Ferrocene-containing polymers. II. Radiation-induced copolymerizations of ferrocenylmethyl methacrylate with styrene,methyl methacrylate,and ethyl acrylate

Ferrocenylmethyl methacrylate (FMMA) was copolymerized with styrene (St), methyl methacrylate (MMA), and ethyl acrylate (EA) in benzene solution at 25°C by γ radiation. The reactions proceeded by a free radical mechanism, and monomer reactivity ratios were derived by the Tidwell–Mortimer method for St(M₁)–FMMA(M₂), r₁ = 0.35 and r₂ = 0.46; for MMA(M₁–FMMA)(M₂), r₁ = 0.85 and r₂ = 1.36; for EA(M₁)–FMMA(M₂), r₁ = 0.36 and r₂ = 3.03. The Q and e values of FMMA determined from copolymerization with St were 0.97 and 0.55, respectively. Terpolymerization of a MMA–FMMA–EA system based on the Alfrey–Goldfinger equations was studied. This is a typical terpolymerization system in which reactivities of the monomers obey the Q–e scheme. Comparing the results obtained here with those previously reported for other monomers, we concluded that FMMA is one of the most highly reactive monomers among alkyl methacrylates.     

Copolymerization of new pyrazolone-containing monomers with certain vinyl comonomers

The polymerization ability of two new pyrazolone-containing monomers—3-methyl-1-phenyl-4-crotonoyl-pyrazolone-5 ( Cr ) and 3-methyl-1-phenyl-4-(3′-phenyl-acryloyl) pyrazolone-5 ( Cy )—was investigated. The monomers were obtained by acylation of 3-methyl-1-phenyl-pyrazolone-5 with crotonyl chloride or cinnamoyl chloride, respectively. It was established that the two monomers do not homopolymerize either under the action of ionic and radical initiators nor with γ-rays (doses between 2 and 10 MRad). In contrast to this, the two monomers copolymerize with other vinyl comonomers. Copolymers of Cr and Cy with methacrylic acid (MAA), methyl methacrylate (MMA), and Styrene (St) were synthesized by radical copolymerization. The molecular weights of the polymer products obtained were in the 10,000–65,000 range. It was established that the molecular weight characteristics of the copolymers were affected by the concentration of the pyrazolone-containing monomer and by the chemical nature of the solvent used. The copolymerization of Cr and Cy with MAA was investigated in detail in order to evaluate the relative activity of the new monomers during copolymerization. The reactivity ratios (r) were calculated by three different methods with good agreement. The values obtained for the monomer pairs are: r_MAA = 0.61 ± 0.01, r_Cr = 0.04 ± 0.01; r_MAA = 0.64 ± 0.05, r_Cy = 0.02 ± 0.02. The Q/e values for Cr and Cy were determined using the reactivity ratios of both monomers.     

Polymerization of complex systems. A study of the system methyl methacrylate–vinyl isobutyl ether–maleic anhydride by means of an NMR technique

It has been shown that the rates of polymerization of individual monomers in a mixture of monomers can be followed by means of an NMR technique. The technique is rapid and simple and requires very little sample. The system MMA–MA–VIBE was investigated by the technique. From the data obtained it was concluded that the polymer formed in a mixture of the three monomers is a block copolymer made up of (MMA)_m and (MA–VIBE)_n units, the lengths of which depend on the monomer concentrations.     

Complex-radical terpolymerization of phenanthrene,maleic anhydride,and trans-stilbene

The radical terpolymerization of the donor-acceptor-donor monomer system, phenanthrene (P)—maleic anhydride (M)—trans-stilbene (S), was studied. These monomers are known to be nonhomopolymerizable. The terpolymerization was carried out in p-dioxane and/or toluene at 70°C in the presence of benzoyl peroxide used as the initiator. P and S were found to form charge transfer complexes (CTC) with M in p-dioxane at 35°C. The results obtained are discussed in terms of the free monomer and complex propagation models. It is shown that terpolymerization is carried out at a stage close to binary copolymerization of two complexomers. The reactivity ratio of P … M and S … M complexes was estimated by the Kelen-Tüdös method. Absorbance ratios at 1770 cm^?1 (v_C=0 of anhydride group), 764 cm^?1 (δ_CH in monosubstituted benzene of S), and 820 cm^?1 (δ_CH in disubstituted benzene of P) as a function of terpolymer composition were established. P—M—S terpolymers are shown to have high thermal stabilities. © 1995 John Wiley & Sons, Inc.     

Polymerizations of olefins and diolefins catalyzed by monocyclopentadienyltitanium complexes containing a (dimethylamino)ethyl substituent and comparison with ansa-zirconocene systems

{[2-(dimethylamino)ethyl]cyclopentadienyl}titanium trichloride (Cp^NTiCl₃, 1 ) was activated with methylaluminoxane (MAO) to catalyze polymerizations of ethylene (E), propylene (P), ethylidene norbornene (ENB), vinylcyclohexene (VCH), and 1,4-hexadiene (HD). The dependence of homopolymerization activity ( A ) of 1 /MAO on olefin concentration ([M]ⁿ) is n = 2.0 ± 0.5 for E and n = 1.8 ± 0.2 for P. The value of n is 2.4 ± 0.2 for CpTiCl₃/MAO catalysis of ethylene polymerization; this system does not polymerize propylene. 1 /MAO catalyzes HD polymerization at one-tenth of A _H for 1-hexene, probably because of chelation effects in the HD case. The copolymerization of E and P has reactivity ratios of r_E = 6.4 and r_P = 0.29 at 20°C, and r_Er_P = 1.9, which suggests 1 /MAO may be a multisite catalyst. The copolymerization activity of CpTiCl₃/MAO is 50 times smaller than that of Cp^NTiCl₃/MAO. Terpolymerization of E/P/ENB has A of 10⁵ g of polymer/(mol of Ti h), incorporates up to 14 mol % (∼ 40 wt %) of ENB, and high MW's of 1 to 3 × 10⁵. All of these parameters are surprisingly insensitive to the ENB concentration. The E/P/VCH terpolymerization has comparable A value of (1.3 ± 0.3) × 10⁵ g/(mol of Ti h). The incorporation of VCH in terpolymer increases with increasing [VCH]. Terpolymerization with HD occurs at about one-third of the A of either ENB or VCH; the product HD–EPDM is low in molecular weight and contains less than 4% of HD. These terpolymerization results are compared with those obtained previously for three zirconocene precursors: rac-ethylenebis(1-η⁵-indenyl)dichlorozirconium ( 6 ), rac-(dimethylsilylene)bis(1-η⁵-indenyl)dichlorozirconium ( 7 ), and ethylenebis(9-η⁵-fluorenyl)dichlorozirconium ( 8 ). The last compound is a particularly poor terpolymerization catalyst; it incorporates very little VCH or HD and no ENB at all. 7 /MAO is a better catalyst for E/P/VCH terpolymerization, while 6 /MAO is superior in E/P/HD terpolymerization. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 319–328, 1998     

Cobalt(III)‐complex‐mediated terpolymerization of CO2, styrene oxide,and epoxides with an electron‐donating group

Terpolymerizations of CO₂, styrene oxide (SO), and epoxides with an electron‐donating group such as propylene oxide (PO) or cyclohexene oxide (CHO) were carried out by using Co(III)–salen complexes in the presence of an intra‐ or intermolecular nucleophilic cocatalyst. The resultant terpolymers have only one thermolysis peak and one glass transition temperature (T_g), which can be easily adjusted by controlling the proportion of styrene carbonate linkages. During the CO₂/SO/PO terpolymerization, the monomer reactivity ratios (r_SO = 0.18 and r_PO = 2.25) evaluated by Fineman–Ross plot indicates a random distribution of the two kinds of carbonate units in the resultant polymer. Contrarily, the monomer reactivity ratios were found to be r_SO = 0.48 and r_CHO = 0.79 in the CO₂/SO/CHO terpolymerization, indicating that an alternating nature of the two different carbonate units predominantly exists in the resultant polycarbonate. The regioselective ring opening of SO has a significant effect on the reactivities of both SO and CHO during the terpolymerization with CO₂. The matched reactivity is contributed to the enhanced regioselective ring opening of SO, caused by the attack of the dissociating polymer carboxylate anion, bearing a cyclohexene carbonate end unit. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Terpolymerization of ethyl methacrylate,N‐phenylmaleimide,and itaconic acid

The terpolymerization of ethyl methacrylate (EMA), N‐phenylmaleimide (NPMI), and itaconic acid (IA) was investigated. The terpolymer composition was determined by elemental analysis and ¹H NMR spectroscopy. The reactivity ratios of the three binary systems (EMA/NPMI, EMA/IA, and NPMI/IA) were calculated and used for the calculation of the terpolymer composition with the terminal model equations. A comparison between the experimental and theoretical compositions was made. The rate of the terpolymerization process was measured dilatometrically at two total monomer concentrations; this was done to establish the presence of intermolecular interactions between the investigated monomers. The thermal analysis of the obtained terpolymers was performed by thermogravimetric analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3180–3187, 2003     

Stereospecific radical polymerization of fluoroalkyl acrylates

The free‐radical polymerization of 2,2,2‐trifluoroethyl acrylate (TFEA), 1,1,1,3,3,3‐hexafluoro‐2‐propyl acrylate (HFiPA) and perfluoro‐tert‐butyl acrylate (PFtBA) was carried out under various conditions and the stereostructure of the obtained polymers was investigated. Most polymerizations of the three monomers afforded polymers rich in diad syndiotacticity (r) in bulk or in solution; the r‐specificity was higher in the HFiPA and PFtBA polymerization than in the TFEA polymerization. Although the tacticity was nearly independent of reaction temperature during the polymerization of TFEA, the r‐specificity increased by lowering the reaction temperature during the polymerization of the other two monomers. The polymerization stereochemistry was also affected by the reaction solvents including toluene, tetrahydrofuran, and fluoroalcohols. It was noted that the stereochemistry of the polymerization of HFiPA and PFtBA also depended on the monomer concentration, and a lower monomer concentration led to a higher r‐specificity. By optimizing the aforementioned reaction conditions, the poly(HFiPA) having r = 81% (polymerization in tetrahydrofuran at −98 °C at [M]_o = 0.2M) and the poly(PFtBA) having r = 77% (polymerization in toluene at −78 °C at [M]_o = 0.2M) were obtained. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1024–1032, 2000     

Terpolymerization of Butadiene,Acrylonitrile, and Methacrylic Acid

Abstract

The terpolymerization of butadiene, acrylonitrile, and methacrylic acid in emulsion, using potassium persulfate as initiator and sodium dioctylsulphosuccinate as emulsifier, was investigated. For the binary system butadiene (M₁) and methacrylic acid (M₂), the following monomer reactivity ratios were determined: r₁₂ = 0.18 ± 0.05 and r₂₁ = 0.52 ± 0.09. When polymerizations were stopped at low conversions they gave terpolymers which show good agreement between experimental and theoretical copolymerization composition data, calculated from the Alfrey-Goldfinger equation. The relationships between monomer feed and terpolymer compositions are presented on triangular coordinate graphs as proposed by Slocombe. By using a computer program, the lines of unique composition and the lines of binary azeotropic composition were established. No point of true azeotropic composition was found, but a “pseudo-azeotropic” region was recognized. The influence of composition on glass transition temperature and thermal characteristics of the terpolymers is described.     

Polymerization with TMA-protected polar vinyl comonomers. II. Catalyzed by nickel complexes containing α-diimine-type ligands

α-Diimine Ni complexes (7, 8) were used as catalyst precursors with MAO in co- and terpolymerization of ethylene/propylene/α-olefins with OH and COOH functional groups. Trimethylaluminium was used to protect the functional group of polar monomers. The presence of 5-hexen-1-ol seems to have no effect on the polymerization rate at all for the N,N′-bis(2,6-diisopropylphenyl) derivative 8 but caused activity decreases of about fivefold in copolymerization and around two times in terpolymerization for the N,N-dimesityl derivative 7. The effect levels off at higher polar comonomer concentration. This system, (7)/MAO, also incorporates well both 10-undecen-1-ol and 10-undecen-1-oic acid. The activities obtained with these α-diimine Ni complexes in co- and terpolymerization are three to twenty times higher than those obtained with group 4 Cp based complexes especially at concentrations of polar monomer in the feed higher than 80 mM. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2471–2480, 1999     

Crystallization of markoffian copolymers

An equilibrium theory is proposed for crystallization of (A, B) binary copolymers whose comonomeric unit sequences are statistically described by conditional pair probabilities P_AA, P_AB, P_BA, and P_BB. These are linked to the product of the reactivity ratios by r = r_Ar_B = (P_AAP_BB)/(P_ABP_BA). Three cases are considered here, (i) B units are rejected from the crystals, (ii) cocrystallization of A and B comonomeric units is possible in the full range of compositions within a single crystal structure (copolymer isomorphism), (iii) cocrystallization takes place either in a poly(A)-type or in a poly(B)-type structure, depending on composition (copolymer isodimorphism). For case (i) crystallization the theory demonstrates, according to expectation, that alternating copolymers (r = 0) produce the largest melting point depression, whereas in case (ii) they give rise to the smallest composition difference between the crystals and the liquid. The theory developed here further illustrates that for binary copolymers which are isodimorphic (case iii), a phase diagram is obtained similar to that for a classical binary system of small molecules.     

(Salan)CrCl,an effective catalyst for the copolymerization and terpolymerization of epoxides and carbon dioxide

The selective transformation of CO₂ and epoxides to afford completely alternating copolymers remains a topic of much interest for the potential utilization of carbon dioxide in chemical synthesis. The use of salicylaldimine (salen)‐metal complexes and their saturated (salan)‐metal versions have proven to be the most effective and robust single‐site catalyst for these processes. Herein, we report on mechanistic aspects of the copolymerization of alicyclic and aliphatic epoxides with CO₂ in toluene solution and in neat epoxides in the presence of a (salan)CrCl/onium salt catalyst system. The activation barriers for both cyclohexene oxide(CHO)/CO₂ and propylene oxide(PO)/CO₂ were shown to be significantly higher in toluene solution than those previously reported for reactions carried out under solventless conditions. Terpolymerization of CHO/vinylcyclohexene oxide/CO₂ was shown via Fineman‐Ross analysis at 60 °C to proceed with little monomer selectivity, for example, r_CHO = 1.03 and r_VCHO = 0.847. On the other hand, terpolymerization of CHO/PO/CO₂ occurred at 25 °C with a propensity for incorporation of PO in the polymer. However, at 40 °C, Fineman‐Ross analysis revealed r_CHO and r_PO values of 0.869 and 1.49, thereby affording a terpolymer with a more equal distribution of monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Vinylhydroquinone. III. Copolymerization of vinylhydroquinone and vinyl monomers by tri-n-butylborane

The copolymerization of vinylhydroquinone (VHQ) and vinyl monomers, e.g., methyl methacrylate (MMA), 4-vinyl-pyridine (4VP), acrylamide (AA), and vinyl acetate (VAc), by tri-n-butylborane (TBB) was investigated in cyclohexanone at 30°C under nitrogen. VHQ is assumed to copolymerize with MMA, 4VP, and AA by vinyl polymerization. The following monomer reactivity ratios were obtained (VHQ = M₂): for MMA/VHQ/TBB, r₁ = 0.62, r₂ = 0.17; for 4VP/VHQ/TBB, r₁ = 0.57, r₂ = 0.05; for AA/VHQ/TBB, r₁ = 0.35, r₂ = 0.08. The Q and e values of VHQ were estimated on the basis of these reactivity ratios as Q = 1.4 and e = ?;1.1, which are similar to those of styrene. This suggests that VHQ behaves like styrene rather than as an inhibitor in the TBB-initiated copolymerization. No homopolymerization was observed either under nitrogen or in the presence of oxygen. The reaction mechanism is discussed.     

Synthesis of Sequence-specific Poly(ester-carbonate) Copolymers via Chemoselective Terpolymerization Controlled by the Stoichiometric Ratio of Phosphazene/Triethylborane

Chemoselective terpolymerization can produce polymer materials with diverse compositions and sequential structures, and thus have attracted considerable attention in the field of polymer synthesis. However, the intrinsic complexity of three-component system also brings great chanllenge, in regard to the reactivity and selectivity of different monomers. Herein, we report the terpolymerization of CO₂/epoxide/anhydride by a binary organocatalytic C₃N₃-Py-P₃/TEB (triethylborane) system. Both the activity and chemoselectivity were highly dependent upon the molar ratio of C₃N₃-Py-P₃ to TEB, and sequence-controlled poly(ester-carbonate) copolymers were readily synthesized through one-pot/one-step methodology by tuning the stoichiometric ratio of phosphazene/TEB. In particular, C₃N₃-Py-P₃/TEB with a molar ratio of 1/0.5 exhibited an unprecedentedly high chemoselectivity for ring-opening alternating copolymerization (ROAC) of cyclohexene oxide (CHO) and phthalic anhydride (PA) first and then ROAC of CO₂/CHO. Thus, well-defined triblock polycarbonate-b-polyester-b-polycarbonate copolymers can be produced from the mixture of CO₂, CHO and PA using a bifunctional initiator. With C₃N₃-Py-P₃/TEB=1/1, tapered copolymers were obtained, while random copolymers with high content of polycarbonate (PC) were synthesized with further increasing the amount of TEB. The mechanism of the unexpected chemoselectivity was further investigated by DFT calculations.     

Cyclodextrins in polymer chemistry: Influence of methylated β-cyclodextrin as host on the free radical copolymerization reactivity ratios of isobornyl acrylate and butyl acrylate as guest monomers in aqueous medium

Methylated β-cyclodextrin (me-β-CD) was used to complex the hydrophobic monomers isobornyl acrylate ( 1 ) and butyl acrylate (2) yielding the water-soluble host/guest complexes isobornyl acrylate/me-β-CD ( 1a ) and butyl acrylate/me-β-CD ( 2a ). The included monomers were copolymerized in water by free-radical mechanism and the kinetics were studied. In order to evaluate these results, the corresponding uncomplexed monomers 1 and 2 were also copolymerized in organic solution. The reactivity ratios of 1a and 2a (r _1a = 0.3, r _2a = 1.7) differ significantly from the reactivity ratios of the corresponding uncomplexed acrylates 1 and 2 in organic solution (r ₁ = 1.3, r ₂ = 1.0). In addition, we found that the weight averages of the copolymers prepared by using me-β-CD are significantly higher than those of the corresponding polymers prepared from uncomplexed monomers in organic solution.     

Silyl enol ethers as monomer. I. Radical copolymerizability of α-trimethylsilyloxystyrene

α-Trimethylsilyloxystyrene (TMSST), the silyl enol ether of acetophenone, was not homopolymerized either by a radical or a cationic initiator. Radical copolymerization of TMSST with styrene (ST) and acrylonitrile (AN) in bulk and the terpolymerization of TMSST, ST, and maleic anhydride (MA) in dioxane were studied at 60°C and the polymerization parameters of TMSST were estimated. The rate of copolymerization decreased with increased amounts of TMSST for both systems. Monomer reactivity ratios were found as follows: r₁ = 1.48 and r₂ = 0 for the ST (M₁)–TMSST (M₂) system and r₁ = 0.050 and r₂ = 0 for the AN (M₁)–TMSST (M₂) system. The terpolymerization of ST (M₁), TMSST (M₂), and MA (M₃) gave a terpolymer containing ca. 50 mol % of MA units with a varying ratio of TMSST to ST units and the ratio of rate constants of propagation, k₃₂/k₃₁, was found to be 0.39. Q and e values of TMSST were determined using the values shown above to be 0.88 and ?1.13, respectively. Attempted desilylation by an acid catalyst for the copolymer of TMSST with ST afforded polystyrene partially substituted with hydroxyl groups at the α-position.     

Synthesis and characterization of styrenic polymers with pendant pyrazole groups. II

The synthesis of styrenic monomers that have pyrazolic or bipyrazolic pendant groups is described. Their homopolymerization and their copolymerization with maleic anhydride (MA) and N-(3-acetoxy propyl) maleimide is reported. The monomers were prepared from the Williamson reaction between 2-pyridine carbinol, hydroxy monopyrazole, hydroxy bipyrazole, and chloromethyl styrene. The homopolymerizations of such styrenic monomers were tried under different conditions, which led to low molecular weight polymers with a high polydispersity. However, alternating copolymers were obtained using maleic anhydride or N-(3-acetoxy propyl) maleimide as comonomers, as shown by ¹H-NMR, elemental analysis, and reactivity ratios r₁ and r₂. Furthermore, the hydrolysis of the acetate function of different copolymers was performed quantitatively. Unlike the acetoxy copolymers, such products do not have any glass transition temperature. Thermogravimetric investigations have shown that these copolymers exhibit good thermostability. © 1994 John Wiley & Sons, Inc.     

Heat of Terpolymerization

Abstract

A novel correlation for predicting the heat of terpolymerization from the binary data is proposed. This correlation is applicable to the ternary system with monomers which obey the Q-e scheme. The heat of terpolymerization for the ternary system methyl methacrylate-styrene-acrylonitrile is calculated from binary data.     

Determination of the reactivity ratios of methyl acrylate with the vinyl acetate,vinyl 2,2-dimethyl-propanoate,and vinyl 2-ethylhexanoate

The course of composition drift in copolymerization reactions is determined by reactivity ratios of the contributing monomers. Since polymer properties are directly correlated with the resulting chemical composition distribution, reactivity ratios are of paramount importance. Furthermore, obtaining correct reactivity ratios is a prerequisite for good model predictions. For vinyl acetate (VAc), vinyl 2,2-dimethyl-propanoate also known as vinyl pivalate (VPV), and vinyl 2-ethylhexanoate (V2EH), the reactivity ratios with methyl acrylate (MA) have been determined by means of low conversion bulk polymerization. The mol fraction of MA in the resulting copolymer was determined by ¹H-NMR. Nonlinear optimization on the thus-obtained monomer feed–copolymer composition data resulted in the following sets of reactivity ratios: r_MA = 6.9 ± 1.4 and r_VAc = 0.013 ± 0.02; r_MA = 5.5 ± 1.2 and r_VPV = 0.017 ± 0.035; r_MA = 6.9 ± 2.7 and r_V2EH = 0.093 ± 0.23. As a result of the similar and overlapping reactivity data of the three methyl acrylate–vinyl ester monomer systems, for practical puposes these data can be described with one set of reactivity data. Nonlinear optimization of all monomer feed–copolymer composition data together resulted in r_MA = 6.1 ± 0.6 and r_VEst = 0.0087 ± 0.023. © 1994 John Wiley & Sons, Inc.     

Anionic copolymerization of optically active α-methylbenzyl methacrylate and trityl methacrylate. I. Reactivity of monomers

The monomer reactivity ratios were determined in the anionic copolymerization of (S)- or (RS)-α-methylbenzyl methacrylate (MBMA) and trityl methacrylate (TrMA) with butyllithium at ?78°C, and the stereoregularity of the yielded copolymer was investigated. In the copolymerization of (S)-MBMA (M₁) and TrMA (M₂) in toluene the monomer reactivity ratios were r₁ = 8.55 and r₂ = 0.005. On the other hand, those in the copolymerization of (RS)-MBMA with TrMA were r₁ = 4.30 and r₂ = 0.03. The copolymer of (S)-MBMA and TrMA prepared in toluene was a mixture of two types of copolymer: one consisted mainly of the (S)-MBMA unit and was highly isotactic and the other contained both monomers copiously. The same monomer reactivity ratios, r₁ = 0.39 and r₂ = 0.33, were obtained in the copolymerizations of the (S)-MBMA–TrMA and (RS)-MBMA–TrMA systems in tetrahydrofuran (THF). The microstructures of poly[(S)-MBMA-co-TrMA] and poly-[(RS)-MBMA-co-TrMA] produced in THF were similar where the isotacticity increased with an increase in the content of the TrMA unit.