Synthesis and homopolymerization kinetics of 7-(methacroyloxy)-2-oxo-heptylphosphonic acid and its copolymerization with methyl methacrylate

Figures & data

Scheme 1. Structure of monomer M1.

Scheme 2. Synthesis of acidic monomer M1.

Table 1. Summary of kinetic characteristics for homopolymarization of monomer M1. Polymerizations in MeOH and dioxane initiated by AIBN.

Solvent		Methanol		Dioxane
Batch Components in [mol/L]		Rp x 10^5 [mol/Ls]	Intensity exponent	Rp x 10^5 [mol/Ls]		Intensity exponent
[Monomer]: ([AIBN] = 0.05 mol/L, 60°C)	0.25	4.1	to M1 1.35	4.5		to M1 1.05
	0.50	10.6		10.3
	0.75	17.8		14.6
[AIBN]: ([Monomer] = 0.5 mol/L, 60°C)	0.025	7.5	to AIBN 0.44	7.5		to AIBN 0.49
	0.05	10.6		10.3
	0.075	12.0		13.1
Temperature [°C]: ([Monomer] = 0.5 mol/L, [AIBN] = 0.05 mol/L)	45	2.88	Ea = 73.2 [kJ/mol]	50	3.1	Ea = 71.5 [kJ/mol]
	55	6.9		60	10.3
	65	15.0		70	17.7

Figure 1. Changes of the part of ATR-FTIR spectra of M1 during homopolymerization. 0.25 mol/L M1; 0.025 mol/L AIBN; MeOH; 60°C.

Figure 2. Monomer conversion of M1 during homopolymerization. [AIBN] = 0,05 mol/L, T = 60°C, MeOH.

Figure 3. Dependence of M1 initial polymerization rates on starting monomer concentrations in MeOH at 60°C; [AIBN] = 0.05 mol/L.

Figure 4. M1 initial polymerization rates in dependence on AIBN initiator concentrations (60°C; monomer concentration 0.5 mol/L; MeOH).

Figure 5. Monomer conversion of M1 during homopolymerization in dioxane. [AIBN] = 0,05 mol/L, T = 60°C.

Figure 6. M1 initial polymerization rates in dependence on monomer concentration in the Arrhenius coordinates ([AIBN] = 0.05 mol/L, 60°C, dioxane).

Figure 7. Details of the ¹H-NMR spectra of the copolymerization of M1 with MMA at various time in deuterated methanol, T = 55°C. Molar ratio M1:MMA = 3.65:1 total monomers concentration = 0.5 mol/L, [AIBN] = 0.025 mol/L, CDCl_3.

Figure 8. (a) Monomer conversions of M1, MMA and total conversion during the copolymerization of mixture M1: MMA = 3.65:1. (b) comonomer ratio M1: MMA in feed versus time.

Figure 9. Jaacks plot obtained from time-conversion plot in Figure 8 (a).

Figure 10. Fineman–Ross plot for the free radical copolymerization of M1 and MMA.

Table 2. Reactivity ratio of M1 and MMA determined by different methods.

Method	rM1	rMMA	rM1 . rMMA
Fineman–Ross	0.92	1.15	1.06
Nonlinear least squares	0.76	0.99	0.75
Jaacks	1.00	0.95	0.95
Average value	0.89	1.03	0.92

Figure 11. Instantaneous copolymer composition F₁ versus commoner feed composition f₁ of M1 in copolymerization with MMA; fit of the data points to r₁ = r_M1 and r₂ = r_MMA.