等规聚丙烯-丙烯酸接枝共聚

详细研究了等规聚丙烯细粒子在丙烯酸水溶液中,以过氧化苯甲酰为引发剂的液－固相接枝共聚反应和十氢化萘乙醇溶液对等规聚丙烯的膨化预处理作用,检测了等规聚丙烯－聚丙烯酸的某些性质,发现随接枝率提高,其吸湿性和碱性染料染色性均提高,熔点略有降低,但熔体流动性下降,按本研究获得的最佳膨化预处理条件和最佳接枝共聚反应条件,接枝产物等规聚丙烯－聚丙烯酸的接枝率可超过13％。     

Graft copolymerization of acrylic acid onto methylcellulose by potassium permanganate‐p‐xylene redox pair

Poly(acrylic acid) was grafted onto methylcellulose in aqueous media by a potassium permanganate‐p‐xylene redox pair. Within the concentration range from 0.93 × 10^?3 to 9.33 × 10^?3M, p‐xylene, the graft copolymerization reaction exhibited minimum and maximum graft yields and was associated with two precursor‐initiating species, a p‐xylyl radical and its diradical derivative. The efficiency of the graft was low, not higher than 12.9% at a p‐xylene concentration of 0.93 × 10^?3M and suggested the dominance of a competitive homopolymerization reaction under homogeneous conditions. The effect of permanganate on the graft yield was normal and optimal at 135% graft yield, corresponding to a concentration of the latter of 33.3 × 10^?3M over the range from 8.3 × 10^?3 to 66.7 × 10^?3M. The conversion in graft yield showed a negative dependence on temperature in the range 30–60°C and suggested a preponderance of high activation energy transfer reaction processes. The calculated composite activation energy for the graft copolymerization was 7.6 kcal/mol. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 278–281, 2004     

Influence of various reaction media on the thermal and rheological properties of poly(acrylamide‐co‐N‐hexadecylacrylamide)

A hydrophobically modified polyacrylamide (PAM) was synthesized by the copolymerization of acrylamide (Am) and N‐hexadecylacrylamide (hAm) through solution copolymerization in a polar organic solvent. Polymer synthesis was performed in three nonaqueous media, including dimethyl sulfoxide (DMSO), a mixture of DMSO and an anionic surfactant such as sodium dodecyl sulfate, and a mixture of DMSO and an acidic surfactant such as dodecyl benzene sulfonic acid. The obtained copolymer, poly(acrylamide‐co‐N‐hexadecylacrylamide) [poly(Am‐co‐hAm)], was characterized by ¹H‐NMR. The physical properties of poly(Am‐co‐hAm)s synthesized in different media were compared with those of PAM and with each other by viscosity measurement, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. We investigated the ways in which the polymerization medium affected the hydrophobic distribution within the resulting copolymer structure. This aspect, in turn, should have altered the solution properties and the microstructure of the copolymer. For this purpose, we studied the viscometric behavior in diluted solutions, the thermal behavior and thermal stability of the copolymers, and finally, the crystalline structure of the copolymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39939.     

Thermal stability and decomposition mechanism of poly(p‐acryloyloxybenzoic acid and poly (p‐methacryloyloxybenzoic acid) and their graft copolymers with polypropylene,Part II

Thermal stability and decomposition mechanism of poly(p‐acryloyloxybenzoic) acid (PABA), p‐methacryloyloxybenzoic acid (PMBA), and their graft coproducts of PP were studied by differential scanning calorimetry, direct pyrolysis mass spectrometry, and TG/IR system, combined thermogravimetric analyzer, and FTIR spectrometer. The homopolymers and corresponding grafts were found to be stable in nitrogen atmosphere but started to decompose under atmospheric conditions when heated above 230°C. PABA and PAPA‐g‐PP showed a better thermal stability compared to the other polymer. The degradation proceeded predominantly by decomposition of side groups giving phenol, benzoic acid, hydroxybenzoic acid, carboxylic and carbonyl groups, and by decomposition of phenol into cyclodiene mainly. It was also seen that the degradation path did not greatly changed whether the PABA or PMBA were homopolymers or grafted onto PP but the induction temperature of grafted polymers was seen at some 10–20°C higher. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Correlation of chemical composition and microstructure with properties of poly(ɛ‐caprolactone‐co‐p‐dioxanone) random copolymers

With the aim to develop novel biodegradable materials with good flexibility and fast degradation rate, random copolymers of ?‐caprolactone (CL) and p‐dioxanone (PDO) with a full range of compositions were synthesized in bulk using stannous octoate as the ring‐opening catalyst. The chemical composition and number average sequence lengths of CL and PDO units determined by ¹H‐NMR were used to correlate with various properties of the copolymers. Although both CL and PDO are crystalline components, only one crystalline phase could be present for each copolymer. The low limit of average block length for the copolymers that could crystallize is 3.22 for L_CL and 3.43 for L_PDO, respectively. The crystallinity and crystalline morphology of the copolymers are dependent on the crystalline component as well as its number average sequence length. Irrespective of composition, all the copolymers have good solubility in chloroform with glass transition temperature much below room temperature, implying good flexibility of the materials. The incorporation of PDO component could significantly increase the water wettability of the copolymer surfaces and thereby accelerate the degradation rate of the materials. In conclusion, flexible biodegradable polymers with adjustable degradation and crystalline properties were acquired by random copolymerization of CL and PDO, which are expected to use in tissue engineering and drug delivery fields. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2978–2986, 2013     

Graft copolymerization of methacrylic acid onto isotactic polypropylene by radiochemical methods

Graft copolymerization of methacrylic acid onto isotactic polypropylene has been studied in water–methanol medium using γ-rays as the source of initiation. Graft copolymerization has been conducted by (1) mutual irradiation, (2) preirradiation, and (3) double irradiation methods. All of the reaction parameters that seem to influence grafting have been studied, and the optimum conditions leading to maximum percentage of grafting have been evaluated. A plausible mechanism for radiation-induced grafting of methacrylic acid onto polypropylene has been suggested, and the results have been explained on the basis of the proposed mechanism. A comparative study of graft copolymerization by different radiation methods has been made, and it was observed that the preirradiation method affords the best results. Evidence of grafting has been obtained from differential scanning calorimetric analysis and the dyeing behavior of the grafted material. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 143–152, 1998     

Poly(l‐lactic acid) with the organic nucleating agent N,N,N′‐tris(1H‐benzotriazole) trimesinic acid acethydrazide: Crystallization and melting behavior

N,N,N′‐Tris(1H‐benzotriazole) trimesinic acid acethydrazide (BD) was synthesized from 1H‐benzotriazole acetohydrazide and trischloride to serve as an organic nucleating agent for the crystallization of poly(l ‐lactic acid) (PLLA). First, the thermogravimetric analysis of BD exhibited a high thermal decomposition temperature; this indicated that BD maybe used as a heterogeneous nucleating agent of PLLA. Then, the effect of BD on the crystallization and melting behavior of PLLA was investigated through differential scanning calorimetry, depolarized light intensity measurements, and wide‐angle X‐ray diffraction. The appearance of a nonisothermal crystallization peak and increases in the glass‐transition temperature and the intensity of the diffraction peak suggested that the presence of BD accelerated the overall PLLA crystallization. Upon cooling at a rate of 1°C/min, the addition of just 0.5 wt % BD to PLLA increased the onset crystallization temperature from 101.4 to 111.3°C, and the nonisothermal crystallization enthalpy increased from 0.1 to 38.6 J/g. The isothermal crystallization behavior showed that the crystallization half‐time of PLLA with 0.5 wt % BD (PLLA/0.5% BD) decreased from 49.9 to 1.1 min at 105°C. However, the equilibrium melting point of PLLA/0.5% BD was lower than that of the pristine PLLA; this resulted from the increasing nucleating density of PLLA. The melting behavior of PLLA/0.5% BD further confirmed that BD improved the crystallization of PLLA, and the double‐melting peaks of PLLA/0.5% BD were assigned to melting–recrystallization. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42402.     

Comparative study of the nucleation activity of third‐generation sorbitol‐based nucleating agents for isotactic polypropylene

The nucleation activity of the sorbitol derivatives 1,2,3,4‐bis(3,4‐dimethylbenzylidene sorbitol) and methyldibenzylidene sorbitol are compared with that of talc, a conventional nucleating agent for the monoclinic crystalline phase of isotactic polypropylene. The thermal parameters associated with the dynamic crystallization process are studied as a function of the cooling rate by differential scanning calorimetry, and the nucleating efficiency is assessed by comparison with self‐nucleation, the highest values being observed for 1,2,3,4‐bis(3,4‐dimethylbenzylidene sorbitol) over the whole concentration range. The nature of the polymer crystals formed in the nucleated polymer was studied by X‐ray diffraction, and the data show an increase in a preferred orientation of the polymer crystallites with increasing concentration of nucleating agent. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2440–2450, 2002     

A DMA study of the interfacial changes on injection‐molded iPP/mica composites modified by a p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene

Present work concerns to the study of the dynamic mechanical and thermal responses of selected polypropylene (iPP)/mica composites with a modified interface from the matrix side by using a p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene, coming from a byproduct of industrial polymerization reactors. Thus, the study is mainly focused on the 75/25 iPP/mica ratio since it was identified in previous works as providing the maximum inter mica particle distance to assure they should participate in the overall process of dissipation of the mechanical energy supplied to the composites. Hence, the present dynamic mechanical analysis discussion tries to correlate the damping responses of the injection‐molded composites with those previously obtained but over compression molded composites as the basis of further studies all along the compositional iPP/mica map. Therefore, the latter let us, on the one hand, to follow how the main values of the different dynamic mechanical analysis parameters vary because of the interfacial modifier presence, and on the other, to develop a robust correlation between them and the corresponding macroscopic mechanical parameters. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45366.     

Evolution of double crystal melting peak in polypropylene foam assisted by β‐nucleating agent and supercritical CO2

Polypropylene (PP) foams with double crystal melting peak structure were prepared using supercritical CO₂ as blowing agent. Such structure was induced by the β‐nucleating agent (NA) and dissolved CO₂ in a lab‐scale autoclave system. From the dynamic rheological behaviors, one can see that long chain branching polypropylene (LCBPP) possess better melt elasticity than linear polypropylene (LPP). In order to improve the foamability, LPP was blended with LCBPP. The results of differential scanning calorimeter and wide‐angle X‐ray diffraction indicated that NA was helpful for the introduction of β‐crystal in LPP, but not for LCBPP and PP blends. Therefore, the foamability and the content of β‐crystal of various PP foams can be effectively controlled by adjusting the ratio of LPP and LCBPP. Meanwhile, both the cooling rate and the content of NA affected the formation of β‐crystal in various PP samples. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46007.     

Poly(ɛ‐caprolactone)/polyhedral oligomeric silsesquioxane hybrids: Crystallization behavior and thermal degradation

Biodegradable organic–inorganic hybrids based on poly(?‐caprolactone) (PCL) and polyhedral oligomeric silsesquioxane (POSS) with 5.3–21.3 wt % POSS were synthesized via ring‐opening polymerization (ROP). Chemical structures of the polymers were characterized by proton nuclear magnetic resonance (¹H NMR), fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). X‐ray diffraction (XRD) analysis illustrated that both POSS and PCL segment in POSS/PCL hybrids could crystallize and form two well‐separated crystalline phases except in the one with low content of POSS (5.3 wt %). Melting behavior and non‐isothermal crystallization kinetics of POSS/PCL hybrids were studied by differential scanning calorimeter (DSC). The results indicated that the POSS segment suppressed crystallization of the PCL segment to some extent. Polarizing optical microscope (POM) images showed that POSS/PCL hybrids with the highest POSS loading (21.3 wt %) possessed “snowflake” shape crystals whereas the ones with relatively low POSS loading exhibited classic spherulites. Thermogravimetry (TG) measurement revealed that thermal degradation of POSS/PCL hybrids proceeded by four‐step while PCL homopolymers degraded by a single step. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44113.     

Preparation and characterization of di‐hexadecanol maleic/triallyl isocyanurate cross‐linked copolymer as solid–solid phase change materials

Di‐hexadecanol maleic/Triallyl isocyanurate cross‐linked copolymers as a novel solid–solid phase change materials were successfully synthesized through bulk polymerization. TAIC is the skeleton and DM is a functional side chain that stores and releases heat during its phase transition process. Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, polarizing optical microscopy, differential scanning calorimetry, and thermogravimetry were employed to study the composition, chemical structure, crystalline properties, phase transition behaviors, and the thermal stability of the cross‐linked copolymers, respectively. The test results indicate that DM/TAIC cross‐linked copolymers have good thermal reliability and heat storage durability after 500 thermal cycles. The phase change temperatures of DM/TAIC cross‐linked copolymers were approximately 28.24–37.02°C, and it has high latent heat storage capacity of more than 83 J/g. At the same time, DM/TAIC cross‐linked copolymers have good thermal stability, and they can be processed or used in high temperature environments. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44065.     

Mechanical properties,thermal, and crystallization behavior of polypropylene composites reinforced by starch and wasted cotton cloth

In this study, wasted cotton cloth was bonded with soluble starches as an adhesive, then dried, cut into fiber fragments and filled into polypropylene (PP) to achieve resource efficiency. The mechanical, thermal, and crystallization properties of the composites were characterized. The results indicated that with the addition of wasted cotton cloth treated without or with silane coupling agent (RC or TRC), PP composites' tensile strength, impact strength, and flexural strength have been improved. The heat distortion temperatures increased slowly, indicating that wasted cotton cloth filled into PP can be turned back into useful items without degradation of PP composites exhibited. Thus, it is a good avenue for the utilization of an otherwise wasted cotton cloth resource. The crystallization activation energy, nucleation constant, and folding surface free energy of PP were markedly reduced in PP/RC composites and its compatibilized composites. The value of F(T) gradually increased with the increasing relative degree of crystallinity. The addition of wasted cotton cloth could significantly reduce the spherulitic size of PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigation on curing reaction of phthalonitrile resin with nanosilica and the properties of their glass fiber-reinforced composites

In this work, Phthalonitrile containing benzoxazine (BA-ph) and Bisphenol A based cyanate ester (CE) were chosen as the matrix resin. Various amount of nano-SiO₂ was incorporated into BA-ph/CE and their glass fiber-reinforced composite laminates were fabricated. Curing reaction and processability of BA-ph/CE/SiO₂ blends were studied by differential scanning calorimetry and dynamic rheological analysis. Results showed that BA-ph and CE exhibited good processability and curing reaction of BA-ph/CE was not obviously affected by SiO₂. Scanning electron microscope images of the composites showed that SiO₂ particles were well dispersed in BA-ph/CE matrix. Moreover, SiO₂ could act as physical crosslinking points and diluent in matrix as well as between the glass fibers to improve the mechanical properties of composite laminates. As the results of dynamic mechanical analysis and thermogravimetry analysis, composite laminates possessed satisfactory T_g and good thermal stability. With incorporation SiO₂ particles into matrix resin, dielectric constant and dielectric loss of BA-ph/CE/SiO₂/GF composites were increased and showed frequency dependence.     

Graft copolymerization studies. III. Methyl methacrylate onto polypropylene and polyethylene terephthalate

The tert‐butoxy radical‐facilitated grafting of methyl methacrylate (MMA) onto commercial polypropylene (PP) pellets and fiber was investigated in heterogeneous conditions similar to practical systems. Free‐radical grafting of several other monomers onto PP fiber was also investigated. Also, preliminary data from the grafting of MMA onto poly(ethylene terephthalate) pellets is presented. The PP‐graft‐PMMA residues were detected by solid‐state ¹³C‐NMR and photoacoustic IR spectroscopy. There was a good correlation between the degree of grafting (DG) determined from these spectroscopic techniques and the results from gravimetric methods. A maximum grafting efficiency of over 50% was found, whereas DG (20%) remained constant at various PP pellet, initiator, and monomer concentrations. However, at relatively low PP fiber concentrations, the DG was 27%; the increase was most likely due to the greater surface area of the fiber. There was also a reduction in DG (14%) at relatively low initiator concentrations. The reaction conditions were altered to favor grafting by the addition of more polymer substrate. When the ratio of tert‐butoxy radicals to PP was decreased, more of the substrate remained unmodified, and empirical calculations showed the formation of grafts with up to 40 monomer units. At high initiator concentrations, calculations showed that the graft residues were 1–2 units long. Therefore, variation of the polymer, initiator, and monomer concentrations was shown to have a significant effect on grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 898–915, 2002     

Influence of thermal history on crystalline morphologies of isotactic polypropylene in its miscible blends with polybutene‐1

The miscibility behaviors in blends of isotactic polypropylene (iPP) and polybutene‐1 (PB) have been studied using in‐situ FTIR imaging. The heterogeneous melt of 3/7 iPP/PB blends were formed at 250, 220, and 180°C and then quenched to the same crystallization temperature of iPP at 125°C, respectively. Evolution processes of composition distribution during crystallization were monitored according to their characteristic peaks, and the results suggest a trend from local concentration to uniform dispersion of PB fraction. Further studies of the PB fraction as the distance from the growth front of iPP spherulite indicate an irreversible phase behavior with the progress of thermal history. The cyclic melting and crystallization favor the mixing of iPP/PB blend. Meanwhile, the nonlinear growth rate of iPP spherulite is mainly responsible for compatible promotion of iPP/PB blend, which hinders the transportation of iPP chains to its growth front. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43282.     

Vanadium(V)/mandelic acid initiated graft copolymerization of acrylamide onto guar gum in an aqueous medium

The graft copolymerization reaction of acrylamide onto guar gum with a vanadium(V)/mandelic acid redox pair was carried out in an N₂ atmosphere. The optimum concentrations of vanadium(V), mandelic acid, hydrogen ions, acrylamide, and guar gum for the maximum percentage of grafting were 6.0 × 10^?3, 2.0 × 10^?2, 55.0 × 10^?2, and 20.0 × 10^?2 mol/dm³ and 110.1 × 10^?2 g/dm³, respectively. The optimum time and temperature of reaction were 90 min and 35°C, respectively, and during the study of [H⁺] variation, a prompt change in the value of the grafting parameters was observed. The maximum percentage of swelling of the graft copolymer was achieved at room temperature in 1 h. Studies of the flocculation, viscosity, and metal‐ion absorption capacity were also performed. The synthesized graft copolymer was characterized by Fourier transform infrared spectroscopy and thermogravimetric analyses, which showed that the grafted guar gum was thermally more stable than the ungrafted guar gum. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Graft copolymerization of acrylic acid onto xanthum gum using a potassium monopersulfate/Fe2+ redox pair

A previously unreported graft copolymer of xanthan gum (XOH) with acrylic acid was synthesized and the reaction conditions were optimized using a potassium monopersulfate (PMS)/Fe²⁺ redox pair. Grafting ratio, add on, and conversion increase with an increase in the ferrous ion concentration (2.0 × 10^?3 to 5.0 × 10^?3 mol dm^?3) and PMS concentration (1.0 × 10^?3 to 4.0 × 10^?3 mol dm^?3). It was observed that grafting takes place efficiently when the acrylic acid concentration and temperature were 5.0 × 10^?2 mol dm^?3 and 35°C, respectively. Samples of xanthan gum and xanthan gum–g–acrylic acid were subjected to thermogravimetric analysis with the objective of studying the effect of grafting of acrylic acid on the thermal stability of xanthan gum. The graft copolymer was found to be more thermally stable than xanthan gum. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1341–1346, 2003     

Polyacrylic acid grafting onto isotactic polypropylene fiber: Methods,characterization, and properties

The graft copolymerization of acrylic acid onto isotactic polypropylene has been investigated. The grafting was carried out using benzoyl peroxide initiator. Grafting is essentially a surface phenomenon and takes place, mostly, in amorphous region of the fiber. Emphasis, therefore, was placed on various pretreatment techniques for swelling of the fiber, viz, pretreatment with toluene and 1,1′2,2′tetrachloroethane, ultrasound, and photoirradiation. Process parameters, characterization study such as IR spectroscopy, TGA, and DTA, and properties such as tensile properties, melting temperature, dyeability towards basic dyes, and ion exchange properties were investigated. Benzene was found to be the most suitable solvent for initiator as against the acetone. Tenacity was found to be increased with increase in graft yield and reached to maximum at about 5% graft add‐on, and then decreased with further increase in graft add‐on. Proportionally, a converse effect was reported in the study of elongation to break. Thermal stability of polypropylene was found to be improved because of grafting. The grafted polypropylene also showed satisfactory dyeability toward basic dyes and also exhibits very good ion exchange properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1152–1165, 2007