Mathias Destarac
email: destarac@chimie.ups-tlse.fr

Dimitri Matioszek

Xavier Vila

Juliette Ruchmann-Sternchuss

Samir Z Zard
email: samir.zard@polytechnique.edu

How can xanthates control the RAFT polymerization of methacrylates ?

published or not. The documents may come

How can xanthates control the RAFT polymerization of methacrylates ?

Introduction

One of the most important scientific and industrial challenges in polymer chemistry is the synthesis of materials with well-defined composition and macromolecular architectures, which are in principle accessible by living polymerization methods. Over the past twenty years, the development of reversible-deactivation radical polymerization (RDRP) has greatly expanded the scope of monomers that can be incorporated in well-defined macromolecular architectures but there are still important bottlenecks. RDRP functions through dynamic equilibrium between growing active chains and latent chains bonded to a moderating agent, the nature of which is adapted to the monomer being polymerized (i.e. to the reactivity of the associated radical). Thus, monomers with very different reactivity (More Activated Monomers or MAMs on one side, Less Activated Monomers or LAMs on the other) cannot be easily controlled with the same moderating agent. This limits the possibility of making P(MAM)-P(LAM) architectures of interest for multiple innovative applications, by sequential addition. Among the various RDRP strategies, reversible addition-fragmentation chain-transfer (RAFT) polymerization is the most versatile and promising for industrial implementation. 1,2 Hence, one of the last great challenges in RDRP remains the identification of a universal system, easy to apply, able to control the polymerization of monomers with very disparate reactivity and allowing access to the corresponding block copolymers. The MAM family of monomers is vast, including not only 1,1-disubstituted monomers such as methacrylate or methacrylamido monomers but also styrenics, acrylonitrile, acrylates and acrylamido monomers, while the LAM group covers vinyl monomers such as vinyl esters and N-vinyl lactams, vinyl phosphonates, diallyl monomers, and mono-and diolefins. To date, combinations of MAM and LAM monomers in a single block copolymer are scarce and the reported strategies lack simplicity and versatility. For example, the use of N,N-diaryldithiocarbamates 3 or O-ethyl xanthates 4-10 RAFT agents, which exhibit a poor to moderate reactivity for MAMs and high reactivity for LAMs, resulted in various block copolymers with controlled molar masses and relatively high dispersities, like PS-b-PVAc, 3 PDMA-b-PVAc 9 and PAA-b-PVP 10 among many others. Moreover, these RAFT agents are unreactive in methacrylate polymerization. Following a different strategy, Moad and co-workers at CSIRO reported the synthesis of low-dispersity diblock copolymers comprising both P(MAM) and P(LAM) blocks by RAFT. This was possible through the use of a switchable RAFT agent, N-methyl-N-(4pyridinyl) 11,12 or N-aryl-N-(4-pyridinyl) 13 dithiocarbamate, the reactivity of which could be changed by reversible protonation by a strong acid/base to control successively MAM and LAM monomers. However, the reversibility of this reaction was not general and its success was highly dependent on the nature of the reaction medium. More recently, the same group designed dithiocarbamate RAFT agents comprising 3,5-dimethylpyrazole Z groups which allowed the synthesis of low Ð PDMA-b-PVAc copolymers without a need for switching, 14 but led to poor control for MMA. Their most recent contribution consisted in the introduction of a chlorine or a bromine atom at the 4-position on the pyrazole ring. This effectively contributed to improve the control of MMA polymerization with Mn slightly higher than theory and Ð close to 1.3. 15 At the same time, it significantly retarded the polymerization of vinyl acetate (VAc) with limited conversions.

In this contribution, we explore the possibility of using a xanthate of adequate reactivity in order to prepare a diblock copolymer made of polymethyl methacrylate (PMMA) and PVAc by simply adjusting the monomer addition profiles during emulsion RAFT polymerization.

Experimental

Materials.

2,2,2-Trifluoroethanol (≥ 99%), trityl chloride (97%), sodium hydride (60% in oil), and potassium O-ethyl xanthate (96%) were purchased from Aldrich and were used without further purification. Carbon disulfide (CS2, ≥ 99.9%) was purchased from Aldrich and distilled over CaH2 prior use. The solvents were dried using standard methods. 2,2'-azobis(isobutyronitrile) initiator (AIBN, ≥ 98%) was purchased from Fluka and recrystallized twice from methanol prior to use. Methyl methacrylate (MMA, 98%) was purchased from Aldrich. Vinyl Acetate (VAc, 99+%) was purchased from Acros Organics. Monomers were purified by passing through a column packed with neutral alumina. Sodium dodecyl sulfate (SDS, ≥ 99%) and sodium persulfate (NaPS, > 98%), tert-butyl hydroperoxyde (TBHP, 70%wt in water), sodium sulfite (Na2SO3, ≥ 98%) were purchased from Sigma-Aldrich and used without further purification. Characterization. NMR spectra were recorded with a Bruker Avance II 300: 1 H (300.13MHz), 13 C (74.48 MHz), 19 F (282.40 Mhz) at 298 K in CDCl3. Chemical shifts are expressed in parts per million with residual solvent signals as internal reference ( 1 H and 13 C) 16 or with an external reference (CF3Cl for 19 F). Melting points were determined using a Reichert microscope apparatus and are uncorrected. Infrared Absorption spectra were recorded as a solution in CCl 4 with a Perkin-Elmer 1600 Fourier Transform Spectrophotometer. Mass spectra were recorded with an HP 5989B mass spectrometer via direct introduction for chemical positive ionization (CI) using ammonia as the reagent gas. HRMS were performed on JEOL JMS-GcMate II, GC/MS system spectrometer. Size-exclusion chromatography (SEC) was used to determine the number-average molar mass (Mn) values and dispersities (Ð) of the polymer samples. Analyses were conducted by using a Waters 2414 refractive index detector, a Multi-Angle Light Scattering detector (MALS) mini DAWN TREOS (Wyatt Technology) equipped with a set of 2 columns (Shodex KF-802.5 and KF-804) in THF as eluent at a flow rate of 1.0 mL.min -1 at 35 °C ((dn/dc)PMMA = 0.087 mL/g 16 and (dn/dc)PVAc = 0.057 mL/g 17 ).

The particle size and polydispersity of the latex were measured with a Malvern Zetasizer Nano-S at 25 °C.

Xanthate synthesis.

Xanthates 2, 18 3, 19 4 19 and 6 20 were synthesized according to procedures reported elsewhere. Ethoxythiocarbonylsulfanylphenylacetic acid methyl ester 1. To a solution of methyl mandelate (3.32 g, 20.0 mmol) in CH2Cl2 (15 mL) cooled to 0 °C was added carefully PCl5 (5.0 g, 24.0 mmol) and stirred at room temperature for 2 h. After that time the reaction mixture was concentrated, the residue was redissolved in EtOH (80 mL) and cooled to 0 °C. Potassium O-ethyl xanthate (3.85 g, 24.0 mmol) was added, and the reaction mixture was stirred at room temperature for 4 h. Then, it was concentrated, the residue redissolved in Et2O, and washed three times with H2O. The organic layer was dried and evaporated, and the residue purified by flash column chromatography (petroleum ether:EtOAc 95:5), furnishing the desired xanthate as a yellow oil (3.10 g, 57%). IR (CCl4) nmax/cm -1 1746 (CO), 1226 (C-O), 1054 (C=S).

Dithiocarbonic acid (1-cyano-1-phenylmethyl) ester ethyl ester 5.

To a solution of mandelonitrile (3 mL, 22.5 mmol) in CH2Cl2 (17 mL) cooled to 0 °C was added carefully PCl5 (5.63 g, 27.0 mmol) and the resulting mixture stirred at room temperature for 1 h. After that time the reaction mixture was concentrated, the residue redissolved in acetone (113 mL) and cooled to 0 °C. Potassium O-ethyl xanthate (4.69 g, 29.3 mmol) was added, and the reaction mixture stirred at room temperature for 2 h. It was then concentrated, the residue redissolved in Et2O, and washed three times with H2O. The organic phase was dried and evaporated, and the residue purified by flash column chromatography (petrol:EtOAc 98:2), to furnish the desired xanthate as a yellow oil (3.76 g, 71%). IR (CCl4) nmax/cm -1 2361 (CN), 1242 (C-O), 1047 (C=S). Dithiocarbonic acid (2,2,2-trifluoroethyl) ester trityl ester 6'. To a solution of 2,2,2-trifluoroethanol (10.00 g, 100.0 mmol) in DMF (200 mL) cooled to -40 °C was added CS2 (152.00 g, 2000.0 mmol) and NaH (4.40 g, 110.0 mmol), and the resulting mixture stirred at this temperature for 2 h. Trityl chloride (30.70 g, 110.0 mmol) was added and the mixture stirred at the same temperature for a further hour. The reaction mixture was diluted with EtOAc and washed four times with H2O. The organic phase was dried and evaporated under reduced pressure, and the residue purified by flash column chromatography (petroleum ether:EtOAc 98:2) to give a yellow solid (83%). mp: 60-61 °C. IR (CCl4) nmax/cm -1 1277 (C-O), 1077 (C=S). 1 H NMR (CDCl3) δ 4.45 (q, 2H, 3 JH-F = 8.4 Hz, OCH2), 7.20-7.40 (m, 15H, C6H5). 19 F-NMR (CDCl3) δ -72.10 (t, 3 JF-H = 8.1 Hz) 13 C-NMR (CDCl3) δ 66.66 (q, 2 JC-F = 37.1 Hz, OCH2), 75.55 (C-CH3), 122.07 (q, 1 JC-F = 278.1 Hz, CF3), 127.45 (CHpara), 128.03 (CHmeta), 129.85 (CHortho), 142.68 (CHipso), 210.20 (C=S). Dithiocarbonic acid (1-cyano-1,1-dimethylmethyl) ester (2,2,2-trifluoro-ethyl) ester 7. To a solution of trityl xanthate 6' (10.00 g, 23.9 mmol) in refluxing in 1,2dichloroethane (98 mL) was added AIBN (4.30 g, 26.3 mmol), and the resulting mixture stirred for 3 h. After that time the reaction mixture was concentrated under reduced pressure, and the residue purified by flash column chromatography (cyclohexane:EtOAc 98:2) to yield a yellow oil (56%). IR (CCl4) nmax/cm -1 2237 (CN), 1279 (C-O), 1173 (C-O), 1087 (C=S). 1 H-NMR (CDCl3) δ 1.82 (s, 6 H, CH3), 4.98 (q, 2H, 3 JH-F = 8.1 Hz, OCH2). 19 F-NMR (CDCl3) δ -72.13 (t, 3 JF-H = 8.2 Hz) 13 C-NMR (CDCl3) δ 27.01(CH3), 41.53 (C-CH3), 67.16 (q, 2 JC-F = 37.1 Hz, OCH2), 120.32 (CN), 122.50 (q, 1 JC-F = 277.6 Hz, CF3), 206.05 (C=S). MS m/z (CI) 244 (MH + ), 261 (MNH4 + ).

Polymerizations. Determination of the chain transfer constants to xanthates.

A stock solution of 0.1 mol% AIBN in MMA was transferred to four glass tubes containing different xanthate concentrations. The tubes were degassed by three freeze-pump-thaw cycles and flame sealed under vacuum. The polymerizations were carried out at 60°C and stopped before 10% conversion. The conversion was determined by gravimetry. Mn was obtained by SEC-RI-MALS. The Ctr value was derived from the Mayo plot. 21 Emulsion polymerization of MMA with RAFT agent 7. The polymerization was performed in a double-jacketed 100 mL glass reactor equipped with a mechanical stirrer, a condenser, and a thermometer. In the reactor was added water (9.84 g), SDS (0.37 g, 1.28 mmol), MMA (0.12 g, 1.23 mmol) and RAFT agent 7 (0.20 g, 0.82 mmol). After degassing 30 minutes by argon bubbling, the solution temperature was set to 85 °C and stirred at 300 rpm. Two degassed solutions of MMA (12.20 g, 122 mmol) and NaPS (0.18 g, 0.74 mmol) in water (20.27 g) were added by syringe pumps over 3h and 3h15 respectively. Samples were withdrawn from the reaction mixture at given intervals. After the complete addition of the initiator, the polymerization was continued for an extra 1h30 (conv. 100%). Final solid content=30.3%. Dp=68 nm and PDI = 0.085 (DLS). Mn MALS = 15100 g.mol - 1 , Ð MALS = 1.28. Synthesis of PMMA-PVAc block copolymer. Block copolymerization was performed in a double-jacketed 100 mL glass reactor equipped with a mechanical stirrer, a condenser, and a thermometer. In the reactor was added PMMA-7 latex (20 g, 0.40 mmol), VAc (12.12 g, 140.00 mmol), TBHP (70%wt in water, 0.17 g, 1.29 mmol) and water (27.88 g). The solution was stirred at 300 rpm at 20 °C and degassed 60 minutes by argon bubbling after while Na2S2O3 was added in one portion into the mixture. After 13 hours (not optimized), the solution was analysed (conv. 73%). Final solid content=22.1%. DLS: 96 nm and PDI = 0.035 (DLS). Mn MALS = 41850 g.mol -1 , Ð MALS = 1.27 (dn/dc = 0.069 mL/g determined based on (dn/dc)PMMA and (dn/dc)PVAc).

Results and Discussion

A series of xanthates 1-7 of general structure R-S(C=S)-OR' (Scheme 1) were prepared for this study. Compounds 1 and 5 were obtained by the standard substitution reaction of potassium O-ethyl xanthate on the precursor chlorides, prepared from methyl mandelate and mandelonitrile, respectively. A similar route was used to access xanthate 3. 19 Xanthates 2 and 4 were produced by benzylation and methylation of the parent malonyl xanthate 1' according to our previously published procedure. 18 Xanthate 6 was manufactured by simply heating AIBN with bis(O-ethyl xanthate) as previously described. 20,22 Finally, trifluoroethyl derived xanthate 7 was secured by a variation of the last method, developed by Benaglia and co-workers. 23 Their chain transfer ability in radical polymerization of MMA has been evaluated through the determination of transfer constants by the Mayo equation 21 (Table 1). Secondary and tertiary leaving R groups with steric hindrance and electronwithdrawing and resonance-stabilizing substituents were selected in order to favor the formation of the R . radical after fragmentation of the RAFT intermediate radical in the pre-equilibrium. 24,25 In spite of our precautions, O-ethyl xanthates 1-6 all exhibit similarly low Ctr values ranging from 1.1.10 -2 and 4.8.10 -2 , thereby making them inefficient RAFT agents for MMA (Table 1). The addition of carbon-centered radicals to the thiocarbonyl group is extremely fast. Indeed, theoretical calculations by Coote 26 have yielded values in the range of 10 6 -10 8 L - 1 .mol -1 .s -1 , consistent with the earlier values from laser flash photolysis experiments reported by Scaiano and Ingold. 27 These rates constants are at least three orders of magnitude greater that the rate constants for the addition of carbon radicals to alkenes. The study of Coote also showed that the fragmentation rate coefficients were much more sensitive to the nature of the substituents and could vary over a very wide range, from 10 -4 to 10 7 s -1 , that is eleven orders of magnitude. 26,28 Thus, while the addition of the PMMA radical to the radicophilic thiocarbonyl group is fast, the back fragmentation is also fast, in view of the relative high stability of the PMMA radical. As a consequence, ordinary xanthates exhibit an apparent low reactivity as chain transfer agents leading to a poor control of the polymerization process (for a more detailed mechanistic discussion, see refs. 28 and 29).

To overcome this problem, on can envisage speeding up the addition step, slowing down the fragmentation or both. This is accomplished by the use of dithiocarbamates and trithiocarbonates, which are better suited for controlling the polymerisation of MMA. In the case of xanthates, one simple solution is to improve their reactivity by altering the substituent on oxygen. Indeed, in the past, our group reported that the reactivity of xanthate RAFT agents could be substantially increased by substituting R'=2,2,2-trifluoroethyl for ethyl. 30 Hence, the best R group, namely 2-cyano-2-propyl of 6, was associated with R'=2,2,2trifluoroethyl in xanthate 7. By doing so, the transfer constant to 7 was increased by a factor of three compared to 6, with a Ctr of 0.137. Based on theoretical calculations, Mueller at al. first reported the possibility of producing low dispersity polymers with low transfer constant species in a degenerative transfer process, provided that the monomer concentration is kept low. 31 Although still low, the Ctr value of 7 is similar to that of PMMA macromonomers, 32,33 whose low reactivity could be counterbalanced by performing the polymerization in emulsion under starved-feed conditions in order to keep the monomer concentration to a minimum. Semi-batch processes were also applied later for RAFT emulsion block copolymerization of MMA and St with dithioesters, 34 and for the preparation of PS-b-PnBA core-shell latexes by emulsion polymerization with a xanthate RAFT agent of low reactivity. 35 In the following section, we set up the process paremeters for efficient control of emulsion RAFT polymerization of MMA with fluorinated xanthate 7.

Scheme 1. Xanthates of the study. The reaction conditions for PMMA latex synthesis and the obtained results are collected in Table 2. Firstly, a blank experiment with no xanthate was set up, with 5% of the total load of MMA at the bottom of the reactor with SDS and water (entry 1 of Table 2). The reaction was carried out at 80°C with MMA and an aqueous solution of NaPS initiator added simultaneously over 3h and 1h30, respectively. 15 min after the end of monomer introduction, the polymerization was stopped. A stable latex was obtained with a MMA conversion of 86% (corresponding to a solid content of the latex of 25.7% for 30% targeted). A number-average particle diameter (Dp) of 105 nm and a relatively broad particle size distribution (entry 1 of Table 2) were determined. Mn was 121 kg.mol -1 and Ð was 2.22. After extending the reaction time after the end of MMA addition from 15 to 30 min, the same polymerization was run with xanthate 7 (entry 2 of Table 2) at the bottom of the reactor. This led to a much higher MMA conversion of 96.2%. Xanthate 7 was responsible for a strong decrease of Mn (27 kg.mol -1 ) and Ð (1.53), together with a decreased Dp value of 65 nm with a much narrower particle size distribution. RAFT agent 7 clearly reacted during polymerization, but not completely as evidenced by a residual intense UV signal in SEC/UV at 290 nm at high elution volumes (not shown), which is characteristic of the presence of unreacted xanthate 7. This is in agreement with a final Mn value which is greater than theoretical 15 kg.mol -1 . Chain transfer to xanthate 7 form R• after fragmentation, the formed radical will exit the particle and reenter micelles and thus nucleate more particles, which can explain the decrease of Dp and PDI. 36 The reaction temperature was increased to 85°C, in order to increase the instantaneous concentration of initiator-derived radicals, and the end of reaction was set up to 1h after the end of MMA introduction (entry 3 of Table 2). Consequently, MMA conversion reached 100% and Mn decreased down to 23 kg.mol -1 , but some unreacted xanthate 7 was still present after polymerization. The characteristics of the formed PMMA latex remained essentially the same by decreasing the MMA load down to 1% of the total amount at the bottom of the reactor (entry 4 of Table 2). Finally, an efficient RAFT procedure was found by decreasing the monomer and initiator feed rates (3h and 3h15 feeding time, respectively). Under these conditions, xanthate 7 fully reacted (as evidenced by SEC/UV) and a stable PMMA latex with Mn of 15.4 kg.mol -1 (for a theoretical Mn of 15.2 kg.mol -1 ) and a dispersity of 1.29 was obtained. The process conditions we established correspond to a strarved-feed regime for MMA concentration, with ~92% of reacted MMA after 1h of addition and ~100% from the second hour of addition onwards (Figure 1). It appears from Figures 1 and2, respectively showing the evolution of Mn MALS as a function of the molar equivalent of MMA added and SEC/MALS distributions after 1h and 3h reaction, that PMMA chain growth is controlled by reversible transfer to xanthate 7, with increase of Mn over the course of the reaction. However, Mn remains greater than theory during most of the polymerization, and only matches the expected value of ~15 kg.mol -1 in the last stages of polymerization (Figure 3), meaning that transfer is slow.

The PMMA-7 latex (entry 5 of Table 1) was used as a macro-RAFT seed for the batch emulsion polymerization of VAc. The reaction was initiated at 20°C with the TBHP/Na2SO3 redox couple. After 13h of reaction, 72% of VAc was converted. As shown on Figure 4, a homogeneous shift of SEC chromatogram towards lower elution volumes with molar masses in agreement with calculations for the formation of a block copolymer (see Table 2 for details) show that a PMMA-PVAc diblock copolymer was successfully obtained. As expected for a controlled process, the number-average particle diameter increased and the particle size distribution remained very low, which goes against the presence of secondary nucleation during VAc polymerization. To the best of our knowledge, this represents the first successful block copolymerization by RAFT of a methacrylate and a less-activated monomer (LAM), without resorting to an external switch of reactivity of the RAFT agent before the polymerization of the LAM. 11 2. 3.

Conclusion

A series of seven xanthates were synthesized and their reactivity in RAFT polymerization of MMA was evaluated. O-ethyl xanthates 1-6 are very poorly reactive RAFT agents. Dithiocarbonic acid (1-cyano-1,1-dimethylmethyl) ester (2,2,2-trifluoro-ethyl) ester 7 was found to be the most reactive of the series. Due to a too low transfer constant (Ctr<1) to get an efficient RAFT control in batch processes, the chain transfer activity of xanthate 7 was increased by keeping MMA concentration to a mínimum through a semi-batch emulsion polymerization. After a proper adjustment of the process parameters, a relatively high solid (30%) PMMA latex of controlled macromolecular characteristics (Mn, Đ) and well-defined colloidal properties (Dp, PDI) was obtained. A wellcontrolled PMMA-PVAc diblock copolymer latex was then synthesized starting from the PMMA seed. This last preliminary result represents the first straightforward synthesis of a PMMA-PVAc block copolymer using a conventional (i.e. not switchable) RAFT agent. In the future, we will apply this synthetic strategy to other MAM-LAM combinations.

  1 H-NMR (CDCl3) d 1.40 (t, J=7 Hz, 3 H, CH3 xanthate), 3.75 (s, 3 H, OCH3), 4.58-4.68 (m, 2 H, OCH2), 5.47 (s, 1 H, CH), 7.30-7.45 (m, 5 H, ArH). 13 C-NMR (CDCl3) d 13.5 (CH3 xanthate), 53.0 (CH), 56.8 (OCH3), 70.2 (OCH2), 128.5 (CH Ar), 128.7 (CH Ar), 128.9 (CH Ar), 133.1 (C Ar), 169.7 (CO), 211.5 (CS). MS m/z (CI) 271 (MH + ), 288 (MNH4 + ). HRMS calculated for C12H14O3S2 270.0385 found 270.0384.

Figure 1 .

 1 Figure 1. Evolution of MMA conversion during introduction as a function of time. Conditions of entry 5, Table2.

Figure 2 .

 2 Figure 2. SEC/RI distributions of PMMA latexes synthesized with xanthate 7 according to the optimized process detailed in entry 5 of Table 2. A comparative example with no xanthate added is shown for comparison.

Figure 3 .

 3 Figure 3. Evolution of Mn MALS and dispersity as a function of the molar equivalent of added MMA. Conditions of entry 5, Table2.

  (a) Mass of MMA at the bottom the reactor / mass of MMA added over time (b) (dn/dc)PMMA = 0.087 mL/g Table 2. Reaction conditions of emulsion RAFT block copolymerization of MMA and VAc with xanthate 7. TBHP/Na2SO3 initiator. Solid content=22%. T=20°C. Reaction time=13h. (dn/dc)PMMA = 0.087 mL/g (b) dn/dc = 0.069 mL/g calculated from (dn/dc)PMMA and (dn/dc)PVAc inTHF

Figure 4 .

 4 Figure 4. SEC/RI chromatograms of PMMA-7 seed and PMMA-PVAc block copolymer. Conditions of Table3.

Table 1 . Chain transfer constants to xanthates 1-7 for MMA

 1

	Xanthate	1	2	3	4	5	6	7
	10 2 .Ctr	1.1	1.3	2.9	3.5	3.7	4.8	13.7

Table 2 . Reaction conditions of emulsion RAFT polymerization of MMA mediated by xanthate 7. Theoretical Mn at full conversion=15200 g.mol -1 . mH2O=9.85 g, mSDS=0.37 g and mxanthate=0.20 g at the bottom of the reactor in 9.85 mL water. mNaPS=0.117 g added over time, [NaPS]=3.67.10 -2 mol.L -1 . Stirring rate=300 rpm.

 2

	Entry	RAFT	MMA	NaPS/MMA	Reaction time	T	Solid	Final	Mn MALS	(b)	Đ MALS	Dp	PDI
			(g) (a)	introduction	after end of		content	MMA				(nm)
				time	MMA addition	(°C)	(%)	conv.
				(min)	(min)			(%)
	1	None	0.62/11.7	90/180	15	80	25.7	86	121000	2.22	105	0.186
	2	7	0.62/11.7	90/180	30	80	29.1	96.2	27000		1.53	65	0.068
	3	7	0.62/11.7	90/180	60	85	30.2	100	23000		1.45	75	0.066
	4	7	0.12/12.2	90/180	60	85	30.3	100	22000		1.47	82	0.082
	5	7	0.12/12.2	195/180	90	85	30.3	100	15400		1.29	96	0.059

(g.mol -1 )

Acknowledgments

The authors wish to thank Rhodia and Solvay for financial support of this work.