28/, 2 LAB MANUAL POLYMER SCIENCE App. CHEN {STR . PHOTOSTATE University of Karachi COURSE NO. 503 38D YEAR 5T4 SEMESTER AVAILABLE AT APPLIED CHEMISTRY PHOTOSTATE SHOP UNIVERSITY OF KARACHI: : : d chemical properties inati hysical an Object: Preparation of sulfide rubber and examination of its phy: i )-dichloroethane), 50mI Materials: Sodium Hydroxide, water, sulfur, ethylene mache eee beaker, 100ml beaker, glass dish, magnetic stirrer, filter-paper therm e Thiokol is as follows: Theory: The reaction mechanism in the preparation of a sulfide rubber lik ACICH;CHCl+nNa-$S-SS-Na->(-CH,CH2SS-SS-)n +2nNaCl Procedure: Dissolve 2gm sodium hydroxide in Oml water in a 100ml beaker. Heat the solution to the boiling point on a hot plate with continuous stirring. Add 4 gm of sulfur and stir until a or almost all of the sulfur has dissolved. This liquid will turn from light yellow to dark brown as the sulfur content of the polysulfide increases. After 5 minutes allow the solution to cool and decant the dark brown liquid from the undissolved sulfur. If much sulfur remains undissolved it can be more effectively removed by filtering. To the filtered liquid add 10 ml of ethylene dichloride. Warm this mixture to 70-80°C and stir thoroughly for 10 minutes. The rubbery polymer forms at the interface between the two immiscible liquids and will collect as a lump at the bottom of the beaker if stirring is continuous throughout the process. Remove the polymer from the solution and wash it thoroughly under water tap. Calculations: Dry the rubber and calculate the percentage yield as a function of amount of sulfur and ethylene dichloride Total weight of reactants = Total weight of product = Yield = Report: 1) Does the polymer have any injection able features? 2) Determine the effect of the following solvents on portions of the polymer. Use test-tubes to take rubber pieces in Sml of solvent and examine after 10-20 minutes. Solvents: Benzene, Acetone, Methyl Alcohol, Sulfuric AcidExperiment 2 Object: Determination of the molecular mass of polyvinyl alcohol by viscosity method. Materials: Ostwald’s viscometer, 5 and 20m! pipettes, 2 beakers (25ml), 20 and 10ml measuring cylinders, polyvinyl alcohol solution prepared by lab-attendant, acetone, stop watch, stand, dryer Theory: Solution viscosity is basically a measure of size in space of polymer molecules. If the intrinsic viscosity is used, then [nl = KM? is molecular weight, and K and a are constants depending vent and their interaction with each other and with the polymer holessoei Ge ou eni aan: BOEG|| The intrinsic viscosity leads re the viscosity average molecular weight. Measurement of the solution viscosity is done by comparing effective time required for a specified volume of the polymer solution to flow through a capillary tube within time t. Comparison of this time of flow for solvent and solution in same viscometer gives a ratio of viscosities. Using Hagen-Poiesuelle equation for such a capillary in viscometer also gives such a ratio. These viscosity measurements are made on a set Sf eoluttons with varying concentrations and the intrinsic viscosity is obtained by a plot of (t- te)/toC versus C. Where [n] is the intrinsic viscosity, M on the proportions of solute and sol The variables involved are given below. Viscosity Symbol Flow Symbol Terminology A te Viscosity of Solvent 7 t Viscosity of Solution c c Concentration in gm/100m1 (n= no)/C (t- t)/C Specific Viscosity (n= No)/ to C (t- to)/ to C Reduced Viscosity {(n- Mol/ to C Jeo {(t- to)/ to Cheoo Intrinsic (limiting) Viscosity Procedure: Please remember that dirt particles block the Ostwald viscometer capillary and therefore dirt-free solvents and solutions are essential. Take an Ostwald viscometer and thoroughly wash it with distilled water and rinse with acetone. Allow it to dry in fan-air for S minutes. Make sure that the thin capillary is clean. Place the viscometé . er peaks undemesth ‘ona stand and place aof pipette sucker suck the flow time between the two it to dry. id dries the water. With the help the acetone. Allow i is t. Rinse an i ith 10 ml distilled 1) Fill the viscometer wil eo rlow and sense solution above the mark. Allow the wate marks, this is ty. Rinse the viscometer with water and then with a 2) Take 10m! of PVA sol asure its flow time. Thi viscometer. 3) In a 10mI cylinder dilute the PVA solution to make it 50%. Add 10 ml solution. This is % dilution Measure its fl 4) Measure flow times and then follow ti ution and mei of water to 10 ml of PVA jow time. he procedure for 1/4, 1/8, 1/16 dilutions Calculations: Concentration Water (to) PVA solution % dilution % dilution 1/8 dilution ans dilution Flow Time tte/lteC Report 1) Plot t-to/teC Vs C on a graph paper 2) Through a calculator find the intercept 3) Using an MSExcel type application, draw a graph and plot a trend line 4) Use the intercept and K anda values and find the molecular weight 5) Describe the method you used to find the molecular weight from solution viscosi 6) Discuss the Mark-Hawick equation and Hagen-Poisuelle equation and i calculations and results. sie haimekae 7) Describe why at low concentratit ane oe Sea ebutakaet fluctuates more than at higher concentrationExperiment 3 Object: Preparation of polystyrene by emulsion polymerization and to observe the dependence of polymerization rate on the concentration of the emulsifier. Materials: Aluminum foil, thermometer, 4 soda bottles, water bath, glass rod, 4 funnels, 4 beakers (200m) 4 filter papers (5"x5"), distilled water, potassium persulfate, sodium hydrogen phosphate, styrene monomer, sodium laury| sulfate (emulsifier), alum (alx(SOz)s) Background: At the beginning of an emulsion polymerization three phases are present: @ continuous aqueous phase containing the initiator; suspended droplets of monomely kept coagulated to a continuous organic phase by agitation and soap micelles containing a small proportion of monomer. Initiator fragments enter some of the micelles where polymerization takes place, supplied with monomer by diffusion to the monomer droplets through the aqueous phase. As these micelles (now more properly called monome! = polymer particles) grow, they are stabilized by soap at the expense of uninitiated micelles, which eventually disappear. The polymerization rate depends upon the number of micelles, and this in turn on the concentration of the soap. The emulsion system can be applied to a wide variety of vinyl, acrylic, and diene monomers with water solubility in the proper range, usually 0.001 - 1%. Safety Considerations: POTASSIUM PERSULFATE, HYDROQUINONE. STYRENE MONOMER, AND METHANOL ARE TOXIC CHEMICALS AND MUST BE HANDLED WITH PROPER PRECAUTIONS. ADEQUATE VENTILATION IS IMPORTANT. DESPITE THE SMALL AMOUNTS OF MONOMERS USED. THERE IS DANGER OF TEMPERATURE AND PRESSURE BUILDUP AND EXPLOSION. THE POLYMERIZATION RATE INCREASE PRECIPITOUSLY. IT IS ESSENTIAL THAT THE SHAKING BATH BE SURROUNDED WITH A SAFETY SHIELD. BOTTLES MUST BE WRAPPED IN A TOWEL. UPON REMOVAL AND OPENED IMMEDIATELY. SAFETY GLASSES MUST BE WORM IN THE LABORATORY AT ALL TIMES. Procedure: 1) into each of 4 clean soda bottles place 15 ml disiled water, 0.04gm KzS20s, 0.04¢m NaHPO., and 5ml styrene monomer. 3} Place the following amount of sodium lauryl sulfate in the bottles: 0.06, 0.12, 0.25 and 0.60 gm. 3) Shake to partially dissolve ingredients and cover each bottle with a foiled cap. 4) Place bottles in water bath maintained at 70° C and after every 5 min shake five times (SH2) 5) Separately prepare a solution of about 2 gm alum in about 100 ml water. 6) After one and half hour of polymerization, remove the bottles from the water bath, transfer the products in given beakers. Then add 10 ml of alum solution (a coagulant for latex) to each beaker. 7) Filter the coagulant polymer and wash with distilled water. 8) Dry the polymers until their weight is constant in an oven i i Y ly at 80° C and weigh to determine the yield. (Weight of Polystyrene/Amount of Styrene *100) 7Report : 1) Calculate the yield for each sample 2) To a good approximation, polymerization is constant for the time period of this polymerization, hence the rate is proportional to th yield. Calculate the exponent 'a' by the plotting log (E) versus log (Y), do this by using calculator or an MSExcel type graph with plotted trend line. Find the slope, intercept = oon i eee wi apparatus and experiment in your own words. 4) Plot of [E], fe along wit ing ‘a’ 7 of “a” and discuss it it relation ieieeae aterm Broph). 5) State Your estimateExperiment 4 Object: Preparation of Polystyrene with initiator through solution polymerization. Materials: Water bath, thermometer, 8 test tubes, beaker (200 mi), filter paper, funnel, spatula, toluene; styrene, benzoyl peroxide, methanol, acetone, ethanol, benzene, carbon tetrachloride, petroleum ether, nylon. Procedure: Commercial styrene monomer containing an inhibitor can be used. In a small beaker add 10 of toulene and 5 mi of styrene. Then dissolve 0.3 gm of benzoyl peroxide and transfer equally in the two tubes and keep the test tubes in a water-bath maintained at a temperature of 90-95°C. After 60 minutes remove the tubes. Allow the contents to cool and add 50 ml of methanol. Obtain the precipitates of polystyrene by filtration using a funnel. Place the filter paper alongwith the ppt. in oven at 100*C for 20 minutes. Then filter paper take out from oven and give 5 minutes to cool down. Now weigh the solid polystyrene precipitates for calculating the yield. Place 6 ml of acetone in a clean test tube, add approximately 0.2 gm of dried polymer to determine its solubility. Repeat the same procedure to determine the solubility of polystyrene in Methyl alcohol. Benzene. Carbon tetrachloride. Because of their high moleculer weight, polymers may go into solution more slowly than organic molecules of low molecular weight. In determining polymer solubility allow the solvent and solid polymer to remain in contact for at least 15 minutes before estimating the solubility. Report: Describe the properties of the polymer as to brittleness, color, and strength? Explain why polymer become soluble? Did melting change the solubility of the polystyrene?thre n polymerization rough emulsio polymerizati e Experiment 5 Object: Preparation ical flasks (21 neck flask,2 coni beaker at con 2a su pel Sequi " styren' of Cross-linked Polysty! ing bead, 3 beakers’ (500ml), measuring mixin} , 00m), istilled water, sodium lauryl sulfate, Materials: (250m), distilled sodium-meta-bisulfate, terials: ion funnel (51 flask or addition it cylinder, styrene, Nitrogen ‘ ide( crosslinking agent). co inked polymers are formed when small ones ints asi ‘uded to the vinyl monomer. The procedure i ization, 1d: In radical polymerization, ; oa t vinyl, acrylic, or diene monomers with re a of difunctional or polyfunctional monomers at described in this experiment can be applied to mos! Ii ce oherization! solubility in Water in a range making them suitable for em OR CONTACT OF Safety Considerations: INHALATION OF MONOMER OR SOLVENT eighth GE USED IN THESE CHEMICALS WITH SKIN, MUST BE AVOIDED. EXTREME UME HGOR Wit HANDLING INITIATORS. POLYMERIZATION SHOULD BE CARRIED OUT IN A Fi tlt THE APPARATUS BEHIND A SAFETY SHIELD. SAFETY GLASSES MUST BE WORN LABORATORY AT ALL TIMES. Procedure; 4) Weigh out 25gm distilled water in a conical flask and keep on hot plate and start agitation, Then add 4gm — sodium lauryl sulfate in it, then add 25gm styrene monomer gradually and 0.5g (2 drops) Acrylamide at high speed until a stable emulsion is formed. Transfer this mixture in the addition funnel. Eleotad stiles water and 0.02 gm of sequesterene NaFe (Chelated tron) in three neck Place the reaction flask in quarter filled bow! with water on hot plate, 5) When the temperature stabilizes in the range of 60*C-65*C then "se, a" rT then begin dropping Do this at a rate (not exceeding 5 ml/min) at wi addition of pre hich temperati mx should take place over about 30-49 minutes, ©" ¥® controlled, TotalReport: 1) Calculate the solid content by placing 10gm of the polymer solution in a petridish dry in oven at 120*C, State the factors that affect the polymerization of the rrononat and the cross-linking process, J 2) Take approx. 0.5gm of dry polymer each in § test tubes to observe the solubility in methanol, Acetone, Carbon tetra chloride, Toluene and Benzene. 3) Relate your practical yield with theoretical yield.polymethyl methacrylate using a tion Experiment 6 object: Determination 0 dilatometer. a Cathetometer, dilatometer, methyl methacry! f rate of polymerizal benzoyl peroxide, long Material: necked funnel Background: The rate of polymerization is given by: Ads 10° —-+® eH yf nomer i sity of mor Where A is cross-sectional area (radius of capillary = 0.15 cm.) 7 a ie a roleciiar (0.922 gm/mi), s is the rate of fall meniscus, F is the conversion factor Se a eer ‘weight of the monomer (100 for MMA), Vis the volume of monomer taken nomen As a result of polymerization there is a net contraction in the volume of the monomer. percentage of contraction for 100% conversion is defined as the conversion factor Ro = Procedure: : In a beaker dissolve 0.2gm benzoyl peroxide and 15ml of MMA. Using a fine funnel fill the dilatometer tube with this solution. Carry out polymerization while the dilatometer is immersed in 2 water-bath at 60°C. Follow, the rate of fall of the meniscus using a cathetometer. Place the telescope of cathetometer so that the meniscus appears crossed with the telescope viewing scale. Note the change in height for every 1 minute. You will have to move the cathetometer to Report: 1. Plot a curve for time Vs. fall of meniscusgaperiment 7 Object: To determine the concentratio nin i measurement of the refractive index and plotting of cbt cee Umer solution by plotting of a calibration curve. Materials: Refractometer, distilled water, solution tation, os od 3 beakers feed Of Polyvinylalcohol in water, tissue papers, volumetric cylinder (10ml), 1 ml pipette Theory If a ny of light passing from darker (denser) medium to a denser (lighter) medium, it er is refracted towards (away from) the normal. The ratio of tile ‘sine of angle of incidence to that of the angle of refraction is constant and given by Snell's law as the refractive index of the second medium. n=Sini Sint Refractive indices of liquids are experimentally measured using the Abbe's refractometer. Procedure: Prepare solutions of of %, % and 1/8 using the 4% solution of polyvinylalcohol. Determine the refractive index using the Abbe's refractometer of these solutions starting with the most concentrated and going on eventually to the solvent. Determine the refractive index of the unknown solution given by us. Report: 1. Draw a calibration curie for concentration V/s refractive indices. 2. Using your calculator find the best fit parameters and draw a straight line on the graph from these parameters. 3. From your plot interpolate the concentration of the unknown solution. 11Experiment 8 rene with Benzoyl Peroxide. Object: Suspension polymerization of St Reagents: Styrene, Benzoyl Peroxide, water Peed magnetic stirrer and ter. Start the stirrer ble. Allow the | Styrene to Procedure: in a 25 mi flask mix 0.2gm Benzoyl — Se tpirodnes : this solution to a 250m! conical flask and add 150ml wa pppeaaee place the flask in a water bath made of 500ml beaker, in: i lets are visil and adjust constant stirring that proper size of monomer ae 7 Aner 1 hr of mixing you temperature to rise up to 80°C. Continue heating and mixing for 1 hour. i ing in size. At the will see decrease in turbidity of the suspension with suspended particles ae a pect Bue end of the ihr you will see a clear solution with particles of uniform size, 7 ae Pee continue stirring. Now cool down by circulating the cold water in the outer beal Piece hardboard in between the beaker and hot-plate to insulate the beaker from residual . 6 Continue stirring until the temperature drops to 30°C. Remove the flask from the water ba! and filter the product polystyrene. Wash the product on the filter paper with cold water to remove un-reacted Styrene. 1. Air dry the polystyrene and weigh it to calculate the yield. 2. With the help of graph paper find the average size of particles in diameter. 3. Check solubility of polystyrene in Methanol, Ethanol, Benzene, Acetone and Carbon tetra chloride. Report: 4. Draw your conclusions about the entire experiment 2 Compare your results with that obtained in emulsion and solution polymerization 3. Comment on solubility of your productjemarks about ‘Discussion/Conclusion? nS giv ach experiment, i mechanism explained in digital manner at htto://pse -ws/macrog/lab/menu htm and (4) A discussie should summarize succinctly what you did and wh: ad hypothesize, extrapolate — Mostly this is done whil at happened, discuss how and why it happened: the reaction or the equation Xd implementation, rationalize }’Bative viscosity obtained because the viscometer was not all the way in the i mary of what you did, its about the essence of the outcome (for example the accuracy and precision of dilute solution viscosity determinations of unknown Polymer molecular weights is low and {unreliable for water soluble polyoxyethylenes). (7) References should include references you found (by Yourself) that helped support or explain what you found/observed/concluded and should includ the name and initials of author(s), book name, page ‘number where you picked from, year of publication. Books: ! have uploaded some books and lab-books related to polymers on Dropbox. You can access these at http://tinyurl.com/booksraapplied The e-books include this manual, Polymer Systems by Rodriquez, Polymer by Manas Chandra, Basic Laboratory Course on Polymers and their Characterisation by Free University Berlin. 133