.; Choudhary, V.; Varma, I.K. Flame retarding epoxides with
phosphorus. J. Macromol. Sci. Polym. Rev., 2002, 42(2), 139-183.
[48] Benito, M.S. Soybean Oil Based Copolymers Containing Silicon,
Boron or Phosphorus: Polymerization, Characterization and Fire
Retardance Properties. Universitat Rovira i Virgili, ISBN: 978-84-
693-1532-3/DL:T-649-2010
[49] Tarasova, N.P.; Smetannikov, Y. V.; Vilesov, A. S.; Zanin, A.A.
Role of reaction media in green radiationinduced polymerization
of white phosphorus. Pure Appl. Chem., 2009, 81(11), 21152122.
[50] Tarasova, N. P. Zanin, A.A.; Smetannikov, Y.V.; Vilesov, A. S.
Advanced approaches in radiation-chemical synthesis of phospho-
rus-containing polymers. Compt. Rend. Chim., 2010, 13(8-9),
10281034.
[51] Aslanov, L.A.; Zaharov, M.A.; Abramycheva, N.L. Ionnye Zhid-
kosti v Ryady Rastvoritelei (Ionic Liquids among Solvents), Mos-
cow State University Publ.; Moscow, 2005.
[52] Belin, E.; Sepiand, E.; Zuckerman, S. Electronic structure of red
amorphous phosphorus studied by X-ray spectroscopy. Solid State
Commun., 1982, 44(3), 413-415.
[53] Desai, K.R.; Kanetkar, V.R. Green Chemistry Microwave Synthe-
sis. Global Media, New York, 2010.
[54] Wang, J .; Huang, S.-W.; Zhang, P.-C.; Mao, H.-Q.; Leong, K. W.
Effect of side-chain structures on gene transfer efficiency of biode-
gradable cationic polyphosphoesters. Int. J. Pharm., 2003, 265(1-
2), 75-84.
[55] Bezdushna, E.; Ritter, H.; Troev, K. Microwave-assisted single-
step synthesis of poly(alkylene hydrogen phosphonate)s by trans-
esterification of dimethyl hydrogen phosphonate with
poly(ethylene glycol). Macromol. Rapid Commun., 2005, 26, 471
476.


Received: April 29, 2013 Revised: June 21, 2013 Accepted: June 21, 2013