Copolymerization of Styrene with Bis(4-methacryloylmethylphenyl) Sulphide

Abstract

A new monomer was prepared in the reaction of bis(4-chloromethylphenyl)sulphide with potassium salt of methacrylic acid. The monomer was characterized by elementary analysis, IR, ^{1 >}H-NMR and ¹³C-NMR analyses. After determination of the structure, studies on its solubility with common as well as vinyl solvents such as styrene, methyl methacrylate, butyl acrylate, acrylonitrile, and divinylbenzene were carried out. Besides, a hardening system for styrene solutions of bis(4-methacryloylmethylphenyl)sulphide (BMMPhS) was chosen. Combinations of the following components: benzoyl peroxide, methyl ethyl ketone peroxide, N,N-dimethylaniline, and cobalt naphthenate were used for hardening. Polymerization of the following styrene solutions of BMMPhS: 50,40,30, 20 and 10% was performed. The obtained copolymers were tested for mechanical properties like: Young's modulus, tensile strength, elongation at break, hardness of Shore's and Brinnell's methods. For the chosen copolymers, thermal properties were determined.     

Copolymerization of methyl methacrylate with N-(methoxyphenyl) itaconimides

This article describes the synthesis and characterization of N-(3-methoxyphenyl) itaconimide (MAI) and N-(4-methoxyphenyl) itaconimide (PAI) obtained by the reaction of itaconic anhydride with m-anisidine and p-anisidine, respectively. Structural and thermal characterization of MAI and PAI monomers was performed with Fourier transform infrared (FTIR), ¹H-NMR, differential scanning calorimetry (DSC), and thermogravimetric analysis. Copolymerization of methyl methacrylate (MMA) with various amounts of MAI or PAI ranging from 0.1 to 0.5 was performed in solution with azobisisobutyronitrile as an initiator. Structural and molecular characterization of copolymers was performed with FTIR, ¹H-NMR, elemental analysis, and gel permeation chromatography. The nitrogen percentage was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MAI copolymers were found to be 1.00 ± 0.01 for MMA and 0.99 ± 0.07 for MAI; those for MMA–PAI copolymers were 0.93 ± 0.02 for MMA and 1.11 ± 0.10 for PAI. The molecular weights of the copolymers were in the range of 0.94–9.7 × 10³ (number-average molecular weight) and 3.3–101.8 × 10³ (weight-average molecular weight), with polydispersity indices in the range of 1.5–4.1. The molecular weight decreased with the increasing molar fraction of imide in the polymer backbone. The glass-transition temperature, as determined from DSC scans, increased with increasing amounts of itaconimides in the copolymers. A significant improvement in the char yield, as determined by thermogravimetry, was observed upon copolymerization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Copolymerization of aromatic polyamide macromonomers with methyl methacrylate

Summary Graft copolymers of end methacrylate-functionalized[MacroAM] or styrene-functionalized[MacroAS] polyamide macromonomers with methyl methacrylate(MMA) were prepared by radical copolymerization, and their thermal, dynamic properties, and miscibility with matrix PMMA have been investigated. The glass transition temperature(Tg)s of the copolymers were significantly elevated with the increase of the macromonomer content in the copolymer. Storage modulus E of the graft copolymers began to decrease at around 85°C, which is close to Tg of PMMA, irrespective of the macromonomer content in the copolymers. As the macromonomer content and its degree of polymerization became higher, the drop in E became significant.     

澳化亚铜催化下的甲基丙烯酸甲醋(MMA)与乙烯的共聚合

以溴化亚铜为催化剂,采用原子转移自由基聚合方法对MMA和乙烯进行共聚合,用核磁共振法表征了共聚物中聚乙烯的含量。结果表明,在压力为6MPa的条件下,MMA与乙烯共聚物中聚乙烯的摩尔分数可达到15.9％。关键词：甲基丙烯     

Copolymerization of 4-cyanophenyl methacrylate with methyl methacrylate: Synthesis,characterization and determination of monomer reactivity ratios

Summary A novel methacrylic monomer, 4-cyanophenyl methacrylate (CPM) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone (MEK) with methacryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPM with methyl methacrylate(MMA) at different composition was prepared by free radical solution polymerization at 70±1 °C using benzoyl peroxide as initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility of the polymers was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in mole fraction of MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPM content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectroscopy. The monomer reactivity ratios estimated by the application of linearization methods such as Fineman-Ross (r₁=2.524±0.038, r₂=0.502±0.015), Kelen-Tudos (r₁=2.562±0.173, r₂=0.487±0.005) and extended Kelen-Tudos methods (r₁=2.735±0.128, r₂=0.4915±0.007).     

Copolymerization of 2-methacryloxytropone with methyl methacrylate and ethyl acrylate

Summary 2-Methacryloxytropone was synthesized via reported methods and it's free radical initiated copolymerization with methyl methacrylate or ethyl acrylate was investigated. The 2-methacryloxytropone was found to be the more reactive monomer in both cases, however the difference in reactivity was more pronounced in the ethyl acrylate case.     

Copolymerization of 2,5-dimethyl-3-vinylthiophene with methyl methacrylate,styrene and isobutyl methacrylate

Summary The title vinyl thiophene monomer was synthesized by dehydration of the corresponding secondary alcohol. Free radical initiated copolymerizations with methyl methacrylate, styrene or isobutyl methacrylate were performed and the copolymer compositions were used in the calculation of reactivity ratios. The data was analyzed via a nonlinear least squares error-in-variables method. The 2,5-dimethyl-3-vinylthiophene was shown to have equal or slightly less reactivity than each of the monomers chosen as comonomers.     

Copolymerization of 6-vinyl-1,4-benzodioxane with methyl methacrylate andn-butyl acrylate

Summary 6-Vinyl-1,4-benzodioxane was synthesized and its copolymerization with methyl methacrylate and n-butyl acrylate was investigated. In this work concentration ladder type copolymerizations were performed. The results of copolymerization were analyzed using a nonlinear least squares method and reactivity ratios were calculated from the analysis. The 6-vinyl-1,4-benzodioxane was found to be a more reactive monomer than either the methyl methacrylate or butyl acrylate, but only slightly so in the methyl methacrylate case.     

Organotin polymers. IX. Copolymerization parameters of di-(tri-n-butyltin) itaconate with styrene and methyl methacrylate

Copolymerization reactions of di-(tri-n-butyltin) itaconate with styrene and methyl methacrylate were carried out in solution at 70°C using 1 mol% azobisisobutyronitrile as a free radical initiator. The copolymer compositions were determined by chemical analysis as well as from ¹H-NMR data. The monomer reactivity ratios for copolymerizations of di-(tri-n-butyltin) itaconate with styrene and methyl methacrylate have been found to be r₁ = 0.228, r₂ = 0.677, and r₁ = 0.220, r₂ = 1.635, respectively. The sequence distribution of the triad fractions were calculated from reactivity ratios and compared with those obtained from ¹H-NMR data.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

The transport of methyl methacrylate monomer in poly(methyl methacrylate)

The absorption kinetics and equlibria of methyl methacrylate monomer into poly(methyl methacrylate) were studied over a range of penetrant activities. The interval sorption kinetics at elevated activities were determined, compared, and contrasted with the integral sorption experiments in previously unpenetrated film samples. The sorption kinetics in previously unpenetrated films were predominantly case II or relaxation controlled at high activities. A Fickian contribution to the overall kinetics was apparent at lower activities. In contrast, interval sorption, at elevated activities in previously equilibrated and plasticized samples, followed Fickian kinetics rather closely, whereas resorption, over an activity range which involved a traversal of the effective T_g, was characterized by more complicated kinetics involving a super case II mechanism at long times. These composite results reinforce the notion that the kinetics describing penetration of a single penetrant into a single polymer are extremely sensitive to the boundary condition imposed upon the polymeric sorbent.     

Copolymerization of 5-vinyl-1,3-benzodioxole with n-butyl acrylate and methyl methacrylate

Summary Copolymers of 5-vinyl-1, 3-benzodioxole (VBD) with n-butyl acrylate and methyl methacrylate were synthesized. The copolymers were synthesized according to a designed experiment methodology and reactivity ratios were estimated using a nonlinear least squares error-in-variables procedure. The values of r₁ and r₂ obtained show that VBD is slightly less reactive than styrene in similar copolymerization reactions.     

Copolymerization of alkyl α-chloroacrylates with methyl methacrylate

Hexyl α-chloroacrylate (HCA) and cyclohexyl α-chloroacrylate (CCA) have been copolymerized with methyl methacrylate (MMA) in toluene at 55°C using azobisisobutyronitrile (AIBN) as initiator. Copolymer compositions have been determined both by ¹H NMR and elemental analyses. For copolymerization of MMA (M1) with HCA (M2), the reactivity ratios (RR) are r₁ = 0.47 ± 0.19 and r₂ = 0.81 ± 0.51 and with CCA the values are r₁ = 0.76 ± 0.31 and r₂ = 2.30 ± 1.73. Thermal properties of these copolymers have also been investigated.     

Copolymerization of 3-methyl-2-vinylthiophene with methyl methacrylate and ethyl acrylate

Summary The copolymerization behavior of 3-methyl-2-vinylthiophene with methyl methacrylate or ethyl acrylate in bulk, using free radical initiation was investigated. The copolymerizations were performed according to the experimental design scheme of Mortimer and Tidwell (1). The experimental results were analyzed by using a nonlinear least squares error-in-variables method. In both cases the 3-methyl-2-vinylthiophene proved to be the more reactive monomer.     

Poly(methyl methacrylate)-block-polysulfide-block-poly(methyl methacrylate) copolymers obtained by free-radical polymerization combined with oxidative coupling

Summary Poly(methyl methacrylate)-block-polysulfide-block-poly(methyl methacrylate) copolymers were synthesized for the first time through a new method involving the free radical polymerization of MMA in the presence of a thiocol oligomer as a chain transfer agent, followed by chemical oxidation of the remaining SH end-groups. The chain transfer constant of the SH end-groups of the thiocol was estimated from the rate of consumption of the thiol groups versus the rate of consumption of the monomer (C_T=0.67). The triblock copolymers synthesized were characterized by SEC and ¹H NMR measurements.     

Stereocomplex formation in polybutadiene-syndiotactic poly(methyl methacrylate) block copolymers blended with isotactic poly(methyl methacrylate)

Summary The process of stereocomplexation in blends of isotactic poly(methyl methacrylate)s and polybutadiene-syndiotactic poly(methyl methacrylate) diblock copolymers was studied by differential scanning calorimetry as a function of molar mass of the constituents, annealing time and temperature. The amount of complex formed is dependent on these three parameters, while the temperature of decomposition of the complex is only dependent on the annealing temperature. Complex formation can be observed in blends containing a copolymer with a very low molar mass syndiotactic poly(methyl methacrylate) block (Mn=700). In contrast to homopolymer blends, for which two endotherms of decomposition were generally reported, only one endotherm is observed for copolymer-homopolymer blends. This behavior is attributed to the elastomer block.     

Preparation of heterotactic-rich poly(methyl methacrylate) with narrow molecular weight distribution bytert-butyllithium/bis(2,6-di-tert-butylphenoxy)methylaluminum

Summary Polymerization of methyl methacrylate (MMA) withtert-butyllithium (t-C₄H₉Li) in toluene in the presence of aluminum alkoxides such as ethoxide,tert-butoxide and 2,6-di-tert-butylphenoxide, were examined at various Al/Li ratios. In the cases of ethoxide andtert-butoxide, predominantly isotactic polymers with broad molecular weight distribution were obtained. Combinations oft-C₄H₉Li and bis(2,6-ditert-butylphenoxy)methylaluminum [MeAl(ODBP)₂] were found to be an efficient initiating system for heterotactic polymerization of MMA, which gives PMMA rich in heterotactic triads up to 68% with narrow molecular weight distribution (Mw/Mn=1.09–1.17). End group analysis by¹H NMR indicated thatt-C₄H₉Li initiates the polymerization and MeAl(ODBP)₂ works as a stereospecific modifier. From stereosequence analysis of the heterotactic PMMA by¹³C NMR, it was found that the calculated pentad fractions from the first-order Markovian statistics (Pm/r=0.742, Pr/m=0.627) fitted the observed ones better than those from Bernoullian statistics. The glass transition temperature of the heterotactic PMMA was 13°C lower than that of syndiotactic PMMA, and the intrinsic viscosity in tetrahydrofuran was close to that of isotactic PMMA with a similar molecular weight but higher than that of syndiotactic PMMA.     

Copolymerization of 5-vinyl-2,2′-bithiophene with methyl methacrylate and n-butyl acrylate

Summary Copolymers of 5-vinyl-2,2-bithiophene with methyl methacrylate or n-butyl acrylate were synthesized. Copolymer compositions were analyzed by nuclear magnetic resonance spectroscopy and reactivity ratios were calculated using the Kelen-Tüdõs method. 5-Vinyl-2,2-bithiophene proved to be a very reactive monomer with a reactivity ratio value of greater than 3 in copolymerization reactions with methyl methacrylate and a value of greater than 4 in Copolymerization reactions with n-butyl acrylate.     

Copolymerization of styrene and methyl methacrylate with nickel acetylacetonate/methylaluminoxane catalyst system

The present work deals with copolymerization of styrene (STY) and methyl methacrylate (MMA) catalysed by nickel acetylacetonate - Ni(acac) ₂ , employing methylaluminoxane (MAO) as cocatalyst. This catalyst system presented low catalyst activities for STY homopolymerization and very high activities for MMA. It seems that the catalyst system based on Ni(acac) ₂ /MAO is effective for the copolymerization of MMA and STY to give block copolymer but it also produced polystyrene and poly(methyl methacrylate) homopolymers. The polymers were characterized by ¹³ C NMR, GPC and FTIR. The polystyrene homopolymer was identified by IR and NMR analyses of the cyclohexane soluble fraction. The presence of absorption bands correspondent to carbonyl group and aromatic ring was observed in the IR spectrum of the acetic acid soluble part. This result is a clue that STY-MMA copolymer with low molecular weight was produced. The high molecular weight copolymer (acetic acid insoluble fraction) was also characterized by IR analysis which indicated the presence of characteristic absorption bands of carbonyl group and aromatic ring. These results were confirmed by ¹³ C NMR analysis. Received: 6 August 1997/Revised version: 29 December 1997/Accepted: 7 January 1998