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     

Demulsification efficiency of some novel styrene/maleic anhydride ester copolymers

Four demulsifiers were prepared in three steps. In the first step, styrene and maleic anhydride were copolymerized. In the second step, a long‐chain alcohol (dodecanol) was reacted with the prepared copolymer to form the monoesterified copolymer. In the final step, the resulting product was further esterified with poly(propylene oxide) (PPO)–poly(ethylene oxide) (PEO) block copolymers of different molecular weights (1.1, 2.5, 3.0, 5.0, and 8.0 × 10³) and different PPO/PEO ratios. The demulsification efficiency of these demulsifiers was investigated with the bottle test (Sany glass). The effects of the molecular weight and ratio of the PPO–PEO block copolymers on the demulsification efficiency were studied. The demulsification efficiency could be enhanced from 66% by an individual demulsifier to 100% by demulsifier blends. The surface‐active and thermodynamic properties of the prepared demulsifiers were measured at 25, 35, and 45°C. The kinematics of the demulsification process were photographed with a binocular microscope. The demulsification mechanism was found to occur in three stages, that is, adsorption and flocculation, coalescence, and channel formation followed by separation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and surface characterization of poly(methyl methacrylate)‐block‐polydimethylsiloxane copolymers from macroazoinitiator

Poly(methyl methyacrylate)‐block‐polydimethylsiloxane (PMMA‐b‐PDMS) copolymers with various compositions were synthesized with PDMS‐containing macroazoinitiator (MAI), which was first prepared by a facile one‐step method in our lab. Results from the characterizations of X‐ray photoelectron spectroscopy (XPS), contact angle measurements, and atomic force microscopy (AFM) showed that the copolymer films took on a gradient of composition and more PDMS segments enriched at the film surfaces, which then resulted in the low surface free energy and little microphase separation at the film surfaces. By contrast, transmission electron microscopy (TEM) analysis demonstrated that distinct microphase separation occurred in bulk. Slight crosslinking of the block copolymers led to much steady morphology and more distinct microphase separation, in particularly for copolymers with low content of PDMS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Properties of crosslinked blends of pellethene and multiblock polyurethane containing poly(ethylene oxide) for biomaterials

A series of multiblock polyurethanes, containing various poly(ethylene oxide) (PEO; number‐average molecular weight = 400–3400) contents (0–80 wt %) and prepared from hexamethylene diisocyanate/PEO/poly(dimethylsiloxane) diol/polybutadiene diol/1,4‐butanediol, were used as modifying additives (30 wt %) to improve the properties of biomedical‐grade Pellethene. Different molecular weights of PEO were used to keep poly(ethylene glycol) at a fixed molar content, if possible, although the PEO content, related to the PEO block length in the multiblock polyurethanes, was varied from 0 to 80 wt %. The hydrophilic PEO component was introduced through the addition of PEO‐containing polyurethanes and dicumyl peroxide as a crosslinking agent in a Pellethene matrix. As the PEO content (PEO block length) increased, the hydrogen‐bonding fraction of the crosslinked Pellethene/multiblock polyurethane blends increased, and this indicated an increase in the phase separation with an increase in the PEO content in the crosslinked Pellethene/multiblock polyurethane blends. According to electron spectroscopy for chemical analysis, the ratio of ether carbon to alkyl carbon in the crosslinked Pellethene/multiblock polyurethane blends increased remarkably with increasing PEO content. The water contact angle of the crosslinked Pellethene/multiblock polyurethane blend film surfaces decreased with increasing PEO content. The water absorption and mechanical properties (tensile modulus, strength, and elongation at break) of the crosslinked Pellethene/multiblock polyurethane blend films increased with increasing PEO content. The platelet adhesion on the crosslinked Pellethene/multiblock polyurethane blend film surfaces decreased significantly with increasing PEO content. These results suggest that crosslinked Pellethene/multiblock polyurethane blends containing the hydrophilic component PEO may have potential for biomaterials that come into direct contact with blood. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2348–2357, 2004     

Architecture of rod consisting of hyperbranched pendant chains‐coil block copolymers by ATRP approach

Atom transfer radical polymerization (ATRP) was applied to a novel synthesis of rod consisting of hyperbranched pendant chains‐coil block copolymers. The procedure included the following steps: (1) esterification reaction of poly(ethylene glycol) methyl ether (PEO) with 2‐bromoisobutyryl bromide (BIBB) yielded a PEO‐Br macroinitiator, (2) ATRP method of 2‐hydroxylethyl methacrylate (HEMA) using PEO‐Br provided PEO‐block‐poly(2‐hydroxyethyl methacrylate) (PHEMA) block copolymers, (3) esterification of PEO‐block‐PHEMA with BIBB yielded block‐type polyinitiator, and (4) ATRP of HEMA‐Br inimer using block‐type polyinitiator provided coil‐rod (consisting of hyperbranched pendant chains) block copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Compatibilization efficacy of poly(isoprene–butyl acrylate) block copolymers in natural/acrylic rubber blends

Poly(isoprene–butyl acrylate) block copolymers with a variety of molecular weights and compositions were prepared via a controlled free‐radical polymerization with an iniferter. Subsequently, the block copolymers were used as compatibilizers in natural/acrylic rubber blends. Scanning electron micrographs revealed a cocontinuous morphology in the case of the normal blends with a low natural rubber content (20 wt %), whereas the blends that contained more natural rubber showed a dispersed‐particle morphology. When the rubbers were blended with 5 wt % block copolymer, the particle size decreased, and the tensile strength of the resulted blends increased, regardless of the block copolymer characteristics. For the blend that exhibited a cocontinuous morphology, the most effective compatibilizer was the block copolymer with an average molecular weight of 22,000 g/mol, containing mainly (87%) polyisoprene block. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 921–927, 2003     

Polyimide‐polyurethane/urea block copolymers for highly sensitive humidity sensor with low hysteresis

Polyimide (PI)‐polyurethane‐urea (PU) block copolymers (PI‐PU75/25, PI‐PU50/50, and PI‐PU25/75) were prepared by reaction between anhydride‐terminated poly(amic acid) prepolymers with various number‐average degree of polymerization = 73/49/25) and isocyanate‐terminated urethane‐urea prepolymers with various (11/21/31) to obtain high performance capacitive humidity sensors. Pure PI and PU were also prepared to compare with PI‐PU copolymers. This study examined the effect of PU content on the water absorption %/water vapor transmission rate, thermal and mechanical properties and sensing properties of PI‐PU block copolymers. The thermal stability and mechanical properties of the copolymer decreased markedly with increasing PU content. The sensitivity of sensor increased sharply with increasing PU content from 0 to 25 wt %, and then increased a little. The hysteresis of sensor decreased sharply with increasing PU content up to 50 wt %, and then decreased a little. These results demonstrate the apparent upside of using two copolymers (PI‐PU75/25 and PI‐PU50/50) compared to using pure PI, in terms of sensor performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44973.     

Self‐assembled structures in blends of disordered and lamellar block copolymers: SAXS,SANS and TEM study

BACKGROUND: The phase behaviour of copolymers and their blends is of great interest due to the phase transitions, self‐assembly and formation of ordered structures. Phenomena associated with the microdomain morphology of parent copolymers and phase behaviour in blends of deuterated block copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA), i.e. (dPS‐block‐dPMMA)₁/(dPS‐block‐PMMA)₂, were investigated using small‐angle X‐ray scattering, small‐angle neutron scattering and transmission electron microscopy as a function of molecular weight, concentration of added copolymers and temperature. RESULTS: Binary blends of the diblock copolymers having different molecular weights and different original micromorphology (one copolymer was in a disordered state and the others were of lamellar phase) were prepared by a solution‐cast process. The blends were found to be completely miscible on the molecular level at all compositions, if their molecular weight ratio was smaller than about 5. The domain spacing D of the blends can be scaled with M_n by D ～ M_n^2/3 as predicted by a previously published postulate (originally suggested and proved for blends of lamellar polystyrene‐block‐polyisoprene copolymers). CONCLUSIONS: The criterion for forming a single‐domain morphology (molecularly mixed blend) taking into account the different solubilization of copolymer blocks has been applied to explain the changes in microdomain morphology during the self‐assembling process in two copolymer blends. Evidently the criterion, suggested originally for blends of lamellar polystyrene‐block‐polyisoprene copolymers, can be employed to a much broader range of block copolymer blends. Copyright © 2008 Society of Chemical Industry     

Compatibilization efficiency of styrene‐butadiene block copolymers as a function of their block number

Effect of block number in linear styrene‐butadiene (SB) block copolymers (BCs) on their compatibilization efficiency in blending polystyrene (PS) with polybutadiene (PB) was studied. Di‐, tri‐, or pentablocks of SB copolymers as well as their combinations were blended with the mentioned homopolymers; supramolecular structure determined by small angle X‐ray scattering method (SAXS), morphology using scanning electron microscopy (SEM) combined with image analysis (IA), and stress transfer characteristics of the blends were chosen as criteria of compatibilization efficiency of the copolymers used. It was proved that the addition of SB BCs led to remarkably finer phase structure and substantially higher toughness of PS/PB blends. Triblock copolymer showed to be the compatibilizer with higher efficiency than diblock, pentablock, and the di/triblock copolymer mixture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and thermal studies of block copolymers from NR and MDI‐based polyurethanes

Five series of block copolymers based on natural rubber and polyurethane were prepared from hydroxyl terminated liquid natural rubber (HTNR) and polyurethane (PU) formed by the reaction of diphenyl methane—4,4′—diisocyanate (MDI) with a chain extender diol, viz., ethylene glycol (EG)/propylene glycol (PG)/1,4‐butane diol (1,4‐BDO)/1,3‐butane diol (1,3‐BDO)/bisphenol A (BPA), by solution polymerization. Structural characterization of the block copolymers was done by infrared (IR) analysis. Thermal studies and kinetic analysis on thermal degradation of the block copolymers were undertaken with the view of characterizing them. Energy of activation and entropy change for the degradation were determined and a probable mechanism for the solid state degradation was suggested which corresponds to a three dimensional diffusion mechanism. DSC analysis has been used for the study of microphase separation in the block copolymers. Thermal transition of the hard segment significantly varies with the extender diol which highlights the effect of extender diol structure on the chain stiffening mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of filler content on the structure‐property behavior of poly(ethylene oxide) based polyurethaneurea‐silica nanocomposites

Poly(ethylene oxide) (PEO) based polyurethaneurea‐silica nanocomposites were prepared by solution blending and characterized by Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Differential Scanning Calorimetry and tensile testing. The colloidal silica nanoparticles with an average size of 50 nm were synthesized by modified Stöber method in isopropanol. Silica particles were incorporated into three cycloaliphatic polyurethaneurea (PUs) copolymers based on PEO oligomers with molecular weights of 2,000, 4,600, and 8,000 g/mol. Hard segment content of PUs was constant at 30% by weight. Silica content of the PU nanocomposites varied between 1 and 20% by weight. Soft segment (SS) glass transition and melting temperatures slightly increased with increasing filler content for all the copolymers. Degree of SS crystallinity first increased with 1% silica incorporation and subsequently decreased by further silica addition. Elastic modulus and tensile strengths of PU copolymers gradually increased with increasing amount of the silica filler. Elongation at break values gradually decreased in PEO‐2000 based PU copolymer with increasing silica content, whereas no significant change was observed in PUs based on PEO‐4600 and PEO‐8000. Enhancement in tensile properties of the materials was mainly attributed to the homogeneous distribution of silica filler in polymer matrices and strong polymer‐filler interactions. POLYM. ENG. SCI., 58:1097–1107, 2018. © 2017 Society of Plastics Engineers     

Synthesis of poly(fluorinated styrene)‐block‐poly(ethylene oxide) amphiphilic copolymers via atom transfer radical polymerization: potential application as paper coating materials

BACKGROUND: The surface of a substrate which comprises a fibrous material is brought into contact with a type of amphiphilic block copolymer which comprises hydrophilic/hydrophobic polymeric blocks. These amphiphilic copolymers have been synthesized by atom transfer radical polymerization (ATRP) technique. The atom transfer radical polymerization of poly(2,3,4,5,6‐pentafluorostyrene)‐block‐poly(ethylene oxide) (PFS‐b‐PEO) copolymers (di‐ and triblock structures) with various ranges of PEO molecular weights was initiated by a PEO chloro‐telechelic macroinitiator. The polymerization, carried out in bulk and catalysed by copper(I) chloride in the presence of 2,2′‐bipyridine ligand, led to A–B–A amphiphilic triblock and A–B amphiphilic diblock structures. RESULTS: With most of the macroinitiators, the living nature of the polymerizations led to block copolymers with narrow molecular weight distributions (1.09 < M_w/M_n < 1.33) and well‐controlled molecular structures. These block copolymers turned out to be water‐soluble through adjustment of the PEO block content (>90 wt%). Of all the block copolymers synthesized, PFS‐b‐PEO(10k)‐b‐PFS containing 10 wt% PFS was found to retard water absorption considerably. CONCLUSION: The printability of paper treated with the copolymers was evaluated with contact angle measurements and felt pen tests. The adsorption of such copolymers at the solid/liquid interface is relevant to the wetting and spreading of liquids on hydrophobic/hydrophilic surfaces. Copyright © 2009 Society of Chemical Industry     

Surface characteristics of water‐soluble cationic fluoro copolymers containing perfluoroalkyl,quaternized amino,and hydroxyl groups

Various water‐soluble cationic fluoro copolymers in quaternized form with perfluoroalkyl, amino, and hydroxyl groups were prepared by varying the contents of perfluoroalkyl ethyl acrylate (FA), 2‐(dimethylamino) ethyl methacrylate (DAMA), and 2‐hydroxyethyl methacrylate (HEMA). The solvent polymerization was carried out in acetone, with the subsequent addition of acetic acid to form a quaternized polymer. Polyurethanes films were prepared by curing aqueous solutions containing water‐soluble cationic fluoro copolymers and a blocked isocyanate at 190°C. The surface characteristics of the water‐soluble cationic fluoro copolymers and the polyurethanes were investigated on the basis of FA and DAMA contents. The contact angles for both water and methylene iodide (MI) on the cationic fluoro copolymer and the polyurethane increase steadily as FA content increases, and decrease gradually with increasing DAMA content. The contact angles on the polyurethane are slightly higher than those on the cationic fluoro copolymer. The cationic fluoro copolymer and the polyurethane with FA content of 40 wt % and DAMA content of <30 wt % show extremely low surface free energies of 13–15 dynes/cm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3702–3707, 2002     

Properties of polyurethane oligomeric blends versus high molecular weight block copolymers

Segmental compatibility has been investigated in both oligomeric polyurethane blends and polyurethane block copolymers. The block copolymers are formed by linking a hard segment, composed of three MDI and two butane diol units on average with various macroglycols. The monodisperse oligomeric hard segment, H₃, with its chain ends reacted with ethanol is used as the urethane component in blends with macroglycols. The macroglycols used in both the blend and block copolymer systems include polyethylene oxide (PEO), polypropylene oxide (PPO), polytetramethylene oxide (PTMO), and polybutadiene (PBD). Blends of H₃ and PEO form a eutectic at a weight ratio of $\text{≈20}\text{80}\text{(}\text{H}{}_3\text{/}\text{PEO}\text{)}$ with a T_m,e = 34°C. H₃ and PTMO blends also give rise to a eutectic composition at $\text{≈20}\text{80}\text{(}\text{H}{}_3\text{/}\text{PTMO}\text{)}$ but with a T_m,e = 10°C. Both PPO and PBD mix with H₃ to form a crystalline—amorphous blend. The miscibility of H₃ and the soft segments at the melting point of H₃ is in the order of PEO > PTMO > PPO > PBD. In the block copolymer systems, stress—strain and dynamic mechanical testing indicate that the block copolymerization of a hard segment with each soft segment results in a microphase separated elastomer as expected. The extent of phase separation increases in the order of PBD > PTMO > PPO > PEO which is coincident with the trend predicated by the application of Hilderbrand's solubility parameter concept. All the soft segments used occur in an amorphous phase in the block copolymers while PEO and PTMO crystallize in a blend with H₃. The differences between the properties of the blends and block copolymers suggest that the phase separation, segment crystallization and domain coalescence are substantially restricted by the urethane—polyol junction points.     

Enrichment of poly(butyl methacrylate) and its graft copolymer of polybutadiene on the surface of polypropylene blend

The enrichment and diffusion of poly (butyl methacrylate) (PBMA) and its graft copolymer of polybutadiene on the surface of polypropylene (PP) blends were investigated using attenuated total reflection infrared spectroscopy (ATR‐FTIR), contact angle measurements (CDA), and scanning electron microscopy (SEM). It has been found that the selective aggregation of the PBMA and its copolymers on the surface of blends is mainly affected by the content, molecular weight, and the segregated domains. Lower content and higher surface energy die are in favor of the enrichment of additives on the surface of PP. PBMA with higher molecular weight has lower diffusivity and bigger phase domains, which results in its lower enrichment on the surface of PP blend film. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of hydroxypropyl terminated polydimethylsiloxane‐polyurethane copolymers

Polyurethane (PU) block copolymers were synthesized using prepared hydroxypropyl terminated polydimethylsiloxane (HTPDMS MW 990) and polyether diols (N‐210) as soft segment with 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol. This low molecular weight polydimethylsiloxanes (PDMS) containing hydroxypropyl end‐groups displayed better compatibility with PU than common PDMS. In this article, we illustrate its synthesis routes and confirmed the proposed molecular structures using NMR and infrared radiation (IR). We varied the contents of HTPDMS and N‐210 in soft segments (HTPDMS—N‐210: 0 : 100, 20 : 80, 40 : 60, 60 : 40, 80 : 20, and 100 : 0) to synthesize a series of PDMS‐PU copolymer. IR spectroscopy showed the assignment characteristic groups of each peak in copolymers and confirmed that the desired HTPDMS‐PU copolymers have been prepared. The different thermal, dynamic mechanical and surface properties of the copolymers were compared by thermogravimetry, DMA, contact angle and solvent resistance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

MesoDyn modeling study of the phase morphologies of miktoarm poly(ethylene oxide)‐b‐poly(methyl methacrylate) copolymers doped with nanoparticles

Earlier studies have shown that poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blocks are compatible at 270 and 298 K, and that their Flory–Huggins interaction parameters have the same blending ratio dependence at both temperatures. At a much higher temperature (400 K), the behavior of PEO/PMMA blends is strikingly different as both components become incompatible, while the Flory–Huggins parameters are low. Here we investigate the effect of doping with nanoparticles on the degree of incompatibility of twelve miktoarm PEO‐b‐PMMA copolymers at 400 K. Since PEO tends to be semicrystalline and long chains aggregate easily, PEO‐rich and long‐chain copolymer blends feature the highest degree of incompatibility for all nanoparticle arrangements and present cubic phase morphologies. In addition, the largest nanoparticles can reinforce the microscopic phase separation of all PEO‐b‐PMMA copolymers. This shows that the main factor affecting the phase morphology is the size of the nanoparticles. Also, only the asymmetric Da3‐type PEO‐rich copolymers show a hexagonal cylindrical phase morphology, which illustrates the effect induced by the nanoparticles on the microscopic phase separation changes of the PEO‐b‐PMMA copolymers. These induced effects are also related to the composition and molecular architecture of the copolymers. © 2013 Society of Chemical Industry     

Synthesis and characterization of thermo‐ and pH‐sensitive block copolymers bearing a biotin group at the poly(ethylene oxide) chain end

A poly(ethylene oxide)‐block‐poly(dimethylamino ethyl methacrylate) block copolymer (PEO‐b‐PDMAEMA) bearing an amino moiety at the PEO chain end was synthesized by a one‐pot sequential oxyanionic polymerization of ethylene oxide (EO) and dimethylamino ethyl methacrylate (DMAEMA), followed by a coupling reaction between its PEO amino and a biotin derivative. The polymers were charac terized with ¹H NMR spectroscopy and gel permeation chromatography. Activated biotin, biotin‐NHS (N‐hydroxysuccinimide), was used to synthesize biotin‐PEO‐PDMAEMA. In aqueous media, the solubility of the copolymer was temperature‐ and pH‐sensitive. The particle size of the micelle formed from functionalized block copolymers was determined by dynamic light scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3552–3558, 2006     

Effects of tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) copolymers containing various amounts of acrylonitrile on the interfacial properties of polycarbonate and poly(styrene‐co‐acrylonitrile) blends

Tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) (TMPC‐block‐SAN) block copolymers containing various amounts of acrylonitrile (AN) were examined as compatibilizers for blends of polycarbonate (PC) with poly(styrene‐co‐acrylonitrile) (SAN) copolymers. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fibre retraction technique and an asymmetric double‐cantilever beam fracture test. Reduction in the average diameter of dispersed particles and effective improvement in the interfacial properties was observed by adding TMPC‐block‐SAN copolymers as compatibilizer of PC/SAN blend. TMPC‐block‐SAN copolymer was effective as a compatibilizer when the difference in the AN content of SAN copolymer and that of SAN block in TMPC‐block‐SAN copolymer was less than about 10 wt%. Copyright © 2004 Society of Chemical Industry     

Celite‐mediated linking of polyurethane block copolymers and the impact on the shape memory effect

Celite, a porous inorganic material with enormous surface area and hydroxyl groups on the surface, was used as a cross‐linker of polyurethane (PU) copolymer chains to improve its shape memory and mechanical properties. PU copolymers with different Celite contents were prepared and characterized by IR, DSC, and universal testing machine. The glass transition temperature of PU copolymers was maintained around 20°C independent of Celite content. The shape memory and mechanical properties were dependent on when Celite was added during the polymerization reaction. The reaction in which Celite was added at the middle stage of polymerization showed the best shape memory and mechanical properties. The best shape recovery of PU was found at 0.3 wt % Celite and increased to 97% even after the third cycle. Likewise, the shape retention also maintained a remarkable 86% after three cycles. The reasons underlining the high shape recovery and shape retention by adopting Celite as a cross‐linker are discussed in this article. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010