RESUMEN
Hyperbranched polymers (HBPs) are widely applied nowadays as functional materials for biomedicine needs, nonlinear optics, organic semiconductors, etc. One of the effective and promising ways to synthesize HBPs is a polyaddition of AB2+A2+B4 monomers that is generated in the A2+CB2, AA'+B3, A2+B'B2, and A2+C2+B3 systems or using other approaches. It is clear that all the foundational features of HBPs that are manufactured by a polyaddition reaction are defined by the component composition of the monomer mixture. For this reason, we have designed a structural kinetic model of AB2+A2+B4 monomer mixture polyaddition which makes it possible to predict the impact of the monomer mixture's composition on the molecular weight characteristics of hyperbranched polymers (number average (DPn) and weight average (DPw) degree of polymerization), as well as the degree of branching (DB) and gel point (pg). The suggested model also considers the possibility of a positive or negative substitution effect during polyaddition. The change in the macromolecule parameters of HBPs formed by polyaddition of AB2+A2+B4 monomers is described as an infinite system of kinetic equations. The solution for the equation system was found using the method of generating functions. The impact of both the component's composition and the substitution effect during the polyaddition of AB2+A2+B4 monomers on structural and molecular weight HBP characteristics was investigated. The suggested model is fairly versatile; it makes it possible to describe every possible case of polyaddition with various monomer combinations, such as A2+AB2, AB2+B4, AB2, or A2+B4. The influence of each monomer type on the main characteristics of hyperbranched polymers that are obtained by the polyaddition of AB2+A2+B4 monomers has been investigated. Based on the results obtained, an empirical formula was proposed to estimate the pg = pA during the polyaddition of an AB2+A2+B4 monomer mixture: pg = pA = (-0.53([B]0/[A]0)1/2 + 0.78)υAB2 + (1/3)1/2([B]0/[A]0)1/2, where (1/3)1/2([B]0/[A]0)1/2 is the Flory equation for the A2+B4 polyaddition, [A]0 and [B]0 are the A and B group concentration from A2 and B4, respectively, and υAB2 is the mole fraction of the AB2 monomer in the mixture. The equation obtained allows us to accurately predict the pg value, with an AB2 monomer content of up to 80%.
RESUMEN
The process of curing the acrylic oligomers for rapid thermal curing coatings in the presence of hexa(methoxymethyl)melamine (HMMM), tetra(butoxymethyl)glycoluril (TBMG), and tetra(methoxymethyl)glycoluril (TMMG) has been studied. When HMMM is used as a hardener, the content of hydroxyl groups in the terpolymer and also the crosslinking agent concentration have little effect on the initial cure rate. It has been established that during the curing of the TMMG composition, the amount of the network polymer and the initial curing rate decrease at short curing times only. It has also been revealed that the use of butoxy groups instead of methoxy groups as blocking agents leads both to a decrease in the initial cure rate and the gel fraction limiting value from 98 to 80%. When it comes to TBMG-containing compositions, a decrease in the part of hydroxyl groups in the copolymer leads to a significant fall in the initial curing rate and also in the gel fraction content. Regardless of the crosslinking agent used, an acceleration of the curing process is observed with an increase in the catalyst content in the compositions.
RESUMEN
We report a simple and convenient approach to the one-pot synthesis of hyperbranched polyurethane-triazoles with desirable properties. This method is based on in situ generation of an AB2 + A2 + B4 azide-acetylene monomer mixture of known composition, due to quantitative reactions of urethane formation between isophorone diisocyanate (IPDI), 1,3-diazidopropanol-2 (DAPOL) (in the first stage) and propargyl alcohol (in the second stage). The obtained monomer mixture can be involved in step-growth polymerization by azide-alkyne cycloaddition without additional purification (in the third stage). The properties of the resulting polymers should depend on the composition of the monomer mixture. Therefore, first the model revealing the correlation between the monomer composition and the ratio and reactivity of the IPDI and DAPOL active groups is developed and proven. In addition, the newly developed structural kinetic model considering the substitution effect at polyaddition of the complex mixture of monomers allows the prediction of the degree of branching of the target polymer. Based on our calculations, the hyperbranched polyurethane-triazoles were synthesized under found conditions. All products were characterized by 1H NMR, FTIR, SEC, DLS, DSC, TGA and viscometry methods. It was shown that the degree of branching, molecular weight, intrinsic viscosity, and hydrodynamic radius of the final hyperbranched polymers can be specified at the first stage of one-pot synthesis. The obtained hyperbranched polyurethane-triazoles showed a degree of branching from 0.21 to 0.44 (calculated DB-0.25 and 0.45, respectively).
RESUMEN
Core/shell pigments allow for the combination of the active anti-corrosion effect of the shell and the barrier effect of the core. This makes it possible to obtain anti-corrosion pigments, with a high-protective effect and low toxicity. Thus, the need for a comprehensive study of the properties of these pigments grows more urgent, before their application to paints and varnishes. The hiding power of core/shell pigments comes close to the one of pure polyaniline (PANi), when the PANi content in the pigment reaches 50 wt.%, with sulfuric and phosphoric acids used as dopants. This paper, also, shows that the blackness value of core/shell pigments with 10 wt.% PANi is around 35 and constant; for pure PANi, their blackness value is 40. When PANi content is 5 wt.%, kaolin-based pigment shows the lowest blackness, which happens due to a generally higher whiteness of kaolin. However, when the PANi content surpasses 10 wt.%, there seems to be no influence on the blackness of the core/shell pigments. The core/shell pigment with a 20 wt.% PANi is, optically, identical to a black-iron-oxide pigment. An increase in the PANi content of the core/shell pigment leads to an increase in the oil absorption of the samples. It was found that the dispersion process would be the most energy efficient for core/shell pigments, containing kaolin and talc as a core.