Berat Molekul dan Solusi Polimer

2.1 Jumlah rata-rata dan berat rata-rata berat molekul

2.2 Solusi polimer

2.3 Pengukuran jumlah berat molekul rata-rata

2.4 Pengukuran berat rata-rata berat molekul

2.5 Viscometry

2,6 Distribusi berat molekul

2.1 Jumlah Rata-rata dan Berat Rata-rata Berat Molekul

A. Berat molekul polimer

a) Beberapa polimer alami (monodisperse):

Semua molekul polimer memiliki berat molekul yang sama.

a) Polimer sintetik (polidisperse):

Berat molekul polimer didistribusikan

c. Sifat mekanik dipengaruhi oleh berat molekul

berat molekul jauh lebih rendah; properti mekanik yang buruk
berat molekul jauh lebih tinggi; terlalu sulit untuk diproses
berat molekul optimal; 105 -106 untuk vinil polimer
15.000 - 20.000 untuk gugus fungsi polar yang mengandung polimer (poliamida)
B. Penentuan berat molekul

a) Metode absolut:
spektrometri massa properti koligatif analisis
kelompok akhir hamburan cahaya ultrasentrifugasi.

b) Metode relatif: viskositas larutan

c) Metode fraksinasi: GPC

C. Definisi berat molekul rata-rata

a. Jumlah berat molekul rata-rata ( Mn )

 Ni Mi
Mn= N
i

(colligative property and end group analysis)

b. berat rata-rata berat molekul( Mw)

WiMi
Mw= W
i

(light scattering)
 C. Definition of average molecular weight

c. z average molecular weight ( MZ )

NiMi3
MZ=
NiMi2
(ultracentrifugation)

d. general equation of average molecular weight :

NiMia+1
M= NiMia

( a=0 , Mn a=1 , Mw a=2 , Mz )

e. Mz > Mw > Mn
D. Indeks polidispersitas: lebar distribusi

polydispersity index (PI) = Mw / Mn ≥ 1

 E. Example of molecular weight calculation

a. 9 moles, molecular weight (Mw) = 30,000

5 moles, molecular weight ( Mw) = 50,000

(9 mol x 30,000 g/mol) + (5 mol x 50,000 g/mol)

Mn = = 37,000 g/mol
9 mol + 5 mol

9 mol(30,000 g/mol)2 + 5 mol(50,000 g/mol)2

Mw = = 40,000 g/mol
9 mol(30,000 g/mol) + 5 mol(50,000 g/mol)
 E. Example of molecular weight calculation

b. 9 grams, molecular weight ( Mw ) = 30,000

5 grams, molecular weight ( Mw ) = 50,000

9g+5g
Mn = = 35,000 g/mol
(9 g/30,000 g/mol) + (5 g/50,000 g/mol)

(9 g/30,000 g/mol) + (5 g/50,000 g/mol)

Mw = = 37,000 g/mol
9g+5g
 2.2 Polymer Solutions

A. Proses pembubaran polimer: dua langkah

 langkah pertama: pelarut berdifusi menjadi massa polimer

untuk dibuat gel polimer bengkak

 langkah kedua: gel polimer bengkak pecah menjadi larutan

2.2 Polymer Solutions

B. Thermodynamics of solubility :
Gibb's free energy relationship

G =H - TS

ΔG < 0 : spontaneously dissolve

T and ΔS are always positive for dissolving process.
Conditions to be negative ΔG,
ΔH must be negative or smaller than TΔS.
 2.2 Polymer Solutions

H. Mark-Howink-Sakurada equation

: The relationship between intrinsic viscosity and molecular weight

[η] : intrinsic viscosity

[η] = KMa K , a : constant for specific polymer and solvent
M : average molecular weight

I. Important properties of polymer solution : solution viscosity

a. paint spraying and brushing

b. fiber spinning
FIGURE 2.2 Schematic representation of a membrane osmometer.
2.3.2 Membrane Osmometry
A. According to van't Hoff equation
 RT
( )C=0 = + A2C
c Mn
limitation of : 50,000～2,000,000
Kesalahan utama muncul dari penyebaran spesies berbobot molekul rendah
melalui membran.
FIGURE 2.3 Automatic membrane osmometer [Courtesy of Wescan Instruments, Inc.]
FIGURE 2.4. Plot of reduced osmotic pressure (/c) versus concentration (c).

/c

RT
Mn
Slope = A2

C
2.3.3 Cryoscopy and Ebulliometry

A. Freezing-point depression (Cryoscopy)

Tf RT2
( )C=0 = + A2C
C Hf Mn

Tf : freezing-point depression,

C : the concentration in grams per cubic centimeter
R : gas constant
T : freezing point
Hf: the latent heats of fusion
A2 : second virial coefficient
 2.3.3 Cryoscopy and Ebulliometry

B. Boiling-point elevation (Ebulliometry)

Tb RT2
( )C=0 = + A2C
C HvMn

Tb : boiling point elevation

H v : the latent heats of vaporization

We use thermistor to major temperature. (1×10-4℃)

limitation of Mn : below 20,000
 2.3.5 Mass spectrometry
A. Conventional mass spectrometer for low molecular-weight compound
energy of electron beam : 8 -13 electron volts (eV)
 2.5 Viscometry
A. IUPAC suggested the terminology of solution viscosities as following.
Relative viscosity :  t
rel =  =  : solution viscosity
o to
o: solvent viscosity
t : flow time of solution
t o: flow time of solvent

Specific viscosity :  - o t - to
sp = = = rel - 1
o to

sp rel - 1
Reduced viscosity : rel = =
c c

In rel
Inherent viscosity : c inh = c

sp
Intrinsic viscosity : [] = ( ) =(ηinh)C = 0
c c=o
FIGURE 2.8. Capillary viscometers : (A) Ubbelohde, and (B) Cannon-Fenske.
B. Mark-Houwink-Sakurada equation

[η] = KMa

log[η] = logK + alogMv

(K, a : viscosity-Molecular weight constant, table2.3)

Mw > M v > Mn

Mv is closer to Mw than Mn
 TABLE 2.3. Representative Viscosity-Molecular Weight Constantsa
Polymer Solvent Temperature, Molecular Weight ab
oC Range  10-4 Kb 103
Polystyrene Cyclohexane 35 d 8-42e 80 0.50
(atactic)c Cyclihexane 50 4-137e 26.9 0.599
Benzene 25 3-61f 9.52 0.74
Polyethylene Decalin 135 3-100e 0.67
67.7
(low pressure)
Poly(vinyl chloride) Benzyl alcohol 155.4d 4-35e 0.50
156
Cyclohexanone 20 7-13f 13.7 1.0
Polybutadiene
98% cis-1,4, 2% 1,2 Toluene 30 5-50f 0.725
30.5
97% trans-1,4, 3% 1,2 Toluene 30 5-16f 0.753
29.4
Polyacrylonitrile DMFg 25 5-27e 0.81
16.6
DMF 25 3-100f 39.2 0.75
Poly(methyl methacrylate-co-
styrene)
17.6
30-70 mol% 1-Chlorobutane 30 5-55e 0.67
24.9
71-29 mol% 1-Chlorobutane 30 4.18-81e 0.63
0.77
Poly(ethylene terephthalate) M-Cresol 25 0.04-1.2f 0.95
240
Nylon 66 M-Cresol 25 1.4-5f 0.61

aValue taken from Ref. 4e.

bSee text for explanation of these constants.
cAtactic defined in Chapter 3.
d temperature.
eWeight average.
fNumber average.
gN,N-dimethylformamide. POLYMER CHEMISTRY
 2.6 Molecular Weight Distribution

2.6.1 Gel Permeation Chromatography (GPC)

A. GPC or SEC (size exclusion chromatography)

a. GPC method is modified column chromatography.

b. Packing material: Poly(styrene-co-divinylbezene),

glass or silica bead swollen and porous surface.

c. Detector : RI, UV, IR detector, light scattering detector

d. Pumping and fraction collector system for elution.

e. By using standard (monodisperse polystyrene), we can obtain Mn , Mw .

FIGURE 2.9. Schematic representation of a gel permeation chromatograph.

POLYMER CHEMISTRY
 FIGURE 2.10. Typical gel permeation chromatogram. Dotted lines represent volume “counts.”

Detector Baseline
response

Elution volume (Vr) (counts)

 FIGURE 2.11. Universal calibration for gel permeation chromatography. THF, tetrahydrofuran.

Log([η]M)

109  



 
108  
Polystyrene (linear)
Polystyrene (comb)  
 Polystyrene (star)
107  Heterograft copolyner 
 Poly (methyl methacrylate)  
Poly (vinyl chloride) 

Styrene-methyl methacrylate graft copolymer
106 Poly (phenyl siloxane) (ladder)
Polybutadiene

105
18 20 22 24 26 28 30
Elution volume ()5 ml counts, THF solvent)
FIGURE 2.12. Typical semilogarithmic calibration plot of molecular weight versus retention volume.

106
Molecular weight (M)

105

104

103

Retention volume (Vr) (counts)

 2.6.4. Thin-layer Chromatography (TLC)

 Plat dilapisi alumina atau silika gel.

 Biaya rendah dan kesederhanaan.

 Penapisan awal sampel polimer atau memantau proses polimerisasi.