Polyesters with 9,10-dihydro-9-oxy-10-phosphaphenanthrene-10-oxide-containing comonomers are synthesized aiming to improve the flame retardancy of aliphatic polyesters such as poly(butylene succinate) and poly(butylene sebacate). The influence of the chemical structure on the thermal decomposition and pyrolysis is examined using a combination of thermogravimetric analysis (TGA), TGA-Fourier transform infrared (FTIR) spectroscopy, pyrolysis-gas chromatography/mass spectrometry, and microscale combustion flow calorimetry. Thermal decomposition pathways are derived and used to select suitable candidates as flame retardants for PBS. The fire behavior of the selected polymers is evaluated by forced-flaming combustion in a cone calorimeter. The materials show two modes of action for flame retardancy: strong flame inhibition due to the release of a variety of molecules combined with charring in the solid state.
The potential of nanocomposites, i.e. mixtures of nanoobjects with acceptable distribution in a polymer matrix, with respect to flame retardancy was discovered in an already early stage of nanocomposite reseach. Since then, a variety of nanocomposites often in combination with conventional flame retardants (FRs) and their effect on the burning behavior has been described.
Here, we show the application of this concept to enhance the flame retardancy of poly(butylene terephthalate) (PBT) and poly(butylene succinate) (PBS) using suitable phosphorus-containing polyesters as FR. The materials studied were prepared by melt compounding in a twin screw extruder using either a mixture of polymer matrix, phosphorus polymer and nanomaterial (direct compounding) or a mixture of a pre-formed batch of phosphorus polymer with nanomaterial and the polymer matrix (batch compounding). The second method has been shown to be very effective if batches prepared by in-situ nanocomposite synthesis via melt transesterification polycondensation were employed. Modified organoclay (montmorillonite, OMMT) as well as multiwalled carbon nanotubes were used as nanoobjects.
Organic modification of MMT resulted in better exfoliation and distribution within the poylmer matrix than observed with pure sodium MMT. However, modification with phosphorus-containing modifiers dis not support exfoliation due to high interaction between modifier and clay.
Analysis of the in-situ prepared nanocomposites of OMMT (Cloisite 30B) with the phosphorus polyester PET-P-DOPO by thermogravimetry, FTIR and pyrolysis-GC/MS showed that OMMT did not alter the principal decomposition pathway of the polyester, but shifted the onset of decomposition to lower temperature (due to the fast decomposition of the tertiary ammonium compound) and increased the amount of char. The fire behavir as observed by microscale combustion calorimetry (MCC) was altered and resulted in significant decrease of heat release capacity.
In-situ prepared batches of the phosphorus polyester PET-P-DOPO with 20 wt.-% OMMT and with MWCNT (1 wt.-%) were blended with PBT in the ratio 25/75 wt/wt to achieve a phosphorus concentration of 1.5 wt.-%. The nanocomposites were injection molded into plates for cone calorimeter measurements and examined using 50 kW/m2. In all samples, a reduction of toral heat evolved and total heat evolved/total mass loss (THE/TML) was observed. Addition of OMMT improved the char, which was even more pronounced in combination with PET-P-DOPO as illustrated in Figure 1. Blends containing PET-P-DOPO additionally showed intumescence. In all cases, a significant reduction of FIGRAmax was obtained. The addition of nanomaterials (both OMMT and MWCNT) to PBT/PET-P-DOPO reduced the effective heat of combustion (THE/TML) from 1.7 to 1.5 MJ/m2.
Polyesters with DOPO substituents can be successfully synthesized with 10-[2,5-Bis(2-hydroxyethoxy)phenyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO-HQ-glycolether) and DOPO-substituted dimethyl succinate (PIta). These polyester materials show an effective flame retardancy which can be fine-tuned by the chemical structure of the polyester backbone.
The impact of phosphorus-containing flame retardants (FR) on rigid polyisocyanurate (PIR) foams is studied by systematic variation of the chemical structure of the FR, including non-NCO-reactive and NCO-reactive dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO)- and 9,10 dihydro-9-oxa-10 phosphaphenanthrene-10-oxide (DOPO)-containing compounds, among them a number of compounds not reported so far. These PIR foams are compared with PIR foams without FR and with standard FRs with respect to foam properties, thermal decomposition, and fire behavior. Although BPPO and DOPO differ by just one oxygen atom, the impact on the FR properties is very significant: when the FR is a filler or a dangling (dead) end in the PIR polymer network, DOPO is more effective than BPPO. When the FR is a subunit of a diol and it is fully incorporated in the PIR network, BPPO delivers superior results.
A series of flexible polyurethane foams (FPUFs) were prepared with single and different combinations of flame retardants and additives. Expandable graphite (EG), phosphorous polyol (OP), copper (II) oxide (CuO), and/or castor oil (CAS) were added to FPUF during the foam preparation in a one-step process. The purpose of the study is to evaluate the synergistic effects of the flame retardants, additives, and the presence of bio-based content on the mechanical properties, flame retardancy, and smoke behavior of FPUFs. The combination of 10 wt % EG and 5 wt % OP in FPUF significantly improves the char yield. In the cone calorimeter experiment, the char yield is nearly three times higher than that with 10 wt % EG alone. The smoke behavior is additionally evaluated in a smoke density chamber (SDC). Comparing the samples with a single flame retardant, 10 wt % EG in FPUF considerably reduces the amount of smoke released and the emission of toxic gases. Replacing the amount of 10 wt % polyether polyol in FPUF with CAS maintains the physical and mechanical properties and fire behavior and enhances the bio-based content. The presence of 0.1 wt % CuO in FPUF effectively reduces the emission of hydrogen cyanide. As a result, this study proposes a multicomponent flame retardant strategy for FPUF to enhance the biomass content and address the weaknesses in flame retardancy, smoke, and toxic gas emissions. A starting point is disclosed for future product development.