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38 AZERBAIJAN C HEMICAL JOURNAL № 3 2021 ISSN 2522-1841 (Online)
ISSN 0005-2531 (Print)
UDC 541.64:678.7
COPPER-CONTAINING NANOCOMPOSITES ON THE BASIS OF ISOTACTIC POLYPROPYLENE AND BUTADIENE-NITRILE RUBBER
T.M.Gulieva
Institute of Polymer Materials, NAS of Azerbaijan turkanquliyeva30@gmail. com Received 22.05.2020 Accepted 14.12.2020
The influence of additives of nanofillers containing nanoparticles of copper oxides stabilized by a polymer matrix of maleinized high-pressure polyethylene obtained by the mechano-chemical method on the structure and properties features of metal-containing nanocomposites based on isotactic polypropylene and butadiene-nitrile rubber by x-ray phase and differential thermal analyses is studied. The improvement of strength, deformation and rheological parameters, as well as thermal-oxidative stability of the obtained nanocomposites was revealed, that is probably due to the synergistic effect of interaction of copper-containing nanoparticles with maleic groups of maleinated high-pressure polyethylene. It is shown that nanocomposites based on iso-tactic polypropylene and butadiene-nitrile rubber can be processed both by pressing method and by injection molding and extrusion methods. The prospects of using a nanofiller containing NPs of copper oxide stabilized by a high-pressure polyethylene matrix obtained by the mechanochemical method as an additive to TPE based on PP/BNR is shown to contribute to the creation of a fine-crystalline structure of the composition, and therefore its properties are improved and thereby expand scope of the obtained nanocomposite.
Keywords: isotactic polypropylene, butadiene-nitrile rubber, metal-containing nanocomposites, copper oxide nanoparticles, maleinized high-pressure polyethylene, thermal properties; XRD, SEM analyses.
doi.org/10.32737/0005-2531-2021-3-38-43
Introduction
The current stage in the development of chemistry and technology of composite materials is largely determined by the search for ways to create materials with an improved set of properties. Intensive development of the global petrochemical industry requires a constant search for new materials with high consumer properties, environmental safety and ease of processing. Such materials, not without reason, are thermoplastic elastomers (TPE). The creation of TPE is a priority area of work in the field of polymer materials science [1, 2].
The most promising direction for the production of new types of TPE is the mixing of elastomers with plastics with the simultaneous vulcanization of the elastomer, which leads to a high degree of dispersion of the rubber phase in the materials. TPEs obtained by this method are called thermoplastic vulcanizates (TPV). A distinctive feature of TPV is the combination of the properties of vulcanized rubbers during operation and thermoplastics during processing. Due to the complex of high physical and mechanical properties, a wide temperature range of operability, lower cost of end products, TPV are considered one of the most promising classes of
polymer composite materials. The areas of their application are very diverse [3, 4].
A large number of studies on TPE and TPV were obtained using polypropylene (PP) as a thermoplastic, and EPDM, natural rubber, butadiene nitrile rubber (BNR), etc. as elastomers, using various fillers or compatibilizers to improve compatibility, physico-mechanical and technological properties of the compositions [5-11].
The use of solid nanoparticles (NPs) of various shapes and chemical nature as fillers for polymeric materials opens up new possibilities for modifying the latter, since the surface properties of a nanoscale substance are characterized by high surface energy and adsorption activity. Composite materials containing NPs have high adhesive strength of the polymer matrix with NPs [12].
The development of research on na-noscale and cluster metal-containing particles in polymer matrices was largely facilitated by the creation of metal-polymer composite materials with specific physical-mechanical and operational properties: increased thermal and electrical conductivity, high magnetic susceptibility, the ability to shield ionizing radiation, etc. [13].
The use of nanoparticles of metals of variable valence (copper, cobalt, nickel, etc.) in
polymers allows one to obtain fundamentally new materials that are widely used in radio and optoelectronics as magnetic, electrically conductive, and optical media [13, 14].
In the present work, we studied the effect of small NF additives containing NPs of metal oxides on the properties of mixed TPEs based on isotactic PP and BNR
Experimental part
In the work were used: isotactic PP "Kaplen" (Russia) of brand 01 030 with a molecular weight of -2-3*105, a polydispersity index of 4.5, MFI of 2.3-3.6 g10-1 min.
BNR-NB 192 HF butadiene nitrile copolymer containing 27% acrylonitrile from BSL Olefinverbund GmbH Shckopau, d=0.98 gcm-3 (Germany).
NP of copper oxide I (Cu2O), stabilized by a polymer matrix of maleinized high-pressure polyethylene (MPE) from Olenta (Russia), obtained by mechanical-chemical method in a polymer melt, was used as the NF. The content of nanoparticles is 5 mass %, the size is 26±1.0 nm, the degree of crystallinity is 35^45% [15]. The ratio of components of the composition (wt.%): PP/BNR/NF=50/50/(0.3, 0.5, 1.0).
Nanocomposite polymer materials were obtained by mixing PP with BNR and copper-containing NF on laboratory rollers at a temperature of 160-1650C for 15 min. For mechanical testing, the resulting mixtures were pressed in the form of plates with a thickness of 1 mm at 1900C and a pressure of 10 MPa.
Physico-mechanical parameters of the obtained compositions were determined on a RMI-250 device.
The melt yield index (MFI) was determined on an IIRT device at a temperature of 2300C, a load of 5.0 kg.
X-ray phase analysis (XRD) of the obtained compositions was carried out on a D2 Phaser instrument from Bruker (Germany).
SEM-analysis of the prepared compositions has been carried out on apparatus JEOL (USA).
Results and discussion
Figures 1, 2 shows the XRD patterns of the initial PP/BNR and PP/BNR with a copper-
containing nanofiller. The reflexes corresponding to the PP: dhkl are shown: 6.19929, 5.17135, 4.73608, 4.48713, 4.17687, 4.03424, 3.47038, 3.11297, 2.11651 A, a halo image is given for an amorphous BNR.
The diffractogram of the PP/BNR/NF sample (Fig.2) also shows reflexes characteristic of copper-containing NP: dhkl 3.02053, 2.46466, 2.13683, 1.74331; 1.51025, 1.28812 A, which corresponds to the dhkl series of copper oxide (I) - Cu2O in the ASTM card file. [d-Spacings (20) -01-071-3645 (Fixed Slit Intensity) - Cu Ka1 1.54056 A. Entry Date: 11/19/2008; Last Modification Date: 01/19/2011].
Table 1 shows the physico-mechanical and rheological parameters of the obtained composite materials.
As can be seen from the data in the table 1, the introduction of 0.3-0.5 mass % NF into the composition leads to an increase in the strength index from 5.04 to 6.15 MPa. An increase in the NF concentration of more than 0.5 mass.% leads to a decrease in the strength of the composite (5.51 MPa), which is probably due to the aggregation of nanoparticles, which leads to the formation of microdefects in the bulk of the polymer matrix. The introduction of 0.3-0.5 mass % NF into the composition leads to an increase in the strain upon rupture of the composite by 1.25-1.5 times, which, apparently, is due to the synergistic effect associated with the presence of copper-containing nanoparticles in the MPE matrix containing maleic groups, a mutual the effect of which increases both the magnitude of the strain value and the strength index.
Table 1. Physico-mechanical and rheological parameters of composite materials_
Composition (mass.%), PP/BNR/NF Breaking strength, MPa Specific elongation,0/« Vicat softening point, °C MFI, g10 min
50/50/0 5.04 16 87 0.089
50/50/0.3 5.55 20 110 0.114
50/50/0.5 6.15 24 115 0.123
50/50/1.0 5.51 21 105 0.169
A study of the Vicat softening point of the obtained compositions showed that the introduction of PP/BNR (0.5 mass.%) of the nano-filler leads to an increase in the heat resistance index from 87 to 1150C. A further increase in
the amount of NF leads to a decrease in the heat resistance index, which is probably due to the microdefectiveness of the resulting composite. At the same time, an increase in the content of the nanofiller (0.5-1.0 mass. % ) increases the melt flow rate (MFI) from 0.089 to 0.123 (0.5 mass.% ) and 0.169 (1.0 mass.% ) g/10 min, which indicates an improvement in the fluidity
of the composition and the possibility of processing it by both pressing and injection molding and extrusion methods. This is important, because it is known that mixed thermoplastics are produced using the technology of extrusion mixing of rubber with thermoplastics [4].
Fig.1. Diffractogram of the sample PP/BNK.
2Theta (Coupled TwoTheta/Theta) WL=1.54060
Fig.2. Diffractogram of the sample PP/BNK/NF.
Numerous experimental data on the mechanical, strength, relaxation, and other properties of polymer-polymer, polymer-filler mixtures are explained in terms of the concept of the presence of an interphase layer [16].
The properties of polymer composites are significantly affected by the supramolecular structure of the polymer (the size of spherulites, the degree of crystallinity, the presence of C=O groups and different branchings, etc.) and the interfacial interaction at the phase boundary [17, 18].
An SEM analysis of the obtained nano-composites was carried out (Figure 3, 4).
Figure 3 shows a micrograph of the initial PP/BNR mixture. It can be seen that the compo-
Fig.3. SEM images of sample structures PP/ BNK.
Conclusion
The effect of a nanofiller containing copper oxide nanoparticles stabilized by a matrix of maleized polyethylene (MPE), obtained by the mechanochemical method, on the properties of PP/BNR-based composites is studied.
X-ray diffraction patterns confirm the presence of copper oxide nanoparticles in the composition of PP / BNR-based composites
The improvement of strength, deformation and rheological parameters, as well as thermal-oxidative stability of the obtained nanocomposites was revealed, which is probably due to the syner-
site structure is compact spherulitic. The introduction of a nanofiller into the mixture promotes the formation of a finer spherulitic layered structure, which leads to an increase in the fluidity of the nanocomposite and thereby an improvement in rheological properties (Figure 4).
SEM analysis of the obtained nanocom-posites showed that small amounts of nanofillers (0.3 - 0.5 mass.%) introduced into the polymer obviously play the role of structure-forming agents-artificial nuclei of crystallization, which contributes to the formation of a fine spherulite structure in the polymer, characterized by improved physical- mechanical, rheological properties of the resulting nanocomposite.
Fig.4. SEM images of sample structures PP/BNK/NF.
gistic effect of interaction of copper-containing nanoparticles with maleic groups of MPE.
It is shown that nanocomposites based on PP/BNR can be processed both by pressing and by injection molding and extrusion methods.
The prospects of using a nanofiller containing NPs of copper oxide stabilized by a matrix of maleized polyethylene obtained by the mechanochemical method as an additive to PP/BNR has been shown, which contributes to the creation of a fine-crystalline structure of the composition, and therefore its properties are improved and thereby the field of application of the obtained nanocomposite is expanded.
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IZOTAKTIK POLIPROPILEN VO BUTADiEN-NiTRlL KAUCUKU OSASINDA MiSTORKlBLi
NANOKOMPOZlTLOR
T.M.Quliyeva
Mexaniki-kimyavi üsulla alinan, maleinla§dirilmiij yüksak tazyiq polietileni matrisinda stabilla§dirilmi§ mis oksid nanohissaciklari saxlayan nanodoldurucu alavanin izotaktik polipropilen va butadien nitril kauguku asasli metaltarkibli nanokompozitlarin qurulu§ va xassalarina tasiri rentgenfaza, diferensial-termiki analiz metodlari vasitasila tadqiq olunmu§dur. Alinan nanokompozitlarin möhkamlik, deformasiya va reoloji xassalarinin, hamginin termooksidla§ma stabilliyinin yax§ila§masi müayyan edilmi§dir. Görünür, bu da maleinla§dirilmi§ yüksak tazyiq polietilenindaki malein qruplari ila mistarkibli nanohissaciklarin qar§iliqli tasirinin sinergetik effekti ila alaqadardir. Göstarilmi§dir ki, izotaktik polipropilen va butadien nitril auguku asasli nanokompozitlar ham preslama, ham da tazyiq altinda tökma va ekstruziya metodlari ila emal oluna bilar. Bu da onun tatbiq sahalarini geni§landirir.
Agar sözlar: izotaktik polipropilen, butadien nitril kauguku, mistarkibli nanokompozitlar, mis oksid nanohissaciklari, maleinla§dirilmi§ yüksak tazyiq polietileni, termiki xassalar, RFA, SEM analizlari.
МЕДЬСОДЕРЖАЩИЕ НАНОКОМПОЗИТЫ НА ОСНОВЕ ИЗОТАКТИЧЕСКОГО ПОЛИПРОПИЛЕНА И БУТАДИЕН-НИТРИЛЬНОГО КАУЧУКА
Т.М.Гулиева
Исследовано влияние добавок нанонаполнителей, содержащих наночастицы оксидов меди, стабилизированные полимерной матрицей малеинизированного полиэтилена высокого давления, полученные механо-химическим методом, на особенности структуры и свойств металлсодержащих нанокомпозитов на основе изотактического полипропилена и бутадиен-нитрильного каучука методами рентгенфазового, дифференциально-термического анализов. Выявлено улучшение прочностных, деформационных и реологических показателей, а также термоокислительной стабильности полученных нанокомпозитов, что, по-видимому, связано с синергетическим эффектом взаимодействия медьсодержащих наночастиц с малеиновыми группами малеинизированного полиэтилена высокого давления. Показано, что нанокомпозиты на основе изотактического полипропилена и бутадиен-нитрильного каучука могут перерабатываться как методом прессования так и методами литья под давлением и экструзией, что расширяет сферы его применения.
Ключевые слова: изотактический полипропиле, бутадиен-нитрильный каучук, медьсодержащие нанокомпозиты, наночастицы оксидов меди, малеинизированный полиэтилен высокого давления, термические свойства, РФА, СЕМ-анализы.
