Running head: POLYMER VISCOSITY 1

Polymer Viscosity

Laboratory 2

University of Technology, Jamaica

Polymer Science

March 29 , 2017

Aim: To determine:

The absolute viscosity of a polystyrene-toluene system of different concentrations

The viscosity average molecular weight of a polystyrene-toluene polymer

Theory:

According to Elert (2015), Viscosity describes the internal friction of a moving fluid that
Running head: POLYMER VISCOSITY 2

causes resistance to flow. All polymers increase the viscosity of the solvent that they are

dissolved in. This increase allows for a convenient method of determining the molecular weight

of polymers. The relation between viscosity and concentration becomes more complicated when,

with increasing concentration, the molecules begin to interact with each other, first through

hydrodynamic interaction that is a long range effect, and then by forming actual contacts,

aggregates, and networks (Weissberg, Simha & Rothman, 1951).

Dilute Solution Viscosity is used as an indication of the molecular weight of polymers,

the test result of this is called the intrinsic viscosity. According to Intertek Plastics Technology

Laboratories (n.d.), the intrinsic viscosity is used for polymers that dissolve completely without

chemical reaction or degradation and can provide an excellent determination of lot-to-lot

consistency or be used to compare molded parts to original resin for determinations of

degradation from molding. The intrinsic viscosity,[ ] as function of average molecular weight,

M is represented by Mark-Houwink-Sakurada equations

[] = KM (1)

where K and are constants for a given polymersolventtemperature system (Yacob et

al., n.d.).

The plots used to find the intrinsic viscosity are called the Huggins plot ( hred vs. c ) and the

Kraemer plot ( ln(h / ho) vs. c ). As shown on the graph below, the curves of both plots should be

linear and have a common intercept that is the intrinsic viscosity.

Running head: POLYMER VISCOSITY 3

In this experiment, the absolute viscosity and the average molecular weight of polystyrene

dissolved in toluene is investigated. A K value of 11.0 E-3 at 30 C and a value of 0.72

(Ebewele, 2000) are used in the calculation for this experiment. Polystyrene is a vinyl polymer.

Structurally, it is a long hydrocarbon chain, with a phenyl group attached to every other carbon

atom. Polystyrene is produced by free radical vinyl polymerization, from the monomer styrene

(The University of Southern Mississippi, 2005a).

Running head: POLYMER VISCOSITY 4

The weight-average molecular weight (Mw) of the commercially-available PS that is widely

used as industrial material is generally 150,000 to 400,000 (Application brief, 1995). However,

according to Wegner (n.d.), the molecular weight for anionically produced polystyrene ranged

from 4500 to 510000.

Toluene on the other hand, is a colorless, water-insoluble liquid with the smell associated

with paint-thinners.

Apparatus & Materials:

Polystyrene Viscometer

Toluene 250ml beaker

100ml measuring cylinder spatula

Methodology: As seen on Laboratory Sheet

Results:

Toluene
Dynamic
Concentration gPS/100g Kinematic Viscosity Density Temperatur
Viscosity
Toluene (mm2/s) (g/cm3) e (oC)
(mPa.s)
Run 1 0.00 0.34139 0.28956 0.8482 40.0060
Run 2 0.00 0.34131 0.28950 0.8482 40.0080
Average
0.00 0.34135 0.28952 0.8482 40.007
s
Table 1. Viscosity results upon measuring pure toluene.

Solution 1
Kinematic Dynamic
Concentration gPS/100g Density Temperatur
Viscosity Viscosity
Toluene (g/cm3) e (oC)
(mm2/s) (mPa.s)
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Run 1 0.01 1.0668 0.92747 0.8507 40.0070

Run 2 0.01 1.0912 0.94378 0.8507 39.9880
Average
0.01 1.079 0.935625 0.8507 39.9975
s
Table 2. Viscosity results upon measuring a solution of 0.01gPs/100g toluene.

Solution 2
Kinematic Dynamic
Concentration gPS/100g Density Temperatur
Viscosity Viscosity
Toluene (g/cm3) e (oC)
(mm2/s) (mPa.s)
Run 1 0.005 0.64874 0.55094 0.8492 40.0080
Run 2 0.005 0.66492 0.56988 0.8496 39.9910
Average
0.005 0.65683 0.56041 0.8494 39.9995
s
Table 3. Viscosity results upon measuring a solution of 0.005gPs/100g toluene..

Solution 3
Kinematic Dynamic
Concentration gPS/100g Density Temperatur
Viscosity Viscosity
Toluene (g/cm3) e (oC)
(mm2/s) (mPa.s)
Run 1 0.0025 0.49286 0.41836 0.8488 40.0110
Run 2 0.0025 0.49652 0.42142 0.8487 40.0060
Average
0.0025 0.49469 0.41989 0.84875 40.0085
s
Table 4. Viscosity results upon measuring a solution of 0.005gPs/100g toluene.

Solution 4
Kinematic Dynamic
Concentration gPS/100g Density Temperatur
Viscosity Viscosity
Toluene (g/cm3) e (oC)
(mm2/s) (mPa.s)
Run 1 0.00125 0.41441 0.35166 0.8486 39.9920
Run 2 0.00125 0.41542 0.35250 0.8486 39.9980
Average
0.00125 0.414915 0.35208 0.8486 39.995
s
Table 5. Viscosity results upon measuring a solution of 0.00125gPs/100g toluene.
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Solution Concentration Averages rel spec red inh

Toluene 0 0.34135 1 0 - -

Solution
1.079
1 0.01 3.160978468 2.160978468 216.0978468 115.0881621

Solution
0.65683
2 0.005 1.924212685 0.924212685 184.842537 130.9033778

Solution
0.49469
3 0.0025 1.449216347 0.449216347 179.6865387 148.409184

Solution
0.414915
4 0.00125 1.215511938 0.215511938 172.4095503 156.1322689

Table 6. Relative, specific, reduced,and inherent viscosity results upon measuring varied

concentrations of Polystyrene-Toluene solutions.

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Viscosity of Polystyrene-Toluene Solution

250

y = 4898.7x + 165.3
200

150

y = -4653.3x + 159.45
100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012

Reduced Viscosity Inherent Viscosity Linear (Reduced Viscosity)

Linear (Reduced Viscosity) Linear (Inherent Viscosity) Linear (Inherent Viscosity)

Graph 1. Reduced and inherent viscosity vs concentration of a polystyrene-toluene solution.

[] = 165.3
K= 11E-03
a= 0.725
M= 577050.77
Table 7. Showing results of viscosity average molecular weight based on the reduced viscosity of

polystyrene-toluene solution
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[] = 159.45
K= 9.30E-03
a= 0.72
M= 549073.04
Table 8. Showing results of viscosity average molecular weight based on the inherent viscosity

of polystyrene-toluene solution

Average Molecular weight

(577050.77 + 549073.04)/2= 563061.96 g/mol

Sample Calculations: Using Kinematic Viscosity

Relative Viscosity

rel = /0

= 1.079/ 0.34135

=3.160978

Specific viscosity

s = r-1

=3.160978-1

=2.16097

Reduced Viscosity

(r-1)/C= red

= 2.16097/0.01
Running head: POLYMER VISCOSITY 9

=216.0978

Inherent Viscosity

inh= (ln (rel))/C

= (ln(3.160978))/0.01

= 115.0882

Intrinsic Viscosity

At concentration =0

red [C=o]= intrinsic

red = 165.3

inherent [C=o]= intrinsic

inh = 159.45
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Discussion:

In the experiment conducted it was expected of the experimenters to determine the

viscosity average molecular weight and the absolute viscosity of polymer solutions. The solution

that was mentioned was of varying concentrations of toluene with a constant mass of

polystyrene.

In this manner both molecules are both nonpolar allowing the dissolution of the

polystyrene in the toluene. The dissolution also occurs due to the fact that the polymer-solvent

interactions are greater than that of the polymer-polymer attractive forces. This phenomena

causes the polymer chain segment to absorb solvent molecules, increasing the volume of the

polymer matrix, and loosening out from their coiled shape, thus altering the solution viscosity

(University of Southern Mississippi, 2005b).

Polystyrene is a thermoplastic polymer made from petroleum, it is a non-sustainable,

non-renewable, heavily polluting and fast-disappearing commodity (The Way To Go, n.d.).

According to ChemicalSafetyFacts.org, polystyrene is made by stringing together, or

polymerizing, styrene, a building-block chemical used in the manufacture of many products.

Toluene, also known as methylbenzene, is an organic chemical compound. Toluene is a very

good solvent because, unlike water, it can dissolve many organic compounds (Nissa Garcia,

n.d.).

Intrinsic Viscosity (IV) is a measure of the polymers molecular weight and therefore

reflects the materials melting point, crystallinity and tensile strength (Lloyd Instruments, 2013).

According to Wagner (n.d.), a less complicated method of determining the weight average

molecular weight is the intrinsic viscosity; this is so as this method yields the viscosity average

molecular weight which is close in value to that of the weight average molecular weight.
Running head: POLYMER VISCOSITY 11

According to Gooch (n.d.), reduced viscosity is the fluid viscosity increase per unit of polymer

solute concentration.

A plot of the Concentration against Reduced Viscosity also known as the Huggins Plot

seeks to satisfy the Mark-Houwink-Sakurada equation. According to Neira-Velazquez et al.

(n.d.) the intrinsic viscosity as the limiting value of the ratio of the solutions specific viscosity to

the concentration of the solute as the concentration approaches zero, reflects the capability of a

polymer in solution to increase the viscosity of the solution. Therefore, the intrinsic viscosity is

the y-intercept on a graph of concentration against reduced viscosity & inherent viscosity; the

intrinsic viscosity was found to be 165.3 ml/g and 159.45 ml/g respectively.

All polymers increase the viscosity of the solvent in which they are dissolved. This

increase allows for a convenient method of determining the molecular weight of polymers

(Hester, 2001). This can be seen in figure 1 as the concentration increases, so does the reduced

viscosity of the system. The Mark-Houwink-Sakurada equation was used to determine the

molecular weight of the polystyrene-toluene system. This was done by utilizing the intrinsic

viscosity found as well as the constants K and a at 11E-03 and 0.725 respectively. The molecular

weight was found to be 563061.96 g/mol which is slightly outside the region stated by Wegner

(n.d) and application brief (1995) of between 4500 and 510000.

Based on the graph, the reduced and inherent viscosity lines are straight lines as expected

however they did not converge at the y intercept hence the average molecular weight was found

by finding the molecular weight of each line and then averaging them. The resulting average

molecular weigh was found to be outside the range of commercially acceptable polystyrene this

could be as a result of the the viscometer used being designed to be used for oil based substances

and not polymers.

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Conclusion

It can be concluded that toluene is categorized as a good solvent thus producing an

intrinsic viscosity for the polystyrene- toluene system of 165.3 ml/g and 159.45 ml/g using the

reduced viscosity and inherent viscosity respectively, this resulted in an average molecular

weight of 563061.96 g/mol.

Running head: POLYMER VISCOSITY 13

References

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on Glass Transition. Retrieved from http: http://www.hitachi-

hightech.com/file/global/pdf/products/science/appli/ana/thermal/application_TA_068e.pdf

Chemical Safety Facts. (2016). Polystyrene. Retrieved from

https://www.chemicalsafetyfacts.org/polystyrene-post/?tab=1

Ebewele, R.(2000). Polymer Science and Technology. CRC Press LLC: USA

Elert, G. (2015). Viscosity. Retrieved from http://physics.info/viscosity/

Garcia, N. (n.d.). What is Toluene?-Structure, Uses & Formula. Retrieved from

http://study.com/academy/lesson/what-is-toluene-structure-uses-formula.html

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Hester, R. (2001). Molecular Weight Determination By Dilute Solution Viscosity Measurements.

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Running head: POLYMER VISCOSITY 14

http://www.azom.com/article.aspx?ArticleID=4577

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http://pslc.ws/macrog/weight.htm

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http://pslc.ws/macrog/vis.htm

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