Hyperbranched Polyesteramide Metal Salts (Oxides) Complexes And Their Application In Rubber

As a small embranchment of hyperbranched polymers (HBP), hyperbranched polyesteramide (HBPEA) can be facilely synthesized by introducing commercial monomer and seems to be the most important member in the HBP family, which may be applied in industry at a lower cost. Hitherto, there are lots of examples for HBPEA to be successfully synthesized and pleasantly characterized. However, research of HBPEA application is still in its infancy, especially, the main object to apply HBPEA in general industry fields such as plastic and rubber processing, is scarcely any. To explore opportunities for HBPEA application with low cost and high value, we developed a series of feasible and relatively simple processes to compound HBPEA with metal salts (oxides) and thus have successfully obtained some functional additives with reactive nature. In the meanwhile, the features of coordination reaction between HBPEA and metal salts (oxides) were characterized and the law of coordination reaction was also suggested to instruct the preparation work to the new-type HBPEA based additive.By employing commercially available products such as maleic anhydride (MA), succine anhydride(SA), diethanolamine (DEA), zinc oxide(ZnO), zinc chloride hydrate (ZnCl₂.H₂O), mix rare earth oxides (RE₂O₃) and lanthanum chloride hydrate (LaCl₃.6H₂O), etc., a series of metal maleates (MA-Zn²⁺ and MA-La³⁺) and metal succinates (SA-Zn²⁺ and SA-La³⁺), HBPEA resins, hyperbranched polyesteramide metal salts (HBPEA-La³⁺), hyperbranched polyesteramide metal oxides (HBPEA/ZnO and HBPEA/RE₂O₃), were successfully synthesized via solid-state reaction (including high temperature, low temperature and quasi solid-state three different process) method, "one-step" AB₂ monomer condensation polymerization (including solution, melt and microwave-assistance polycondensation three different process) process, solution blending route, "in-situ" solution condensation of AB₂ monomer and envelopment technique, respectively. All synthesis techniques mentioned above were improved or simplified from the conventional methods, whose advantages and disadvantages were comparatively discussed in order to find out a more feasible route for applying in lowest production. Moreover, the structure and properties of some representative resultant products were mainly characterized by using Fourier-transform infrared spectra (FT-IR), ultraviolet-visible absorption spectra (UV-Vis), X-ray photoelectron spectroscopy (XPS), powder X-ray diffractometry (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), viscosity determination, and so on. Particularly, MA-Zn²⁺ , MA-La³⁺ , SA-Zn²⁺ , SA-La³⁺ , HBPEA/ZnO and HBPEA/RE₂O₃ were applied in BR rubber for traditional vulcanization, and all the resultant effects were mainly investigated by rheological analysis methods with AR2000 dynamic rheometer and UC-2030 rheometer. MA-Zn²⁺ , MA-La³⁺ , SA-Zn²⁺ , SA-La³⁺ , HBPEA/ZnO and HBPEA/RE₂O₃ can activate vulcanization reaction in different degree. There are notable difference in rheometric properties between lanthanum additive applied BR and zinc additive applied BR, which is due to the difference coordination nature of lanthanum and zinc element.It is the feeble cross-linking bond that may attribute to inducing all present thermoplastic rubber hold rather inferior mechanical properties in contrast to thermoset rubber. And coordinated cross-linking rubber has been universally deemed to be the most promising one member of thermoplastic rubber that could substitute for thermoset rubber in one day. Unfortunately, for the coordinated cross-linking rubber, little work has been authentically carried out, due to distorting comprehension is prevalent to this kind of thermoplastic rubber and most relational investigations reported have only been concern polyion elastomer actually. With large numbers of branches, numerous active polar groups and unique properties, HBPEA metal series products obtained in present work, may be available functional additives for preparing coordinated cross-linking rubber. Efforts to fabricate the new type thermoplastic rubber circumventing to graft polar groups onto the molecules of rubber resin, are going on, aiming at to breaking through the traditional producing process for coordinated cross-linking rubber.