Monomer apparent reactivity ratios for acrylonitrile/ammonium itaconate radical copolymerization systems

Ammonium itaconate was first used to copolymerize with acrylonitrile. This was achieved by using azobisisobutyronitrile as the initiator and dimethyl sulfoxide as the solvent. Effects of copolymerization systems on monomer apparent reactivity ratios for acrylonitrile/ammonium itaconate copolymers were studied. The values of monomer apparent reactivity ratios were calculated by Kelen‐Tudos method. The apparent reactivity ratios in the aqueous suspension polymerization system are similar to those in the solution polymerization system at polymerization conversions of less than 18% [reactivity ratio of acrylonitrile (r_AN) = 0.47 ± 0.01, reactivity ratio of ammonium itaconate (r_AIA) = 3.08 ± 0.01]. At conversions of more than 50%, the changes of monomer apparent reactivity ratios become less prominent (r_AN = 0.68 ± 0.01, r_AIA = 2.47 ± 0.01). In water‐rich reaction medium [(H₂O/dimethylsulfoxide (DMSO) > 80/20)], the monomer apparent reactivity ratios are approximately equivalent to those in the aqueous suspension polymerization system. In DMSO‐rich reaction medium (DMSO/H₂O > 80/20), the apparent reactivity ratios are similar to those in the solution polymerization system. With an increase in the polarity of the solvent, the values of apparent reaction ratios both decrease. The values of apparent reaction ratios gradually tend to 1 with increasing the copolymerization temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3920–3923, 2007     

Monomer apparent reactivity ratios for acrylonitrile/methyl vinyl ketone copolymerization system

Methyl vinyl ketone was firstly used to successfully copolymerize with acrylonitrile. This was achieved by using azobisisobutyronitrile as the initiator, and dimethyl sulfoxide as the solvent. Effect of copolymerization systems on monomer apparent reactivity ratios for copolymer of acrylonitrile with methyl vinyl ketone was studied for contrast. Values of monomer apparent reactivity ratios were calculated by Kelen–Tudos method. It has been found that the apparent reactivity ratios in aqueous suspension polymerization system were similar to those in solution polymerization system at polymerization conversion less than 20%. Beyond 50% of conversion, the changes of monomer apparent reactivity ratios become less prominent. In water‐rich reaction medium [(H₂O/dimethylsulfoxide (DMSO)>80/20), monomer apparent reactivity ratios were approximately equivalent to those in aqueous suspension polymerization system. In DMSO‐rich reaction medium (DMSO/H₂O > 80/20), apparent reactivity ratios were similar to those in solution polymerization system. Values of apparent reaction ratios both decreased when AN/MVK copolymer was synthesized in DMF and DMAc. The values of apparent reaction ratios gradually tend to 1 with increasing the copolymerization temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4045–4048, 2006     

Monomer reactivity ratios of some methyl aryloxymethacrylates

Summary The monomer reactivity ratios of methyl phenoxymethacrylate (MPMA), methyl p-cresoxymethacrylate (MCMA) and methyl p-nitrophenoxymethacrylate (MNMA) were evaluated both by Fineman-Ross and Kelen-Tüdös methods. The tendency to form alternating copolymers of these monomers is discussed.     

A method of calculating copolymerization reactivity ratios

An improved linearization method is proposed for determining the monomer reactivity ratios of free-radical copolymerizations by fitting the data of cumulative copolymer compositions and overall weight fractional conversions, or cumulative copolymer compositions and residual monomer compositions of the reaction mixture. The reactivity ratios of monomers for four different copolymerization reactions are determined. The results are very close to those of literature reports and account well for the experimental results.     

Monomer reactivity ratios for acrylonitrile/ammonium itaconate during aqueous‐deposited copolymerization initiated by ammonium persulfate

Monomer reactivity ratios of acrylonitrile/ammonium itaconate during aqueous‐deposited copolymerization initiated by ammonium persulfate were investigated. Kelen–Tudos method was used to examine the reactivity ratios. It was shown that the reactivity ratios were influenced by the conversions and temperatures of copolymerization. The reactivity ratios in aqueous‐deposited copolymerization system were similar to those in the solution polymerization system at polymerization conversions of less than 5% [reactivity ratio of acrylonitrile (r₁) 0.842 ± 0.02, reactivity ratio of ammonium itaconate (r₂) = 3.624 ± 0.02]. The reactivity ratio of AN rises and that of (NH₄)₂IA decreases, when the polymerization conversion increases till 13%. Aqueous‐deposited copolymerization initiated by AIBN was also studied. It was found that some polymers were formed in water phase and the monomers had different reactivity ratios by comparison with those initiated by ammonium persulfate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4645–4648, 2006     

负载钛系催化丁二烯-异戊二烯共聚合的竞聚率及共聚物的结构

采用TiCl4/MgCl2-Al(i-Bu)3体系催化丁二烯-异戊二烯共聚合,经DSC与FTIR分析表明,共聚物为高反式-1,4-结构,控制单体初始配比可以获得低熔点(30～35℃),Tg接近-72℃的共聚物。用TUDOS法求得溶液共聚合反应的竞聚率rBd为5.7,rIp为0.17,并用13C-NMR方法研究了共聚物的链结构,定量计算了共聚物二元组的摩尔分数和数均序列长度,分析了共聚物的组成分布,证明共聚物的序列分布服从一级Markov模型。     

Monomer and radical reactivity ratios in 4‐vinylbenzenesulfonic acid sodium salt–acrylamide copolymerization in 0.1M NaCl solution

Reaction kinetics and composition of 4‐vinylbenzenesulfonic acid sodium salt (VB)–acrylamide (Aam) copolymerization in 0.1M NaCl solution are investigated. Data obtained by the automatic continuous monitoring of copolymerization system, up to 80% conversion, are analyzed by an “error‐in‐variables method” developed for obtaining the reactivity ratios by on‐line monitoring. Monomer reactivity ratios are found as r_Aam = 0.085 ± 0.020, r_VB = 2.0 ± 0.33. Although the terminal model describes the composition data well, it is seen to be inconsistent with the reaction rates. This discrepancy is attributed to implicit penultimate effects and using the recently developed calculation method, effective radical reactivity ratios are found as s_VB = 0.26 and s_Aam = 0.027, and both composition and rate data fit the implicit penultimate model extremely well. On‐line monitored data showed that in the reactions where the VB was completely consumed, the subsequent Aam homopolymerization was very rapid; thus, the reaction showed definitely two rate regimes, before and after VB depletion. Acrylamide take up rate also showed these two rate regimes. We conclude that low conversion results can be misleading and reactions must be monitored up to a high conversion for a robust control of composition and reaction kinetics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Gel formation in free-radical crosslinking copolymerization

Polymer gels with varying amounts of crosslinker and solvent were prepared by solution free-radical crosslinking copolymerization of methyl methacrylate/ethylene glycol dimethacrylate (MMA/EGDM) and styrene/p-divinyl benzene (S/p-DVB) comonomer systems. The structural characteristics of the gels were examined using equilibrium swelling in toluene and gel fraction measurements. Experimental results were compared with the predictions of a kinetic model developed recently for free-radical crosslinking copolymerizations. Experimental data on S/EGDM networks reported by Hild, Okasha, and Rempp were also used to test this model. It was found that the model correctly predicts the development of the gel properties in free-radical crosslinking copolymerization. © 1995 John Wiley & Sons, Inc.     

Pendant vinyl group reactivity during the free-radical copolymerization of methyl methacrylate and ethylene glycol dimethacrylate

Summary Methyl methacrylate-ethylene glycol dimethacrylate (MMA-EGDM) copolymerization has been investigated in toluene at a monomer concentration of 22 w/v %. The kinetic models developed recently along with the experimental conversion curve and gel point data provided the calculation of the average reactivity of pendant vinyl groups. It was found that the pendant vinyl reactivity for intermolecular links is much less than the monomeric vinyl reactivity and it decreases further as the EGDM concentration increases. At 5–15 mol % EGDM, the average pendant reactivity is 1–2 orders of magnitude lower than the monomeric vinyl reactivity. The reduced pendant reactivity is mainly responsible for the shift of the gel point towards higher conversions.     

Effect of medium pH on the reactivity ratios in acrylamide acrylic acid copolymerization

The copolymerization reactivity ratios of acrylic acid and acrylamide are found at pH 5 and pH 2. Automatic continuous online monitoring of polymerization reactions (ACOMP) has been used for the first time to monitor the synthesis of polyelectrolytic copolymers. The composition drift during the reactions revealed that at pH 5, the acrylamide participates more in the copolymer, and at pH 2, the acrylic acid incorporates in the system at a higher ratio. The copolymerization data were analyzed by a recent error in variables (EVM) type calculation method developed for obtaining the reactivity ratios by on‐line monitoring and gave at pH 5 reactivity ratios r_Aam = 1.88 ± 0.17, r_Aac = 0.80 ± 0.07 and at pH 2 r_Aam = 0.16 ± 0.04, r_Aac = 0.88 ± 0.08. The results show that the reactivity ratios depend strongly on the pH of the medium. The effect of polyelectrolytic interactions on the reactivity ratios is discussed in detail. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 968–974, 2007     

Correlation between copolymerization reactivity ratios and rates of radical additions to alkenes

Summary Rates of addition of cyclohexyl radicals to alkenes are measured using the mercury method. These rates can be correlated with data of styrene copolymerization. Copolymerization reactivity ratios therefore describe relative reactivities of polymer radicals in addition reactions to alkenes. It turns out that the polymeric benzylic radicals are less selective than the cyclohexyl radicals.     

Synthesis of polystyrene modified with fluorine atoms: Monomer reactivity ratios and thermal behavior

Homo‐ and copolymers of 4‐fluorostyrene (FSt) and styrene (St) were synthesized with different feed ratios using free radical bulk polymerization with azobisisobutyronitrile (AIBN) as initiator. It yielded series of (co)polymers with various amounts of included FSt, P(St‐co‐FSt) (5–50 mol%) and PFSt. The effect of the initiator concentration on the molecular weights of the homopolymers, that is, PSt and PFSt was investigated. Copolymer compositions were determined by nuclear magnetic resonance spectroscopy. The relative reactivity ratios of both comonomers were determined by applying the conventional linearization methods of Jaacks (J), Finemann–Ross (F–R), inverted Finemann–Ross (IF–R), and Kelen‐Tüdos (K–T). The reactivity ratios values of St and FSt obtained from J plot are 1.06 and 0.84, F–R plot are 1.18 and 1.06, IF–R 1.01 and 0.86, and K–T plot 1.04 and 0.88, respectively. Thermal properties of prepared (co)polymers, that is, glass transition temperature (T_g) and thermal stability, were determined from differential scanning calorimetry and thermogravimetrical measurements. The lack of significant influence of FSt comonomer content on T_g of (co)polymers was observed. Additionally, the thermal degradation kinetics of obtained PSt and PFSt was studied by thermogravimetric analysis. Kinetic parameters such as the thermal decomposition activation energy (E) and frequency factor (A) were estimated by Ozawa model [E(O) and A(O), respectively] and Kissinger model [E(K) and A(K), respectively]. The activation energy and the frequency factor of PFSt (253 kJ/mol) were higher than PSt (236 kJ/mol). The resulting activation energies estimated using the two methods were quite close. POLYM. ENG. SCI., 54:1170–1181, 2014. © 2013 Society of Plastics Engineers     

纳米氧化镁对甲基丙烯酸-丙烯腈共聚体系竞聚率的影响

以偶氮二异丁腈(AIBN)为引发剂,引发甲基丙烯酸(MAA)和丙烯腈(AN)本体聚合。采用滴定法和称重法测定了在低转化率(小于10%)下不同单体配比的共聚物组成,并采用Fineman-Ross法及Kelen-Tudos法计算、作图得到两种单体的竞聚率,它们的最大差值为0.09,说明滴定法和称重法具有一定的可信度。用上述方法测定了反应体系在纳米MgO存在下共聚单体竞聚率的变化,结果表明:加入纳米MgO,MAA和AN的竞聚率均下降。     

Determination of the mode of termination in free-radical copolymerization

In this study the apparent rate constant model was used to determine the mechanism of termination and other rate constants for free radical copolymerizations that are chemically controlled with no penultimate effect. The data required were the number average molecular weight and the conversion obtained at various initial initiator concentrations and monomer compositions, and two rate constants of propagation of the homopolymerizations of its two monomers. The bulk free radical copolymerization of methyl methacrylate (MMA) and styrene(St) at 60°C was studied. Three published literature values of the propagation rate constants k₁₁ and k₂₂. 750, 150; 515, 145; 705, 145, were used for the determination. The unit of the rate constants used was liter/mole/s. The modes of the termination reaction obtained, depending on k₁₁, k₂₂ used, are given as follows:

Effect of solvent and promoter on the reactivity ratios in the copolymerization of hexamethylcyclotrisiloxane and hexaphenylcyclotrisiloxane

The solvent and promoter effects on the monomer reactivity ratios, r₁ and r₂, for the living copolymerization of hexamethylcyclotrisiloxane (D₃) and hexaphenylcyclotrisiloxane (P₃) in the case of relatively high [monomer]₀/[initiator]₀ ratio and low phenyl content (less than 50%) are reported. The amount of promoter DMSO had significant effects on the reactivity ratios, r₁ and r₂, in toluene as well as in THF with different trend. The values of r₁ decreased while r₂ increased with the decreasing of the amount of DMSO in toluene. Both r₁ and r₂ increased with a decrease of the amount of DMSO in THF. For copolymerizations in mixed solvents, r₁ was less sensitive to the change of THF portion than r₂ in the presence of 0.5 wt% of promoter DMSO. Eventually, r₁ became equal to r₂ in 100 % THF (r₁ = r₂ = 0.19). However, without DMSO, r₁ became more sensitive to the change in THF concentration.     

Photo-induced controlled/living copolymerization of styrene and acrylic acid and determination of reactivity ratios

A controlled/living photopolymerization of styrene (St) and acrylic acid (AA) mediated by FeCl₃·6H₂O/tetramethylethylenediamine (TMEDA) was performed in N,N-dimethylformamide using 4-bromomethylbenzophenon (4-BMBP) as photoinitiator at room temperature under UV irradiation. 4-BMBP was first used as ATRP initiator and photoinitiator. A well-defined poly(styrene-co-acrylic acid) with predetermined molecular weight and narrow molecular weight distribution was obtained. The kinetic rule of controlled free radical photopolymerization of St and AA was studied. The kinetic results showed that the obtained random poly(St-co-AA) copolymers produced narrow polydispersity (PDI) within the range of 1.25–1.32 when the conversion was beyond 16.5 %, which was characterized by GPC. The plots of number average molecular weight versus conversion and ln([M]₀/[M]) versus time were linear, indicating a controlled/living photopolymerization process. The system proceeded under mild and environmentally friendly conditions. The effects of initiator, catalyst, ligand, and vitamin C(VC) concentrations on polymerization process were investigated. The copolymers were characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (¹H NMR). The methods of Mayo-Lewis (ML), Kelen-Tudos (KT), and Yzrielev-Brokhina Roskin (YBR) were used to calculate the monomer reactivity ratios of controlled/living photopolymerization of St and AA at low conversions under selected conditions. The monomer reactivity ratios of St and AA were calculated to be r _St = 0.82 and r _AA = 0.30, respectively in this system. The living characteristics were demonstrated by chain extension experiment.