Preparation and characterization of waterborne polyurethane containing PET waste/PPG as soft segment

Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis using a 1 : 3 molar ratio of PET repeating unit to glycols like neopentyl glycol (NPG) and dipropylene glycol (DPG). Further, a series of waterborne polyurethanes (WPUs) was synthesized using pure polypropylene glycol (PPG), and glycolyzed oligoesters/PPG blends in different molar ratios as soft segment. Thermal property of WPU was tested by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Moreover, viscosity and particle size of WPU were also investigated. The results show that introduction of a certain amount of glycolyzed oligoester to soft segment makes the degree of hard‐soft domain microphase separation smaller, and can also improve thermal stability of WPU. Furthermore, WPUs synthesised from glycolyzed oligoesters and PPG blends possess larger particle size, better particle size distribution, relative lower and more stable viscosity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42757.     

Novel phosphorus‐based flame retardants containing 4‐tert‐butylcalix[4]arene: Preparation and application for the fire safety of epoxy resins

A novel flame retardant (FR) containing phosphorus and 4‐tert‐butylcalix[4]arene was synthesized and characterized. The FR combined with ammonium polyphosphate (APP) was then incorporated into epoxy resins (EPs) at different ratios. The flame retardancy, thermal stability, and smoke‐releasing properties were investigated. The limiting oxygen index was as high as 30.8% when the mass fraction ratio of the FR to APP was 1:2. The improved FR effect have been due to the combined FR effects between the FR and APP. The char residue content at 800 °C under a nitrogen atmosphere increased notably from 8.22% to 17.6% when the FR APP was incorporated into EP; this indicated an improvement in the thermooxidation resistance. From the cone test, we found that both the total heat‐release and peak heat‐release rate of the FR resins were reduced. Compared to the resins containing no FRs, the smoke‐production rate and total smoke‐production results indicate that the FR resins also exhibited good smoke‐suppression properties. Generally, the stable char layer of the FR APP–EP not only effectively prevented the release of combustion gases but also hindered the propagation of oxygen and heat into the interior substrate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45105.     

Kinetics of degradation of PVC‐containing novel neem oil as stabilizer

The effectiveness of adding epoxidized neem oil (ENO) in poly(vinyl chloride) (PVC) to enhance heat stability was investigated. Neem oil, of vegetable extract, was characterized for its fatty acid profile and other properties. The virgin oil was epoxidized at 60°C with peroxymethanoic acid (performic acid) generated in situ in the reaction mixture by reacting hydrogen peroxide and methanoic acid. ENO was characterized by FTIR and NMR studies, and the degree of epoxidation was measured with iodine value and oxirane oxygen content. Solubility parameters of neem oil and ENO were estimated. Thermal degradation of PVC‐containing ENO was studied using the static heat stability test and artificial aging at temperatures of 100, 110, 120, and 130°C. Results were compared with the samples prepared with conventional heat stabilizers systems used in PVC, such as Ca/Zn stearates and mixtures of both Ca/Zn stearates and ENO. The changes in elastic modulus of the ENO/PVC combination and the conventionally stabilized Ca/Zn system during aging were kinetically modeled, and the rate constants for the degradative influence of modulus were determined. The activation energies and preexponential factors for the degradative process were obtained from Arrhenius plots and their relationship through a compensation effect was found. In general, ENO was found to be an effective retarder of the degradation of PVC; use of 10 phr level of ENO showed the least degradation with the highest activation energy. A synergistic effect of ENO and Ca/Zn stearate system was also observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Imide‐containing ladder polyphenylsilsesquioxanes with high thermal stability and thermoplastic properties

This work reports for the first time the synthesis of ladder polyphenylsilsesquioxanes containing imide building blocks as parts of the main parallel chains. The ladder structure of the synthesized polymers was documented by means of small angle X‐ray scattering (SAXS) measurements. The obtained ladder polymers exhibit stability with respect to decomposition up to temperatures as high as 460°C; additionally, they have melting points far below their decomposition temperatures, which make them interesting candidate materials for thermoplastic processing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40085.     

聚氯乙烯用Ca/Zn热稳定剂的研究概况

综述了聚氯乙稀Ca／Zn稳定剂的研究进展,讨论了Ca／Zn稳定剂稳定聚氯乙烯的机理以及多元醇、沸石、亚磷酸酯、β-二酮等对Ca／Zn稳定剂的协同作用。     

Thermal degradation and combustion behavior of intumescent flame‐retardant polypropylene with novel phosphorus‐based flame retardants

The objective of this study was to develop an environmentally friendly fire‐retardant polypropylene (PP) with significantly improved fire‐retardancy performance with a novel flame‐retardant (FR) system. The system was composed of ammonium polyphosphate (APP), melamine (MEL), and novel phosphorus‐based FRs. Because of the synergistic FR effects among the three FRs, the FR PP composites achieved a V‐0 classification, and the limiting oxygen index reached as high as 36.5%. In the cone calorimeter test, both the peak heat‐release rate (pHRR) and total heat release (THR) of the FR PP composites were remarkably reduced by the incorporation of the novel FR system. The FR mechanism of the MEL–APP–FR–PP composites was investigated through thermogravimetric analysis and char residue characterization, and the results reveal that the addition of MEL–APP–FRs promoted the formation of stable intumescent char layers. This led to the reduction of pHRR and THR and resulted in the improvement of the fire retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45962.     

Insights into the use of zinc–mannitol alkoxide as a novel thermal stabilizer for rigid poly(vinyl chloride)

Zinc–mannitol alkoxide (Zn–Man) was synthesized through alcohol exchange reaction, and investigated by means of Fourier transform infrared spectroscopy and elemental analysis. The thermal stability of Zn–Man for rigid poly(vinyl chloride) (PVC) was evaluated by Congo red testing, conductivity measurements, thermal aging testing, thermogravimetric analysis (TGA), and ultraviolet–visible (UV–vis) spectroscopy test. The experimental results demonstrate that the addition of Zn–Man not only apparently prolonged the static thermal stability time to approximately 96.5 min but also evidently improved the initial color of PVC. More importantly, the color of the PVC sheets stabilized with Zn–Man did not change to black within 180 min; this showed that no zinc‐burning phenomenon occurred. In addition, the results of TGA reveal that Zn–Man raised the initial degradation temperature of PVC to about 273.4°C. UV–vis testing indicated that the presence of Zn–Man decreased the content and shortened the length of the conjugated double bonds of PVC. The possible thermal stability mechanism is discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42038.     

Effects of medium phases on the thermal degradation of hydrogenated nitrile rubber O‐rings under compression

The degradation of hydrogenated nitrile rubber O‐rings under exposure to either air or hydraulic oil under compression were investigated at elevated temperatures. The physical and chemical changes of the samples aged for various durations were studied by measuring the weight, compression set, tensile strength, elongation at break, crosslinking density, fracture morphology, and attenuated total reflection–Fourier transform infrared (ATR–FTIR) spectroscopy. The results indicate that the weight decreased with exposure time and temperature and that weight loss was greater in oil. Crosslinking and chain scission both occurred during the aging process. The significant changes in the mechanical properties indicate that more severe degradation occurs in air. The fracture morphologies results show that the fracture surfaces aged in oil become rougher and have more defects. The ATR–FTIR results demonstrate that the hydroxyl groups were formed in air and oil, while carboxyl groups were only generated in air. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45864.     

Rheological and thermal properties of thermoplastic natural rubbers based on poly(methyl methacrylate)/epoxidized‐natural‐rubber blends

Epoxidized natural rubbers (ENRs) with epoxide levels of 10, 20, 30, 40, and 50 mol % were prepared. The ENRs were later blended with poly(methyl methacrylate) (PMMA) with various blend formulations. The mixing torque of the blends was observed. The torque increased as the PMMA contents and epoxide molar percentage increased in the ENR molecules. Furthermore, the shear stress and shear viscosity of the polymer blends in the molten state increased as the ENR content and epoxide molar percentage increased in the ENR molecules. Chemical interactions between polar groups in the ENR and PMMA molecules might be the reason for the increases in the torque, shear stress, and viscosity. All the ENR/PMMA blends exhibited shear‐thinning behavior. This was observed as a decrease in the shear viscosity with an increase in the shear rate. The power‐law index of the blends decreased as the ENR contents and epoxide molar percentage increased in the ENR molecules. However, the consistency index (or zero shear viscosity) increased as the ENR contents and epoxide molar percentage increased. A two‐phase morphology was observed with scanning electron microscopy. The small domains of the minor components were dispersed in the major phase. For the determination of blend compatibility, two distinct glass‐transition‐temperature (T_g) peaks from the tan δ/temperature curves were found. Shifts in T_g to a higher temperature for the elastomeric phase and to a lower temperature for the PMMA phase were observed. Therefore, the ENR/PMMA blends could be described as partly miscible blends. According to the thermogravimetry results, the decomposition temperatures of the blends increased as the levels of ENR and the epoxide molar percentage increased. The chemical interactions between the different phases of the blends could be the reason for the increase. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3561–3572, 2004     

Preparation and properties of three novel poly(phosphazene‐aryl amide)s containing cyclotriphosphazene structures

1,1,3,5‐tetraphenoxy‐3,5‐bis(4‐aminoanilino)cyclotriphosphazene, 1,1,3,5‐tetraphenoxy‐3,5‐bis[4‐(4‐aminophenysulfone)anilino)]cyclotriphosphazene, and 1,1,3,5‐tetraphenoxy‐3,5‐bis(N,N′‐ethanediamine)cyclotriphosphazene were synthesized in two steps from the p‐Phenylenediamine, 4,4′‐diaminodiphenylsulfone, and ethylenediamine via nucleophilic substitution and catalytic reduction with hexachlorocyclotriphosphazene. Three novel aromatic polyamides such as poly(cyclotriphosphazene‐p‐phenylene amide), poly(cyclotriphosphazene‐p‐sulfuryl amide), and poly(cyclotriphosphazene‐ethyl amide) were synthesized from these diamines by direct polycondensation reaction with terephthaloyl chloride and pyridine in N‐methyl pyrrolidone, respectively. The chemical structures of the diamine monomers and three novel poly(cyclotriphosphazene‐aryl amide)s were characterized by Fourier Transform Infrared, (¹H and ³¹P) Nuclear Magnetic Resonance, and Elemental Analysis. The thermal properties of the polyamides were determined by Differential Scanning Calorimetry and Thermogravimetric Analysis (TGA). The crystallization behaviors of the polyamides were studied by Wide‐ray X‐ray diffraction, and the morphology of the pyrolysis residues were observed by Scanning Electron Microscope. The three poly(cyclotriphosphazene‐aryl amide)s with amorphous structure would exhibit an enhanced solubility in polar aprotic solvents and a superior thermal stability with initial decomposition temperature being at about 198–259°C. TGA curves of the poly(cyclotriphosphazene‐aryl amide)s exhibit mainly three thermal decomposition steps, and the poly(cyclotriphosphazene‐p‐phenylene amide) presents the highest solid residue rate 62.6% heated to 600°C. In the morphology analysis of the poly(cyclotriphosphazene‐aryl amide) solid residues, organophosphorus gelatum forms in the surface layer were observed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Colorants based on renewable resources and food‐grade colorants for application in thermoplastics

A series of colorants based on renewable resources and food‐grade colorants have been evaluated for use in polypropylene (PP) and polyvinylchloride (PVC). It has been found that most of these colorants can be processed in PP at 200°C or even 260°C while maintaining good color intensity and color brightness. The colorants evaluated cover a large part of the color spectrum. In PP, the light stability of alizarin (red), carmine (red), indigo (blue), purpurin (red), quinizarin (red), and the aluminium lakes of quinoline yellow (yellow) and indigo carmine (blue) is close to the requirements for indoor applications. The blue colorants indigo and the aluminium lake of indigo carmine are, in principle, sufficiently light stable in PP for indoor applications. A few colorants showed bleeding from PP. Bonding of migrating colorants to the reactive carrier maleic anhydride grafted polypropylene, however, reduced bleeding of the colorant to a large extent. Also after processing in PVC at 200°C, good color intensity and saturation is maintained. Quinizarin, a structural analog of alizarin and purpurin, shows a light stability performance that is close to commercial lead chromate/molybdate orange based colorants. The best performing natural colorants are sufficiently heat and light stable for applications where moderate properties concerning heat resistance and (UV) light stability are required, such as underground PVC water drainage pipes and indoor PP applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2961‐2969, 2004     

Preparation of intercalated Mg‐Al layered double hydroxides and its application in PVC thermal stability

The Mg‐Al oxide precursor prepared by the calcination of Mg‐Al‐carbonated layered double hydroxide (LDH) at 500 K for 4 h is used as the host material, 2‐hydroxy‐4‐methoxybenzophenone‐5‐sulfonic acid (BP) is used as the guest material, BP‐intercalated LDH (LDH‐BP) is prepared by ion‐exchange method. The structure of LDH‐BP is characterized by X‐ray diffraction (XRD), Fourier transform infrared (FTIR), and thermogravimetry and differential thermal analysis (TG‐DTA). The thermal stability of PVC/BP, PVC/LDH, PVC/LDH‐BP composites, as well as pure PVC is investigated by conventional Congo Red test and dynamic thermal stability analysis in both the open and closed processing environments. According to XRD and FTIR, BP anions have been intercalated into interlayer galleries of LDH. TG‐DTA results show that the layer‐anionic interaction results in the improvement of the thermal stability of BP. Congo Red tests indicate that the addition of BP catalyzes the thermal degradation of PVC. A little amount of LDH (such as 1 phr) makes PVC more stable, but excessive addition accelerates the thermal degradation of PVC. The addition of LDH‐BP markedly improves the static thermal stability of PVC. The results of dynamic thermal stability tests in both the open and closed processing environments are consistent with that of Congo Red tests. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Design of green zinc‐based thermal stabilizers derived from tung oil fatty acid and study of thermal stabilization for PVC

In this study, a new type of mixed calcium (Ca) and zinc (Zn) thermal stabilizers was prepared and evaluated for poly(vinyl chloride) (PVC) thermal stabilization. The mixed stabilizers were based on the Ca and Zn salts of polycarboxylic acid derived from eleostearic acid—the dominant fatty acid of tung oil fatty acids. Eleostearic acid was converted to a 21‐carbon diacid (C21DA) and a 22‐carbon triacid (C22TA), respectively, which were subsequently turned into calcium (Ca) and zinc (Zn) salts. Thermal stability of PVC compounds was examined by thermogravimetric analysis (TGA), discoloration test, Congo red test, and thermal decomposition kinetics. In comparison, commercial mixed Ca/Zn thermal stabilizers composed of stearate salts (CaSt₂/ZnSt₂), were employed as controls. Because the salts of C21DA, C22TA and stearate have different metal contents, thermal stabilization effects were compared on the basis of both equal salt weight and equal metal ion content. It was noted that under both cases the long‐term thermal stability of the PVC samples followed the order of C21DA‐Ca/C21DA‐Zn > C22TA‐Ca/C22TA‐Zn > CaSt₂/ZnSt₂. The results suggest that the mixed Ca/Zn salts based on tung oil‐derived polycarboxylic acids have higher metal ion contents and cycloaliphatic structures and can effectively improve the thermal stability of PVC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44679.     

Compatibilized blends of PVC/PA12 and PVC/PP containing poly(lauryl lactam‐block‐caprolactone)

Specially designed block copolymers have played a role as compatibilizing agents in the system of immiscible polymer blends. We applied lauryl lactam (LA)–caprolactone (CL) block copolymer [P(LA‐b‐CL)] as a compatibilizing agent for immiscible poly(vinyl chloride) (PVC) blends with various polymers. These blends possess high thermal performance and toughness. We investigated the effect of P(LA‐b‐CL) as a compatibilizing agent for immiscible PVC blends with poly(ω‐lauryl lactam) [polyamide 12 (PA12)]. We also described the invention of a new compatibilizing agent system involving P(LA‐b‐CL) for PVC/polypropylene (PP) blends. The mechanical and thermal properties of (1) PVC/PA12 blend compatibilized with P(LA‐b‐CL) and (2) PVC/PP blend compatibilized with P(LA‐b‐CL)/PA12/maleic anhydride–modified PP were both enhanced. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1983‐1992, 2004     

Rigid polyisocyanurate–waterglass foam composite: Preparation,mechanism, and thermal and flame‐retardant properties

A rigid polyisocyanurate–waterglass foam (PIWGRF) composite was prepared with polyaryl poly(methylene isocyanate) and waterglass (WG) as the main materials; water as a blowing agent, and no polyols. We speculated the formation mechanism of the PIWGRFs on the basis of the analysis of experiment data, scanning electron microscopy characterization, and transmission electron microscopy. The results show that three‐dimensional nanoflakes derived from the cured WG was observed; this was connected with polyisocyanurate by secondary bonding (Si? O? H?N). Thermogravimetric testing indicated that the thermal stability and residual mass (34%) of the PIWGRFs were significantly higher than those of rigid traditional polyurethane foams (T‐PUFs). When the core density of the PIWGRFs was 32.6 kg/m³, the strength was up to 162.9 KPa by excessive filling. The flame retardancy of the PIWGRFs, including the time to ignition, heat‐release rate, total smoke of release, and limiting oxygen index, was obviously better than that of the T‐PUFs. The structure of the residual char was more dense and orderly; this was also an effective barrier layer. The reason was attributed to the fact that the WG did not contain combustible elements. So, the PIWGRFs had excellent thermal stability, flame retardancy, and environmental friendliness. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46182.     

Thermally conductive high-density polyethylene as novel phase-change material: Application-relevant long-term stability

The long-term stability of thermally conductive high-density polyethylene (HDPE)-based compounds as phase-change material (PCM) is investigated. For this purpose, the HDPE's thermal conductivity (TC) is first enhanced via compounding two different filler types (expanded graphite and aluminum) into the polymeric matrix. Bulky specimens of these compounds are then stored in air for up to 7289 h in the melt state to investigate the compounds' long-term stability as PCM. Their thermo-oxidative/thermal stability and their ability to maintain the isotropic material character (homogeneous distribution of the incorporated particles) is investigated. The compounds' degradation behavior is monitored via Fourier-transform infrared spectroscopy and the maintenance of the homogeneous filler distribution is examined via a combined differential scanning calorimetry/thermogravimetric analysis mapping of each exposed specimen. The storage capacity decreases minimally after 7289 h of exposure. Furthermore, the incorporated filler particles enhance the thermo-oxidative stability of HDPE as PCM. Consequently, thermally conductive HDPE is a highly interesting PCM. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48269.     

Preparation and application of phosphorous‐containing bio‐polyols in polyurethane foams

A bio‐polyol phosphonate acting as the polyol component in the preparation of polyurethane foam was synthesized from the liquefaction product of bagasse by the halogenation of the liquefaction product followed by the Michaelis–Arbuzov rearrangement. The FT‐IR spectra showed that phosphorus‐containing groups were introduced into the polyol chain. The data of the viscosity and the hydroxyl number suggested that the bio‐polyol phosphonate would be a good polyol component in the preparation of polyurethane foam. The limiting oxygen index of polyurethane foam containing bio‐polyol phosphonate varied in the range of 24–28, while that of polyurethane foam without bio‐polyol phosphonate was 23, demonstrating that the introduction of the phosphorus‐containing group into the polymer helped to improve the flame retardancy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40422.     

Thermal induced shape‐memory and self‐healing of segmented polyurethane containing diselenide bonds

Herein, we synthesized a series of polyurethane copolymers (PUs) with poly(1,4‐butylene adipate) glycol as soft segment and 2,4‐toluene diisocyanate as well as extenders including 1,4‐butanediol and di(1‐hydroxyethylene) diselenide as hard segment. The chemical structure, thermal property, crystallization behavior, shape memory, and self‐healing performances of the PUs were systematically characterized by a series of experiments. It was found that the PU2 containing a higher diselenide component (～33 mol %) exhibited both shape memory and self‐healing behaviors under a moderate temperature (～57 °C). Meanwhile, the PUs showed a good repeatability of shape memory function, and their fixity and recovery ratios were all above 90%. Additionally, the dynamic exchangeable feature of diselenide bonding endues the PUs chains with an acceptable reprocessability and self‐healing performances, and the PU2 sample could be healed for five times by thermal treatment with the healing efficiencies above 70%. This work provides a heuristic perspective for the development of shape memory and self‐healing materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46326.     

Flame‐retarded polystyrene with phosphorus‐ and nitrogen‐containing oligomer: Preparation and thermal properties

A phosphorus‐ and nitrogen‐containing compound (2‐dimethylamino ethyl phenyl hydroxyethyl acrylate phosphate) and its oligomer (poly(2‐dimethylamino ethyl phenyl hydroxyethyl acrylate phosphate), PDPHP) were synthesized and characterized. The polystyrene (PS) composites with various amounts of PDPHP were prepared by melt blending. The thermal stability of the PDPHP and PS composites was investigated by thermogravimetric analysis. The flame retardancy of the composites was evaluated using microscale combustion calorimeter and limiting oxygen index test. A Fourier transform infrared (FTIR) spectroscopy coupled with a thermogravimetric analyzer was also used to study the gas phase from the degradation of PS composites. The char residues of the PS composites containing 30 wt % PDPHP were analyzed by FTIR and scanning electron microscopy. The results suggest that the incorporation of PDPHP into PS can evidently enhance the char formation and improve the flame retardancy of virgin PS. The compact and coherent char formed during degradation was attributed to the enhancement of char quality and flame retardance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation,cure kinetics,and thermal properties of novel acetylene terminated silazanes

A new kind of acetylene terminated silazanes, N‐(3‐acetylenephenyl)‐diorganosilazanes (abbreviated as APSZs) with three kind of substituents, were synthesized by the aminolysis of dichlorosilane with 3‐aminophenylacetylene (3‐APA). Structure of APSZs was confirmed by Fourier transform infrared spectroscopy (FT‐IR) and nuclear magnetic resonance (NMR). Thermal behavior of the cured silazanes was determined by thermogravimetry analysis (TGA), revealing that cured silazanes exhibited high temperature resistance. The ceramic yields of APSZ‐Me₂, APSZ‐MeVi, and APSZ‐Ph₂ at 1000°C under nitrogen were 77.6, 81.9, and 68.7%, respectively. The peak separation of derivative thermogravimetric data was employed to evaluate the three major regions of the thermolysis, and the kinetic parameters of thermolysis were calculated by the method of Kissinger from dynamic thermogravimetric measurement in nitrogen atmosphere at several different heating rates. Influence of substituents on the thermal behavior of cured silazanes in each separated region was discussed. The results showed that the vinyl derivative exhibit higher thermal stability than methyl and phenyl derivatives due to the high decomposition activation energy and small pendant group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012