Graft polymer
Graft Polymers are segmented copolymers with a lin-
ear backbone of one composite and randomly distributed
branches of another composite. The picture labeled
“graft polymer” shows how grafted chains of species B
are covalently bonded to polymer species A. Although the
side chains are structurally distinct from the main chain,
the individual grafted chains may be homopolymers or
copolymers. Graft polymers have been synthesized for
many decades and are especially used as impact resis-
tant materials, thermoplastic elastomers, compatibilizers,
or emulsifiers for the preparation of stable blends or al-
loys. One of the more well known examples of a graft
polymer is high impact polystyrene, which consists of a
polystyrene backbone with poly butadiene grafted chains.
The graft copolymer consists of a main polymer chain or back-
bone (A) covalently bonded to one or more side chains (B)
1 General Properties
Graft copolymers are a branched copolymer where the
components of the side chain are structurally different
than that of the main chain. Graft copolymers con-
taining a larger quantity of side chains are capable of
wormlike conformation, compact molecular dimension,
and notable chain end effects due to their confined and
tight fit structures.[1] The preparation of graft copoly-
mers has been around for decades. All synthesis meth-
ods can be employed to create general physical proper-
ties of graft copolymers. They can be used for materi-
als that are impact resistant, and are often used as ther-
moplastics elastomers, compatibilizers or emulsifiers for
1
the preparation of stable blends or alloys.[2] Generally,
grafting methods for copolymer synthesis results in ma-
terials that are more thermostable than their homopoly-
mer counterparts.[3] There are three methods of synthe-
sis, grafting onto, grafting from, and grafting through that
are used to construct a graft polymer.[4]
2 Synthesis Methods
There are many different approaches to synthesizing
graft copolymers. Usually they employ familiar poly-
merization techniques that are commonly used such
as atom transfer radical polymerization (ATRP), ring-
opening metathesis polymerization (ROMP), anionic and
cationic polymerizations, and free radical living polymer-
ization. Some other less common polymerization in-
clude radiation-induced polymerization,[5] ring-opening
olefin metathesis polymerization,[6] polycondensation
reactions,[7] and iniferter-induced polymerization.[8]
The three common methods of synthesis Grafting onto (top left),
grafting from (middle right), grafting through (bottom left), and
their generalized reaction scheme are featured.
2.1 Grafting-Onto Method
Grafting-onto method involves the use of a back-
bone chain with functional groups A that are dis-
tributed randomly along the chain.[9] The formation of
the graft copolymer originates from the coupling re-
action between the functional backbone and the end-
groups of the branches that are reactive. These cou-
pling reactions are made possible by modifying the
backbone chemically.[10] Common reaction mechanisms
used to synthesize these copolymers include free-radical
polymerization, anionic polymerization, atom-transfer
2 3 APPLICATIONS

radical-polymerization, and living polymerization tech- of the terminal functional group on the macromolecu-
niques. lar to the monomer.[11] The difference in distribution of
Copolymers that are prepared with the grafting-onto grafts has significant effects on the physical properties of
method often utilize anionic polymerization techniques. the grafted copolymer. Polyethylene, polysiloxanes and
This method uses a coupling reaction of the electrophilic poly(ethylene oxide) are all macromonomers that have
groups of the backbone polymer and the propagation site been incorporated in a polystyrene or poly(methyl acry-
of an anionic living polymer. This method would not be late) backbone.
possible without the generation of a backbone polymer The macromonomer or grafting through method can be
that has reactive groups. This method has become more employed using any known polymerization technique.
popular with the rise of click chemistry. A high yield Living polymerizations gives special control over the
chemical reaction called atom transfer nitroxide radical molecular weight, molecular weight distribution, and
coupling chemistry is for the grafting-onto method for chain-end functionalization.
polymerization.

3 Applications
2.2 Grafting-from method
Graft copolymers became widely studied due to their in-
In the grafting-from method, the macromolecular back- creased number of applications due to their unique struc-
bone is chemically modified in order to introduce active tures relative to other copolymers such as alternating, pe-
sites capable of initiating functionality. The initiating riodic, statistical, and block copolymers which generally
sites can be incorporated by copolymerization, can be in- linear chains.
corporated in a post-polymerization reaction, or can al-
ready be a part of the polymer.[10] If the number of ac- Some common applications of graft copolymers include:
tive sites along the backbone participates in the formation
of one branch, then the number of chains grafted to the • Membranes for the separation of gases or liquids[12]
macromolecule can be controlled by the number of ac-
• Hydrogels[13]
tive sites. Even though the number of grafted chains can
be controlled, there may be a difference in the lengths • Drug deliverers[14]
of each grafted chain due to kinetic and steric hindrance
effects.[9] • Thermoplastic elastomers[15]
“Grafting-from” reactions have been conducted from • Compatibilizers for polymer blends[16]
polyethelene, polyvinylchloride and polyisobutylene.
Different techniques such as anionic grafting, cationic • Polymeric emulsifiers
grafting, atom-transfer radical polymerization, and free- • Impact resistant plastics
radical polymerization have been used in the synthesis of
grafting from copolymers.
Graft copolymers that are employed with the grafting- 3.1 High Impact Polystyrene
from method are often synthesized with ATRP reactions
and anionic and cationic grafting techniques. High impact polystyrene (HIPS) was discovered by
Charles F. Fryling in 1961.[17] HIPS is a low cost, plastic
material that is easy to fabricate and often used for low
2.3 Grafting-Through Method strength structural applications when impact resistance,
machinability, and low cost are required. Its major appli-
The grafting-through also known as the macromonomer cations include machined prototypes, low-strength struc-
method is one of the more simpler ways of synthesiz- tural components, housings, and covers.[18] In order to
ing a graft polymer with well defined side chains.[10] produce the graft polymer, polybutadiene (rubber) or any
Typically a monomer of a lower molecular weight is similar elastomeric polymer is dissolved in styrene and
copolymerized with free radicals with an acrylate func- polymerized. This reaction allows for two simultaneous
tionalized macromonomer. The ratio of monomer to polymerizations, that of styrene to polystyrene and that
macromonomer molar concentrations as well as their of the graft polymerization of styrene-rubber.[17] During
copolymerization behavior determines the number of commercial use, it can be prepared by graft copolymer-
chains that are grafted. As the reaction proceeds, the ization with additional polymer to give the product spe-
concentrations of monomer to macromonomer change cific characteristics. The advantages of HIPS includes:[18]
causing random placement of branches and formation
of graft copolymers with different number of branches. • FDA compliant
This method allows for branches to be added hetero-
geously or homogenously based on the reactivity ratio • Good impact resistance
3.2 New Properties as a Result of Grafting 3

• Easy to paint and glue

• Low cost
• Excellent aesthetic qualities

3.2 New Properties as a Result of Grafting

By grafting polymers onto polymer backbones, the final
grafted copolymers gain new properties from their par-
ent polymers. Specifically, cellulose graft copolymers
have various different applications that are dependent on
the structure of the polymer grafted onto the cellulose.[19]
Some of the new properties that cellulose gains from dif-
ferent monomers grafted onto it include:

• Absorption of water
• Improved elasticity
• Hydrophilic/Hydrophobic character
• Ion-exchange
• Dye adsorption capabilities[20]
High Impact Polystyrene (HIPS) consists of the polystyrene back-
bone with polybutadiene chains branching from it in each direc- • Heat Resistance
tion.
• Thermosensitivity[21]
• pH sensitivity[22]
• Antibacterial effect[23]

These properties give new application to the ungrafted

cellulose polymers that include:

• medical body fluid absorbent materials[24]

• enhanced moisture absorbing ability in fabrics[25]
• permselective membranes[26]
• stronger nucleating properties than ungrafted cellu-
lose, and adsorption of hazardous contaminants like
heavy metal ions or dyes from aqueous solutions by
temperature swing adsorption[21]
• sensors and optical materials[27]
• reducing agents for various carbonyl compounds[28]

4 References
[1] Feng, Chun; Li, Yongjun; Yang, Dong; Hu, Jianhua;
CD case made from general purpose polystyrene (GPPS) and
Zhang, Xiaohuan; Huang, Xiaoyu (2011). “Well-defined
high impact polystyrene in the black portion (HIPS)
graft copolymers: from controlled synthesis to multipur-
pose applications”. Chemical Society Reviews. 40 (3):
1282–95. doi:10.1039/b921358a. PMID 21107479.
• Excellent machinability
[2] Matyjaszewski, Krzysztof. “Graft Copolymers”. Re-
• Good dimensional stability trieved 14 March 2014.
4 4
[3] Pearce, Eli M. (May 1987). “New commercial poly-
mers 2, by Hans-George Elias and Friedrich Vohwinkel,
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[5] Hegazy, El-Sayed A.; Dessouki, Ahmed M.; El-Sawy,
Naeem M.; Abd El-Ghaffar, Mahmoud A. (Febru-
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[6] Grutke, Stefan; Hurley, James H.; Risse, Wilhelm
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[7] Eisenbach, Claus D.; Heinemann, T. (July 1995). “Syn-
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[8] Yamashita, K.; Ito, K.; Tsuboi, H.; Takahama, S.; Tsuda,
K.; Otsu, T. (5 November 1990). “Graft copolymer-
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copolymer by glass transition temperature”. Journal
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[9] Hadjichristidis, N., S. Pispas, H. Iatrou, and D. J. Lohse.
“Graft Copolymers.” Graft Copolymers. John Wiley and
Sons Inc, 15 July 2002. Web. 14 Feb. 2014.
[10] Matyjaszewski, Krzysztof. “Graft Copolymers”.
Carnegie Mellon. Retrieved 14 February 2014.
[11] Ito, Koichi; Hiroyuki Tsuchida; Akio Hayashi; Toshi-
aki Kitano (1985). “Reactivity of Poly(ethylene oxide)
Macromonomers in Radical Copolymerization”. Polymer
Journal. 17 (7): 827–839. doi:10.1295/polymj.17.827.
[12] Nagase, Yu; Naruse, Akira; Matsui, Kiyohide (Jan-
uary 1990). “Chemical modification of polysul-
phone: 2. Gas and liquid permeability of poly-
sulphone/polydimethylsiloxane graft copolymer mem-
branes”. Polymer. 31 (1): 121–125. doi:10.1016/0032-
3861(90)90361-2.
[13] Dualeh, Abdulkadir J.; Steiner, Carol A. (Jan-
uary 1991). “Bulk and microscopic properties of
surfactant-bridged hydrogels made from an am-
phiphilic graft copolymer”. Macromolecules. 24
(1): 112–116. Bibcode:1991MaMol..24..112D.
doi:10.1021/ma00001a018.
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[14] MURAMATSU, Nobuhiro; YOSHIDA, Yasushi;
KONDO, Tamotsu (1990). “Possible application of
polyamine graft copolymer to targeting drug deliv-
ery”. Chemical & Pharmaceutical Bulletin. 38 (11):
3175–3176. doi:10.1248/cpb.38.3175.
[15] Eisenbach, Claus D.; Heinemann, Torsten (August
1995). “Thermoplastic graft copolymer elastomers with
chain-folding or bifurcated side chains”. Macromolec-
ular Chemistry and Physics. 196 (8): 2669–2686.
doi:10.1002/macp.1995.021960818.
[16] Se¸k, Danuta; Kaczmarczyk, Bożena (June 1997). “In-
vestigations of graft copolymer compatibilizers for blends
of polyethylene and liquid crystalline polyester: 1.
FT i.r. study”. Polymer. 38 (12): 2925–2931.
doi:10.1016/S0032-3861(96)00813-0.
[17] Fryling, Charles. “High Impact Polystyrene”. Patent.
Koppers Co Inc. Retrieved 14 February 2014.
[18] Plastics International. "(HIPS) High Impact Polystyrene”
(PDF). Retrieved 14 February 2014.
[19] editors, Susheel Kalia, M.W. Sabaa, (2013). Polysaccha-
ride based graft copolymers (1., 2013 ed.). Heidelberg:
Springer. ISBN 9783642365652.
[20] Waly, A.; Abdel-Mohdy, F. A.; Aly, A. S.; Hebeish, A.
(27 June 1998). “Synthesis and characterization of cel-
lulose ion exchanger. II. Pilot scale and utilization in
dye-heavy metal removal”. Journal of Applied Polymer
Science. 68 (13): 2151–2157. doi:10.1002/(SICI)1097-
4628(19980627)68:13<2151::AID-APP11>3.0.CO;2-2.
[21] Xie, Jiangbing; Hsieh, You-Lo (25 July 2003). “Ther-
mosensitive poly(n-isopropylacrylamide) hydrogels
bonded on cellulose supports”. Journal of Applied Poly-
mer Science. 89 (4): 999–1006. doi:10.1002/app.12206.
[22] Wang, Deqian; Tan, Junjun; Kang, Hongliang; Ma,
Lin; Jin, Xin; Liu, Ruigang; Huang, Yong (February
2011). “Synthesis, self-assembly and drug release behav-
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PDEAEMA through ATRP”. Carbohydrate Polymers. 84
(1): 195–202. doi:10.1016/j.carbpol.2010.11.023.
[23] Lee, Sang Beom; Koepsel, Richard R.; Morley, Scott
W.; Matyjaszewski, Krzysztof; Sun, Yujie; Russell, Alan
J. (May 2004). “Permanent, Nonleaching Antibacte-
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Polymerization”. Biomacromolecules. 5 (3): 877–882.
doi:10.1021/bm034352k. PMID 15132676.
[24] Toledano-Thompson, T.; Loría-Bastarrachea, M.I.;
Aguilar-Vega, M.J. (October 2005). “Characterization of
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mers. 62 (1): 67–73. doi:10.1016/j.carbpol.2005.06.024.
[25] Mondal, Md. Ibrahim H.; Uraki, Yasumitsu; Ubukata,
Makoto; Itoyama, Koki (18 March 2008). “Graft poly-
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 5

[26] Nishioka, Noboru; Watase, Keiji; Arimura, Keiji; Ko-

sai, Kouichi; Uno, Masakuni (December 1984). “Per-
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Vinyl Monomers in a Homogeneous System I. Diffu-
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doi:10.1295/polymj.16.867.

[27] Tang, Xinde; Gao, Longcheng; Fan, Xinghe; Zhou,

Qifeng (1 May 2007). “Controlled grafting of ethyl
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[28] Dhiman, Poonam K.; Kaur, Inderjeet; Mahajan, R. K. (5

April 2008). “Synthesis of a cellulose-grafted polymeric
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6 5 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

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