Poly(vinyl chloride)‐b‐poly(hydroxypropyl acrylate)‐b‐Poly(vinyl chloride): Understanding the synthesis of an amphiphilic PVC block copolymer on a pilot scale

The aim of this work was to develop an understanding of the major difficulties associated with the scale‐up of the technology for the synthesis of poly(vinyl chloride) (PVC) block copolymers that contain hydrophilic segments, thus providing important directions to be followed in order to produce such new materials on the industrial scale. The synthesis was carried out in a two‐step process. First, the macroinitiator α,ω‐di(iodo)poly(hydroxypropyl acrylate) was synthesized in an aqueous medium by (single electron transfer)/(degenerative chain transfer) living radical polymerization (SET‐DTRP) catalyzed by Na₂S₂O₄. The block copolymer was then prepared by SET‐DTRP of vinyl chloride (VC) from the iodine‐terminal active chain ends of the macroinitiator, thereby leading to the formation of the block copolymer poly(vinyl chloride)‐b‐poly(hydroxypropyl acrylate)‐b‐poly(vinyl chloride). This report covers important aspects related to the characterization of the block copolymer produced and to the identification of the major limitations that must be overcome in order to produce this new material on the industrial scale. The results clearly show the differences between the theoretical predictions and the block copolymer compositions obtained by using a suspension polymerization method, which is the most‐used polymerization process in the PVC industry. J. VINYL ADDIT. TECHNOL., 19:94–104, 2013. © 2013 Society of Plastics Engineers     

Processability and characterization of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) prepared by living radical polymerization of vinyl chloride. Comparison with a flexible commercial resin formulation prepared with PVC and dioctyl phthalate

This work reports the synthesis and processing of a new flexible material based on PVC produced by living radical polymerization. The synthesis was carried out in a two‐step process. In the first step the macroinitiator α, ω‐di(iodo)poly(butyl acrylate) [α, ω‐di(iodo)PBA] was synthesized in water by single electron transfer/degenerative chain transfer mediated living radical polymerization (SET‐DTLRP) catalyzed by Na₂S₂O₄. In the second step this macroinitiator was reinitiated by SET‐DTLRP of vinyl chloride (VC), thereby leading to the formation of the block copolymer poly(vinyl chloride)‐b‐poly(butyl acrylate)‐b‐poly(vinyl chloride) [PVC‐b‐PBA‐b‐PVC]. This new material was processed on a laboratory scale. The DMTA traces showed only a single glass transition temperature, thus indicating that no phase segregation was present. The copolymers were studied with regard to their processing, miscibility, and mechanical properties. The first comparison with commercial formulations made with PVC and dioctyl phthalate (DOP) is presented. J. VINYL ADDIT. TECHNOL., 12:156–165, 2006. © 2006 Society of Plastics Engineers     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Synthesis and characterization of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers with dibutylmagnesium as catalyst

Two series of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers were prepared by the ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) and dibutylmagnesium in 1,4‐dioxane solution at 70°C. The triblock structure and molecular weight of the copolymers were analyzed and confirmed by ¹H NMR, ¹³C NMR, FTIR, and gel permeation chromatography. The crystallization and thermal properties of the copolymers were investigated by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results illustrated that the crystallization and melting behaviors of the copolymers were depended on the copolymer composition and the relative length of each block in copolymers. Crystallization exothermal peaks (T_c) and melting endothermic peaks (T_m) of PEG block were significantly influenced by the relative length of PCL blocks, due to the hindrance of the lateral PCL blocks. With increasing of the length of PCL blocks, the diffraction and the melting peak of PEG block disappeared gradually in the WAXD patterns and DSC curves, respectively. In contrast, the crystallization of PCL blocks was not suppressed by the middle PEG block. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

AB,BAB and (AB)3 poly(ε‐caprolactone)‐based block copolymers with functionalized poly(meth)acrylate segments

Linear and star‐shaped poly(ε‐caprolactone) (PCL) block copolymers containing poly(meth)acrylate segments with glycidyl, 2‐(trimethylsilyloxy)ethyl and tert‐butyl pendant groups were synthesized using mono‐, di‐ and trifunctional PCL macroinitiators and appropriate (meth)acrylate monomers by controlled radical polymerization. The well‐defined structures with narrow molecular weight distributions indicate the coexistence of semi‐crystalline PCL and amorphous poly(meth)acrylic phases. The hydrophobic nature of the block copolymers can be easily converted to amphiphilic, which with biodegradable and biocompatible PCL segments are promising as polymeric carriers in drug delivery systems. © 2012 Society of Chemical Industry     

Deviation from the theoretical predictions in the synthesis of amphiphilic block copolymers in a wide range of compositions based on poly(vinyl chloride) by single electron transfer: Degenerative chain living radical polymerization in suspension medium

This work deals with the synthesis of different poly(vinyl chloride) (PVC) based block copolymers, containing poly(hydroxypropyl acrylate) segments having different compositions and molecular weights. These copolymers were synthesized via single electron transfer‐degenerative chain living radical polymerization. The block copolymers prepared showed deviations from the theoretical predictions in terms of molecular weight and polydispersity, which were ascribed to the heterogeneous nature of the reaction mixture. The technical problems addressed are important to the establishment of the required technological improvements for the industrial implementation. It has been shown that the control over the composition of the block copolymers is only achieved when the amount of vinyl chloride used in the second step of the polymerization was relatively high. The adhesion performance of these block copolymers in PVC‐wood flour composite formulations was studied by assessing the mechanical performance of such composites, when the copolymers were included in the composite formulations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of the novel block copolymer poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine) by the combination of coordination and controlled free‐radical polymerizations

A novel block copolymer, poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine), was synthesized with a bifunctional initiator strategy. Poly(ε‐caprolactone) prepolymer with a 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) end group (PCL_T) was first obtained by coordination polymerization, which showed a controlled mechanism in the process. By means of ultraviolet spectroscopy and electron spin resonance spectroscopy, the TEMPO moiety was determined to be intact in the polymerization. The copolymers were then obtained by the controlled radical polymerization of 4‐vinyl pyridine in the presence of PCL_T. The desired block copolymers were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, and NMR spectroscopy in detail. Also, the effects of the molecular weight and concentration of PCL_T on the copolymerization were investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2280–2285, 2004     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,characterization, and application of novel amphiphilic poly(D‐gluconamidoethyl methacrylate)‐b‐polyurethane‐b‐ poly(D‐gluconamidoethyl methacrylate) triblock copolymers

Novel amphiphilic ABA‐type poly(D ‐gluconamidoethyl methacrylate)‐b‐polyurethane‐b‐poly(D ‐gluconamidoethyl methacrylate) (PGAMA‐b‐PU‐b‐PGAMA) tri‐block copolymers were successfully synthesized via the combination of the step‐growth and copper‐catalyzed atom transfer radical polymerization (ATRP). Dihydroxy polyurethane (HO‐PU‐OH) was synthesized by the step‐growth polymerization of hexamethylene diisocyanate with poly(tetramethylene glycol). PGAMA‐b‐PU‐b‐PGAMA block copolymers were synthesized via copper‐catalyzed ATRP of GAMA in N, N‐dimethyl formamide at 20°C in the presence of 2, 2′‐bipyridyl using Br‐PU‐Br as macroinitiator and characterized by ¹H‐NMR spectroscopy and GPC. The resulting block copolymer forms spherical micelles in water as observed in TEM study, and also supported by ¹H NMR spectroscopy and light scattering. Miceller size increases with increase in hydrophilic PGAMA chain length as revealed by DLS study. The critical micellar concentration values of the resulting block copolymers increased with the increase of the chain length of the PGAMA block. Thermal properties of these block copolymers were studied by thermo‐gravimetric analysis, and differential scanning calorimetric study. Spherical Ag‐nanoparticles were successfully synthesized using these block copolymers as stabilizer. The dimension of Ag nanoparticle was tailored by altering the chain length of the hydrophilic block of the copolymer. A mechanism has been proposed for the formation of stable and regulated Ag nanoparticle using various chain length of hydrophilic PGAMA block of the tri‐block copolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of the synthesis conditions on the structural and thermal properties of poly(l‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l‐lactide)

The poly(l ‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l ‐lactide) block copolymers (PLLA‐b‐PEG‐b‐PLLA) were synthesized in a toluene solution by the ring‐opening polymerization of 3,6‐dimethyl‐1,4‐dioxan‐2,5‐dione (LLA) with PEG as a macroinitiator or by transterification from the homopolymers [polylactide and PEG]. Two polymerization conditions were adopted: method A, which used an equimolar catalyst/initiator molar ratio (1–5 wt %), and method B, which used a catalyst content commonly reported in the literature (<0.05 wt %). Method A was more efficient in producing copolymers with a higher yield and monomer conversion, whereas method B resulted in a mixture of the copolymer and homopolymers. The copolymers achieved high molar masses and even presenting similar global compositions, the molar mass distribution and thermal properties depends on the polymerization method. For instance, the suppression of the PEG block crystallization was more noticeable for copolymer A. An experimental design was used to qualify the influence of the catalyst and homopolymer amounts on the transreactions. The catalyst concentration was shown to be the most important factor. Therefore, the effectiveness of method A to produce copolymers was partly due to the transreactions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40419.     

Amphiphilic diblock copolymers poly(2‐hydroxyethylmethacrylate)‐b‐(N‐phenylmaleimide) and poly(2‐hydroxyethylmethacrylate)‐b‐(styrene) using the macroinitiator poly(HEMA)‐Cl by ATRP: Preparation,characterization, and thermal properties

In recent years, much attention has been given to the development of specialty polymers from useful materials. In this context, amphiphilic block copolymers were prepared by atom transfer radical polymerization (ATRP) of N‐phenylmaleimide (N‐PhMI) or styrene using a poly(2‐hydroxyethylmethacrylate)‐Cl macroinitiator/CuBr/bipyridine initiating system. The macroinitiator P(HEMA)‐Cl was directly prepared in toluene by reverse ATRP using BPO/FeCl₃ 6 H₂O/PPh₃ as initiating system. The microstructure of the block copolymers were characterized using FTIR, ¹H‐NMR, ¹³C‐NMR spectroscopic techniques and scanning electron microscopy (SEM). The thermal behavior was studied by differential scanning calorimetry (DSC), and thermogravimetry (TG). The theoretical number average molecular weight (M_n,th) was calculated from the feed capacity. The microphotographs of the film's surfaces show that the film's top surfaces were generally smooth. The TDT of the block copolymer P(HEMA)₈₀‐b‐P(N‐PhMI)₂₀ and P(HEMA)₉₀‐b‐P(St)₁₀ of about 290°C was also lower than that found for the macroi′nitiator poly(HEMA)‐Cl. The block copolymers exhibited only one T_g before thermal decomposition, which could be attributed to the low molar content of the N‐PhMI or St blocks respectively. This result also indicates that the phase behavior of the copolymers is predominately determined by the HEMA block. The curves reveal that the polymers show phase transition behavior of amorphous polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers by atom‐transfer radical polymerization

Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl₃ as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000     

Poly(vinyl chloride)–polyol (AB)x block copolymers: Synthesis,characterization, and mechanical properties

Poly(vinyl chloride)–polyol (AB)_x block copolymers have been prepared by the condensation polymerization of low-molecular-weight hydroxy-terminated poly(vinyl chlorides) (PVC) and diisocyanate-capped polyester and polyether diols. The difunctional poly(vinyl chlorides) were synthesized by ozonization of commercial resin followed by metal hydride reduction. The (AB)_x block copolymers, which contained 3000 or 4300 molecular weight PVC block sizes and 1000–2000 molecular weight polyol segments, had a wide range of mechanical properties, depending on overall polymer structure. Tensile strengths ranged from 7.8 to 31.5 MPa, elongations from 125% to 610% and torsional stiffness temperatures (T_f) from 25°C to ?22°C.     

Poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene by combination of ATRP and aminolysis processes

Block copolymers of very hydrophilic poly(N‐hydroxyethyl acrylamide) (PHEAA) with polystyrene (PS) were successfully synthesized by sequential atom transfer radical polymerization of ethyl acrylate (EA) and styrene monomers and subsequent aminolysis of the acrylic block with ethanolamine. Quantitative aminolysis of poly(ethyl acrylate) (PEA) block yielded poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene in well‐defined structures, as evidenced by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy techniques. Three copolymers with constant chain length of PHEAA (degree of polymerization: 80) and PS blocks with 21, 74, and 121 repeating units were prepared by this method. Among those, the block copolymer with 21 styrene repeating units showed excellent micellation behavior in water without phase inversion below 100°C, as inferred from dynamical light scattering, environmental scanning electron microscopy, and fluorescence measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers through atom transfer radical polymerization

Poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers have been synthesized successfully through atom transfer radical polymerization of methyl methacrylate using telechelic bromo‐terminated polyurethane/CuBr/N,N,N,N″,N″‐pentamethyldiethylenetriamine initiating system. As the time increases, the number‐average molecular weight increases linearly from 6400 to 37,000. This shows that the poly methyl methacrylate blocks were attached to polyurethane block. As the polymerization time increases, both conversion and molecular weight increased and the molecular weight increases linearly with increasing conversion. These results indicate that the formation of the tri‐block copolymers was through atom transfer radical polymerization mechanism. Proton nuclear magnetic resonance spectral results of the triblock copolymers show that the molar ratio between polyurethane and poly (methyl methacrylate) blocks is in the range of 1 : 16.3 to 1 : 449.4. Differential scanning calorimetry results show T_g of the soft segment at ?35°C and T_g of the hard segment at 75°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyamide4‐block‐poly(vinyl acetate) via a polyamide4 azo macromolecular initiator: Thermal and mechanical behavior,biodegradation, and morphology

A series of polyamide4‐block‐poly(vinyl acetate)s were synthesized by the radical polymerization of vinyl acetate (VAc) using an azo macromolecular initiator composed of polyamide4 (PA4). The block copolymers were investigated by examining their molecular weight, structure, thermal and mechanical properties, biodegradation, and the morphology of the film surface. The compositions and molecular weights (Mw) ranging from 46,800 to 163,700 g mol^?1 of the block copolymers varied linearly with increasing molar ratio of VAc to azo‐PA4. The block copolymers have high melting points of 248.2–262.5°C owing to PA4 blocks and heats of fusion, which were linearly dependent on the PA4 content. The mechanical properties of the block copolymers were monotonically dependent on the composition, i.e., increasing the PA4 content increased the tensile strength, whereas increasing the poly(vinyl acetate) content increased the elongation at break. The morphology of the block copolymers suggested the appearance of microphase separation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42466.     

Crystallization behavior of biodegradable amphiphilic poly(ethylene glycol)‐poly(L‐lactide) block copolymers

Poly(ethylene glycol)‐poly(L ‐lactide) diblock and triblock copolymers were prepared by ring‐opening polymerization of L ‐lactide with poly(ethylene glycol) methyl ether or with poly(ethylene glycol) in the presence of stannous octoate. Molecular weight, thermal properties, and crystalline structure of block copolymers were analyzed by ¹H‐NMR, FTIR, GPC, DSC, and wide‐angle X‐ray diffraction (WAXD). The composition of the block copolymer was found to be comparable to those of the reactants. Each block of the PEG–PLLA copolymer was phase separated at room temperature, as determined by DSC and WAXD. For the asymmetric block copolymers, the crystallization of one block influenced much the crystalline structure of the other block that was chemically connected to it. Time‐resolved WAXD analyses also showed the crystallization of the PLLA block became retarded due to the presence of the PEG block. According to the biodegradability test using the activated sludge, PEG–PLLA block copolymer degraded much faster than PLLA homopolymers of the same molecular weight. © 1999 John Wiley amp; Sons, Inc. J Appl Polym Sci 72: 341–348, 1999     

Solid and thermal properties of ABA‐type triblock copolymers designed using difunctional fluorine‐containing polyimide macroinitiators with methyl methacrylate

BACKGROUND: ABA‐type poly(methyl methacrylate) (PMMA) and fluorine‐containing polyimide triblock copolymers are potentially beneficial for electric materials. In the work reported here, triblock copolymers with various block lengths were prepared from fluorine‐containing difunctional polyimide macroinitiators and methyl methacrylate monomer through atom‐transfer radical polymerization. The effects of structure on their solid and thermal properties were studied. RESULTS: The weight ratios of the triblock copolymers derived using thermogravimetric analysis were shown to be almost identical to the ratios determined using ¹H NMR. The solid properties (film density and maximum d‐spacing value) and thermal properties (glass transition and thermal expansion) were shown to be strongly dependent on the weight ratios of both PMMA and polyimide components. Furthermore, a porous film, which showed a lower dielectric constant of 2.48 at 1 MHz, could be prepared by heating a triblock copolymer film to induce the thermal degradation of the PMMA component. CONCLUSION: The use of the polyimide macroinitiator was useful in the preparation of ABA‐type triblock copolymers to control each block length that influences the solid and thermal properties. Additionally, the triblock copolymers have great potential in preparing porous polyimides in the application of electric materials as interlayer insulation membranes of large‐scale integration. Copyright © 2009 Society of Chemical Industry     

Synthesis and characterization of Pst‐b‐PDMS‐b‐PSt copolymers by atom transfer radical polymerization

Polystyrene‐b‐poly(dimethylsiloxane)‐b‐polystyrene (Pst‐b‐PDMS‐b‐PSt) triblock copolymers were synthesized by atom transfer radical polymerization (ATRP). Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide, resulting in the PDMS macroinitiators for the ATRP of styrene (St). The latter procedure was carried out at 130°C in a phenyl ether solution with CuCl and 4, 4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as the catalyzing system. By using this technique, triblock copolymers consisting of a PDMS center block and polystyrene terminal blocks were synthesized. The polymerization was controllable; ATRP of St from those macroinitiators showed linear increases in M_n with conversion. The block copolymers were characterized with IR and ¹H‐NMR. The effects of molecular weight of macroinitiators, macroinitiator concentration, catalyst concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3764–3770, 2004     

Rheological behavior and thermal properties of poly(butyl acrylate‐co‐2‐ethylhexyl acrylate)‐grafted vinyl chloride resin

The rheological behavior and thermal properties of a poly(butyl acrylate‐co‐2‐ethylhexyl acrylate) [P(BA‐EHA)]‐grafted vinyl chloride (VC) composite resin [P(BA‐EHA)/poly(vinyl chloride) (PVC)] and its materials were investigated. The rheological behavior, thermal stability, and Vicat softening temperature (VST) of P(BA‐EHA)/PVC were measured with capillary rheometry, thermal analysis, and VST testing, respectively. The effects of the P(BA‐EHA) content and the polymerization temperature of grafted VC on the rheological behavior of the composite resin were examined. The weight loss of the composite resin and its extracted remainder via heating were analyzed. The influence of the content and crosslinking degree of P(BA‐EHA) and the polymerization temperature of the grafted VC on VST of the materials was determined. The results indicated the pseudoplastic‐flow nature of the composite resin. The flow property of the modified PVC resin was improved because of the incorporation of the acrylate polymer. The molecular weight of PVC greatly influenced the flow behavior and VST of the composite resin and its materials. The flowability of the composite resin markedly increased, and the VST of its materials decreased as the polymerization temperature of the grafted VC increased. The initial degradation temperature of the composite resin increased as the P(BA‐EHA) content increased. The VST of the samples was enhanced a little as the content of the crosslinking agent increased in P(BA‐EHA). As expected, the composite resin, with good impact resistance, had better heating stability and flowability than pure PVC, whereas the VST of the material decreased little with increasing P(BA‐EHA) content. Therefore, P(BA‐EHA)/PVC resins prepared by seeded emulsion polymerization have excellent potential for widespread applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 419–426, 2005