Polymer–leather composites. II. Kinetics of the deposition of selected acrylate monomers by polymerization into chrome-tanned cattlehide

Limited kinetic information on a convenient process for depositing polymer in 5-oz cattlehide is presented in this article. The work includes a systematic study of the total polymerization rate and of the derived rates of deposition into the fibrous matrix, of bound polymer formation, and of polymer production in the external aqueous phase (the float) for three acrylic monomers. The monomers used, with a persulfate–bisulfite redox initiating system at 27°C, were methyl methacrylate (MMA), n-butyl acrylate (BA) and a fixed mixture of n-butyl acrylate and methyl methacrylate (BA + MMA). The effects of the reaction variables on rate, as measured by their intensity exponents, were not in agreement with a rate expression proposed to describe grafting in homogeneous polymerization, nor were they wholly compatible with classical and modified Smith–Ewart theories for heterogeneous emulsion polymerization. The experimental behavior, however, was in harmony with self-nucleation in the aqueous phase. Exponential orders of dependence were initiator > 0.5 (MMA, 0.72; BA + MMA, 0.66); monomer, zero; surfactant, ～0.5. The approximately 0.6 order dependence (MMA, 0.9) on leather amount was shown to be largely apparent and to decline as total polymerization proceeded. Thus a dominant grafting reaction was not supported. In support of this conclusion, simple impregnation of the matrix with preformed emulsion polymer yielded the same amount of bound polymer as that formed in situ. It was concluded that monomer is initiated largely from active centers formed initially near fibers or fibrils to form embryo polymer particles, which join penetrating swollen polymer particles and become unstable. These nucleate a polymer front, containing occluded radicals, which grows by diffusion regulated transport of monomer to complete deposition.     

Polymer–leather composites. IV. Mechanical properties of selected acrylic polymer–leather composites

An extensive study was made of the mechanical properties of the polymer–leather composite materials reported in previous articles. Polymer was deposited into leather by both emulsion and bulk (or solution) polymerization. Either methyl methacrylate, n-butyl acrylate, or a fixed comonomer mixture of n-butyl acrylate and methyl methacrylate were used over the widest feasible range of composition. Tensile strengths, in analogy with many polymer-treated fibers, were generally smaller than untreated controls, but entensions to break remained fairly constant as composition changed. Polymer–leather composites prepared by both methods were rheologically similar when correlated against the volume fraction of the polymer used. Relative tensile and torsional moduli were greater than unity at small volume fractions of polymer, but higher compositions assumed more of the viscoelastic characteristics of the modifying polymer. The constancy of the glass transition temperature of the polymeric component as composition changed indicated poor domain interactions. However, residual porosity reduced low-temperature moduli anomalously. A modified Halpin–Tsai equation was proposed that qualitatively predicted moduli increase by incremental space filling as either fiber aggregation (from simple air drying of untreated controls) or polymer content increased. The simultaneous rheological dependence of polymer–fiber interactions in composites was also accounted for by the equation.     

Seeded emulsion terpolymerization of dimethyl meta-isopropenyl benzyl isocyanate (TMI®) with acrylic monomers

Dimethyl meta-isopropenyl benzyl isocyanate (TMI®) is a novel bifunctional monomer. It has a double bond and an isocyanate group. The seeded emulsion terpolymerization of TMI with the acrylic monomers, methyl methacrylate and n-butyl acrylate, has been studied. A copolymer of methyl methacrylate and n-butyl acrylate was used as the seed latex. In order to minimize the risk of hydrolysis of TMI, polymerizations were carried out at 40°C using redox initiators. No additional surfactant was added during the second-stage polymerization in order to avoid the nucleation of secondary particles. TMI was found to retard the polymerization kinetics. The effect of variables, such as the total number of particles, initiator concentration, and the monomer feed rate on polymerization kinetics, was investigated. The composition of the second-stage polymer could be controlled by running the polymerization under monomer-starved conditions. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 685–694, 1998     

Polymer–leather composites. III. Morphology and water absorptivities of selected acrylic polymer–leather composite materials

The morphology of composite materials made by polymerizing methyl methacrylate into chrome-tanned cattlehide was examined by both light and scanning electron microscopy. The composites were selected from a series previously prepared and characterized, and their kinetics were reported. Micrographs of the polymer phase of the composites, prepared by preferential removal of collageneous material with 6N hydrochloric acid, yielded negative replicas of the fiber conformations. These provided evidence in support of proposed mechanisms of polymer deposition for two different methods of composite preparation. One method involved emulsion polymerization of monomer into hydrated leather and the other, preferentially filling leather free space. Both light and scanning electron microscopy of all composites and replicas revealed poly(methyl methacrylate) deposited largely in coarse aggregates around individual fibers. In emulsion systems, fiber bundles expanded with continuous deposition. No difference was observed in the morphology of bound and deposited polymers. However, high magnification of bound-polymer replicas exposed polymer surrounding some fibril traces. Deposition of polymer in the fine structure of bulk or solution prepared composites was not found; instead, all free space was occupied. A theory specifying polymer location in previous publications of this series, and extended here to define replica parameters, was abundantly supported by measured physical properties. A dominant grafting mechanism was precluded because the large domains limited points of possible attachment. Water absorptivities of emulsion prepared composites and controls were identical when the data were corrected to neat leather, although the rates were slightly perturbed. In contrast, both rate and equilibrium absorption data of the bulk and solution composites were retarded by polymer presence.     

Thermal behavior of graft copolymers of cotton cellulose and acrylate monomers

Cotton cellulose yarn was grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate at various percentages of grafting. The effects of concentration of the initiator, concentration of the acid, and of temperature on grafting was studied and the mechanism discussed. The effect of reactivity of the monomer on the percentage graft-on is pointed out. Thermal behavior of natural and grafted cotton yarn was studied using dynamic thermogravimetry in air at a heating rate of 6°C/min up to a temperature of 500°C. The thermal stabilities of the samples grafted with various acrylate monomers to various percentages of grafting were computed from their primary thermograms by calculating the values of IDT, IPDT, and E^*. The results show that the thermal stability increases with increase in graft-on per cent, and the thermal stabilities of natural cotton and cotton grafted with different monomers are in the order ethyl > methyl > natural cellulose > methyl methacrylate > n-butyl acrylate.     

Bulk and emulsion copolymerizations of n-butyl acrylate and poly(methyl methacrylate) macromonomer

Bulk and emulsion copolymerizations of an ω-unsaturated poly(methyl methacrylate) (PMMA) macromonomer with n-butyl acrylate (n-BA) were investigated. The reactivity of PMMA macromonomer in bulk copolymerization with n-BA was found to be lower than that of methyl methacrylate monomer with n-BA. The incorporation of PMMA macromonomer into poly(butyl acrylate) (PBA) latex particles by miniemulsion copolymerization was proved by high performance liquid chromatography-silica adsorption spectroscopy. Dynamic mechanical studies showed that PMMA macromonomer was grafted to the PBA backbone, and the degree of grafting increased as the ratio of PMMA macromonomer to n-BA increased. Microphase separation of the PMMA macromonomer grafts was observed at higher ratio of macromonomer (higher or equal to 10% weight of macromonomer based on total polymer phase). The n-BA/PMMA macromonomer copolymer behaved completely differently from the physical blend of PBA and PMMA macromonomer particles of the same composition. © 1996 John Wiley & Sons, Inc.     

Modification of polyvinyl chloride-vinyl acetate latex by seed emulsion polymerization of acrylic monomers

Fundamental studies were carried out to modify the thermal properties of polyvinyl chloride (PVC)-based latices. General features of composite PVC-vinyl acetate (VAc) copolymer latices synthesized from the seed emulsion polymerization of acrylic monomers are reported, in particular, the observation of particle morphology and the measurements of minimum film formation temperature (MFT) and DSC spectra. Acrylic monomers used as modifiers were methyl methacrylate (MMA), n-butyl methacrylate (BMA), methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (nBA), and MMA-nBA 75:25,50:50 and 25:75 wt%. Styrene whose polymer is incompatible with PVC-VAc was used as a counterpart of compatible PMMA. Compatibility between seed and modifier polymer and the mode of operation, either batch (flooded and pre-swollen) or semi-batch (starved and no swelling), induced morphology differences, and consequently variations of thermal properties.     

Graft polymerization of methyl methacrylate onto short leather fibers

Summary In this work, the graft polymerization of methyl methacrylate (MMA) monomer onto short leather fibers (SLF) was investigated as a function of the monomer/leather fiber ratio. This chemical modification was made by aqueous emulsion polymerization initiated by a redox system. The effect of' the monomer concentration on the grafting parameters (deposited and grafted polymer, as well as grafting efficiency) were determined. Composites formulated with SLF without chemical modification have showed lower tensile and impact properties in comparison with composites formulated with treated fibers. However, the elongation at break values for both systems remained similar as the MMA content changed. The morphology of SLF grafted with MMA was examined by both optical light microscopy (OLM) and scanning electron microscopy (SEM). Micrographs have shown polymer deposition on individual fibers and bundles of SLF. They have also revealed that PMMA may interpenetrate the SLF network and be deposited in large and coarse aggregates around individual fibers, but without occupation of the free space in the fiber net. Received: 1 October 1998/Revised version: 25 January 1999/Accepted: 25 January 1999     

Production of leather‐like composites using chemically modified short leather fibers. I: Chemical modification by emulsion polymerization

In order to evaluate the possible use of short leather fibers to produce leather‐like composites, five kilograms of fibers (extracted from leather wastes) were modified by in situ emulsion polymerization of methyl methacrylate (MMA). This treatment was performed in order to increase the compatibility of leather fibers with several commodity polymers used in the shoe and furrier industries. The chemical modification was carried out by aqueous emulsion polymerization initiated by a redox system (potassium persulfate and sodium metabisulfite). The effects of the monomer and redox initiator content as well as the reaction temperature were evaluated. The modified short leather fibers were characterized by instrumental techniques such as Infrared Spectroscopy (IR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), X‐ray Diffraction and Scanning Electronic Microscopy (SEM). The results show that the polymer is formed on the exterior of fibers (deposited fraction) as well as in the interior (by grafting or forming interpenetrated networks). The treatment significantly improves the thermal stability of fibers. It also reduces their water adsorption capacity, as a coating of PMMA is produced over the leather surface, as microscopic analysis has revealed. The last characteristic could be an advantage in certain applications.     

Emulsion terpolymerization of dimethyl meta-isopropenyl benzyl isocyanate (TMI®) with acrylic monomers: Process development and kinetics

Dimethyl meta-isopropenyl benzyl isocyanate (TMI®) is a bifunctional monomer possessing a double bond and an isocyanate group. Emulsion terpolymerization of TMI with the acrylic monomers, methyl methacrylate and n-butyl acrylate, was studied. Polymerizations were carried out at 40°C using a redox initiator system in order to minimize the extent of hydrolysis of the isocyanate in the aqueous emulsion environment. The kinetics of the polymerization reaction were investigated. The polymerization rate was found to decrease with increasing TMI concentration. The effects of several preparative variables such as the monomer, surfactant, and initiator concentration on the polymerization kinetics was studied. Several semicontinuous polymerization processes were developed in order to enhance the incorporation of TMI at appreciable rates. These processes also allow us to control the polymer composition, latex particle size, and the locus of isocyanate groups in the latex particle. Process variables such as the mode of initiator addition (batch versus semicontinuous) were found to greatly influence the polymerization behavior. © 1996 John Wiley & Sons, Inc.     

A comprehensive kinetic model for high‐temperature free radical production of styrene/methacrylate/acrylate resins

n‐Butyl methacrylate/styrene/n‐butyl acrylate (BMA/ST/BA) high‐temperature starved‐feed solution semibatch copolymerization and terpolymerization experiments with varying monomer feed composition, final polymer content, monomer feed time, and reaction temperature were carried out. A comprehensive mechanistic terpolymerization model implemented in PREDICI includes methacrylate depropagation, acrylate backbiting, chain scission, and macromonomer propagation, as well as penultimate chain‐growth and termination kinetics. The generality of the model was verified by comparison with terpolymerization data sets from two laboratories that demonstrate the impact of high‐temperature secondary reactions on polymerization rate and polymer molecular weight. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Synthesis of well‐defined,functionalized polymer latex particles through semicontinuous emulsion polymerization processes

The design of a semicontinuous emulsion polymerization process, primarily based on theoretical calculations, has been carried out with the objective of achieving overall independent control over the latex particle size, the monodispersity in the particle size distribution, the homogeneous copolymer composition, the concentration of functional groups (e.g., carboxyl groups), and the glass‐transition temperature with n‐butyl methacrylate/n‐butyl acrylate/methacrylic acid as a model system. The surfactant coverage on the latex particles is very important for maintaining a constant particle number throughout the feed process, and this results in the formation of monodisperse latex particles. A model has been set up to calculate the surfactant coverage from the monomer feed rate, surfactant feed rate, desired solid content, and particle size. This model also leads to an equation correlating the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture. This equation can be used to determine the maximum polymerization rate, only below or at which monomer‐starved conditions can be achieved. The maximum polymerization rate provides guidance for selecting the monomer feed rate in the semicontinuous emulsion polymerization process. The glass‐transition temperature of the resulting carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) copolymer can be adjusted through variations in the compositions of the copolymers with the linear Pochan equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 30–41, 2003     

Study on the influence factors of the stability during preparation of high-solid content P(MMA/BA/AA) latex. Part I: re-nucleation and percent coagulum

Using large-sized and mono-dispersed seeded latex as medium plus a semi-continuous monomer-feeding technology was an effective method for preparing high-solid content (HSC) latex. A series of runs indicated that the influence of key factors, such as surfactant, monomer composition, seed particle size, reaction temperature, and feeding rate were the most sensitive issues in maintaining the stability during preparation of HSC Poly (methyl methacrylate/n-butyl acrylate/acrylic acid) [P(MMA/BA/AA)] latex. It was also shown that the effect of these factors on the coagulum content played an important role in preparation process. In addition, the amount of gel content was more related to re-nucleation and particle size distribution (PSD) control. And the results seemed to be more different from that of produced in a low disperse phase system by conventional semi-continuous emulsion polymerization.     

Graft polymerization of some vinyl monomers onto acrylic rubber. I. Chain transfer and grafting reaction

The grafting reactions of styrene (St), methyl methacrylate (MMA), and vinyl acetate (VAc) were investigated in the presence of n-butyl acrylate–acrylonitrile copolymer. Results showed that the nature of monomer and initiator were the major factors influencing the grafting activity. The grafting efficiency was 0.87 for St, 0.26 for MMA, and 0.18 for VAc under the most favorable conditions. Acrylic rubber reduced the rate of polymerization, and the retarding effect increased in the order St, MMA, VAc. The chain transfer constants for acrylic rubber were evaluated to be 4.8 × 10^?4 for St, 1.27 × 10^?3 for MMA, and 1.45 × 10^?3 for VAc. The rate of polymerization and the grafting efficiency decreased with increasing acrylonitrile content in acrylic rubber, while the chain transfer constant of St for acrylic rubber remained practically unchanged.     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. II. Chemical Structure of Grafted Power Feed Polymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through a non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. With the increase of PVA, grafting was also increased. Feeding method did not affect grafting nor grafting efficiency to a great extent. However, the amount of initiator had a negative correlation against grafting or grafting efficiency. From NMR spectroscopy, it was known that n-butyl acrylate monomer grafted onto PVA rather than copolymerized with styrene monomer. In order to increase the cohesive strengths of each phase, grafting was introduced to the power feed polymerization. In these cases, the chemical structure of grafted power feed polymer was investigated.     

Preparation and characterization of poly(styrene-co-butyl acrylate)-encapsulated single-walled carbon nanotubes under ultrasonic irradiation

Polymeric composite materials filled with single-walled carbon nanotubes (SWNTs) have attracted much attention, but successful applications of such composites require uniform dispersion of SWNTs in the polymeric matrix and the strong SWNTs-polymer interface interaction. In this paper, chemical modification combined with ultrasonically initiated in situ polymerization was successfully employed to prepare poly(styrene-co-butyl acrylate)/single-walled carbon nanotubes composites [P(St-BA)/SWNTs]. The whole procedure contained two steps: in the first step, 3-(trimethoxy)-propylmethacrylate-silane (silane-coupling agent, KH570), a kind of polymerizable vinyl monomer, was grafted onto the surface of SWNTs, forming KH570-g-SWNTs by reacting KH570 with hydroxyl groups on the surface of SWNTs, which was proved by combination of FTIR and XPS results. Due to the presence of polymerizable KH570 on the surface of SWNTs, this provides a basis for the next stage of polymerization to prepare polymer-encapsulated SWNTs composites. In the second step, an ultrasonically initiated in situ emulsion polymerization of monomer styrene (St) and n-butyl acrylate (BA) proceeded in the presence of KH570-g-SWNTs. Consequently, P(St-BA)/SWNTs composite emulsion was obtained. TEM confirmed that SWNTs were coated with the obtained polymer. FTIR and XPS further showed that even after 72 h of soxhlet extraction with boiling toluene, there were still unextracted polymers in P(St-BA)/SWNTs composite, indicating strong interaction between the polymer and carbon nanotubes. Finally, a mechanism for formation of polymer-encapsulated SWNTs through ultrasonically initiated in situ emulsion polymerization was proposed. This study could provide a new way to resolve the problems of the dispersion, stabilization, and compositing of SWNTs with polymer matrix and prepare polymer/SWNTs composites.     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. II. Chemical Structure of Grafted Power Feed Polymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through a non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. With the increase of PVA, grafting was also increased. Feeding method did not affect grafting nor grafting efficiency to a great extent. However, the amount of initiator had a negative correlation against grafting or grafting efficiency. From NMR spectroscopy, it was known that n-butyl acrylate monomer grafted onto PVA rather than copolymerized with styrene monomer. In order to increase the cohesive strengths of each phase, grafting was introduced to the power feed polymerization. In these cases, the chemical structure of grafted power feed polymer was investigated.     

Study on the Copolymerization Kinetics of 8-Quinolinyl Methacrylate with Methyl Methacrylate,n-Butyl Methacrylate and Styrene

Abstract

The 8-quinolinyl methacrylate (8-QMA) monomer was prepared and characterized by the conventional methods of analysis. The 8-QMA monomer was copolymerized with methyl methacrylate (MMA), n-butyl methacrylate (BMA) and styrene under different monomer feed ratio using azobisisobutyronitrilic (AIBN) as an initiator by solution copolymerization. The polymerization reaction was allowed to proceed only upto sim; 10%. The composition of the resulting copolymers was determined by UV-visible spectrophotometry and reactivity ratio for each monomer pair was calculated. The relative reactivity of the monomers was discussed on the basis of the size of alkyl group in methacrylates and effect of resonance on the stability of the styryl radicals during the copolymerization.     

Block copolymers obtained by free radical mechanism. II. Butyl acrylate and methyl methacrylate

Block copolymers were synthesized using methyl methacrylate and butyl acrylate as the monomers and a multifunctional initiator, di-t-butyl 4,4'-azobis(4-cyanoperoxyvalerate). The polymerizations for the formation of the block copolymers were carried out in two stages. First the poly(methyl methacrylate) polymeric initiator was synthesized and isolated. In the second stage, the thermallyactivated azo group in the polymer backbone initiated the polymerization of butyl acrylate. Upon termination by combination a tri-block results. Selective solvent fractionation was used to separate the block from the homopolymers.     

Seeded emulsion polymerization of n-butyl acrylate utilizing miniemulsions

Nucleation of polymer particles in the seeded emulsion polymerization of n-butyl acrylate (BuA) was studied through experiments designed to control the amount of new particles formed. The results show that for the batch and semicontinuous seeded polymerization of BuA, a small amount of new particles was formed in the system in which the monomer was added neat, whereas a singificant amount of new particles was formed when the monomer was added as a miniemulsion. This suggests that new particles formed in the miniemulsion process were from nucleation of the monomer droplets. These experiments also showed that monomer-droplet nucleation decreased with increasing seed concentration in the reactor. For the seeded semicontinuous polymerizations, monomer-droplet nucleation decreases with decreasing BuA miniemulsion feed rate. The results also show that monomerdroplet nucleation takes place whenever miniemulsion droplets exist in the reactor. This study suggests that miniemulsions can be used to control the particle size distribution of a polymer latex system.