Krzysztof Kaluzynski

Branched polyether with multiple primary hydroxyl groups: polymerization of 3-ethyl-3-hydroxymethyloxetane

Cationic polymerization of 3-ethyl-3-hydroxymethyloxetane gives branched, soluble macromolecules with multiple glycolic end groups. There are approximately 3–4 “normal” units per one branched unit.

Double‐Hydrophilic Block Copolymers with Monophosphate Ester Moieties as Crystal Growth Modifiers of CaCO3

The synthesis of double-hydrophilic block copolymers with a poly(ethylene glycol) block (PEG) and a block with pendant monophosphate ester groups based on a hydroxylated polybutadiene block (poly[2-(2- hydroxy ethyl)ethylene] (PHEE) with variable degrees of phosphate substitution (up to 40%) is described. It is shown that these block copolymers are very efficient scale inhibitors for CaCO 3 . The efficiency of these polymers is compared with block copolymers with an ionic block based on phosphorylated polyglycidol (PGL) with phosphorylation degrees up to 100%. The phosphorylated polyglycidols were also used to modify the morphology of CaCO 3 crystals. Instead of the typical rhombohedral calcite single crystals, superstructures of nanometer-sized particles are formed in the presence of these block copolymers when two different techniques were used: the fast double-jet technique and the slow Kitano-method. In the double-jet method, only spherical superstructures are obtained, whereas for the slower growth region covered by the Kitano method, complex cone-like or flower-like superstructures are formed.

Dihydrophilic block copolymers with ionic and nonionic blocks. I. Poly(ethylene oxide)-b-polyglycidol with OP(O)(OH)2, COOH, or SO3H functions: Synthesis and influence for CaCO3 crystallization

Dihydrophilic block copolymers of poly(ethylene oxide)-b-polyglycidol were prepared and polyglycidol blocks converted into ionic blocks containing OP(O)(OH)2, COOH, or SO3H groups. Although phosphorylation of polyhydroxy compounds with POCl3 usually leads to insoluble products, phosphorylation of poly(ethylene oxide)-b-polyglycidol using a POCl3/OH ratio equal to 1/1 gave soluble products, predominantly monoester of phosphoric acid (after hydrolysis) (provided that the reaction was conducted in triethyl phosphate as solvent). All copolymers were characterized by 1H NMR, 13C NMR, and/or 31P NMR spectra for confirming their structure. The degree of substitution was determined from quantitative 13C NMR spectroscopy (inverted-gate decoupling-acquisition mode). Preliminary results indicate that from these three groups of block copolymers the phosphoric acid esters are the most effective ones at least in controlling the growth of CaCO3 crystals in aqueous solution.

Hybrids of dihydrophylic ionic-nonionic block copolymers and CaCO3. Determination of the number of CaCO3 molecules attached to the ionic groups

Polymer mediated crystallization of CaCO3, in the presence of dihydrophilic ionic-nonionic block copolymer (DHBC), gave hybrid crystalline particles in the form of partially open empty spheres. The DHBC used were composed of a poly(ethylene oxide) block and a block of phosphorylated glycidol. The outer skin of the empty spheres (hybrid particles) is formed of a double layer of small spherical particles of diameter equal to 20 nm. NMR measurements enabled determination of the DHBC content in the hybrids. The calculations on this basis gave a number of macromolecules of DHBC attached to one small sphere (approx. equal to 50). Finally, it was estimated that every fourth CaCO3 molecule on the surface of the small sphere is attached to one phosphate unit of DHBC.

The MPEG monophosphate ester: synthesis and characterization.

Methods of preparation of the phosphoric ester of monomethyl ether of poly(ethylene glycol) (MPEG-P) from MPEG (M n = 550 and 2000) and phosphoric acid (P), or its derivatives — pyrophosphoric acid (PY), polyphosphoric acid (PP) and POCl3– are described and compared. MPEG-P was isolated in a pure state (no detectable impurities) and characterized.

Monolithic Photorefractive Molecular Glass with Electron-Transporting Fluorene Unit

Multifunctional succinates have been prepared as monolithic molecular photorefractive materials which contain an electron-transporting fluorene moiety and an electrooptically active (EO) chromophore. The synthesized succinates form amorphous glass at room temperature with the aid of a flexible diester spacer and butoxycarbonyl group attached to the fluorene unit. Long-wavelength absorption bands were observed in addition to the peaks from fluorene and the EO chromophore, which are due to the charge transfer interaction between electron-accepting fluorene and electron-donating aniline units. Compounds showed photorefractivity without the addition of a photosensitizer, a polymeric binder or a plasticizer, indicating that they are completely monolithic photorefractive materials. Succinate with a 4-dicyanovinylaniline chromophore showed excellent properties, i.e., 32% diffraction efficiency at 55 V/µm and 125 cm-1 coupling gain at 65 V/µm. The electron-transporting nature of space-charge field buildup was confirmed from the coupling direction.

Phosphorylation of Polyols with H3PO4: Towards Simple Synthesis of Poly(alkylene phosphate)s

Polycondensation of ethylene glycol and of glycerol with H 3 PO 4 elaborated recently is summarized. Surprisingly, this apparently simple reaction, leading to a new class of synthetic polymers, has not previously been studied. In both reactions, soluble oligomers are formed, in spite of H 3 PO 4 , the class A3 component, being used. Dealkylation prevents the formation of high molar mass products, while also influencing the stability of the triesters in the case of ethylene glycol condensation. Polycondensation does not proceed directly with H 3 PO 4 . Independent kinetic experiments reveal that in the rate-controlling step, pyrophosphoric acid is formed. In polycondensation of glycerol, five- and six-membered rings are present in the main chain, indicating that the A3/B3 system has been converted into the A2/B2 system (at least partially). Both polymers have been shown to be efficient modulators of the CaCO 3 crystallization.

Synthesis and some properties of poly(alkylene phosphorothioate)s prepared from the corresponding poly(alkylene H-phosphonate)s

Several high molecular weight poly(alkylene phosphorothioate)s were synthesized by reacting poly(H-phosphonate)s with sulfur. The molecular weight of the resulting polymers are similar to the respective starting poly(alkylene H-phosphonate)s indicating that during sulfurization process no chain degradation occurred. The structure of poly(alkylene phosphorothioate)s was confirmed by the analysis of 1H, 13C and 31P NMR spectra.

Copolymers of 7‐oxabicyclo[2.2.1] heptane with 1,3‐dioxane and promesogenic telechelic oligomers thereof

Copolymers of 7-oxabicyclo[2.2.1 heptane (B) ( and of its 2-methyl derivatives) with 1,3-dioxane (D) were obtained by cationic copolymerization initiated with benzoylium hexafluoroantimonate. Structure of copolymers was determined by 1 H- and 13 C-NMR. The proportion of the acetal bonds in copolymers was additionally confirmed in studies of the products of hydrolysis (only the acetal bonds hydrolyze). D is unable to homopolymerize for the thermodynamic reasons and therefore mostly pseudoperiodic copolymers (-DB x -) y are formed. Nevertheless, the reshuffling reactions are responsible for the appearance of wrong units. These are: the separate oxymethylene and oxy-1,3-propylene units (P, subunits of D) located between two B units. Only the acetal bonds are cleaved in the acidic hydrolysis with dilute HCI. This gives the promesogenic telechelic oligomers of mostly HO-P-B x -OH structure. This article is the first to describe successful cationic copolymerization of cyclic acetal with a cyclic ether. Moreover, the inability of D to homopolymerize gives the thermodynamic basis of the pseudoperiodic copolymer formation.

Towards polymer-inorganic hybrid molecular composites: calorimetric studies of the polymer-inorganic particles interaction

Abstract Inorganic particles of 3 CaO ⋅ SiO2 were reacted in water dispersion with dihydrophilic ionic-nonionic block copolymers, and the heat effect of interaction was measured by calorimetry. The ionic block was constituted of monoesters of phosphoric acid or alkyl phosphonic acid, both built on the polyglycidol block, attached to the poly(ethylene oxide) block. The heat evolved during the interaction is a function of the degree of phosphorylation (phosphonylation). The higher the degree of -OH substitution the stronger the interaction, the latter being stronger for phosphates than for phosphonates.