Research Article Synthesis and Characterization of Polycarbonate Copolymers Containing Benzoyl Groups on the Side Chain for Scratch Resistance Hohyoun Jang, Jaeseong Ha, Jiho Yoo, Jaeseung Pyo, Kunyoung Choi, Chaekyun Lee, Taewook Ryu, Sungkwun Lee, and Whangi Kim Department of Applied Chemistry, Konkuk University, 322 Danwol, Chungju 380-701, Republic of Korea Correspondence should be addressed to Whangi Kim; [email protected] Received 18 March 2016; Revised 11 July 2016; Accepted 23 July 2016 Academic Editor: Marta Fern´ andez-Garc´ ıa Copyright © 2016 Hohyoun Jang et al. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. e purpose of this study was to enhance the scratch resistance of polycarbonate copolymer by using 3,3 -dibenzoyl-4,4 - dihydroxybiphenyl (DBHP) monomer, containing benzoyl moieties on the ortho positions. DBHP monomer was synthesized from 4,4 -dihydroxybiphenyl and benzoyl chloride, followed by the Friedel-Craſt rearrangement reaction with AlCl 3 . e polymerizations were conducted following the low-temperature procedure, which is carried out in methylene chloride by using triphosgene, triethylamine, bisphenol-A, and DBHP. e chemical structures of the polycarbonate copolymers were confirmed by 1 H-NMR. e thermal properties of copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry, and also surface morphologies were assessed by atomic force microscopy. e scratch resistance of homopolymer film (100 m) changed from 6B to 1B, and the contact angle of a sessile water drop onto the homopolymer film also increased. 1. Introduction Over the past few decades, the demand for polycarbonate as a major engineering plastic has increased because they have attracted a significant attention for a range of applications in several industrial fields. Polycarbonate is an amorphous, clear polymer that exhibits three key characteristic properties: toughness, transparency, self-extinguishing characteristic, and heat resistance [1–5]. ese desirable properties, com- bined with superior dimensional stability and good electrical resistance, have led to wide applications in automobile parts, electrical parts, optical materials, and steam sterilizable med- ical equipment. In contrast, to improve the polycarbonate properties such as abrasion and scratch resistance, trans- parency, nonflammability, and the impact resistance, many endeavors have been reported to overcome these concerns [6–8]. Among them, the vulnerability of polycarbonate is because of antiscratch surface property. Several methods have been investigated to enhance the antiscratch resistance. ey generally involve modifications by physical or chemical methods. e surface treatment or blend only modifies a very shallow surface of polymer film and sheet and thus does not change the natural characteristics of polymer. In contrast, the chemical modifications provide the means of permanently altering polymer film and sheet [9–11]. Several methods have been investigated to enhance antis- cratch property. (1) e antiscratch property of polycarbonate by graſting and block copolymers with PMMA were trans- parent in contrast to PC/PMMA blend polymers and had a higher surface hardness [12]. (2) e blends/composites of polycarbonate with PMMA, siloxane, and polysilox- ane were developed for increasing the stabilization effect such as photodegradation and toughness. However, these blends/composites show phase-separated morphology with poor interfacial adhesion and poor properties [13–15]. (3) Many researchers studied transparent ultrahydrophobic silica films modified alkoxysilane by the sol-gel process under UV irradiation [16]. Several authors reported to enhance the scratch resistance of polycarbonate with SiO 2 and TiO 2 using microwave-assisted sol-gel heating [17, 18]. e morphology of the fabric with alkali treatment and polycarbonate coating was studied using the scanning electron microscopy and Hindawi Publishing Corporation International Journal of Polymer Science Volume 2016, Article ID 2814529, 6 pages http://dx.doi.org/10.1155/2016/2814529
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Research ArticleSynthesis and Characterization of PolycarbonateCopolymers Containing Benzoyl Groups on the SideChain for Scratch Resistance
Hohyoun Jang Jaeseong Ha Jiho Yoo Jaeseung Pyo Kunyoung ChoiChaekyun Lee Taewook Ryu Sungkwun Lee and Whangi Kim
Department of Applied Chemistry Konkuk University 322 Danwol Chungju 380-701 Republic of Korea
Correspondence should be addressed to Whangi Kim wgkimkkuackr
Received 18 March 2016 Revised 11 July 2016 Accepted 23 July 2016
Academic Editor Marta Fernandez-Garcıa
Copyright copy 2016 Hohyoun Jang et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
The purpose of this study was to enhance the scratch resistance of polycarbonate copolymer by using 331015840-dibenzoyl-441015840-dihydroxybiphenyl (DBHP) monomer containing benzoyl moieties on the ortho positions DBHP monomer was synthesizedfrom 441015840-dihydroxybiphenyl and benzoyl chloride followed by the Friedel-Craft rearrangement reaction with AlCl
3 The
polymerizations were conducted following the low-temperature procedure which is carried out in methylene chloride by usingtriphosgene triethylamine bisphenol-A and DBHP The chemical structures of the polycarbonate copolymers were confirmedby 1H-NMR The thermal properties of copolymers were investigated by thermogravimetric analysis and differential scanningcalorimetry and also surface morphologies were assessed by atomic force microscopyThe scratch resistance of homopolymer film(100120583m) changed from 6B to 1B and the contact angle of a sessile water drop onto the homopolymer film also increased
1 Introduction
Over the past few decades the demand for polycarbonate asa major engineering plastic has increased because they haveattracted a significant attention for a range of applicationsin several industrial fields Polycarbonate is an amorphousclear polymer that exhibits three key characteristic propertiestoughness transparency self-extinguishing characteristicand heat resistance [1ndash5] These desirable properties com-bined with superior dimensional stability and good electricalresistance have led to wide applications in automobile partselectrical parts optical materials and steam sterilizable med-ical equipment In contrast to improve the polycarbonateproperties such as abrasion and scratch resistance trans-parency nonflammability and the impact resistance manyendeavors have been reported to overcome these concerns[6ndash8] Among them the vulnerability of polycarbonate isbecause of antiscratch surface property Several methodshave been investigated to enhance the antiscratch resistanceThey generally involve modifications by physical or chemicalmethodsThe surface treatment or blend onlymodifies a very
shallow surface of polymer film and sheet and thus does notchange the natural characteristics of polymer In contrast thechemical modifications provide the means of permanentlyaltering polymer film and sheet [9ndash11]
Several methods have been investigated to enhance antis-cratch property (1)The antiscratch property of polycarbonateby grafting and block copolymers with PMMA were trans-parent in contrast to PCPMMA blend polymers and hada higher surface hardness [12] (2) The blendscompositesof polycarbonate with PMMA siloxane and polysilox-ane were developed for increasing the stabilization effectsuch as photodegradation and toughness However theseblendscomposites show phase-separated morphology withpoor interfacial adhesion and poor properties [13ndash15] (3)Many researchers studied transparent ultrahydrophobic silicafilms modified alkoxysilane by the sol-gel process under UVirradiation [16] Several authors reported to enhance thescratch resistance of polycarbonate with SiO
2and TiO
2using
microwave-assisted sol-gel heating [17 18] The morphologyof the fabric with alkali treatment and polycarbonate coatingwas studied using the scanning electron microscopy and
Hindawi Publishing CorporationInternational Journal of Polymer ScienceVolume 2016 Article ID 2814529 6 pageshttpdxdoiorg10115520162814529
2 International Journal of Polymer Science
polarized optical microscopic techniques [19] (4)The chem-ical modification such as Parmax containing side carbonylaffects the surface properties including the surface morphol-ogy and other properties [20] Research on the effectivemodification of polycarbonate is necessary because the mainattraction these days is the thin film application of mobilewindow replacing tempered glass
Thepurpose of this studywas to improve the scratch resis-tance of polycarbonate while retaining its beneficial prop-erties Thin film polycarbonates are difficult to coat by UVcuring because they are very soft with only 6B hardness Inthis study we introduced a new copolymer for enhancing thescratch resistanceThe copolymerwas designed by bisphenol-A and 33-dibenzoyl-44-dihydroxybiphenyl and the effect ofside functional group was confirmed The chemical analysisand thermal properties of this polycarbonate containing ben-zoyl groups on side chain and the waterproof andmechanicalproperties of the polymers were investigated The surfacemorphologies were investigated by waterproof and AFMstudies The experimental data show that all the polymersare quite thermally stable and showed good waterproof andimproved scratch resistance
2 Experimental
21 Materials Bisphenol-A 44-biphenol benzoyl chloridealuminum chloride triethylamine (TEA) and triphosgenewere purchased from Sigma-Aldrich Junsei and Acroschemical companies and used as received Common reagentssuch as 12-dichlorobenzene ethyl acetate acetone methy-lene chloride hexane and sodium hydroxide were also usedas received TEAwas used as a 15 (wv) aqueous solution forsynthesizing linear polycarbonate
22 Measurement NMR spectra were recorded using aBruker DRX (400MHz) spectrometer using CDCl
3as the
solvent and tetramethylsilane as the internal standard Theintrinsic viscosity (120578inh) was determined at a 05 gdL con-centration of polycarbonate in methylene chloride witha Cannon-Fenske routine viscometer at 30∘C Differentialscanning calorimetry (DSC) analysis was performed usinga Perkin-Elmer DSC 6 at a heating rate of 20∘Cmin undernitrogen 119879
119892was taken as the midpoint of the inflection
observed on the curve of heat capacity versus temperatureThermogravimetric analysis (TGA) was performed using aScinco TGA-N 1000 analyzer The surface morphologies ofpolycarbonates were observed by atomic force microscopy(AFM) Tapping mode atomic force microscopic observa-tions were performed using a Digital Instrument Nanoscope(R) IIIA using microfabricated cantilevers and amplitudeset point 07785V The contact angle was measured by acontact angle analyzer (Phoenix-300 Surface ElectroOptics)The volume of the water drop was controlled to sim02 120583Lby a microsyringe The average value of both sides of eachdrop was considered as the contact angle Antiscratch wasmeasured by KIPAE Promate 5000M and test angle was45∘ with a test load of 1 Kg The transparency was measuredby VMS-1 parallel beam-path of SCINCO in the wavelengthrange 400ndash1000 nm to use a tungsten halogen lamp
23 Synthesis of 33-Dibenzoyl-441015840-dihydroxybiphenyl(DBHP) The monomer was prepared by Friedel-Craftreaction In a 250mL round flask 441015840-biphenol (50 g268mmol) and aluminum chloride (179 g 1342mmol) weredissolved in 12-dichlorobenzene To this mixture benzoylchloride (93mL 805mmol) was slowly added at roomtemperature and stirred for 18 h at 160∘C After the reactionthe liquid was poured in distilled water containing a smallamount of hydrochloric acid and methylene chloride wasadded The separated organic layer was washed twice withwater and evaporatedThe solid was recrystallized using ethylacetate and dried in a vacuum oven at 60∘C MP 186∘C 1HNMR (CDCl
3 ppm 120575) 710ndash712 (s 2H o-ArH) 1194ndash1205
(s 2H ArOH) 772ndash781 (m 6H -CO-119900-ArH) 751ndash767 (m8H119898 119901-ArH)
24 Synthesis of Linear Polycarbonate (BPA-PC) The poly-merization was carried out by the following general proce-dure at room temperature Bisphenol A (3 g 13mmol) andan aqueous NaOH solution (325 g 812mmol) were addedto a 250mL three-necked round bottom flask Triphosgene(267 g 9mmol) dissolved in methylene chloride and TEA(006mL) were added to the solution and stirred for 2 hat room temperature The methylene chloride layer wasseparated and the polymer solution was washed with distilledwater neutralized with HCl and precipitated in a mixture ofacetone and distilled water before drying in a vacuum oven at80∘C (50 50 vv) 119879
119892= 151∘C 1HNMR (CDCl
3 ppm 120575) 168
(s 6H -C(CH3)2-) 715ndash726 (m 8H ArH)
25 Synthesis of Polycarbonate Copolymers with Side BenzoylGroup (DBHP-PC) Polycarbonate containing 50mol ofthe DBHP moiety was prepared by the low-temperatureesterification reaction Bisphenol-A (30 g 131mmol) DBHP(52 g 131mmol) and TEA (106mL 788mmol) were dis-solved inmethylene chloride in a 250mL three-necked roundbottom flask Triphosgene (52 g 174mmol) dissolved inmethylene chloride was dropped slowly in the solution at 0∘Cand stirred for 4 h at room temperatureThe polymer solutionwaswashed several timeswith distilledwater and precipitatedin a mixture of acetone and distilled water (50 50 vv) beforedrying in a vacuum oven at 80∘C 1HNMR (CDCl
3 ppm 120575)
697ndash717 (s 2H 119900-ArH) 781ndash788 (m 6H -CO-119900-ArH) 751ndash767 (m 8H119898 119901-ArH) 168 (s 6H -C(CH
3)2-) 715ndash726 (m
8H ArH)
3 Results and Discussion
Themonomer of DBHP was prepared by the modified litera-ture procedure [17ndash19] In the literaturemono- anddibenzoylbiphenols were obtained as the products and they could beonly separated by column chromatography resulting in a lowyield Therefore the experimental procedure was exclusivelymodified to obtain single material dibenzoyl biphenol prod-uct followed by the Friedel-Craft reaction with aluminumchloride and benzoyl chloride Moreover the desired mono-and dibenzoyl biphenols were recrystallized from ethylacetate The esterification of polycarbonate was performedby both the interfacial and low-temperature polymerizations
International Journal of Polymer Science 3
O
O
+
OO
O
O O
O
OO
OOO
n m
O+
12-Dichlorobenzene
HO OH
OH OH
2 Cl
AlCl3
TEAMCClCl
Cl
Cl
Cl
Cl
BPA
DBHP
HO HO
Benzoyl chloride
Triphosgene
n = 0 m = 1
n = 05 m = 05
n = 1 m = 0
49984004-Biphenol
Scheme 1 Synthesis of DBHP monomer and DBHP-PCs
Interfacial polymerization is a commercial reaction methodbetween sodium hydroxide solution and organic layer con-taining chloride Low-temperature polymerization uses aninsoluble monomer with hydroxide functional group in ahydroxide solution Trimethylamine was used for dissolvingmonomer and as the catalyst in the reaction Moreover thisreaction was controlled by temperature because of rapidreactivity The polycarbonate copolymers were prepared bylow-temperature esterification reaction and synthesized fromDBHP (25 50 75 and 100 mol) bisphenol-A andtriphosgene as shown in Scheme 1 In this case DBHPmonomer did not dissolve in hydroxide solution because ofthe steric hindrance from the side chain Therefore poly-mers were synthesized by low-temperature polymerizationmethod
The chemical structure of monomer and polymers wasidentified by 1HNMR shown in Figure 1 The 1HNMR spec-tra of DBHP and BPA-DBHP polycarbonate also confirmedthe structure because all the peaks of the protons appeared atthe expected positions In theDBHPmonomer the ortho twoproton peaks of main phenyl rings appeared at 702 ppm andthe 6 protons of phenyl rings near the ketone groups appeared
e
CDCl3
13 12 11 10 9 8 7 6 5 4 3 2 1(ppm)
O
O
O
O O
O
O
HO OH
b
b
c
c
d
d
a
ae
m
H2O
Figure 1 1H NMR of DBHP monomer and DBHP-PC
at 76 ppm The 2 proton peaks of the hydroxide groupappeared at 124 ppm The residual proton peaks appeared inthe range 715ndash726 ppm In the polymer The 6 proton peaksof the BPA-methyl group appeared at 168 ppm and the 8proton peaks of BPA-phenyl rings appeared in the range 715ndash726 ppm The ortho 2 proton peaks of the main phenyl ringsappeared at 702 ppm and the 6 protons of phenyl rings nearthe ketone groups appeared at 76 ppm The residual protonpeaks appeared in the range 715ndash726 ppm
The thermal behavior of the polycarbonates was exam-ined by differential scanning calorimetry (DSC) The glasstransition temperature (119879
119892) values of DBHP polycarbonates
changed as increasing DBHP monomer segments As shownin Figure 2 119879
119892of DBHPrsquos polymer appeared 143 and 148∘C
compared to 151∘C for BPA-PC 119879119892values decreased with
increasing content of DBHP because the bulky benzoylgroups have more aromatic rings than BPA-PC but the sidephenyl rings have a large free volume and steric hindranceThe molecular weight of the polymers was determined bygel permeation chromatography (GPC) All the polymersshowed a weight average molecular weight (119872
119908) ranging
from 54400 to 68100 as listed in Table 1The thermal stability of polymers was examined by
thermogravimetric analysis (TGA) As shown in Figure 3the initial weight loss of DBHP-PC copolymer started at
4 International Journal of Polymer Science
Table 1 Properties of polycarbonates
Polymers 119879119892(∘C) TGA (∘C 5wt loss) 119872
119908Contact angle (∘) Surface hardness
BPA-PC 151 495 54400 963 6BDBHP 25 148 431 58200 1032 5BDBHP 50 143 385 61700 1086 3BDBHP 75 145 372 64900 1123 2BDBHP 100 146 363 68100 1157 1B
4837
80
100
120
140
160
180
200
220
240
260
Temperature (∘C)
2216220
215
210
205
200
195
190
Hea
t flow
endo
dow
n (m
W)
BPA-PC
DBHP 100DBHP 50
Figure 2 DSC of BPA-PC and DBHP-PCs
320sim350∘C and was assigned to the degradation start of theketone of the side benzoyl group The second decompositionat 580∘C was attributed to the fragment of polymer mainchainThe initial weight loss of DBHP polymer started in therange 320sim400∘C andwas attributed to the degradation of theketone of the side benzoyl group The second decompositionat 430∘C was attributed to the fragment of phenyl rings ofthe side chain benzoyl group The third decomposition of600∘C was attributed to the splitting of the polymer mainchain DBHP-PC increased the thermal stability than BPA-PC because of the presence of bulky side benzoyl groups andbiphenyl rings
The polymerrsquos surface morphologies were assessed on1 120583m times 1 120583m scale by atomic force microscopy in thetapping mode under ambient conditions Figure 4 showedmicrophase separation and was compared by the content ofDBHP Uneven surface was visible by the contained sidephenyl groups The bright and dark regions of the imagescorrespond to the linear and dark areas respectively corre-sponding to the DBHP part A common and useful methodfor determining the surface energy is to measure the contactangle of a water droplet on the surface
The water droplet on a hydrophobic surface shows ahigher contact angle because of the lower surface energyagainst the surface tension of the droplet and vice versaFigure 5 shows the images of the polymer of water drop onpolymersrsquo film The synthesized DBHP had a higher contactangle than BPA-PC and the curvature of the water surfacewas different because of the content of DBHP as listed inTable 1 BPA-PC had some hydrophilic part because the car-bonyl groups of BPA-PChave steric bulk from the close to the
110
100
90
80
70
60
50
40
30
20
10
0
Wei
ght (
)
0 100 200 300 400 500 600 700 800
Temperature (∘C)
BPA-PC
DBHP 100DBHP 50
Figure 3 TGA of BPA-PC and DBHP-PCs
surface However DBHP-PCs showed a lower surface resis-tance than BPA-PC because DBHP have free-volume for thebulky structure of the side benzene The surface hardness ofpolycarbonate sheet increased from B4 to B2 however thehardness of a filmwith a thickness of 100120583mwasmeasured as6B The surface hardness of the synthesized copolymers wasconfirmed from 5B to 1B by content of DBHP as listed Table 1According to research polymers containing side ketonegroups had a high mechanical performance with the surfacehardness The surface hardness of the polymers of DBHPincreased because of the side ketone groups
The polycarbonates showed transparency as shown inFigure 6 compared to BPA-PC In our daily lives trans-parency is affected at 550 nm as an important part DBHP 75and 100 have a transparency of 75 and 79 lower than BPA-PC of 85 Moreover this polymer was confirmed as a roughsurface like outer glass Transparency of DBHP 25 and 50 wassimilar to those of BPA-PC and polymer film and was clearwithout a rough surface
4 Conclusions
Polycarbonate copolymers were synthesized by low-temper-ature esterification reaction with DBHP bisphenol-A andtriphosgene The DBHP exhibited lower 119879
119892than linear poly-
carbonateThe polymer showed satisfactory thermooxidativestability The surface morphologies of the films of the syn-thesized copolymer were also different The surface hardness
International Journal of Polymer Science 5
025
050
075
0 025 050 075 1000 025 050 075 100
DBHP 50 DBHP 100
0 025 050
BPA-PC
075 1000
025
050
075
100
(120583m) (120583m)(120583m)
0
100
(120583m
)
(120583m
)0
025
050
075
100
(120583m
)
Figure 4 AFM of BPA-PC and DBHP-PCs
BPA-PC DBHP 25 DBHP 50 DBHP 75 DBHP 100
Figure 5 Image of water drop on the polymersrsquo film
700 800 900600 1000500Wavelength (nm)
60
65
70
75
80
85
90
95
100
Tran
spar
ency
()
BPA-PCDBHP 25DBHP 50
DBHP 75DBHP 100
Figure 6 Transparency of polymers
of the copolymers was measured from 5B to 1B comparedto 6B of BPA polycarbonate Moreover the transparency ofpolymers was measured from 75 to 89 and DBHP 50 had asimilar value as that of BPC-PC This encouraging result wasdemonstrated to be used for engineering plasticrsquos application
Competing Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This work was supported by the Human Resource TrainingProgram for Regional Innovation and Creativity through theMinistry of Education and National Research Foundationof Korea (NRF-2014H1C1A1066447) and by the NationalResearch Foundation of Korea (NRF) grant funded by theKorea government (MSIP) (2016R1A2B4010600)
References
[1] H T Pham S Munjal and C P Bosnyak ldquoPolycarbonatesrdquo inHandbook of Thermoplastics O Olabisi Ed Marcel DekkerNew York NY USA 1997
[2] T M Madkour ldquoPolycarbonaterdquo in Polymer Data HandbookJ E Mark Ed Oxford University Press New York NY USA1999
[3] H T Pham C LWeckle and JM Ceraso ldquoRheology enhance-ment in PCABS blendsrdquoAdvancedMaterials vol 12 no 23 pp1881ndash1885 2000
[4] H Schnell Chemistry and Physics of Polycarbonates WileyInterscience New York NY USA 1964
6 International Journal of Polymer Science
[5] C Nguyen and J Kim ldquoSynthesis of a novel nitrogen-phospho-rus flame retardant based on phosphoramidate and its applica-tion to PC PBT EVA and ABSrdquoMacromolecular Research vol16 no 7 pp 620ndash625 2008
[6] S Krishnan and R J White US Patent 4772655 1988[7] P P Policastro P K Hernandez G C Davis and J D Rich US
Patent 4916194 1990[8] L N Lwis and S C Bunnel US Patent 4954549 1990[9] H L Vincent D J Kimball and R R Boundy ldquoPolysiloxane
silica hybrid resins abrasion resistant coatings for plastic sub-stratesrdquo Polymeric Materials Science and Engineering vol 50pp 143ndash146 1984
[10] T Ebeling MMMarugan Z Qu and S Siripurapu EuropeanPatent EP 1 624 025 A1 2005
[11] K Horisawa K Okada and W Zhou WO Patent 152741 A12008
[12] M Okamoto ldquoEffect of polycarbonate-poly(methyl methacry-late) graft copolymer as a modifier improving the surfacehardness of polycarbonaterdquo Journal of Applied Polymer Sciencevol 83 no 13 pp 2774ndash2779 2002
[13] S A Xu and S C Tjong ldquoTensile deformation mechanisms ofthe blends of polycarbonate with poly(methyl methacrylate)rdquoEuropean Polymer Journal vol 34 no 8 pp 1143ndash1149 1998
[14] L R Hutchings R W Richards R L Thompson A S Cloughand S Langridge ldquoInterface development in polycarbonatepoly(methyl methacrylate) bilayer filmsrdquo Journal of PolymerScience Part B Polymer Physics vol 39 no 20 pp 2351ndash23622001
[15] W-P Hsu ldquoSolvent effects on the miscibility of poly(methylmethacrylate)poly(bisphenol A carbonate) blendsrdquo Journal ofApplied Polymer Science vol 80 no 14 pp 2842ndash2850 2001
[16] K K Park H J Lee E H Kim and S K Kang ldquoFacile syn-thesis and photo-Fries rearrangement of 2-benzoyl-4-benzoy-loxyphenol leading to dibenzoyldihydroxybenzene derivativesrdquoJournal of Photochemistry and Photobiology A Chemistry vol159 no 1 pp 17ndash21 2003
[17] A M A G Oliveira A M F Oliveira-Campos M M MRaposo J Griffiths and A E H Machado ldquoFries rearrange-ment of dibenzofuran-2-yl ethanoate under photochemical andLewis-acid-catalysed conditionsrdquo Tetrahedron vol 60 no 29pp 6145ndash6154 2004
[18] M R Mauricio T D S Silva M H Kunita E C Muniz G MDe Carvalho and A F Rubira ldquoSynthesis of luminescent poly-carbonate grafted with methyl methacrylateeuropium com-plex using supercritical CO
2technology as a green chemistry
methodrdquo Journal of Materials Science vol 47 no 12 pp 4965ndash4971 2012
[19] J Jayaramudu G Siva Mohan Reddy K Varaprasad E RSadiku S Sinha Ray and A Varada Rajulu ldquoEffect of alkalitreatment on the morphology and tensile properties of CordiaDichotoma fabricpolycarbonate compositesrdquoAdvances in Poly-mer Technology vol 32 no 3 Article ID 21349 2013
[20] S E Morgan R Misra and P Jones ldquoNanomechanical and sur-face frictional characteristics of a copolymer based on benzoyl-14-phenylene and 13-phenylenerdquo Polymer vol 47 no 8 pp2865ndash2873 2006
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Journal ofNanomaterials
2 International Journal of Polymer Science
polarized optical microscopic techniques [19] (4)The chem-ical modification such as Parmax containing side carbonylaffects the surface properties including the surface morphol-ogy and other properties [20] Research on the effectivemodification of polycarbonate is necessary because the mainattraction these days is the thin film application of mobilewindow replacing tempered glass
Thepurpose of this studywas to improve the scratch resis-tance of polycarbonate while retaining its beneficial prop-erties Thin film polycarbonates are difficult to coat by UVcuring because they are very soft with only 6B hardness Inthis study we introduced a new copolymer for enhancing thescratch resistanceThe copolymerwas designed by bisphenol-A and 33-dibenzoyl-44-dihydroxybiphenyl and the effect ofside functional group was confirmed The chemical analysisand thermal properties of this polycarbonate containing ben-zoyl groups on side chain and the waterproof andmechanicalproperties of the polymers were investigated The surfacemorphologies were investigated by waterproof and AFMstudies The experimental data show that all the polymersare quite thermally stable and showed good waterproof andimproved scratch resistance
2 Experimental
21 Materials Bisphenol-A 44-biphenol benzoyl chloridealuminum chloride triethylamine (TEA) and triphosgenewere purchased from Sigma-Aldrich Junsei and Acroschemical companies and used as received Common reagentssuch as 12-dichlorobenzene ethyl acetate acetone methy-lene chloride hexane and sodium hydroxide were also usedas received TEAwas used as a 15 (wv) aqueous solution forsynthesizing linear polycarbonate
22 Measurement NMR spectra were recorded using aBruker DRX (400MHz) spectrometer using CDCl
3as the
solvent and tetramethylsilane as the internal standard Theintrinsic viscosity (120578inh) was determined at a 05 gdL con-centration of polycarbonate in methylene chloride witha Cannon-Fenske routine viscometer at 30∘C Differentialscanning calorimetry (DSC) analysis was performed usinga Perkin-Elmer DSC 6 at a heating rate of 20∘Cmin undernitrogen 119879
119892was taken as the midpoint of the inflection
observed on the curve of heat capacity versus temperatureThermogravimetric analysis (TGA) was performed using aScinco TGA-N 1000 analyzer The surface morphologies ofpolycarbonates were observed by atomic force microscopy(AFM) Tapping mode atomic force microscopic observa-tions were performed using a Digital Instrument Nanoscope(R) IIIA using microfabricated cantilevers and amplitudeset point 07785V The contact angle was measured by acontact angle analyzer (Phoenix-300 Surface ElectroOptics)The volume of the water drop was controlled to sim02 120583Lby a microsyringe The average value of both sides of eachdrop was considered as the contact angle Antiscratch wasmeasured by KIPAE Promate 5000M and test angle was45∘ with a test load of 1 Kg The transparency was measuredby VMS-1 parallel beam-path of SCINCO in the wavelengthrange 400ndash1000 nm to use a tungsten halogen lamp
23 Synthesis of 33-Dibenzoyl-441015840-dihydroxybiphenyl(DBHP) The monomer was prepared by Friedel-Craftreaction In a 250mL round flask 441015840-biphenol (50 g268mmol) and aluminum chloride (179 g 1342mmol) weredissolved in 12-dichlorobenzene To this mixture benzoylchloride (93mL 805mmol) was slowly added at roomtemperature and stirred for 18 h at 160∘C After the reactionthe liquid was poured in distilled water containing a smallamount of hydrochloric acid and methylene chloride wasadded The separated organic layer was washed twice withwater and evaporatedThe solid was recrystallized using ethylacetate and dried in a vacuum oven at 60∘C MP 186∘C 1HNMR (CDCl
3 ppm 120575) 710ndash712 (s 2H o-ArH) 1194ndash1205
(s 2H ArOH) 772ndash781 (m 6H -CO-119900-ArH) 751ndash767 (m8H119898 119901-ArH)
24 Synthesis of Linear Polycarbonate (BPA-PC) The poly-merization was carried out by the following general proce-dure at room temperature Bisphenol A (3 g 13mmol) andan aqueous NaOH solution (325 g 812mmol) were addedto a 250mL three-necked round bottom flask Triphosgene(267 g 9mmol) dissolved in methylene chloride and TEA(006mL) were added to the solution and stirred for 2 hat room temperature The methylene chloride layer wasseparated and the polymer solution was washed with distilledwater neutralized with HCl and precipitated in a mixture ofacetone and distilled water before drying in a vacuum oven at80∘C (50 50 vv) 119879
119892= 151∘C 1HNMR (CDCl
3 ppm 120575) 168
(s 6H -C(CH3)2-) 715ndash726 (m 8H ArH)
25 Synthesis of Polycarbonate Copolymers with Side BenzoylGroup (DBHP-PC) Polycarbonate containing 50mol ofthe DBHP moiety was prepared by the low-temperatureesterification reaction Bisphenol-A (30 g 131mmol) DBHP(52 g 131mmol) and TEA (106mL 788mmol) were dis-solved inmethylene chloride in a 250mL three-necked roundbottom flask Triphosgene (52 g 174mmol) dissolved inmethylene chloride was dropped slowly in the solution at 0∘Cand stirred for 4 h at room temperatureThe polymer solutionwaswashed several timeswith distilledwater and precipitatedin a mixture of acetone and distilled water (50 50 vv) beforedrying in a vacuum oven at 80∘C 1HNMR (CDCl
3 ppm 120575)
697ndash717 (s 2H 119900-ArH) 781ndash788 (m 6H -CO-119900-ArH) 751ndash767 (m 8H119898 119901-ArH) 168 (s 6H -C(CH
3)2-) 715ndash726 (m
8H ArH)
3 Results and Discussion
Themonomer of DBHP was prepared by the modified litera-ture procedure [17ndash19] In the literaturemono- anddibenzoylbiphenols were obtained as the products and they could beonly separated by column chromatography resulting in a lowyield Therefore the experimental procedure was exclusivelymodified to obtain single material dibenzoyl biphenol prod-uct followed by the Friedel-Craft reaction with aluminumchloride and benzoyl chloride Moreover the desired mono-and dibenzoyl biphenols were recrystallized from ethylacetate The esterification of polycarbonate was performedby both the interfacial and low-temperature polymerizations
International Journal of Polymer Science 3
O
O
+
OO
O
O O
O
OO
OOO
n m
O+
12-Dichlorobenzene
HO OH
OH OH
2 Cl
AlCl3
TEAMCClCl
Cl
Cl
Cl
Cl
BPA
DBHP
HO HO
Benzoyl chloride
Triphosgene
n = 0 m = 1
n = 05 m = 05
n = 1 m = 0
49984004-Biphenol
Scheme 1 Synthesis of DBHP monomer and DBHP-PCs
Interfacial polymerization is a commercial reaction methodbetween sodium hydroxide solution and organic layer con-taining chloride Low-temperature polymerization uses aninsoluble monomer with hydroxide functional group in ahydroxide solution Trimethylamine was used for dissolvingmonomer and as the catalyst in the reaction Moreover thisreaction was controlled by temperature because of rapidreactivity The polycarbonate copolymers were prepared bylow-temperature esterification reaction and synthesized fromDBHP (25 50 75 and 100 mol) bisphenol-A andtriphosgene as shown in Scheme 1 In this case DBHPmonomer did not dissolve in hydroxide solution because ofthe steric hindrance from the side chain Therefore poly-mers were synthesized by low-temperature polymerizationmethod
The chemical structure of monomer and polymers wasidentified by 1HNMR shown in Figure 1 The 1HNMR spec-tra of DBHP and BPA-DBHP polycarbonate also confirmedthe structure because all the peaks of the protons appeared atthe expected positions In theDBHPmonomer the ortho twoproton peaks of main phenyl rings appeared at 702 ppm andthe 6 protons of phenyl rings near the ketone groups appeared
e
CDCl3
13 12 11 10 9 8 7 6 5 4 3 2 1(ppm)
O
O
O
O O
O
O
HO OH
b
b
c
c
d
d
a
ae
m
H2O
Figure 1 1H NMR of DBHP monomer and DBHP-PC
at 76 ppm The 2 proton peaks of the hydroxide groupappeared at 124 ppm The residual proton peaks appeared inthe range 715ndash726 ppm In the polymer The 6 proton peaksof the BPA-methyl group appeared at 168 ppm and the 8proton peaks of BPA-phenyl rings appeared in the range 715ndash726 ppm The ortho 2 proton peaks of the main phenyl ringsappeared at 702 ppm and the 6 protons of phenyl rings nearthe ketone groups appeared at 76 ppm The residual protonpeaks appeared in the range 715ndash726 ppm
The thermal behavior of the polycarbonates was exam-ined by differential scanning calorimetry (DSC) The glasstransition temperature (119879
119892) values of DBHP polycarbonates
changed as increasing DBHP monomer segments As shownin Figure 2 119879
119892of DBHPrsquos polymer appeared 143 and 148∘C
compared to 151∘C for BPA-PC 119879119892values decreased with
increasing content of DBHP because the bulky benzoylgroups have more aromatic rings than BPA-PC but the sidephenyl rings have a large free volume and steric hindranceThe molecular weight of the polymers was determined bygel permeation chromatography (GPC) All the polymersshowed a weight average molecular weight (119872
119908) ranging
from 54400 to 68100 as listed in Table 1The thermal stability of polymers was examined by
thermogravimetric analysis (TGA) As shown in Figure 3the initial weight loss of DBHP-PC copolymer started at
4 International Journal of Polymer Science
Table 1 Properties of polycarbonates
Polymers 119879119892(∘C) TGA (∘C 5wt loss) 119872
119908Contact angle (∘) Surface hardness
BPA-PC 151 495 54400 963 6BDBHP 25 148 431 58200 1032 5BDBHP 50 143 385 61700 1086 3BDBHP 75 145 372 64900 1123 2BDBHP 100 146 363 68100 1157 1B
4837
80
100
120
140
160
180
200
220
240
260
Temperature (∘C)
2216220
215
210
205
200
195
190
Hea
t flow
endo
dow
n (m
W)
BPA-PC
DBHP 100DBHP 50
Figure 2 DSC of BPA-PC and DBHP-PCs
320sim350∘C and was assigned to the degradation start of theketone of the side benzoyl group The second decompositionat 580∘C was attributed to the fragment of polymer mainchainThe initial weight loss of DBHP polymer started in therange 320sim400∘C andwas attributed to the degradation of theketone of the side benzoyl group The second decompositionat 430∘C was attributed to the fragment of phenyl rings ofthe side chain benzoyl group The third decomposition of600∘C was attributed to the splitting of the polymer mainchain DBHP-PC increased the thermal stability than BPA-PC because of the presence of bulky side benzoyl groups andbiphenyl rings
The polymerrsquos surface morphologies were assessed on1 120583m times 1 120583m scale by atomic force microscopy in thetapping mode under ambient conditions Figure 4 showedmicrophase separation and was compared by the content ofDBHP Uneven surface was visible by the contained sidephenyl groups The bright and dark regions of the imagescorrespond to the linear and dark areas respectively corre-sponding to the DBHP part A common and useful methodfor determining the surface energy is to measure the contactangle of a water droplet on the surface
The water droplet on a hydrophobic surface shows ahigher contact angle because of the lower surface energyagainst the surface tension of the droplet and vice versaFigure 5 shows the images of the polymer of water drop onpolymersrsquo film The synthesized DBHP had a higher contactangle than BPA-PC and the curvature of the water surfacewas different because of the content of DBHP as listed inTable 1 BPA-PC had some hydrophilic part because the car-bonyl groups of BPA-PChave steric bulk from the close to the
110
100
90
80
70
60
50
40
30
20
10
0
Wei
ght (
)
0 100 200 300 400 500 600 700 800
Temperature (∘C)
BPA-PC
DBHP 100DBHP 50
Figure 3 TGA of BPA-PC and DBHP-PCs
surface However DBHP-PCs showed a lower surface resis-tance than BPA-PC because DBHP have free-volume for thebulky structure of the side benzene The surface hardness ofpolycarbonate sheet increased from B4 to B2 however thehardness of a filmwith a thickness of 100120583mwasmeasured as6B The surface hardness of the synthesized copolymers wasconfirmed from 5B to 1B by content of DBHP as listed Table 1According to research polymers containing side ketonegroups had a high mechanical performance with the surfacehardness The surface hardness of the polymers of DBHPincreased because of the side ketone groups
The polycarbonates showed transparency as shown inFigure 6 compared to BPA-PC In our daily lives trans-parency is affected at 550 nm as an important part DBHP 75and 100 have a transparency of 75 and 79 lower than BPA-PC of 85 Moreover this polymer was confirmed as a roughsurface like outer glass Transparency of DBHP 25 and 50 wassimilar to those of BPA-PC and polymer film and was clearwithout a rough surface
4 Conclusions
Polycarbonate copolymers were synthesized by low-temper-ature esterification reaction with DBHP bisphenol-A andtriphosgene The DBHP exhibited lower 119879
119892than linear poly-
carbonateThe polymer showed satisfactory thermooxidativestability The surface morphologies of the films of the syn-thesized copolymer were also different The surface hardness
International Journal of Polymer Science 5
025
050
075
0 025 050 075 1000 025 050 075 100
DBHP 50 DBHP 100
0 025 050
BPA-PC
075 1000
025
050
075
100
(120583m) (120583m)(120583m)
0
100
(120583m
)
(120583m
)0
025
050
075
100
(120583m
)
Figure 4 AFM of BPA-PC and DBHP-PCs
BPA-PC DBHP 25 DBHP 50 DBHP 75 DBHP 100
Figure 5 Image of water drop on the polymersrsquo film
700 800 900600 1000500Wavelength (nm)
60
65
70
75
80
85
90
95
100
Tran
spar
ency
()
BPA-PCDBHP 25DBHP 50
DBHP 75DBHP 100
Figure 6 Transparency of polymers
of the copolymers was measured from 5B to 1B comparedto 6B of BPA polycarbonate Moreover the transparency ofpolymers was measured from 75 to 89 and DBHP 50 had asimilar value as that of BPC-PC This encouraging result wasdemonstrated to be used for engineering plasticrsquos application
Competing Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This work was supported by the Human Resource TrainingProgram for Regional Innovation and Creativity through theMinistry of Education and National Research Foundationof Korea (NRF-2014H1C1A1066447) and by the NationalResearch Foundation of Korea (NRF) grant funded by theKorea government (MSIP) (2016R1A2B4010600)
References
[1] H T Pham S Munjal and C P Bosnyak ldquoPolycarbonatesrdquo inHandbook of Thermoplastics O Olabisi Ed Marcel DekkerNew York NY USA 1997
[2] T M Madkour ldquoPolycarbonaterdquo in Polymer Data HandbookJ E Mark Ed Oxford University Press New York NY USA1999
[3] H T Pham C LWeckle and JM Ceraso ldquoRheology enhance-ment in PCABS blendsrdquoAdvancedMaterials vol 12 no 23 pp1881ndash1885 2000
[4] H Schnell Chemistry and Physics of Polycarbonates WileyInterscience New York NY USA 1964
6 International Journal of Polymer Science
[5] C Nguyen and J Kim ldquoSynthesis of a novel nitrogen-phospho-rus flame retardant based on phosphoramidate and its applica-tion to PC PBT EVA and ABSrdquoMacromolecular Research vol16 no 7 pp 620ndash625 2008
[6] S Krishnan and R J White US Patent 4772655 1988[7] P P Policastro P K Hernandez G C Davis and J D Rich US
Patent 4916194 1990[8] L N Lwis and S C Bunnel US Patent 4954549 1990[9] H L Vincent D J Kimball and R R Boundy ldquoPolysiloxane
silica hybrid resins abrasion resistant coatings for plastic sub-stratesrdquo Polymeric Materials Science and Engineering vol 50pp 143ndash146 1984
[10] T Ebeling MMMarugan Z Qu and S Siripurapu EuropeanPatent EP 1 624 025 A1 2005
[11] K Horisawa K Okada and W Zhou WO Patent 152741 A12008
[12] M Okamoto ldquoEffect of polycarbonate-poly(methyl methacry-late) graft copolymer as a modifier improving the surfacehardness of polycarbonaterdquo Journal of Applied Polymer Sciencevol 83 no 13 pp 2774ndash2779 2002
[13] S A Xu and S C Tjong ldquoTensile deformation mechanisms ofthe blends of polycarbonate with poly(methyl methacrylate)rdquoEuropean Polymer Journal vol 34 no 8 pp 1143ndash1149 1998
[14] L R Hutchings R W Richards R L Thompson A S Cloughand S Langridge ldquoInterface development in polycarbonatepoly(methyl methacrylate) bilayer filmsrdquo Journal of PolymerScience Part B Polymer Physics vol 39 no 20 pp 2351ndash23622001
[15] W-P Hsu ldquoSolvent effects on the miscibility of poly(methylmethacrylate)poly(bisphenol A carbonate) blendsrdquo Journal ofApplied Polymer Science vol 80 no 14 pp 2842ndash2850 2001
[16] K K Park H J Lee E H Kim and S K Kang ldquoFacile syn-thesis and photo-Fries rearrangement of 2-benzoyl-4-benzoy-loxyphenol leading to dibenzoyldihydroxybenzene derivativesrdquoJournal of Photochemistry and Photobiology A Chemistry vol159 no 1 pp 17ndash21 2003
[17] A M A G Oliveira A M F Oliveira-Campos M M MRaposo J Griffiths and A E H Machado ldquoFries rearrange-ment of dibenzofuran-2-yl ethanoate under photochemical andLewis-acid-catalysed conditionsrdquo Tetrahedron vol 60 no 29pp 6145ndash6154 2004
[18] M R Mauricio T D S Silva M H Kunita E C Muniz G MDe Carvalho and A F Rubira ldquoSynthesis of luminescent poly-carbonate grafted with methyl methacrylateeuropium com-plex using supercritical CO
2technology as a green chemistry
methodrdquo Journal of Materials Science vol 47 no 12 pp 4965ndash4971 2012
[19] J Jayaramudu G Siva Mohan Reddy K Varaprasad E RSadiku S Sinha Ray and A Varada Rajulu ldquoEffect of alkalitreatment on the morphology and tensile properties of CordiaDichotoma fabricpolycarbonate compositesrdquoAdvances in Poly-mer Technology vol 32 no 3 Article ID 21349 2013
[20] S E Morgan R Misra and P Jones ldquoNanomechanical and sur-face frictional characteristics of a copolymer based on benzoyl-14-phenylene and 13-phenylenerdquo Polymer vol 47 no 8 pp2865ndash2873 2006
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
International Journal of Polymer Science 3
O
O
+
OO
O
O O
O
OO
OOO
n m
O+
12-Dichlorobenzene
HO OH
OH OH
2 Cl
AlCl3
TEAMCClCl
Cl
Cl
Cl
Cl
BPA
DBHP
HO HO
Benzoyl chloride
Triphosgene
n = 0 m = 1
n = 05 m = 05
n = 1 m = 0
49984004-Biphenol
Scheme 1 Synthesis of DBHP monomer and DBHP-PCs
Interfacial polymerization is a commercial reaction methodbetween sodium hydroxide solution and organic layer con-taining chloride Low-temperature polymerization uses aninsoluble monomer with hydroxide functional group in ahydroxide solution Trimethylamine was used for dissolvingmonomer and as the catalyst in the reaction Moreover thisreaction was controlled by temperature because of rapidreactivity The polycarbonate copolymers were prepared bylow-temperature esterification reaction and synthesized fromDBHP (25 50 75 and 100 mol) bisphenol-A andtriphosgene as shown in Scheme 1 In this case DBHPmonomer did not dissolve in hydroxide solution because ofthe steric hindrance from the side chain Therefore poly-mers were synthesized by low-temperature polymerizationmethod
The chemical structure of monomer and polymers wasidentified by 1HNMR shown in Figure 1 The 1HNMR spec-tra of DBHP and BPA-DBHP polycarbonate also confirmedthe structure because all the peaks of the protons appeared atthe expected positions In theDBHPmonomer the ortho twoproton peaks of main phenyl rings appeared at 702 ppm andthe 6 protons of phenyl rings near the ketone groups appeared
e
CDCl3
13 12 11 10 9 8 7 6 5 4 3 2 1(ppm)
O
O
O
O O
O
O
HO OH
b
b
c
c
d
d
a
ae
m
H2O
Figure 1 1H NMR of DBHP monomer and DBHP-PC
at 76 ppm The 2 proton peaks of the hydroxide groupappeared at 124 ppm The residual proton peaks appeared inthe range 715ndash726 ppm In the polymer The 6 proton peaksof the BPA-methyl group appeared at 168 ppm and the 8proton peaks of BPA-phenyl rings appeared in the range 715ndash726 ppm The ortho 2 proton peaks of the main phenyl ringsappeared at 702 ppm and the 6 protons of phenyl rings nearthe ketone groups appeared at 76 ppm The residual protonpeaks appeared in the range 715ndash726 ppm
The thermal behavior of the polycarbonates was exam-ined by differential scanning calorimetry (DSC) The glasstransition temperature (119879
119892) values of DBHP polycarbonates
changed as increasing DBHP monomer segments As shownin Figure 2 119879
119892of DBHPrsquos polymer appeared 143 and 148∘C
compared to 151∘C for BPA-PC 119879119892values decreased with
increasing content of DBHP because the bulky benzoylgroups have more aromatic rings than BPA-PC but the sidephenyl rings have a large free volume and steric hindranceThe molecular weight of the polymers was determined bygel permeation chromatography (GPC) All the polymersshowed a weight average molecular weight (119872
119908) ranging
from 54400 to 68100 as listed in Table 1The thermal stability of polymers was examined by
thermogravimetric analysis (TGA) As shown in Figure 3the initial weight loss of DBHP-PC copolymer started at
4 International Journal of Polymer Science
Table 1 Properties of polycarbonates
Polymers 119879119892(∘C) TGA (∘C 5wt loss) 119872
119908Contact angle (∘) Surface hardness
BPA-PC 151 495 54400 963 6BDBHP 25 148 431 58200 1032 5BDBHP 50 143 385 61700 1086 3BDBHP 75 145 372 64900 1123 2BDBHP 100 146 363 68100 1157 1B
4837
80
100
120
140
160
180
200
220
240
260
Temperature (∘C)
2216220
215
210
205
200
195
190
Hea
t flow
endo
dow
n (m
W)
BPA-PC
DBHP 100DBHP 50
Figure 2 DSC of BPA-PC and DBHP-PCs
320sim350∘C and was assigned to the degradation start of theketone of the side benzoyl group The second decompositionat 580∘C was attributed to the fragment of polymer mainchainThe initial weight loss of DBHP polymer started in therange 320sim400∘C andwas attributed to the degradation of theketone of the side benzoyl group The second decompositionat 430∘C was attributed to the fragment of phenyl rings ofthe side chain benzoyl group The third decomposition of600∘C was attributed to the splitting of the polymer mainchain DBHP-PC increased the thermal stability than BPA-PC because of the presence of bulky side benzoyl groups andbiphenyl rings
The polymerrsquos surface morphologies were assessed on1 120583m times 1 120583m scale by atomic force microscopy in thetapping mode under ambient conditions Figure 4 showedmicrophase separation and was compared by the content ofDBHP Uneven surface was visible by the contained sidephenyl groups The bright and dark regions of the imagescorrespond to the linear and dark areas respectively corre-sponding to the DBHP part A common and useful methodfor determining the surface energy is to measure the contactangle of a water droplet on the surface
The water droplet on a hydrophobic surface shows ahigher contact angle because of the lower surface energyagainst the surface tension of the droplet and vice versaFigure 5 shows the images of the polymer of water drop onpolymersrsquo film The synthesized DBHP had a higher contactangle than BPA-PC and the curvature of the water surfacewas different because of the content of DBHP as listed inTable 1 BPA-PC had some hydrophilic part because the car-bonyl groups of BPA-PChave steric bulk from the close to the
110
100
90
80
70
60
50
40
30
20
10
0
Wei
ght (
)
0 100 200 300 400 500 600 700 800
Temperature (∘C)
BPA-PC
DBHP 100DBHP 50
Figure 3 TGA of BPA-PC and DBHP-PCs
surface However DBHP-PCs showed a lower surface resis-tance than BPA-PC because DBHP have free-volume for thebulky structure of the side benzene The surface hardness ofpolycarbonate sheet increased from B4 to B2 however thehardness of a filmwith a thickness of 100120583mwasmeasured as6B The surface hardness of the synthesized copolymers wasconfirmed from 5B to 1B by content of DBHP as listed Table 1According to research polymers containing side ketonegroups had a high mechanical performance with the surfacehardness The surface hardness of the polymers of DBHPincreased because of the side ketone groups
The polycarbonates showed transparency as shown inFigure 6 compared to BPA-PC In our daily lives trans-parency is affected at 550 nm as an important part DBHP 75and 100 have a transparency of 75 and 79 lower than BPA-PC of 85 Moreover this polymer was confirmed as a roughsurface like outer glass Transparency of DBHP 25 and 50 wassimilar to those of BPA-PC and polymer film and was clearwithout a rough surface
4 Conclusions
Polycarbonate copolymers were synthesized by low-temper-ature esterification reaction with DBHP bisphenol-A andtriphosgene The DBHP exhibited lower 119879
119892than linear poly-
carbonateThe polymer showed satisfactory thermooxidativestability The surface morphologies of the films of the syn-thesized copolymer were also different The surface hardness
International Journal of Polymer Science 5
025
050
075
0 025 050 075 1000 025 050 075 100
DBHP 50 DBHP 100
0 025 050
BPA-PC
075 1000
025
050
075
100
(120583m) (120583m)(120583m)
0
100
(120583m
)
(120583m
)0
025
050
075
100
(120583m
)
Figure 4 AFM of BPA-PC and DBHP-PCs
BPA-PC DBHP 25 DBHP 50 DBHP 75 DBHP 100
Figure 5 Image of water drop on the polymersrsquo film
700 800 900600 1000500Wavelength (nm)
60
65
70
75
80
85
90
95
100
Tran
spar
ency
()
BPA-PCDBHP 25DBHP 50
DBHP 75DBHP 100
Figure 6 Transparency of polymers
of the copolymers was measured from 5B to 1B comparedto 6B of BPA polycarbonate Moreover the transparency ofpolymers was measured from 75 to 89 and DBHP 50 had asimilar value as that of BPC-PC This encouraging result wasdemonstrated to be used for engineering plasticrsquos application
Competing Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This work was supported by the Human Resource TrainingProgram for Regional Innovation and Creativity through theMinistry of Education and National Research Foundationof Korea (NRF-2014H1C1A1066447) and by the NationalResearch Foundation of Korea (NRF) grant funded by theKorea government (MSIP) (2016R1A2B4010600)
References
[1] H T Pham S Munjal and C P Bosnyak ldquoPolycarbonatesrdquo inHandbook of Thermoplastics O Olabisi Ed Marcel DekkerNew York NY USA 1997
[2] T M Madkour ldquoPolycarbonaterdquo in Polymer Data HandbookJ E Mark Ed Oxford University Press New York NY USA1999
[3] H T Pham C LWeckle and JM Ceraso ldquoRheology enhance-ment in PCABS blendsrdquoAdvancedMaterials vol 12 no 23 pp1881ndash1885 2000
[4] H Schnell Chemistry and Physics of Polycarbonates WileyInterscience New York NY USA 1964
6 International Journal of Polymer Science
[5] C Nguyen and J Kim ldquoSynthesis of a novel nitrogen-phospho-rus flame retardant based on phosphoramidate and its applica-tion to PC PBT EVA and ABSrdquoMacromolecular Research vol16 no 7 pp 620ndash625 2008
[6] S Krishnan and R J White US Patent 4772655 1988[7] P P Policastro P K Hernandez G C Davis and J D Rich US
Patent 4916194 1990[8] L N Lwis and S C Bunnel US Patent 4954549 1990[9] H L Vincent D J Kimball and R R Boundy ldquoPolysiloxane
silica hybrid resins abrasion resistant coatings for plastic sub-stratesrdquo Polymeric Materials Science and Engineering vol 50pp 143ndash146 1984
[10] T Ebeling MMMarugan Z Qu and S Siripurapu EuropeanPatent EP 1 624 025 A1 2005
[11] K Horisawa K Okada and W Zhou WO Patent 152741 A12008
[12] M Okamoto ldquoEffect of polycarbonate-poly(methyl methacry-late) graft copolymer as a modifier improving the surfacehardness of polycarbonaterdquo Journal of Applied Polymer Sciencevol 83 no 13 pp 2774ndash2779 2002
[13] S A Xu and S C Tjong ldquoTensile deformation mechanisms ofthe blends of polycarbonate with poly(methyl methacrylate)rdquoEuropean Polymer Journal vol 34 no 8 pp 1143ndash1149 1998
[14] L R Hutchings R W Richards R L Thompson A S Cloughand S Langridge ldquoInterface development in polycarbonatepoly(methyl methacrylate) bilayer filmsrdquo Journal of PolymerScience Part B Polymer Physics vol 39 no 20 pp 2351ndash23622001
[15] W-P Hsu ldquoSolvent effects on the miscibility of poly(methylmethacrylate)poly(bisphenol A carbonate) blendsrdquo Journal ofApplied Polymer Science vol 80 no 14 pp 2842ndash2850 2001
[16] K K Park H J Lee E H Kim and S K Kang ldquoFacile syn-thesis and photo-Fries rearrangement of 2-benzoyl-4-benzoy-loxyphenol leading to dibenzoyldihydroxybenzene derivativesrdquoJournal of Photochemistry and Photobiology A Chemistry vol159 no 1 pp 17ndash21 2003
[17] A M A G Oliveira A M F Oliveira-Campos M M MRaposo J Griffiths and A E H Machado ldquoFries rearrange-ment of dibenzofuran-2-yl ethanoate under photochemical andLewis-acid-catalysed conditionsrdquo Tetrahedron vol 60 no 29pp 6145ndash6154 2004
[18] M R Mauricio T D S Silva M H Kunita E C Muniz G MDe Carvalho and A F Rubira ldquoSynthesis of luminescent poly-carbonate grafted with methyl methacrylateeuropium com-plex using supercritical CO
2technology as a green chemistry
methodrdquo Journal of Materials Science vol 47 no 12 pp 4965ndash4971 2012
[19] J Jayaramudu G Siva Mohan Reddy K Varaprasad E RSadiku S Sinha Ray and A Varada Rajulu ldquoEffect of alkalitreatment on the morphology and tensile properties of CordiaDichotoma fabricpolycarbonate compositesrdquoAdvances in Poly-mer Technology vol 32 no 3 Article ID 21349 2013
[20] S E Morgan R Misra and P Jones ldquoNanomechanical and sur-face frictional characteristics of a copolymer based on benzoyl-14-phenylene and 13-phenylenerdquo Polymer vol 47 no 8 pp2865ndash2873 2006
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
4 International Journal of Polymer Science
Table 1 Properties of polycarbonates
Polymers 119879119892(∘C) TGA (∘C 5wt loss) 119872
119908Contact angle (∘) Surface hardness
BPA-PC 151 495 54400 963 6BDBHP 25 148 431 58200 1032 5BDBHP 50 143 385 61700 1086 3BDBHP 75 145 372 64900 1123 2BDBHP 100 146 363 68100 1157 1B
4837
80
100
120
140
160
180
200
220
240
260
Temperature (∘C)
2216220
215
210
205
200
195
190
Hea
t flow
endo
dow
n (m
W)
BPA-PC
DBHP 100DBHP 50
Figure 2 DSC of BPA-PC and DBHP-PCs
320sim350∘C and was assigned to the degradation start of theketone of the side benzoyl group The second decompositionat 580∘C was attributed to the fragment of polymer mainchainThe initial weight loss of DBHP polymer started in therange 320sim400∘C andwas attributed to the degradation of theketone of the side benzoyl group The second decompositionat 430∘C was attributed to the fragment of phenyl rings ofthe side chain benzoyl group The third decomposition of600∘C was attributed to the splitting of the polymer mainchain DBHP-PC increased the thermal stability than BPA-PC because of the presence of bulky side benzoyl groups andbiphenyl rings
The polymerrsquos surface morphologies were assessed on1 120583m times 1 120583m scale by atomic force microscopy in thetapping mode under ambient conditions Figure 4 showedmicrophase separation and was compared by the content ofDBHP Uneven surface was visible by the contained sidephenyl groups The bright and dark regions of the imagescorrespond to the linear and dark areas respectively corre-sponding to the DBHP part A common and useful methodfor determining the surface energy is to measure the contactangle of a water droplet on the surface
The water droplet on a hydrophobic surface shows ahigher contact angle because of the lower surface energyagainst the surface tension of the droplet and vice versaFigure 5 shows the images of the polymer of water drop onpolymersrsquo film The synthesized DBHP had a higher contactangle than BPA-PC and the curvature of the water surfacewas different because of the content of DBHP as listed inTable 1 BPA-PC had some hydrophilic part because the car-bonyl groups of BPA-PChave steric bulk from the close to the
110
100
90
80
70
60
50
40
30
20
10
0
Wei
ght (
)
0 100 200 300 400 500 600 700 800
Temperature (∘C)
BPA-PC
DBHP 100DBHP 50
Figure 3 TGA of BPA-PC and DBHP-PCs
surface However DBHP-PCs showed a lower surface resis-tance than BPA-PC because DBHP have free-volume for thebulky structure of the side benzene The surface hardness ofpolycarbonate sheet increased from B4 to B2 however thehardness of a filmwith a thickness of 100120583mwasmeasured as6B The surface hardness of the synthesized copolymers wasconfirmed from 5B to 1B by content of DBHP as listed Table 1According to research polymers containing side ketonegroups had a high mechanical performance with the surfacehardness The surface hardness of the polymers of DBHPincreased because of the side ketone groups
The polycarbonates showed transparency as shown inFigure 6 compared to BPA-PC In our daily lives trans-parency is affected at 550 nm as an important part DBHP 75and 100 have a transparency of 75 and 79 lower than BPA-PC of 85 Moreover this polymer was confirmed as a roughsurface like outer glass Transparency of DBHP 25 and 50 wassimilar to those of BPA-PC and polymer film and was clearwithout a rough surface
4 Conclusions
Polycarbonate copolymers were synthesized by low-temper-ature esterification reaction with DBHP bisphenol-A andtriphosgene The DBHP exhibited lower 119879
119892than linear poly-
carbonateThe polymer showed satisfactory thermooxidativestability The surface morphologies of the films of the syn-thesized copolymer were also different The surface hardness
International Journal of Polymer Science 5
025
050
075
0 025 050 075 1000 025 050 075 100
DBHP 50 DBHP 100
0 025 050
BPA-PC
075 1000
025
050
075
100
(120583m) (120583m)(120583m)
0
100
(120583m
)
(120583m
)0
025
050
075
100
(120583m
)
Figure 4 AFM of BPA-PC and DBHP-PCs
BPA-PC DBHP 25 DBHP 50 DBHP 75 DBHP 100
Figure 5 Image of water drop on the polymersrsquo film
700 800 900600 1000500Wavelength (nm)
60
65
70
75
80
85
90
95
100
Tran
spar
ency
()
BPA-PCDBHP 25DBHP 50
DBHP 75DBHP 100
Figure 6 Transparency of polymers
of the copolymers was measured from 5B to 1B comparedto 6B of BPA polycarbonate Moreover the transparency ofpolymers was measured from 75 to 89 and DBHP 50 had asimilar value as that of BPC-PC This encouraging result wasdemonstrated to be used for engineering plasticrsquos application
Competing Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This work was supported by the Human Resource TrainingProgram for Regional Innovation and Creativity through theMinistry of Education and National Research Foundationof Korea (NRF-2014H1C1A1066447) and by the NationalResearch Foundation of Korea (NRF) grant funded by theKorea government (MSIP) (2016R1A2B4010600)
References
[1] H T Pham S Munjal and C P Bosnyak ldquoPolycarbonatesrdquo inHandbook of Thermoplastics O Olabisi Ed Marcel DekkerNew York NY USA 1997
[2] T M Madkour ldquoPolycarbonaterdquo in Polymer Data HandbookJ E Mark Ed Oxford University Press New York NY USA1999
[3] H T Pham C LWeckle and JM Ceraso ldquoRheology enhance-ment in PCABS blendsrdquoAdvancedMaterials vol 12 no 23 pp1881ndash1885 2000
[4] H Schnell Chemistry and Physics of Polycarbonates WileyInterscience New York NY USA 1964
6 International Journal of Polymer Science
[5] C Nguyen and J Kim ldquoSynthesis of a novel nitrogen-phospho-rus flame retardant based on phosphoramidate and its applica-tion to PC PBT EVA and ABSrdquoMacromolecular Research vol16 no 7 pp 620ndash625 2008
[6] S Krishnan and R J White US Patent 4772655 1988[7] P P Policastro P K Hernandez G C Davis and J D Rich US
Patent 4916194 1990[8] L N Lwis and S C Bunnel US Patent 4954549 1990[9] H L Vincent D J Kimball and R R Boundy ldquoPolysiloxane
silica hybrid resins abrasion resistant coatings for plastic sub-stratesrdquo Polymeric Materials Science and Engineering vol 50pp 143ndash146 1984
[10] T Ebeling MMMarugan Z Qu and S Siripurapu EuropeanPatent EP 1 624 025 A1 2005
[11] K Horisawa K Okada and W Zhou WO Patent 152741 A12008
[12] M Okamoto ldquoEffect of polycarbonate-poly(methyl methacry-late) graft copolymer as a modifier improving the surfacehardness of polycarbonaterdquo Journal of Applied Polymer Sciencevol 83 no 13 pp 2774ndash2779 2002
[13] S A Xu and S C Tjong ldquoTensile deformation mechanisms ofthe blends of polycarbonate with poly(methyl methacrylate)rdquoEuropean Polymer Journal vol 34 no 8 pp 1143ndash1149 1998
[14] L R Hutchings R W Richards R L Thompson A S Cloughand S Langridge ldquoInterface development in polycarbonatepoly(methyl methacrylate) bilayer filmsrdquo Journal of PolymerScience Part B Polymer Physics vol 39 no 20 pp 2351ndash23622001
[15] W-P Hsu ldquoSolvent effects on the miscibility of poly(methylmethacrylate)poly(bisphenol A carbonate) blendsrdquo Journal ofApplied Polymer Science vol 80 no 14 pp 2842ndash2850 2001
[16] K K Park H J Lee E H Kim and S K Kang ldquoFacile syn-thesis and photo-Fries rearrangement of 2-benzoyl-4-benzoy-loxyphenol leading to dibenzoyldihydroxybenzene derivativesrdquoJournal of Photochemistry and Photobiology A Chemistry vol159 no 1 pp 17ndash21 2003
[17] A M A G Oliveira A M F Oliveira-Campos M M MRaposo J Griffiths and A E H Machado ldquoFries rearrange-ment of dibenzofuran-2-yl ethanoate under photochemical andLewis-acid-catalysed conditionsrdquo Tetrahedron vol 60 no 29pp 6145ndash6154 2004
[18] M R Mauricio T D S Silva M H Kunita E C Muniz G MDe Carvalho and A F Rubira ldquoSynthesis of luminescent poly-carbonate grafted with methyl methacrylateeuropium com-plex using supercritical CO
2technology as a green chemistry
methodrdquo Journal of Materials Science vol 47 no 12 pp 4965ndash4971 2012
[19] J Jayaramudu G Siva Mohan Reddy K Varaprasad E RSadiku S Sinha Ray and A Varada Rajulu ldquoEffect of alkalitreatment on the morphology and tensile properties of CordiaDichotoma fabricpolycarbonate compositesrdquoAdvances in Poly-mer Technology vol 32 no 3 Article ID 21349 2013
[20] S E Morgan R Misra and P Jones ldquoNanomechanical and sur-face frictional characteristics of a copolymer based on benzoyl-14-phenylene and 13-phenylenerdquo Polymer vol 47 no 8 pp2865ndash2873 2006
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
International Journal of Polymer Science 5
025
050
075
0 025 050 075 1000 025 050 075 100
DBHP 50 DBHP 100
0 025 050
BPA-PC
075 1000
025
050
075
100
(120583m) (120583m)(120583m)
0
100
(120583m
)
(120583m
)0
025
050
075
100
(120583m
)
Figure 4 AFM of BPA-PC and DBHP-PCs
BPA-PC DBHP 25 DBHP 50 DBHP 75 DBHP 100
Figure 5 Image of water drop on the polymersrsquo film
700 800 900600 1000500Wavelength (nm)
60
65
70
75
80
85
90
95
100
Tran
spar
ency
()
BPA-PCDBHP 25DBHP 50
DBHP 75DBHP 100
Figure 6 Transparency of polymers
of the copolymers was measured from 5B to 1B comparedto 6B of BPA polycarbonate Moreover the transparency ofpolymers was measured from 75 to 89 and DBHP 50 had asimilar value as that of BPC-PC This encouraging result wasdemonstrated to be used for engineering plasticrsquos application
Competing Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This work was supported by the Human Resource TrainingProgram for Regional Innovation and Creativity through theMinistry of Education and National Research Foundationof Korea (NRF-2014H1C1A1066447) and by the NationalResearch Foundation of Korea (NRF) grant funded by theKorea government (MSIP) (2016R1A2B4010600)
References
[1] H T Pham S Munjal and C P Bosnyak ldquoPolycarbonatesrdquo inHandbook of Thermoplastics O Olabisi Ed Marcel DekkerNew York NY USA 1997
[2] T M Madkour ldquoPolycarbonaterdquo in Polymer Data HandbookJ E Mark Ed Oxford University Press New York NY USA1999
[3] H T Pham C LWeckle and JM Ceraso ldquoRheology enhance-ment in PCABS blendsrdquoAdvancedMaterials vol 12 no 23 pp1881ndash1885 2000
[4] H Schnell Chemistry and Physics of Polycarbonates WileyInterscience New York NY USA 1964
6 International Journal of Polymer Science
[5] C Nguyen and J Kim ldquoSynthesis of a novel nitrogen-phospho-rus flame retardant based on phosphoramidate and its applica-tion to PC PBT EVA and ABSrdquoMacromolecular Research vol16 no 7 pp 620ndash625 2008
[6] S Krishnan and R J White US Patent 4772655 1988[7] P P Policastro P K Hernandez G C Davis and J D Rich US
Patent 4916194 1990[8] L N Lwis and S C Bunnel US Patent 4954549 1990[9] H L Vincent D J Kimball and R R Boundy ldquoPolysiloxane
silica hybrid resins abrasion resistant coatings for plastic sub-stratesrdquo Polymeric Materials Science and Engineering vol 50pp 143ndash146 1984
[10] T Ebeling MMMarugan Z Qu and S Siripurapu EuropeanPatent EP 1 624 025 A1 2005
[11] K Horisawa K Okada and W Zhou WO Patent 152741 A12008
[12] M Okamoto ldquoEffect of polycarbonate-poly(methyl methacry-late) graft copolymer as a modifier improving the surfacehardness of polycarbonaterdquo Journal of Applied Polymer Sciencevol 83 no 13 pp 2774ndash2779 2002
[13] S A Xu and S C Tjong ldquoTensile deformation mechanisms ofthe blends of polycarbonate with poly(methyl methacrylate)rdquoEuropean Polymer Journal vol 34 no 8 pp 1143ndash1149 1998
[14] L R Hutchings R W Richards R L Thompson A S Cloughand S Langridge ldquoInterface development in polycarbonatepoly(methyl methacrylate) bilayer filmsrdquo Journal of PolymerScience Part B Polymer Physics vol 39 no 20 pp 2351ndash23622001
[15] W-P Hsu ldquoSolvent effects on the miscibility of poly(methylmethacrylate)poly(bisphenol A carbonate) blendsrdquo Journal ofApplied Polymer Science vol 80 no 14 pp 2842ndash2850 2001
[16] K K Park H J Lee E H Kim and S K Kang ldquoFacile syn-thesis and photo-Fries rearrangement of 2-benzoyl-4-benzoy-loxyphenol leading to dibenzoyldihydroxybenzene derivativesrdquoJournal of Photochemistry and Photobiology A Chemistry vol159 no 1 pp 17ndash21 2003
[17] A M A G Oliveira A M F Oliveira-Campos M M MRaposo J Griffiths and A E H Machado ldquoFries rearrange-ment of dibenzofuran-2-yl ethanoate under photochemical andLewis-acid-catalysed conditionsrdquo Tetrahedron vol 60 no 29pp 6145ndash6154 2004
[18] M R Mauricio T D S Silva M H Kunita E C Muniz G MDe Carvalho and A F Rubira ldquoSynthesis of luminescent poly-carbonate grafted with methyl methacrylateeuropium com-plex using supercritical CO
2technology as a green chemistry
methodrdquo Journal of Materials Science vol 47 no 12 pp 4965ndash4971 2012
[19] J Jayaramudu G Siva Mohan Reddy K Varaprasad E RSadiku S Sinha Ray and A Varada Rajulu ldquoEffect of alkalitreatment on the morphology and tensile properties of CordiaDichotoma fabricpolycarbonate compositesrdquoAdvances in Poly-mer Technology vol 32 no 3 Article ID 21349 2013
[20] S E Morgan R Misra and P Jones ldquoNanomechanical and sur-face frictional characteristics of a copolymer based on benzoyl-14-phenylene and 13-phenylenerdquo Polymer vol 47 no 8 pp2865ndash2873 2006
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
6 International Journal of Polymer Science
[5] C Nguyen and J Kim ldquoSynthesis of a novel nitrogen-phospho-rus flame retardant based on phosphoramidate and its applica-tion to PC PBT EVA and ABSrdquoMacromolecular Research vol16 no 7 pp 620ndash625 2008
[6] S Krishnan and R J White US Patent 4772655 1988[7] P P Policastro P K Hernandez G C Davis and J D Rich US
Patent 4916194 1990[8] L N Lwis and S C Bunnel US Patent 4954549 1990[9] H L Vincent D J Kimball and R R Boundy ldquoPolysiloxane
silica hybrid resins abrasion resistant coatings for plastic sub-stratesrdquo Polymeric Materials Science and Engineering vol 50pp 143ndash146 1984
[10] T Ebeling MMMarugan Z Qu and S Siripurapu EuropeanPatent EP 1 624 025 A1 2005
[11] K Horisawa K Okada and W Zhou WO Patent 152741 A12008
[12] M Okamoto ldquoEffect of polycarbonate-poly(methyl methacry-late) graft copolymer as a modifier improving the surfacehardness of polycarbonaterdquo Journal of Applied Polymer Sciencevol 83 no 13 pp 2774ndash2779 2002
[13] S A Xu and S C Tjong ldquoTensile deformation mechanisms ofthe blends of polycarbonate with poly(methyl methacrylate)rdquoEuropean Polymer Journal vol 34 no 8 pp 1143ndash1149 1998
[14] L R Hutchings R W Richards R L Thompson A S Cloughand S Langridge ldquoInterface development in polycarbonatepoly(methyl methacrylate) bilayer filmsrdquo Journal of PolymerScience Part B Polymer Physics vol 39 no 20 pp 2351ndash23622001
[15] W-P Hsu ldquoSolvent effects on the miscibility of poly(methylmethacrylate)poly(bisphenol A carbonate) blendsrdquo Journal ofApplied Polymer Science vol 80 no 14 pp 2842ndash2850 2001
[16] K K Park H J Lee E H Kim and S K Kang ldquoFacile syn-thesis and photo-Fries rearrangement of 2-benzoyl-4-benzoy-loxyphenol leading to dibenzoyldihydroxybenzene derivativesrdquoJournal of Photochemistry and Photobiology A Chemistry vol159 no 1 pp 17ndash21 2003
[17] A M A G Oliveira A M F Oliveira-Campos M M MRaposo J Griffiths and A E H Machado ldquoFries rearrange-ment of dibenzofuran-2-yl ethanoate under photochemical andLewis-acid-catalysed conditionsrdquo Tetrahedron vol 60 no 29pp 6145ndash6154 2004
[18] M R Mauricio T D S Silva M H Kunita E C Muniz G MDe Carvalho and A F Rubira ldquoSynthesis of luminescent poly-carbonate grafted with methyl methacrylateeuropium com-plex using supercritical CO
2technology as a green chemistry
methodrdquo Journal of Materials Science vol 47 no 12 pp 4965ndash4971 2012
[19] J Jayaramudu G Siva Mohan Reddy K Varaprasad E RSadiku S Sinha Ray and A Varada Rajulu ldquoEffect of alkalitreatment on the morphology and tensile properties of CordiaDichotoma fabricpolycarbonate compositesrdquoAdvances in Poly-mer Technology vol 32 no 3 Article ID 21349 2013
[20] S E Morgan R Misra and P Jones ldquoNanomechanical and sur-face frictional characteristics of a copolymer based on benzoyl-14-phenylene and 13-phenylenerdquo Polymer vol 47 no 8 pp2865ndash2873 2006
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
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