Copolymerization Behavior of Some Acidic and Basic Monomers

Copolymerization reactivity ratios of the systems 4-vinyl-pyridine (VP)-methacrylic acid (MA), dimethylamino methacrylate (DMAM)-MA, and VP-DMAM were obtained using the Fineman-Ross procedure. The experimental values were found to differ considerably from the values calculated from the Q-e scheme. R₁ and r₂ values calculated using seven different models for the VP-MA system have been compared with the experimental values.     

Radiation-Induced Cryogenic Copolymerization of Some Monomers with Sulfur Dioxide

A comparative study was performed on the radiation postpolymerization of a number of dienes and -olefins with sulfur dioxide occurring both on heating of the samples radiolyzed at 77 K and spontaneously by mutual dissolution. The cryopolymerization of sulfur dioxide with butadiene was studied in most detail. It was found that, unlike the case of the isoprene–SO₂system, a polycrystalline phase with the eutectic that corresponded to the equimolar composition was formed on rapidly freezing over the entire range of initial ratios between the butadiene and SO₂comonomers. It was suggested that the 1 : 1 donor–acceptor complex takes part in the postpolymerization process, and the monomers enter the resulting copolymer in a near-equimolar ratio. The copolymer obtained was found to behave as a crosslinked system. It is likely that a three-dimensional network resulted from the opening of C=C bonds in butadiene.     

酚醛树脂中亚甲基对热降解的影响

将固化后的酚醛树脂在不同温度下进行热处理,对固化后的样品进行热重分析,对热处理后的试样进行傅立叶红外光谱分析.实验结果表明,酚醛树脂的热降解与亚甲基的取代位有关.酚醛树脂中的亚甲基分两个阶段进行热解降,350~450℃的温度区间主要是部分邻-邻(o-o′)位亚甲基和邻-对(o-p)位亚甲基的分解,400~620℃温度区间为对-对(p-p′)位亚甲基的分解,p-p′位亚甲基比o-o′位亚甲基的起始热分解温度高50℃左右.     

Influence of Comonomer Functional Groups on the Reactivity Ratios of Some Phenolic Monomers

The reactivity ratios of some halogen-substituted phenolic monomers have been determined by the linear graphical method of Kelen and Tüdöls. The nature of functional groups present in the comonomer influence the order of reactivity of p-chlorophenol, p-bromophenol, and p-iodophenol. The behavior of these monomers during copolymerization reaction has been interpreted in terms of 1) different degrees of resonance stabilization of the monomers, and 2) opposite polarization caused by the substituents present in the comonomer.     

Polymerization and Copolymerization of Some Monomers as Adducts with β-Cyclodextrin

The feasibility of chemical bond formation, especially in the chain-transfer reaction between polymer and β-cyclodextrin (β-CD) molecules in the products of the radiation polymerization of β-CD with vinylidene chloride (VDC) its adducts has been considered. The lack of these bonds in the polymerization products of similar β-CD adducts with methyl methacrylate (MM), styrene (St), a mixture of VDC and allyl chloride (AC) and a mixture of VDC and MM (10:90 molar ratio) has been established. On the basis of the results obtained the lack of chemical bonds in the polymerization product of β-CD· VDC adduct is suggested.     

Effect of Nitrosodurene on Radical Copolymerization of Styrene with Acrylic Monomers

The effect of nitrosodurene as a source of stable nitroxyl radicals on radical copolymerization of styrene with methyl methacrylate and butyl acrylate was studied.     

Radiation-Induced Copolymerization of Fluorine-Containing Monomers

Radiation-induced copolymerizations of various monomers, including perfluoro-olefines with CF₂ O and of α-olefines with monochlorotrifluoro-ethylene, have been studied. It was found that CF₂O can be copolymerized randomly via radical process, with most of monomers examined and that alternating copolymers can be obtained from the copolymerization of a-olefines with monochlorotrifluoroethylene. The structural study of these copolymers was carried out by infrared, X-ray diffraction and NMR measurements. The structure of isobutylene-monochlorotrifluoroethylene copolymer was determined precisely through proton and fluorine resonances.     

Reactivity and Characterization of the Radical Copolymerization of Itaconic Acid with Some Conventional Monomers

Abstract

Radical copolymerizations of itaconic acid (IA) with acrylamide (Am), N-vinyl pyrrolidone (NVP), ethyl methacrylate (EMA), and methyl methacrylate (MMA) were carried out in dioxane in the presence of azobisisobutyronitrile as the initiator at 65°C. The monomer reactivity ratios (r ₁, r ₂), Q, and e for IA with the four monomers were determined. The reactivity ratios show a tendency toward alternation, while the Q and e of IA indicate that it is an electron-accepting monomer. The polymers obtained were characterized by FT-IR, x-ray diffraction, intrinsic viscosity, and thermal stability measurements.     

Radical Copolymerization of Acrylic Monomers. II Effect of Solvent on Radical Copolymerization of Methyl Methacrylate and Styrene

The influence of various solvents on the copolymerization behavior of methyl methacrylate with styrene has been investigated. In these systems there is a significant solvent effect on both r_S and r_M which may be attributed to changes in the dielectric constant of the solvents used. The calculated relative reactivity of the polystyryl radical towards the methyl methacrylate monomer increases with increasing solvent polarity, whereas the reactivity of poly(methyl methacrylate) radical towards styrene monomer decreases. The results obtained are discussed taking into account the behavior of both monomers in homopolymerization with the same experimental conditions as in copolymerization.     

Radical Copolymerization of Acrylic Monomers. I. Effect of Solvent on the Copolymerization of Methyl Methacrylate and 1-Naphthyl Methacrylate

A study of the radical copolymerization of methyl methacrylate and 1-naphthyl methacrylate in benzene, chlorobenzene, and o-dichlorobenzene was made at 50°C. There is a marked effect of solvent on both r₁ and r₂ in all these systems, which can be correlated with the variation in the polarity of solvents. The glass transition temperatures of copolymers were discussed taking into consideration the sequence distribution of the copolymers and the homopolymers tg - values.     

Copolymerization Reactivities of α-Substituted Crotonyl Monomers

The radical copolymerizations of various α- substituted crotonyl monomers with styrene (St) and acrylonitrile (AN) were investigated, and the copolymerization parameters were determined by a least-squares procedure reported previously. The relative reactivities of the α-substituted crotonyl monomers toward polymer radicals of St and AN were found to correlate with the equation: log (relative reactivity of CH₃CH[dbnd]CXY) = ρ (σ + σ_Y) + A(Δlog Q_x + Δlog Q_Y), where Σ and Δlog Q are the polar Hammett and resonance substituent constants, respectively, and p and A are reaction constants. From the observed straight line relationships, the values of p and A were obtained to be as follows: ρ = 0.66, A = 0.75 for attack of poly-St radical, and ρ = -3.20, A = 1.3 for attack of poly-AN radical.     

Block Copolymerization of Vinyl Monomers with Macroiniferer

Abstract

Block copolymers composed of a polyether, such as poly(oxytetra-methylene), and vinyl polymers, such as polystyrene, poly(methyl methacrylate), poly(butyl acrylate), and poly(vinyl acetate), were prepared by photopolymerizations of vinyl monomers initiated with a polyether macroiniferter, α - (diethyldithiocarbamylacetyl) - ω - (diethyldithiocar-bamylacetoxy)-poly(oxytetramethylene). ESR spectroscopy and end-group analysis of diethyldithiocarbamyl indicated that block copolymers should be predominantly ABA-type copolymers. The block copolymers were characterized in detail by NMR, GPC, and DSC analysis.     

Remote Unit Effects in the Copolymerization of Unconjugated Monomers

The kinetics of the radical copolymerization of the three binary systems vinyl chloride (C)-vinyl acetate (Ac), vinylidene chloride (V)-vinyl acetate, and vinyl chloride-vinylidene chloride have been investigated in the whole range of monomer feed composition using the chromatographic method. Penultimate or antepenultimate effects have been observed in all cases. The better values of the corresponding reactivity ratios are: For C-Ac copolymers, r_Ac = 0.29, r_CCC = 1.67, r_AcCC. = 4.60, and r_AcC = 2.05. For V-Ac copolymers, r_Ac = 0.07, r_VVV = 5.30, r_AcVV = 11.5, r_AcAcV = 8.0, and r_VAcV = 6.0. For C-V copolymers, r_VAcV = 0.22, r_VV = 2.94, and r_CV = 4.31. An internal transfer mechanism is suggested for the antepenultimate effect in the vinyl acetate copolymers.     

Influence of the Inductive Effect of Substituents on the NMR Parameters of Phosphorylated Alkenes

The inductive effect model was used to adequately describe and predict the P-H coupling constants in the ¹H NMR spectra of phosphorylated alkenes. A procedure was developed for determination of the steric structure of phosphorylated alkenes from the ¹H NMR spectra of one of the isomers.     

Graft Copolymerization on to Cellulose Using Binary Mixture of Monomers

The graft copolymerization of acrylonitrile (AN) and ethyl acrylate (EA) comonomers onto cellulose has been carried out using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 35±0.1°C. The addition of ethyl acrylate as comonomer has shown a significant effect on overall and individual graft copolymerization of acrylonitrile on cellulose. The graft yield (%G_Y) and other grafting parameters viz. true grafting (%G_T), graft conversion (%C_G), cellulose number (Ng) and frequency of grafting (G_F) were evaluated on varying the concentration of comonomers from 6.0–30.0×10^?1 mol dm^?3 and ceric (IV) ions concentration from 2.5–25×10^?3 mol dm^?3 at constant feed composition (f_AN 0.6) and constant concentration of nitric acid (7.5×10^?2 mol dm^?3) in the reaction mixture. The graft yield (%G_Y) and other grafting parameters were optimal at 15×10^?1 mol dm^?3 concentration of comonomers and at 10×10^?3 mol dm^?3 concentration of ceric ammonium nitrate. The graft yield (%G_Y) and composition of grafted chains (F_AN) was optimal at a feed composition (f_AN) of 0.6. The energy of activation (Ea) for graft copolymerization has been found to be 16 kJ mol^?1. The molecular weight (Mw) and molecular weight distribution (Mw/Mn) of grafted chains was determined by GPC and found to be optimum at 15×10^?1 mol dm^?3 concentration of comonomer in the reaction mixture. The composition of grafted chains (F_AN) determined by IR method was used to calculate the reactivity ratios of monomers, which has been found to be 0.62 (r₁) and 1.52 (r₂), respectively for acrylonitrile (AN) and ethyl acrylate (EA) monomers used for graft copolymerization. The energy of activation for decomposition of cellulose and grafted cellulose was determining by using different models based on constant and different rate (β) of heating. Considering experimental observations, the reaction steps for graft copolymerization were proposed.     

Graft Copolymerization of Vinyl Monomers onto Silk Fibers

Modification of the properties of textile fibers in order to get a fiber of improved textile performance is the subject of study of several groups of scientists and technologists [1–4]. Of the several methods available, grafting promises to be a potentially effective means of altering the fiber properties through the added polymer formed in situ without destroying the basic properties of the parent fiber. Copolymerization is attractive to chemists as a means of modifying macromolecules since, in general, degradation can be minimized. The desirable properties of the polymer are retained and copolymerization provides additional properties through the added polymer. The added polymer may be formed in situ by polymerization of a monomer or monomers, by condensation of reactants, or by the deposition of preformed polymer.     

Copolymerization of Tri-n-butyltin Acrylate and Tri-n-butyltin Methacrylate Monomers with Vinyl Monomers Containing Functional Groups

A new approach to obtaining thermoset organotin polymers, which permits control of crosslinking site distribution and, through it, a better control of properties of organotin antifouling polymers, is reported. Tri-n-butyltin acrylate and tri-n-butyltin methacrylate monomers were prepared and copolymerized, by the solution polymerization method with the use of free-radical initiators, with several vinyl monomers containing either an epoxy or a hydroxyl functional group. The reactivity ratios were determined for six pairs of monomers by using the analytical YBR method to solve the differential form of the copolymer equation. For copolymerization of tri-n-butyltin acrylate (M₁) with glycidyl acrylate (M₂), these reactivity ratios were n = 0.295 ± 0.053, r₂ = 1.409 ± 0.103; with glycidyl methacrylate (M₂) they were r₁ = 0.344 ± 0.201, r₂ = 4.290 ± 0.273; and with N-methylolacrylamide (M₂) they were r₁ = 0.977 ± 0.087, r₂ = 1.258 ± 0.038. Similarly, for the copolymerization of tri-n-butyltin methacrylate (Mi) with glycidyl aery late (M₂) these reactivity ratios were r₁ = 1.356 ± 0.157, r₂ = 0.367 ± 0.086; with glycidyl methacrylate (M₂) they were r₁ = 0.754 ± 0.128, r₂ = 0.794 ± 0.135; and with N-methylolacrylamide (M₂) they were r₁ ?4.230 ± 0.658, r₂ = 0.381 ± 0.074. Even though the magnitude of error in determination of reactivity ratios was small, it was not found possible to assign consistent Q,e values to either of the organotin monomers for all of its copolymerizations. Therefore, Q,e values were obtained by averaging all Q,e values found for the particular monomer, and these were Q = 0.852, e = 0.197 for the tri-n-butyltin methacrylate monomer; and Q = 0.235, e = 0.401 for the tri-n-butyltin acrylate monomer. Since the reactivity ratios indicate the distribution of the units of a particular monomer in the polymer chain, the measured values are discussed in relation to the selection of a suitable copolymer which, when cross-linked with appropriate crosslinking agents through functional groups, would give thermoset organotin coatings with an optimal balance of mechanical and antifouling properties.     

Investigations of the Mechanism of Alternating Copolymerization with Charge-Transfer Interaction of the Monomers

The applicability of the method of Giese to the measurement of the influence of monomer reactivity is examined. The reaction of alkyl mercuric salts with sodium borohydride permits the production of alkyl (cyclohexyl and butyl) radicals. Since hydrogen radicals are present in high concentration, the addition of alkenes to the reaction mixture leads to radicals from the alkenes. Further addition of alkene (polymerization) can be nearly completely excluded in this way. The composition of the reaction products is determined by gas chromatography. The addition rate of the alkenes relative to styrene allows correlation with the e value of the Q-e scheme of Alfrey and Price. The method answers the question of how far addition of the monomer complex occurs in one step or as separate addition of both monomers during copolymerization in the presence of charge-transfer (CT) complexes of the monomers. The investigations are performed by using the styrene/acrylonitrile/ZnCl₂system, and it is demonstrated that the reactivity of the complexed     

Internal Transfer Reactions in the Copolymerization of Vinyl Acetate with Chlorinated Monomers

In the copolymerization of vinyl acetate (A) with either vinyl chloride (C) or vinylidene chloride (V), an internal transfer (backbiting) reaction—of the C- or V-ended radi-cals on an antepenultimate A unit—is proposed to be responsible for the deviation of the copolymerization kinetics from the Lewis and Mayo theory. The deviations disappear if A is replaced by isopropenylacetate [I_p], Then one gets, for the I_p -C copolymerization. r_{I p} =0.35 and :r_c=2.4, and for I -V copolymerization, r_{I p}=0.13 and r_v=5.9. The internal transfer reaction causes the formation of branches which may be evidenced by NMR analysis of constant composition suspension A-C copolymers. A kinetic scheme is proposed and the corresponding reactivity ratios derived r_A=0.29, r_c=1.60, r=0.3 (radical resulting from the transfer reaction), and k_T=1500 (rate constant of the transfer reaction at 50°C). The distribution of branches is calculated together with the sequence distribution functions for the .A. or Cunits.     

Graft Copolymerization of Vinyl Monomers onto Cellulose and Cellulosic Materials

Abstract

Graft copolymerization is a novel method which has wide application in synthesizing new forms of polymeric materials and also in modifying the properties of natural polymers [1,2]. Much research has been done on grafting polymeric molecules on to cellulose to produce materials of new properties intermediate between those of cellulose and those of synthetics. A variety of property changes can be imparted to cellulose through grafting without destroying the crystallinity or crystallization potential of the substrate or reducing its melting point. Some of the most dramatic changes in properties which have been brought about by grafting to cellulose are viscoelasticity, stereoregularity, hygroscopicity, water repellency, improved adhesion to a variety of substances, settability, soil resistance, bacteriocidal properties, and thermal stability.