Synthesis,characterization and micellization of heterograft copolymers based on phosphoester functionalized macromonomers via “grafting through” method

Novel amphiphilic heterograft copolymers consisting of phosphoester functionalized PEG (phosPEG) and PCL (phosPCL) were synthesized by the ring‐opening polymerization via “grafting through” method. The heterograft structure and thermal properties of these copolymers with various compositions were characterized by ¹H‐NMR, ³¹P NMR, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) in detail. These amphiphilic copolymers could self‐assemble into micellar structures in aqueous solution, and their critical micellization concentrations (CMC) were determined to be 0.69–1.25 mg/L by fluorescence technique. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements show that these heterograft copolymer micelles are spherical in shape with the particle size ranging from 20 to 60 nm, which has potential in biomedical application. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

“Click” Polymer‐Supported Palladium Nanoparticles as Highly Efficient Catalysts for Olefin Hydrogenation and Suzuki Coupling Reactions under Ambient Conditions

Complexation of palladium(II) acetate [Pd(OAc)₂] or dipotassium tetrachloropalladate [K₂PdCl₄] to “click” polymers functionalized with phenyl, ferrocenyl and sodium sulfonate groups gave polymeric palladium(II)‐triazolyl complexes that were reduced to “click” polymer‐stabilized palladium nanoparticles (PdNPs). Transmission electron microscopy (TEM) showed that reduction using sodium borohydride (NaBH₄) produced PdNPs in the 1–3 nm range of diameters depending on the nature of the functional group, whereas slow reduction using methanol yielded PdNPs in the 22–25 nm range. The most active of these PdNPs (0.01% mol Pd), stabilized by poly(ferrocenyltriazolylmethyl)styrene, catalyzed the hydrogenation of styrene at 25 °C and 1 atm hydrogen, with turnover numbers (TONs) of 200,000. When stabilized by the water‐soluble poly(sodium sulfonate‐triazolylmethyl)styrene, the PdNPs (0.01% mol Pd) catalyze the Suzuki–Miyaura coupling between iodobenzene (PhI) and phenylboronic acid [PhB(OH)₂] in water/ethanol (H₂O/EtOH) at 25 °C with TONs of 8,200. This high catalytic activity is comparable to that obtained with “click” dendrimer‐stabilized PdNPs under ambient conditions.     

Synthesis of poly(epichlorohydrin‐g‐methyl methacrylate) and poly(epichlorohydrin‐g‐styrene) graft copolymers by a combination of cationic and photopolymerization methods

Poly(epichlorohydrin‐g‐styrene) and poly (epichlorohydrin‐g‐methyl methacrylate) graft copolymers were synthesized by a combination of cationic and photoinitiated free‐radical polymerization. For this purpose, first, epichlorohydrin was polymerized with tetrafluoroboric acid (HBF₄) via a cationic ring‐opening mechanism, and, then, polyepichlorohydrin (PECH) was reacted ethyl‐hydroxymethyl dithio sodium carbamate to obtain a macrophotoinitiator. PECH, possessing photolabile thiuram disulfide groups, was used in the photoinduced polymerization of styrene or methyl methacrylate to yield the graft copolymers. The graft copolymers were characterized by ¹H‐NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyethylene‐block‐poly(ε‐caprolactone) diblock copolymers: synthesis and compatibility

A strategy is introduced for the synthesis of polyethylene‐block‐poly(ε‐caprolactone) block copolymers by a combination of coordination polymerization and ring‐opening polymerization. First, end‐hydroxylated polyethylene (PE‐OH) was prepared with a one‐step process through ethylene/3‐buten‐1‐ol copolymerization catalyzed by a vanadium(III) complex bearing a bidentate [N,O] ligand ([PhN?C(CH₃)CHC(Ph)O]VCl₂(THF)₂). The PE‐OH was then used as macroinitiator for ring‐opening polymerization of ε‐caprolactone, leading to the desired nonpolar/polar diblock copolymers. The block structure was confirmed by spectral analysis using ¹H NMR, gel permeation chromatography and differential scanning calorimetry. The unusual topologies of the model copolymers will establish a fundamental understanding for structure–property correlations, e.g. compatibilization, of polymer blends and surface and interface modification of other polymers. © 2014 Society of Chemical Industry     

Aliphatic–aromatic poly(butylene carbonate‐co‐terephthalate) random copolymers: Synthesis,cocrystallization, and composition‐dependent properties

A series of aliphatic–aromatic poly(carbonate‐co‐ester)s poly(butylene carbonate‐co‐terephthalate)s (PBCTs), with weight‐average molecular weight of 113,000 to 146,000 g/mol, were synthesized from dimethyl carbonate, dimethyl terephthalate, and 1,4‐butanediol via a two‐step polycondensation process using tetrabutyl titanate as the catalyst. The PBCTs, being statistically random copolymers, show a single T_g over the entire composition range. The thermal stability of PBCTs strongly depends on the molar composition. Melting temperatures vary from 113 to 213°C for copolymers with butylene terephthalate (BT) unit content higher than 40 mol %. The copolymers have a eutectic melting point when about 10 mol % BT units are included. Crystal lattice structure shifts from the poly(butylene carbonate) to the poly(butylene terephthalate) type crystal phase with increasing BT unit content. DSC and WAXD results indicate that the PBCT copolymers show isodimorphic cocrystallization. The tensile modulus and strength decrease first and then increase according to copolymer composition. The enzymatic degradation of the PBCT copolymers was also studied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41952.     

Synthesis and characterization of ABA triblock and novel multiblock copolymers from ethylene glycol,L‐lactide,and ϵ‐caprolactone

Three types of copolymers were synthesized and characterized. First, triblock ABA copolymers [where A is a homopolymer of ?‐caprolactone and B is poly(ethylene glycol)] were prepared by the ring‐opening polymerization of poly(ethylene glycol) with ?‐caprolactone in the presence of stannous octoate (Sn(Oct)₂). The spectral, thermal, and mechanical properties of one sample of these copolymers were studied, and it was discovered that these types of copolymers were more hydrophilic, possessed lower melting points, and had superior mechanical properties (greater toughness) than poly(?‐caprolactone). Second, triblock ABA copolymers [where A is a homopolymer of L ‐lactide and B is poly(ethylene glycol)] were prepared by the ring‐opening polymerization of poly(ethylene glycol) with L ‐lactide in the presence of Sn(Oct)₂. The mechanical properties of these copolymers were studied, and it was found that they were tougher and softer than poly(L ‐lactide). Third, novel ABA triblock copolymers [where A is a copolymer of ?‐caprolactone and L ‐lactide and B is poly(ethylene glycol)] were prepared, and ¹H‐NMR and ¹³C‐NMR spectra of these copolymers indicated a microblock structure for the two end blocks. The stress–strain behavior revealed low yields and high toughness for these copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2072–2081, 2002     

Synthesis and characterization of well‐defined random and block copolymers of ε‐caprolactone with l‐lactide as an additive for toughening polylactide: Influence of the molecular architecture

Well‐defined multiarmed star random and block copolymers of ε‐caprolactone with l ‐lactide with controlled molecular weights, low polydispersities, and precise numbers of arms were synthesized by the ring‐opening polymerization of respective cyclic ester monomers. The polymers were characterized by ¹H‐NMR and ¹³C‐NMR to determine their chemical composition, molecular structure, degree of randomness, and proof of block copolymer formation. Gel permeation chromatography was used to establish the degree of branching. Star‐branched random copolymers exhibited lower glass‐transition temperatures (T_g's) compared to a linear random copolymer. When the star random copolymers were melt‐blended with poly(l ‐lactic acid) (PLA), we observed that the elongation of the blend increased with the number of arms of the copolymer. Six‐armed block copolymers, which exhibited higher T_g's, caused the maximum improvement in elongation. In all cases, improvements in the elongation were achieved with no loss of stiffness in the PLA blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43267.     

Sulphonated “Click” Dendrimer‐Stabilized Palladium Nanoparticles as Highly Efficient Catalysts for Olefin Hydrogenation and Suzuki Coupling Reactions Under Ambient Conditions in Aqueous Media

Water‐soluble 1,2,3‐triazolyl dendrimers were synthesized by “click chemistry” and used to stabilize palladium nanoparticles (PdNPs). These new “click” dendrimer‐stabilized nanoparticles (DSN) are highly stable to air and moisture and are catalytically active for olefin hydrogenation and Suzuki coupling reaction, in aqueous media, under ambient conditions using a low amount of palladium (0.01 mol% Pd). Kinetic studies show high catalytic efficiency and high stability for the new “click” DSN in both reactions. The complexation of potassium tetrachloropalladate (K₂PdCl₄) to the triazole ligands present in the dendritic structures was monitored by UV/vis and, after reduction, the nanoparticles were characterized by transmission electron microscopy (TEM).     

Preparation and characterization of a type of ladder‐like poly(phenyl silsesquioxane) based hybrid star‐shaped copolymer of ε‐caprolactone

Combination of the organic–inorganic hybrid such as silsesquioxane with ε‐caprolactone will lead to materials expected to be environmentally friendly and applicable to biomedical usages. A ladder‐like poly(phenyl silsesquioxane) based hybrid star‐shaped copolymer of ε‐caprolactone was prepared by ring opening polymerization of ε‐caprolactone catalyzed by Sn(Oct)₂ with hydroxyl terminated ladder‐like poly(phenyl silsesquioxane) as initiator. The copolymers were characterized by proton nuclear magnetic resonance (¹H‐NMR), silicon nuclear magnetic resonance (²⁹Si‐NMR), Fourier‐transform infrared spectrometer (FT‐IR), size exclusion chromatography (SEC), thermo gravimetric analysis (TGA), and differential scanning calorimetry (DSC) in detail. Furthermore, the enzymatic degradation property of the copolymers was also investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42335.     

Synthesis functional poly(carbonate‐b‐ester) copolymers and micellar characterizations

Functional poly(carbonate‐b‐ester)s were synthesized in buck by ring‐opening polymerization of the carbonate (TMC, MBC, or BMC) with tert‐butyl N‐(2‐hydroxyethyl) carbamate as an initiator, and then with ε‐CL (or ε‐BCL) comonomer. Subsequently, the PMMC‐b‐PCL with pendent carboxyl groups and the PTMC‐b‐PHCL with pendent hydroxyl groups were obtained by catalytic debenzylation. DSC analysis indicated that only one T_g at an intermediate temperature the T_gs of the two polymer blocks. A decrease T_g was observed when an increase contents of ε‐CL incorporated into the copolymers. In contrast, two increased T_ms were observed with increasing PCL content. The block copolymers formed micelle in aqueous phase with critical micelle concentrations (cmcs) in the range of 2.23–14.6 mg/L and with the mean hydrodynamic diameters in the range of 100–280 nm, depending on the composition of copolymers. The drug entrapment efficiency and hydrolytic degradation behavior of micelle were also evaluated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of an amphiphilic hyperbranched poly(amine‐ester)‐co‐D,L‐lactide (HPAE‐co‐PLA) copolymers and their nanoparticles for protein drug delivery

A series of hyperbranched poly(amine‐ester)‐co‐D ,L ‐lactide (HPAE‐co‐PLA) copolymer were synthesized by ring‐opening polymerization of D ,L ‐lactide with Sn(Oct)₂ as catalyst to a fourth generation branched poly(amine‐ester) (HPAE‐OHs4). The chemical structures of copolymers were determined by FTIR, ¹H‐NMR, ¹³C‐NMR, and TGA. Double emulsion (DE) and nanoprecipitation (NP) method were used to fabricate the nanoparticles of these copolymers encapsulating bovine serum albumin (BSA) as a model. DSC thermo‐grams indicated that the nanoparticles with BSA kept stable below 40°C. Different factors which influence on particular size and encapsulation efficiency (EE) were investigated. Their EE to BSA could reach 97.8% at an available condition. In vitro release behavior of NPs showed a continuous release after a burst release. The stability maintenance of BSA in the nanoparticle release in vitro was also measured via circular dichroism and fluorescence spectrometry. The results showed that the copolymer nanoparticles have a promising potential in protein delivery system. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High yield synthesis of diverse well‐defined end‐functionalized polymers by combination of anionic polymerization and “click” chemistry

Well‐defined poly(methyl methacrylate) (M_n = 3630 g mol^?1, PDI = 1.06) with a primary benzylic bromide prepared using anionic polymerization was successfully transformed into diverse end‐functionalities (ω‐carboxyl, ω‐hydroxy, ω‐methyl‐vinyl, ω‐trimethylsilane, and ω‐glycidyl‐ether) via “click” reaction. The bromine end‐terminated poly(methyl methacrylate) was first substituted by an azide function and sequentially was reacted with various functional alkynes (propiolic acid, propargyl alcohol, 2‐methyl‐1‐buten‐3‐yne, propargyl trimethylsilane, and propargyl glycidylether). In all the cases, ¹H‐NMR, ¹³C NMR, FT‐IR, and GPC measurements show qualitative and quantitative transformation of the chain‐end poly(methyl methacrylate) into the desired functionalities with high conversion (above 99%). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of semi‐crystalline poly(ε‐caprolactone) and non‐crystalline polylactide blocks on the thermal properties of polydimethylsiloxane‐based block copolymers

Poly(A)‐block‐poly(B), poly(A)‐block‐poly(B)‐block‐poly(A) and B(A)₂ block copolymers were prepared through coordinated anionic ring‐opening polymerization of ε‐caprolactone (CL) and lactic acid (LA) using hydroxy‐terminated polydimethylsiloxane (PDMS) as initiator. A wide range of well‐defined combinations of PDMS‐block‐PCL and PDMS‐block‐PLA diblock copolymers, PCL‐block‐PDMS‐block‐PCL and PLA‐block‐PDMS‐block‐PLA triblock copolymers and star‐PDMS(PCL)₂ copolymers were thus obtained. The number‐average molar masses and the structure of the synthesized block copolymers were identified using various analytical techniques. The thermal properties of these copolymers were established using differential scanning calorimetry. Considering PDMS‐block‐PCL copolymers, the results demonstrate the complex effect of polymer architecture and PCL block length on the ability of the PDMS block to crystallize or not. In the case of diblock copolymers, crystallization of PCL blocks originated from stacking of adjacent chains inducing the extension of the PDMS block that can easily crystallize. In the case of star copolymers, the same tendency as in triblock copolymers is observed, showing a limited crystallization of PDMS when the length of the PCL block increases. In the case of PDMS‐block‐PLA copolymers, melting and crystallization transitions of the PLA block are never observed. Considering the diblock copolymers, PDMS sequences have the ability to crystallize. © 2019 Society of Chemical Industry     

Linear‐dendritic copolymers as nanocatalysts

Functionalized poly(ethylene glycol) (PEG) containing four chloride end functional groups (PEG‐Cl₄) was synthesized through reaction between cyanuric chloride and PEG‐(OH)₂. Chloride end functional groups of PEG‐Cl₄ were able to initiate the ring opening polymerization of 2‐ethyl‐2‐oxazoline and star copolymers containing a PEG core, and poly(2‐ethyl‐2‐oxazoline) (POX) arms were obtained. Polymerization was quenched using diethanolamine, and star copolymers containing hydroxyl end functional groups (PEG‐POX‐OH) were obtained. ε‐Caprolactone was then polymerized using the hydroxyl end functional groups of star copolymers and amphiphilic linear‐dendritic copolymers containing PEG and POX, and poly(caprolactone) (PCL) blocks were synthesized. Linear‐dendritic copolymers were able to load the organic and inorganic guest molecules. Application of host‐guest systems such as nanocatalyst for Heck chemical reaction was also investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of biodegradable and biocompatible ABC triblock copolymers

A facile approach is offered to synthesize well‐defined amphiphilic ABC triblock copolymers composed of poly(ethylene glycol) monomethyl ether (MPEO) as A block, poly(L ‐lysine) (PLLys) as B block, and poly(ε‐caprolactone) (PCL) as C block by a combination of ring‐opening polymerization (ROP) and click reactions. The propargyl‐terminated poly(Z‐L ‐lysine)‐block‐poly(ε‐caprolactone) (MPEO‐PzLLys‐PCL) diblock copolymers were synthesized via the ring‐opening polymerization of N^ε‐carbobenzoxy‐L ‐lysine N‐carboxyanhydride (Z‐L ‐Lys NCA) in DMF at room temperature using propargyl amine as an initiator and the resulting amino‐terminated poly(Z‐L ‐lysine) then used in situ as a macroinitiator for the polymerization of ε‐caprolactone in the presence of stannous octoate as a catalyst. The triblock copolymers poly(ethylene glycol) monomethyl ether –block‐poly(Z‐L ‐lysine)‐block‐poly(ε‐caprolactone) (MPEO‐PzLLys‐PCL) were synthesized via the click reaction of the propargyl‐terminated PzLLys‐PCL and azido‐terminated poly(ethylene glycol) monomethyl ether (PEO‐N₃) in the presence of CuBr and 1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) catalyst system. After the removal of Z groups of L ‐lysine units, amphiphilic and biocompatible ABC triblock copolymers MPEO‐PLLys‐PCL were obtained. The structural characteristics of these ABC triblock copolymers and corresponding precursors were characterized by NMR, IR, and GPC. These results showed the click reaction was highly effective. Therefore, a facile approach is offered to synthesize amphiphilic and biocompatible ABC triblock copolymers consisting of polyether, polypeptide and polyester. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication and drug release properties of poly(5‐benzyloxy‐trimethylene‐co‐glycolide) microspheres

Poly(5‐benzyloxy‐trimethylene carbonate‐co‐glycolide) random copolymers were synthesized through the ring‐opening polymerization of 5‐benzyloxy‐trimethylene carbonate and glycolide (GA). The copolymers with different compositions, PBG‐1 with 17% GA units and PBG‐2 with 45% GA units, were obtained. Using these copolymers, microsphere drug delivery systems with submicron sizes were fabricated using an “ultrasonic assisted precipitation method.” The in‐vitro drug release from these microspheres was investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of novel thermo‐ and redox‐sensitive polypeptide hydrogels

Multi‐responsive hydrogels have recently received considerable attention for bioapplications. Here, novel temperature‐ and redox‐responsive polypetide hydrogels have been developed. Thermo‐sensitive hydrogels based on poly(ethyleneglycol)‐block ‐poly(γ‐propargyl‐l ‐glutamate) (PEG‐PPLG ) were first synthesized by the ring opening polymerization of γ‐propargyl‐l ‐glutamate N ‐carboxyanhydride (PLG‐NCA ) with amino group terminated PEG monomethyl ether (mPEG‐NH₂ ) as macroinitiator and were then functionalized via the ‘thiol‐yne’ click reaction between the propargyl pendents and the thiol‐containing 1‐propanethiol. The sol ? gel phase transition of the obtained copolymer aqueous solution in response to temperature change was studied. The mass loss of the hydrogel in vitro was accelerated in the presence of H₂O₂ , exhibiting a redox‐responsive property. Further, the methyl thiazolyl tetrazolium viability results revealed that this polypetide hydrogel has excellent biocompatibility, presenting potential applications in the biomedical field. © 2016 Society of Chemical Industry     

Monolith‐ and Silica‐Supported Carboxylate‐Based Grubbs–Herrmann‐Type Metathesis Catalysts

The synthesis of silica‐ and monolith‐supported Grubbs–Herrmann‐type catalysts is described. Two polymerizable, carboxylate‐containing ligands, exo, exo‐7‐oxanorborn‐2‐ene‐5,6‐dicarboxylic anhydride and 7‐oxanorborn‐2‐ene‐5‐carboxylic acid were surface‐immobilized onto silica‐ and ring‐opening metathesis (ROMP‐) derived monolithic supports using “grafting‐from” techniques. The “1^st generation Grubbs catalyst”, RuCl₂(CHPh)(PCy₃)₂, was used for these purposes. In addition, a poly(norborn‐2‐ene‐b‐exo, exo‐norborn‐2‐ene‐5,6‐dicarboxylic anhydride)‐coated silica 60 was prepared. The polymer supported anhydride and carboxylate groups were converted into the corresponding mono‐ and disilver salts, respectively, and reacted with the Grubbs–Herrmann catalyst RuCl₂(CHPh)(IMesH₂)(PCy₃) [IMesH₂=1,3‐bis(2,4,6‐trimethylphenyl)‐4,5‐dihydroimidazol‐2‐ylidene]. Heterogenization was accomplished by exchange of one chlorine ligand with the polymeric, immobilized silver carboxylates to yield monolith‐supported catalysts 4, 5 , and 6 as well as silica‐supported systems 7, 8 and 9 . The actual composition of these heterogenized catalysts was proven by the synthesis of a homogeneous analogue, RuCl[7‐oxanorbornan‐2‐(COOAg)‐3‐COO](CHPh)(IMesH₂)(PCy₃) ( 3 ). All homogeneous and heterogeneous catalysts were used in ring‐closing metathesis (RCM) of diethyl diallylmalonate, 1,7‐octadiene, diallyldiphenylsilane, methyl trans‐3‐pentenoate, diallyl ether, N,N‐diallyltrifluoracetamide and t‐butyl N,N‐diallylcarbamate allowing turnover numbers (TON's) close to 1000. In a flow‐through set‐up, an auxiliary effect of pendant silver carboxylates was observed with catalyst 5 , where the silver moiety functions as a (reversible) phosphine scavenger that both accelerates initiation and stabilizes the catalyst by preventing phosphine elution. Detailed catalytic studies were carried out with the monolith‐supported systems 4 and 6 in order to investigate the effects of temperature and chain‐transfer agents (CTA's) such as cis‐1,4‐diacetoxybut‐2‐ene. In all RCM experiments Ru‐leaching was low, resulting in a Ru‐content of the RCM products ≤3.5 μg/g (3.5 ppm).     

Synthesis and characterization of homo‐ and copolymers of 3‐(2‐cyano ethoxy)methyl‐ and 3‐[methoxy(triethylenoxy)]methyl‐3′‐methyl‐oxetane

Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF₃· Et₂O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and¹H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (T_g), the DSC data imply that the resulting copolymers have a lower T_g than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10^?5 S cm^?1 at room temperature and 2.79 × 10^?4 S cm^?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry     

Ring‐opening bulk polymerization of five‐ and six‐membered cyclic phosphonates using maghnite,a nontoxic proton exchanged montmorillonite clay

A new method of preparation of poly(alkylene H‐phosphonate)s by ring‐opening bulk polymerization of the five‐ and six‐membered cyclic phosphonates monomers using the nontoxic Maghnite‐H⁺ as the initiator is described. Cyclic phosphonate monomers have been first synthesized. In particular, a new one‐step synthesis of 2‐hydro‐2‐oxo‐1,3,2‐dioxaphospholane is reported with a yield of 70%. The efficiency of the montmorillonite sheet silicate clay which exchanged with protons, called Maghnite‐H⁺, as cationic initiator has been proved and the resulting biomimetic poly(alkylene H‐phosphonate)s have been characterized. The Maghnite‐H⁺ regenerated after one turn‐over has showed to be still efficient as initiator for the ring‐opening polymerization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011