Aqueous polymerization of methacrylic acid initiated by permanganate/oxalic acid redox system

The polymerization of methacrylic acid initiated by permanganate / oxalic acid redox pair has been studied in aqueous media at 30 ± 0.2°C in nitrogen atmosphere. The initial rate of polymerization has been found to be proportional to nearly the first power of the catalyst (KMnO₄) concentration ((0.8-6.0)·10^?4 mole/l.) at low monomer concentration (5.89·10^?2 mole/l.) but the catalyst exponent varies from 1.2 to 0.2 at comparatively high monomer concentration (17.68·10^?2 mole/l.) and falls at comparatively higher concentrations of the activator ((COOH)₂) at constant concentration of catalyst (1.6·10^?4 mole/l.) and monomer (5.89·10^?2 mole/l.). The rate is proportional to the first power of the monomer concentration within the range (2.36–14.1)·10^?2 mole/l. and catalyst (2.8·10^?4 mole/l.). The initial rate increases with increase in polymerization temperature up to 45°C. The overall activation energy has been found to be 9.87 kcal/mole within the temperature range 30-45°C. Organic solvents (water miscible only) and salts (KCl, Na₂SO₄ and Na₂C₂O₄) depress the rate considerably but the manganous salt (MnSO₄) is found to increase the initial rate. A complexing agent, NaF, decreases the rate as well as the maximum conversion. Introduction of new catalyst at intermediate stages of polymerization increases the rate and the maximum conversion.     

Study of the initiation mechanism of the vinyl polymerization with the system persulfate/N,N,N′,N′-tetramethylethylenediamine

The reaction mechanism of the redox initiation system persulfate/N,N,N′,N′-tetramethyl-ethylenediamine (TMEDA) was studied by spin trapping technique and ESR spectra. The free radical (CH₃)₂NCH₂CH₂(CH₃)NCH (1) is one of the initial free radicals responsible for the initiation of the vinyl polymerization in addition to the sulfate free radical (HO³SO^˙). The result of amino end group analysis confirmed the fact that the free radical 1 initiates vinyl polymerization and becomes the end group of the resulting polymers. The effect of TMEDA concentration on the final percentage of conversion of acrylamide polymerization and on the molecular weights of the resulting polymer were also studied. An initiation mechanism was proposed.     

Polymer of Controlled Chain Length Carrying Hydrophilic Galactose Moieties for Immobilization of DNA Probes

The synthesis and the “living” cationic polymerization of a new saccharidic monomer namely the 1,2 : 3,4‐di‐O‐isopropylidene‐6‐O‐(2‐vinyloxy ethyl)‐D ‐galactopyranose have been investigated. The monomer structure has been characterized by ¹H and ¹³C NMR, elemental analysis and mass spectrometry. It has been polymerized with acetaldehyde diethyl acetal/trimethylsilyl iodide as initiating system in presence of ZnCl₂ as co‐initiator. Macromolecules of controlled chain length (from 2 500 g·mol^–1 to 7 500 g·mol^–1) were obtained, bearing protected saccharidic moieties as side‐groups, and aldehyde as ω‐end‐groups which could be turned into amine ω‐end‐groups. Finally, the saccharidic residues were deprotected in order to perform the binding of DNA probes (oligonucleotides) onto the hydrophilic polymer chains through the anomeric site of the galactose moieties.     

Aqueous polymerization of acrylic acid initiated by KMnO4 — H2C2O4 redox system

Polymerization of acrylic acid in aqueous solution initiated by permanganate-oxalic acid redox pair has been studied at 32 ± 0.2°C in nitrogen atmosphere. The rate of polymerization has been found to be nearly independent of oxalic acid concentration within the range 1.87 to 9.33 · 10^?3 mole/l. and decreases only at higher concentrations of the oxalic acid. The rate has also been found to vary with the first power of the monomer concentration (within the range 1.44 to 5.76 · 10^?2 mole/l.) and the first power of the catalyst concentration (8.0 to 28.0 · 10^?5 Mole/l.). It is, however, proportional to half power at relatively high catalyst concentration, at fixed concentrations of oxalic acid (1.03 · 10^?2 mole/l.) and the monomer (5.76 · 10^?2 mole/l.). At higher concentration of monomer the catalyst exponent has been found to be nearly unity for both the higher and lower concentrations of the catalyst. The initial rate of polymerization increases with increase in temperature. The overall energy of activation has been found to be 19.56 kcal/mole within the temperature range 30 – 45°C. Organic solvents and salts (KCI, Na₂SO₄, and Na₂C₂O₄) depress the rate but MnSO₄ 4H₂O has been found to increase the initial rate but depress the maximum conversion.     

Determination of rate constants of initiation and propagation in the cationic polymerization of α-methylstyrene with CF3SO3H and H2SO4

The polymerization of α-methylstyrene with CF₃SO₃H and H₂SO₄ as initiators was studied at 30°C in dichloroethane by the stopped-flow/rapid-scan spectroscopic technique. The propagating cation shows λ_max at 336–340 nm. The initiation process and the early stage of propagation were analyzed kinetically on the basis of the cation formation and monomer consumption by taking into account the equilibrium monomer concentration. The rate of initiation with CF₃SO₃H was found to be proportional to the concentrations of CF₃SO₃H and monomer, but the initiation with H₂SO₄ is not proportional to the H₂SO₄ concentration. The rate constant of initiation was estimated to be (2 ± 1)·10³ 1.mol^?1.s^?1 with CF₃SO₃H, and similar values were found with H₂SO₄. The rate constant of propagation is 3.10⁴ 1.mol^?1.s^?1 with CF₃SO₃H as initiator and 10⁶ ? 10⁷ 1.mol^?1.s^?1 with H₂SO₄ as initiator. These k_p values are close to that obtained previously in the radiation polymerization. Finally, λ_max values of the propagating cation, obtained by the stopped-flow technique, were collected.     

Aqueous polymerization of methacrylamide initiated by the redox system K2S2O8/ascorbic acid

The polymerization of methacrylamide initiated by the redox system K₂S₂O₈/ascorbic acid has been studied at 35 ± 0,2°C under the influence of atmospheric oxygen. The molecular oxygen autocatalyses the polymerization rate. The rate of polymerization is independent of the activator (ascorbic acid) concentration within the range 2,83 · 10^?3 to 11,3 · 10^?3 mol · l^?1, this does not hold below or above the given concentration range. The rate varies linearly at low monomer concentration (up to 17,76 · 10^?2 mol · l^?1). The catalyst exponent decreases from nearly unity (0,94) to 0,57 with increasing concentration of the catalyst probably due to participation of primary radicals in the termination of growing chain. The initial rate is not changed by the addition of a strong acid (H₂SO₄) within the range 15 · 10^?5 to 30 · 10^?5 mol · l^?1. With the activator (ascorbic acid) alone, an optimum is observed within the pH range 2,9–3,5. The initial rate and the limiting conversion increases with increasing polymerization temperature. The overall energy of activation as calculated from the ARRHENIUS plot has been found to be 16,0 kcal.mol^?1 within the temperature range 30–45°C. Organic solvents (water miscible only) and small amounts of neutral salts, (KCl, Na₂SO₄) depress the initial rate and the maximum conversion. The addition of small amounts of catalysts like Cu^2⊕, Mn^2⊕, Ag^oplus; increases the initial rate but no appreciable increase in the limiting conversion is observed.     

Redox polymerization of 2-hydroxyethyl methacrylate, 2. Kinetics,mechanism and solvent effect using manganese triacetate/cyanoacetic acid as the redox system

Polymerization of 2-hydroxyethyl methacrylate (HEMA) initiated by the redox system manganese triacetate (Mn)(III)/cyanoacetic acid (CAA) was investigated kinetically in DMF and in HOAc/water (80 : 20 v/v). Monomer (M) conversion was followed gravimetrically. Polymerization was carried out at 31°C and at 41°C. The rate of polymerization R_p in DMF is expressed by the equation, R_P, ∝ [M]^1,4 [Mn(III)]^0,4 [CAA]^0,4. In HOAc/water, the polymerization exhibited a strong dependence on the concentration of Mn(III). That is, at low concentrations of Mn(III), the rate variations are [M]^1,0, [CAA]^0,5 and [Mn(III)]^0,5, while at high Mn(III) concentration the polymerization rates are independent of [Mn(III)] and vary as a function of [M]^1,5 and [CAA]^0,5. Enhanced oxidation of the primary radicals by Mn(III) at higher concentrations has been elicited to explain the observed orders. The degree of polymerization was found to increase with increase in concentrations of monomer and decrease in concentrations of CAA and Mn(III). The polymerization rates as well as the molecular weights of the polymers are higher in HOAc/water than in DMF. The enhanced polymerization rates have been attributed to the increased propagation and the reduced termination rates.     

Cationic polymerization of styrenes by protonic acids and their derivatives, 2. Two propagating species in the polymerization by CF3SO3H

The bimodal molecular weight distribution (MWD) of the polymers and the polymerization rate in the cationic polymerization of styrene by CF₃SO₃H were studied under a variety of conditions. Both the decrease of the dielectric constant of the reaction mixture and the addition of a common-ion salt (Bu₄N⁺SO₃CF) reduced the polymerization rate and the formation of the higher molecular weight portion of the polymers (the high polymer). It appears that of the two propagating species the one which forms the high polymer is more ionically dissociated and more reactive in propagation. Salt effects indicate that in nitrobenzene the propagating species is a solvent-separated ion pair and/or a free ion. The effects of monomer concentration on the bimodal MWD have shown that there are different chain-breaking reactions for the two propagating species. The possibility that the monomer is complexed with one of the growing species is also discussed.     

Equilibria and kinetics of the cationic ring-opening polymerization of permethylated 1,4-dioxa-2,3,5,6-tetrasilacyclohexane. Comparison with cyclosiloxanes

Equilibrium constants were determined for the formation of cyclic oligomers of the general formula $ {\hbox{-\hskip-5pt-\hskip-5pt-}[({\rm CH}_3})_2 {\rm Si \hbox{---} Si(CH_3})_2\hbox{---} {\rm O\hbox{-\hskip-6.5pt-}]}_n , n = 2 - 6$, in the polymerization of the n = 2 homologue, octamethyl-1,4-dioxa-2,3,5,6-tetrasilacyclohexane ( 1 ). The formation of a linear polymer is thermodynamically favoured in bulk and in concentrated solutions. The equilibrium concentration of cyclics is little dependent on temperature. The six-membered ring, n = 2, used here as a monomer, is the most abundant cyclic in the equilibrium mixture. Kinetics of the conversion of 1 during the polymerization initiated with CF₃SO₃H, CH₃SO₃H and CF₃COOH was studied in methylene dichloride solution. In its first stage, the reaction follows first order, but it slows down at higher monomer conversion. The order of the reaction with respect to the acid is two. Some kinetic features of the polymerization initated with CF₃SO₃H were similar to those exhibited by the polymerization of octamethylcyclotetrasiloxane (D₄). In particular small amounts of additional water have rather small effect on the rate, but change to a considerable extent the entropy and enthalpy of activation. The concentration of cyclic oligohomologues passes through a maximum during monomer conversion, which indicates the kinetic enhancement of the cyclisation process. This observation is somewhat similar to those in the polymerization of hexamethylcyclotrisiloxane (D₃). However, in contrast to the polymerization of D₃ and similarly to the polymerization of D₄, the excessive formation of oligomers being multiples of the monomer is not observed.     

Aqueous polymerization of methacrylamide initiated by KMnO4/H2C2O4 redox system

The polymerization of methacrylamide initiated by potassium permanganate/oxalic acid redox system has been studied at 35 ± 0.2°C in a nitrogen atmosphere. The rate of polymerization is independent of the activator (oxalic acid) concentration within the range 5·10^?3 to 10·10^?3 mole·1^?1, except at very high (above 10·10^?3 mole·1^?1) or at very low (below 5·10^?3 mole·1^?1) concentrations of the activator. The rate varies linearly at low monomer concentration (up to 5.87·10^?2 mole·1^?1). The catalyst exponent decreases from nearly unity (0.91) to 0.66 with increase in concentration of the catalyst (KMnO₄) probably due to participation of primary radicals in the termination of the growing chain. The addition of strong acid (H₂SO₄) within the range 5 · 10^?4–15 · 10^?4 mole · l^?1, shows a constant pH of 2.7 resulting in no change in initial rate. With activator alone (H₂C₂O₄ · 2H₂O), within the pH range 2.7 to 2.9 an optimum is observed. The initial rate increases with increase in polymerization temperature. The overall energy of activation as calculated from the ARRHENIUS plot has been found to be 15.1 kcal · mole^?1 within the temperature range 30–50°C. Organic solvents (water miscible only) depress the initial rate and the maximum conversion. Small amounts of neutral salts (KCl and Na₂SO₄), however, show no appreciable effect on the polymerization rate, but small amounts of manganous salts (MnSO₄) can increase the initial rate to a considerable extent. High concentrations of MnSO₄ result in termination of the growing chain. A complexing agent, Na₂F₂, decreases the initial rate but increases the maximum conversion. Introduction of fresh catalyst at intermediate stages of polymerization increases both the rate of the reaction and the conversion.     

Mechanism of the polymerization of acrylamide initiated by the glycerol/Ce(IV) redox system

The mechanism of the polymerization of acrylamide in aqueous medium initiated by the glycerol (R)/Ce(IV) redox system was studied. The rate of monomer disappearance was found to be directly proportional to [M]^3/2, and R^1/2 at lower concentrations of Ce(IV). The rate of the disappearance of ceric ions was found to be inversely proportional to [M] and directly proportional to [Ce(IV)] and [R]. Consistent with the findings of earlier investigations, a complex formation between monomer, acrylamide, and ceric ion is indicated. The experimental results show the termination to be mutual. On the basis of these and other kinetic results, an appropriate mechanism is proposed. At higher concentration of Ce(IV), a different mechanism seems to operate. The rates of disappearance of both the monomer and ceric ions are retarded on addition of anions like HSO₄^?, SO₄^{? ?}, or CIO₄^?, but they are accelerated on the addition of Mn(II) ions. Interpretations of the above observations are furnished.     

Novel polymeric surfactants: Synthesis of semi‐branched,non‐ionic triblock copolymers using ATRP

This article reports the synthesis of novel amphiphilic triblock copolymers with a semi‐branched PLURONIC^®7R structure by atom transfer radical polymerization (ATRP) in aqueous media. Poly(ethylene oxide)s (PEOs) with molecular weights 10 000 and 16 000 were end‐functionalized and used as bifunctional macroinitiators for the polymerization of oligo(propylene oxide) monomethacrylate by ATRP in a 1/3 v/v water/methanol mixture and in a 1/1 v/v water/1‐propanol mixture. Deviations from first‐order kinetics with respect to the monomer concentration were observed indicating that termination reactions were taking place. However, linear plots were obtained, when ln[M]₀/[M] was plotted against time^2/3 as suggested by Fischer. The effect on the control of the polymerization by adding Cu(II)Br₂ to the polymerization medium has been investigated. When 10 mol‐% of Cu(II)Br₂ was substituted for Cu(I)Br, normal first‐order kinetics were observed. A large reduction in the rate of polymerization was observed for the polymerization initiated by bifunctional PEO10 000 initiator, but almost no reduction in the rate of polymerization was observed, when the bifunctional PEO16 000 initiator was used. When the polymerizations were conducted in 1/1 v/v water/1‐propanol, unexpectedly high rates of polymerization were observed.

Synthesis of amphiphilic block copolymers with a semi‐branched PLURONIC^®R architecture using ATRP.     

Spontaneous polymerization of amphiphilic vinyl monomers, 1. Spontaneous polymerization of sodium dodecyl 2-hydroxy-3-methacryloypropyl phosphate

Sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate as an amphiphilic vinyl monomer was found to polymerize spontaneously without initiator in water. The polymerization takes place at a monomer concentration higher than the critical micelle concentration via a free-radical mechanism, and complete conversion is achieved even at a very low initial monomer concentration (3 mmol/L) and a rather low temperature (35°C). In benzene, capable of forming inverse micelles, the polymerization also occurs spontaneously. In methanol, which gives an isotropic solution, the spontaneous polymerization proceeds only at high concentration (near 300 mmol/L). The ¹H spin-spin relaxation time (T^*₂) of the monomer changes discontinuously in a range of monomer concentration from 250 to 300 mmol/L in CD₃OD, suggesting that some kind of monomer mutual interaction takes place in methanol too. Thus, it can be concluded that the micellar aggregation monomer molecules triggers the polymerization.     

Functionalized monomers, 2. Kinetics of radical polymerization of oxirane- and oxetane-derivatives of styrene and copolymerization of 4-vinylphenyloxirane with styrene

The kinetics of radical polymerization of 4-vinylphenyloxirane ( 1 ), 4-vinylbenzyloxirane ( 2 ), and 2-(4-vinylphenyl)oxetane ( 3 ) initiated by 2,2′-azoisobutyronitrile (AIBN) was studied. In the case of 1 the initial rate of polymerization was found to depend on the initiator and monomer concentrations as (r_p)_total ∝? [AIBN]^0,5 · [M₁]^1,36. The higher order of the polymerization rate with respect to 1 was interpreted as due to a concurrent thermally initiated polymerization; the rate of the latter was found to depend on the monomer concentration squared. The value of the ratio propagation rate constant over square root of termination rate constant k_p/k_t^1/2 = 2,8 · 10^?2 dm^3/2 · mol^?1/2 · s^?1/2 was determined from the measured dependences (r_p)_total = f[AIBN] and (r_p)_total = f([M₁]), corrected for the rate of thermally initiated polymerization of 1 . On the other hand, the kinetics of radical polymerization of 2 and 3 did not deviate from the standard scheme valid for radical polymerization; in both cases the observed reaction order with respect to initiator and monomer was 0,5 and 1, respectively. Radical copolymerization of 4-vinylphenyloxirane (M₁) with styrene (M₂) was characterized by monomer reactivity ratios r₁ = 1,06 and r₂ = 0,78, respectively, corresponding to the Q, e-scheme values Q = 0,9 and e = ?0,36 for monomer 1 .     

Peculiar Behavior of Degenerative Chain Transfer Polymerization of a Phosphonated Methacrylate

Living/controlled radical polymerization of dimethyl(methacryloyloxy)methyl phosphonate (MAPC₁) has been attempted using degenerative transfer to produce block copolymers. RAFT polymerization of this monomer is sensitive to very low level of oxygen and in any case limited to low monomer conversion. Reverse iodine transfer polymerization (RITP) leads to higher monomer conversion with a limited amount of living polymer (55% by ¹H NMR), precluding an efficient synthesis of block copolymers. A PMMA‐b‐PMAPC₁ diblock copolymer was therefore synthesized by iodine transfer polymerization (ITP) of MAPC₁ from a PMMA‐I macro‐chain transfer agent prepared by RITP. The diblock copolymer, purified by selective precipitation, contains an average of five MAPC₁ units and has potential an adhesive and as a corrosion inhibitor.

     

Kinetic studies of the anionic polymerization of methyl methacrylate in tetrahydrofuran with Na+ as counter ion,using monofunctional initiators

A newly designed automatically controlled stirred reactor suitable for kinetic measurements of reactions with half lives ≥2s has been applied to follow the anionic polymerization of methyl methacrylate in THF with Na⁺ as a counter ion in the presence of an excess of NaB(C₆H₅)₄. As initiators were used: benzylsodium reacted with α-methylstyrene (I), fluorenylsodium (II), and 9-methylfluorenylsodium (III). With I the initiation is fast as compared with the polymerization reaction which is first order in monomer concentration. Within the range of ?50°C to ?100°C an almost unperturbed “living” polymerization is observed. The Arrhenius plot of the rate constants results in a straight line with activation energy E_a = 4,4kcal·mol^?1 (= 18kJ·mol^?1) and frequency exponent A = 7,0.II and III are slow initiators, II giving rise to side reactions because of the “acidic” proton in 9-position after initiation, III exhibiting a rate constant of initiation k_i = 1l·mol^?1·s^?1 at ?72°C. The termination reaction is becoming increasingly important with increasing temperature and seems to be a unimolecular reaction with E_a,t = 11,5kcal·mol^?1 (= 48 kJ·mol^?1) and A_t = 10. Since the basic feature of the reactor is the possibility of drawing samples, polymers from each state of the reaction were available to be investigated also with respect to their tacticity. The monomer addition was shown to follow Bernoullian statistics. A structure of the “living” end being in harmony with the results observed is discussed.     

Cationic polymerization of 2-methyl-1.3-dioxepane

2-Methyl-1.3-dioxepane was polymerized in 1.2-dichloroethane with triethyl oxonium tetrafluoroborate and boron trifluoride as initiators. This polymerization involves a monomer-polymer equilibrium and the polymer consists of regularly alternating tetrahydrofuran and acetaldehyde units. The thermodynamic parameters for the polymerization were determined from the temperature dependence of the equilibrium monomer concentration as follows: ΔH_SS = ?2.1 ± 0.3 kcal/mole and ΔS⁰_SS = ?8.9 ± 1.3 cal/mole deg. The ceiling temperature for the 1 mole/1. solution is ?37°C. The attempted polymerization of 2.2-dimethyl-1.3-dioxepane gave only a crystalline cyclic dimer.     

Kinetic and ESR studies of the radical-initiated polymerization of N-(2,6-dimethylphenyl)itaconimide

The polymerization of N-(2,6-dimethylphenyl)itaconimide (1) with azoisobutyronitrile (2) was studied in tetrahydrofuran (THF) kinetically and spectroscopically with the electron spin resonance (ESR) method. The polymerization rate (R_p) at 50°C is given by the equation: R_p = K [2] ^0,5 · [1] ^2,1. The overall activation energy of the polymerization was calculated to be 91 kJ/mol. The number-average molecular weight of poly (1) was in the range of 3500–6500. From an ESR study, the polymerization system was found to involve ESR-observable propagating polymer radicals of 1 under the actual polymerization conditions. Using the polymer radical concentration, the rate constants of propagation (k_p) and termination (k_t) were determined at 50°C. k_p (24–27 L · mol^?1 · s^?1) is almost independent of monomer concentration. On the other hand, k_t (3,8 · 10⁴–2,0 · 10⁵ L · mol^?1 · s^?1) increases with decreasing monomer concentration, which seems mainly responsible for the high dependence of R_p on monomer concentration. Thermogravimetric results showed that thermal degradation of poly (1) occurs rapidly at temperatures higher than 360°C and the residue at 500°C was 12% of the initial polymer. For the copolymerization of 1 (M₁) with styrene (M₂) at 50°C in THF the following copolymerization parameters were found; r₁ = 0,29, r₂ = 0,08, Q₁ = 2,6, and e₁ = +1,1.     

Kinetic and ESR studies on radical polymerization. Radical polymerization behavior of N-octadecylmaleimide in benzene

The polymerization of N-octadecylmaleimide ( 1 ) initiated with azodiisobutyronitrile ( 2 ) was investigated kinetically in benzene. The overall activation energy of the polymerization was calculated to be 94,2 kJ·mol^?1. The polymerization rate (R_p) at 50°C is expressed by the equation, R_p = k[ 2 ]^0,6[ 1 ]^1,7. The homogeneous polymerization system involves ESR-detectable propagating polymer radicals. Using R_p and the polymer radical concentration determined by ESR, the rate constants of propagation (k_p) and termination (k_t) were evaluated at 50°C. k_p (33 L · mol^?1 · s^?1 on the average) is substantially independent of the monomer concentration. On the other hand, k_t (0,3 · 10⁴ – 1,0 · 10⁴ L · mol^?1 · s^?1) is fairly dependent on the monomer concentration, which is ascribable to a high dependence of k_t on the chain length of rigid poly( 1 ). This is the predominant factor for the high order with respect to the monomer concentration in the rate equation. In the copolymerization of 1 (M₁) and St (M₂) with 2 in benzene at 50°C, the following copolymerization parameters were obtained: r₁ = 0,11, r₂ = 0,09, Q₁ = 2,1, and e₁ = +1,4.     

Monomers for Adhesive Polymers, 7a

Homopolymerization and copolymerization of N‐(2‐hydroxyethylmethyl)acrylamide ( 1 ) with N,N′‐diethyl‐1,3‐bis(acrylamido)propane ( 2 ) have been studied in ethanol/water solvents or in bulk. The polymerization rate exponent depends on the polymerization temperature and increased from 0.99 at 50 °C to 1.21 at 75 °C. The initial polymerization rate dependence on temperature between 50 and 75 °C in Arrhenius coordinates was linear. However, the slope increased with an increase in monomer concentration. The overall activation energy E_a varied from 64 kJ · mol^?1 at 0.5 mol · L^?1 to 76 kJ · mol^?1 at 2.0 mol · L^?1 monomer concentration. In addition, the reaction order with respect to the initiator AIBN deviated from the standard free radical polymerization kinetics. The exponent 0.42 indicated a significant participation of primary radicals in termination reactions. The polymerization reaction order declined from ideality as well, and the E_a and polymerization enthalpy changed with the batch composition variation, which could be explained through monomer/monomer, monomer/solvent, or monomer/polymer complexation. The chain transfer to polymer was considered as an origin for the polymer network formation in monomer 1 homopolymerization if its concentration in the batch was 1 mol · L^?1 or higher. The more intensive polymerization acceleration with the monomer dilution and the greater heat released reduction with decrease in the monomer 1 to 2 ratios were evidenced in copolymerization. Nevertheless, the deviations from conventional reaction kinetics were not as pronounced as with acrylic or methacrylic acid polymerizations.