Compatibilization of intumescent flame retardant/polypropylene composites based on α‐methacrylic acid grafted polypropylene

A phosphoric acid–pentaerythritol–melamine copolymer was selected as an intumescent flame retardant (IFR). The influence of α‐methacrylic acid grafted polypropylene (PP‐g‐MAA) on the properties and compatibility of IFR/PP composites was studied. The results obtained from mechanical tests and scanning electron microscopy showed that PP‐g‐MAA was a true coupling agent for IFR/PP blends, but it did not change the necessary flame retardancy. The cocrystallization between bulk PP and PP segments of PP‐g‐MAA was proved by wide‐angle X‐ray diffraction analysis. A flow test showed that the flow behaviors of composites in the melt were those of a pseudoplastic liquid and it was very small for PP‐g‐MAA and affected the rheological behavior of the PP/IFR composite. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3128–3132, 2002; DOI 10.1002/app.10099     

Studies on compatibilization of intumescent flame‐retardant/PP composites based on etched PP

The phosphoric acid–pentaerythritol–melamine copolymer was selected as an intumescent flame retardant (IFR). The influence of dicromate acid–etching polypropylene (EPP) on the properties and compatibility of IFR/PP composites was studied. The results obtained from mechanical tests and SEM showed that EPP was a true coupling agent for IFR/PP blends, but without changing the necessary flame retardancy. The cocrystallization between bulk PP and PP segments of EPP was proved by WAXD analysis. Flow tests showed that the flow behavior of composites in the melt is that of a pseudoplastic liquid, which is almost insignificant for EPP affecting the rheological behavior of an IFR/PP composite. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 522–527, 2002; DOI 10.1002/app.10261     

Studies of polypropylene–intumescent flame‐retardant composites based on etched polypropylene as a coupling agent

The ammonium polyphosphate (APP)–pentaerythritol (PT)–melamine (M) system was selected as an intumescent flame retardant (IFR). The influence of dichromic acid–etched polypropylene (EPP) on the properties and compatibility of IFR/polypropylene (PP) composites was studied. The results obtained from mechanical tests and SEM showed that EPP was a true coupling agent for IFR/PP blends, but without changing the necessary flame retardancy. The cocrystallization between bulk PP and PP segments of EPP was confirmed by WAXD analysis. Flow tests showed that the flow behavior of composites in the melt is that of a pseudoplastic liquid, which is significant for EPP's effect on the rheological behavior of IFR/PP composite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1388–1391, 2004     

Using PA6 as a charring agent in intumescent polypropylene formulations based on carboxylated polypropylene compatibilizer and nano‐montmorillonite synergistic agent

The intumescent fire retardant polypropylene (IFP/PP) filled with ammonium polyphosphate (APP), melamine (M), and PA6 (charring agent) is discussed. Intumescing degree (ID) and the char yield were determined. Only when the three main components of IFR coexist at appropriate proportions, it has optimal ID and higher char yield. The appropriate proportion is PA6 : APP : M = 10 : 10 : 5. A new compatibilizer, carboxylated polypropylene (EPP), was added to PP/PA‐6 blend. Flow tests indicated that the apparent viscosity increased with the addition of EPP, thermal characterization suggested that EPP has reacted with PA6, PA6‐g‐EPP cocrystallized with PA6, and EPP‐g‐PA6 cocrystallized with PP; SEM micrographs illustrated that the presence of EPP improved the compatibility of PP and PA6. All the investigations showed that EPP was an excellent compatibilizer, and it was a true coupling agent for PP/PA6 blends. Using PA6 as a charring agent resulted in the IFR/PP dripping, which deteriorated the flammability properties. The addition of nano‐montmorillonite (nano‐MMT) as a synergistic agent of IFR enabled to overcome the shortcoming. The tensile test testified that the addition of nano‐MMT enhanced the mechanical strength by 44.3%. SEM showed that nano‐MMT improved the compatibility of the composites. It was concluded that the intumescent system with nano‐MMT was an effective flame retardant in improving combustion properties of polypropylene. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 739–746, 2006     

Study of dynamically cured PP/MAH‐g‐PP/talc/epoxy composites

In the present study, an epoxy resin was dynamically cured in a polypropylene (PP)/maleic anhydride–grafted PP (MAH‐g‐PP)/talc matrix to prepare dynamically cured PP/MAH‐g‐PP/talc/epoxy composites. An increase in the torque at equilibrium showed that epoxy resin in the PP/MAH‐g‐PP/talc composites had been cured by 2‐ethylene‐4‐methane‐imidazole. Scanning electron microscopy analysis showed that MAH‐g‐PP and an epoxy resin had effectively increased the interaction adhesion between PP and the talc in the PP/talc composites. Dynamic curing of the epoxy resin further increased the interaction adhesion. The dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had higher crystallization peaks than did the PP/talc composites. Thermogravimetric analysis showed that the addition of MAH‐g‐PP and the epoxy resin into the PP/talc composites caused an obvious improvement in the thermal stability. The dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had the best thermal stability of all the PP/talc composites. The PP/MAH‐g‐PP/talc/epoxy composites had better mechanical properties than did the PP/MAH‐g‐PP/talc composites, and the dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had the best mechanical properties of all the PP/talc composites, which can be attributed to the better interaction adhesion between the PP and the talc. The suitable content of epoxy resin in the composites was about 5 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Effect of maleic anhydride/vinyltrimethoxysilane‐co‐grafting polypropylene on the properties of wood‐flour/polypropylene composites by electron‐beam preirradiation

The electron‐beam preirradiation and reactive extrusion technologies were used to prepare maleic anhydride (MAH)/vinyltrimethoxysilane (VTMS)‐co‐grafting polypropylene (PP) as a high‐performance compatibilizer for wood‐flour/PP composites. The grafting content, chemical structure, and crystallization behavior of the compatibilizers were characterized through Fourier transform infrared spectroscopy, differential scanning calorimetry, and an extraction method. The effects of the compatibilizers on the mechanical properties, water absorption, morphological structure, and torque rheological behavior of the composites were investigated comparatively. The experimental results demonstrate that MAH/VTMS‐g‐PP markedly enhanced the mechanical properties of the composites. Compared with MAH‐g‐PP and VTMS‐g‐PP, MAH/VTMS‐g‐PP clearly showed synergistic effects on the increasing mechanical properties, water absorption, and compatibility of the composites. Scanning electron microscopy further confirmed that the adhesion and dispersion of wood flours in the composites were effectively improved by MAH/VTMS‐g‐PP. These results were also proven by the best water resistance of the wood‐flour/PP composites with MAH/VTMS‐g‐PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of a novel phosphorus‐containing compound on the flame retardancy and thermal degradation of intumescent flame retardant polypropylene

A novel flame retardant, tetra(5,5‐dimethyl‐1,3‐ dioxaphosphorinanyl‐2‐oxy) neopentane (DOPNP), was synthesized successfully, and its structure was characterized by FT‐IR, ¹H NMR, and ³¹P NMR. The thermogravimetric analysis (TGA) results demonstrate that DOPNP showed a good char‐forming ability. Its initial decomposition temperature was 236.4°C based on 1% mass loss, and its char residue was 41.2 wt % at 600°C, and 22.9 wt % at 800°C, respectively. The flame retardancy and thermal degradation behavior of novel intumescent flame‐retardant polypropylene (IFR‐PP) composites containing DOPNP were investigated using limiting oxygen index (LOI), UL‐94 test, TGA, cone calorimeter (CONE) test, and scanning electron microscopy (SEM). The results demonstrate that DOPNP effectively raised LOI value of IFR‐PP. When the loading of IFR was 30 wt %, LOI of IFR‐PP reached 31.3%, and it passed UL‐94 V‐0. TGA results show that DOPNP made the thermal decomposition of IFR‐PP take place in advance; reduced the thermal decomposition rate and raised the residual char amount. CONE results show that DOPNP could effectively decrease the heat release rate peak of IFR‐PP. A continuous and compact char layer observed from the SEM further proved the flame retardance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Flame retardancy and water resistance of novel intumescent flame‐retardant oil‐filled styrene–ethylene–butadiene–styrene block copolymer/polypropylene composites

A novel halogen‐free flame‐retardant composite consisting of an intumescent flame retardant (IFR), oil‐filled styrene–ethylene–butadiene–styrene block copolymer (O‐SEBS), and polypropylene (PP) was studied. On the basis of UL‐94 ratings and limiting oxygen index (LOI) data, the IFRs consisted of a charring–foaming agent, ammonium polyphosphate, and SiO₂ showed very effective flame retardancy and good water resistance in the IFR O‐SEBS/PP composite. When the loading of IFR was only 28 wt %, the IFR–O‐SEBS/PP composite could still attain a UL‐94 V‐0 (1.6 mm) rating, and its LOI value remained at 29.8% after a water treatment at 70°C for 168 h. Thermogravimetric analysis data indicated that the IFR effectively enhanced the temperature of the main thermal degradation peak of the IFR–O‐SEBS/PP composites because of the formation of abundant char residue. The flammability parameters of the composites obtained from cone calorimetry testing demonstrated that water treatment almost did not affect the flammability behavior of the composite. The morphological structures of the char residue and fractured surfaces of the composites were not affected by the water treatment. This was attributed to a small quantity of IFR extracted from the composite. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39575.     

Crystallization behavior of PP/PP‐g‐MAH/GFR PA66 blends: Establishment of their continuous‐cooling‐transformation of relative crystallinity diagrams

Polypropylene/polypropylene‐grafted‐maleic anhydride/glass fiber reinforced polyamide 66 (PP/PP‐g‐MAH/GFR PA 66) blends‐composites with and without the addition of polypropylene‐grafted‐maleic anhydride (PP‐g‐MAH) were prepared in a twin screw extruder. The effect of the compatibilizer on the thermal properties and crystallization behavior was determined using differential scanning calorimetry analysis. The hold time was set to be equal to 5 min at 290°C. These conditions are necessary to eliminate the thermomechanical history in the molten state. The crystallization under nonisothermal conditions and the plot of Continuous‐Cooling‐Transformation of relative crystallinity diagrams of both PP and PA 66 components proves that PP is significantly affected by the presence of PP‐g‐MAH. From the results it is found that an abrupt change is observed at 2.5 wt % of PP‐g‐MAH as a compatibilizer and then levels off. In these blends, concurrent crystallization behavior was not observed for GFR PA66. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1620–1626, 2007     

Synergistic effects of dual imidazolium polyoxometalates on intumescent flame retardant polypropylene

The role of dual imidazolium polyoxometalates (POMs) in the flame retardancy of polypropylene/intumescent flame retardant (PP/IFR) composites was studied. The results showed that the structures of dual imidazolium POMs have a great effect on the flame retardancy of PP composites. The dual imidazolium POMs based on an ethyl group (EMIPMA) obtain the best flame retardant efficiency. With 15.5 wt % IFR and 0.5 wt % EMIPMA, the PP composites reach a limiting oxygen index of 25.7 and the UL‐94 V‐0 standard. However, the dual imidazolium POMs containing a butyl (BMIPMA) or hexyl (HMIPMA) group cannot achieve the UL‐94 V‐0 standard at the same formulation. Dual imidazolium POMs not only promote the formation of good char, but also induce the formation of intumescent char with a hierarchical and microporous structure that helps to prevent gas and heat from transferring from the flame to the resin. Therefore, the flame retardancy of PP/IFR composites is improved. However, excessive combustible components produced by BMIPMA or HMIPMA deteriorate the flame retardancy of PP/IFR composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45491.     

Preparation of a chitosan‐based flame‐retardant synergist and its application in flame‐retardant polypropylene

A novel flame‐retardant synergist, chitosan/urea compound based phosphonic acid melamine salt (HUMCS), was synthesized and characterized by Fourier transform infrared spectroscopy and ³¹P‐NMR. Subsequently, HUMCS was added to a fire‐retardant polypropylene (PP) compound containing an intumescent flame‐retardant (IFR) system to improve its flame‐retardant properties. The PP/IFR/HUMCS composites were characterized by limiting oxygen index (LOI) tests, vertical burning tests (UL‐94 tests), microscale combustion calorimetry tests, and thermogravimetric analysis to study the combustion behavior and thermal stability. The addition of 3 wt % HUMCS increased the LOI from 31.4 to 33.0. The addition of HUMCS at a low additive amount reduced the peak heat‐release rate, total heat release, and heat‐release capacity obviously. Furthermore, scanning electron micrographs of char residues revealed that HUMCS could prevent the IFR–PP composites from forming a dense and compact multicell char, which could effectively protect the substrate material from combusting. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40845.     

Effects of clay contents on the dynamic mechanical and rheological properties of polypropylene/MAH‐g‐POE/clay composites

A series of polypropylene/maleic anhydride grafted polypropylene octane elastomer (MAH‐g‐POE)/clay (PPMC) nanocomposites were prepared with a novel compatilizer MAH‐g‐POE and different contents of octadecyl amine modified montmorillonite, and the effects of clay contents on the dynamic mechanical and rheological properties of these PPMC composites were investigated. With clay content increasing, the characteristic X‐ray diffraction peak changed from one to two with intensity decreasing, indicating the decreasing concentration of the intercalated clay layers. The gradual decrease of crystallization temperature of PPMC composites with the increase of clay loading should be attributed to the preferred intercalation of MAH‐g‐POE molecules into clay interlayer during blending, which is also reflected by scanning electron microscopy observations. By evaluating the activation energy for the glass transition process of MAH‐g‐POE and polypropylene (PP) in the PPMC composites, it is found that clay intercalation could cause the restriction effect on the glass transition of both MAH‐g‐POE and PP, and this restriction effect appears stronger for PP and attained the highest degree at 5 wt % clay loading. The melt elasticity of PP could be improved apparently by the addition of MAH‐g‐POE, and 5 wt % clay loading is enough for further enhancing the elastic proportion of PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal and flammability performance of polypropylene composites containing melamine and melamine phosphate‐modified α‐type zirconium phosphates

In this article, melamine (MA) and melamine phosphate (MP) have been intercalated into α‐type zirconium phosphate (α‐ZrP) interlayer spaces. The structure and thermal properties of the corresponding powders, MA‐ZrP and MP‐ZrP, were ascertained by X‐ray diffraction, Fourier transform infrared spectra, X‐ray photoelectron spectroscopy measurement, and thermogravimetric analyses (TGA). Furthermore, polypropylene (PP) and its intumescent flame retardant (IFR) composites containing the two organically modified α‐ZrP powders using maleic anhydride‐grafted PP (JPP) as compatibilizer were fabricated by melt blending. The results from TGA and cone calorimetry demonstrated that PP/JPP and PP/JPP/IFR composites containing MA‐ZrP and MP‐ZrP exhibited better thermal stability and burning behavior in comparison with their corresponding counterparts, PP/JPP and PP/JPP/IFR, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40254.     

钛酸酯偶联剂在膨胀型阻燃聚丙烯中的偶联作用

研究了钛酸酯偶联剂（TTOPP）对聚丙烯/膨胀型阻燃剂（PP/IFR）复合材料阻燃性能和力学性能的影响,并采用扫描电子显微镜、偏光显微镜和X射线衍射研究了复合材料的微观形态和结晶行为。结果表明,加入TTOPP后,IFR在PP中的分散更加均匀,PP球晶的大小趋于一致,适量的TTOPP改善了IFR与PP间的相容性,促进了IFR对PP形成β晶的诱导作用。当PP/IFR/TTOPP为75/25/0.375时,复合材料的综合性能最佳,自熄时间降到24 s,拉伸强度和冲击强度比PP/IFR分别提高了14.0 %和12.0 %。     

Synthesis of phosphorus‐ and phenyl‐based ROMP polymers and investigation of their effects on the thermomechanical and flammability properties of a polypropylene–IFR system

In this study, we present an approach for the synthesis of novel phosphorous‐ or phenyl‐ containing polymers, 2_phenyl, 3_phospho, and 2_phenyl‐co‐3_phospho, derived from ring‐opening metathesis polymerization (ROMP), to reduce the flammability of polypropylene (PP). The composites were processed by melt‐blending ROMP polymers and octaphenyl–polyhedral oligomeric silsesquioxane with PP/intumescent flame retardant (IFR) compounds at different compositions. The composites were characterized by limiting oxygen index (LOI), UL‐94, and mechanical tests as well as thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The molecular structures of phosphorous‐ and phenyl‐containing polymers were proved by ¹H‐NMR, ¹³C‐NMR, and Fourier transform infrared spectroscopy. The online rheological measurements indicated that the addition of additives to the PP/IFR system increased the melt viscosity of the compounds regardless of the type. The DSC analysis showed that the addition of ROMP polymers to the PP/IFR system influenced the crystal perfection and degree of crystallization. TGA analysis of the composites revealed that the addition of ROMP polymers to PP/IFR compounds deteriorated the thermal stability as the amount of phosphorus increased in the matrix. Dynamic mechanical properties such as storage modulus (E′) and loss modulus (E″) of the composites were lowered by the addition of ROMP polymers. The LOI and UL‐94 rating of PP/IFR were enhanced by the addition of ROMP polymers. It was successfully demonstrated that the novel phosphorous‐ or phenyl‐containing polymers were highly potent additives in optimizing the flammability of PP composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45998.     

Effect of maleic‐anhydride‐grafted polypropylene as a compatibilizer on the properties of polypropylene/(modified carbon black) composites

Maleic‐anhydride‐grafted polypropylene (PP‐g‐MAH) was added, as a compatibilizer, to polypropylene (PP) composites filled with a hindered phenol and modified carbon black (CB). The interaction between the modified CB and PP‐g‐MAH, as proved by Fourier transform infrared spectroscopy, had a beneficial effect on the mechanical properties of the PP/(modified CB) composites and prevented the sharp decrease of the mechanical properties of these composites at higher filler concentration. The storage modulus of PP/(modified CB) was increased significantly by the incorporation of PP‐g‐MAH, especially when the temperature was lower than 0°C. When the content of PP‐g‐MAH was 5 wt% and the loading of the modified CB was 2 wt%, the best tensile strength was obtained. The system showed the best flexural strength and impact strength when the loading of the modified CB was 1 wt%. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Improvement of the physico‐mechanical properties and stability of waste polypropylene in the presence of wood flour and (maleic anhydride)‐grafted polypropylene

This paper deals with (maleic anhydride)‐grafted polypropylene (MAH‐g‐PP) and wood flour reinforcement and their effects on the dynamic, mechanical, morphological, and rheological properties of waste polypropylene (PP) composites. MAH‐g‐PP was used as a compatibilizer to improve the physical interaction between the filler and matrix. The composites were prepared by using a twin‐screw extruder followed by injection molding. Thermal stability and mechanical properties of the compatibilized system increased as compared to their values for the uncompatibilized system. Also, nearly 60% and 30% loss was found for mechanical properties and weight loss, respectively, in a biodegradability study. J. VINYL ADDIT. TECHNOL., 20:24–30, 2014. © 2014 Society of Plastics Engineers     

Flammability,thermal stability,and mechanical properties of ethylene-propylene-diene monomer/polypropylene composites filled with intumescent flame retardant and inorganic synergists

Three kinds of inorganic particles, zinc borate (ZB), organic montmorillonite (OMMT), and expanded graphite (EG) as synergistic flame retardants, are incorporated into ethylene-propylene-diene monomer/polypropylene (EPDM/PP) composites filled with intumescent flame retardants (IFR). The effect of three synergistic flame retardants on the combustion, thermal stability, and mechanical properties of the EPDM/PP/IFR composites are investigated by limiting oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), scanning electron microscopy, mechanical property testing, and dynamic mechanical analysis (DMA). The results from LOI, UL-94, and CCT show that the synergistic effect of IFR with ZB and EG is better than IFR with OMMT in the flame retardant EPDM/PP/IFR composites. The TGA results indicate that the thermal stability and char residues of the composites is improved with the addition of inorganic particles, which is attributed to the formation of dense char layers to isolate heat flow. DMA results including storage modulus (G'), loss modulus (G"), and loss factor (tan δ) suggest that the composites with inorganic particles exhibit more rubber-filler interaction, which limits the movement of the rubber chains.     

Extrusion foaming behavior of a polypropylene/nanoclay microcellular foam

With maleic anhydride grafted polypropylene (PP‐g‐MAH) as a compatibilizer, composites of block‐copolymerized polypropylene (B‐PP)/nanoclay were prepared. The effects of the PP‐g‐MAH and nanoclay content on the crystallization and rheological properties of B‐PP were investigated. The microcellular foaming behavior of the B‐PP/nanoclay composite material was studied with a single‐screw extruder foaming system with supercritical (SC) carbon dioxide (CO₂) as the foaming agent. The experimental results show that the addition of nanoclay and PP‐g‐MAH decreased the melt strength and complex viscosity of B‐PP. When 3 wt % SC CO₂ was injected as the foaming agent for the extrusion foaming process, the introduction of nanoclay and PP‐g‐MAH significantly increased the expansion ratio of the obtained foamed samples as compared with that of the pure B‐PP matrix, lowered the die pressure, and increased the cell population density of the foamed samples to some extent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44094.     

Effect of silane‐grafted polypropylene on the mechanical properties and crystallization behavior of talc/polypropylene composites

Talc‐filled polypropylene (PP) composites coupled with silane‐grafted polypropylene (PP‐g‐Si) were prepared. Effect of PP‐g‐Si on the mechanical properties, crystallization, and melting behavior of PP composites was investigated. Compared with the uncoupled composites, the mechanical properties of Talc/PP composites coupled with a small amount of PP‐g‐Si were increased to some extent. Meanwhile, PP‐g‐Si can promote crystallization rate and increase crystallization temperature of PP in the composites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2974–2977, 2000