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Graft polymer

Graft Polymers are segmented copolymers with a lin- the preparation of stable blends or alloys.[2] Generally,
ear backbone of one composite and randomly distributed grafting methods for copolymer synthesis results in ma-
branches of another composite. The picture labeled terials that are more thermostable than their homopoly-
“graft polymer” shows how grafted chains of species B mer counterparts.[3] There are three methods of synthe-
are covalently bonded to polymer species A. Although the sis, grafting onto, grafting from, and grafting through that
side chains are structurally distinct from the main chain, are used to construct a graft polymer.[4]
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,
2 Synthesis Methods
or emulsifiers for the preparation of stable blends or al-
loys. One of the more well known examples of a graft There are many different approaches to synthesizing
polymer is high impact polystyrene, which consists of a graft copolymers. Usually they employ familiar poly-
polystyrene backbone with poly butadiene grafted chains. 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 graft copolymer consists of a main polymer chain or back-


bone (A) covalently bonded to one or more side chains (B)
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.

1 General Properties
Graft copolymers are a branched copolymer where the 2.1 Grafting-Onto Method
components of the side chain are structurally different
than that of the main chain. Graft copolymers con- Grafting-onto method involves the use of a back-
taining a larger quantity of side chains are capable of bone chain with functional groups A that are dis-
wormlike conformation, compact molecular dimension, tributed randomly along the chain.[9] The formation of
and notable chain end effects due to their confined and the graft copolymer originates from the coupling re-
tight fit structures.[1] The preparation of graft copoly- action between the functional backbone and the end-
mers has been around for decades. All synthesis meth- groups of the branches that are reactive. These cou-
ods can be employed to create general physical proper- pling reactions are made possible by modifying the
ties of graft copolymers. They can be used for materi- backbone chemically.[10] Common reaction mechanisms
als that are impact resistant, and are often used as ther- used to synthesize these copolymers include free-radical
moplastics elastomers, compatibilizers or emulsifiers for polymerization, anionic polymerization, atom-transfer

1
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 REFERENCES

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[6] Grutke, Stefan; Hurley, James H.; Risse, Wilhelm
(August 1994). “Poly(phenylene oxide) macromonomers [18] Plastics International. "(HIPS) High Impact Polystyrene”
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6 5 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

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