Handout Teknologi Polimer

Teknologi Polimer Tinggi - Handout
TEKNOLOGI POLIMER TINGGI

PENDAHULUAN
Polimer dari kata :
Poli : banyak
Meros : bagian yang terulang
Produksi komersial untuk beberapa polimer
Bahan Polimer Tahun Tempat
1. Selulosa nitrat 1870 USA
2. Selulosa asetat 1985 Jerman
3. Polistiren (PS) 1930 Jerman
4. Polimetil metakrilat (PMMA) 1934 Inggris
5. PVC 1933 Jerman, USA
6. LDPE (Low Density Polietilen) 1939 Inggris
7. Poliamida (PA Nylon) 1939 USA
8. PTFE 1950 USA
9. Akrilonitril-Butadiena-Stiren (ABS) 1952 USA
10. PETP 1953 USA
11. HDPE (High Density Polietilen) 1955 Jerman
12. Polipropilen 1957 Italia
13. Polikarbonat (PC) 1959 Jerman, USA
14. LLDPE (Linear Low Density Polyetilen) 1977 USA
15. Fenol Formaldehid (PF) 1909 USA
16. Urea Formaldehid 1926 Inggris
17. Melamin Formaldehid 1938 Jerman
18. Poliuretan (PUR) 1943 Jerman
19. Epoksi (EP) 1947 USA
20. Karet Alam (vulkanisasi) 1839 Inggris, USA
21. SBR (Stiren Butadiena Rubber) 1937 Jerman
22. Akrilonitril-Butadiena 1937 Jerman
SBR = karet sintetis styrene butadiene rubber
Semula polimer disebut makro molekul.
Jurusan Teknik Kimia, Fakultas Teknik, Universitas Gadjah Mada
1
Polimer >< monomer
monomer
Istilah polimer dikemukakan oleh Staudinger
Polimer alam : = selulosa C
6
H
10
O
5
- C
6
H
10
O
5
- -
= karbohidrat
= karet alam
= protein
Polimer sintetis : = polistiren, polietilen
Dilihat dari rantainya :
1. Linier
H H H H
C = C C C C - C -
H H H H
Etilen polietilen
H H H H
C = C C = C -C C = C C-
H H
Butadiena
2. Jaring (network)
Monomer karet alam : isoprene (punya ikatan rangkap, divulkanisasi, ikatan rangkap terbuka,
senyawa S masuk dan terikat dalam rantai).
Termoplastik
Polimer yang apabila dipanaskan akan melunak/meleleh.
Bila dididinginkan akan kembali ke bentuk semula.
Polimer ini mengandung ikatan linier.
Termosetting
Polimer yang apabila dipanaskan akan tetap padat dan suatu saat akan rusak.
Mempunyai struktur rantai jaring
Senyawa organik jika dipanaskan pada suhu tinggi >>> terjadi cracking (ikatan putus) atau disebut
pirolisis (rusak pada suhu tinggi).
2
Plastik-thermoplastics :
polyethylene PE
polypropylene PP
polystyrene PS
polyvinylchloride PVC
polyacetate POM
acrylic PMMA
polyamine (nylon) PA
polycarbonate PC
polytetrafluorethylene PTFE
Plastik-thermosetting :
epoxy EP
melamine-formaldehid MF
urea-formaldehid UF
unsaturated polyester UP
phenol-formaldehyde PF
alkyd
polyurethane PUR
Elastomers :
natural rubber NR
styrene-butadiene rubber SBR
polybutadiene BR
buthyl rubber HR
polychloroprene CR
synthetis polyisoprene IR
nitrille NBR
silicone rubber
Reaksi polimerisasi
Polimerisasi adisi
H
2
H
2
H
2
H
2
C = C + C = C - C C C C
Polimerisasi kondensasi
Penggabungan 2 molekul kecil menjadi molekul besar dengan hasil samping molekul sederhana.
O O
- C OH + HO- - C O - + H
2
O
HOOC OH + HOOC OH HOOC OH
Reaksi etilen oksid :
3
O O O
C C C C + HO OH C C C C O OH
H
2
H H H
2
OH
Sifat : polimer kondensasi
Reaksi : polimerisasi adisi
Derajat polimerisasi (DP) = degree of polymerization simbol x atau n
H
2
H
2
H
2
H
2
C = C + C = C (- C C - ) (- C C - )
x = derajat polimerisasi
H
2
H
2
H
2
H
2

( CH
2
CH
2
)
n
O
HO(-C - ~~~)
n
H n besar polimer
n kecil oligomer
O O
H-(O-C - ~~~)
n
OH -O C - ~~~ >>> repeating unit
Gugus fungsional : -OH
-COOH Gugus yang bereaksi
-C=C-
-NH
2
Formation of linear-branched chains :
Linear formation chain
+
Branched chain (network polymer) formation
+
Polimerisasi adisi :
4
bersifat chain reaction
Reaksinya cepat
Pembukaan ikatan rangkap (mengaktifkan ikatan rangkap)
Polimerisasi kondensasi :
Bersifat step reaction
Reaksinya lebih lambat
Reaksinya berhenti saat kehabisan gugus fungsional
Reaksinya satu per satu
POLI KONDENSASI
Poliester
Asam ftalat + etilen glikol : HOOC COOH + HO-CH
2
- CH
2
-OH
(Terephtalic acid)
HOOC COO-CH
2
-CH
2
-OH + H
2
O
HOOC OH
HOOC OH + HOOC OH HOOC OH + H
2
O
Pada reaksi dihampakan agar reaksi bergeser ke kanan (H
2
O menguap karena hampa)
Jika terjadi perubahan fasa menjadi padat maka reaksi akan berhenti (molekul tak dapat bergerak)
PET serat poliester
Dietilen glikol HO-CH
2
-CH
2
-O-CH
2
-CH
2
-OH
Untuk serat lebih kuat : HOOC COO-CH
2
-CH
2
-OH
Poliamida
Asam adipat + heksametilendiamin :
HOOC-CH
2
-CH
2
-CH
2
-CH
2
-COOH + H
2
N-(CH
2
)
6
-NH
2

HOOC-(CH
2
)
4
-C-N-(CH
2
)
6
-NH
2
+ H
2
O
O H
Supaya reaksi bergeser ke kanan, pada pertengahan reaksi dihampakan.
2 HOOC NH
2
HOOC NH
2
+ H
2
O
Nylon 66 (senar)
Caprolactam caproic acid
5
H
2
H
2
H
2
C C C
CH
2
CH
2

+ H
2
O

H
2
N-(CH
2
)
5
-COOH
HN C=O Nylon 6 (serat)
O H
HOOC C-N NH
2
Kevlar : serat dengan kekuatan = kekuatan serat baja
O O
Cl-C C-Cl
Polimer dari Formaldehid
O
formaldehid H
2
CO atau H C H
1. Fenol Formaldehid
a. Adisi
OH OH
H CH
2
OH
+ CH
2
O
mono metilol fenol
b. Kondensasi
OH OH OH OH
CH
2
OH H CH
2
OH -CH
2
- -- CH
2
-
+ + H
2
O
OH OH
Bentuk lain : -CH
2
- -CH
2
- -CH
2
-
OH
CH
2
OH

Fenol formaldehid: untuk alat-alat elektronik >> termosetting
>> untuk lem >> tahan air
Fenol murni: padat >> titik leleh + 50
o
C >> putih
Fenol (karbol): coklat >> teroksidasi oleh udara >> PCB >> coklat >> fenol teknis
6
2. Urea Formaldehid
a. Adisi
HNH HN-CH
2
-OH
C=O + CH
2
O C=O
HNH HNH
Monometilol urea
Urea : gugus fungsional >> 2 NH
2
>> potensial mengikat 4 formaldehid
b. Kondensasi
HN-CH
2
OH HN-CH
2
OH HN-CH
2
-N-CH
2
-N-
C + C C=O C=O C=O
NH
2
NH
2
NH
2
NH
2
NH
2
Memungkinkan terbentuk polimer jenis jaring.
Urea formaldehid >> untuk lem multiplek (triplek).
Pabrik plywood biasanya mempunyai pabrik urea formaldehid sendiri.
Urea formaldehid >> putih >> kurang tahan terhadap air.
3. Melamin
>> bening seperti kaca >> mahal
NH
2
C
N N >>> mempunyai 6 gugus fungsional
H
2
N-C C-NH
2
N
Adisi dari monometilol melamin sampai dengan heksa metilol melamin.
REAKTIVITAS TETAP
O
A. H(CH
2
)
n
COOH + C
2
H
5
OH
HCl
H(CH
2
)
n
C-OC
2
H
5

B. HOOC-( CH
2
)
n
COOH + C
2
H
5
OH
HCl
r = k.C
COOH
.C
OH
Konstanta kecepatan reaksi k, (grek/L)
-1
(det)
-1
pada 25
o
C
7
Panjang rantai (n) k
A
x 10
4
k
B
x 10
4

1 22,1 -
2 15,3 6,0
3 7,5 8,7
4 7,4 8,4
5 7,4 7,8
6 - 7,3
7 -
8 7,5
9 7,4
>9 7,6
R-COOH + R-OH R-COO-R + H
2
O
A B E W
r = k
1
C
A
C
B
k
2
C
E
C
W
Reaksinya digeser ke kanan dengan cara menghilangkan airnya sehingga C
W
<< 0
r = k
1
C
A
C
B
r = kC
COOH
C
OH

= k
0
C
kat
C
COOH
C
OH
= k
0
C
H+
C
COOH
C
OH
>>> r = kC
COOH
C
OH
k
Jika dibuat C
COOH
= C
OH
= C, maka
r = kC
2
1
1
1
1 1
0
'
0
0
'
0
2 '
+

t C k
p C
C C
p
t k
C C
C k
dt
dC
Kemudian dibuat grafik :

1/(1-p)
waktu (t)
Contoh :
Asam adipat + etilen glikol
8
r = k
0
C
H+
C
COOH
C
OH
-COOH COO
-
+ H
+
Dibuat C
H+
~ C
COOH
Tidak akan sama benar karena ada konstanta disosiasi
Jika tidak mengabaikan konstanta disosiasi
C
COOH
= C
OH
r = k
C
COOH
C
COOH.
C
COOH
( )
1 2
1
1
2
1 1
' 2
0
2
'
0
2
3 '
+
+

t k C
p
t k
C C
C k
dt
dC
Konstanta disosiasi tidak diabaikan:
( )
( )
( )
( )
1
2
3
1
1
:
.
'
2
3
0
2
3
2
5
'
2
1
'
0
+
+
+
+
+
+
t k C
p
C k
dt
dC
sehingga
C C C k r
C C C k r
C K C
C
C
K
C C sehingga lain sumber ada tidak
C
C C
K
OH COOH COOH
OH COOH
H
COOH
H
COOH
H
H COO
COOH
COO H
Kemudian dibandingkan antara order 3 dengan order 5/2 ternyata order 5/2 lebih cocok
1/(1-p)
2
t
Berat molekul
9
1 2 3 ...........................x
monomer : repeating unit = N
0
setelah reaksi = N
derajat polimerisasi = x
N
0
= N x
C
C
N
N
x
0 0

dengan N = N
0
(1-p) maka :
p
x
1
1
p
xn
1
1
; x
n
: rata-rata jumlah
analog dengan Berat Molekul
BM rata-rata jumlah (number average)

N
i
: jumlah total : N
M
i
: berat molekul

i
i
y
N
N
( fraksi mol)
BM rata-rata berat (weight everage)
i i
i i
W
M N
M N
M

2
>>>>
i
i i
W
W
M N
M

2
>>>> W
i
= W
total

i x
total
i i i
W
M W
W
M M N
M
Berat Molekul z average
Z
i i
Z
i i
Z
M N
M N
M
1
x
n
sama untuk kedua polimer, tetapi distribusi BM berbeda
(jenis polimer sama, tapi cara membuat polimer berbeda)
10
i i
n
i i
n
i
i i
n
M y M
N
M N
M
N
M N
M

x
N
i
Derajad polimerisasi untuk jumlah gugus fungsional tidak sama
A A + B B dimana N
Ao
< N
Bo
Extent of reaction A = p
N
A
= (1-p) N
Ao
N
B
= N
Bo
p N
Ao
Bila :
r
N
N
Bo
Ao
N
B
= N
Ao
( 1/r p )
Saat reaksi, jumlah rata-rata = (N
A
+ N
B
)
( )
( )
( )
( ) 1 2 1
1
2
1
1
1
1
1
1
1
1
2
1
2
1
+
+

+
+
,
_
+ +
,
_
+
+

r p
r
X
p
r
r
N p
r
N p
r
N
N N
N N
reaksi saat jumlah
awal jumlah
X
n
Ao Ao
Ao
B A
Bo Ao
n
Bila reaksi sempurna p 1
Maka
r
r
X
n
1
1
Contoh : Poliesterifikasi (reaksi keseimbangan)
p p 1- p
1/(1-p)
1 2 3 .......................... x
Misal p reaksi = 40 % >>> probabilitas yang bereaksi = 0,4
Secara statistik, probabilitas x-mer:
11
N
x
= p
x-1
(1-p)
( )
( )

1
1
1
1
1
1
1
1
1 1
x
x
x
x
x
x
p
p
p p N
Distribusi Berat Molekul (derajad polimerisasi) Rantai Linear
Mol fraksi : N
x
= p
x-1
(1-p)
Jumlah molekul polimer N = N
0
(1-p)
Jumlah x-mer N
x
= Np
x-1
(1-p)
N
x
= N
0
(1-p)
2
p
x-1

Nx p=0,95

p=0,98
p=0,99
x
Fraksi berat
0
N
xN
W
x
x

= x (1-p)
2
p
x-1
Bila A tidak sama dengan B dan reaksi sempurna p=1
W
x
= x r
(x-1)/2
(1-r)
2
/ (1 + r )
W
x
p=0,90
p=0,95
p=0,98
p=0,99
x
Rantai cabang (network)
: branching coefficient A
: fraksi yang bercabang ( A A , A ) terhadap total gugus A
A
Perbandingan jumlah gugus fungsional r = N
A
/N
B
= rpA
2
/ [1-rpA
2
(1-)]
12
= pB
2
/ [1-pB
2
(1-)]
Nilai kritis :
= 1/(f-1) >>> pada saat terjadi gel (gel point)
Derajad polimerisasi (x
n
)
( )
( ) p p
r
p f
p
r
p f
x
A
n
2 2
1
1
2
1
1
+ +
+ +

.....A A.....
A A + B B A ( B-BA-A)
2
-B-BA
A .....A A......
A
A
Carothers
fav x
fav
p
n

2 2
tidak hanya untuk yang bercabang
Equimolar :
Bo Ao
Bo B Ao A
n n
n f n f
fav
+
+
Non Equimolar :
( )
C B B A C A
C B A
f f p r f rpf f f
f f rf
fav
+ +
1
2
Untuk membuat bahan termosetting gel jangan sampai terjadi / harus dihindari
Gel point : x
n
= ~ p
c
= ........

fav
p
2

A
A + B B
A
1 mol = 3 grek 1,5 mol = 3 grek
13
83 , 0
4 , 2
2 2
4 , 2
5 , 2
5 , 1 . 2 1 . 3

fav
p
fav
c
Distribusi berat molekul dalam 3 dimensi (dalam fraksi berat)
Untuk masing-masing monomer mempunyai gugus fungsional f :
2 2 1
) 1 (
)! 2 2 ( )! 1 (
)! (
+
1
]
1
x fx x
x
p p
x fx x
f x fx
w
RING FORMATION
R C = O ring
HO-R-COOH O
H(-OR-CO-)
n
-OH linier
Kecepatan pembentukan
Ring/siklis r = k
1
C
Linier r = k
2
C
2
Stoll, Rouve dan Stoll-Comte
Siklis (k
1
)
HO(-CH
2
)
n-2
COOH
Linier (k
2
)
4
3
2
log C 1
0
-1
-2
4 6 8 10 11 12 13 14 16 18 20 n

Pada n=9 , nilai C minimum
n < 4 tidak mungkin membentuk siklis
14
POLI ADISI
C = C - C C C C
Chain reaction :
Initiation (pemicuan)
M M
aktif
Propagation (perambatan)
M + M
aktif
MMM
aktif
Spontan dan terjadi rantai yang sangat panjang
Termination
Monomer aktif (M
aktif
) mati karena bertumbukan rantai sudah panjang
Reaksi poliadisi :
1. Mekanisme radikal
2. Secara ionik (kationik, anionik)
3. Koordinasi
ad) 1. Mekanisme Radikal
Initiation >> peroxide
I
kd
2R
*
Initiator yang sering digunakan : Benzoyl peroxide (pecah karena panas)
O O
-C O O C - COO
*

*
+ CO
2
Initiator yang dipilih :
yang mudah bereaksi
yang mudah membentuk radikal
Cara initiation/cara pembentukan radikal :
dengan initiator
dengan radiasi
15
dengan initiator yang pecahnya karena radiasi lebih aman karena lebih awet
disimpan.
Selanjutnya R
*
+ M RM
*
Contoh : CH
3
CH
3
R
*
+ H
2
C = C R CH
2
C
*
CH
3
CH
3

Propagation
RM
*
+ M
kp
RMM
*
RM
x
*
+ M
kp
RM
*
x+1
Termination
M
x+y
(terminasi secara coupling)
M
x
*

+ M
y
*

M
x
+ M
y
(disproporsionasi)
Keduanya kehilangan radikal
Initiator yang lain :
Azobis Isobutyronitrile (AIBN) >> pecah karena panas.
CH
3
CH
3
CH
3
CH
3
NC C N = NC CN NC C
*
+ N
2
+
*
C CN
CH
3
CH
3
CH
3
CH
3
Initiation
[ ]
[ ]
[ ]
i d
r
dt
R d
I k
dt
I d

[ ]
[ ] I fk
dt
RM d
ri
d
2
ra = ka [R
*
][M] dengan f : faktor efisiensi
Propagation
RM
*
+ M
kp
RMM
*
r
p
= k
p
[M
*
][M]
RM
x
*
+ M
kp
RM
*
x+1
Termination
RM
x
M
y
R
RM
x
*

+ RM
y
*
r
t
= 2 k
t
[M
*
]
2
RM
x
+ RM
y

[ ]
[ ]
2 *
*
2 M k
dt
M d
t

Konsentrasi radikal tetap
>>>>> r
i
= r
t
16
2 f k
d
[I] = 2 k
t
[M
*
]
2
[M
*
] = (fk
d
[I]]/k
t
)
1/2
[ ][ ]
[ ]
[ ]
[ ]
[ ] [ ]
[ ]
[ ] [ ]
t k
t
d
p
p a p
t
d
p p p
d
e I I
sehingga
M
k
I fk
k
dt
M d
r r r
dt
M d
M
k
I fk
k M M k r
1
]
1

+
1
]
1

0
2
1
2
1
*
:
[ ] [ ] [ ]
[ ]
[ ]
t
k
I fk
k
M
M
k
I fk
k
dt
M d
t
d
p
t
d
p
2
1
0
2
1
ln
ln
1
]
1

1
]
1

Contoh grafik lihat buku referensi (Bilmeyer, dll)
Autoacceleration
r
i
r
t
Grafik lihat buku referensi
Kinetic Chain Length
Jumlah monomer yang dapat digandeng oleh satu radikal
RMMM ........ MMR
Terminasi coupling v =1/2 X
n
t
p
i
p
r
r
r
r
v
Terminasi disproporsionasi v = X
n
[ ] [ ]
[ ]
[ ]
[ ]
*
t
p
*
t
*
p
t
p
n
M k
M k
M k
M M k
r
r
~ X
2 2
2

[ ]
[ ]
[ ] [ ] [ ]
[ ]
[ ]
[ ]
[ ]
p t
p
p
p
t
p
n
p
p
* *
p p
t
d *
r k
M k
M k
r
k
M k
~ X
M k
r
M M M k r
k
I fk
M
2
2
2 2
2
1

1
]
1

17
Chain Transfer
Dengan solvent
M
x
*
+ SH
ktr,S
M
x
H + S
*
Dengan initiator
M
x
*
+ (C
6
H
5
COO)
2
ktr,I
M
x
-OCOC
6
H
6
+ C
6
H
6
COO
*
Dengan monomer
X X X
-CH
2
CH
*
+ CH
2
=CH
ktr,M
-CH=CHX + CH
2
CH*
Persamaan derajat polimerisasi untuk chain transfer
[ ] [ ] [ ] [ ] [ ] [ ] [ ]
[ ]
[ ]
[ ] [ ]
p
T , tr
t
p
S , tr
S
p
M , tr
M
p
d p
t
t
p
p
t S
M
n
p
*
T , tr
*
S , tr
*
M , tr d
n
k
k
C
k
k
C
k
k
C
M
R
fk k
k
C
M
R
k
k
M
S C
C
X
r
M I k M S k M M k I fk
X

+ + +
+ + +
2
2
2 2 2
1
1
Bila tanpa solvent
[ ] [ ]
2
2
2 2 2
1
M
R
fk k
k
C
M
R
k
k
C
X
p
d p
t
t
p
p
t
M
n
+ +

Regulator
M
x
*
+ RSH M
x
H + RS
*

+M
RS M
*

>> Bisa mengatur M
>> Disebut juga transfer agent
>> Paling dominan : Merkaptan (bersifat racun)
18
Inhibitor
O O
R-M
x
R-M
x
H H
O (Ia) O
*
(Ib)
O R-M
x
-O

R-M
x
*
+

O O
*
(II)
Quinon
OH
+ R-M
x
OH O
*
(III)

: hidroquinone

OH
Styrene inhibitornya tertier butyl catechol ( TBC + 50 ppm ) >> bisa menahan styrene tidak
terpolimerisasi selama beberapa bulan.
Retarder
NO
2
H NO
2

R-M
x
*
+ R-M
x

(plus resonance structure)
Batlet and co-worker concluded that addition to the nitro group also occurs. Price and Read found
that several m-dinitrobenzene molecules were combined with the polymer for each fragment from
the p-bromobenzoyl peroxideused as initiator in the retarded polymeration of styrene. They inferred
that radical responding to IV transfers its hydrogen atom to a molecule of styrene follows :
NO
2
IV + C
6
H
5
CH=CH
2
R-Mx - + CH
3
-CH-C
6
H
5
NO
2
19
POLIMERISASI KATIONIK
Initiation
Catalyst-cocatalyst : asam Lewis (Friedel-Craft) AlCL
3
, BF
3
, SnCl
4
, ZnCl
2
BF
3
+

H
2
O H
+
(BF
3
OH)
CH
3
H
+
(BF
3
OH)
-
+
(CH
3
)
2
-C=CH
2

CH
3
C
+
(BF
3
OH)

CH
3
RCl + SnCl
4
R
+
(SnCl
5
)
A + RH
K

H
+
(AR)

H
+
(AR)
-

+ M
ki
HM
+
(AR)
-

R
i
= Kk
i
[A][RH][M]
Propagation
HM
n
+
(AR)
-
+ M
kp
HM
n
M
+
(AR)

R
p
= k
p
[HM
n
+
(AR)
-
][M]
Termination
HM
n
+
(AR)
-

kt
M
n
+ H
+
(AR)

R
t
= k
t
[HM
n
+
(AR)
-
]
>> Spontaneous termination
>> Chain transfer to counter ion
Chain transfer:
HM
n
+
(AR)
-
+ M
kp
M
n
+ HM
+
(AR)

R
t
= k
tr,M
......
Combination :
HM
n
+
(AR)
-
HM
n
(AR)
Steady State
R
i
= R
t
[ ]
[ ] [ ] [ ]
[ ] [ ] [ ]
[ ]
t
p
t
p
n
t
p i
p
t
i
k
M k
R
R
X
k
M RH A k Kk
R
k
M RH A Kk
AR HM

+
2
Dominan chain transfer R
i
= R
tr,M
20
[ ]
[ ] [ ] [ ]
[ ] [ ] [ ]
[ ]
M M tr
p
M tr
p
n
M tr
p i
p
M tr
i
C k
M k
R
R
X
k
M RH A k Kk
R
k
M RH A Kk
AR HM
1
, ,
,
2
,

+
C
M
: transfer constant
Sebagian reaksi polimerisasi kationik berjalan sangat cepat
Isobutylene, AlCl
3
bereaksi pada - 100
o
C
anggapan steady-state tidak tepat.
POLIMERISASI ANIONIK
Metal amida
KNH
2

K
K
+
+

H
2
N:
-
Styrene, -33
o
C, solvent NH
3
(titik didihnya)
H
H
2
N:
-
+ CH=CH
2

ki
H
2
N CH
2
C :
-
Propagasi
H
2
N M
n

+ M
kp
H
2
N M
n
M
Chain by transfer : ke solvent

H
2
N M
n

+ NH
3

ktr
H
2
N M
n
H + H
2
N:
-
Initiation by Electron Transfer
. _
Na +
:
Na
+
. _
. . .
--

:
Na
+
+ CH=CH
2
+ CH
2
CH
2
Na
+
21
dapat terjadi :
.. . -- -- H H --
2 CH
2
CH
2
Na
+
Na
+
: C CH
2
CH
2
C : Na
+
Initiation by Metal Alkyls
H H
C
4
H
9
Li + CH
2
=C C
4
H
9
CH
2
C :
-
Li
+
X X
Propagation
M
n
Me
+
+ M M
n
M
Me
+
R
p
= k
p
[M
-
][M]
Living Polimer
[ ]
[ ]
[ ]
[ ] C
M
X atau
C
M
X
n n
2

POLIMERISASI KOORDINASI
Skema Reaksi Polimerisasi
: Permukaan logam transisi
M
e
R : Organometal group I-III
+ M
e
R K
1
--M
e
R
+ M K
2
M--
Initiation
M-- --M
e
R
Ki
--M
e
M R
Propagation
M-- --M
e
M
n
R
Kp
--M
e
M
n
M R
Termination
Chain transfer with monomer
M-- --M
e
M
n
R
ktr,M
--M
e
M R + M
n

Spontaneous internal hydride transfer

--M
e
M
n
R
k2,M
--M
e
H + M
n
R
22
unsaturate
Transfer to M
e
- R
R M
e
-- --M
e
M
n
R
ktr,C
--M
e
R + M
n
M
e
R
Forming inactive site
M M
e
M-- --M
e
M
n
R
ktr,M
+ M
n
R
Ziegler-Natta:
Organometal : Al(Cl)
3
; AlClEt
3
Garam logam transisi : TiCl
4
Active Site :
RM
x
*
+ M RM
x+1
*

Bimetallic Mechanism

CH
2
=CCH
2
CH
2
CH
2
CCH
2
CH
2
Ti Al Ti Al
R R
CH
2
CH
3
CHCH
3
CH
CH
2
CH
2
CH
2
Ti Al Ti Al
R R
23
Mono metallic Mechanism
CH
2
Cl CH
2
=CHCH
3
CHCH
3

Cl Ti (active site) Cl Ti
Cl Cl Cl Cl CH
2
CH
2
CHCH
3
CH
2
Cl Cl CH
2
CH
2
CHCH
3

Cl Ti Cl Ti CH
2
CHCH
3
Cl Ti CH
2

Cl Cl Cl Cl Cl Cl Cl
Polipropilen
CH
3
-- C C C C C C --
CH
3
CH
3

Atactic: poliadisi radikal struktur tidak teratur, sifatnya lembek

24
-- C C C C C C --
CH
3
CH
3
CH
3

Isotactic: menggunakan Ziegler-Natta polimer kuat
Langmuir Adsorption
Fraksi M
e
R di permukaan
[ ]
[ ] [ ] M K R M K
R M K
e
e
A
2 1
1
1 + +

Fraksi M di permukaan
[ ]
[ ] [ ] M K R M K
M K
e
A
2 1
1
1 + +

R
i
= k
i
M
R
p
= k
p
M
C
*
C
*
: konsentrasi growing polimer
R
tr,M
= k
tr,M
M
C
*
R
tr,C
= k
tr,C
[M
e
R] C
*
R
tM
= k
tM
M
C
*
Bila dianggap steady-state:
R
i
= R
t
k
i
M
= k
tM
M
C
*
+ k
tr,C
A
C
*
+ k
tr,M
M
C
*
C
*
= (.....k
1
M
......)/(...............)

[ ]
( )
*
,
C k k
dt
M d
A M tr p
+
PEMBUATAN POLIMER
1. Polimerisasi curah (bulk polymerization)
Proses sederhana, untuk kapasitas kecil
Hasilnya kental, padat sehingga perpindahan panasnya jelek
2. Polimerisasi larutan (solution polymerization)
Larutan tidak kental, perpindahan panas baik
Perlu pemisahan hasil dengan pelarut
Efek pelarut terhadap BM (lebih rendah)
3. Polimerisasi suspensi (pearl, bead)
Menggunakan air ( +suspension agent )
25
Kontrol suhu baik
Hasil berbentuk butir berukuran 0,1 mm 1 mm
4. Polimerisasi emulsi
Menggunakan air + surfactant
Kontrol suhu baik
Hasil berbentuk emulsi (ukuran butir 1 mikron)
Polimerisasi suspensi: initiator lebih mudah larut dalam monomer.
Polimerisasi emulsi: initiator lebih mudah larut dalam air.
POLIMERISASI EMULSI
surfactant
Bagian surfactant :
hidrofil > suka air > ionik
hidrofob > benci air > kationik
Jenis surfactant
Anionik
Contoh :
Sabun O
C O
--
Na
+

hidrofob hidrofil
Dodekil Sulfonat detergent
SO
3
Na
+

rantai linier cepat hancur dibanding bercabang
Kationik
H N
+
Cl
+ sangat efektif untuk mencuci >> mahal

+ tak tahan suhu tinggi
Non-ionik
O CH
2
CH
2
O CH
2
CH
2
- .........OH
hidrofil
26
Micelle
Stabil tapi menggerombol pada suatu saat konstan

Critical micelle capacity
C
Resep polimerisasi emulsi :
Monomer 100 bagian berat
Air 180
Emulsifier 1-5
Initiator 0,2-0,5
Initiator Persulfat
K
2
S
2
O
8
S
2
O
8
2-
2SO
4
-
(Na, NH
4
)
Teori Smith-Ewart
menganggap surfactant inert
menganggap 1 partikel hanya menerima 1 radikal (karena apabila 2 radikal akan terminated)
C
A
= H.C
M
N
A
~ a
g
.k
c
(C
As
C
A
) N
A
: kecepatan pergerakan
b
g
d
a

6
d
b
: diameter butir/gelembung
Yang lebih banyak menerima radikal diameter kecil
Periode awal reaksi
Polimerisasi terjadi di butiran kecil (misel) membentuk inti polimer
Suatu saat surfactant akan habis melapisi inti polimer yang terus berkembang.
jumlah inti polimer tetap
27
Periode reaksi lanjut
Polimerisasi di inti polimer
R
p
= k
p
[M][M
*
]
R
p
: kecepatan 1 partikel
R
p
= k
p
[M]N/2 per cm
3
water
Karena satu hidup satu mati
N : konsentrasi partikel polimer
Kecepatan penambahan volume partikel
[ ]
( )
m
u
p
V
V
M
k
,
_
1 2
v
m
: fraksi mol monomer
v
u
: spesific volume monomer
Sebuah partikel yang terbentuk pada waktu :
Partikel yang terbentuk
t
1

t
Volum = ( t - )
dianggap 1 partikel hanya menerima 1 radikal (karena apabila 2 partikel akan terminated)
Pada waktu t, volum partikel = ( t - )
luas permukaannya : ( ) ( )
2
3
2
1
3 4
1
]
1
t a
Luas permukaan semua partikel yang terbentuk :
( ) ( )
( )
3
5
2
3
2
1
0
2
3
2
3
2
1
3 4
5
3
3 4
t A
d t A
t
t
t

1
]
1

1
]
1
Pada saat t
1
semua surfactant habis:
Luas surfactant: A
t
= C
s
.a
s
C
s
.a
s
= 3/5 [(4)
1/2
3]
3/2
t
1
5/3
t
1
= [ ......... ] (C
s
a
s/
)
3/5

-2/5
Jumlah partikel yang terbentuk :
N = t
1
= 0,53 (C
s
a
s
)
3/5
(/)
2/5
Teori ini benar untuk kelarutan kecil
tetapan 0,53 dikoreksi menjadi 0,4
28
COPOLYMERIZATION
M
1
*
+ M
1

k11
M
1
*
jumlah radikal M
1
tetap
M
1
*
+ M
2

k12
M
2
*
M
2
*
+ M
2

k22
M
2
*
jumlah radikal M
2
tetap
M
2
*
+ M
1

k21
M
1
*
Yang berpengaruh : sifat monomer yang ada di belakang.
Pada saat reaksi, konsentrasi radikal dianggap tetap sehingga:
k
21
[M
2
*
][M
1
] = k
12
[M
1
*
][M
2
] ...........(2)
Kecepatan konsumsi monomer M
1
and M
2

adalah:
........................(3)
.........................(4)
Substitusi Pers.(2) ke Pers. (3) dan (4), serta Pers (3) dibagi Pers. (4), diperoleh:
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]

,
_
+
+
,
_
2
2
1
2
1
1
2
1
2
1
1
r
M
M
M
M
r
M
M
M d
M d
.......................(5)
dengan r
1
and

r
2
adalah monomer reactivity ratio:
21
22
2
12
11
1
k
k
r
k
k
r
....................(6)
[ ]
[ ] [ ] [ ]
2
2 1
1
1
1 F
M M d
M d
F
+
.....................(7)
Bila f
1
dan f
2
adalah mol fraksi untuk monomer M
1
and M
2
yang belum bereaksi:
[ ]
[ ] [ ]
2
2 1
1
1
1 f
M M
M
f
+
Pers. (5) menjadi:

( )
( )
2
2 2 2 1
2
1 1
2 1
2
1 2
1
2 f r f f f r
f f f r
F
+ +
+
.....................(8)
Bila r
1
dan r
2
diketahui, dan komposisi monomer ditetapkan (tertentu), maka komposisi polimer
(dalam increment rantai) dapat dihitung.
Komposisi molekul polimer secara keseluruhan merupakan penjumlahan increment polimer yang
terbentuk.
Monomer 1 Monomer 2 r
1
r
2
29
[ ]
[ ][ ] [ ][ ]
[ ]
[ ][ ] [ ][ ]
1 2 22 2 1 12
2
1 2 21 2 1 11
1
M M k M M k
dt
M d
M M k M M k
dt
M d
* *
* *
+
+
Etilen Vinil Asetat 0,130 1,230
Karbon monooksida 0,025 0,004
Propilen 3,200 0,620
Stiren Akrolinitrile 0,290 0,020
Butadiene 0, 820 1,380
Divinilbenzena 0,260 1,180
Maleat anhidrid 0,097 0,001
Metilmetakrilat 0,585 0,478
4-khlorostiren 0,816 1,062
Vinileden khlorida 1,700 0,110
Vinil khlorida Vinileden khlorida 0,205 3,068
Ideal Copolymerization
Reaktivitasnya sama baik sejenis maupun berlainan jenis
r
1
r
2
= 1
Persamaan menjadi:
..............(10)
...............(11)
5
28
F
1
mole fraction of 1 0,5
M
1
in polymer
0,2
f
1
mole fraction of M
1
in monomer mixture
Alternating Copolymerization
Kopolimerisasi selang-seling
M
1
lebih suka bereaksi dengan M
2
daripada dengan M
1
; dan sebaliknya juga M
2
M
1
>> k
11
~ 0
>> r
1
= k
11
/k
12
0
30
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
2 1 1
1 1
1
1
2
1
2
1
1
2
1
ln
ln
f f r
f r
F
r
M d
M d
M
M
r
M d
M d
+

f
1
0
PENENTUAN BERAT MOLEKUL
Analisis gugus ujung/fungsional
Biasanya analisis secara kimia, misalnya COOH dengan titrasi
Hanya untuk BM rendah, < 5000
Boiling point elevation and freezing point depression
polimer harus dalam larutan
dapat mengukur BM sampai 10.000-an
Kenaikan titik didih (boiling point elevation):
M
RT
C
T b
b

,
_

,
_

2
...........(4)
R: gas constant, T: absolute temperature, : rapat massa solvent,
b
: latent heat of vaporization of
solvent (per gram), C: konsentrasi solute (gram per m
3
), M: berat molekul solute.
Freezing point depression:
M
i
RT
C
T f

,
_

,
_

2
0
1
...........................(5)
i
f
: latent heat of fusion per gram solvent.
Dengan alat vapour pressure osmometer:
untuk zat standar
untuk bahan yang ingin diketahui BM nya
Tekanan Osmosis
,
_

i
i
n
M
c
C
M
..........................(10)
Tekanan osmosis untuk larutan:
31
2
2
2
1
2
1
1
1
M
RT
C
T
M
RT
C
T
,
_

,
_
,
_

,
_

,
_
n
M
RT
c
0
...........................(11)
Untuk gas: p = C.R.T
Untuk larutan: = C.R.T
= c/M RT
(/C)
o
= 1/M RT
Light Scattering (hamburan cahaya)
C
W T
S
P L D
1

D
2
R
Light Scattering Instrument
>> scattering
>> turbidity memantulkan cahaya
Where
i
o
is the turbidity due to molecules of molecular weight M
i
.
32
( )
( )
koreksi . faktor
o
R
bias indeks n
avogadro bilangan N
o
0 . c
lim
o
: Dengan
i
o
i
o
2
cos 1
o
R
3
16
o
2
o
dc
dn
2
o
n
N
4
3
3
32
H
where
HcM
o
,
_
,
_
,
_

Since dn/dc will be practically identical for a series of polymer homologues, a single value of H
applies to all of them and we obtain in analogy with Eq. (22).
i
o
= H ci.Mi
The forbidding appearance of the summation sign may be avoided merely by writing :
i
o
= H. c. M
w
.........(25)
where M
w
is the weight average molecular weight defined by any of the following alternate
expression :

i i
i i
i i
i i
W
M N
M N
M w
c
M c
M
2
.........(26)
Sedimentation
At point in a cell a distance x from the axis of rotation the force acting on a particle of mass m and
(partial) specific volume v immersed in a medium of density is given by :
M(1-v) r
2
Where is the angular velocity of rotation.
Equating this to frictional force, obtained by multiplying the velocity dx/dt by the frictional
coefficient f, leads to the primary sedimentation velocity relationship
( )
f
v m
dt
dx
x

,
_
,
_
1 1
2
The quantity on the left, which is determined by measuring the rate of movement of the
sedimentation constant s. Thus :
s
( )
f
v m 1
.............(40)
The mass of the sedimentation particle could be deduced from its rate of sedimentation at high
dilution in a given field, i.e. from its sedimentation constant, if the frictional coefficient f could be
determined independently.
Rate of diffusion may be utilized to secure this necessary supplementary information, since the
diffusion constant D depends also on the frictional coefficient. Thus :
f
c d
d
kT
D

,
_
ln
ln
1

..............(41)
where is the activity coefficient of the solute. This reduce at infinite dilution to
0
f
kT
D
...............(42)
which in combination with eq. (40) at infinite dilution (multiplied by Avogadros number) given :
33
( )
P
M
RT D

1
0
0
.................(43)
Hence the molecular weight may be calculated from the ratio of the limiting value of D and s at
infinite dilution. The problem is to secure accurate value for D
o
and s
o
.
The change in the sedimentation constant with concentration enters solely from the change in 1/f
1
an it is customary therefore to extrapolate i plot 1/s against c to infinite dilution.
F
f
= m
2
R m/
s

2
R
F(dr/dt) = m
2
R(1-v)
v=1/
s
Sedimentation equilibrium :
( ) ( )
( )
( )
( )
( )
( )

,
_
2
1
2
1
1
1
1
1
1
~
1
ln 2
2
2
2
2
2
2
1
2
2
2
1
2
x
x
C
C A
A
A
A
A
A
A
xdx v
RT
M
C
dC
C v
RT
x DM
dx
dC
D
v
RT
x DM
u
v x m
kT
D
u
v
f
x m
dt
dx
dt
dx
u
uC
dx
dC
D N
x x v
c
c
RT
M
A
A

Intrinsic Viscosity Molecular Weight Relationship
34
[ ]
[ ] [ ] c ' K
c
ta tan kons ' K
M ' K
o
2

K : approximately constant for a series of polymer homologues in given solvent.

= 0,35 0,40
Intrinsic viscosity may also be defined :
[ ]
[ ] [ ]
reduksi viskositas
pelarut viskositas
tan laru viskositas
c ' K
c
ln
c
ln
r
r
r
c
r
+
1
]
1
0
0
0
2
0

Gel permeation chromatography
Seperti liquid chromatography
Dapat menentukan BM tiap fraksi polimer
Perlu polimer standar untuk penentuan BM
PEMAKAIAN POLIMER
Polimer tunggal
Kadang kurang menguntungkan (misalnya : PVC murni terlalu getas)
Penambahan aditif
o Bahan pengisi (filter) : selulosa, tepung, TiO
2
, karbon
o Zat warna
o Stabilizer
o Plasticizer : untuk PVC, ditambah DIOP
o Lubricant (pelumas anti lengket >> silikon)
Agar mendapat bahan dengan sifat yang diinginkan penambahan aditif
Polimer campuran
Kopolimerisasi : monomer A + monomer B
Polymer blending (polyblend)
Penambahan karbon black pada karet menambah keras
Stabilizer :
Thermal: PVC + Ca stearat / Zn stearat / Sn stearat / Cd stearat
UV
Oxygen: ditambah anti oksidan
35
Bingham =
o
+ dv/dx
Dilatant
ln
Newtonion = -dv/dx
Pseudoplastik
ln(dv/dy)
Fluida Bingham baik untuk cat agar bisa merata
SIFAT FISIS DAN STRUKTUR MIKRO
Sifat fisis dipengaruhi oleh struktur molekul (konfigurasi) dan berat molekul (distribusi BM)
Struktur:
Letak ikatan di dalam rantai
Letak rantai cabang : isotaktik, sindiotaktik, ataktik
Amorf, kristal
Glass point, melting point
alternating
random
block
Graft
Terpolimer
36
CH
3
H CH
3
CH
2
C=C C=C
CH
2
CH
2
CH
2
H
cis trans
H
2
H H H
2
H
2
H H H
2
C = C C = C - C C = C C
H H
C - C = C C = C
C = C C H C C C
- C H
2
H
2
H
2

trans cis
Isotaktik
cabangnya teratur (ke atas semua)
polypropylene
H R H R H R H
- C C C C C C C -
H H H H H H H
Sindiotaktik
teratur atas-bawah
H R H R H R H
- C C C C C C C -
H H R H H H H
Ataktik
tak teratur cabangnya
H R H H H R R
- C C C C C C C -
H H H R H H H
37
Sketsa bentuk kristalin dan amorf
kristalin
amorf

Struktur amorf
Diffuse transition zone Diffuse transition zone
T Viscous T Viscous Rubbery
Liquid Rubbery liquid Melting point
Glass transition flexible crystalline polymer
Glass transition
Glassy Rigid Crystalline Polymer
BM BM
Amorf Moderately Crystalline
POLIMER Tg,
o
C
38
Polieteilen (LDPE)
Polipropilen (ataktik)
Polipropilen (isotaktik)
Polivinil asetat (PVAc)
Polietilentereftalat (PET)
Polivinil alkohol (PVA)
Polivinil chlorida (PVC)
Polistirine
Polimetilmetakrilat (ataktik)
-125
-20
100
28
69
85
81
100
105
PENGARUH LUAR TERHADAP POLIMER
Pengaruh senyawa kimia lain (chemical effects)
Misalnya ketahanan terhadap pelarut (solvent) dari solubility parameter ()
Pengaruh panas dan suhu tinggi
Melting point polimer
Pada suhu tinggi dapat terurai (dekomposisi) pyrolysis
Pengaruh sinar/radiasi
Sinar UV
Biological and weathering effects
Mikroorganisme alam dapat merusak polimer
SOLUBILITY PARAMETER ()
Meskipun dengan pendekatan ideal, solubility parameter digunakan untuk patokan larut tidaknya
polimer di dalam cairan/solvent. Pelarutan terjadi bila energi bebas (free energy) untuk
pencampuran (mixing) negatif.
G = H - TS
H adalah panas pencampuran, S adalah perubahan entropi.
Untuk molekul nonpolar dan tidak ada efek hydrogen bonding, H positif. Hildebrand mendekati
H dengan persamaan:
H = v
1
.v
2
(
1
-
2
)
2

Indeks 1 untuk solvent dan 2 untuk polimer. v adalah fraksi volum, dan adalah cohesive energy
density, atau sering disebut solubility parameter.
Bila tidak ada interaksi yang kuat, seperti hydrogen bonding, bisa larut bila (
1
-
2
) kurang dari
3,5 4. Berikut beberapa contoh besarnya solubility parameter.
Diambil dari of Polymers", Encyclopedia of Polymer Technology, 2nd. Ed.
chemical solubility
parameter
decafluorobutane 10.6
neopentane 12.9 A A letter next to the solvent
n-hexane 14.9 A solubility parameter indicates
diethyl ether 15.1 that the polymer corresponding
cyclohexane 16.8 A to the letter (listed below)
carbon tetrachloride 17.6 A B dissolves in the solvent.
benzene 18.8 A B
chloroform 19.0 A B C
methyl ethyl ketone 19.0 B C
39
actone 20.3 B C
carbon disulfide 20.5
1,4-dioxane 20.5 B C
dimethylformamide 24.8 B C (D) (at high temperatures only)
m-cresol 27.2 B C D
formic acid 27.6 B D
methanol 29.7
water 47.9
A Poly(isobutylene) 16.2
B Poly(methylmethacrylate) 18.6
C Poly(vinyl acetate) 19.2
D Poly(hexamethylene adipamide) 27.8
POLYMER PROCESSING
Moulding: compression, injection, blow
Extrusion: piston, screw
Calendering
Spinning: melt, dry, wet
Thermoforming
POLIMER YANG DIGUNAKAN SEKARANG
Polyethylene, polypropylene, polyvinylchloride, polystyrene
Selulose, karet
40

Injection molding: Overview
Injection molding is used extensively for the
manufacture of polymeric items. A
reciprocating/rotating screw both melts polymer
pellets and provides the pressure required to
quickly inject the melt into a cold mold. The
polymer cools in the mold and the part is ejected.
Injection molding machines are sized primarily by
the force available in the mold clamping unit;
ranging from 20 tons in laboratory machines to
over 5000 tons in large commercial machines.
Process Schematic
References
Gerd Potsch, Injection Molding: An Introduction, Hanser Publishers, New York (1995) ISBN 1-569-90193-7.
41
Reaction injection molding:
Reaction injection molding (RIM) is a processing
technique for the formation of polymer parts by
direct polymerization in the mold through a mixing
activated reaction. A simplified process schematic
is shown at right. Two reactive monomeric liquids,
designated in the figure as A and B, are mixed
together by impingement and injected into the
mold. In the mold, polymerization and usually
phase separation occur, the part solidifies, and is
then ejected. Primary uses for RIM products include
automotive parts, business machine housings, and
furniture.
Process Schematic
References
C.W. Macosko, RIM, Fundamentals of Reaction Injection Molding, Hanser Publishers, New York (1989) ISBN 3-
446-15196-6.
Film blowing: Overview
The majority of polymer films are
manufactured by film blowing (blown film
extrusion). A single screw extruder is used to
melt the polymer and pump it into a tubular
die, as shown in cross-section at right. Air is
blown into the center of the extruded tube and
causes it to expand in the radial direction.
Extension of the melt in both the radial and
down-stream direction stops at the freeze line
(frost line) due to crystallization of the melt.
The nip rolls collect the film, as well as sealing
the top of the bubble to maintain the air
pressure inside. This process is used
extensively with polyethylene and
polypropylene.
Process Schematic
References
J.F. Agassant, P. Avenas, J.Ph. Sergent, P.J. Carreau,
Polymer Processing Principles and Modeling, Hanser, New York (1986). ISBN 0-19-520864-1, pages 252-262.
42
Extrusion: Overview
Single screw extrusion is one of the core
operations in polymer processing and is also a key
component in many other processing operations.
The foremost goal of a single screw extrusion
process is to build pressure in a polymer melt so
that it can be extruded through a die or injected
into a mold. Most machines are plasticating: they
bring in solids in pellet or powder form and melt
them as well as building pressure.
Process Schematic
References
J.L. White, Twin Screw Extrusion: Technology and Principles, Hanser Publishers, New York (1991) ISBN
3446156917.
Overview
Twin screw extrusion is used extensively for
mixing, compounding, or reacting polymeric
materials. The flexibility of twin screw extrusion
equipment allows this operation to be designed
specifically for the formulation being processed.
For example, the two screws may be corotating or
counterrotating, intermeshing or nonintermeshing.
In addition, the configurations of the screws
themselves may be varied using forward
conveying elements, reverse conveying elements,
kneading blocks, and other designs in order to
achieve particular mixing characteristics.
Process Schematic
References
J.L. White, Twin Screw Extrusion: Technology and Principles, Hanser Publishers, New York (1991) ISBN
3446156917.
43
Dry spinning: Overview
Dry spinning is used to form polymeric fibers
from solution. The polymer is dissolved in a
volatile solvent and the solution is pumped
through a spinneret (die) with numerous holes
(one to thousands). As the fibers exit the
spinneret, air is used to evaporate the solvent so
that the fibers solidify and can be collected on a
take-up wheel. Stretching of the fibers provides
for orientation of the polymer chains along the
fiber axis. Cellulose acetate (acetone solvent) is
an example of a polymer which is dry spun
commercially in large volumes. Due to safety and
environmental concerns associated with solvent
handling this technique is used only for polymers
which cannot be melt spun.
Process Schematic
References
A. Ziabicki, Fundamentals of Fiber Formation, Wiley, New York (1976). ISBN 0471982202.
A more detailed study of dry spinning is :
Y. Ohzawa, Y. Nagano, and T. Matsuo, J. Appl. Polym. Sci., 13, pp. 257-283 (1969).
Melt Spinning: Overview
Melt spinning is the preferred method of
manufacture for polymeric fibers. The
polymer is melted and pumped through a
spinneret (die) with numerous holes (one to
thousands). The molten fibers are cooled,
solidified, and collected on a take-up wheel.
Stretching of the fibers in both the molten and
solid states provides for orientation of the
polymer chains along the fiber axis. Polymers
such as poly(ethylene terephthalate) and
nylon 6,6 are melt spun in high volumes.
Process Schematic
References
A. Ziabicki, Fundamentals of Fiber Formation, Wiley, New York (1976). ISBN 0471982202.
A classic article which emphasizes structure development during melt spinning is:
J.R. Dees and J.E. Spruiell, J. Appl. Polym. Sci., 18, pp. 1053-1078 (1974).
44
Filament winding: Overview
Filament winding is used for the manufacture of
parts with high fiber volume fractions and
controlled fiber orientation. Fiber tows are
immersed in a resin bath where they are coated
with low or medium molecular weight reactants.
The impregnated tows are then literally wound
around a mandrel (mold core) in a controlled
pattern to form the shape of the part. After
winding, the resin is then cured, typically using
heat. The mold core may be removed or may be
left as an integral component of the part.
Process Schematic
A comprehensive reference on filament winding is:
Filament Winding: Its Development, Manufacture, Applications, and Design
D.V. Rosato, Interscience Publishers, New York (1964).
Calendering
45
Thermoforming
46

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TEKNOLOGI POLIMER TINGGI

Jurusan Teknik Kimia, Fakultas Teknik, Universitas Gadjah Mada

Chain by transfer : ke solvent

Spontaneous internal hydride transfer

+ sangat efektif untuk mencuci >> mahal

Pers. (5) menjadi:

Teknologi Polimer Tinggi - Handout

Teknologi Polimer Tinggi - Handout

Teknologi Polimer Tinggi - Handout

K : approximately constant for a series of polymer homologues in given solvent.

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