SCES2434 : Polymer Chemistry 1______________________________________

EXPERIMENT 1 Identification of Polymers from Solubility Tests Introduction A macromolecule becomes a single phase in solution according to the same thermodynamics laws as the micromolecular solution substances. However, differences in molecular size influence the solubility properties of both these substances. For example, a macromolecule dissolves slowly due to its entangled constitution opposing the penetration of the solvent; but most polymer-solvent pairs can mix in all of the proportions. On contrary, though micromolecular substances normally are much easier to dissolve than the polymer, the solubility of micromolecules is generally limited to saturated solution. The solvent of a macromolecule can be considered good by one of these two standards, i. e. the kinetic standard or the thermodynamic standard. A good solvent from the kinetic point of view is a solvent that easily dissolves the polymer in a short time. The solubility can be made faster by decreasing the particle size of the polymer sample because more of its surfaces are exposed to the solution. From the thermodynamic point of view, a good solvent has to be able to strongly interact with the solution substances due to it similarity in their chemical structure. Thus, a good solvent in terms of kinetics is fast while that in terms of thermodynamics is efficient. An amorphous polymer contains a network of entangled, flexible chains in a continuous motion. When the polymer is sunk in a solvent, the polymer network will swell from the osmotic activity of the solvent; the segmental motion will finally increase. Provided the solvent is still available, the polymer will continue to expand and increase its freedom to move. When the solvation process has sufficiently advanced to allow transitional movement to the chains, the substances will separate out to form a solution. Consequently, as the solution becomes more diluted, the intermolecular forces that exist between the polymer chains will become less and finally the solution properties will only exhibit polymer-solvent interaction forces. Solubility of a polymer will happen if the free energy of the solution (G) is given by: G = H - TS (1)

is negative. Entropy of the solution (S) is normally small but positive, thus the sign and magnitude of the enthalpy of the solution (H) will determine whether the dissolution process can happen or not. Scatchard-Hildebrand equation can be written as H / Vsp = (s - p)2 (2)

where V is the total volume of the mixture, s and p are the volume fractions of the solvent and polymer respectively, while s and p are the solubility parameters of the solvent and polymer respectively. Generally, if (s - p) = 0, equation (2) will show H = 0 and the dissolution process will happen because of the S factor. Solvent solubility parameter can be calculated fr - 1 -om the expression

SCES2434 : Polymer Chemistry 1______________________________________

s = [(Hv RT) / (M /d)]1/2 (3)

where Hv is the molar heat of vapourization, M and d are the molecular mass and density of solvent respectively. Polymer solubility parameter is obtained from: p = d G/M (4)

where d is the density of polymer with repeating units of molecular mass M, and G is the molar attraction constants (see Table 1.1). Here, refers to the total of all the chemical structure groups in the repeating unit of the polymer. Normally without strong interactions like hydrogen bonds, the solubility of a polymer can be predicted if s - p < 1. Calculation Example Polymer: poly(vinyl acetate) = -[-CH2CH(OCOCH3)-]nDensity = 1.19 g cm-3 Molecular mass of repeating unit = 86.1 g mol-1 Group 1 -CH3 1 -CH2 1 -CH 1 -COO G = p G (J1/2 cm3/2 mol-1) 420 280 140 512______ 1,352

= _______density x G_________ molecular mass of repeating unit = (1.19 x 1,352) 86.1 = 18.7 J1/2 cm3/2

Method Each student is provided with 2 polymer samples to identify. Place ~0.001 g of the polymer sample in a test-tube of measurement (13 x 100 mm) and add 5 mL of the solvent required for the test. The dissolution process can be made faster whenever necessary by heating the test-tube in a hot water-bath in the fume cupboard. The solubility test is considered negative if, after stirring once a while with a glass rod, two phases still remain after 5 min of heating at the boiling point of the solution, or the two phases are formed from the solution while cooling it to room temperature. A polymer sample can be found in the following flow-chart which must be used as guide. When the arm of the flow chart shows towards the right, the polymer will dissolve or the test is positive; and when the arm shows towards the left, the polymer will show the opposite result.

SCES2434 : Polymer Chemistry 1______________________________________

Data in the table below is for you to use in your calculations. Table 1.1 Molar attraction constants at 25oC (Van Krevelen) Group -CH3 -CH2-CH-C-CH=CH-C=CHG (J1/2 cm3/2 mol-1) 420 280 140 0 444 304 1517 1377 5 or 6 200 membered ring Group -F -Cl -OH -O-C-OO -C-NHO -C-NO 430 1228 G (J1/2 cm3/2 mol-1) 164 471 754 256 512

Table 1.2 Density (g cm-3) of Polymers Polymer Ethyl cellulose Polyamide-6,6 Poly(ethylene) Poly(isobutylene) Poly(carbonate) Poly(methyl methacrylate) Poly(oxymethylene) Isotactic poly(propylene) Poly(styrene) Poly(tetrafluoroethyllene) Poly(vinyl alcohol) Poly(vinyl acetate) Poly(vinyl chloride) Poly(vinyl pyrolydone) Code EC PA66 PE PIB PC PMMA POM PP PS PTFE PVAl PVAc PVC PVPy Amorphous 1.15 1.09 0.85 0.91 1.20 1.17 1.25 0.85 1.05 2.00 1.29 1.19 1.41 1.25 Crystalline 1.24 1.00 1.94 1.23 0.94 1.12 2.40 1.35 1.44 -

SCES2434 : Polymer Chemistry 1______________________________________

Table 1.3 Solvent solubility parameters Solvent Water Acetone Dimethylformamide(N,N) Ethyl acetate Carbon tetrachloride Chloroform m-Cresole Methanol Cyclohexanone Toluene p-Xylene s (J cm-3)1/2 48.0 20.0 24.9 18.6 17.7 18.9 22.7 29.5 19.5 18.2 17.9 H-bonding s m m m p p s s m p p

Note: s = strong hydrogen bonding m = moderate hydrogen bonding p = poor hydrogen bonding Flow-chart to identify polymer from solubility test
Sample Insoluble Toluene Cyclohexanone Cresole DMF Xylene Chloroform POM PP/PE (soluble in toluene and xylene, T>80oC) PTFE PC (slowly soluble in) cyclohexanone) Ethyl acetate PVAc (soluble in cold toluene) EC (soluble in hot toluene) PVC polyamide Methanol PVAl PVPy Water Soluble Chloroform

Acetone PIB PS PMMA

Note: EC = ethyl cellulose PVAl = poly(vinyl alcohol) POM = polyoxymethylene PE = polyethylene PVC = poly(vinyl chloride) PTFE = polytetrafluoroethylene

PMMA = poly(methyl methacrylate) PC = polycarbonate PVAc = poly(vinyl acetate) PP = polypropylene PIB = polyisobutylene PVP = poly(vinyl pyrolydone)

PS = polystyrene

SCES2434 : Polymer Chemistry 1______________________________________

EXPERIMENT 2 Separation and Purification of Polymer Introduction Polymers are always synthesized in the laboratory by solution or emulsion polymerization methods. Separation methods of polymers from the reaction mixture depend on the properties of the polymer and the system of polymerization. Polymers prepared in solution are usually isolated by adding the reaction mixture in excess nonsolvent and this will cause the polymer to precipitate out and can be filtered or strained. Sometimes the precipitated polymer remains in the form of suspended colloid; the polymer can be removed by cooling the mixture with ice or by adding an electrolyte like sodium chloride or diluted acid solution. Other methods such as long stirring time, shaking or centrifuging can also complete the separation. Separation of polymers from aqueous emulsion is often difficult to carry out. Methods frequently used are diluting using aqueous electrolyte solution, freezing or pouring or spraying into alcohol. Polymers separated using methods described above are likely to get contaminated by impurities such as residual monomer, initiator, solvent and possibly additives like surfactant or transfer agent. Purification of the polymer using methods such as distillation and recrystallisation is obviously impossible to carry out. Instead methods like reprecipitation, freeze-dry, normal dryingand solvent extraction are used. Objective To carry out separation and purification of polymer quantitatively. Summary Students will be provided with 10.0 + 0.1 mL solution of poly(methyl metacrylate) in chloroform having a concentration of about 5% w/v. The solution is contaminated with cinnamic acid to a level of about 1% w/v. The polymer is separated and purified using the re-precipitation method. The purified polymer will be analysed by UV method. (Cinnamic acid absorbs strongly in the UV region and can easily be detected). Procedure Separate the polymer from the polymer solution by precipitating it in methanol. Add all the polymer solution dropwise into the methanol with a volume of more than 5 times the volume of the polymer solution. (~50 mL). While adding the polymer solution, the mixture must be stirred vigorously either with a magnetic stirrer or glass rod. When precipitation is completed, filter the polymer using a clean and dried sintered glass with its mass known beforehand. Wash the polymer with a small amount of methanol and leave it to dry by suction (vacuum pump) for about 20 min.

SCES2434 : Polymer Chemistry 1______________________________________

Dry the sample in vacuum oven at about 50oC at least for a night. After drying, weigh the container again and record the weight of the polymer product. Keep about 0.02 0.05 g of the dried polymer. The balance of the polymer is used to carry out further purification by dissolving it in not more than 5 mL of chloroform and reprecipitating as in the method described above. The UV test is done on the products of both purifications. For each UV analysis, weight out accurately ~0.01 g polymer sample and dissolve it in 25 mL acetonitrile. Get the UV spectrum of the solution in the range of 300 200 nm. Table 2.1 UV Absorption Reagent Poly(methyl methacrylate) Cinnamic acid

215 nm / mol-1 dm3 cm-1

1.7 x 102 ?

272 nm / mol-1 dm3 cm-1

1.5 1,89 x 104

Note In the case of polymer with an unknown molecular mass, the extinction coefficient is reported as the mole of the repeating unit. For example, in this case, the repeating unit of poly(methyl metacrylate) is CH2-C(CH3)COOCH3- and is equivalent to molecular mass of 100. Data Analysis Beers Law : A =

.b.c

A = Absorption. Directly obtained from the u.v. chart

= Molar extinction coefficient b = Cell distance (in this case, b = 1 cm) c = Concentration (mol dm-3)

SCES2434 : Polymer Chemistry 1______________________________________

EXPERIMENT 3 Emulsion Polymerization of Styrene Introduction Emulsion polymerization is one of the common processes for manufacturing polystyrene. The dependence of the polymerization rate on the concentration of the emulsifier is studied, and the polymer is reserved for used in later experiment - Determination of Mv of polystyrene by viscometer (Experiment 5) or determination of Mn by membrane osmometer (Experiment 6) Principle At the beginning of an emulsion polymerization, three phases are present: a continuous aqueous phase containing the water-soluble initiator, suspended droplets of monomer, kept from coagulating to a continuous organic phase by agitation; and surfactant micelles containing a small proportion of monomer. Initiator fragments enter some of the micelles, where polymerization takes place, supplied with monomer by diffusion from the monomer droplets through the aqueous phase. As these micelles grow, they are stabilized by more surfactant 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 surfactant. Applicability The emulsion polymerization system can be applied to a wide variety of vinyl, acrylic, and diene monomers with water solubility in the range, usually 0.001-1%. Apparatus, Reagent and Materials (i) Glass soft drink with caps or stoppered conical flasks (size about 250 - 350 ml) (ii) Water bath set to 60 80C (iii) Nitrogen gas (iv) Styrene, reagent grade. (v) Potassium persulfate, reagent grade. (vi) Sodium hydrogen phosphate, reagent grade. (vii) Sodium laural sulphate (SLS) or sodium dodecyl sulphate (SDS), reagent grade. (viii) Aluminium sulphate, reagent grade. (ix) Methanol (x) Sodium hydroxide. This experiment will be carried out by three (3) or four (4) students. Each student will be assigned three out of the following 12 sets (as stated in the table).

SCES2434 : Polymer Chemistry 1______________________________________

Preparation (a) Preparing styrene Styrene is a reactive monomer that can easily polymerize by itself when store over a short period. It is normally stabilized by an inhibitor, usually an aromatic compound such as hydroquinone or t-butylpyrocatechol. Prior to use, the inhibitor must be removed by washing with 10% dilute NaOH solution. Roughly equal parts of styrene and 10% NaOH solution are placed in a separating funnel and mixed by shaking gently for 2-3 minutes, and allow to stand until the mixture separate into two distinct layers. The heavier aqueous phase is drained off. The procedure is repeated one more time. The styrene is then washed with distilled water three times. Suggestion: The total amount of styrene monomer required by four students is 180 ml. Assigned two students to each wash of 100 ml of styrene monomer. After the washing, pool the washed styrene together, to be shared by all the four students.

(b) Emulsion polymerization Into each of the glass bottle add: (i) 60.0 ml distilled water, (ii) 0.0300 g K2S2O8 (fill in actual weight used into the table), (iii) 0.0300 g Na2HPO4 (fill in actual weight used into the table) and (iv) Surfactant, SLS or SDS (as stated in the table) Shake the flask slowly until all the chemicals dissolved in the water. Add 15 ml styrene to each of the bottle, and immediately bubbled nitrogen gas through the mixture for 2 minutes and quickly cap the bottle. Shake vigorously to mix the monomer and the aqueous phase to form emulsion (look like milk or latex). Claim bottles in water bath, set to temperature (as specified by the lecturer) at 60 - 80C. Allow for 1 minute for the content to reach the temperature of the bath and start timing the reaction. Every 15 minutes, take the bottles up for shaking 20 seconds, and immediately put back into the bath. N K2S2O8 o. 1 2 3 4 5 6 7 8 9 10 11 12 Na2HPO4 Surfactant/g 0.0600 0.0800 0.1000 0.1200 0.1500 0.1800 0.2100 0.2500 0.3000 0.3500 0.4000 0.5000 [surfactant] Styrene Wt of PS 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml

SCES2434 : Polymer Chemistry 1______________________________________

Stop the reaction after 90 minutes, by opening the cap of the bottle and put in 10 ml of coagulant solution (2.5% w/v of aluminium sulphate solution in water, prepared by lab assistant). Transfer the coagulated polymer into a beaker, decant off the liquid, and wash the solid PS with 30 ml methanol twice. Wash PS with distilled water twice. Place PS in plastic sample envelope and send for drying in vacuum oven at 70C for 1 hr. Record the weight of PS formed. Calculation (1) What is the average weight of K2S2O8 used ? Expressed the average concentration as mol dm-3. (2) What is the density of styrene at room temperature? Calculate the concentration of styrene in the experiment as mol dm-3. (3) Express the concentration of surfactant as mol dm-3. In this experiment, the concentrations of initiator and monomer are maintained more or less constant. The Na2HPO4 serves as buffering agent. The surfactant concentration has been varied. The polymerization is stopped at 90 minutes (before complete conversion), the rate of reaction is reflected in the yield of PS. Rate of reaction yield of PS = [surfactant]x Plot log PS yield vs log [surfactant] Determine the order of reaction with respect to the surfactant. [Pass up PS samples with your report]

SCES2434 : Polymer Chemistry 1______________________________________

EXPERIMENT 4 Preparation of Polyester by Condensation Polymerization Introduction Differences between step and chain polymerizations The distinction between step and chain polymerization is an important concept in polymer chemistry. Firstly, in step polymerization, any two molecules in the system can react with each other. Initially, the monomers react to form dimers, dimers can react with dimers to form tetramers and so on. On the other hand, in chain polymerization, chain growth takes place only at the reactive terminals of a few initiated chains. Secondly, as a result of this difference, step reactions are characterized by a disappearance of the monomer at end early stage of the polymerization, and by the existence of a broad molecular-weight distribution in the later stages of the reaction. With chain polymerizations, the monomer concentration decreases steadily throughout the reaction and, ideally, at any stage the reaction mixture contains only monomer and high polymer. Thirdly, the variation in molecular weight at different stages in the reaction provides another distinguishing feature. In step reactions the polymer molecular weight increases slowly and steadily with the degree of conversion. In a chain reaction, high polymer is formed rapidly from each initiated monomer. Hence the molecular weight of each polymer molecule does not increase appreciably after the initial rapid propagation. At longer reaction time, there may be an increase in the number of polymer molecules, but not in the molecular weight of those already formed.

Polyester In principle a polyester can be produced from a monomer that has both OH and COOH functional groups, such as the lactic acid. The general reaction is represented by HO-R-COOH + HO-R-COOH HO-R-COR-COOH + H2O || O

HO-(R-CO-R)n-COOH + (n-1)H2O || O Such types of monomers are difficult to obtain in pure state, since reaction can begin even when the monomer is being stored. In addition, the control of molecular weight of the polyester becomes very difficult to achieve.

10

SCES2434 : Polymer Chemistry 1______________________________________

More frequently, polyesters are being commercially produced from the combination of two different monomers, one with two (or more) hydroxyl groups and the other with two (or more) carboxylic groups. The general reaction is as follow: O || HO-R-OH + HOOC-R-COOH HO-R-O-C-R-COOH + H2O n O || HO-[-R-O-C-R-]n-COOH

+ (n-1)H2O

Examples of some well known commercially important polyester are PET, PBT, PC and alkyds.

The Basic Carothers Equation For simplicity, we consider the synthesis of polyester from equimolar amounts of a diol and a diacid. One molecule of diol contains 2 groups of OH, and the functionality f = 2. The diacid (dicarboxylic) molecule contains 2 groups of COOH , and the functionality f = 2. { for a triol, f=3 .} Initially, Ao and Co represents the total OH and COOH groups respectively O O || || HO-R-OH + HOOC-R-COOH H-[O-R-O-C-R-C-]nOH + H2O Ao= 1/2 Uo Co= 1/2 Uo 0 0

where 1/2 Uo = number of diol molecules = number of diacid molecules total number of hydroxyl group, Ao = 1/2 Uof = Uo total carboxylic group, Co = 1/2Uof= Uo no. ester group, Zo = 0 no. water formed, Wo = 0 At time t, A and C represent the remaining OH and COOH groups respectively, and the polymerization medium might contain a mixture of the various chain length as follows: HO---COOH HO----COOH HO------COOH HO-------COOH HO-------------COOH .... The extent of reaction (polymerization) p would be given by p amount functional group that have reacted initial amount of functional group

p = (Co - C) /Co = (Ao - A)/Ao Co = Ao = Uo, dan C = A, Hence p = (Co - C) /Uo = (Uo - A)/Uo

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SCES2434 : Polymer Chemistry 1______________________________________

pUo = Uo - A = Uo-C, or C = A = Uo - pUo = (1-p)Uo

One -OH and -COOH react to produce one ester linkage and evolve one water molecule, Hence (Ao-A) -OH and same number of -COOH would produce (Ao-A) ester linkages (Z) and (Ao-A) molecule of water (W). Z = W = (Ao-A) = p Uo

Average degree of polymerization Pn The polymer molecules formed at any time t would not be of the same molecular weight (or same chain length). The average degree of polymerization can be estimated from the extent of polymerization p.

Total number of polymer chain Nt = total number of end-groups (since each polymer chain has 2 ends) Nt = 1/2 (C+A) = (1-p)Uo Total amount of monomers 1/2C0+1/2A0 = U0 , and these would become the total number of repeating units in the polymers. Average degree of polymerization, Pn = total number of repeat units / number of polymer chains = Uo/Nt = Uo /{(1-p)Uo} = 1/(1-p) Pn = 1/(1-p) The relationship between Pn and p : p Pn 0 1 0.5 2 0.75 4 0.9 10 0.95 20 0.99 100 0.999 1 1000 Basic Carothers equation

In this experiment, we are going to make polyester from phthalic anhydride and ethylene glycol, and keep the extent of reaction p between 60-80%, so that the polymer would have a low degree of polymerization. 2 < Pn < 10. The resulting polyester would be in the form of a vicious liquid. Stage 1: HO-CH2CH2-OH + C6H4(CO)2O HO-CH2CH2-OOC-C6H4COOH [62] [148.2] bp198 mp131, bp284 + no water

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Stage 2: 2HO-CH2CH2-OOC-C6H4COOH HO-CH2CH2-OOC-C6H4COO-CH2CH2-OOC-C6H4COOH polyester Experimental procedure: Put 74.10 g (0.50 mol) phthalic anhydride into the reactor (round-bottom flask). Add in equimolar amount of ethylene glycol (31.00 g). Initially heat the mixture slowly on a heating mantle, and swirl the flask from time to time. Increase the temperature to 160-180C and hold for about 20 minutes or longer until all the acetic anhydride has dissolved and the mixture reflux slowly. At this stage, there is no water evolved. Allow the reaction mixture to cool down to below 120C. Rearrange the apparatus, and set up for distillation, as shown below. Increase the temperature slowly, until the lower thermometer reach 200-240C. The reaction at the second stage would start to generate water of reaction, which would then distill over as steam, condense through the condenser, and collect at the graduated tube. Monitor the temperature of the higher thermometer to ensure that no reactant is lost. Stop heating, when the reaction reaches the specified extent (See lecturer for individual assigned extent of reaction, which would be between 70-90%). Allow the temperature to fall below 100C. Dismantle the apparatus, and pour your product into a sample bottle. Label with your name, group, and date of synthesis. Calculate the following projected properties: (i) (ii) (iii) (iv) (v) (vi) The initial amounts of OH and COOH in the starting materials. The ratio r, [-COOH]/[-OH] From the amount of water of reaction collected, calculate the actual extent of reaction, and average degree of polymerization? What would be average molecular weight? The extent of reaction from the total amount of water evolved. What would happen if the extent of reaction approaches 100%? Figure 1 + H2 O

Figure 2

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SCES2434 : Polymer Chemistry 1______________________________________

EXPERIMENT 5 Viscosity-Average Molecular Weight Introduction to Viscometry Measurements of the viscosity of dilute polymer solution provide the simplest and most widely used technique for routinely determining molecular weights of polymer samples. However, it is not an absolute method because each polymer system must first be calibrated with absolute molecular weight determinations (usually by light scattering) run on fractionated polymer samples. Viscosities are measured at concentrations of about 0.5 g/100 mL of solvent by determining the flow time of a certain volume of solution through a capillary of fixed length. Flow time in seconds is recorded as the time for the meniscus to pass between two designated marks on the viscometer. Viscosities of the polymer solutions are measured at constant temperature; usually at 30.0 0.1 C.

The Ubbelohde type of viscometer is the most convenient to use in that it is not necessary to have exact volumes of solution to obtain reproducible results. Furthermore, additional solvent can be added (as long as the total volume can be accommodated by the reservoir); thus concentration can be reduced without having to empty and refill the viscometer. CAUTION: It is necessary to ensure that the polymer solution is free from and solid particle, either due to dust or incompletely dissolved polymer, as any particle that got stuck at the capillary tube would affect the flow time.

Viscosity can be expressed in several ways as described below. Relative viscosity r Relative viscosity is the ratio of solution viscosity to solvent viscosity, which is proportional to a first approximation for dilute solutions to the ratio of the solution flow time to solvent flow time.

r =

= 0

t t0

(1)

where and 0 are the viscosities of the solution and solvent respectively; t and t0 are the respective flow time of the solution and the solvent respectively.

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Specific viscosity, sp Specific viscosity is the fractional increase in viscosity, defined as..

sp

- 0
0

t - t0 t0

r - 1

(2)

Both r and sp are dimensionless (i.e. without a unit). As concentration increases, so does viscosity. Hence to account for the concentration effects, the specific viscosity is divided by concentration to give the reduced viscosity, red

re d =

s p c

(3)

Not uncommonly, viscosities are determined at a single concentration and the inherent viscosity (inh) as defined below is used as an approximate indication of molecular weight.

inh

ln r c

(4)

where concentration c is commonly expressed as g per 100 ml. The change in solution viscosity with increasing concentration can be expressed as a series in concentration c as given by the Huggins Equation and the Kraemer equation as shown below.

sp c

[ ] + k 1 [] c
2

(5)

[ M. L. Huggins, J. Am. Chem. Soc., 64(1942) 2716]

ln r c

2 [ ] - k 1' [ ] c

(6)

[ E. D. Kraemer, Ind. Eng. Chem., 30(1938) 1200] Both the inherent and reduced viscosities extrapolate to give the intrinsic viscosity, [], at zero concentration.

[]

sp

c=0

ln c

(7)

c=0

The Huggins constant k1 is related to the molecular structure and the degree of association of the polymer chains in the solvent. It could be shown mathematically that the two equations (5 & 6) would converge to intercept at the y-axis to the same [ ] and k1 + k = (8)

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SCES2434 : Polymer Chemistry 1______________________________________

Experimental Procedure (a) Determination of t0 Set the water bath to 30.0 0.1 C. Measure 10 ml of toluene (which has been filtered through a filter stick) into an Ubbelohde viscometer. Allow the system to attain thermal equilibrium (let the viscometer be in the water bath for at least 2 minutes). Apply nitrogen gas to force the toluene to rise through up the capillary tube to fill the bulb between the mark XY and reach the bulb above X. (Get the demonstrator or the laboratory assistant to show you the correct technique). Allow the solution to flow under gravity. Start timing with a stop-watch when the upper meniscus reaches X, and stop the stop-watch when the meniscus reaches Y. Repeat 4 to 5 times, and take the average of the three most consistent readings to be the solvent flow time t0. Pour out all the toluene, and hang the viscometer upside down in the fume cupboard to drip dry while you prepare the polystyrene solution as follow. (b) Preparation of 1% w/v polystyrene solution Prepare a solution of the polystyrene sample ( H, L or X, get assignment from the lecturer in charge) by weighing accurately about 0.25 g of the polystyrene into a 25 ml volumetric flask. Add toluene into the flask and allow the polystyrene to dissolve completely (need to wait at least 15 minutes, with occasional shaking), adjust to the mark of the volumetric flask. (c) Determination of solution flow time t Pipette 10 ml of polystyrene solution into the viscometer. Follow the same procedure as in (a) to measure the solution flow time. Reduce the concentration of the solution in the viscometer by adding 3 ml of solvent directly into the viscometer. Make sure you shake the viscometer for a few minutes to ensure homogeneous mixing, before you start to determine the solvent flow time. Repeat the dilution 4 to 5 times, each time by adding 3 ml solvent into the viscometer. For each concentration, repeat the measurement of flow time at least 4 times and the average value is computed. Note: At the end of the experiment, pour the content of the viscometer into a waste bottle. Fill the viscometer with clean toluene, before you return it back to the laboratory assistant.

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SCES2434 : Polymer Chemistry 1______________________________________

Analysis of data Tabulate your results as follow: Measurement of solvent flow time t0 No. 1 2 3 4 5 Solvent flow time t0 /s

Average of three most consistent measurement = c g/100 ml Solution flow time /s 1 2 3 4 Average t

r = t/t0

sp

sp/c

Ln r/c

Plot (sp/c) and (ln r /c ) versus c in the same graph paper, and determine the intrinsic viscosity [ ]. Determine the viscosity average molecular weight of your polystyrene sample. The intrinsic viscosity of a polymer is related to the viscosity average molecular weight by the Mark-Houwink Equation. [ ] = K (Mv)a (9)

where K and a are constants for a specific polymer and are dependent on the temperature and solvent. In the case of polystyrene in toluene at 30C, K = 9.2 x 10-3 ml g-1 and a = 0.72.

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EXPERIMENT 6-A Vapour Pressure Osmometry (VPO) Introduction Generally, two techniques are used to determine the number average molecular weight (Mn) of polymer samples; there are Membrane Osmometry (MO) and Vapour Pressure Osmometry (VPO). MO is used to determine Mn of values greater than 35,000, while VPO regularly used to measure relatively smaller molecular weight range, i.e. Mn of values below 20,000. In this experiment, VPO technique will be used. Schematic diagram of VPO [1] is shown below.

The first step in running VPO is to ensure that the sample chamber is saturated with solvent vapour at a certain temperature. Thermistor is a smart device that can measure temperature (T) change as low as ~10-5 K. Two wicks, one for polymer solution (PS) and the other for pure solvent (S) are used to attach one drop of PS to one end of the thermistor and one drop of S of the same size to the end of other thermistor. According to Raoults Law for ideal solution, the drop in partial vapour pressure of the solvent PS drop is lower than that of the solution S. Therefore, the vapour of the solution from the gas phase will condense at the PS drop. This condensation process releases heat energy, thus the temperature of PS will increase. Due to the excess amount of solvent in this system, evaporation and freezing of S drop can be ignored. The temperature difference ( T) between both thermistors mentioned above is proportional to the difference in electrical resistance ( R) measured electronically. In nonequilibrium system, there is a semi-empirical relationship between dilute PS with concentration, c (g/kg),

1 R = K M + Bc c n

(1)

where K is the cell constant and B is the parameter that relate to the second virial coefficient [2].

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The constant K is determined by calibration with a compound of known Mn, say Mn = Mo, so equation (1) becomes,

R c
'

2 = K 1 + M o Bc '

(2)

where c' = c/Mo (mol/kg). Intercept derived from the linear-plot of R/c' versus c' gives K. If a best fit straight line is made according to equation (1) gives an intercept of I, then

Mn =

K I

(3)

Operational procedures In this experiment, VPO Osmomat O7O-B (calibrated with benzyl, Mo = 210.23 g/mol) will be used. The calibration data are: Solvent Temperature (cell set pt.), T Concentration, c (g/50 g) = = = toluene 45.0oC 0.04, 0.07, 0.10 and 0.13

Students must work in a group of two. Prepare four standard solutions of poly( -methyl styrene) (PAMS) in toluene with concentration as shown below: Series 1 2 3 Sample PAMS H M L Concentration, c (g/kg) c2 c3 c1 30.0 50.0 70.0 15.0 25.0 35.0 10.0 17.0 25.0

c4 90.0 50.0 35.0

Attention: Prepare only one batch of samples, either H, M or L. Refer to your lecturer for sample selection. Solution must be prepared in accurate concentration. In each sample preparation, weigh out accurately 10.0 g of solvent ( 12.0 ml) and put it into a 25 ml volumetric flask that can be tightly closed. Refer to OTR Operation Manual, Section 5.3 - 5.4.6 (pg. 5.1 - 5.4) to get data of R. Data Analysis (i) (ii) (iii) (iv) Record K value and the experimental conditions. Make a table of R and c values. Plot R/c versus c and determine Mn and B using equations (1) and (3). Discuss VPO method and results in your report.

References [1] [2] Operation Manual for VPO, page. 2-5 & 2-6 A. Rudin, The Elements of Polymer Science and Engineering, Academic Press, Chap. 3 (1982)

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EXPERIMENT 6-B Determination of Number Average Molecular Weight, Mn of polystyrene by measurements of osmotic pressure Instrument: Membrane Osmometer The following apparatus are needed: Apparatus Syringe (accessories of osmometer) Volumetric flask 50 ml Glass sample bottle with cap Pipette 5ml (for transferring stock solution) Pipette 5 ml & 10 ml (for toluene only) Pipette Pump Stop clock Preparation of stock solution 1. Weigh accurately 1.xxxx g of polystyrene (to 4 decimal points) into a 50ml volumetric flask. (There are 3 different types of polystyrene labeled with H, L and X. Ask the lecturer to assign and record your sample code) 2. Record down the exact weight (referred as w ). 3. Add in about 30 ml toluene to the sample; shake the mixture until all PS has dissolved and form a homogenous solution. 4. Top up with toluene to the 50ml graduated mark. 5. The concentration of the stock solution would be .. w g / 50 ml = 2w g/100 ml Preparation of the sample solutions for osmometer measurements Solution A The stock solution is of highest concentration, let it be C5 = 2w /100 ml Solution B Pipette 15ml of stock solution into a sampling bottle. Add 5ml of toluene. The concentration will be C4 = 15/20 x C5 = 15/20 x 2w g /100 ml = 3w/2 g/100 ml Solution C Pipette 10ml of stock solution into a sampling bottle. Add 10ml of toluene solvent. The concentration C3 = 10/20 x C5 = w g/100ml. Solution D Pipette 5ml of stock solution into a sampling bottle. Add 10ml of toluene solvent. The concentration C2 = 5/15 x C5 = 2w/3 g/100 ml Quantity 2 1 4 1 1 each 1 1

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SCES2434 : Polymer Chemistry 1______________________________________

Solution E Pipette 5ml of stock solution into a sampling bottle. Add 20 ml of toluene solvent. The concentration C1 = 5/25 x C5 = 0.4w g/100ml. Example of concentration calculation: If w = 1.0244 g, concentration expressed as g /100 ml toluene: No. 1 2 3 4 5 Solution Concentration E C1 = 0.4 w g / 100 ml D C2 = 2w/3 g /100 ml B C3 = w g/ 100 ml C C4 = 3w/2 g/100 ml A C5 = 2 w g /100 ml Expressed as g/100 ml toluene 0.4100 0.6829 1.0244 1.5366 2.0488

(The values on the last column are those to be keyed into the computer) Membrane Osmometer Operation Procedure 1. Turn on the power supply of the machine. 2. LEDs (light) for Power and Heating are on, indicating the instrument is ready. (The Lab. Assistant might have turned the instrument on earlier, and left to stabilize before your measurement.) Operation procedure 1. Click on the File, go to new measurement, click on 090 molecular weight measurement. 2. Click start -- > 3. Key in the sample ID (e.g.: PS, H - your name). 4. Click on the blank area of Solution No 1, key in the concentration of the sample solution in the unit of g/100ml. Follow by the No. 2, No. 3, No. 4 & No. 5 (in increasing order of the concentration). 5. Click start -- > Make sure the liquid level in the suction bottle is low, otherwise pour the liquid into the waste solvent bottle. This is important to prevent the solvent back flow into the suction bulb. Baseline adjustment 1. 2. 3. 4. Click on the Select for Baseline adjustment. Press the suction bulb. Open the lid of inlet funnel Inject toluene into the inlet funnel with the syringe until the maximum level of the inlet funnel (marked as black line). (Reserve this syringe for transferring toluene only). 5. Close the lid. 6. Start the stop clock and wait for 2 minutes.

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SCES2434 : Polymer Chemistry 1______________________________________

7. Release the extension bar for the valve (anticlockwise direction) and let the toluene inside the inlet funnel flow till around 1cm from the bottom. (do not let the liquid flow empty, this could introduce the air bubble into the machine and cause error.). 8. Click on start -- > 9. Repeat step 1 to step 9 until the different between the two reading less than 3. Sample solution measurement. 1. 2. 3. 4. 5. 6. 7. 8. 9. Click on the Select for Solution No 1. Press the suction bulb. Open the lid of inlet funnel Inject solution No.1 into the inlet funnel with the syringe until the maximum level of the inlet funnel (marked as black line). (Reserve this syringe for solution only. DO NOT MIX UP WITH THE FIRST SYRINGE !!) Close the lid. Start the stop clock and wait for 2 minutes. Release the extension bar for the valve (anticlockwise direction) and let the toluene inside the inlet funnel flow till around 1cm from the bottom. (do not let the liquid flow empty, this will course the air suction into the machine). Click on start -- > Repeat step 1 to step 8 to obtain five readings on solution No 1.

Repeat the measurements for remaining sample solutions (No. 2, 3. 4 and 5) Every time you are measuring a new solution, first rinse the syringe (reserved for solution) with the new solution a few times, to ensure the contamination from the previous solution is at a minimum). Baseline correction Click on the Select for Baseline correction. Press the suction bulb. Open the lid of inlet funnel Inject toluene into the inlet funnel with the syringe until the maximum level of the inlet funnel (marked as black line). 5. Close the lid. 6. Start the stop clock and wait for 2 minutes. 7. Release the extension bar for the valve (anticlockwise direction) and let the toluene inside the inlet funnel flow till around 1cm from the bottom. (do not let the liquid flow empty, this will course the air suction into the machine). 8. Click on start -- > 9. Repeat step 1 to step 9 until the different between the two reading less than 3. 10. Click Finish 11. Click linear regression The computer software of the Osmometer would carry out the calculation and plot the graph for you. 1. 2. 3. 4.

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SCES2434 : Polymer Chemistry 1______________________________________

EXPERIMENT 7 Determination of glass transition temperature, Tg: Dilatometry technique Introduction Macromolecules exist in a variety of aggregate states according to the structure, temperature and other environmental conditions. Four of these states are rubbery, glassy, crystalline and liquid. One polymer may exist in all of these states or some of them. Polymers are different compared to materials with lower molecular weight, because they normally exist in more than one state for the same sample and in rare special condition exhibit 100% crystalline state. Therefore, in one polymer sample, some may exist in the form of rubbery or glassy portion and some in crystalline portion. In crystalline state, polymeric chains are arranged in order, forming crystal lattice, while in rubbery or glassy state, polymeric chains are in random orientation and is called amorphous. Characteristic that differentiate between the crystalline with amorphous states is not orientation, but motion. Below the glass transition temperature (Tg), the segmental motion of polymer chains, especially short segment rotations ( 510 carbon atom) stop and will be in the glassy state. It should be noted that the transformation from a rubbery state to a glassy state or vice versa is a second order transition, i.e. no transition in polymer chain orientations, therefore there is no change in volume. It is different compared to the change from crystalline state to rubbery state or liquid, where there are changes in both polymer orientations and movements, followed by a change in volume. This is called first order transition. The actual value of glass transition depends on several factors, but the main factor is the structure of repeating unit of that polymer. The glass transition is correlated to the beginning or stopping (freezing) of segmental motion through the bond rotation which in turn depends on the structure of repeating unit. For organic molecules with low molecular weight, e.g.

H H R1 C C

Y H R2

the activation energy for rotation of C-C bond depends on the properties of the substituted groups. An increase in size or polarity of the substituted groups can restrict the bond rotation, thus activation energy will increase. The frequency of bond rotation can be categorized by Arrhenius equation:
E a K = Xe RT

where X is assumed to have the same value as the frequency of torsional oscillation of C-C bond and Ea is activation energy of the bond rotation. Consequently, when the temperature is reduced, a value can be derived where the frequency of C-C bond rotation takes longer time than the experimental time period and rotation can no longer be detected. At this critical temperature, rotation is assumed to have stopped.

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SCES2434 : Polymer Chemistry 1______________________________________

Polymers can also be treated in the same way. In normal repeating unit, e.g.
P1 H H C C Y P2 H

(where P1 and P2 represent the polymer chain)

will contain two big substitutions, P1 and P2 (if C-C bond is not part of the end group, beside the other substituted units). Activation energy for C-C bond rotation in polymers is usually in the order of 10-20 kcal mol-1 and depends on the size and polarity of the substituted groups. Therefore, the critical temperature (Tg) where the rotation can be observed to have stopped is in the range of -100oC to +200oC. At glass transition temperature, there is a unique transformation in polymer properties, from hard and relatively brittle at lower temperature to a rubbery state at high temperature. Beside an abrupt change in hardness and brittleness at glass transition, other properties such as the thermal expansion coefficient, heat transition, heat capacity, dielectric constant and deflection index also change. By observing the changes in these properties against temperature, Tg can be determined. In this experiment, Tg will be determined with dilatometry technique, i.e. by observing the change in height of the meniscus of the capillary tube / specific volume (thermal expansion coefficient) of the polymer over a certain temperature range. Procedure Fill a dilatometer, containing about 17 g poly(isobutyl methacrylate) with distilled water. Use long hypodermic tube until the water reaches about 1/3 of capillary tube. Grease oil can be used at the joints if necessary. Place dilatometer into the water bath set at 70oC to remove any air bubbles by rotating it. Then cool it down to room temperature. Immerse the dilatometer with the whole bulb in a water bath, equipped with temperature controller and heater. Take the value of the meniscus for every 3oC increase within the temperature range of 20-70oC. Temperature must be controlled to constant value (+ 1.0oC) for 5 minutes before the value of the meniscus is noted down. Data Analysis Plot the change in value of the meniscus against temperature. The point of inflexion in the curve gives the Tg value.

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SCES2434 : Polymer Chemistry 1______________________________________

EXPERIMENT 8 Determination of Glass Transition Temperaure Tg : Rebound Resilience Method Introduction When stress is applied on a piece of elastomeric material, the rate of opening-up of the polymer molecule chain at any particular time depends on the proportion of the molecules which are still immobile. The rate of which can be given as 1/ , known as stress relaxation time, defined as the time taken for the shape to deform (1 - 1/) of its equilibrium time. The time-deformation curve after the application of stress on a polymeric mass is given by the equation,

Dt = D 1 e t

(1)

Where Dt refers to the deformation at time t and D the deformation after infinite time (Figure 1.)

Figure 1: Deformation of a Highly Elastic Material on Application of Stress A very important consequent of this theory is that for a particular material, whether it behaves as rubber or glass depends on the test time scale. For example, when the time taken to highly deform a material is extremely short, t << , the material will behave like a glass, but at longer test time, t >> , the material will behave like rubber. While t is influenced by the speed of the test, relaxation time is influenced by test temperature and obeys the normal exponential rate law

= Ae E RT
where E is related to the activation energy of a bond rotation. By combining equations (1) and (2), we will obtain

(2)

Dr D = 1 e [ t / Ae

E / RT

(3)

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At high activation energy, the equation shows that Dt/D changes from 0 to 1 for only a small change of temperature (Figure 2) Figure 2: Change of Dt/D with temperature T at fixed t, A and E.

As such, a sharp change from glassy to rubbery is expected to occur within a small range of temperature at a particular test speed. According to this theory, the actual Tg will depend on the speed of the test conducted. Tests at lower speed will show lower Tg. This experiment shows the significance of both parameters, time and temperature, in determining the elasticity of an elastic material. When an elastomeric ball is is dropped onto a hard surface it will rebound; the time of contact between the ball and the surface is very brief. The extent of rebounce depends on the temperature and can be shown by the rebound resilience defined as the ratio of regained energy in relation to the applied energy. If h0 is the initial height, and h is the rebounce height, the rebound resilience, is given by h/h0 and the energy loss for each rebounce isis (1 - h/h0). In this experiment, a plot of h/h0 against T will produce a curve which will go through a minimum at which the value T corresponds to the glass transition temperature Tg.

Experimental Procedure
1) Two samples, a natural rubber (NR) ball and a butyl rubber ball, are used in this experiment. At room temperature, the NR ball will rebound higher than the butyl rubber ball. 2) The experiment will be conducted at temperatures from -80oC to +60oC. Temperatures below 0 oC is obtained by mixing liquid N2 with water. Use a Dewar flask to prepare a sub-zero environment. Immersed the rubber balls, together with the metal tong, in the flask for 3 minutes. Set up a meter ruler to read vertically upwards. Using the tong, hold the rubber ball at a height of 60 cm (ho), then relaese it to drop onto a hard surface of your work-bench. Note the height of the rebounce (h). Take two readings. Repeat the process with the other sample. Continue the experiment for other temperatures.

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SCES2434 : Polymer Chemistry 1______________________________________ Analysis of Data

Plot h/ho against temperature for each rubber on a single graph. Determine the temperature at lowest value of h/ho. This temperature is closely related to the transition temperature Tg. The relationship is given by the William-Landel-Ferry (WLF) equation below:

Tg = Tg' +

51.6 log a 17.4 log a

(4)

where a = t/t. here, Tg is obtained from a technique of known test time t, while Tg' corresponds to t'. The values of t for different test is given in the Table 1 below: Table 1 : Test Time (t) Test Thermal expansion Mechanical Loss Rebound Resilience Dielectric loss Broadline NMR t(s) 104 1 - 104 10-5 10-2 - 10-8 10-4 - 10-5

Example of Calculation using WLF Equation

If, in the rebound resilience experiment, minimum h/ho occurs at 100K, the Tg of the material can be predicted using the values corresponding to the thermal expansion as follows, Tg = 100 K, Tg' = ? K, So, a = 109 t = 10-5 s (rebound reslience) ; t' = 104 s (thermal expansion).

Equation (5) gives,

Tg = Tg' +

51.6 log a 17.4 log a

51.6 log 10 9 17.4 log 10 9

100 = Tg' +

100 = Tg' + 55.3

100 = Tg' + 55.3 Tg' = 44.7 K

Similarly, Tg for the rubber sample in the experiment can be determined based thermal expansion.

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SCES2434 : Polymer Chemistry 1______________________________________

EXPERIMENT 9 Determination of The Crosslink Parameters of a Vulcanised Natural Rubber This experiment has two parts PART A : Stress-Strain Method A special feature of natural rubber (NR) is elasticity. Materials such as metal and glass can only be deformed elastically to a small degree, normally less than 1%, while NR can be extended to 700% or more. Elastic deformation means a material will recover to its original shape and dimension when released after being deformed. The basis of elasticity in NR is that polymer chains without any external application of strain, will have the most appropriate configuration, statistically; i.e. randomly coiled. When strain is applied, the chain will be effectively extended to a longer, less appropriate configuration, followed by a decrease in entropy. If the strain is released, the chain will return to the most probable configuration and maximum entropy in accordance to the Boltzman expression:

S = k log W

(1)

The idea that polymer, with its high molecular weight, should display elasticity, obviously, is not totally true because there are actually four basic criteria for the elasticity of rubber: (i) The material must be made up of long chain molecules which can rotate freely,

(ii) Has weak intra-molecular atrractive forces (iii) The molecules are joined or crosslinked along the chains, and (iv) The polymer is above its glass transition temperature Tg Unvulcanised rubber does not fulfil these criteria because the polymer chains are not crosslinked. However, apparent crosslinks exist from the entanglement of the polymer chains. The elasticity of NR can be improved by chemically introducing the crosslinks through a process known as vulcanisation or curing. Although rubber does not behave like solid, gas or liquid, part of its behaviour can be understood from the analogy of the properties of a perfect gas. Pressure exerted by gas on the wall of a vessel is caused by the continuous and random bombardment of the gas molecules; tension on an extended rubber is caused by the random thermal movement of segments of the polymer chain. Gas molecules are inclined towards a most probable distribution in space. Similarly, the segments of the polymer chains are inclined towards the most probable, randomly coiled condition.

We can also produce an equation for rubber, similar to the ideal gas equation, P = nRT/V. the equation for the situation is,

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SCES2434 : Polymer Chemistry 1______________________________________

F=

dRT 2 Mc

(2)

where F is the tensional force (i.e. the force per cross-sectional area of the unextended rubber sample, kg cm-2), d is the density of rubber (g cm-3), R the gas constant, T the absolute temperature (K), Mc is the molecular weight between crosslinks, and the ratio of the extended length to its original. Just as no gas behaves as ideal gas, similarly, rubber will display a deviation from its ideal behaviour, such that the equation is modified to fit actual observation,

F=

gdRT M 2 1 2 c Mc M

(3)

where g is a correction factor for the additional (apparent) crosslinks caused by the physical entanglement of polymer chains, M the molecular weight of the elastomer, and the expression (1 - 2Mc/M) is a modification which takes into consideration the existance of free ends in a 3-dimensional network. In this experiment, the degree of vulcanisation, Mc as determined by the Mooney-Rivlin equation (3) will only be true at low extension ( < 1.5). Experimental Procedure Mark two positions, a distance of 5 cm (lo) on the rubber sample. Grip the sample with 2 clips; make sure the markings are visible. Hang the sample as shown in Figure 1. Weigh the container which will be attached to the lower clip. Measure the distance between the markings. Add weights successively and measure the corresponding lengths (l) of the sample until it it is extended to about 25 cm. Remove the weight successively and again measure the corresponding length of the sample. Determine w, the weight (g) per cm of the sample. See equation (5)

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SCES2434 : Polymer Chemistry 1______________________________________

Analysis of Data a) b) Plot on one graph, the weight L (kg) against extension for both addition and removal of weights, in order to show the effect of hysterisis. Use the data from the addition of weights to analyse the following:

Mooney-Rivlin equation is given as follows,

L /( 2 ) = l + S1

(4)

where l and S are constants that can be determined from the plot L/( - -2) against -1. Mc, can be calculated from the equation Mc = W'RT/I (g/mol) where W' = R = weight of sample/lo (g/cm) 84.7 kg.cm.mol-1.K-1 (5)

PART B : Swelling Method Raw rubber (e.g. latex and unvulcanised rubber) can be perfectly miscible with good solvents such as toluene and chloroform; but once vulcanised, it becomes almost insoluble. It cannot be dispersed by solvent but will undergo swelling; the amount of solvent absorbed depends on the extent of crosslinking. This is almost similar to the solubility of a polymer. However, in swelling the penetration of solvent into the polymer network has an opposing effect to the elastic shrinkage of the network. At equilibrium, these two effects are in balance. The equilibrium degree of swelling can be understood from the combination of the theories of solution and elasticity of rubber. The equations enable the calculation of Mc, from the degree of swelling of a rubber. Experimental Procedure TWO steps are involved. (1) Determination of density of rubber Cut the rubber sample into small pieces ( 5 mm), and place them in a 100 ml beaker. Pour into it 25 ml of glycerol. Using a burette, gradually add methanol into the beaker, with occassional shaking, until the rubber pieces remain suspended in the methanol/glyecerol mixture. At this instance, the densities of the rubber and the solution mixture are the same. Detremine the density of the mixture using a SG bottle. (2) Determination of the swelling of the rubber sample Cut about 3 cm of the rubber sample and accurately determine its weight. Place the sample in a conical flask containing 25 ml toluene. Stopper the flask and place it in a dark corner of a cupboard for at least 12 hours. Take the rubber out and place it on a wire mesh for 5 seconds. Transfer the rubber to a weighing bottle of known weight, close it, and determine the weight of the rubber.

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Analysis of Data The ratio of the volume of solvent trapped in the rubber sample is,

Wg - W ] d Qm = W [ ] d [

(6)

where Wg is the weight of swollen rubber, W the initial weight of rubber, d' the density of toluene (0.867 g.ml-1) and d the density of rubber [from (1)]. The volume fraction of rubber in the swollen sample is,

V2 =

1 1 + Qm

(7)

The molecular weight Mc can then be calculated from the following equation,

dV0V21 3 Mc = ln (1 V2 ) + V2 + V22

(8)

where Vo is the molar volume of toluene (mol. wt / density), and the interactive constant between natural rubber and toluene (= 0.42). Determination of the density of rubber: 1. Cut a portion of the rubber sample (~10 cm) and determine its ACCURATE weight. 2. Fill a 5 ml. measuring cylinder with distilled water to its 3.00 0.05 ml. 3. Cut the rubber into smaller pieces and put them into the measuring cylinder. [Make sure there are no AIR BUBBLES on the rubber samples]. 4. Accurately read the new water level in the flask. 5. Determine the volume (V) of the rubber. 6. Calculate thedensity of the rubber,

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