Functional Polymers. L Terpolymers of 10-Undecenoate Derivatives with Ethylene and Propylene

Terpolymers of 2,6-dimethylphenyl 10-undecenoate with ethylene and propylene have been synthesized. With titanium-based coordination initiator systems, a crystalline terpolymer was obtained which consists of blocks of ethylene and propylene, indicated by two distinct melting transitions. With vanadium-based systems, an amorphous ethylene/ propylene terpolymer was obtained. The crystalline terpolymer was hydrolyzed to the sodium carboxylate salt, which was acidified to give the polymeric carboxylic acid. All polymers were characterized by their infrared,¹H-, and ¹³C-NMR spectra, by differential scanning caiorim-etry, elemental analysis, and dilute-solution viscometry. In addition the polymeric sodium salt was characterized by wide-angle x-ray diffraction.     

Functional polymers. XLVIII. Polymerization of ω-alkenoate derivatives

Esters of ω-alkenoic acids have been homopolymerized with transition metal initiating systems. The key to the successful polymerization was the complexation of the monomer prior to its addition to the initiating system. Titanium trichloride, aluminum activated, was found to be best as the transition metal part of the initiator systems, with diethyl-, or better, diisobutylaluminum chloride as the reducing agents and n-hexane or toluene as the solvents. Best results for polymerizations were obtained with 2,6-dimethylphenyl esters of the functional α-olefin monomers; however, other phenyl esters also polymerized well. Attempts to polymerize methyl 10-undecenoate gave the corresponding polymer in only low yields. Polymers of the 2,6-dimethylphenyl esters, obtained in high molecular weight, were characterized. Polymers were also obtained from 2,6-dimethylphenyl 7-octenoate, but not from ω-alkenoates with less than three methylene units between the ester group and the terminal olefin group. Poly(2,6-dimethylphenyl 10-undecenoate) was hydrolyzed in an aqueous sodium hydroxide/1,4-dioxane solution to poly(sodium 10-undecenoate) that in turn was neutralized with acetic acid to poly(10-undecenoic acid).     

Co‐ and terpolymerization of ethylene,propylene, and higher α‐olefins with high propylene contents using metallocene catalysts

The copolymerization of propylene/ethylene and terpolymerization of propylene/ethylene/α‐olefins using long‐chain α‐olefins such as 1‐octene and 1‐decene have been carried out using EtInd₂ZrCl₂//methylaluminoxane. High concentrations of propylene and low concentrations of α‐olefins (near 2 mol % of the total olefin concentration in the liquid phase) were used. The effect of the ethylene concentration in copolymerizations of propylene/α‐olefins was studied at medium ethylene contents (12 and 40 mol % in the gas phase). The polymers were molecularly characterized by gel permeation chromatography‐multiangle laser light scattering, wide‐angle X‐ray scattering, Fourier transform infrared spectroscopy, and DSC analyses. The shorter α‐olefin studied (1‐octene) produced the highest improvement of activity in terpolymerization at 12 mol % ethylene in the gas phase. About 2 mol % of 1‐octene in the liquid phase increases the activity and decreases the molecular weight of terpolymers with respect to corresponding copolymers, whereas the mp is increased by almost 30 °C. The “termonomer effect” is less evident when higher amounts of ethylene are used. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1136–1148, 2001     

Copolymerization of ethylene or propylene with α‐olefins containing hydroxyl groups with zirconocene/methylaluminoxane catalyst

Copolymerization of olefins (ethylene and propylene) and 5‐hexen‐1‐ol pretreated with alkylaluminum was performed using [dimethysilylbis(9‐fluorenyl)]zirconium dichloride/methylaluminoxane as the catalyst. The copolymerization required extra addition of alkylaluminum to prevent deactivation of the catalyst when 5‐hexen‐1‐ol was pretreated with trimethylaluminum, whereas the triisobutylaluminum‐treated system did not require any addition of alkylaluminum. The molecular weight of the copolymer depended on the kind of alkylaluminum compound (masking reagent, additive, and cocatalyst). ¹³C NMR analysis proved that poly(ethylene‐co‐5‐hexen‐1‐ol) containing 50 mol % of 5‐hexen‐1‐ol acted as an alternating copolymer, whereas the poly(propylene‐co‐5‐hexen‐1‐ol) acted as a random copolymer. The surface property of the copolymers was simply evaluated by means of water drop contact angle measurement. It was found that the copolymers containing large amounts of 5‐hexen‐1‐ol units showed good hydrophilic properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 52–58, 2004     

Poly(alkylene oxide) ionomers. XI. Polymerization and copolymerization of methyl ω-epoxyundecanoate and characterization of the polymers

Methyl 10-undecenoate was epoxidized in nearly quantitative yield with m-chloroperoxy-benzoic acid to methyl 10,11-epoxyundecanoate. The functional epoxide monomer was polymerized by the reaction product of triethylaluminum/water/acetylacetone (1.0/0.5/1.0) to a high molecular weight elastomer having pendent carboxyl groups, and a molecular weight distribution near the most probable distribution. With the same initiator system, methyl 10,11-epoxyundecanoate was copolymerized with ethylene oxide, propylene oxide, 1-butene oxide, 1-hexene oxide, phenyl glycidyl ether, epichlorohydrin, and 4,4,4-trichloro-1-butene oxide. The copolymers were typically high in molecular weight, elastomeric, and had methyl 10,11-epoxyundecanoate incorporations similar to the initial feed ratio of comonomers. The new family of functional polymers were characterized by their infrared and NMR spectra, dilute solution viscosity and thermal transitions.     

Olefin copolymerization with metallocene catalysts. I. Comparison of catalysts

A number of metallocene/methylaluminoxane (MAO) catalysts have been compared for ethylene/propylene copolymerizations to find relationship between the polymerization activities, copolymer structures, and copolymerization reactivity ratio with the catalyst structures. Stereorigid racemic ethylene bis (indenyl) zirconium dichloride and the tetrahydro derivative exhibit very high activity of 10 ⁷ g (mol Zr h bar)^?1, giving copolymers having comonomer compositions about the same as the feed compositions, molecular weights increasing with the increase of ethylene in the feed, random incorporation of comonomers, and narrow molecular weight distribution indicative of a single catalytic species. Nonbridged bis (indenyl) zirconium behaved differently, favoring the incorporation of ethylene over propylene, producing copolymers whose molecular weight decreases with the increase of ethylene in the feed, broad molecular weight distribution, and a methanol soluble fraction. This catalyst system contains two or more active species. Simple methallocene catalysts have much lower polymerization activities. C_pTiCl₂/MAO produced copolymers with tendency toward alternation, whereas Cp₂HfCl₂/MAO gave copolymer containing short blocks of monomers.     

Synthesis of propylene-ethylene copolymers in liquid propylene using <Emphasis Type="Italic">ansa</Emphasis>-metallocenes of the <Emphasis Type="Italic">C</Emphasis><Subscript>1</Subscript> symmetry

The copolymerization of ethylene with propylene in the liquid propylene initiated by ansa-metallocenes of the C ₁ symmetry, rac-[1-(9-η⁵-fluorenyl)-2-(5,6-cyclopenta-2-methyl-1-η⁵-indenyl)ethane]zirconium dichloride and rac-[1-(9-η⁵-fluorenyl)-2-(5,6-cyclopenta-2-methyl-1-η⁵-indenyl)ethane]hafnium dichloride, activated by methylaluminoxane has been studied. Triisobutylaluminum has been used as a cocatalyst. The propylene-ethylene copolymers thus prepared contain 5–60 mol % ethylene units. The reactivity ratios have been measured. In the case of the zirconocene-based catalyst, the molecular mass of the copolymers decreases with an increase in the content of ethylene units. The reverse situation is observed in the case of the hafnocene-based catalytic system. The copolymers are characterized by the low T _g values (down to ?45°C). Incorporation of a small amount of ethylene units (5 mol %) results in a rise in the elastomeric behavior of the polymers.     

Synthesis and characterization of materials prepared via the copolymerization of ethylene with 1‐octadecene and norbornene using a [(π‐cyano‐nacnac)Cp] zirconium complex

[3‐Cyano‐2‐(2,6‐diisopropylphenyl)aminopent‐2‐en‐4‐(phenylimine)tris (pentafluorophenyl)borate](η⁵‐C₅H₅)ZrCl₂, [(B(C₆F₅)₃‐ NC‐nacnac)CpZrCl₂], precatalyst ( 2 ) can be treated with low concentrations of methylaluminoxane (MAO) to generate active sites capable of copolymerizing ethylene with 1‐octadecene or norbornene under mild conditions. A series of poly(ethylene‐co‐octadecene) and poly(ethylene‐co‐norbornene) copolymers were prepared, and their properties were characterized by NMR, differential scanning calorimetry, and mechanical analysis. The results show that this system produced poly(ethylene‐co‐octadecene) copolymers with a branching content of about 8 mol %. However, upon increasing the comonomer concentration, a drastic reduction in the M_n of the product is observed concomitant with an increase in comonomer incorporation. This leads to a gradual decrease in Young's modulus and stress at break, indicating an increase in the “softness” of the copolymer. In the case of copolymerizations of ethylene and norbornene, the catalytic system ( 2 /MAO) shows a substantial decrease in reactivity in the presence of norbornene and generates copolymer chains in which 5–10 mol % norbornene is in blocks. We also observe that ethylene norbornene copolymers exhibit a high degree of alternating insertions (close to 50%), as determined by NMR spectroscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

FTIR, 13C NMR,and GPC analysis of high‐propylene content co‐ and terpolymers with ethylene and higher α‐olefins synthesized with EtInd2ZrCl2/MAO

This article reports the results of propylene/α‐olefin copolymerization and propylene/ethylene/α‐olefin terpolymerization using low concentrations (less than 5 mol %) of long α‐olefins such as 1‐octene, 1‐decene, and 1‐dodecene. Kinetics data are presented and discussed. The highest activity was found with the longest α‐olefin studied (1‐dodecene). A possible explanation is proposed for this and other characteristics of the polymers obtained. The effect of low‐ethylene contents (4 mol % in the gas phase) on the copolymerization of propylene/α‐olefins was also examined. The polymers synthesized were characterized by ¹³C NMR, gel permeation chromatography, DSC, Fourier transform infrared spectroscopy, and wide‐angle X‐ray scattering. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2005–2018, 2001     

茂－茚锆金属络合物催化乙烯/1－己烯共聚和丙稀均聚研究

Complexes （R^1Cp）（R^2Ind）ZrCl2, the catalysts previously reported active for ethylene polymerization showed high activity in ethylene/1-hexene copolymerization and propylene polymerization in the presence of MAO. The content of 1-hexene in copolymers ranged from 1.2% to 3.2%. In propylene polymerization the complex 1 showed the highest activity, up to 1.2×10^6 g of polypropylene per mol of catalyst per hour. Based on the analysis of NMR spectral data, the relationships between complex structures and polymerization results were explored.     

Poly(ethylene terephthalate) copolymers containing 5‐nitroisophthalic units. II. Crystallization studies

The microstructure and crystallization behavior of a set of poly(ethylene terephthalate‐co‐5‐nitroisophthalate) copolymers (PETNI) containing 5‐nitroisophthalic units in the 10–50 mol % range were examined and compared to those of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐isophthalate) (PETI) copolymers. A ¹³C NMR analysis of PETNI copolymers in a trifluoroacetic acid solution indicates that they are random copolymers with average sequence lengths in accordance with ideal polycondensation statistics. Differential scanning calorimetry (DSC) studies show that PETNI containing 5‐nitroisophthalic units up to 20 mol % are able to crystallize and that crystallization takes place in these copolymers at much slower rates than in PET. Wide‐angle X‐ray diffraction from powder and fibers reveals that crystallizable PETNI adopts the same triclinic crystal structure as PET, with the nitroisophthalate units being excluded from crystallites. Fourier transform infrared in combination with cross‐polarization/magic‐angle spinning ¹³C NMR spectroscopy demonstrates the occurrence of a gauche–trans conversion encompassing the crystallization process. A correlation between DSC and spectroscopic data leads us to conclude that the content of trans conformer in the noncrystallized phase of PETNI is higher than in both PET and PETI copolymers and suggests that secondary crystallization in the homopolymer must proceed by a mechanism different than that in copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1553–1564, 2001     

Diels–Alder modification of poly(ethylene terephthalate‐co‐anthracene‐2,6‐carboxylate) with N‐substituted maleimides

Dimethyl 2,6‐anthracene dicarboxylate is used as a comonomer in the synthesis of functional copolymers that are subject to modification with Diels–Alder reactions. The formation of poly(ethylene terephthalate‐co‐2,6‐anthracenate), containing less than 20 mol % of the anthracene‐2,6‐dicarboxylate structural units, provides materials that are tractable and soluble. The anthracene units of the copolymers undergo Diels–Alder reactions with N‐substituted maleimides. The grafting of N‐alkylmaleimides affords soluble, hydrophobic polymers, whereas grafting with maleimide‐terminated poly(ethylene glycol) affords hydrophilic polymers. Because this reaction proceeds below the melting point of the copolymers, the procedure can be applied to thin films, whereby the surface properties are modified. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3256–3263, 2002     

Copolymerizations of propylene with functionalized long‐chain α‐olefins using group 4 organometallic catalysts and their membrane application

Introduction of functional groups into polyolefins has the potential of broadening their end use. An attractive method for preparing polyolefins containing functional groups is the copolymerization of the olefins with α‐olefins containing a functional group. Copolymerizations of propylene with 10‐undecen‐1‐ol, containing a hydroxyl group protected by either TIBA or TBDMSCl, 11‐chloro‐1‐undecene, 5‐bromopent‐1‐ene and N‐allyl‐2,2,2‐trifluoroacetamide were performed using three organometallic catalysts: the metallocene rac‐Et(Ind)₂ZrCl₂ and two new benzamidinate catalysts [3‐C₅H₄NC(NSiCH₃)₂]₂TiCl₂ and [(m‐OMe‐C₆H₄NC(NSiCH₃)₂]₂ZrCl₂. 10‐Undecene‐1‐ol protected “in situ” with TIBA and N‐(dec‐9‐enyl)‐2,2,2‐trifluoroacetamide gave copolymers with similar polar monomer incorporation percentages and molecular weights 17%; 28,900 g/mol for the protected 10‐undecene‐1‐ol, and 15%; 27,100 g/mol for N‐(dec‐9‐enyl)‐2,2,2‐trifluoroacetamide. 11‐Chloro‐1‐undecene gave copolymers with up to 22% incorporation for 0.12 M of the comonomer in the reaction feed. The obtained copolymers were characterized by NMR, DSC, and GPC. Membranes were prepared from two copolymers containing the hydroxyl groups (6 and 10%) and one copolymer containing chlorine groups (7%). The membranes prepared could be wetted in contrast to polypropylene membranes which do not contain functional groups. In addition, it was observed that for both type of membranes prepared from the different copolymers containing the hydroxyl groups, the flux was significantly greater than for the membrane prepared from the copolymer containing a chlorine groups. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Unconstrained geometry complexes: Ethylene/α‐olefin copolymerizations with a tetramethyldisilyl‐bridged Cp‐amido titanium complex

A new disilyl‐bridged complex, [(N‐tert‐butylamido)(3‐indenyl)tetramethyldisilyl]titanium dichloride ( 3 ), was synthesized and activated with methylaluminoxane (MAO) for propylene homopolymerization and ethylene/propylene and ethylene/1‐hexene copolymerizations. A polypropylene with a slight isotactic enrichment was obtained. The number of regioerrors present in the polypropylene was somewhat smaller than that found in most polypropylenes made from monosilyl‐bridged [(N‐tert‐butylamido)(3‐indenyl)dimethylsilyl]titanium dichloride. The regioerrors detected in the copolymers obtained from 3 /MAO were on the order of the amounts observed in polymers made with the monosilyl‐bridged constrained geometry catalysts. Ethylene copolymers of propylene and 1‐hexene had random sequence distributions and showed significant comonomer incorporation. Because of the presence of regioerrors, a modified method for determining the monomer composition and sequence distribution was developed from the direct measurement of the monomer content from the number of methylene and methine carbons per polymer chain, regardless of propylene inversion. An estimate of the error in the copolymerization reactivity ratio determination for regioirregular ethylene/α‐olefin copolymers was obtained by the calculation of the reactivity ratios from monomer dyad sequences, with consideration given to the contribution of major regioirregular sequences. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3840–3851, 2005     

New Linear and Star‐Shaped Thermogelling Poly([R]‐3‐hydroxybutyrate) Copolymers

The synthesis of multi‐arm poly([R]‐3‐hydroxybutyrate) (PHB)‐based triblock copolymers (poly([R]‐3‐hydroxybutyrate)‐b‐poly(N‐isopropylacrylamide)‐b‐[[poly(methyl ether methacrylate)‐g‐poly(ethylene glycol)]‐co‐[poly(methacrylate)‐g‐poly(propylene glycol)]], PHB‐b‐PNIPAAM‐b‐(PPEGMEMA‐co‐PPPGMA), and their subsequent self‐assembly into thermo‐responsive hydrogels is described. Atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide (NIPAAM) followed by poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) and poly(propylene glycol) methacrylate (PPGMA) was achieved from bromoesterified multi‐arm PHB macroinitiators. The composition of the resulting copolymers was investigated by ¹H and ¹³C J‐MOD NMR spectroscopy as well as size‐exclusion chromatography (SEC), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The copolymers featuring different architectures and distinct hydrophilic/hydrophobic contents were found to self‐assemble into thermo‐responsive gels in aqueous solution. Rheological studies indicated that the linear one‐arm PHB‐based copolymer tend to form a micellar solution, whereas the two‐ and four‐arm PHB‐based copolymers afforded gels with enhanced mechanical properties and solid‐like behavior. These investigations are the first to correlate the gelation properties to the arm number of a PHB‐based copolymer. All copolymers revealed a double thermo‐responsive behavior due to the NIPAAM and PPGMA blocks, thus allowing first the copolymer self‐assembly at room temperature, and then the delivery of a drug at body temperature (37 °C). The non‐significant toxic response of the gels, as assessed by the cell viability of the CCD‐112CoN human fibroblast cell line with different concentrations of the triblock copolymers ranging from 0.03 to 1 mg mL^?1, suggest that these PHB‐based thermo‐responsive gels are promising candidate biomaterials for drug‐delivery applications.     

Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25°C, a dose rate of 1 × 10⁶ rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene was nearly 1/2 over a wide range of the monomer compositions. The Mayo–Lewis method gave negative r₁ (FVA) and r₁ (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model.     

Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006     

Homo‐ and copolymerization of ethylene and norbornene with bis(β‐diketiminato) titanium complexes activated with methylaluminoxane

Homo‐ and copolymerization of ethylene and norbornene were investigated with bis(β‐diketiminato) titanium complexes [ArNC(CR₃)CHC(CR₃)NAr]₂TiCl₂ (R = F, Ar = 2,6‐diisopropylphenyl 2a; R = F, Ar = 2,6‐dimethylphenyl 2b ; R = H, Ar = 2,6‐diisopropylphenyl 2c ; R = H, Ar = 2,6‐dimethylphenyl 2d) in the presence of methylaluminoxane (MAO). The influence of steric and electric effects of complexes on catalytic activity was evaluated. With MAO as cocatalyst, complexes 2a–d are moderately active catalysts for ethylene polymerization producing high‐molecular weight polyethylenes bearing linear structures, but low active catalysts for norbornene polymerization. Moreover, 2a – d are also active ethylene–norbornene (E–N) copolymerization catalysts. The incorporation of norbornene in the E–N copolymer could be controlled by varying the charged norbornene. ¹³C NMR analyses showed the microstructures of the E–N copolymers were predominantly alternated and isolated norbornene units in copolymer, dyad, and triad sequences of norbornene were detected in the E–N copolymers with high incorporated content of norbornene. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 93–101, 2008     

C2‐symmetry dimethylated zirconocenes activated with triisobutyl aluminum as effective homogeneous catalysts for copolymerization of olefins

We investigated the catalytic performance of both bridged unsubstituted [rac‐EtInd₂ZrMe₂, rac‐Me₂SiInd₂ZrMe₂] and 2‐substituted [rac‐Et(2‐MeInd)₂ZrMe₂), rac‐Me₂Si(2‐MeInd)₂ZrMe₂] dimethylbisindenylzirconocenes activated with triisobutyl aluminum (TIBA) as a single activator in (a) homopolymerizations of ethylene and propylene, (b) copolymerization of ethylene with propylene and hexene‐1, and (c) copolymerization of propylene with hexene‐1 (at Al_TIBA/Zr = 100‐300 mol/mol). Unsubstituted catalysts were inactive in homopolymerizations of ethylene and propylene and copolymerization of propylene with hexene‐1 but exhibited high activity in copolymerizations of ethylene with propylene and hexene‐1. 2‐Substituted zirconocenes activated with TIBA were active in homopolymerizations of ethylene and propylene and exhibited high activity in copolymerization of ethylene with propylene and hexene‐1, and in copolymerization of propylene with hexene‐1. Comparative microstructural analysis of ethylene‐propylene copolymers prepared over rac‐Me₂SiInd₂ZrMe₂ activated with TIBA or Me₂NHPhB(C₆F₅)₄ has shown that the copolymers formed upon activation with TIBA are statistical in nature with some tendency to alternation, whereas those with borate activated system show a tendency to formation of comonomer blocks. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2934–2941, 2010     

Functionalization of polyethylene based on metallocene catalysis and its application to syntheses of new graft copolymers possessing polar polymer segments

The control of hydroxylated polyethylene (PE) structures was investigated in the copolymerization of ethylene with allyl alcohol or 10-undecen-1-ol with a specific metallocene, methylaluminoxane, and trialkyl aluminum catalyst system through changes in the copolymerization conditions. The incorporation of allyl alcohol into the PE backbones was controllable through changes in the trialkyl aluminum, leading to terminally hydroxylated PE or a copolymer possessing hydroxyalkyl side chains. The copolymerization of ethylene with 10-undecen-1-ol gave copolymers with hydroxyalkyl side chains of various contents with a variety of molecular weights through changes in the copolymerization conditions. The obtained copolymers were useful as macroinitiators that allowed polar polymer segments to grow on the PE backbones, leading to the creation of graft copolymers that possessed PE and polar polymer segments. In this way, polyethylene-g-poly(propylene glycol) (PE-g-PPG) and polyethylene-g-poly(ϵ-caprolactone) (PE-g-PCL) were synthesized. The ¹³C NMR analysis of PE-g-PPG suggested that all the hydroxyl groups were consumed for propylene oxide polymerization, and transmission electron microscopy demonstrated nanoorder phase separation and indistinct phase boundaries. ¹³C NMR and gel permeation chromatography analyses indicated the formation of PE-g-PCL, in which 36–80 mol % of the hydroxyl groups worked as initiators for ϵ-caprolactone polymerization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3657–3666, 2003