Applications of High Molecular Weight Poly(Methyl

Methacrylate)
Subjects: Polymer Science
Contributor: Ming Yuan, Dayun Huang, Yixuan Zhao

Poly(methyl methacrylate) (PMMA), commonly known as plexiglass, is a kind of polymer synthesized by free radical
polymerization, ionic polymerization and coordination polymerization. Poly(methyl methacrylate) (PMMA) is widely used in
aviation, architecture, medical treatment, optical instruments and other fields because of its good transparency, chemical
stability and electrical insulation.

Keywords: poly(methyl methacrylate) ; high molecular weight ; polymerization

1. Application of High Molecular Weight PMMA in Medical Field

1.1. PMMA Bone Cements

Osteoporotic vertebral compression fracture (OVCF) is one of the most common complications of osteoporosis. At
present, percutaneous vertebroplasty (PVP) is widely used for the treatment of OVCF. PMMA bone cement shows an
important function in PVP. In a PVP surgery, PMMA bone cement is injected into the injured vertebra of the patient, which
can quickly relieve pain, stabilize and strengthen the injured vertebra, and restore the height and angle of the injured
vertebra [1][2][3]. However, the strength of ordinary PMMA bone cement is weaker than the bone [4]. Therefore, high
molecular weight PMMA can use to prepare higher strength PMMA bone cement. PMMA with viscosity-average molecular
weights (Mυ) range from 1.7 × 105 Da to 7.5 × 105 Da are successfully used for the preparation of PMMA bone cements
[5], indicating that high molecular weight PMMA might be an excellent raw material for PMMA bone cements.

Inadequate strength at the cement/bone interface is one of the main drawbacks of PMMA bone cement in the current
orthopedic surgeries. PMMA cement strength, surface roughness properties and osteo-blast cell growth can be improved
by incorporating additives such as MgO, chitosan and hydroxyapatite to PMMA [6][7][8]. Khandaker and coworkers have
investigated the fracture toughness (KIC) of bone-PMMA with nano MgO particles or micro MgO particles, finding that the
KIC of bone-PMMA with nano MgO particles and bone-PMMA with micro MgO particles are much higher than the KIC of
bone-PMMA [9].

Lin and coworkers report that the bone/cement interfacial strength can be enhanced by partially degradable PMMA/Mg
[10].
composite bone cement (PMC) This reinforcement is accomplished via the increase in the osteo-conductivity of
PMMA and the enhancement of the mechanical interlocking between bone tissue and the porous PMMA surface. The
effects of Mg composition, particle size and content on the injectability, biocompatibility, mechanical, and degradation
properties of PMCs are investigated. They find that the biocompatibility, mechanical and degradation properties of PMCs
are influenced by the particle size (75–550 μm), concentration (9–17 wt%) and alloy composition of Mg particles.
Moreover, antibacterial capabilities are increased owing to the degradation of Mg, resulting in a decrement in the infection
rate.

Roldo and coworkers report a preparation and characterization of antibacterial PMMA composite cement [11]. The chitosan
(CS) and methacryloyl chitosan (CSMCC) with concentrations ranging from 10 to 30% w/w are added to PMMA cement,
finding that the mechanical behavior of PMMA cement can be modified by the addition of CS and CSMCC. Bioactive
PMMA surfaces at the site of implantation are obtained via the addition of amphiphilic molecule phosphorylated 2-
[12].
hydroxyethylmethacrylate (HEMA-P) in PMMA bone cement The addition of HEMA-P shows a positive effect with
respect to differentiation and proliferation of the osteoblast-like cell (SaOs-2) without the detrimental changes in other
properties. The effects of the addition of soluble calcium and carbonate salts on the properties of PMMA bone cement are
investigated. A small amount (1–5%) of soluble salts can enhance the clinical performance of bone cement.
1.2. PMMA Denture

PMMA resin is commonly used dental material because of the low cost and lightweight performances. However, the
properties such as tenacity, fracture strength of PMMA used for dental material should meet a suitable value. Kusy and
coworkers find that the fractions of viscosity-average molecular weight less than 105 make no contribution to the plastic
[13]
toughening of the material . Huggett and coworkers have investigated the relationship between molecular weight and
properties of PMMA denture base, finding that denture base systems with weight-average molecular weights >105 display
[14]
optimum fracture strength properties . Therefore, the high molecular weight PMMA (Mn > 105 Da) should be a suitable
candidate for dental material.

Both heat- and cold-cured PMMA materials are used for the relining of dentures [15]. Heat-cured PMMA has good bonding
strength and wear resistance. However, the roughening of the surface results in a difficulty in cleaning of dental material.
Similarly, cold-cured PMMA has poor mechanical properties, leaching of monomers, and associated biocompatibility
issues [15][16].

Acrylic (PMMA) teeth are a novel dental material which is manufactured by compression or injection molding techniques.
Compared to heat-cured PMMA, acrylic teeth are less brittle owing to the high resilience and flexibility. Distinct from
[17]
porcelain teeth, acrylic teeth are lightweight and do not cause clicking sounds . However, the strength and adhesion of
acrylic teeth are still to be considered. The strength can be improved by the use of additive (nanofillers) or using silanized,
feldspar-reinforced PMMA.

Alaa Mohammed and coworkers prepare a new composite material via the mixing of eggshell powder and PMMA resin
[18]
. The effects of different eggshell powder concentration (1%, 3%, 5% and 7% w/w) on the property of the material have
been studied. The tensile properties and fracture toughness are enhanced by the addition of 7% w/w of eggshell powder,
while the elongation percentage at break and impact strength are decreased compared with other specimens. Eggshell
has a poor dispersion ability in PMMA and this may cause a formation of agglomerates in the PMMA matrix. This might be
a main reason for the decrement in percentage at break and impact strength. A similar result is obtained when using some
other nanofillers as additives [19].

The addition of silica to PMMA has a negative impact on flexural strength. However, the flexural strength can be slightly
improved by using silanized feldspar as an additive. Raszewski and coworkers find that properties such as Brinell
hardness, elastic modulus, maximal displacement, and flexural strength of PMMA modified with silanized feldspar are
[19]
obviously improved . In addition, the PMMA modified with silanized feldspar has no adverse effect on Isolde impact
resistance compared with the conventional acrylic resin. When using silica filler as the additive, the Brinell hardness and
elastic modulus of PMMA are increased. However, this causes a significant decrease in the flexural strength and Isolde
impact resistance.

Various types of PMMA materials such as heat-cured PMMA, cold-cured PMMA and light-cured PMMA are used for
[20].
denture repair The heat-cured PMMA has a better mechanical property than cold-cured PMMA. However, the heat-
cured PMMA has some disadvantages such as time consuming and denture warpage. Compared with heat-cured PMMA
and cold-cured PMMA, the light-cured PMMA has some advantages of ease of manipulation, controlled polymerization
[21][22].
time, no monomer issues, and better mechanical properties In addition, light-cured PMMA has a better repair
strength (40–44 MPa) than heat-cured PMMA (21–34 MPa) and cold-cured PMMA (~13 MPa) [23].

2. Applications of High Molecular Weight PMMA in Optical and Electricity

Area
The PMMA-based polymer nanocomposites have attracted the considerable interest of chemists due to their excellent
optical, mechanical and electrical properties [24][25][26].

Polymer field-effect transistors (PFETs) have attracted the significant attention of scientists owing to their potential
[27][28].
applications in smart card, displays and sensor The property of a polymer thin film transistor is not only affected by
semiconductors, but also by gate insulating film. Therefore, suitable insulating gate dielectric film is very important for the
investigation of high-performance polymer field-effect transistors. As the development of donor-acceptor (D-A)
copolymers, it has long been known that the molecular weights of polymeric semiconductors play significant roles in
enhancing performances of polymer field-effect transistors [29]. PMMA is a commonly used dielectric material owing to its
excellent electrical properties.
Mao and coworkers reported that the electron and hole mobilities in polymer field-effect transistors can be enhanced by
[29]
tailoring the molecular weight of polymeric dielectric . PMMA with different molecular weights are used to investigate
the electrical properties of polymer field-effect transistors (Table 1).

Table 1. Performance parameters of PFET devices using the PMMA dielectric with different molecular weights [29].

Mw n-Channel p-Channel n-Channel p-Channel

Entry
(Da) μe,max (cm2 V−1 S−1) μh,max (cm2 V−1 S−1) Ntrap (×1011 cm−2) Ntrap (×1011 cm−2)

1 1.2 × 105 0.30 0.01 5.46 3.64

2 5.5 × 105 0.55 0.18 4.67 2.33

3 1.0 × 106 0.85 0.35 1.38 1.10

It shows that the PFETs based on PMMA (Mw = 1.2 × 105 Da) exhibit a large electron mobility of 0.30 cm2 V−1 s−1 but
show a low hole mobility of 0.01 cm2 V−1 s−1 (Table 1, entry 1). When the molecular weight of PMMA increases to 5.5 ×
105 Da, hole mobility of the PFETs is greatly increased to 0.18 cm2 V−1 s−1 and electron mobility is also improved to 0.55
cm2 V−1 s−1 (Table 1, entry 2). Moreover, electron mobility and hole mobility are increased to 0.85, 0.35
cm2 V−1 s−1 respectively when using PMMA with a molecular weight of 1.0 × 106 Da as the dielectric (Table 1, entry 3). In
addition, when the molecular weight of PMMA increases from 1.2 × 105 to 1.0 × 106 Da, the trap density (Ntrap) for
electron traps decrease from 5.46 to 1.38 × 1011 cm−2 and the trap density (Ntrap) for hole traps decrease from 3.64 to
1.10 × 1011 cm−2. Therefore, using high molecular weight PMMA as dielectric is beneficial for simultaneously enhancing
electron and hole mobilities. Consequently, high molecular weight PMMA is an excellent candidate for electrical
applications.

Organic field effect transistors (OFETs) have also attracted significant attention owing to their potential applications in
[30]
electronics . Dinaphtho[2,3-b:2′,3′-f]thieno [3,2-b]thiophene (DNTT) based OFET devices with a bilayer dielectric
system comprising of poly (vinyl alcohol) (PVA) and poly (methyl methacrylate) (PMMA) are fabricated by Dhar and
[31]
coworkers . The influence of molecular weight of PMMA on the property of DNTT based OFET is investigated. They
find that high molecular weight PMMA devices are more effective for achieving high photosensitivity and responsivity from
the transistors.

Recently, the rare earth luminescent materials have attracted considerable attention owing to their potential applications in
optoelectronic devices [32]. However, properties such as processing features, thermal stability and mechanical strength of
lanthanide complexes are relatively poor. The addition of polymer is an effective method for the improvement in thermal
stability and mechanical strength of lanthanide complexes. Kara and coworkers find that the high molecular weight PMMA
(Mw = 3.50 × 105 Da) is an excellent material for the preparation of Sm/PMMA luminescent composite fiber [33]. Compared
to the pure Sm(III) complex, the photostability and temperature stability of Sm/PMMA composite fibers are enhanced due
to the modification via PMMA matrix. PMMA provides a rigid environment to prevent the decomposition of the pure Sm(III)
complex under high temperature and UV irradiation. The luminescent spectra of Sm/PMMA composite fibers display
intense characteristic emissions of the Sm3+ ion.

The Co doped ZnO nanoparticle (NP) is used to prepare PMMA (Mw = 3.50 × 105 Da) and poly (ethyl methacrylate)
[34]
(PEMA) nanocomposite via casting method . The conductivity of the nanocomposite is increased with the increase in
nanofiller contents due to the formation of charge transfer complexes. Furtheemore, the dielectric constancy of the
nanocomposite is increased with the increase in temperature. Moreover, the nanocomposite shows excellent thermal and
electric properties. Therefore, PEMA/PMMA-Co/ZnO polymer electrolyte is a promising candidate for applications in
electrochemical devices.

3. Applications of High Molecular Weight PMMA in Other Areas

Metal injection molding (MIM) is an important method for the production of small parts with complex shape. The key factor
in MIM is the selection of the binder, which should permit the mixing and injection molding of feedstocks with high powder
loading. Ideally, the debinding should occur in a short time without causing defects. Bakan et al. report that the complexes
consisted of PMMA (Mn = 1.00 × 106 Da), PEG and stearic acid can be used as a binder for the MIM of 316L stainless
steel powder [35]. The viscosity of the system can be reduced by the decrease in the molar ratio of PMMA/PEG, which is
beneficial to the molding of feedstocks with high powder loading. However, the strength, stiffness and toughness of the
molding are decreased after the binder solidifies. Therefore, the PMMA can harden the solidified molding product.
Membrane gas separation technology is widely used in nitrogen purification, oxygen enrichment, hydrogen recovery from
reactor purge gas, and stripping of carbon dioxide from natural gas [36]. Compared to traditional gas separation
technologies, the membrane gas separation technology is more competitive. The main subject of membrane gas
separation technology is the improvement in the permeability and selectivity of polymer membranes [36][37]. PMMA
membrane has a good O2/N2 selectivity, but it is difficult to operate under a high-pressure condition due to its brittleness
[38]. Fu and coworkers report that the high molecular weight PMMA films (Mw = 9.96 × 105 Da) with different free volumes
(FFV) are synthesized in different solvents (dichloromethane, ethyl acetate, tetrahydrofuran, butyl acetate, methyl isobutyl
[36]
ketone) . This membrane can be operated under a high pressure (30 atm) condition. The permeability coefficients of
different gases (He, O2, N2, CO2) in the PMMA membrane are studied, finding that the gas permeability is increased with
the increase in FFV. Moreover, they have found that the high molecular weight PMMA membranes possess higher gas
permeability than the low molecular weight membranes.

References
1. Ahn, Y.; Lee, J.H.; Lee, H.Y.; Lee, S.H.; Keem, S.H. Predictive factors for subsequent vertebral fracture after percutane
ous vertebroplasty. J. Neurosurg. Spine 2008, 9, 129–136.

2. Zhang, W.; Liao, S.S.; Cui, F.Z. Hierarchical self-assembly of nano-fibrils in mineralized collagen. Chem. Mater. 2003, 1
5, 3221–3226.

3. Yu, X.; Xu, L.; Cui, F.Z.; Qu, Y.; Lian, X.J.; Wang, X.M.; Wang, Y. Clinical evaluation of mineralized collagen as a bone g
raft substitute for anterior cervical intersomatic fusion. J. Biomater. Tissue Eng. 2012, 2, 170–176.

4. Soha, S.; Pal, S. Mechanical properties of bone cement: A review. J. Biomed. Mater. Res. 1984, 18, 435–462.

5. Kuhn, K.D. PMMA Cements; Springer: Berlin/Heidelberg, Germany, 2014.

6. Heo, S.J.; Shin, H.J.; Park, S.A.; Lee, Y.J.; Yoon, T.R.; Seo, H.Y.; Ahn, K.C.; Kim, S.E.; Shin, J.W. Evaluation of bonding
stress for the newly suggested bone cement: Comparison with currently used PMMA through animal studies. Key Eng.
Mater. 2007, 342, 373–376.

7. Lewis, G. Alternative acrylic bone cement formulations for cemented arthroplasties: Present status, key issues, and futu
re prospects. J. Biomed. Mater. Res. Part B Appl. Biomater. 2007, 84, 301–319.

8. Liu, H.; Webster, T.J. Nanomedicine for implants: A review of studies and necessary experimental tools. Biomaterials 2
007, 28, 354–369.

9. Khandaker, M.; Li, Y.; Morris, T. Micro and nano MgO particles for the improvement of fracture toughness of bone-ceme
nt interfaces. J. Biomech. 2013, 46, 1035–1039.

10. Lin, X.; Chan, A.; Tan, X.; Yang, H.; Yang, L. Fabrication and characterizations of metallic Mg containing PMMA-based
partially degradable composite bone cements. Acta Metall. Sin. 2019, 32, 808–816.

11. Mori, A.D.; Gregorio, E.D.; Kao, A.P.; Tozzi, G.; Barbu, E.; Sanghani-Kerai, A.; Draheim, R.R.; Roldo, M. Antibacterial P
MMA composite cements with tunable thermal and mechanical properties. ACS Omega 2019, 4, 19664–19675.

12. Wolf-Brandstetter, C.; Roessler, S.; Storch, S.; Hempel, U.; Gbureck, U.; Nies, B.; Bierbaum, S.; Scharnweber, D. Physi
cochemical and cell biological characterization of PMMA bone cements modified with additives to increase bioactivity.
J. Biomed. Mater. Res. Part B Appl. Biomater. 2013, 101, 599–609.

13. Kusy, R.P.; Turner, D.T. Influence of the molecular weight of poly(methyl methacrylate) on fracture surface energy in not
ched tension. Polymer 1976, 17, 161–166.

14. Huggett, R.; Bates, J.F.; Packham, D.E. The effect of the curing cycle upon the molecular weight and properties of dent
ure base materials. Dent. Mater. 1987, 3, 107–112.

15. Nejatian, T.; Pezeshki, S.; Yaqin Syed, A.U. Acrylic denture base materials. In Advanced Dental Biomaterials; Khurshid,
Z., Najeeb, S., Zafar, M.S., Sefat, F., Eds.; Woodhead Publishing: Cambridge, UK, 2019; pp. 79–104.

16. Habib, S.R.; Vohra, F.A. Replacing existing dentures by copy-denture technique for geriatric patients: A case report. JP
DA 2013, 22, 265–270.

17. Zafar, M.S. Prosthodontic applications of polymethyl methacrylate (PMMA): An update. Polymers 2020, 12, 2299.

18. Mohammed, R.A. PMMA-eggshell composite preparation and studying mechanical properties as a dental material. J. E
ng. Sustain. Dev. 2020, 24, 30–47.

19. Raszewski, Z.; Nowakowska-Toporowska, A.; Wezgowiec, J.; Nowakowska, D.; Wieckiewicz, W. Influence of silanized
silica and silanized feldspar addition on the mechanical behavior of polymethyl methacrylate resin denture teeth. J. Pro
 sthet. Dent. 2020, 123, 647–653.

20. Gad, M.M.; Rahoma, A.; Al-Thobity, A.M.; ArRejaie, A.S. Influence of incorporation of ZrO2 nanoparticles on the repair s
trength of polymethyl methacrylate denture bases. Int. J. Nanomed. 2016, 11, 5633–5643.

21. Shifman, A. Clinical applications of visible light-cured resin in maxillofacial prosthetics. part I: Denture base and reline
material. J. Prosthet. Dent. 1990, 64, 578–582.

22. Fellman, S. Visible light-cured denture resin used in making dentures with conventional teeth. J. Prosthet. Dent. 1989,
62, 356–359.

23. Polyzois, G.L.; Handley, R.W.; Stafford, G.D. Repair strength of denture base resins using various methods. Eur. J. Pro
sthodont. Restor. Dent. 1995, 3, 183–186.

24. Khodair, Z.T.; Saeed, M.H.; Abdul-Allah, M.H. Study of optical properties of (PMMA) doped by methyl red and methyl bl
ue films. Iraqi J. Phys. 2014, 12, 47–51.

25. Al-Ammar, K.; Hashim, A.; Husaien, M. Synthesis and study of optical properties of (PMMA-CrCl2) composites. Chem.
Mater. Eng. 2013, 1, 85–87.

26. Gupta, A.K.; Bafna, M.; Vijay, Y.K. Study of optical properties of potassium permanganate (KMnO4) doped poly(methyl
methacrylate) (PMMA) composite films. Bull. Mater. Sci. 2018, 41, 160.

27. Yan, H.; Chen, Z.; Zheng, Y.; Newman, C.; Quinn, J.R.; Dötz, F.; Kastler, M.; Facchetti, A. A high-mobility electron-trans
porting polymer for printed transistors. Nature 2009, 457, 679–686.

28. Wu, W.; Liu, Y.; Zhu, D. π-Conjugated molecules with fused rings for organic field-effect transistors: Design, synthesis a
nd applications. Chem. Soc. Rev. 2010, 39, 1489–1502.

29. Mao, Z.; Guo, Y.; Chen, H.; Zhang, W.; Yu, G. Tailoring molecular weight of polymeric dielectric to enhance electron an
d hole mobilities in polymer field-effect transistors. Polymer 2016, 99, 496–502.

30. Ren, H.; Cui, N.; Tang, Q.; Tong, Y.; Liu, Y. High-performance, ultrathin, ultraflexible organic thin-film transistor array via
solution process. Small 2018, 14, 1801020.

31. Panigrahi, D.; Dhar, A. Tuning dielectric-semiconductor interfacial properties in organic phototransistors for ultralow ligh
t detection. Org. Electron. 2019, 70, 107–112.

32. Bibi, S.; Mohamad, S.; Manan, N.S.A.; Ahmad, J.; Kamboh, M.A.; Khor, S.M.; Yamin, B.M.; Abdul Halim, S.N. Synthesi
s, characterization, photoluminescence, and electrochemical studies of novel mononuclear Cu (II) and Zn (II) complexe
s with the 1-benzylimidazolium ligand. J. Mol. Struct. 2017, 1141, 31–38.

33. Kara, H.; Oylumluoglu, G.; Coban, M.B. Photoluminescence properties of a new Sm(III) complex/PMMA electrospun co
mposite fibers. J. Clust. Sci. 2020, 31, 701–708.

34. Rajeh, A.; Ragab, H.M.; Abutalib, M.M. Co doped ZnO reinforced PEMA/PMMA composite: Structural, thermal, dielectri
c and electrical properties for electrochemical applications. J. Mol. Struct. 2020, 1217, 128447.

35. Bakan, H.I.; Jumadi, Y.; Messer, P.F.; Davies, H.A.; Ellis, B. Study of processing parameters for MIM feedstock based o
n composite PEG-PMMA binder. Powder Metall. 1998, 41, 289–291.

36. Fu, Y.J.; Hu, C.C.; Lee, K.R.; Tsai, H.A.; Ruaan, R.C.; Lai, J.Y. The correlation between free volume and gas separation
properties in high molecular weight poly(methyl methacrylate) membranes. Eur. Polym. J. 2007, 43, 959–967.

37. Ghosal, K.; Chern, R.T.; Freeman, B.D. Effect of basic substituents on gas sorption and permeation in polysulfone. Mac
romolecules 1996, 29, 4360–4369.

38. Wright, C.T.; Paul, D.R. Gas sorption and transport in poly(tertiary-butyl methacrylate). Polymer 1997, 38, 1871–1878.

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