Polymer degradation. V. Changes in molecular weight distributions during sonic irradiation of polyisobutene

Gel permeation chromatography was used to follow changes in the molecular weight distribution of a polyisobutene, initial M _v = 466,000, during degradation induced by sonic irradiation. Seven samples taken at times of 200–163,500 sec. were studied. In general, a steady decrease in molecular weight was observed, although a bimodal distribution was present after 20,000 sec. irradiation. Various measures of inhomogeneity, M _w/M _n, U, etc., were examined. The function, σ_n/M _w, where σ_n is the standard deviation of the number distribution, is considered as a measure of the relative distribution. It is shown to be almost constant throughout the degradation.     

Molecular weight distribution of commercial PVC

The molecular weight distribution (MWD) of commercial suspension grade poly(vinyl chloride) (PVC) resins with K values from 50 to 93 and mass grade PVC resins with K values from 58 to 68 has been determined by size exclusion chromatography (SEC), using literature Mark‐Houwink coefficients. The MWD is characterized by the number average molecular weight (M_n), the weight average molecular weight (M_w) and the polydispersity (M_w/M_n). Our results for M_w are consistent with recently published data, but we find different results for M_n and consequently for M_w/M_n. The polydispersity of PVC increases with increasing K value. This effect can be explained by two mechanisms. The first mechanism is a reduced terminating reaction rate between two growing polymer chains (disproportionation) at higher molecular weight owing to the reduced mobility of the polymer chains. The second mechanism is long‐chain branching of molecules with high molecular weight which lets the molecules grow at two ends. For two examples graphs of the measured MWD are compared with the theoretically expected MWD.     

Modification of polypropylene with maleic anhydride: Ultrasonic irradiation effects

The mechanochemical reaction of modificated of polypropylene (PP) with maleic anhydride (MAH) has been studied by ultrasonic irradiation as an energy source at 60°C. Through 2³ factorial experimental design, three variables and their interactions were studied: the percentage of MAH, the percentage of benzoyl peroxide (BPO), and ultrasonic irradiation intensity (Watts). According to the results, an increase of wt % of MAH gave a negative effect in the grafting yield; in addition, this negative effect was observed in the interaction of MAH : BPO at a high range of wt %, this behavior is attributed to the homopolymerization of MAH at the experimental conditions employed. The higher positive effect onto the grafting yield was observed for the variable watts (ultrasonic irradiation intensity), even at low intensity. The better interaction of variables gave a MAH grafting degree of 4.65 wt % (93% yield). In addition, the effect of ultrasonic irradiation on the number-average molar mass (M_n), weight-average molar mass (M_w), and polydispersity index (M_w/M_n) was measured. It was observed that the M_w decreased 13.73% and the M_w/M_n also decreased by 11.98%. The o observed effect was attributed to the degradation mechanism induced by the ultrasound, which consists in the generation of macroradicals and their recombination. The product PP-g-MAH was characterized by infrared spectroscopy, also was used to prepare polypropylene–nylon-6 blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:45–52, 1998     

Determination of the absolute molecular weight of a styrene–butyl acrylate emulsion copolymer by low-angle laser light scattering (LALLS) and GPC/LALLS

The application of low-angle laser light scattering (LALLS) and combined GPC/LALLS for the measurement of absolute molecular weight distribution of a styrene–butylacrylate (30/70) emulsion copolymer is discussed. From the static light scattering measurements in four different solvents, i.e., toluene, tetrahydrofuran (THF), methyl ethyl ketone (MEK), and dimethylformamide (DMF), the true weight average molecular weight (M _w) and heterogeneity parameters are determined. The apparent M _w obtained from the static measurement in THF was in good agreement with the M _w determined from the multiple solvent analysis, suggesting the validity of using THF as the mobile phase in the combined GPC/LALLS analysis.     

Polymerization of p-nitrobenzyl acrylate under microwave irradiation and their optical properties

p-Nitrobenzyl acrylate was polymerized under microwave irradiation initiated by benzoyl peroxide. The effect of the reaction conditions on the conversion, average molecular weights and the polydispersity index (M_w/M_n) were investigated. The polymers were characterized by IR, ¹H and ¹³C-NMR spectroscopies and molecular weights were analyzed with size exclusion chromatography (SEC). Optical properties in seven solvents were studied. The most outstanding characteristics of this monomer were slow kinetics of polymerization and low average molecular weight (M_w ~ 3000) as result of the chain transfer reaction to monomer, as it was demonstrated by experimental test and theoretical calculations. Solvatochromic effect of polymer solutions by changing the solvent polarity was quantitatively expressed by means of the linear solvation energy relationship using the empirical Kamlet-Taft solvents parameters set. The analyses demonstrated that the solute-solvent dipolar interactions were mainly responsible of the observed shift of ν_max and attributed to the para-nitrobenzyl group of the monomer, which enhanced the optical properties of the polymer.     

Rheological properties of polypropylenes with different molecular weight distribution characteristics

Relationships between the rheological properties and the molecular weight distribution of two polypropylene series with different molecular weight distribution characteristics were studied. The end correction coefficient in capillary flow is determined by the molecular weight M_w and the molecular weight distribution M_w/M_n, and is higher as both characteristic values are larger. The die swell ratio at a constant shear rate depends on M_w, M_w/M_n, and M_z/M_w, and is higher as the three characteristic values are larger. The critical shear rate at which a melt fracture begins to occurs depends on the molecular weight M_w and the molecular weight distribution M_z/M_w, and is proportional to M_z/M_w² in a log–log plot. The critical shear stress does not depend on the molecular weight, and is higher as M_z/M_w is higher. The zero‐shear viscosity is determined by a molecular weight of slightly higher order than M_w, and the characteristic relaxation time is determined by M_z. The storage modulus at a constant loss modulus scarcely depends on the molecular weight, and is higher as the molecular weight distribution M_w/M_n is higher. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2128–2141, 2002     

Effect of SiC whisker on benzoxazine‐epoxy‐phenolic ternary systems: Microwave curing and thermomechanical characteristics

Microwave radiation at 2.45 GHz with variable power input was investigated as a tool to facilitate the curing reaction of benzoxazine‐epoxy‐phenolic molding compound i.e., BEP893. Dielectric filler for microwave coupling was silicon carbide whisker (SiC_w). Factors such as whisker loading and input irradiation power were found to have a profound effect on the microwave heating of the BEP893 particularly on the rate of temperature rise and maximum heating temperature. The SiC_w loading of 10% by weight with the microwave irradiation condition of 300 W for 10 min renders the ultimate curing of the molding compound. Significant reduction in processing time of the microwave cured sample compared with the conventional heat cured sample i.e., 150 min at 200°C using conventional heating is the key benefit of this technique. Mechanical properties of the microwave cured and conventional heat cured samples show similar characteristics with slightly lower T_g in the microwave cured samples. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Multifunctional carbochain organosilicon polymers. I. A new approach to the synthesis of high molecular weight cyclolinear polycarbosiloxane

Controlled synthesis of high molecular weight cyclolinear polycarbosiloxanes (PCCS) is considered, using the following reactions sequence: (1) anionic polymerization of vinyldimethylphenylsilane, (2) replacement of the Ph group in polyvinyldimethylphenylsilane (M _n=83.900,M _w/M _n=1.48) by a Cl group to prepare polyvinyldimethylchlorosilane (PVMCS), and (3) hydrolytic intramolecular condensation of PVMCS. The formation of carbochain polymer with predominantly six-membered carbosiloxane rings is demonstrated (M _n=81.400,M _w/M _n=1.54).     

Relations of weight-average molecular weights and the thermal properties of N-cyclohexyl maleimide–methyl methacrylate

N-cyclohexyl maleimide (CHMI) was used to copolymerize with methyl methacrylate (MMA) by a suspension copolymerization method to produce heat-resistant poly(MMA) (PMMA) in this article. The copolymers were synthesized by changing the weight fractions of azobisisobutyronitrile (AIBN) and dodecanethiol (DDM), while the weight ratio of CHMI to MMA was defined. The effects of the weight fractions of AIBN and DDM on weight-average molecular weight (M_w) were studied. Meanwhile, relations between M_w and the glass transition temperature (T_g) and decomposition temperature (T_d) and M_w and the melt flow index (MFI) were described. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2001–2005, 1998     

Study on controlled radical alternating copolymerization of styrene with maleic anhydride under UV irradiation

The copolymerization of styrene with maleic anhydride (MAh) in the presence of 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate was carried out under UV irradiation at room temperature, and showed ‘living’ polymerization nature which was evidenced by: linear evolution of molecular weight with conversion; and narrow molecular weight distribution (M_w/M_n = 1.08–1.20). The compositional analysis and the sequence structural information of the copolymer obtained from Distortionless Enhancement by Polarization Transfer (DEPT) NMR experiments demonstrated that the copolymers obtained possess strictly alternating structure. © 2003 Society of Chemical Industry     

Poly(methyl acrylate) and copolymer of acrylic acid and butyl acrylate prepared by γ‐irradiation in the presence of 1,1‐diphenylethene: Synthesis and application in emulsion polymerization

Poly(methyl acrylate) and amphiphilic copolymer of butyl acrylate and acrylic acid were prepared in the presence of 1,1‐diphenylethene (DPE) by γ‐irradiation‐induced polymerization. The influences of polymerization time, amounts of DPE in system on conversion, molecular weight (MW), and its distribution (M_w/M_n) were studied. The results indicate that the polymerization in the presence of DPE and initiated by γ‐irradiation shows the character of controlled radical reaction. The prepared copolymer was used as the polymeric emulsifier in the emulsion polymerizations of butyl acrylate (BA) and styrene (St), respectively, to assess the possibility of making monodisperse latices of relatively high solids content (～ 35–45%) in an one‐step batch process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nonisothermal crystallization kinetics of linear metallocene polyethylenes

The effect of weight‐average molecular weight (M_w) on the nonisothermal crystallization kinetics of linear metallocene polyethylene (m‐PE) was studied with modulated differential scanning calorimetry. Six linear m‐PEs of molecular weights in the range 122–934 kg/mol were prepared by gas‐phase polymerization. The cooling rate (R) was varied in the range 2–20°C/min, and it significantly affected the crystallization behavior. M_w had a weak influence on both the peak crystallization temperature and the crystallization onset temperature. All m‐PEs showed primary and secondary crystallizations. At both low and high R's, the crystallinity showed a significant drop (～ 30%) when M_w was increased from 122 to 934 kg/mol. At low R's (< 10°C/min), the rate parameters in the modified Avrami method [primary rate constant (k_R)] and Mo method [F(T)] of analyses agreed in suggesting that an increased M_w slowed the rate of crystallization. The M_w dependency of k_R followed the Arrhenius type (k_R = k_Roe²⁸¹/M_w, where k_Ro is a rate‐dependent constant). However, at higher R's, k_R approached a constant value. The order parameters obtained by the different methods of analysis (n and α) were independent of M_w, which suggests that the crystal type remained the same. Hoffman–Lauritzen theory was used for data analysis, and activation energy per segment showed a significant decrease, from 225.0 to 11.8 kJ/mol, when M_w was increased from 152 to 934 kg/mol. Finally, all methods of analysis suggested a significant effect of M_w on slowing the overall crystallization process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Semicontinuous copolymerization of 80/20 wt % [2‐(acryloyloxy)ethyl]trimethyl ammonium chloride/acrylamide in an inverse microemulsion at high comonomer concentrations

The semicontinuous inverse microemulsion copolymerization of 80/20 wt % [2‐(acryloyloxy)ethyl]trimethylammonium chloride/acrylamide in an isoparaffin solvent at high comonomer concentrations (30–42 wt %) was studied with a mixture of nonionic surfactants (Crill 43 and Softanol 90) as the emulsifier and sodium metabisulfite as the initiator. The influence of the total comonomer concentration (TCC), emulsifier concentration (EC), hydrophilic–lipophilic balance (HLB), isopropyl alcohol (chain‐transfer agent) concentration (IPC), and crosslinking agent concentration (CAC) on the weight‐average molar mass (M_w), absolute viscosity (BV), and viscometric structuring index (VSI) of the obtained copolymers was analyzed. M_w and BV increased with TCC and HLB and decreased with EC. At the higher TCC, M_w decreased with IPC; meanwhile, at the lower TCC, M_w increased with IPC above 0.5 wt %. VSI increased with TCC, HLB, and IPC and decreased with EC. VSI increased dramatically with CAC, whereas BV showed a peak at the CAC of 10 ppm. In the absence of both chain‐transfer and crosslinking agents, M_w increased linearly with VSI, and this suggests that linear copolymers of very high M_w values cannot be obtained by inverse microemulsion copolymerization, at least for high TCCs. The results are explained in terms of both the collapsed state of the copolymer chains inside the latex particles and changes in the interface structure and composition. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of molecular structure on the rheological and processing behavior of polyethylene resins

The rheological and processing behavior (melt fracture performance) of linear lowdensity polyethylenes (LLDPEs) is studied as a function of both the weight average molecular weight (M_w) and its distribution (MWD). A number of LLDPE resins having different molecular characteristics were tested, with essentially one characteristic (M_w or MWD) changing at a time. The first series of resins consisted of nine samples having a wide range of polydispersities (3.3–12.7) and nearly constant M_w and short chain branching. The second series had six resins with varying M_w (51,000–110,000) but fixed MWD (about 4). The influence of M_w and MWD on the viscosity profiles, linear viscoelastic moduli as expressed by means of a discrete spectrum of relaxation times, extrudate swell, and melt fracture behavior for these resins is reported. Correlations between the molecular characteristics of the resins and their rheological and processing behavior are also reported. It is found that for a given molecular weight, the optimum melt fracture performance is obtained at a specific polydispersity value, and it is characterized by a minimum relaxation time for the resin defined in terms of recoverable shear.     

Absolute online monitoring of acrylic acid polymerization and the effect of salt and pH on reaction kinetics

Using recently introduced Automatic Continuous Online Monitoring of Polymerization reactions (ACOMP), the kinetics of acrylic acid polymerization was studied. ACOMP yields the absolute weight‐averaged mass (M_w), monomer conversion, and other quantities. As the initiator concentration increased, it was shown that the rate increased and the M_w decreased as in regular free‐radical polymerization. The effect of salt on acrylic acid polymerization in an aqueous solution was investigated. The polymerization rate and M_w both decreased with an increasing salt concentration. ACOMP molecular weights were also compared with size‐exclusion chromatography on aliquots periodically withdrawn during the reaction, and good agreement was found. The effect of the pH on the rate and the molecular weight was also investigated, and when the medium pH was changed from 2 to 5 with sodium hydroxide, the rate and M_w both decreased as the pH increased. Light‐scattering results of reaction end products in the reference solvent showed that molecules synthesized at higher pH were in a more expanded form. When equimolar sodium hydroxide was added to the acrylic acid (pH ? 5) and sodium acrylate formed, adding salt did not effect the reaction kinetics of the poly(sodium acrylate); its effect on the products was a relatively minor decrease of M_w. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1352–1359, 2004     

The reactive modification of polyethylene. I: The effect of low initiator concentrations on molecular properties

Commercial samples of high density, linear low density, and low density polyethylene were modified by injection of low concentrations of free radical initiator during extrusion. Molecular properties monitored included molecular weight distribution, degree of unsaturation, and branching. When the polyethylene teed to this reactive extrusion process had similar values of M_w, but varying polydispersity, degree of branching and degree of unsaturation, the magnitude of the change in molecular weight distribution was found to be in the following order: HDPE 1 > LDPE2 > LLDPE. In general, terminal vinyls enhanced molecular weight increase, and branching promoted degradation. However, for a second high density polyethylene sample with M_w = 154,000 (rather than the previous sample's M_w of 85,600), the change in molecular weight distribution was small and located at the lower molecular weight end. This work provided data for the kinetic model development detailed in Part II.     

Molecular weight and chain conformation of amylopectin from rice starch

By using laser light scattering (LS) and size exclusion chromatography combined LS, we have investigated the molecular weight and chain conformation of amylopectin from rice of India (II‐b), japonica (IJ‐b), and glutinous (IG‐b) in dimethyl sulfoxide (DMSO) solution. The weight‐average molecular weight (M_w) and radius of gyration (〈S²〉^½) of amylopectin were determined to be 4.06 × 10⁷ and 128.5 nm for India rice, 7.41 × 10⁷ and 169.6 nm for japonica rice, 2.72 × 10⁸ and 252.3 nm for glutinous rice, respectively. The 〈S²〉^½ values were much lower than that of normal polymers, indicating a small molecular volume of amylopectin, as a result of highly branched structure. Ignoring the difference of degree of branching, approximated dependences of 〈S²〉^½ and intrinsic viscosity ([η]) on M_w for amylopectin in DMSO at 25°C were estimated to be 〈S²〉^½ = 0.30M_w^0.35 (nm) and [η] = 0.331M_w^0.41 (mL g^?1) in the M_w range studied. Moreover, from the 〈S²〉^½ values of numberless fractions obtained from many experimental points in the SEC chromatogram detected with LS, the dependence of 〈S²〉^½ on M_w for the II‐b sample was estimated also to be 〈S²〉^½ = 0.34 M_w^0.347, coinciding with the above results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Determination of number-average and weight-average molecular weights of polymer sample from diffusion and sedimentation velocity measurements in theta solvent

Several methods to determine number-average molecular weight M_n and weight-average molecular weight M_w, of a polymer sample are proposed from diffusion and sedimentation velocity measurements at the θ point. According to these methods, M_n and M_w are determined from the diffusion constant vs. molecular weight relationship, and also from the equations of Svedberg and Flory–Mandelkern, using the 2nd-order and the –2nd-order diffusion constants. These methods have been applied to four samples of polydisperse polystyrene in the θ solvent, cyclohexane at 35°C. It was experimentally ascertained that M_n and M_w of each sample determined by the present methods were in good agreement with the results of column fractionation, light scattering, and calculated values from molecular weight distribution curve within experimental errors. It is concluded that the present methods are useful for determining M_n and M_w, since the reliabilities of M_n and M_w values, which are fundamental quantities of polymer characterization, can be raised by comparing the experimental data observed by conventional methods such as osmotic pressure, light scattering, and the Archibald method with those observed by the present methods.     

Solid‐state polymerization of poly(ethylene terephthalate): Effect of organoclay concentration

Poly(ethylene terephthalate) (PET)/Cloisite 30B (C30B) nanocomposites of different organoclay concentrations were prepared using a water‐assisted extrusion process. The reduction of the molecular weight (M_w) of the PET matrix, caused by hydrolysis during water‐assisted extrusion, was compensated by subsequent solid‐state polymerization (SSP). Viscometry, titration, rheological, and dynamic scanning calorimetry measurements were used to analyze the samples from SSP. The weight‐average molecular weight (M_w) of PET increased significantly through SSP. PET nanocomposites exhibited solid‐like rheological behavior, and the complex viscosity at high frequencies was scaled with the M_w of PET. The Maron–Pierce model was used to evaluate the M_w of PET in the nanocomposites before and after SSP. It was found that the extent and the rate of the SSP reaction in nanocomposites were lower than those for the neat PETs, due to the barrier effect of clay platelets. Consequently, the SSP rate of PET increased with decreasing particle size for the neat PET and PET nanocomposites. The effect of the M_w of PET on the crystallization temperature, crystallinity, and the half‐time, t_½, of nonisothermal crystallization was also investigated. With increasing M_w of PET, t_½ increased, whereas T_c and X_c decreased. POLYM. ENG. SCI., 54:2925–2937, 2014. © 2014 Society of Plastics Engineers     

Controlled/‘living’ radical polymerization of methyl methacrylate with p-TsCl/CuBr/BPY initiating system under microwave irradiation

Atom-transfer radical polymerization of methyl methacrylate under microwave irradiation (MI) using p-TsCl/CuBr/BPY as the initiating system was successfully carried out. The polymerization of methyl methacrylate under MI shows linear first-order rate plots, a linear increase in the number-average molecular weight with conversion and low polydispersities, 1.1 < M_w/M_n < 1.3. The influence of polymerization time, temperature and monomer/initiator ratio on the conversion, molecular weight and polymer distribution were studied using the MI process, and compared with that obtained by the corresponding conventional heating (CH) process. The MI process not only increases the rate of polymerization, but also narrows the polydispersity index of polymers. The apparent rate constant, , under MI is 6–8 times higher than that under CH with an identical initiating system and polymerization temperature. The effect of MI on the stereoregularity and T_g of PMMA were investigated by ¹³C NMR spectroscopy and DSC, respectively. Copyright © 2004 Society of Chemical Industry