Research Article Vegetable Oil Derived Solvent, and Catalyst...

Research ArticleVegetable Oil Derived Solvent and Catalyst Free lsquolsquoClickChemistryrsquorsquo Thermoplastic Polytriazoles

Michael C Floros1 Alcides Lopes Leatildeo2 and Suresh S Narine1

1 Trent Centre for Biomaterials Research Departments of Physics and Astronomy and Chemistry Trent University 1600 West BankDrive Peterborough ON Canada K9J 7B8

2 College of Agricultural Sciences Sao Paulo State University (UNESP) 18610-307 Botucatu SP Brazil

Correspondence should be addressed to Suresh S Narine sureshnarinetrentuca

Received 6 February 2014 Accepted 21 May 2014 Published 17 June 2014

Academic Editor Hongjuan Liu

Copyright copy 2014 Michael C Floros et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Azide-alkyne Huisgen ldquoclickrdquo chemistry provides new synthetic routes for making thermoplastic polytriazole polymersmdashwithoutsolvent or catalyst This method was used to polymerize three diester dialkyne monomers with a lipid derived 18 carbon diazide toproduce a series of polymers (labelled C18C18 C18C9 and C18C4 based on monomer chain lengths) free of residual solvent andcatalystThree diester dialkynemonomers were synthesized with ester chain lengths of 4 9 and 18 carbons from renewable sourcesSignificant differences in thermal and mechanical properties were observed between C18C9 and the two other polymers C18C9presented a lower melting temperature higher elongation at break and reduced Youngrsquos modulus compared to C18C4 and C18C18This was due to the ldquoodd-evenrdquo effect induced by the number of carbon atoms in the monomers which resulted in orientation ofthe ester linkages of C18C9 in the same direction thereby reducing hydrogen bonding The thermoplastic polytriazoles presentedare novel polymers derived from vegetable oil with favourable mechanical and thermal properties suitable for a large range ofapplications where no residual solvent or catalyst can be tolerated Their added potential biocompatibility and biodegradabilitymake them ideal for applications in the medical and pharmaceutical industries

1 Introduction

Dwindling reserves and price increases are driving researchfor alternatives to petrochemical feedstocks used in materialsand fuels Polymers derived from nonpetrochemical sourcesare becoming more viable and economical as improvementsin feedstock processing and technology are developed Onearea receiving significant attention is that of polymers derivedfrom vegetable oils Vegetable oils are abundant renewableand possess favourable properties including biofragmentabil-ity and biocompatibility compared to petrochemical analogs[1] They can be relatively easily converted and modified intoan ever-increasing variety ofmaterialswith diverse functionalproperties Triglycerides fatty acids alcohols and othermodified vegetable oil derived monomers have been used tocreate a large range of thermoset and thermoplastic polymerssuch as polyesters [2] polyurethanes [3 4] epoxides andpolyethers as well as thiol-ene and triazole based polymers

[5ndash7] Research targeted at improving the properties andscope of vegetable oil derived polymers is rapidly growing andinvolves multidisciplinary approaches

Environmentally favourable chemistries using benignconditions and producing little or no byproducts are thesubject of extensive research Polymers are generally synthe-sized using solvents andmetal catalysts Although tolerated atsmall levels for commodity polymers some solvents such asDMF and 12-dichlorobenzene and metal catalysts are toxicand potentially carcinogenic and are very hard to removeThis is particularly critical in biomedical and pharmaceuticalapplications where solvent and catalyst free synthesis routesare highly preferred [8] More generally it is important tolimit the use of catalyst and solvent because of toxicity andenvironmental concerns

Recently azide-alkyne Huisgen 13-dipolar cycloadditionhas begun to find its way into the repertoire of tools availableto green chemists [6] This reaction employs reactive

Hindawi Publishing CorporationBioMed Research InternationalVolume 2014 Article ID 792901 14 pageshttpdxdoiorg1011552014792901

2 BioMed Research International

ldquospring loadedrdquo terminal azide and alkyne groups to afford1-4- or 1-5-substituted 123-triazolesmdashdepending on thecatalyst Uncatalyzed reactions produce a mixture of the 14-and 15-substituents with the 14-[123-triazole] regioisomerfavoured by a ratio around 2 1 [9] The interest in the azide-alkyne Huisgen cycloaddition reaction was renewed in theearly 2000s after Barry Sharpless popularized the copper cat-alyzed variant and classified it as one type of ldquoclickrdquo chemistrya reactionwhich can rapidly and easily produce awide varietyof functional materials having high yields easy purificationshigh atomic economy and mimics nature [10 11] Someadvantages of azide-alkyne ldquoclickrdquo reactions include the lackof requirement for solvent or catalyst complete consumptionof reactants with no byproduct or gas formed and uniqueproperties of the triazole moiety [10 12 13] Triazole con-taining compounds have been found to possess antimicrobialand self-extinguishing characteristicsmdashthese are desirablecharacteristics in polymers [12] Polymerizations using azide-alkyne ldquoclickrdquo chemistry have been applied to various typesof monomers including vegetable oil triglycerides forminga series of cross-linked and thermoset polymers [6 14]The utility of azide and alkyne ldquospring-loadedrdquo reactantsas building blocks for complex molecules like polymersis beginning to be realized opening a door to producingmacromolecules with novel and unique functionality [15]

The goal of this work was to create lipid derived ther-moplastic polymers using the commonly available and eco-nomical feedstocks succinic acid azelaic acid and octadec-9-enedioic acidmdashall of which are produced from renewableresources [16] Succinic acid is produced by the bacterialfermentation of carbohydrates in a green process whichconsumes CO

2 It is a common commercial feedstock and

can be used to produce industrially important products suchas 14-butanediol and polyesters [17] Worldwide productionwas approximately 300 kt in 2010 and global demandhas beenestimated at 30mtyear while optimizations in productionmay lower costs to $036kg [18 19] Both azelaic acid andoctadec-9-enedioic acid are produced from oleic acid closelytying their price to that of the feedstock Azelaic acid isproduced on a commercial scale by the ozonolysis of oleicacid and used as a plasticizer and in polymers includingnylon 69 [20] Octadec-9-enedioic acid is produced by theself-metathesis of oleic acid or by biotransformation of 18carbon fatty acids using modified yeast fermentation [21 22]These renewable monomeric feedstocks provide comparableproperties to conventional petroleum derived products andare of growing importance as their supply improves and theprice of petroleum continues to increase

The intent of varying the chain length of the monomerwas to establish the degree of dependence on monomerchain length and degree of asymmetry Furthermore therelationship between even and odd chain length monomersknown as the odd-even effect can be probed by comparingthe properties of the azelaic acid based monomer (9 carbons)with the two other monomers each having an even numberof carbon atoms Polyesters with even carbon numberedmonomers demonstrate higher melting temperatures andenthalpies of fusion than their odd carbon number analogues[23 24]

In the present work three thermoplastic polytriazolesfrom diester dialkynes and a diazide monomer derivedfrom oleic acid (with the exception of the C4 dialkynewhich is produced from succinic acid a product of bac-terial fermentation of carbohydrates) were synthesized andcharacterized The numbers of carbon atoms in the diesterdialkyne monomers are 4 9 and 18 with 18 for the diazidemonomer This work presents a new route to the creationof melt-processable polymers from renewable vegetable oilswithout residual solvent or catalyst Furthermore becauseof the presence of unsaturated sites in the monomers itmay be possible to perform polymerization on a suitablesubstrate in situ and furthermodify the unsaturation to afforda potentially biocompatible polymer with easily tunablefunctionalities

2 Experimental

21 Materials Azelaic acid (98) oleic acid (85) sodiumazide (99) propargyl alcohol (99) 4-toluenesulfonylchloride (98) triethyl amine (99) succinic acid (99)Grubbs catalyst 2nd generation LiAlH

4(95)NN1015840-dicyclo-

hexylcarbodiimide (DCC) (99) and 4-dimethylaminopy-ridine (DMAP) (99) were purchased from Sigma-Aldrichand used as received (119864)-octadec-9-ene-118-diol and (119864)-118-octadec-9-endiacid were synthesized using a previouslyreported procedure [3] that is the olefin metathesis of oleicacid followed by the subsequent reduction of the diacid intothe dialcohol

3 Methods

31 Synthesis of Monomers Oleic acid was converted intoa dicarboxylic acid through olefin metathesis reduced intoa dialcohol tosylated and finally azidated into a diazide(Scheme 1) Three diester dialkynes monomers were sub-sequently synthesized from dicarboxylic acids of differentcarbon lengthsmdash(119864)-118-octadec-9-endiacid (C18) azelaicacid (C9) and succinic acid (C4) through either Steglich orFischer esterification (Scheme 2)

(E)-Octadec-9-ene-118-diyl bis(4-methylbenzenesulfonate)(1) (119864)-Octadec-9-ene-118-diol (120 g 422mmol) wasadded to a round bottom flask kept in an ice bath (0∘C)4-Toluenesulfonyl chloride (182 g 954mmol) dissolvedin 150mL of CH

2Cl2and was added dropwise then 030 g

(25mmol) of DMAP and 120 g (119mmol) of triethylaminedissolved in 20mLCH

2Cl2was added dropwiseThe reaction

was allowed to warm to room temperature and proceededuntil complete consumption of the starting material asdetermined by TLC (approximately 6 hours Rf = 030 5 1hexaneethyl acetate) The contents of the flask were dilutedwith 150mL CH

2Cl2and washed with water (3 times 150mL)

25 N HCl solution (3 times 150mL) 4 aqueous sodiumbicarbonate (3 times 150mL) and finally saturated NaCl brine(3 times 150mL) The organic layer was dried with anhydrousNa2SO4and concentrated under reduced pressure yielding

223 g of slightly yellow crystal The solid product was

BioMed Research International 3

O O

O

OH

OH

OHHO

S SO

OO

O

N3N3

(a)

(b)

(c)

(d)

Scheme 1 Synthesis of vegetable derived diazide monomer (a) Grubbs 2nd gen neat 45∘C 12 h (b) LiAlH4 THF 0∘C rarr RT 4 h (c) TsCl

TEA DMAP CH2Cl20∘C rarr RT 6 h (d) NaN

3 DMSO H

2O 100∘C 12 h

OO

OO

O O

R

R

OHHO

(a) or (b)

Scheme 2 Synthesis of vegetable derived dialkyne monomers(a) For saturated dicarboxylic acids propargyl alcohol + 5 dropsH2SO4 toluene 100∘C 12 h (b) For unsaturated dicarboxylic acid

DCCDMAP CHCl3 50∘C 12 h

purified by recrystallization from hexanes twice and dried ina vacuum oven 180 g of a white solid was recovered (72yield) 1H-NMR (500MHz in CDCl

3) 120575 121 (m 20H) 162

(p 4H) 194 (m 4H) 245 (s 6H) 401 (t 4H) 536 (dtt 2H)734 (d 4H) and 779 (d 4H)

(E)-118-Diazidooctadec-9-ene (2) 82 g of (1) was added to around bottom flash equipped with a reflux condenser 90mLof DMSO was added and 120 g of NaN

3dissolved in 10mL

deionized water was introduced with stirring Immediatelyfollowing addition the reaction turned slightly yellow andwas warm to the touch It was heated to 100∘C and stirred for12 hours at this temperature Upon completion the mixturewas cooled to room temperature and poured into 250mL ofice water to precipitate the product and separate the DMSOinto the aqueous phase The organic layer was extracted withethyl acetate (3times150mL) andwashedwith water (2times150mL)and NaCl brine (2 times 150mL) The organic phase was driedoverNa

2SO4and concentrated under reduced pressure It was

then purified by column chromatography on silica gel usinga 50 1 ratio of hexanes to ethyl acetate to afford a colourlessliquid (43 g yield = 93) 1H-NMR (500MHz in CDCl

3) 120575

129 (m 20H) 159 (p 4H) 196 (m 4H) 325 (t 4H) and 538(dtt 2H)

(E)-Di(prop-2-yn-1-yl) octadec-9-enedioate (3) (119864)-118-octadec-9-ene diacid (200 g 64mmol) was added toa round bottom flask with 200mL of chloroform andheated to 50∘C The mixture was stirred until it becameclear and then 789 g propargyl alcohol (140mmol) wasadded to the flask NN1015840-dicyclohexylcarbodiimide (289 g140mmol) in 50mL CHCl

3was added dropwise with 05 g

4-dimethylaminopyridine (DMAP) over 30min A refluxcondenser was then equipped and the solution was stirredfor 12 hours at 50∘C then cooled to room temperature andfiltered over celite to remove precipitated dicyclohexylureaThe chloroform was removed under reduced pressure andthe compound was dissolved in hot hexanes and filteredwhile hot over celite The product was recrystallized fromhexanes twice with only the trans product recovered anddried in a vacuum oven overnight to yield 204 g of a whitepowder (yield 82) 1H-NMR (500MHz in CDCl

3) 120575 131

(m 16H) 165 (quin 4H) 197 (m 4H) 236 (t 4H) 247 (t2H) 468 (d 4H) and 538 (dtt 2H)

Di(prop-2-yn-1-yl) nonanedioate (4) Azelaic acid (100 g53mmol) was added to a round bottom flask with 75mLtoluene and heated to 100∘CThemixture was stirred until thesolution became clear then 20mL (347mmol) of propargylalcohol was added Five drops of concentrated sulfuric acidin 2mL toluene was slowly added to the mixture and thesolution was stirred for 12 hours The reaction was cooled toroom temperature and then it was diluted with an additional75mL toluene and washed with water (3 times 100mL) thena sodium bicarbonate solution (3 times 100mL) and finallysaturated NaCl brine (2 times 100mL) The organic layer wasdried with anhydrous sodium sulfate and concentrated underreduced pressure The product was purified by vacuumdistillation at 150 mtorr and the fraction boiling between133∘C and 136∘C collected as a colourless liquid (1160 g yield


83) 1H-NMR (500MHz in CDCl3) 120575 132 (m 6H) 163 (m

4H) 235 (t 4H) 247 (t 2H) and 467 (d 4H)

Di(prop-2-yn-1-yl) succinate (5) Succinic acid (100 g847mmol) was added to a round bottom flask with 75mLtoluene and heated to 100∘C The mixture was stirred untilthe solution became clear and 20mL propargyl alcohol(357mmol) was added 5 drops of concentrated sulfuricacid in 2mL toluene was then slowly added to the mixtureand the solution was stirred for 12 hours The reaction wascooled to room temperature then the mixture was dilutedwith an additional 75mL toluene and washed with water(3 times 100mL) then a sodium bicarbonate solution (3 times100mL) and finally with saturated NaCl brine (2 times 100mL)The organic layer was dried with anhydrous sodium sulfateand concentrated under reduced pressure The product waspurified by vacuum distillation at 160 mtorr and the fractionboiling between 89∘C and 91∘C was collected as a colourlessliquid (1406 g yield 85) 1H-NMR (500MHz in CDCl

3) 120575

248 (t 2H) 269 (s 4H) 469 (d 4H)

32 Polymerization Equal molar ratios of a dialkynemonomer and a diazide monomer were added to a polytetra-fluoroethylene (PTFE) round bottom flask The flask waspurged with nitrogen for 15 minutes then placed in an oilbath under nitrogen protection and heated from roomtemperature to 110∘C gradually over a 2-hour period toprevent thermal decomposition of the reactants in theexothermic polymerization It was then stirred for anadditional 20 hours at this temperature The polymerproduct was cooled to room temperature and cast intofilms by melting at 170∘C inside a stainless steel mold(70 times 30 times 06mm) covered with a sheet of PTFEThemoltensample was pressed on a Carver 12-ton hydraulic heatedbench press (Model 3851-0 Wabash IN USA)Three metrictons of pressure were applied isothermally for 15min to themold The sample was then cooled to 20∘C over 30min bypumping coolant through the plates on the hydraulic pressperiod using a Julabo temperature controlled circulatingbath (Model FP50-ME Seelbach Germany) The polymerfilm was stored in a sealed container until analysis

33 Characterization Techniques The 1H spectra wererecorded on a Varian Unity-INOVA at 499695MHz1H chemical shifts were internally referenced to CDCl

3

(726 ppm) for spectra recorded in CDCl3and 719 ppm for

spectra recorded in 12-dichlorobenzene-1198894 All spectra were

obtained using an 86120583s pulse with 4 transients collectedin 16202 points Datasets were zero-filled to 64000 pointsand a line broadening of 04Hz was applied prior to Fouriertransforming the sets The spectra were processed in ACDLabs NMR Processor version 1201

In a typical 1H NMR of the monomers vinylic pro-tons minusCH=HC= present around 120575 538 ppm and allylicminusC=CHminusCH2minus at 120575 197 In the alkyne monomers thepropargylic proton minusC(=O)OCH

2CequivCH appears at 120575 247-

248 ppm and the minusC(=O)OCH2CequivCH appears at 120575 467ndash469 ppmThe ester minusCH2C(=O)Ominus occurs at 120575 235-236 for

the C9 and C18 alkynes but is shifted to 120575 269 ppm in the C4monomer due to the close proximity of the ester groups toeach other In the tosylate intermediate shifts at 120575 734 ppmand 120575 779 ppm both correspond to different sets of protonson the aromatic ring and the benzylic minusBzminusCH3 presents at120575 245 The tosylate ester influences both the minusCH2OSminus andminusCH2CH2OSminus with shifts appearing at 120575 401 and 162 ppmrespectively Furthermore in the azide monomer we seea disappearance of the indicative shifts of the tosyl groupThe minusCH2N3 presents at 120575 325 ppm and ndashCH2CH2N3 at159 ppm The remaining alkane minusCH

2CH2CH2- protons fall

between 120575 121 and 145 ppmThermogravimetric Analysis was conducted on a TGA

Q500 (TA Instruments Newcastle DE USA) The sample(10ndash20mg) was heated from room temperature to 600∘C ata rate of 100∘Cmin under a nitrogen flow of 600mLminCalorimetry studies were performed following ASTM E1356standard on a DSC Q200 (TA Instruments Newcastle DEUSA) equipped with a refrigerated cooling system Thesample (5-6mg) was initially heated to 180∘C for 10min toremove thermal history and then cooled at a rate of 50∘Cmindown to minus80∘C where it was held isothermally for 5minFinally the sample was heated from minus80∘C to 180∘C at a rateof 50∘Cmin

Dynamic mechanical analysis (DMA) measurementswere carried out following ASTMD7028 standard on a Q800(TA Instruments Newcastle DE USA) analyzer equippedwith a liquid nitrogen cooling system The sample was cutinto a rectangular shape (175mm times 120mm times 060mm) andwas analyzed in the single cantilever bending mode It washeated at a constant rate of 10∘Cmin from minus100∘C to 40∘CThemeasurements were performed at a frequency of 1Hz andfixed oscillation displacement of 15120583m

Tensile tests were performed according to ASTM D882standard using a mechanical analyser (Texture TechnologiesCorp NJ USA) equipped with a 25-kg load cell The filmwas die-cut by an ASTMD638 type V cutter The sample wasstretched at a rate of 60mmmin from a gauge of 35mm atroom temperature

ATR-FTIR spectra were collected using a Thermo Sci-entific Nicolet 380 FTIR spectrometer (Thermo ElectronScientific Instruments LLC USA) fitted with a PIKEMIRacleattenuated total reflectance (ATR) system (PIKE Technolo-gies Madison WI USA) 060mm thick polymer sampleswere placed onto theATR crystal and pressed by amechanicalarm Spectra of the polymer films were acquired over ascanning range of 500ndash4000 cmminus1 for 128 repeated scansat a spectral resolution of 04821 cmminus1 16 repeated scanswere used for monitoring the polymerization The data wasbackground corrected and baselined by themachine software(EZOMNIC version 73) and exported in spreadsheet formatfor graphing

The crystalline structure and relative crystallinity ofthe polymers were examined by wide-angle X-ray diffrac-tion (WAXD) using an EMPYREAN diffractometer system(PANanalytical Netherlands) equipped with a filtered CundashK120572 radiation source (120582 = 1540598 A) and a PIXcel3D detectorThe scanning range was 20062∘ndash30000∘ (2120579) with a step


size of 00263∘ Data analysis was performed using PANa-lyticalrsquos XrsquoPert HighScore 304 software The relative degreeof crystallinity was estimated according to a well-establishedprocedure [27]The percentage degree of crystallinity (119883

119862) is

calculated by

119883119862= 100 times

119860119862

119860119862+ 119860119860

(1)

where 119860119862is the area under the resolved crystal diffraction

peak contribution and 119860119860

is the area of the amorphouscontribution

4 Results and Discussion

Vegetable derived dicarboxylic acids with 119899 = 4 9 and 18carbon atoms were transformed into a dialkyne terminateddiester monomers The length of the dialkyne was variedby choosing three economically priced and plant deriveddicarboxylic acids succinic acid (C4) azelaic acid (C9) andoctadec-9-enedioic acid (C18) The choice of ester linkageswas made because they are simpler to synthesize from car-boxylic acids which are readilymanufactured from vegetabletriglycerides on a commercial scale Ester linkages have alsobeen shown to add biodegradability to polymers [28] Thediazide monomer (119864)-118-diazidooctadec-9-ene which wasprepared from the same C18 diacid has 18 carbon atomsseparating two high energy (azide) nitrogen groups Thesignificance of this is that the ratio of 3 carbon to 1 nitrogenatoms fulfills an important safety consideration for azidesThis ratio is generally accepted as sufficient to prevent therapid decomposition or explosion of azide groups and toallow safe storage and processing [29]

41 Polymerization and Characterization of the PolymersIn solvent polymerization the solvent can aid in dissipat-ing heat of exothermic events which was not possible inthis system To circumvent this issue the monomers weregradually oligomerized by heating to the polymerizationtemperature (110∘C) over 2 hours with stirring The viscosityincreased gradually as oligomerization proceeded allowingprolonged mixing (which did not occur with rapid heating)Characterization of the polymer molecular weights was notpossible due to poor solubility in common solvents includingDMFDMSOCHCl

3 CH2Cl2 THF 12-dichlorobenzene119873-

methyl-2-pyrrolidone methanol 2-propanol diethyl etherethyl acetate acetone hexanes and acetonitrile1H NMR of the polymers in 12-dichlorobenzene-119889

4

was run at 45∘C for improved polymer solubility Thistemperature was a good compromise between increasingsolubility and thermal noise 1H NMR spectrum of C18C9representative of the C18C119899 polymers is shown in Figure 1 (Amagnified proton NMR spectra of the polymer C18C9 fromFigure 1 showing enhanced resolution of the triazole regionshifts is provided in Figure S1 in the Supplementary Materialand available online at httpdxdoiorg1011552014792901)The limited solubility of the polymer caused significantline broadening of the NMR peaks but the characteristicpeaks for both the 14-(at 120575 747) and the 15-substituted

C 6D4Cl

2

C 6D4Cl

2

C C

CCOC

C O

H

H

H2

H2

N

NN N

N NCH2

CH2

Inte

nsity

10 8 6 4 2 0

Chemical shift (ppm)

b998400

b

b

998400

a998400

aa

998400

c998400

cc

ca

b

998400

Figure 1 Select 1H NMR spectra of C18C9 showing labelled peaksfor the 15 (a1015840 b1015840 and c1015840) and 14-substituted (a b and c) 123-triazoles

123-triazoles (at 120575 762) were observed in all the polymersamples As can be seen in Figure 1 no signals were detectedfor characteristic protons of the azide (ndashCH2N3 120575 325)or alkyne (ndashCequivCndashH 120575 246) groups on the monomersindicating complete conversionThe ratio of the 14- to the 15-substitution estimated by integrating the area of each triazoleCndashH peak was 2 1

Selected ATR-FTIR spectra obtained during themonitor-ing of the polymerization of C18C18 are shown in Figure 2(a)ATR-FTIR spectra of the polymers are shown in Figure 2(b)The characteristic azide peak (ndashN=N=N) (i 2091 cmminus1 inFigure 2(a)) and alkyne peaks (equivCndashH and ndashCequivC) (ii 3290and iii 2128 cmminus1 in Figure 2(a) resp) which were presentin the spectra of the starting materials were absent from thespectra of the polymers In fact as the reaction progressedthese peaks decreased in intensities and disappeared after 20hours at 110∘C Concomitantly the characteristic triazole ringpeak (at 3142 cmminus1) [30] appeared after 2 hours reaction timeand increased steadily in intensity until the monomers werecompletely reacted

The triazole grouprsquos CndashH bond is known to be a hydrogenbond donor resulting from the increased electronegativityof carbons within the triazole ring [31] The sharp peakat 1736 cmminus1 in all the polymers represents the free estercarbonyl C=O stretch Only one peak representing the estercarbonyl C=O stretch is visible in the FTIR of C18C18 anda second peak was observed at 1730 cmminus1 and 1720 cmminus1 forC18C9 andC18C4 (see insert in Figure 2(b)) respectivelyThesecond peak emerged as a shoulder for C18C9 and as a well-resolved peak for C18C4 The splitting or shifts in the estercarbonyl C=O stretching peak are a common indicator ofhydrogen bonding in polymers [32]The shift inwavenumberand increasedmagnitude of the split peak suggest that a largeramount of carbonyl groups are hydrogen bound in C18C4

The peak at 1222 cmminus1 was very intense in C18C18 com-pared to the other two polymers It is characteristic of triazoleself-association where triazoles hydrogen bond to each other


(i)

(iii)(ii)

Azide

C9 dialkyne

C18C9

(iv) 50

Abso

rban

ce

3500 3000 2500 2000 1500 1000

Wavenumber (cmminus1)

(a)

C18C18

C18C9

C18C4

Abso

rban

ce

3000 2500 2000 1500 1000


(b)

Figure 2 (a) ATR-FTIR of the azide monomer (characteristic peak i 2091 cmminus1) alkyne monomer (characteristic peaks ii 3290 and iii2128 cmminus1) and polymer C18C9 showing formation of a triazole (characteristic peak iv 31445 cmminus1) (b) FTIR spectra of the C18C4 C18C9and C18C18 polymers Arrow points to the triazole self-association absorption peak at 1222 cmminus1 Insert is a higher resolution zoom into thecarbonyl region

[33] suggesting that hydrogen bonding is occurring betweenthe triazole rings of C18C18 (NndashHsdot sdot sdotN bonding Figure 3)Furthermore the lack of a carbonyl peak splitting in this poly-mer suggests that hydrogen bonding is predominantly basedon a triazole self-association mechanism The 1222 cmminus1peak is absent for the C18C9 polymer and small in C18C4indicating that a minority of the hydrogen bonding in thesetwo polymers occurs through self-association

The hydrogen bonding structures which are consistentwith the FTIR data of the polymers are presented in Figure 3In C18C18 hydrogen bonding is occurring primarily betweentriazole groups whereas in C18C9 and C18C4 it occurspredominantly between the triazole and carbonyl groups(Figure 3) Note that in C18C9 some of the hydrogen bonddonating groups (triazole CndashH) are unable to participate inhydrogen bonding due to their relative orientation a result ofthe odd carbon number of its 9 carbon diester repeating unitgiving rise to the known odd-even effect

42 Thermal Properties TheDSC heating profiles (5∘Cmin)of the polymers followed by the subsequent cooling(5∘Cmin) are shown in Figure 4(b) and the correspondingthermodynamic data are listed in Table 1 The heating ther-mograms of the polymers (Figure 4) revealed four transi-tions a glass transition then an exothermic recrystallizationfollowed by melting endotherms C18C4 and C18C18 pre-sented two well-resolved melting peaks and C18C9 exhibitedconvoluted peaks One can note that C18C9 and C18C18presented similar glass transition temperatures (119879

119892= minus300 plusmn

16∘C) recrystallization temperatures (119879

119877= 120 plusmn 17∘C

and 116 plusmn 04∘C resp) and peak temperatures of melting(119879 = 658 plusmn 07∘C and 644 plusmn 02∘C resp) However peaktemperature of the secondmelt was relatively higher inC18C9(1198791198722

= 865plusmn01∘C) compared toC18C18 (1198791198722

= 735plusmn12∘C)

The enthalpy of the first and second endotherms in C18C9was 60 plusmn 08 and 141 plusmn 02 Jg respectively and in C18C18was 30 plusmn 03 Jg and 305 plusmn 09 Jg respectively The peaktemperature of the two endotherms in C18C4 were at 975 plusmn14 and 1213 plusmn 15∘C significantly higher than in C18C9 andC18C18

The presence of two melting peaks is often observed inpolymers upon cold crystallization or crystallization from themelt [34] In polyurethanes the melt recrystallization formsan incomplete poorly organized crystalline polymorph orliquid crystal [35] The enthalpy measured for the firstendotherm of all of the polymers was approximately equal tothe enthalpy of the recrystallization peak suggesting that thelower melting peak (119879

1198721) corresponds to the portion which

has recrystallizedThe enthalpy of the second endothermwasroughly equal to the enthalpy measured for the exothermobtained during the crystallization from the melt (coolingrate of 5∘Cmin) in each polymer (Table 1) This indicatesthat the second endotherm is attributable to the meltingof a more stable phase that has been formed during thecooling from the melt of the sample Taking into account theodd-even effect the melting point for the polymers of thisstudy followed common trends observed in polyesters whereshorter monomer chain length imparts higher melting points[36] The odd-even effect manifested in C18C9 where thenumber ofmethylene carbons between the two ester groups isodd resulting in the ester groups repeating symmetrically onthe same side of the chain (Figure 2)This configuration limitsthe accessibility of hydrogen bonding when compared to aneven number of methylene atoms between the esters placingldquoterminal groupsrdquo of each monomer on opposing sides Anexplanation of this effect based on the odd-evens reductionin crystallinity has been previously used in polyesters wheremonomers from odd-chain length exhibit reduced enthalpiesof melt and crystallization [37] The density of triazole


NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NNN

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

C18C9

O

O

NNN

NN N

O

O

O

O

NNN

NN N

H

H

H

H

O

O

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

OO

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

C18C18

C18C4

Figure 3 Schematic representation of the structure and hydrogen bonding of the polymers

Table 1 Thermodynamic data obtained from the DSC cooling and heating cycles of C18C18 C18C9 and C18C4 polymers

Polymer 119879119862(∘C) Δ119867

119862(∘C) 119879

1198981(∘C) 119879

1198982(∘C) Δ119867

1198981(Jg) Δ119867

1198982(Jg) 119879

119877(∘C) Δ119867

119877(Jg)

C18C4 509 plusmn 04 276 plusmn 44 975 plusmn 14 1213 plusmn 15 129 plusmn 15 141 plusmn 02 120 plusmn 17 61 plusmn 10C18C9 200 plusmn 11 139 plusmn 02 658 plusmn 07 735 plusmn 12 60 plusmn 08 mdash mdash mdashC18C18 408 plusmn 08 324 plusmn 28 644 plusmn 02 865 plusmn 01 30 plusmn 03 305 plusmn 09 116 plusmn 04 35 plusmn 05Crystallization temperature (119879119862) and crystallization enthalpy (Δ119867119862) melting temperatures (1198791198981 and 1198791198982) and enthalpy of melt (Δ1198671198981 and Δ1198671198981)temperature of recrystallization119879119877 and enthalpy of recrystallization (Δ119867119877) Values and uncertainties attached are respectively average and standard deviationof triplicates

hydrogen bonding within a polymer has previously beendemonstrated to be a factor influencing the glass transitiontemperature of polymers and dictatingmany thermal proper-ties as well [38] In the study by Binauld et al monomers withequal carbon numbers were synthesized with both ester andether linkages then polymerized into polytriazoles containing

only ether linkages polytriazoles with ester linkages onlyand a copolymer consisting of both They reported thatthermal properties including melt temperature and glasstransition were minimally affected by exchanging the esterand ether groups suggesting that the triazole group waspredominantly dictating the polymersrsquo thermal properties


Table 2 WAXD data obtained for C18C18 C18C9 and C18C4 polymers at room temperature

Polymer Monoclinic phase Triclinic phase Relative crystallinity ()hkl 119889 (A) hkl 119889 (A)

C18C4 (100) 437 (100) 452 206(010) 386 (110) 396

C18C9 (100) 444 (002) 430 151(010) 389

C18C18 (100) 440 mdash mdash 263(010) 391

119889 Bragg distances (hkl) corresponding indices

Hea

t flow

(Wg

)Ex

o up

C18C4

C18C9

C18C18

minus50 0 50 100 150

Temperature (∘C)

TgTR

TM1 TM2

01

(a)

Hea

t flow

(Wg

)Ex

o up

minus50 0 50 100 150

Temperature (∘C)

C18C4

C18C9

C18C18

Tc

01

(b)

Figure 4 DSC heating (a) and cooling (b) thermograms of C18C18C18C9 and C18C4 polymers119879

119892= glass transition temperature119879

119877=

recrystallization temperature 119879119888= crystallization temperature and

1198791198721

and 1198791198722

= peak melt temperatures

[38] Our findings suggest that an odd length chain in apolytriazole significantly reduces the melt and crystallizationenthalpies of that polymer when compared with even lengthchains

43 Crystal Structure of the Polymers WAXD spectra ofthe polymers are shown in Figure 5(a) and correspondingd-spacing and Miller indices of the crystal reflections arelisted in Table 2 As can be seen the experimental WAXDprofiles of all the polymer samples consisted of resolveddiffraction peaks superimposed to a relatively largewide haloindicative of the presence of an amorphous phase This typeof WAXD patterns is commonly observed in semicrystallinepolyurethanes [39] The amorphous contribution was sub-tracted using HighScore V304 software and the resultingWAXDspectra of the polymerswith only the crystal peaks areshown in Figure 5(b) The WAXD lines were indexed usingdata obtained from similar compounds found in the literature[2 40]

C18C18 presented two lines at 440 A (100) and 391 A(010) characteristic of the monoclinic subcell similarly towhat was reported for vegetable oil derived poly (ester-urethanes) [2] C18C9 presented the two monoclinic peaksdetected in C18C18 at 444 A (100) 389 A (010) and anadditional peak at 430 A (002) a reflection associated witha triclinic subcell [40] In C18C4 the two monoclinic peaksslightly shifted to 437 A (100) and 386 A (010) and twonew reflections from the triclinic phase appeared at 452 A(100) and at 396 A (110) [2 40] The data obtained for thecrystalline phases of the polymers are consistent with theproposed bonding structures C18C18 shows a single crystalstructural phase compatible with predominantly hydrogenbonding whereas C18C9 and C18C4 showed coexistingtriclinic and monoclinic crystalline phases which can berelated to the two bonding types suggested for these twopolymers

44 Thermal Gravimetric Analysis TGA and DTG curves ofthe polymers are shown in Figures 6(a) and 6(b) respec-tively C18C18 and C18C9 exhibited very similar degradationprofiles characterized by a DTG with two well-resolvedpeaks indicative of a two-step degradation process Bothpolymers presented onsets of degradation (at 5 weightloss) at sim360∘C and maximum rate of weight loss (DTGpeak) at approximately 460∘C The onset of degradation of(5 weight loss) of C18C4 was measured at 306∘C a muchlower temperature than the two others Furthermore its DTGpresented four resolved peaks two of which corresponded tothose observed in C18C9 and C18C18 and two others at 352∘C


16 18 20 22 24 26

Scattering angle 2120579 (deg)

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)

Figure 5 (a) Representative WAXD spectra of the polymers at room temperature and (b) crystal contributions to the WAXD spectra aftersubtracting the baseline and amorphous contributions Subscripts 119879 and119872 of the Miller indices (hkl) are for the triclinic and monoclinicstructures respectively

Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)

Figure 6 (a) TGA and (b) DTG curves of C18C18 C18C9 and C18C4 polymers

and 446∘C The DTG of C18C4 in fact appeared to be thesuperimposition of two similar thermal degradation profilesone occurring after the other This suggests the presence oftwo phases which although degrading through the samemechanisms did involve different atomic environments

The first decomposition peak in the DTG (Figure 6(b))for C18C4 is broad and represents a higher area than theother two due to the shorter chain length and greater estercontribution to the polymersrsquo weightThis peak is commonlyassociated with ester degradation in polyesters [2] Whenthe two ester groups are closest to each other as in C18C4the electron withdrawing effect of the ester groups in closeproximity to the electronegative triazole is strongest on the2 120572-carbon atoms between the esters [41] This may beresponsible for the more rapid degradation

45 Mechanical Properties The viscoelastic properties of thepolytriazoles were studied using DMA The loss modulusstorage modulus and tan 120575 of the polymers are shown inFigures 7(a) to 7(c) respectively Loss modulus and tan 120575versus temperature curves indicated homogeneous systemswith single glass transitions The prolonged glass transitionobserved by DSC is probably due to enthalpy of relaxationeffects The first peak observed at simminus85∘C is attributableto the so-called 120573 transition As clearly seen in the lossmodulus graph in Figure 7(a) the 120573-transitions in C18C4were much more intense than C18C9 and C18C18 whereit was very weak This transition may be attributed tothe limited mobility of the ester carbonyl group or theshorter methylene chain segments both of which increasethrough the series from 119899 = 4 to 18 [42 43] This would


Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0

minus100 minus80 minus60 minus40 minus20 0 20 40

Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)

Figure 7 Representative DMA results of C18C18 C18C4 and C18C9 polymers (a) Loss modulus (b) storage modulus and (c) tan 120575

explain the reduction and disappearance of the peak withincreasing 119899 as the chain length increased its mobility woulddecrease

In Figure 7(b) the storage modulus in the glassy andleathery regions are the highest value for C18C4 and lowestfor C18C18 In the rubbery region storage modulus is thesame for the three polymers The sharp drop in the storagemodulus around minus40 to minus10∘C represents the beginning ofthe transition from the glassy to rubbery state The 119879

119892of

C18C18 and C18C9 as determined from the peak tan 120575 curveFigure 7(c) was found to be very close (minus164 plusmn 02 andminus128plusmn08

∘C) and significantly lower than that ofC18C4 (66plusmn11∘C Table 3) The trends observed for 119879

119892as measured by

DMA can be explained in terms of the structural differencesbetween the polymers and related to the competing effects ofthe hydrogen bonding introduced by the triazole groups andthe esters contributions which in fact determine a ldquohydrogenbond density and distributionrdquo Note that the trends in the119879119892obtained by DMA in Table 3 mirrored those recorded by

Table 3 Glass transition temperature (119879119892) as determined by DSC

and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (

∘C)C18C4 minus118 plusmn 07 66 plusmn 11C18C9 minus300 plusmn 13 minus128 plusmn 08C18C18 minus300 plusmn 16 minus164 plusmn 02Values and uncertainties attached are respective average and standarddeviations of triplicates

DSC although the DMA was more resolved as it was able todetect a 119879

119892difference between C9 and C18

Stress-strain curves of the polymers are shown inFigure 8(a) Tensile properties range from relatively brittle toductile thermoplastics with elongation to break percentagescomparable to LDPE for C18C9 Youngrsquos modulus (E) closelyfollowed the degree of crystallinity of the polymer In factas shown in Figure 8(b) representing both 119864 and 119883

119862 the


Table 4 Mechanical properties of the polymers in this study compared to three common commercial polymers

Youngrsquos modulus(MPa)

Elongation at break()

Ultimate tensile strength(MPa)

Polymers in this studyC18C4 1822 plusmn 50 396 plusmn 38 111 plusmn 04C18C9 1185 plusmn 63 1966 plusmn 165 148 plusmn 15C18C18 1960 plusmn 41 107 plusmn 38 103 plusmn 05

Polymers for comparisonCommercial LDPE [25] 140ndash300 200ndash900 7ndash17Vegetable Oil derived Cross-linked polytriazole [6] Not Reported 311ndash610 062ndash339Vegetable Oil derived thermoplastic polyurethane [26] 07ndash111 25ndash600 13ndash56

Values and uncertainties attached are respectively average and standard deviation of triplicates

two parameters are strongly correlated This is not surprisingas the effect of crystallinity on polymers Youngrsquos moduli iswell known [44] All three of the polymers in this study haveYoungrsquos moduli comparable with LDPE (Table 4)

The elongation at break of the less crystalline C18C9 was1966 plusmn 165 much higher than C18C4 at 396 plusmn 38 andC18C18 at 107 plusmn 38 (Table 4) This result can be explainedby differences in hydrogen bonding and crystallinity A lowerhydrogen bonding density caused by the odd-even effectresults in decreased crystallinity in C18C9 (Figure 8(b))

46 The Odd-Even Effect on the Physical Properties As thepredominating hydrogen bonding mechanism shifts fromtriazole self-association to triazolemdashcarbonyl on shorteningof the diester chain segment a transition in properties isobserved with C18C9 presenting mid-way characteristicsFTIR data suggests that the hydrogen bonding from triazole-triazole and triazole-ester hydrogen bonding is reduced inC18C9 compared to C18C18 and C18C4 The crystallinity ofthe C18C9 polymer was also significantly reduced Previousstudies have shown that odd-carbon length monomers canprevent up to 50 of the hydrogen bonding interactionsdue to altered orientations [45] An odd carbon numbercan also create repulsive interactions between the flippedcarbonyl groups with the chain due to the close stackingof the ester groups [45] In contrast an even-carbon lengthmonomer allows the groups on each terminus to be in oppo-site relative orientations allowing more ordered hydrogenbonding networks and more favourable packing [45] Theodd-even effectrsquos influence in crystallinity has also been welldocumented in polyurethanes [46] Similar findings for avariety of hydrogen bonding systems including nylon [47]glucoseamide polymers [48] polycarbonate [45] fatty acids[49] fatty alcohols [50] and polyesters [37] describe similartrends The findings of this study are consistent with thepolymer chains of C18C9 being adapted into contractedsterically unfavourable configurations forming disordered orreduced hydrogen bonding similar towhat has been reportedfor nylon [45] and polyurethane [46] The diester dialkyneswith odd carbon number chain length form polymers with

both the ester and triazole groups on the same side alter-ing the degree of crystallinity melting and crystallizationtemperatures glass transition temperatures and mechanicalproperties

5 Conclusions

Three novel thermoplastic polytriazoles were produced byuncatalyzed and solvent free polymerization of vegetable oilderived diester alkyne and diazide monomers The threedialkynes were synthesized from economically priced suc-cinic acid (C4) azelaic acid (C9) and oleic acid (C18) Thediazide monomer prepared from C18 diacid had a ratio of 3carbon to 1 nitrogen atoms generally accepted as sufficient toprevent the rapid decomposition or explosion of azide groupsand to allow safe storage and processing

The monomers and polymers were fully characterized byNMR and ATR-FTIR Crystal structure thermal behaviorand mechanical properties of the polymers measured usingXRD TGA DSC DMA and tensile test were related tothe structural details of the repeating unit compared andcontrasted to the paper The trends observed in the thermalbehaviour and mechanical properties of the polymers wereexplained based on differences in their crystallinity and abil-ity to hydrogen bond The polymers synthesized from evenchain length monomers had significantly higher crystallinityhigher melting points and melt enthalpy higher Youngrsquosmodulus values and lower elongation-to-break percentageswhen compared with the odd chain length monomer Thecrystallinity and melt and crystallization enthalpies of C18C9were approximately half of those of the other polymersThe odd-even effect which dictates ordering of groups insymmetrical or asymmetrical configurations based on themonomer chain length was used to explain this behaviourThe differences observed in physical property between thepolymers are consistent with the presence of two differ-ent hydrogen bonding systems hydrogen bonding betweenestermdashtriazole groups and triazolemdashtriazole groups C18C18was suggested to have predominantly estermdashtriazole hydro-gen bonding C18C4 predominantly triazolemdashtriazole hydro-gen bonding and the third polymer C18C9 which has an odd


16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)

Figure 8 (a) Representative stress strain curves for of C18C18 C18C4 andC18C9 polymers (b) Youngrsquosmodulus (e) and relative crystallinity(998771) of the polymers Error bars represent standard deviation from at least triplicates

carbon length monomer a mixture of these two hydrogenbonding systems This work advances effective routes forldquogreenrdquo polymerization and provides a catalyst and solventfreemethod tomake functional thermoplastic polymers fromvegetable oils This opens the possibility of future use inapplications sensitive to catalyst or solvent contaminationincluding medical and pharmaceutical applications

Conflict of Interests

All authors declare that there is no conflict of interestsconcerning the material within this publication

Acknowledgments

The financial support of Elevance Renewable SciencesNSERC Grain Farmers of Ontario GPA-EDC IndustryCanada and Trent University is gratefully acknowledged

References

[1] C K Williams and M A Hillmyer ldquoPolymers from renewableresources a perspective for a special issue of polymer reviewsrdquoPolymer Reviews vol 48 no 1 pp 1ndash10 2008

[2] L Hojabri J Jose A L Leao L Bouzidi and S S NarineldquoSynthesis and physical properties of lipid-based poly(ester-urethane)s I effect of varying polyester segment lengthrdquoPolymer vol 53 no 17 pp 3762ndash3771 2012

[3] L Hojabri X Kong and S S Narine ldquoFunctional thermoplas-tics from linear diols and diisocyanates produced entirely fromrenewable lipid sourcesrdquo Biomacromolecules vol 11 no 4 pp911ndash918 2010

[4] M-J Dumont X Kong and S S Narine ldquoPolyurethanes frombenzene polyols synthesized from vegetable oils dependenceof physical properties on structurerdquo Journal of Applied PolymerScience vol 117 no 6 pp 3196ndash3203 2010

[5] M Desroches S Caillol V Lapinte R Auvergne and BBoutevin ldquoSynthesis of biobased polyols by thiol-ene coupling

from vegetable oilsrdquo Macromolecules vol 44 no 8 pp 2489ndash2500 2011

[6] JHongQ Luo XWan Z S Petrovic andB K Shah ldquoBiopoly-mers from vegetable oils via catalyst- and solvent-free ldquoclickrdquochemistry effects of cross-linking densityrdquo Biomacromoleculesvol 13 no 1 pp 261ndash266 2012

[7] Y Xia and R C Larock ldquoVegetable oil-based polymeric mate-rials synthesis properties and applicationsrdquo Green Chemistryvol 12 no 11 pp 1893ndash1909 2010

[8] CWitschi and EDoelker ldquoResidual solvents in pharmaceuticalproducts acceptable limits influences on physicochemicalproperties analytical methods and documented valuesrdquo Euro-pean Journal of Pharmaceutics and Biopharmaceutics vol 43no 3 pp 215ndash242 1997

[9] A J Scheel H Komber and B I Voit ldquoNovel hyperbranchedpoly([123]-triazole)s derived from AB2 monomers by a 13-dipolar cycloadditionrdquo Macromolecular Rapid Communica-tions vol 25 no 12 pp 1175ndash1180 2004

[10] H C Kolb M Finn and K B Sharpless ldquoClick chemistrydiverse chemical function from a few good reactionsrdquo Ange-wandte Chemie International Edition vol 40 pp 2004ndash20212001

[11] V V Rostovtsev L G Green V V Fokin and K B SharplessldquoA stepwise huisgen cycloaddition process copper (I)-catalyzedregioselective ldquoligationrdquo of azides and terminal alkynesrdquo Ange-wandte Chemie vol 114 pp 2708ndash2711 2002

[12] B Y Ryu and T Emrick ldquoThermally induced structural trans-formation of bisphenol-123-triazole polymers smart self-extinguishing materialsrdquo Angewandte Chemie vol 122 pp9838ndash9841 2010

[13] L Xue L Wan Y Hu X Shen F Huang and L Du ldquoThermalstability of a novel polytriazole resinrdquoThermochimica Acta vol448 no 2 pp 147ndash153 2006

[14] J Hong B K Shah and Z S Petrovic ldquoVegetable oil cast resinsvia click chemistry effects of cross-linkersrdquo European Journal ofLipid Science and Technology vol 115 no 1 pp 55ndash60 2013

[15] WH Binder andR Sachsenhofer ldquolsquoClickrsquo chemistry in polymerandmaterials sciencerdquoMacromolecular Rapid Communicationsvol 28 no 1 pp 15ndash54 2007


[16] J O Metzger ldquoFats and oils as renewable feedstock for chem-istryrdquo European Journal of Lipid Science and Technology vol 111no 9 pp 865ndash876 2009

[17] J Akhtar A Idris and R A Aziz ldquoRecent advances in pro-duction of succinic acid from lignocellulosic biomassrdquo AppliedMicrobiology and Biotechnology vol 98 no 3 pp 987ndash10002013

[18] L Luo E van der Voet and G Huppes ldquoBiorefining of lig-nocellulosic feedstock-technical economic and environmentalconsiderationsrdquo Bioresource Technology vol 101 no 13 pp5023ndash5032 2010

[19] C Efe L A M van der Wielen and A J J Straathof ldquoTechno-economic analysis of succinic acid production using adsorptionfrom fermentationmediumrdquoBiomass andBioenergy vol 56 pp479ndash492 2013

[20] B Cornils and P Lappe ldquoDicarboxylic acids aliphaticrdquo inUllmannrsquos Encyclopedia of Industrial Chemistry Wiley-VCH2006

[21] E De Jong A Higson P Walsh and M Wellisch ldquoProductdevelopments in the bio-based chemicals arenardquo Biofuels Bio-products and Biorefining vol 6 no 6 pp 606ndash624 2012

[22] Y YangW Lu X ZhangW XieM Cai andR A Gross ldquoTwo-step biocatalytic route to biobased functional polyesters from120596-carboxy fatty acids and diolsrdquo Biomacromolecules vol 11 no1 pp 259ndash268 2010

[23] S Chang and C D Han ldquoEffect of flexible spacer lengthon the phase transitions and mesophase structures of main-chain thermotropic liquid-crystalline polyesters having bulkypendent side groupsrdquoMacromolecules vol 30 no 6 pp 1670ndash1684 1997

[24] D K Lee and H B Tsai ldquoSynthesis and properties ofpoly(alkylene pp1015840-bibenzoate-co-adipate)srdquo Journal of AppliedPolymer Science vol 65 pp 893ndash900 1997

[25] J E Mark Physical Properties of Polymers Handbook Springer2007

[26] C Bueno-Ferrer E Hablot M D C Garrigos S Bocchini LAverous and A Jimenez ldquoRelationship between morphologyproperties and degradation parameters of novative biobasedthermoplastic polyurethanes obtained from dimer fatty acidsrdquoPolymer Degradation and Stability vol 97 no 10 pp 1964ndash19692012

[27] N S Murthy and H Minor ldquoGeneral procedure for evaluatingamorphous scattering and crystallinity from X-ray diffractionscans of semicrystalline polymersrdquo Polymer vol 31 no 6 pp996ndash1002 1990

[28] R L Shogren Z Petrovic Z Liu and S Z Erhan ldquoBiodegrada-tion behavior of some vegetable oil-based polymersrdquo Journal ofPolymers and the Environment vol 12 no 3 pp 173ndash178 2004

[29] S Brase C Gil K Knepper and V Zimmermann ldquoOrganicazides an exploding diversity of a unique class of compoundsrdquoAngewandte Chemie International Edition vol 44 no 33 pp5188ndash5240 2005

[30] Y Li L Wan H Zhou F Huang and L Du ldquoA novelpolytriazole-based organogel formed by the effects of copperionsrdquo Polymer Chemistry vol 4 pp 3444ndash3447 2013

[31] Y Hua and A H Flood ldquoClick chemistry generates privilegedCH hydrogen-bonding triazoles the latest addition to anionsupramolecular chemistryrdquo Chemical Society Reviews vol 39no 4 pp 1262ndash1271 2010

[32] R W Seymour G M Estes and S L Cooper ldquoInfrared studiesof segmented polyurethan elastomers I Hydrogen bondingrdquoMacromolecules vol 3 no 5 pp 579ndash583 1970

[33] Y J Huang Y S Ye Y C Yen L D Tsai B J Hwang and FC Chang ldquoSynthesis and characterization of new sulfonatedpolytriazole proton exchange membrane by click reaction fordirect methanol fuel cells (DMFCs)rdquo International Journal ofHydrogen Energy vol 36 no 23 pp 15333ndash15343 2011

[34] Y Lee and R S Porter ldquoDouble-melting behavior of poly(etherether ketone)rdquo Macromolecules vol 20 no 6 pp 1336ndash13411987

[35] J T Koberstein and A F Galambos ldquoMultiple melting insegmented polyurethane block copolymersrdquo Macromoleculesvol 25 no 21 pp 5618ndash5624 1992

[36] Y Minoura S Yamashita H Okamoto T Matsuo M Izawaand S-I Kohmoto ldquoCrosslinking and mechanical property ofliquid rubber I Curative effect of aliphatic diolsrdquo Journal ofApplied Polymer Science vol 22 no 7 pp 1817ndash1844 1978

[37] G Z Papageorgiou and D N Bikiaris ldquoCrystallization andmelting behavior of three biodegradable poly(alkylene succi-nates) A comparative studyrdquo Polymer vol 46 no 26 pp 12081ndash12092 2005

[38] S Binauld D Damiron T Hamaide J-P Pascault E Fleuryand E Drockenmuller ldquoClick chemistry step growth poly-merization of novel 120572-azide-120596- alkyne monomersrdquo ChemicalCommunications no 35 pp 4138ndash4140 2008

[39] H P Bhunia R N Jana A Basak S Lenka and G BNando ldquoSynthesis of polyurethane from cashew nut shell liquid(CNSL) a renewable resourcerdquo Journal of Polymer Science APolymer Chemistry vol 36 no 3 pp 391ndash400 1998

[40] R Chen K A Jakes and D W Foreman ldquoPeak-fitting analysisof cotton fiber powder X-ray diffraction spectrardquo Journal ofApplied Polymer Science vol 93 no 5 pp 2019ndash2024 2004

[41] L Raghunanan and S S Narine ldquoInfluence of structure onchemical and thermal stability of aliphatic diestersrdquoThe Journalof Physical Chemistry B vol 117 pp 14754ndash14762 2013

[42] P J M Serrano E Thuss and R J Caymans ldquoAlternat-ing polyesteramides based on 14-butylene terephthalamide2 Alternating polyesteramides based on a single linear diol(4NTm)rdquo Polymer vol 38 no 15 pp 3893ndash3902 1997

[43] J S Shelley P TMather and K L DeVries ldquoReinforcement andenvironmental degradation of nylon-6clay nanocompositesrdquoPolymer vol 42 no 13 pp 5849ndash5858 2001

[44] M J Doyle ldquoOn the effect of crystallinity on the elastic proper-ties of semicrystalline polyethylenerdquo Polymer Engineering andScience vol 40 no 2 pp 330ndash335 2000

[45] L Franco J A Subirana and J Puiggali ldquoStructure andmorphology of odd polyoxamides [Nylon 92] A new exampleof hydrogen-bonding interactions in two different directionsrdquoMacromolecules vol 31 no 12 pp 3912ndash3924 1998

[46] J Blackwell M R Nagarajan and T B Hoitink ldquoStructure ofpolyurethane elastomers effect of chain extender length on thestructure of MDIdiol hard segmentsrdquo Polymer vol 23 no 7pp 950ndash956 1982

[47] W Zhu XHuang C Li Y XiaoD Zhang andGGuan ldquoHigh-molecular-weight aliphatic polycarbonates by melt polycon-densation of dimethyl carbonate and aliphatic diols synthesisand characterizationrdquo Polymer International vol 60 no 7 pp1060ndash1067 2011

[48] T Shimizu and M Masuda ldquoStereochemical effect of even-odd connecting links on supramolecular assemblies madeof 1-glucosamide bolaamphiphilesrdquo Journal of the AmericanChemical Society vol 119 no 12 pp 2812ndash2818 1997


[49] D Wintgens D G Yablon and G W Flynn ldquoPackingof HO(CH

2)14COOH and HO(CH

2)15COOH on graphite at

the liquid-solid interface observed by scanning tunnelingmicroscopy methylene unit direction of self-assembly struc-turesrdquo Journal of Physical Chemistry B vol 107 no 1 pp 173ndash1792003

[50] M Soutzidou V-A Glezakou K Viras M Helliwell A J Mas-ters and M A Vincent ldquoLow-frequency Raman spectroscopyof n-alcohols LAM vibration and crystal structurerdquo Journal ofPhysical Chemistry B vol 106 no 17 pp 4405ndash4411 2002

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


ldquospring loadedrdquo terminal azide and alkyne groups to afford1-4- or 1-5-substituted 123-triazolesmdashdepending on thecatalyst Uncatalyzed reactions produce a mixture of the 14-and 15-substituents with the 14-[123-triazole] regioisomerfavoured by a ratio around 2 1 [9] The interest in the azide-alkyne Huisgen cycloaddition reaction was renewed in theearly 2000s after Barry Sharpless popularized the copper cat-alyzed variant and classified it as one type of ldquoclickrdquo chemistrya reactionwhich can rapidly and easily produce awide varietyof functional materials having high yields easy purificationshigh atomic economy and mimics nature [10 11] Someadvantages of azide-alkyne ldquoclickrdquo reactions include the lackof requirement for solvent or catalyst complete consumptionof reactants with no byproduct or gas formed and uniqueproperties of the triazole moiety [10 12 13] Triazole con-taining compounds have been found to possess antimicrobialand self-extinguishing characteristicsmdashthese are desirablecharacteristics in polymers [12] Polymerizations using azide-alkyne ldquoclickrdquo chemistry have been applied to various typesof monomers including vegetable oil triglycerides forminga series of cross-linked and thermoset polymers [6 14]The utility of azide and alkyne ldquospring-loadedrdquo reactantsas building blocks for complex molecules like polymersis beginning to be realized opening a door to producingmacromolecules with novel and unique functionality [15]

The goal of this work was to create lipid derived ther-moplastic polymers using the commonly available and eco-nomical feedstocks succinic acid azelaic acid and octadec-9-enedioic acidmdashall of which are produced from renewableresources [16] Succinic acid is produced by the bacterialfermentation of carbohydrates in a green process whichconsumes CO

2 It is a common commercial feedstock and

can be used to produce industrially important products suchas 14-butanediol and polyesters [17] Worldwide productionwas approximately 300 kt in 2010 and global demandhas beenestimated at 30mtyear while optimizations in productionmay lower costs to $036kg [18 19] Both azelaic acid andoctadec-9-enedioic acid are produced from oleic acid closelytying their price to that of the feedstock Azelaic acid isproduced on a commercial scale by the ozonolysis of oleicacid and used as a plasticizer and in polymers includingnylon 69 [20] Octadec-9-enedioic acid is produced by theself-metathesis of oleic acid or by biotransformation of 18carbon fatty acids using modified yeast fermentation [21 22]These renewable monomeric feedstocks provide comparableproperties to conventional petroleum derived products andare of growing importance as their supply improves and theprice of petroleum continues to increase

The intent of varying the chain length of the monomerwas to establish the degree of dependence on monomerchain length and degree of asymmetry Furthermore therelationship between even and odd chain length monomersknown as the odd-even effect can be probed by comparingthe properties of the azelaic acid based monomer (9 carbons)with the two other monomers each having an even numberof carbon atoms Polyesters with even carbon numberedmonomers demonstrate higher melting temperatures andenthalpies of fusion than their odd carbon number analogues[23 24]

In the present work three thermoplastic polytriazolesfrom diester dialkynes and a diazide monomer derivedfrom oleic acid (with the exception of the C4 dialkynewhich is produced from succinic acid a product of bac-terial fermentation of carbohydrates) were synthesized andcharacterized The numbers of carbon atoms in the diesterdialkyne monomers are 4 9 and 18 with 18 for the diazidemonomer This work presents a new route to the creationof melt-processable polymers from renewable vegetable oilswithout residual solvent or catalyst Furthermore becauseof the presence of unsaturated sites in the monomers itmay be possible to perform polymerization on a suitablesubstrate in situ and furthermodify the unsaturation to afforda potentially biocompatible polymer with easily tunablefunctionalities

2 Experimental

21 Materials Azelaic acid (98) oleic acid (85) sodiumazide (99) propargyl alcohol (99) 4-toluenesulfonylchloride (98) triethyl amine (99) succinic acid (99)Grubbs catalyst 2nd generation LiAlH

4(95)NN1015840-dicyclo-

hexylcarbodiimide (DCC) (99) and 4-dimethylaminopy-ridine (DMAP) (99) were purchased from Sigma-Aldrichand used as received (119864)-octadec-9-ene-118-diol and (119864)-118-octadec-9-endiacid were synthesized using a previouslyreported procedure [3] that is the olefin metathesis of oleicacid followed by the subsequent reduction of the diacid intothe dialcohol

3 Methods

31 Synthesis of Monomers Oleic acid was converted intoa dicarboxylic acid through olefin metathesis reduced intoa dialcohol tosylated and finally azidated into a diazide(Scheme 1) Three diester dialkynes monomers were sub-sequently synthesized from dicarboxylic acids of differentcarbon lengthsmdash(119864)-118-octadec-9-endiacid (C18) azelaicacid (C9) and succinic acid (C4) through either Steglich orFischer esterification (Scheme 2)

(E)-Octadec-9-ene-118-diyl bis(4-methylbenzenesulfonate)(1) (119864)-Octadec-9-ene-118-diol (120 g 422mmol) wasadded to a round bottom flask kept in an ice bath (0∘C)4-Toluenesulfonyl chloride (182 g 954mmol) dissolvedin 150mL of CH

2Cl2and was added dropwise then 030 g

(25mmol) of DMAP and 120 g (119mmol) of triethylaminedissolved in 20mLCH

2Cl2was added dropwiseThe reaction

was allowed to warm to room temperature and proceededuntil complete consumption of the starting material asdetermined by TLC (approximately 6 hours Rf = 030 5 1hexaneethyl acetate) The contents of the flask were dilutedwith 150mL CH

2Cl2and washed with water (3 times 150mL)

25 N HCl solution (3 times 150mL) 4 aqueous sodiumbicarbonate (3 times 150mL) and finally saturated NaCl brine(3 times 150mL) The organic layer was dried with anhydrousNa2SO4and concentrated under reduced pressure yielding

223 g of slightly yellow crystal The solid product was


O O

O

OH

OH

OHHO

S SO

OO

O

N3N3

(a)

(b)

(c)

(d)



3 DMSO H

2O 100∘C 12 h

OO

OO

O O

R

R

OHHO

(a) or (b)




3) 120575 121 (m 20H) 162



3dissolved in 10mL




3) 120575





3) 120575 131





4H) 235 (t 4H) 247 (t 2H) and 467 (d 4H)


3) 120575

248 (t 2H) 269 (s 4H) 469 (d 4H)



3

















119862) is

calculated by

119883119862= 100 times

119860119862

119860119862+ 119860119860

(1)









4


C 6D4Cl

2

C 6D4Cl

2

C C

CCOC

C O

H

H

H2

H2

N

NN N

N NCH2

CH2

Inte

nsity

10 8 6 4 2 0


b998400

b

b

998400

a998400

aa

998400

c998400

cc

ca

b

998400







(i)

(iii)(ii)

Azide

C9 dialkyne

C18C9

(iv) 50

Abso

rban

ce

3500 3000 2500 2000 1500 1000


(a)

C18C18

C18C9

C18C4

Abso

rban

ce

3000 2500 2000 1500 1000


(b)







119877= 120 plusmn 17∘C



= 735plusmn12∘C)






NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NNN

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

C18C9

O

O

NNN

NN N

O

O

O

O

NNN

NN N

H

H

H

H

O

O

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

OO

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

C18C18

C18C4



Polymer 119879119862(∘C) Δ119867

119862(∘C) 119879

1198981(∘C) 119879

1198982(∘C) Δ119867

1198981(Jg) Δ119867

1198982(Jg) 119879

119877(∘C) Δ119867

119877(Jg)







C18C4 (100) 437 (100) 452 206(010) 386 (110) 396

C18C9 (100) 444 (002) 430 151(010) 389

C18C18 (100) 440 mdash mdash 263(010) 391


Hea

t flow

(Wg

)Ex

o up

C18C4

C18C9

C18C18

minus50 0 50 100 150

Temperature (∘C)

TgTR

TM1 TM2

01

(a)

Hea

t flow

(Wg

)Ex

o up

minus50 0 50 100 150

Temperature (∘C)

C18C4

C18C9

C18C18

Tc

01

(b)



119877=


1198791198721

and 1198791198722







16 18 20 22 24 26


Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)


Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)






Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




O O

O

OH

OH

OHHO

S SO

OO

O

N3N3

(a)

(b)

(c)

(d)



3 DMSO H

2O 100∘C 12 h

OO

OO

O O

R

R

OHHO

(a) or (b)




3) 120575 121 (m 20H) 162



3dissolved in 10mL




3) 120575





3) 120575 131





4H) 235 (t 4H) 247 (t 2H) and 467 (d 4H)


3) 120575

248 (t 2H) 269 (s 4H) 469 (d 4H)



3

















119862) is

calculated by

119883119862= 100 times

119860119862

119860119862+ 119860119860

(1)









4


C 6D4Cl

2

C 6D4Cl

2

C C

CCOC

C O

H

H

H2

H2

N

NN N

N NCH2

CH2

Inte

nsity

10 8 6 4 2 0


b998400

b

b

998400

a998400

aa

998400

c998400

cc

ca

b

998400







(i)

(iii)(ii)

Azide

C9 dialkyne

C18C9

(iv) 50

Abso

rban

ce

3500 3000 2500 2000 1500 1000


(a)

C18C18

C18C9

C18C4

Abso

rban

ce

3000 2500 2000 1500 1000


(b)







119877= 120 plusmn 17∘C



= 735plusmn12∘C)






NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NNN

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

C18C9

O

O

NNN

NN N

O

O

O

O

NNN

NN N

H

H

H

H

O

O

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

OO

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

C18C18

C18C4



Polymer 119879119862(∘C) Δ119867

119862(∘C) 119879

1198981(∘C) 119879

1198982(∘C) Δ119867

1198981(Jg) Δ119867

1198982(Jg) 119879

119877(∘C) Δ119867

119877(Jg)







C18C4 (100) 437 (100) 452 206(010) 386 (110) 396

C18C9 (100) 444 (002) 430 151(010) 389

C18C18 (100) 440 mdash mdash 263(010) 391


Hea

t flow

(Wg

)Ex

o up

C18C4

C18C9

C18C18

minus50 0 50 100 150

Temperature (∘C)

TgTR

TM1 TM2

01

(a)

Hea

t flow

(Wg

)Ex

o up

minus50 0 50 100 150

Temperature (∘C)

C18C4

C18C9

C18C18

Tc

01

(b)



119877=


1198791198721

and 1198791198722







16 18 20 22 24 26


Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)


Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)






Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





4H) 235 (t 4H) 247 (t 2H) and 467 (d 4H)


3) 120575

248 (t 2H) 269 (s 4H) 469 (d 4H)



3

















119862) is

calculated by

119883119862= 100 times

119860119862

119860119862+ 119860119860

(1)









4


C 6D4Cl

2

C 6D4Cl

2

C C

CCOC

C O

H

H

H2

H2

N

NN N

N NCH2

CH2

Inte

nsity

10 8 6 4 2 0


b998400

b

b

998400

a998400

aa

998400

c998400

cc

ca

b

998400







(i)

(iii)(ii)

Azide

C9 dialkyne

C18C9

(iv) 50

Abso

rban

ce

3500 3000 2500 2000 1500 1000


(a)

C18C18

C18C9

C18C4

Abso

rban

ce

3000 2500 2000 1500 1000


(b)







119877= 120 plusmn 17∘C



= 735plusmn12∘C)






NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NNN

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

C18C9

O

O

NNN

NN N

O

O

O

O

NNN

NN N

H

H

H

H

O

O

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

OO

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

C18C18

C18C4



Polymer 119879119862(∘C) Δ119867

119862(∘C) 119879

1198981(∘C) 119879

1198982(∘C) Δ119867

1198981(Jg) Δ119867

1198982(Jg) 119879

119877(∘C) Δ119867

119877(Jg)







C18C4 (100) 437 (100) 452 206(010) 386 (110) 396

C18C9 (100) 444 (002) 430 151(010) 389

C18C18 (100) 440 mdash mdash 263(010) 391


Hea

t flow

(Wg

)Ex

o up

C18C4

C18C9

C18C18

minus50 0 50 100 150

Temperature (∘C)

TgTR

TM1 TM2

01

(a)

Hea

t flow

(Wg

)Ex

o up

minus50 0 50 100 150

Temperature (∘C)

C18C4

C18C9

C18C18

Tc

01

(b)



119877=


1198791198721

and 1198791198722







16 18 20 22 24 26


Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)


Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)






Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





119862) is

calculated by

119883119862= 100 times

119860119862

119860119862+ 119860119860

(1)









4


C 6D4Cl

2

C 6D4Cl

2

C C

CCOC

C O

H

H

H2

H2

N

NN N

N NCH2

CH2

Inte

nsity

10 8 6 4 2 0


b998400

b

b

998400

a998400

aa

998400

c998400

cc

ca

b

998400







(i)

(iii)(ii)

Azide

C9 dialkyne

C18C9

(iv) 50

Abso

rban

ce

3500 3000 2500 2000 1500 1000


(a)

C18C18

C18C9

C18C4

Abso

rban

ce

3000 2500 2000 1500 1000


(b)







119877= 120 plusmn 17∘C



= 735plusmn12∘C)






NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NNN

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

C18C9

O

O

NNN

NN N

O

O

O

O

NNN

NN N

H

H

H

H

O

O

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

OO

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

C18C18

C18C4



Polymer 119879119862(∘C) Δ119867

119862(∘C) 119879

1198981(∘C) 119879

1198982(∘C) Δ119867

1198981(Jg) Δ119867

1198982(Jg) 119879

119877(∘C) Δ119867

119877(Jg)







C18C4 (100) 437 (100) 452 206(010) 386 (110) 396

C18C9 (100) 444 (002) 430 151(010) 389

C18C18 (100) 440 mdash mdash 263(010) 391


Hea

t flow

(Wg

)Ex

o up

C18C4

C18C9

C18C18

minus50 0 50 100 150

Temperature (∘C)

TgTR

TM1 TM2

01

(a)

Hea

t flow

(Wg

)Ex

o up

minus50 0 50 100 150

Temperature (∘C)

C18C4

C18C9

C18C18

Tc

01

(b)



119877=


1198791198721

and 1198791198722







16 18 20 22 24 26


Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)


Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)






Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(i)

(iii)(ii)

Azide

C9 dialkyne

C18C9

(iv) 50

Abso

rban

ce

3500 3000 2500 2000 1500 1000


(a)

C18C18

C18C9

C18C4

Abso

rban

ce

3000 2500 2000 1500 1000


(b)







119877= 120 plusmn 17∘C



= 735plusmn12∘C)






NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NNN

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

C18C9

O

O

NNN

NN N

O

O

O

O

NNN

NN N

H

H

H

H

O

O

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

OO

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

C18C18

C18C4



Polymer 119879119862(∘C) Δ119867

119862(∘C) 119879

1198981(∘C) 119879

1198982(∘C) Δ119867

1198981(Jg) Δ119867

1198982(Jg) 119879

119877(∘C) Δ119867

119877(Jg)







C18C4 (100) 437 (100) 452 206(010) 386 (110) 396

C18C9 (100) 444 (002) 430 151(010) 389

C18C18 (100) 440 mdash mdash 263(010) 391


Hea

t flow

(Wg

)Ex

o up

C18C4

C18C9

C18C18

minus50 0 50 100 150

Temperature (∘C)

TgTR

TM1 TM2

01

(a)

Hea

t flow

(Wg

)Ex

o up

minus50 0 50 100 150

Temperature (∘C)

C18C4

C18C9

C18C18

Tc

01

(b)



119877=


1198791198721

and 1198791198722







16 18 20 22 24 26


Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)


Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)






Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NNN

O

OH

H

H

H

NN N

NNN

OO

O

O

NN N

NN

N

O

OH

H

H

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

OO

OO

NN

N

NNN

OO

OO N

NN

HH

HNN N

H

C18C9

O

O

NNN

NN N

O

O

O

O

NNN

NN N

H

H

H

H

O

O

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

OO

NNN

NN N

O

O

OO

NNN

NN N

H

H

H

H

C18C18

C18C4



Polymer 119879119862(∘C) Δ119867

119862(∘C) 119879

1198981(∘C) 119879

1198982(∘C) Δ119867

1198981(Jg) Δ119867

1198982(Jg) 119879

119877(∘C) Δ119867

119877(Jg)







C18C4 (100) 437 (100) 452 206(010) 386 (110) 396

C18C9 (100) 444 (002) 430 151(010) 389

C18C18 (100) 440 mdash mdash 263(010) 391


Hea

t flow

(Wg

)Ex

o up

C18C4

C18C9

C18C18

minus50 0 50 100 150

Temperature (∘C)

TgTR

TM1 TM2

01

(a)

Hea

t flow

(Wg

)Ex

o up

minus50 0 50 100 150

Temperature (∘C)

C18C4

C18C9

C18C18

Tc

01

(b)



119877=


1198791198721

and 1198791198722







16 18 20 22 24 26


Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)


Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)






Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






C18C4 (100) 437 (100) 452 206(010) 386 (110) 396

C18C9 (100) 444 (002) 430 151(010) 389

C18C18 (100) 440 mdash mdash 263(010) 391


Hea

t flow

(Wg

)Ex

o up

C18C4

C18C9

C18C18

minus50 0 50 100 150

Temperature (∘C)

TgTR

TM1 TM2

01

(a)

Hea

t flow

(Wg

)Ex

o up

minus50 0 50 100 150

Temperature (∘C)

C18C4

C18C9

C18C18

Tc

01

(b)



119877=


1198791198721

and 1198791198722







16 18 20 22 24 26


Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)


Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)






Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




16 18 20 22 24 26


Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(a)

16 18 20 22 24 26 28


(100) M

(100) T

(002) T

(110) T

(010) M

(010) M(100) M

Inte

nsity

(cou

nts)

C18C4

C18C9

C18C18

(b)


Wei

ght (

)

100

80

60

40

20

0

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(a)

DTG

05

100 200 300 400 500 600

Temperature (∘C)

C18C4

C18C9

C18C18

(b)






Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




Loss

mod

ulus

(MPa

)300

250

200

150

100

50

0


Temperature (∘C)

C18C4

C18C9

C18C18

120573

(a)

Stor

age m

odul

us (M

Pa)


Temperature (∘C)

5000

4000

3000

2000

1000

0

C18C4

C18C9

C18C18

(b)

Temperature (∘C)

C18C4

C18C9

C18C18

025

020

015

010

005

000

Tan120575


(c)




119892of






and DMA

Polymer 119879119892 (DSC) (

∘C) 119879119892 (DMA) (





119862 the













5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials















5 Conclusions




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




16

14

12

10

8

6

4

2

0

0 50 100 150 200

Strain ()

Stre

ss (M

Pa)

C18C4

C18C9

C18C18

(a)

220

200

180

160

140

120

100

28

Youn

grsquos m

odul

us (M

Pa)

26

24

22

20

18

16

14

Relat

ive c

ryst

allin

ity (

)

C18C4 C18C9 C18C18

(b)





Acknowledgments


References





















































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials







































2)14COOH and HO(CH











CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



Research Article Vegetable Oil Derived Solvent, and Catalyst...

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