In Situ Polymerization Of Nylon-Cellulose Nano Composite
Research ArticleiMedPub JournalsPolymer SciencesISSN 2471-9935http://www.imedpub.com2017Vol. 3 No. 1: 2DOI: 10.4172/2471-9935.100017In situ Polymerization of NylonCellulose Nano CompositeAbstractPolymeric Nano composite has been strongly studied due to the improvementachieved when a little amount of Nano sized particles are added to the polymermatrix. This is primarily due to large surface area which increased the interactionbetween the nanoparticles and the polymer. There are different routes forpreparation of the polymer Nano composite with Nano fillers it can be meltcompound, in situ polymerization and the solvent method. The in situ methodwas found to be best method due to that the nanoparticle is introduced directlyto the monomer and it allowed for few minutes to disperse well to the monomerbefore the initiator is added to start polymerization. The in situ method givescontrol over the particle size and morphology. The present studies investigate thesurface morphology and thermal properties of nylon when the cellulose Nanowhiskers of different content was added into nylon monomer. SEM for surfacestudies, TGA for thermal stabilities and FTIR for chemical properties were studied.TGA results reveal that nylon thermal properties changes with addition of Nanocrystals compared to pure nylon.Keywords: In situ polymerization; Cellulose; CompositesReceived: March 30, 2017; Accepted: April 27, 2017; Published: May 07, 2017IntroductionPolymer Nano composite is composed of polymer materialand filler component in which is at least one dimension ( 100nm). Polymeric reinforced composite properties are stronglyaffected by the size, shape and degree of material filler adhesion;Nano composite can be prepared by melting compound, in situpolymerization and solvent method [1-4]. Dispersion of thenanoparticles to the monomer interface is a critical step dueto the fact that it determines the mechanical properties of theproduced Nano composite. It is well known that poor dispersionof nanoparticle will affect the mechanical properties Nanocomposite [5]. Poor dispersion can be avoided by Nano compositeprepared by in situ method because with in situ polymerisationthe filler solution is added directly into the monomer allowing itfor few minutes to dispersed well as the results its gives a bettercontrol to size and morphology of the Nano composite produced[2,4].Polymeric Nano compositefibers and inorganic fillers.replacement for syntheticvarious reasons includingcan be obtained by using naturalNatural fibers are mostly used asfibers in automotive due to theenvironmental friendliness andTshwafo E Motaung,Mokgaotsa J Mochane,Zikhona L Linganiso andAyanda P MashigoDepartment of Chemistry, University ofZululand , Private Bag X1001, Kwadlangezwa3886, South AfricaCorresponding author: Tshwafo E Motaung motaungt@unizulu.ac.zaDepartment of Chemistry, University ofZululand, Private Bag X1001, Kwadlangezwa3886, South Africa.Tel: 27 (0) 35 902 6786Citation: Motaung TE, Mochane MJ,Linganiso ZL, et al. In situ Polymerization ofNylon-Cellulose Nano Composite. Polym Sci.2017, 3:1.inexpensiveness. Mostly used natural fiber is cellulose due itsproperties like strength, stiffness and high performance [5]. In fact,cellulose nanocrystals are mostly used as fillers reinforcementmaterial due to primarily higher modulus and availability [6]. Thenanoparticles are generally in cooperated in different polymersfor preparing new materials with better properties than pristinecounterparts. However, very little information is known aboutreinforcement of nylon by cellulose, particularly sourced frombiomass.Nylon is aliphatic or semi-aromatic polyamides which can beprocessed into fibres, films or different shapes depending ondesired applications. Like any other polymers, nylon could bereinforced with different fillers including cellulose to vary someproperties. In order to study the nylon/NCC composite differentconcentrations of NCC could be used expecting good results andimprovements on the thermal, mechanical and morphology.Material science in ceramics and polymers they frequentlyuse the word Nano composite. Nano composite has uniqueproperties which led to studies about limitations and tetheringpolymers which has grown the interest to the science field formaterial development in order to study the formation, structuresand dynamic of polymer Nano composite interface. Under License of Creative Commons Attribution 3.0 License This article is available in: http://polymerscience.imedpub.com/archive.php1
2471-9935Literature ReviewPolymers and nano compositePolymer is made by macromolecules in which consists of smallmolecular units that are repeated over and over again to formalong chain and are held by covalent bonds. Monomer is a smallmolecular unit. Nylon, polyvinyl chloride and polystyrene areexamples of polymers and are synthetic polymers [2,3]. Polymersare normal synthesized by one of two ways can be addition orstep – growth pathway. Addition polymerisation the polymer isformed by monomers connected together by addition reaction.Step growth the monomers link together and grows into dimers,trimer so forth. Condensation pathway the condensationpolymerisation the polymer is formed by monomers connectedwith the release of the side product such as HCl and water. Oneof the examples of condensation pathway is the polymerizationof a diacid and diamine to make nylon 6 and producing water asa by-product.Both thermoplastic and thermosetting have limited applicationin automobile, electrical, electronics, packaging textile and household applications due to mechanical properties [7]. In order toovercome that they were reinforced mostly with inorganic Nanofillers for a desired Nano composite material. This has broughtincreased interest in the applications of thermoplastics. Polymericreinforced composite properties are strongly affected by the size,shape and degree of material filler adhesion; Nano compositecan be prepared by melting compound, in situ polymerizationand solvent method. Melt blending and in situ polymerizationare mostly used to synthesize polymer Nano composite. Meltblending method the molten thermoplastic is blended with thenanofiller in order to elevate the polymer-nanofiller contacts.For a solution blending suitable solvents are used to dispersenanofillers followed by dissolving the polymer in the samesolvent and mixing the two at room temperature. The Nanocomposite is collected by precipitating or casting a film [4,8]. Inan in situ polymerization, a filler solution is dispersed directly intoa monomer before an initiator is added for polymerization.Dispersion of the nanoparticles to the monomer interface is acritical step due to that it determines the mechanical propertiesof the produced Nano composite therefore poor dispersion ofnanoparticle will affect the mechanical properties Nano composite[4]. Poor dispersion can be avoided by Nano composite preparedby in situ method for Nano composite produced. Polymer Nanocomposite benefits over pure material are robust, being ecofriendly and can be re-usable [3]. Composites materials have beenidentified as measure substitutes over conventional materialsincluding metals, metal alloys, wood ceramics and polymers [8].Composites materials developed today are categorized based ontheir reinforcement and matrix. Reinforcement types used thereare particle reinforced composites, fiber reinforced compositesand structural composites. With Polymer- matrix compositesare prepared by mixing polymers with inorganic filler materialssuch as reinforcing fibers (e.g. glass, carbon, aramid,etc) andparticulate solids (talc, carbon black, calcium carbonates, mica).22017Vol. 3 No. 1: 2Such composite exhibit physical properties synergisticallyderived from both the organic and inorganic components e.g.they show superior mechanical properties and higher heatdeflection temperature compared to the pristine polymers whilemaintaining processibility. It is important to develop compositesystem based on the application [8]. The fillers have threekinds, nanoparticles which comprise of particles having all threedimensions in nanometres range e.g. semiconductor and colloidaldispersion of polymers, two dimensional nanofiller wherein twodimension of the filler are in nanometres scale- cellulose whiskersand nanotubes are the examples and nanofiller corresponds tothe case in which there is only one dimension on a nano levellayered silicates or clays which are platelet shaped.The work presented in this dissertation is focused on polymerNano composite incorporated with nanofiller having twodimensions cellulose whiskers. To enhance the polymerproperties performance the fillers with micrometre rangedimensions are widely used to form composites. The propertiesof the composites alter depending on filler loading, shape andsize. For fibres, fillers having larger aspect ratio can improve theproperties of polymers.There are three possible structures polymer Nano compositecan be made: phase separated micro composite, intercalatedNano composite and exfoliated Nano composite. The structuresformation depends on the nature of components used includingpolymer matrix, clay and organic cation. Polymer Nano compositesare having wider applications. In 1980 Toyota Company was thefirst company to develop and commercialize polymer/clay Nanocomposite (Figure 1). They used nylon 6 as the matrix phase andmontmorillonite as the clay filler for a timing belt cover in oneof their car models which became the first commercial polymerNano composite. Application of polymer Nano composite usingdifferent polymer matrices and nanofillers are based on theirimproved mechanical properties (tensile strength and young’smodulus), improved heat by 30 C stability and enhanced barrierto water.CelluloseCellulose is a natural polymer and polysaccharide which is havingβ-1, 4-linked anhydro-D-glucose units. The strong hydrogenbonds are established by the presence of the hydroxyl (-OH)groups (Figure 2) in the cellulose structure. Cellulose mainsources are wood, cotton, hemp, flax, sisal, sugarcane bagasse,Figure 1 Reaction scheme for in-situ polymerization nylon 6.This article is available in: http://polymerscience.imedpub.com/archive.php
2471-9935Figure 2 Shows Cellulose Structure.corncob, cassava bagasse, banana rachis, soy hulls and rice husk[9-11].Hemicellulose and lignin are other major components found innatural fibers with cellulose. Cellulose have great features overother fibres such as the biodegradability [12], coupled with thelow cost, high specific strength and lighter weight than glass andthis have led to the extensive development of studies in orderto produce green materials [13]. The cellulose properties led tocellulose to be used as filler or reinforcement material.When is compared with inorganic reinforcements, derivedcellulose nanomaterial’s have great benefits such as renewabilityand low density, highly specific strength, high aspect ratio, goodmechanical properties, low thermal expansion, low toxicity,and hydroxyl groups (-OH) [5,14]. Cellulose nanomaterial’s areisolated and extracted differently. One can be isolated by acidand other by mechanical procedure in which as a result producingnanomaterial having different morphologies. The characteristicsare a consequence of the cellulose source and extraction methodused. The commonly used cellulose are microcrystalline cellulose(MCC), micro fibrillated cellulose (MFC), nano fibrillated (NFC),cellulose nanocrystals (CNC). There are several approachesto isolate nanoparticles including mechanical with acidextraction producing nano crystals (CNC’s) and with mechanicalproducing nano fibrils (CNFs). CNCs are crystalline in natureare have wide applications due to the nano size having equalor less than 100 nm and are needle-like cellulose particles [15].Cellulose nanoparticles are widely used as fillers in the polymerNano composite due to an improvement in performance.Intermolecular forces of the cellulose molecule are in charge forcertain firmness of the unit chains. The intramolecular hydrogenbonding formed between hydroxyl groups and oxygen’s of theadjoining ring molecules alleviates the connection and thatresults in the linear configuration of the cellulose. Cellulosesource and material extraction method are factors responsiblefor variation crystallinity degree of cellulose [15].2017Vol. 3 No. 1: 2low temperatures, combined with its other properties, such asstiffness, wear and abrasion resistance, low friction coefficientand good chemical resistance [16]. These properties have madenylons the strongest of all man-made fibers in common use.Nylon’s are very important in the thermoplastic industry theyoffer good mechanical and thermal properties. The features arevery useful because they determine the applications of the fiberproduced [7]. Nylon can be used as standalone or composites.What is more attracting about it is an ease to clean, quickly driesand rigidity. The composites of nylon are mostly applied in theautomobile industry. There are different types of nylon, whichdiffer with monomer, for commercial purposes such as nylon 6,11, 12, 6/6, 6/10, 6/12, etc. The popular nylons used are nylon6 and nylon 6/6 in which is used in textile industry. The polymercan be also used in coating of metal objects, molding and tubingextrusion.Nylon 6/10 shown in Figure 3 is a polyamide made by aminemolecules which has group {–NH2} at each end and acid chloridehaving {–COCl} group at each end as well. The diamine and thediacid chloride link together at the end-on-end to form chain. Thisreaction the polymerisation is called interfacial polymerisationbecause the monomers are two immiscible liquids which forms alayer and comes to contact at the interface. Nylon 6, 10 is givenby number of carbon atoms present in diamine monomer andnumber of carbons in the diacid chloride. Six carbons come fromdiamine and ten comes from diacid chloride produced. Nylonsare some of the most important fibers produced commercially.With nylons the intermolecular force hydrogen bonding is themost important. The nitrogen- bonded hydrogen’s of one nylonchain will hydrogen bond very strong with carbonyl oxygen’s ofanother nylon chain.These hydrogen bonds make crystals of nylon very strong, becausethey hold the nylon chain together very tightly as the resultsmaking fiber to be stronger. The nylon is crystalline product at agiven sample in a solid form. There is in the amorphous phase, thecombination of crystalline and strongly associated amorphousphases is what makes nylon thermoplastic so tough. Nylon Nanocomposite are prepared by in situ polymerisation, the filler isadded to the monomer and dispersed by ultrasonification inorder to allow gain growth aggregation of nano particles to themonomer before polymerisation starts. This adds the advantageto the nylon Nano composite nylons.Materials and MethodsChemicalsThe sugar bagasse was obtained at Empangeni (KwaZulu Natal),South Africa. Sodium hydroxide (NaOH) low chloride for analysisNylonNylon is synthetic, aliphatic or semi-aromatic polyamides. It canbe melt-processed into fibers, films or different desirable shapes[7]. Polyamide fiber, originated from a diamine and a dicarboxylicacid, there are a very large number amide group - (-CO-NH-) provides hydrogen bonding between polyamide chains, givingnylon high strength at elevated temperatures, toughness at Under License of Creative Commons Attribution 3.0 LicenseFigure 3 Reaction scheme for synthesis of nylon 6, 10.3
2471-99352017Vol. 3 No. 1: 2and Sodium Sulphite (NaS) were bought from Merck SouthAfrica. Sodium chlorite (NaClO2), Hexamethylene Diamine (98%)and Sebacoly chloride were purchased from Spectro chem andSulphuric Acid (98%) was purchased from Merck South Africa.Preparation of celluloseSugar bagasse was washed with boiling water four times forone hour with changing of water replacing with fresh one inorder to remove unwanted dirty stuffs. The sugar-bagassewas then further treated with 2% NaOH solution, 0.7% NaClO2(which has acetic acid in order to gain pH4 solution) and 1% NaSrespectively for one hour. Each treatment was repeated fourtimes accompanying with repeated wash using deionised waterto remove excess chemicals and to gain neutral pH 6-7. Schematicdiagram (Figure 4) of the extracted cellulose from sugar-bagasseis shown below.Figure 5 Schematic showing sugar bagasse transformation tonanocrystals.Preparation of cellulose nano whiskersCellulose obtained from sugar-bagasse after NaS treatment washydrolysed using 50% Sulphuric acid concentration under strongagitate of mechanical stirrer at under the ice bath for 30 min.The hydrolysis was stopped by adding 500 ml of deionized. Thesuspensions were centrifuged at 4400 r.p.m. for 30 min anddialyzed using membrane in water for 5 days until the pH was 6-7.The suspension was dispersed by ultrasonification for 5 min andstored in the refrigerator for further use. Different methods werereported for the extraction cellulose from sugarcane bagasse [6](Figure 5).Synthesis of nylonHexamethylene diamine of about 1 g was dissolved in 25 ml ofwater in a 250 ml beaker. Solution of Sebacoly chloride (1 g) andHexane of 25 ml was made in a separate beaker. Hexane/Sebacolychloride solution was added onto hexamethylene solution usinga glass rod to pour down with a film formation at the interface.The thread was drawn out of the interface firstly by tweezers,slowly was winded (Figure 6) up into the glass rod. After all thepolymer (nylon) collected. Nylon was washed thoroughly withwater and it was let too dry in air.Synthesis of nylon-cellulose nano compositeHexamethylene diamine of about 1 g was dissolved in 25 ml ofwater in a 250 ml beaker. Cellulose whiskers (1%, 3% and 5%)were added in situ in the Hexamethlyene diamine/H2O and wereFigure 6 Schematic representation for the nylon of howwas collected.allowed to disperse in the monomer solution for 10 min usingultrasonification. Quickly solution of Sebacoly chloride (1 g) andHexane of 25 ml was made in a separate beaker. Hexane/Sebacolychloride solution was added onto Hexamethylene solution forpolymerization, using a glass rod to pour down with a film formationat the interface. The thread was drawn out of the interface firstly bytweezers, slowly and was winded up into the glass rod. After all thepolymer (nylon) collected, nylon was washed thoroughly with waterand it was let too dry in air (Figure 7).Characterisation MethodsMorphology and surface studiesScanning electron microscopy (SEM): Samples for analysis wereprepared and used to characterize the crystal structure anddistribution of nylon Nano composite.Chemical analysisFigure 4 Schematic showing extraction of cellulose from sugarbagasse.4FT-IR spectra: The spectra of cellulose, nylon and nylon/CNCcomposite and were obtained using FTIR-ATR Perkin- Elmer.All samples were scanned over a range of 400 to 4000 per 100samples scan.This article is available in: http://polymerscience.imedpub.com/archive.php
ISSN2471-9935Vol. 3 No. 1: 2table summarizes higher bands observed in the FTIR spectrumof sugarcane bagasse and their assignments to chemical groupvibrations and molecules.The chemical composition of nylon and nylon Nano compositesare shown in Figure 10. Nylon is made from Carboxylic acidand amine therefore spectral bands peak at 3302, 2986, 2924,and 1636 cm-1 are significant bands and are intense. The bandat 3302 cm-1 is associated with amine (N-H stretch). NylonNano composites were also having band 3302 cm-1 but theirband is broad due to the present of OH group from celluloseFigure 7 Reaction scheme for synthesis of NylonCellulose nanocomposite.Thermal analysis: Thermal gravimetric analysis of the cellulose,nylon and nylon-cellulose Nano composite sa
In situ Polymerization of Nylon-Cellulose Nano Composite. Polym Sci. 2017, 3:1. Introduction Polymer Nano composite is composed of polymer material and filler component in which is at least one dimension ( 100 nm). Polymeric reinforced composite properties are strongly
2) Nylon is commonly made by step-growth polymerization. In class we made nylon 6,10. a) Give the structure of Nylon 6,10 circling the chemical group that defines this polymer as nylon. b) Draw the structure of the two chemicals that were used in class to make nylon 6,10. c) Explain why this is a condensation polymerization and what molecule .
after polymerization. For example, after Nylon 6,6 forms, the leftover product was water. Step-growth polymerization often requires two different monomers to form one polymer. Step-growth polymerization occurs when monomers start to join together. Any monomer can star forming chains, so the molecular weight is low.
Figure 1. Nylon-6 In practice, however, Nylon-6 and other polyamides can also be synthesized from the ring-opening polymerization of the cyclic versions of these monomers, lactams. For instance, Nylon-6 and Nylon-12 can be synthesized from ε-caproplactam and dodecanolactam, respectively (Figure 2).3 Ring-opening
CONNECTORS Connectors Conectores Connecteurs . . 2 Nylon Insulated Terminals Terminales de Nylon Aislados Bornes Isolées en Nylon . 17 Heat Sealable Nylon Terminals Terminales de nylon termosellables Bornes Thermoscellables en Nylon . 20 Terminal Lugs Terminales Cosses Pour Bornes .21 Solderless Battery
POLYAMIDE (NYLON) 6 By Susan L. Bell (November 2012) ABSTRACT Zimmer AG’s continuous two-stage polymerization process is widely licensed for the production of polyamide 6 (nylon 6). The polymerization of caprolactam with a catalyst is performed in a two-stage process using two vertical tube reactors in series.
the area of polymerization reaction engineering in and in the simulation on Nylon 6 in particular. These have been compiled in several recent books and review articles. In the field of Nylon 6 polymerization itself, there have been several review article - empha- sizing various physicochemical aspects. An important point that emerges
1600 Bellwood Road Richmond, VA 23237, U.S.A. TEL 1-804-271-7677 USA. 01 Introduction/What is Radical Polymerization? 01 Radical polymerization is initiated by the formation of free radicals. Free radicals are formed by thermac energy, light, or radioactivity. Radical polymerization
Weight of pile above scour level Wp1 220.893 kN Weight of pile below scour level Wp2 301.548 kN Tota l ultimate resistance of pile Qsf Qb – Wp2 8717.452 kN Allowable load (8717.452 / F.S.) – Wp1 3266 kN. From above calculations, Required depth 26.03m below design seabed level E.G.L. ( ) 1.15 m CD . International Journal of Engineering Trends and Technology (IJETT) – Volume .
