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KIMIA POLIMER
M. Chalid
DEPARTEMEN TEKNIK METALURGI DAN MATERIAL
FAKULTAS TEKNIK UNIVERSITAS INDONESIA
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
2/30
ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Buku Acuan Mata Kuliah Kimia PolimerDra. Sari Katili, MS.
Dr. Mochamad Chalid, S.Si, M.Sc.Eng.
Polymer Chemistry: An Introduction, G. Challa.
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Definisi Polimer
Polimer berasal dari katapoly(banyak) dan meros/mer(bagian/unit)
Molekul raksasa yang terdiri dari
ribuan bahkan jutaan unit
pengulangan (mer) dalam satu
molekul polimer
Berdasarkan atom penyusun rantai
utama, terdapat polimer organik
(C,N,O) dan anorganik (non C,N,O)
Apa i tu pol imer?
Polietilenaterepthalat (PET)
Silikon
Polimer anorganik Polimer organik
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
4/30
ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
f i lmblowing with
potato starchpo ly -
ethylene
po ly -
styrene
potato
starch3-d puzzle from p otato starch
ASAL MATERIAL PLASTIK DAN POLIMER
A
L
A
M
B
U
A
T
A
N
Petro-pol imer
Bio-pol imer
Apa i tu pol imer?
SEMI-BUATAN: modifikasi polimer alam dan polimer buatan
http://localhost/var/www/Movie%20Bank%20of%20Lecturing/Injection%20Molding/Understanding%20Plastic%20Materials_Definition%20of%20Plastics.mp4http://localhost/var/www/Movie%20Bank%20of%20Lecturing/Injection%20Molding/Understanding%20Plastic%20Materials_Definition%20of%20Plastics.mp4http://www.google.com/imgres?imgurl=http://kelarutan.files.wordpress.com/2009/12/biji-plastik.jpg&imgrefurl=http://kelarutan.wordpress.com/2009/12/23/plastik-organik/&usg=__UXQc9W67Bm7dpYHjTJtjpLwEhdg=&h=480&w=491&sz=108&hl=en&start=8&sig2=6ecX1SgLYVKsIAQPm_ZA-Q&zoom=1&um=1&itbs=1&tbnid=yGpZCVP1jUhO3M:&tbnh=127&tbnw=130&prev=/images%3Fq%3Dbiji%2Bpolimer%26um%3D1%26hl%3Den%26rls%3Dcom.microsoft:en-us:IE-SearchBox%26rlz%3D1I7SKPB_en%26tbs%3Disch:1&ei=Lzd7TOzADoqXccjIqeUFhttp://www.google.com/imgres?imgurl=http://allabout10.co.cc/wp-content/uploads/2010/01/54582_kilang_minyak.jpg&imgrefurl=http://allabout10.co.cc/2010/01/29/10-negara-penghasil-cadangan-minyak-terbesar-di-dunia/&usg=__ys04rbKKfQ23mHEG_gnKGpiZZno=&h=300&w=400&sz=84&hl=en&start=7&sig2=UG3XrxWaSQ1zEsw5PSOiFg&zoom=1&um=1&itbs=1&tbnid=2_LjEw_UHAMqNM:&tbnh=93&tbnw=124&prev=/images%3Fq%3Dkilang%2Bminyak%26um%3D1%26hl%3Den%26rls%3Dcom.microsoft:en-us:IE-SearchBox%26rlz%3D1I7SKPB_en%26tbs%3Disch:1&ei=7Dd7TK2tC8rzcYWY8PEFhttp://www.google.com/imgres?imgurl=http://imghost.indiamart.com/data/4/G/MY-216591/Vinyl-Co-polymer-Resin_250x250.jpg&imgrefurl=http://www.waxexporter.com/industrial-resin.html&usg=__hIVLdjorrbFy_J-ExIpkmC1FGfY=&h=240&w=240&sz=13&hl=en&start=3&sig2=EXiRSbvrvkaqRXBZlIuZUA&zoom=1&um=1&itbs=1&tbnid=hVqhIQxDCmgjUM:&tbnh=110&tbnw=110&prev=/images%3Fq%3Dresin%2Bpolymer%26um%3D1%26hl%3Den%26sa%3DN%26rls%3Dcom.microsoft:en-us:IE-SearchBox%26rlz%3D1I7SKPB_en%26tbs%3Disch:1&ei=nzd7TJuQCYfJcYyUgPUFhttp://www.google.com/imgres?imgurl=http://www.craftywoodpicker.com/products/API/Resin/resin.jpg&imgrefurl=http://www.craftywoodpicker.com/default.asp%3FCWPmenu%3Dmaterials&usg=__nKfL3YLrJczYhAtMFaET4wnR_p0=&h=210&w=280&sz=26&hl=en&start=12&sig2=F0nFYRdLGnA4VStYCQMD0Q&zoom=1&um=1&itbs=1&tbnid=ukvN8Exx6nDQuM:&tbnh=86&tbnw=114&prev=/images%3Fq%3Dresin%2Bpolymer%26um%3D1%26hl%3Den%26sa%3DN%26rls%3Dcom.microsoft:en-us:IE-SearchBox%26rlz%3D1I7SKPB_en%26tbs%3Disch:1&ei=pjZ7TJDuK8idceKIkeMF7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Jenis kopolimer (a) monomer selang seling,(b) monomer acak, (c) kopolImer blok, and(d) kopolimer cangkok. Perbedaan ukurandan warna sebagai perbedaan jenismonomer.
Kopolimer (>1 Jenis Monomer)
Terpolimer (> 2 jenis monomer)
Jenis Monomer Penyusun Polimer
Homopolimer (hanya 1 Jenis Monomer)
Apa i tu pol imer?
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Karakteristik polimertermoplastik.
Termasuk polimertermoplastik.
Various structures of polymer molecules: (b) branched
Karakteristik polimerelastomer/karet.
Karakteristik polimertermoset
Konfigurasi Struktur Rantai Polimer
Apa i tu pol imer?
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Polimer padat dipanaskan: Suhu pemanasan rantai molekul bergetar (vibrasi)
antar rantai saling menjauh ruang kosong (free volume) selanjutnya ??
1. Pada rantai lurus: mobilitas molekul polimer, hingga suatu saat (Tg dan Tm) semua
molekul polimer mobil dan material berubah wujud menjadi cair(leleh)
2. Pada rantai bercabang: mobilitas molekul polimer , hingga suatu saat (Tg dan Tm)
semua molekul polimer mobil dan material berubah wujud menjadi cair(leleh)
3. Pada rantai hubung silang: mobilitas molekul polimer, namun dibatasi oleh hubung
silang. Sehingga material hanya mengalami pelunakan dan tidak meleleh (Tg)
4. Pada rantai jaringan: mobilitas molekul polimer , namun dibatasi oleh hubung silang
yang telah terbentuk. Pada saat bersamaan, pemanasan lebih lanjut (Tc) mengakibatkan
pembentukkan hubung silang baru, sehingga material semakin keras dan tidak melunak,
apalagi meleleh.
Struktur 1 dan 2 adalah TERMOPLASTIK, 3 adalah KARET dan 4 adalah TERMOSET
Polimer termoplastik leleh didinginkan: vibrasi rantai molekul polimer pelipatan atau
pembelitan rantai molekul (tergantung struktur molekul dan kecepatan pendinginan) ruang
kosong (free volume) mobilitas molekul polimer, hingga suatu saat material menjadi
padat. BAGAIMANA dengan karet & termoset ??
Prilaku rantai polimer terhadap termal
Apa i tu pol imer?
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Penataan substituen
pada polimer
bercabang, sepertipolipropilena (PP)
dan polistirena (PS)
Taksisitas Rantai Polimer
Cabang tertata pada
satu bidang
Cabang tertata
secara selang seling
Cabang tertata
secara acak
Apa i tu pol imer?
polistirena (PS)
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
MonomerPolimer(Resin)
Resin +Additives(Plastik)
ProdukSemi Jadi
ProdukSiap Pakai
Application Waste
Siklus Polimer
Apa i tu pol imer?
http://www.google.com/imgres?imgurl=http://allabout10.co.cc/wp-content/uploads/2010/01/54582_kilang_minyak.jpg&imgrefurl=http://allabout10.co.cc/2010/01/29/10-negara-penghasil-cadangan-minyak-terbesar-di-dunia/&usg=__ys04rbKKfQ23mHEG_gnKGpiZZno=&h=300&w=400&sz=84&hl=en&start=7&sig2=UG3XrxWaSQ1zEsw5PSOiFg&zoom=1&um=1&itbs=1&tbnid=2_LjEw_UHAMqNM:&tbnh=93&tbnw=124&prev=/images?q=kilang+minyak&um=1&hl=en&rls=com.microsoft:en-us:IE-SearchBox&rlz=1I7SKPB_en&tbs=isch:1&ei=7Dd7TK2tC8rzcYWY8PEF7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
10/30
ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Requirements for a monomer
A monomer must be AT LEAST DIFUNCTIONAL
A monomer must be sufficiently REACTIVE
A monomer must be VERY PURE
THERMODINAMICS must allow a monomer to
polymerize
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Functionality of monomers: . must be at least difunctional
Functionality of monomer molecule is the number of chemical bonds it
can form with other molecules under the prevailing reaction condition
For polymerization, requires a minimum functionality of 2 of the
monomers (difunctional)
Example:
Polyesterification is possible by taking a diol and a diacid
A hydroxy acid is also difunctional, but contains both types of
complementary functional groups in one molecul
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Difunctional: . more examples.
Diols Diamines Diisocyanates Reactive ring
Dicarboxylic acids Hydroxy acids
Amino acids Reactive double bond
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Trifunctional Glycerol with three OH-groups
Phenol with two reactive ortho
positions and one reactive
para position
Tetrafunctional Isoprene
Butadiene
They have a possibility for making crosslinking to
build an elastomer and a thermoset
Functionality of monomers: . must be at least difunctional
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Reactivity of monomers: .. must be sufficiently reactive
Slowly reacting monomer would be unattractive,
because high degrees of polymerization would require
unacceptably long reaction time
Catalyst accelerate chain growth process
Increasing temp Side reatcion like chain scission by
thermal degradation
Steric hindrance around functional group should beavoided
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Purity of monomers: must be very pure
Monofunctional impurities may cause premature
stopping of chain growth
Sometimes desired to avoid the formation of too high a
molar mass polymer from very pure monomers.
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Thermodynamics of polymerization: must
allow to polymerize
and are n- and (n+1)-mers carrying radical endgroups and M is a monomer molecule
Further polymerization is only possible as long as the
Gibbs free energy G of the system decrease
If G>0, depolimerization will occure
G=0, denotes a situation of chemical quilibrium
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
At constant absolute temperature T we further know that
It follows that the equiluilibrium occurs at a critcal
absolute temperature:
Exothermic polymerization, i.e. H 0, polymerization would be possible at each T
For S< 0, polymerization is possibble if T|S| < |H| For S< 0, polymerization is not possible if T|S| > |H|
For S< 0, polymerization exhibi tsa so called ceiling
temperature Tc= H/ S
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Endothermic polymerization, i.e. H 0, polymerization is possibble if TS > H
For S> 0, polymerization is not possible if TS < H
For S> 0, polymerization exhibits a so called floor
temperature Tf= H/ S
Entropy decreases (S< 0) upon polymerization.
Most polymerization must be exothermic (H< 0) and
should be performed below the ceilling temperature.
If the temperature rises above the ceilling temperature,
then depolymerization starts from reactive chain ends.
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
When a polymer is to be processed afterwards of used
at a temperature above the ceiling temperature, then it
might be necessary to stabilize its end groups
A polymer with stabilized end group can still
depolymerization if chain scission by thermal degradation
above the ceiling temperature creates new reactive chain
ends
This problem might be restricted by incorporating a
comonomer
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
The values of the critical temperatures Tc and Tf are
governed by thermodynamics of the chemical equilibriumitself.
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Florys Principle of Equal Reactivity
The reactivites of all like functional groups are equal to each
other, irrespective of the size of the polymer molecules to
which they belong
Reactivity of Polymer Molecules
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Influence of Viscosity on Reactivity
In former times, one expected that long molecule should
be less reactive than a short one because of its lower
mobility and diffusion rate.
Theoretical basis for vanishing mobility effect by Flory
and G.V. Schulte
They made use the concept of frequent collision during
one encounter of two reactants
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Influence of Viscosity on Reactivity
Owing a truly lower relative mobility of macromolecules,
any pair encountering functional groups attached
todifferent macromolecules in a more viscous medium
will remain together for longer period
The number of collision during each encounter will
increase
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Influence of Viscosity on Reactivity
This effect compensates longer period of time elapsing
before the functional groups encounter another reactive
partner at new positions in the reaction medium
Only the distribution over time of the collisions is
changed by a possibly lower mobility
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Influence of Viscosity on Reactivity
A more quantitative description of the aboce ideas can be
given in terms of a kinetic scheme including a difusion step
of reactans:
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
27/30
ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
The Functional Group Approach
All like functional groups behaved similarly and could be
regarded as the reactants
The polymer chain segments between or beside these
groups were considered as kind of solvent
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
From kinetic analysis is should then appear whether k and
k remain really constant in the course of polymerizationwith increasing viscosity
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Transesterifications may also occur during the above
condensation polymerization
This reaction cannot be analysed in terms of functional
groups as their number does not change
7/29/2019 Kimia Polimer_Chalid 2013.Usai UTSppt
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ENMT 6 0 0009 - KIMIA POLIMER - M. CHALID
DEPARTEMEN METALURGI DAN MATERIAL FAKULTAS TEKNIK UNIVERSITAS INDONESIA
Its interesting to describe it in terms of molecules :
The average chain length remains the same, but the chainlength distribution alters.
It is not a polymerization but a redistribution.