(bio)degradable ionomeric polyurethanes based on xanthan: … · 2019. 7. 30. · as packaging,...

Research Article(Bio)degradable Ionomeric Polyurethanes Based on XanthanSynthesis Properties and Structure

T V Travinskaya A N Brykova Yu V Savelyev N V Babkina and V I Shtompel

Institute of Macromolecular Chemistry NAS of Ukraine Kharkovskoe Shosse 48 Kiev 02160 Ukraine

Correspondence should be addressed to T V Travinskaya travinskaya-tamararamblerru

Received 1 June 2017 Revised 21 July 2017 Accepted 9 August 2017 Published 24 September 2017

Academic Editor Shida Miao

Copyright copy 2017 T V Travinskaya 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

New (bio)degradable environmentally friendly film-forming ionomeric polyurethanes (IPU) based on renewable biotechnologicalpolysaccharide xanthan (Xa) have been obtained The influence of the component composition on the colloidal-chemical andphysic-mechanical properties of IPUXa and based films as well as the change of their properties under the influence ofenvironmental factors have been studied The results of IR- PMS- DMA- and X-ray scattering study indicate that incorporationof Xa into the polyurethane chain initiates the formation of a new polymer structure different from the structure of the pure IPU(matrix) an amorphous polymer-polymer microdomain has occurred as a result of the chemical interaction of Xa and IPU Itpredetermines the degradation of the IPUXa films as a whole unlike the mixed polymer systems and plays a key role in theimprovement of material performance The results of acid alkaline hydrolysis and incubation into the soil indicate the increaseof the intensity of degradation processes occurring in the IPUXa in comparison with the pure IPU It has been shown that theintroduction of Xa not only imparts the biodegradability property to polyurethane but also improves the mechanical properties

1 Introduction

Problem of environmental pollution with polymeric wastehas shown a clear need for ecologically friendly materialsbased on renewable resources vegetable oils and naturalpolymers in particular polysaccharides which results in thedevelopment of a new trend in polymer chemistry creationof sustainable biodegradable polymers having a wide range ofapplications [1ndash4] Severalmethods of incorporating polysac-charides into the polyurethanes are discussed depending onthe desired final properties of the polyurethane [5] Due to thesuccess of biotechnologies a particular attention in modernchemistry of biodegradable polymers is paid to microbialpolysaccharides (exopolysaccharides) which are climate andseason independent One of the leading places in this linebelongs to xanthan an extracellular polysaccharide of thebacteria Xanthomonas campestris Xanthan molecules areprone to the self-association in aqueous solutions a riseof solution ionic strength or polysaccharide concentrationresults in gel formation [6 7] Xanthan provides the syntheticpolymers in particular polyurethanes with ability to degrade

under the influence of natural factors It was shown that thechemical bond between synthetic and natural componentsplayed a crucial role in giving to the synthetic polymerbiodegradability opposed to mechanical mixtures whereonly the natural component decomposed with time [8 9]Aqueous film-forming polyurethane dispersions have founddiverse applications as finishing impregnating stiffenerprotectivematerials and adhesives in leather textile and fur-niture industry [10 11] The synthesis and characterization ofnovel aqueous polyurethane dispersions derived from plantoil and starch with the use of dimethylolpropionic acid asinternal emulsifierwhich allows us to incorporate hydrophilicgroups into the polymer chain and achieve stable self-emulsifying dispersions are discussed in [12ndash14] It should benoted that the synthesis of degradable polyurethanes basedon renewable feedstock is one of developing branches ofgreen polyurethane chemistry Such materials may be usedas packaging finishing impregnating stiffener protectivematerials and adhesives in leather textile and furnitureindustry biologically active substances in agriculture Adistinctive feature of degradable polymers is to preserve

HindawiInternational Journal of Polymer ScienceVolume 2017 Article ID 8632072 10 pageshttpsdoiorg10115520178632072

2 International Journal of Polymer Science

the necessary operational parameters during the time oftheir use in combination with accelerated degradation underthe influence of various natural factors after the expira-tion Microorganisms are the main biological systems whichdestroy the polymeric compounds The ability of polymersto degrade and be assimilated by microorganisms dependson a number of their characteristics the chemical structureof the polymer molecular weight branching of macrochainand supramolecular structure [15] The aim of the latestdevelopments in the field of degradable polymers is toestablish the common principles in selecting the componentsfor synthesis of polymer which combine a high level ofperformance with the (bio)degradation ability and knack ofadjusting the (bio)degradation processes to ensure fast andsafe (bio)degradation of polymer materials at the expirationof their working time The paper considers the synthesis andcomplex study of ldquocomposition structure properties and(bio)degradation abilityrdquo relationship of structurally modi-fied polymeric materials based on polyurethane ionomer andmicrobial exopolysaccharide xanthan

2 Experimental

21 Materials Hexamethylene diisocyanate (HMDI)(Merck) polyoxytetramethylene glycol (POTMG 1000)dimethylolpropionic acid (DMPA) triethylamine (TEA)and Xa in the form of powder (Brookfield viscosity of1 solution according to Certificate of analysis amounts959 cps) were purchased from Aldrich and used as receivedacetone was purchased from Fluka

22 Preparation of Xanthan Containing Ionomer Polyure-thane Xanthan containing ionomer polyurethanes (IPUXa)in the form of aqueous dispersions was prepared by the reac-tion of an isocyanate precursor based on POTMG andHMDIwith DMPA as ion centers carrier taken in a molar ratioof 1 2 06 The reaction time for the isocyanate precursorformation was 2 h at 80∘C until the NCO content reached thetheoretical value to produce NCO-terminated prepolymerThe content of NCO groups was controlled according to[16] Then DMPA was added and reacted with prepolymerat 80∘C for 1 h Suitable amount of acetone was added tothe system to decrease the viscosity of reaction mixtureXa (C35H49O29)119899 was added to the reaction mixture in aform of dry powder (the reaction time was 1 h at 56∘C)Neutralization of the DMPA fragmentsrsquo carboxyl groups ofobtained IPUXa hard block was performed with TEA (themolar ratio of TEA DMPA = 1 1) Next a simultaneouselongation and water dispersion were carried out followedby removal of acetone Film-forming opalescent dispersionswere then obtained by phase inversion Polymer films wereformed at room temperature on a Teflon disk followed bydrying in an oven at 65∘C and in a vacuum oven at 55∘C toconstant weight

IPUXa systems with different Xa weight concentrations5 10 and 30 (IPU5Xa IPU10Xa IPU30Xa) wereprepared IPU matrix was synthesized similar to IPUXa(using water as chain extender without addition of Xa) andhas been selected as an object of comparison

23 Characterization

231 pHValues pH values were determined using pH-meterldquopH-150 Mrdquo (Russia)

232 Particle Size Particle size measurements were deter-mined from the turbidity spectrum using FEK-56M accord-ing to [17]

233 Mechanical Properties Measurements were performedusing a tensile testing machine FU-1000 (VEB MWK ldquoFritzHeckertrdquo Germany) at a tensile speed of 100mmmin andtemperature 25∘C The number of samples used in eachmeasurement was three Samples were prepared in a form ofstrips (width 4mm operating length 2mm) Measurementswere carried out in accordance with standard 14236-81allowed error is 3

234 Water Absorption Preliminary weighed dry films ofIPU matrix IPUXa were immersed in water for 24 hwhereupon the excess water was removed with filter paperand samples were weighed Water absorption (119882H2O wt)was calculated according to 119882H2O() = [(119882119908 minus 119882119889)119882119889] sdot100 where 119882119908 and 119882119889 are weight of the films in a wet anddry state correspondingly

235 Degree ofHydrolysis inAcid andAlkaliMedium Degreeof hydrolysis in acid and alkali medium was determinedby evaluation of the weight change and physic-mechanicalcharacteristics of the samples after hydrolysis Preweighedsamples were immersed in 01 N solution of KOH and HCland kept in a thermostat for 30 days at 119879 = 25∘C afterwardsthe films were dried to constant weight with following weightcontrol and tensile test

236 IR Measurements IR measurements were performedon Bruker ldquoTensor-37rdquo Fourier transform infrared spectrom-eter in the region of wave numbers of 4500 cmminus1ndash500 cmminus1Samplesrsquo surfaces were studied by attenuated total internalreflection infrared spectroscopy

237 Thermodestruction of Xa-Containing IPU Thermode-struction of Xa-containing IPU was studied by pyrolyticmass spectrometry (PVS) A device consisting of a massspectrometer MX-1321 for determination of the componentsof gasmixtures in the range ofmass numbers of 1ndash4000 and ofcells for linearly programmable pyrolysis in the temperaturerange 25ndash400∘b was used The sample was placed into thecell which was evacuated (133 sdot 10minus4 Pa) for 30 minutesat 25∘C The same pressure was maintained during theexperimentThe heating rate was (6plusmn 1)∘bminThe accuracyof determining the temperature of the sample was plusmn1∘C Theionization energy in the chamber of the mass spectrometerwas 70 eV

238 The X-Ray Diffraction Patterns The wide-angleX-ray diffraction patterns (WAXS) were recorded with

International Journal of Polymer Science 3

Table 1 Properties of aqueous IPUXa dispersions and based films

Xa content Dispersion properties Film characteristics

119903avlowast nm aX

Water absorption 24hours

Contact angledegree

Tensile strength 120590VP1

Elongation at a breakpoint 120576

0 71 784 26 68 73 110050 176 755 23 50 81 742100300

272 717 65 45 169 530504 682 405 29 364 360

1000 mdash mdash The film wasdissolved mdash lowastlowast lowastlowast

119903avlowast average particle radiuslowastlowastnot applicable (the film is brittle)

X-ray diffractometer DRON-4-07 with roentgen schemamade according to Debye-Scherrer method (transmission)Supramolecular structure was studied by small-angle X-raydiffraction (SAXS) using small-angle camera KRM-1 withflat-filled collimator made according to Kratky method AllX-ray measurements were carried out in CuK120572 radiationmonochromatic with Ni-filter at 119879 = 22 plusmn 2∘C

239 Dynamic Mechanical Analysis (DMA) Dynamicmechanical measurements were carried out on a dynamicmechanical analyzer Q 800 TA Instruments in the tensionmode at frequency of 10Hz and heating rate of 20∘bminThe samples for DMA study were cut from the polymer filmsand had the following dimensions length 1275mm width4mm and thickness 03mm The viscoelastic propertiesthat is mechanical loss factor (tan 120575) and storage modulus(1198641015840) were recorded as function of temperature The glasstransition temperature (119879119892) was determined by the positionof the loss factor maximum

3 Results and Discussion

31 Colloid-Chemical Properties The composition colloid-chemical and physic-mechanical properties of synthesizedIPUXa dispersions and films are presented in Table 1

The average particle size reports the degree of physicalinteraction of the constituent macromolecules and the dis-persionmediumThe introduction of Xa results in increasingof 119903av owing to growth of the specific content of three-dimensional Xa fragments in macromolecules (as previouslywas shown using the small Xa concentrations [18]) whichhowever does not lead to a loss of dispersionsrsquo stability[19] With increase of Xa content the pH of dispersions issystematically reduced as a result of the presence in Xa of alarge number of acid pyruvic cycles

32 Water Absorption The degree of swelling of polymercomponents and their affinity to water is one of the indicesof decomposition rate of polymeric materials under theinfluence of environmental factors The investigation of thehydrolytic stability of IPUXa has shown the increase of thewater absorption up to a maximum value of 405 at 30Xa content Such increase may be due to the presence of freepolar fragments (carboxyl andOH groups) which determine

the hydrophilic properties of the polymer Probably a partof Xa hydrophilic hydroxyls involved in the formation ofintermolecular bonds with the polar groups of IPUs remainsunengaged following an increase of their concentration inthe surface layers and contributing to the elevation of thehydrophilicity degree and normally to decreasing of contactangle values (Table 1)

33 Physic-Mechanical Properties The tensile strength ofIPUXa films significantly increases as the Xa contentincreases and exceeds this index of the IPU matrix in 1ndash5times (Table 1) The increase of tensile strength for theIPUXa films indicates the occurrence of the intermolecularinteraction between IPU and Xa The loss of elasticity isspecified by decrease of the specific weight of the flexibleIPU segments in polymer composition which is in agreementwith the IR spectroscopic data indicating the hydrogenassociation of ether oxygen of POTMG with OH groups ofXa and steric hinders effected by volume molecules of Xa

34 IR Spectroscopy IR spectra of IPU matrix (1) IPU10Xa(2) and Xa (3) are presented in Figure 1(a) The IR spec-trum of the initial Xa is characterized by intense absorp-tion bands of stretching vibrations of O-H bonds in theregion of 3236ndash3613 cmminus1 1031 cmminus1 by peak of mediumintensity of stretching vibrations of b-X bonds (2926 cmminus1)an intense band with a frequency of 1736 cmminus1 apparentlycorresponding to the vibrations of ester groups IPU matrixshows all characteristic bands of polyurethanes ](NH)assoc3314 cmminus1 ](bH2) and ](bH3) intermolecular hydrogenbonds 2939 cmminus1 and 2850 cmminus1 respectively ](b=)free1720 cmminus1 and ](b=)assoc 1705 cm

minus1 of urethane groups120575(NH)free 1540 cm

minus1 ](b-N) 1415 cmminus1 ](b) (esterfragments of urethane group) 1250 cmminus1 and ](b--b)(of flexible segments of the matrix) 1105 cmminus1 The high-frequency shoulder at the peak of the stretching vibrationsof NH groups in the IPU spectrum (3375 cmminus1) indicates thepresence of free NH groups In the spectrum of IPU10Xa(Figure 1(a)) this shoulder disappears and the intensityof hydrogen-bonded NH groups (3314 cmminus1) increases Aredistribution of the intensities of free 1720 cmminus1 and bonded1705 cmminus1 CO groups is observed The appearance of low-frequency shoulder (1031 cmminus1) which refers to the stretching


(1)

(2)(3)3533

1031

1720

3375

00

02

04

06

08

10

Inte

nsity

(rel

uni

t)

1500 2000 2500 3000 3500 40001000Wave number (cmminus1 )

(a)

1400 1350 1300

(2)

(1)

reactive

1298 cmminus1

1334 cmminus1

free CH2OH

CH 2OH

(cmminus1 )

(b)

Figure 1 IR spectra (1) IPU (1) IPU10Xa (2) and Xa (3) (b) IPU 10Xa (1) and Xa (2)

vibrations of C-O and decrease of intensity of the valencesymmetric vibrations of C-O-C 1105 cmminus1 (Figures 1(a) and2) indicates the hydrogen association of ether oxygen ofpolyurethane with OH -groups of Xa The appearance of abroad weak band at 3533 cmminus1 is associated with the presenceof free OH groups of Xa

At the same time the appearance in the spectrum of theIPUXa (Figure 1(b) curve (1)) of the band at 1334 cmminus1assigned to the C-H bond of CH2OH group with intensitylower than that for the native Xa and absence of the band1298 cmminus1 (Figure 1(b) curve (2)) indicates the participationof these groups in the formation of a chemical bond with theNCO groups of ionomeric oligourethane

35 DMA Results The temperature dependencies oftan 120575 K 1198641015840 and viscoelastic characteristics for the IPU andIPUXa films are shown in Figure 2 and Table 2 Thedependence tan 120575-119879 (Figure 2(a)) for the IPU is typical forsegmented polyurethanes there are two relaxation processescorresponding to the soft and hard blocks The maximumin the temperature range of minus70 to 10∘b (119879119892 = minus30∘b)corresponds to the IPU soft blocksrsquo relaxation transition Inthe same temperature range a sharp drop of 1198641015840 (Figure 2(b))is observed Sharp peak of tan 120575 at 90∘b and sharp drop of 1198641015840higher that 70∘b indicate the existence of hard block in IPU

Such viscoelastic behavior is inherent tomany segmentedIPU This is due to the segmental mobility in the hardblocksrsquo microregions (hard domains) and their destructionThe relaxation transition typical for the soft block of IPUis also observed for all IPUXa films along with the fixedbeginning of the relaxation transition for the hard block(Figure 2(a)) However the viscoelastic behavior of theIPUXa is significantly affected by incorporation of XaThe increase of Xa content results in significant loweringof the relaxation peak corresponding to the soft blockand in 119879119892 reduction (Table 2) Thus 30 of Xa content(IPU30Xa) leads to lowering of 119879119892 by 20∘C in regard to 119879119892 ofIPU

Table 2 Viscoelastic characteristics of xanthan containing IPU

Xa content 119879119892 ∘b(according to tan 120575max)

tan 120575max1198641015840VP1(25∘b )

0 minus30 054 655 minus42 021 13610 minus45 018 24730 minus50 009 1230

Such changes in relaxation behavior may be causedby three-dimensional Xa molecules which form steric hin-drances during the IPUXa soft block formation It leads toits partial destruction and 119879119892 lowering At the same timethe decrease of specific weight of IPUXa soft-segmentedpart and interaction between the polar groups of the IPUand the OH groups of Xa results in the blocking of flexi-ble polymer chains mobility and consequently decreasingtan 120575max The relaxation transition corresponding to the hardblock of IPUXa begins at higher temperatures compared toIPU matrix and is characterized by a smoother increase ofmechanical loss factor (Figure 2(a)) Possibly the destructionof hard domains in IPUXa is preceded by the gradualdestruction of intermolecular hydrogen bonds between theOH groups of Xa and urethane and urea groups of IPUWhen Xa content amounts to 30 the growth of mechanicalloss factor is not observed up to 240∘C Perhaps a significantincrease in the proportion of bound urethane groups at suchXa concentration leads to a sharp restriction or completeblocking of segmental mobility in the hard block The low-intensity relaxation maxima on the temperature dependenceof tan 120575 indicate the heterogeneity of the IPUXa systemsand the presence of amorphous microregions with differentcompositions Incorporation of Xa results in substantialincrease of storage modulus (Figure 2(b)) Thus at 119879 = 25∘Cthe value of the storage modulus for IPU5Xa is more than20 times higher than that for the pure IPUWhen the contentof Xa reaches 30 (IPU30Xa) the value of storage modulusincreases almost in 200 times (Table 2) Such significant


(4)

(1)

(3)(2)

01

02

03

04

05

06

07ＮＨ

1500 50 100 200 250minus50minus100T (∘C)

(a)

(4)

(2)

(1)

(3)

1

10

100

1000

E

(MPa

)

1500 50 100 200 250minus50minus100T (∘C)

(b)

Figure 2 Temperature dependence of tan 120575 (a) and 1198641015840 (b) of IPU matrix (1) IPU5Xa (2) IPU10Xa (3) and IPU30Xa (4)

increase of the storage modulus of Xa-comprising IPUsconfirms the presence of chemical and hydrogen bondingbetween the components

Thus viscoelastic properties of IPU30Xa are determinedby Xa content and intermolecular interactions between thecomponents

36 Acid and Alkaline Hydrolysis The presence of Xa inthe IPU chain determines the nature of hydrolysis oneof the main factors of the materialsrsquo degradation underenvironmental conditions The higher the Xa content thegreater the mass loss and the lower the strength and elasticityof the films after hydrolysis (Table 3) that is IPUXa filmsare more susceptible to hydrolytic destruction in comparisonwith the IPU matrix

The IPUXa (bio)degradation ability was studied by atechnique that allows us to simulate the processes taking placeunder the natural conditions [20] Samples were incubatedin containers with soil of medium biological activity (pH =682 relative humidity 60 119879 = 14ndash25∘C) for a period of1ndash4months [21]The analysis of the soilrsquos bacterial populationhas shown the presence of fungi of the following generaRhizopus Aspergillus and Penicillium

The rate of degradation was controlled by weight loss ofincubated samples through regular intervals The higher theXa content the greater the mass loss of the samples (Table 4)and within 4 months it reaches 102 (IPU5Xa) and 38(IPU30X a) which exceeds the actual Xa content and thespecified matrix characteristic This indicates the possibilityof control of destruction rate by changing the componentcomposition

Soil-born microorganisms (MO) affect the filmsrsquo proper-ties They provoke a decrease of physic-mechanical parame-ters (120590120576) after remaining 4months in the soil for IPUmatrixby 2814 for IPU5Xa by 50118 0 respectively andfor IPU10Xa and IPU30Xa these indices are not availablebecause the films have lost their integrity Thus the presenceof Xa promotes biodegradation of polymer materials Visualassessment of the films after testing in the soil also indicatesa sufficiently high degree of samplesrsquo damage with MO

Inte

nsity

(rel

uni

t)

3522

0

02

04

06

12

10

14

083232

17171698 1683

1045

(2)(1)

3000 2500 2000 1500 10003500Wave number (cmminus1 )

Figure 3 IR spectra of IPU10Xa before (1) and after (2) incubationinto the soil for 4 months

The degradation of the samples was confirmed by IRspectroscopy on the example of IPU10Xa Figure 3 showsIR spectra of IPU10Xa before (1) and after (2) incubationinto the soil In the absorption region (1000ndash1800) cmminus1 ofthe after-ground sample (spectrum 2) a redistribution of theintensities of the bonded 1698 cmminus1 and free 1717 cmminus1 C=Ogroups is observed The appearance of a new band 1683 cmminus1is associated with the decomposition of COOH groups theester group turns into an ether one In addition the expanseof the OH- groupsrsquo band to the more (3522 cmminus1) and less(3232 cmminus1) frequency region is observed The appearanceof a new band 1045 cmminus1 is a result of the ether bondsdecomposition after sample incubation in the soil

37Thermodestruction Theprocesses of thermal destructionof IPU and IPUXa a comparative analysis of their structureand the depth of (bio)degradation in the soil were estimatedby the PMS method

Analysis of the temperature dependence of the total ioncurrent of the emission of volatile degradation products of theIPU (Figure 4(a)) has shown its complete thermal decompo-sition in two stageswithmaximumdecomposition rates at the


Table 3 Physic-mechanical characteristics of the IPU IPUXa films after acid and alkaline hydrolysis

Xa content 01 N solution of PX 01 N solution of XCl

Weight loss Tensile strength120590VP1

Elongation at a breakpoint 120576 Weight loss Tensile strength

120590VP1Elongation at a break

point 120576 0 01 57 970 022 67 86050 18 13 442 17 17 40210 33 lowast lowast 34 lowast lowast30 106 lowast lowast 11 lowast lowastlowastFragmentation of the film

0

50

100

150

200

(1)

(2)

I

50 100 150 200 250 300 350 400 4500

T (∘C)

(a)

(1)

(2)

(3)

50 100 150 200 250 300 350 400 4500

T (∘C)

0

50

100

150

200

250

300

I

(1)

(2)

(b)

Figure 4The temperature dependence of the ion current intensity for IPU (a) IPU10Xa (1 2) and IPU30Xa (11015840 21015840) (b) (1 11015840) initial sample(2 21015840) sample after incubation in the soil (4 months) (3) initial Xa

Table 4 Results of of IPUXa incubation in the soil

Characteristic(4 months)

Xa content 0 50 100 300

Weight loss 13 102 13 38Changing ofphysic-mechanical indicesafter the test (120590120576)

2814 501180 lowast lowastlowastFragmentation of the film

temperatures of 250∘C and 350∘C which corresponds to thedecomposition temperatures of hard and soft blocksThe firststage corresponds to the pyrolysis of urethane and urea bondsand the second to the pyrolysis of oligoether fragments [22]Themaximum of the peak of IPU kept in the soil shifts to thelower temperature (220∘C) and is supplemented by a decreaseof the intensity of the decomposition peak of hard blocksThe maximum decomposition peak of soft blocks remains atthe same temperature of 350∘C however the intensity of thetotal ion current of volatile products is significantly increasedThus keeping the IPU films in the soil results in the primarydegradation of oligoether component since it is known [23]that the oligoether fragments are predominantly situated inthe IPU surface layers In the initial IPU10Xa (Figure 4(b))

the high intensity of the volatile productsrsquo release is observedat the hard blocksrsquo decomposition and is accompanied bythe release of water as well as the following fragments(mz 28 (CO C2H4 N2 CHNH) 31 (CH3O CH2OH)43 (C2H5N) C3H7) CH3CO) 55 (C4H7) CH2CHCO) 71(CH2CHCH2CHO) and 73 (OHCCH2CHOH)) which arethe pyrolysis products of urethane and urea groups Withthe increase of Xa content (sample IPU30Xa) the intensityof release of the volatile products of the hard block decom-position increases (Figure 4(b) (11015840)) After the incubationinto the soil similar to IPU a greater intensity of volatileproductsrsquo release is observed at the decomposition of thesoft blocks for both IPU10Xa and IPU30Xa The shift ofthe maximum (350∘C) is not observed For the incubatedIPU10Xa and IPU30Xa samples the temperature of themaximum intensity of the release of volatile decompositionproducts of the hard block is shifted towards the lowertemperatures from 230 to 210∘C for IPU10Xa and from 230to 200∘C for IPU30Xa

The dependence of the ion current on temperature for Xahas only onemaximum at 250∘C (Figure 4(b))The fragmentswith mz 18 and 44 corresponding to water and carbondioxide have the maximum specific content It should benoted that there are practically no fragments typical for thedegradation of native Xa (mz 15 (CH3) 17 (OH) 32 (O2)


15

30

45

(2)

(3)

20 3010

I(r

el u

nit)

2 (degree)

(1)(1)

(2)

(a)

10 20 30

15

30

I(r

el u

nit)

2 (degree)

(1)

(2)

(3)

(3)

(b)

Figure 5 WAXS patterns of IPU and Xa-containing IPU (a) initial IPU (1) IPU5Xa (2) Xa (3) and being exposed in a soil for 4 monthsIPU (11015840) and IPU5Xa (21015840) (b) initial IPU (1) IPU5Xa (2) and IPU10Xa (3 31015840) (3) experimental and (31015840) additive

and 60 (CH2CO2H)) among the degradation products ofIPU10Xa and IPU30Xa which indicates the chemical bind-ing of Xa As it follows from the temperature dependencethe destruction of the IPU hard block occurs with higherintensity in comparison with the IPU10Xa and IPU30Xawhich may be a result of intra- and intermolecular hydrogenbonding between OH groups of Xa and urethane and ureagroups of IPU Therefore the destruction of intermolecularhydrogen bonds precedes the destruction of the hard blocksand results in the decrease of the IPUXa hard blocksrsquodecomposition intensity However the higher the Xa contentthe lower the degradation temperature

38 X-Ray Analysis The presence of a single diffuse diffrac-tion maximum with angular position 2120579m = 203∘ in WAXSpatterns of IPU and IPU5Xa (Figure 5(a) curves (1 2))shows that these polymers are characterized by short-rangeorder at the translation in expanse of their macrochainfragments

The average distance (119889) between the centers of macro-molecular chain layers of IPU and IPU5Xa according tothe Bragg equation 119889 = 120582 (2 sin 120579) minus 1 (where 120582 is thewavelength of the CuK120572 radiation 120582 = 0154 nm) amounts to0437 nm

Two discrete diffraction maxima singlet and multipletat 2120579119898 = 193∘ and 262∘ respectively appeared against abackground of evident asymmetric diffraction peak 2120579119898 asymp206∘ in WAXS pattern of Xa (Figure 5(a) curve (3))testifying to the amorphous-crystalline structure of Xa

Nonlinear change of scattering intensity in the range of2120579 sim 112∘ndash170∘ is indicated by poorly detected diffractionmaximum at 2120579119898 sim 158∘ (arrow) This maximum describesthe short-range order at the translation in the Xa volume ofits side branch fragments

We evaluated the relative level of crystallinity 119883cr ofpolysaccharide Xa in accordance with Matthewsrsquos method[24] 119883cr asymp 20 and determined effective size L of Xacrystallites using Scherer method [25] 119871 asymp 18 nm

The amorphous-crystalline structure of Xa was notdetected on the X-ray diffraction pattern of IPU5Xa andIPU10Xa (Figure 5(b) curve (2 3)) due to intermolecularinteraction between components Comparison of experi-mental and calculated additive (when interaction betweencomponents is absent) X-ray diffraction patterns of IPU10Xa(Figure 5(b) curves (3 31015840)) has served as evidence thatthe absence of Xa crystalline structure phenomenon inIPUXa composition is caused by intermolecular interactionsbetween IPU and Xa components

Calculated additive X-ray diffraction pattern of IPU10Xa(Figure 5(b) curve (31015840)) has shown that in case of the absenceof componentsrsquo interaction there is a weak expression ofthe most intense diffraction peaks (at 2120579119898 = 193∘ and262∘) that characterize the crystalline structure of Xa Thisis a conformation of intermolecular interactions betweenIPU and Xa which results in suppression of Xa capacity forcrystallization

The invariable intensity and angular position of theamorphous halo (2120579119898 asymp 203∘) of the initial and aged in thesoil IPU and IPU5Xa samples (Figure 5(a) curves (1 11015840) and(2 21015840)) indicate that there is no change in their amorphousstructure

For more complete structural characterization of theinitial 13 and aged for 4 months in the soil IPU and IPU5Xasamples we study their microheterogeneous structure SAXSresults (Figures 6(a) and 6(b)) have shown that all studiedpolymers have microheterogeneous structure There are theareas of microheterogenity in their volume the electrondensity (Δ120588) between which is different from zero Δ120588 =


1 2

12

24

(1)(2)

(3)(4)

2 (degree)

I(r

el u

nit)

(a)

1 2

12

24

(3)

2 (degree)

I(r

el u

nit)

(1)(2)

(b)

Figure 6 SAXS patterns of IPU and Xa-containing IPU (a) initial IPU (1) and IPU5Xa (2) and being exposed in soil for 4 months IPU (3)and IPU5Xa (4) and (b) initial IPU (1) IPU5Xa (2) and IPU10Xa (3)

120588 minus ⟨120588⟩ where 120588 and ⟨120588⟩ are the local and average value ofthe electron density in two-phase system

The comparison of the profiles of the initial and agedfor 4 months in soil IPU and IPU5Xa samples has shownthat the initial IPU has the lowest scattering intensity as aresult of thermodynamic incompatibility between soft andhard IPUunits [26]The sample IPU5Xa has a slightly higherscattering intensity than the IPU Even higher scatteringintensity and correspondingly the value of the electrondensity contrast have the sample IPU10Xa At that the lackof interference maximum on the intensity profiles indicates adisordered placement of microareas of heterogeneity in poly-mer volume (Figure 6(b)) Attention is drawn to the fact thatexposure of samples to soil for 4 months results in a growthof scattering intensity of both IPU and particularly IPU5XaThe appearance of the interference maximum 2120579119898 asymp 092∘in a form of ldquoshoulderrdquo (Figure 6(a) curves (3 4)) indicatesthe existence of periodicity in distribution of microareas ofheterogeneity with different size of local electron density inIPU5Xa volume According to the above Bragg equation thevalue of period 119863 of alternation in the volume of monotype120588-sized microareas of heterogeneity is 96 nm It should benoted that the increase of the SAXS intensity at the transitionfrom IPU to IPU5Xa and IPU10Xa as well as the resultof exposure of the first two samples for 4 months in soilcharacterizes the variations of the level of heterogeneity oftheir structure To quantify the relative level of heterogeneityof the structure we calculated the structural parameterldquoPorod invariantrdquo 1198761015840 [27] the value of which is independent(invariant) of the form of microareas of heterogeneity

1198761015840 = intinfin

0119902119868 (119902) 119889119902 (1)

where q is directed magnitude of wave vector s (119902 = 2120587119904)

Table 5 Parameters of microheterogeneous structure of initial IPUIPU5Xa IPU10Xa and IPU IPU5Xa after 4 months of exposurein soil

Sample 1198761015840 rel unit 119897119901 nmIPU 59 65IPU5Xa 64 54IPU10Xa 78 61IPU 4 months in soil 65 58IPU5Xa 4 months in soil 78 53

This parameter characterizes the integral intensity of X-ray scattering by two-phase system and has a direct connec-tion with the quadratic fluctuation of electron density in itsvolume

According to calculated values of 1198761015840 (Table 5) IPUpossesses the least level of structure heterogeneity whileIPU10Xa and IPU5Xa which are kept for 4 months in soilhave the largest level of structure heterogeneity

Another characteristic of microheterogeneous structureof studied systems is the average size of microareas of hetero-geneity existing in their volumeThe range of heterogeneity 119897119901was determined by the Ruland method [28] This parameteris directly related to the average diameter of the microareasof heterogeneity in the two-phase system It was determinedthat presence of Xa results in a decrease of the effective sizeof microareas of heterogeneity both in the initial samples andafter 4 months of exposure in soil (Table 4) Unlike the levelof heterogeneity 1198761015840 the transition from IPU to IPU5Xa andIPU10Xa causes in general the reduction of the range ofheterogeneity 119897119901 (Table 4)

Thus as a result of X-ray study Xa has been found tomiss its ability to crystallization due to the intermolecular


interactions between components in IPUXa systems Theincrease of Xa content in IPUXa systems reduces the sizeof microareas of heterogeneity The disappearance of thediffraction maximum (2120579119898 asymp 122∘) after exposure of thesample IPU5Xa in the soil indicates a change of its amor-phous structure as a result of (bio)degradation following aconsecutive increase of structure heterogeneity on nanosizedlevel

4 Conclusions

New ecologically friendly IPUs were prepared on the basisof the renewable exopolysaccharide Xa Introduction ofXa allows partially replacing exhaustible oil row materialsand improving the strength properties of pure IPU matrixthe tensile strength of IPUXa systems is 1ndash5 times highercompared with IPU Along with retention of other func-tional characteristics of the IPU Xa imparts it a propertyof (bio)degradation after the end of lifetime that leads tothe deep chemical transformations occurring in the IPUXasystemsThe proven covalent and hydrogen bonding betweencomponents ensures the occurrence of destructive processesof the entire system as a whole With an increase of Xacontent the mass loss of IPUXa systems as a result ofhydrolytic splitting and degradation in the soil increasesand exceeds the actual content of Xa and the value of massloss of the IPU matrix The results of PMS DMA and X-ray scattering indicate that the presence of Xa in polymermacrochain leads to the formation of a new structuralorganization different from the structure of the IPU matrixdue to the chemical bonding between the exopolysaccharideand diisocyanate The structural and operational propertiesand degradability of studied polymers are determined bythe structure and content of the natural component Film-forming aqueous polyurethane dispersions on the basis ofexopolysaccharide Xa are perspective as biologically activesubstances in agriculture immunostimulants and protectivecoating for seeds and plants antitranspirants for reducingwater scarcity and optimization of the production processof crops in drought conditions and binders for biologicallyactive substances granulation The advantages of such mate-rial lie in environmentally friendly production technologydue to the absence of organic solvent economy throughthe use of cheap renewable raw materials and reducing theharmful impact on the environment through the regulatedlevel of (bio)degradation after the expiration of life time

Conflicts of Interest

The authors declare that there are no conflicts of interest

References

[1] S Rogovina K Aleksanyan E Prut and A Gorenberg ldquoBiode-gradable blends of cellulose with synthetic polymers and someother polysaccharidesrdquo European Polymer Journal vol 49 no 1pp 194ndash202 2013

[2] S A Ashter ldquoOverview of biodegradable polymersrdquo in Intro-duction to Bioplastics Engineering pp 19ndash30 Elsevier Amster-dam Netherlands 2016

[3] T Travinskaya and Y Savelyev ldquoAqueous polyurethanedispersionsmdashsodium alginate based blends and hydrogelsrdquoFrontiers in Heterocyclic Chemistry vol 2 no 1 pp 20ndash25 2016

[4] P Alagi Y J Choi and S C Hong ldquoPreparation of vegetableoil-based polyols with controlled hydroxyl functionalities forthermoplastic polyurethanerdquoEuropean Polymer Journal vol 78pp 46ndash60 2016

[5] M J Donnelly J L Stanford and R H Still ldquoThe conversionof polysaccharides into polyurethanes A reviewrdquo CarbohydratePolymers vol 14 no 3 pp 221ndash240 1991

[6] J G Southwick H Lee A M Jamieson and J Blackwell ldquoSelf-association of xanthan in aqueous solvent-systemsrdquo Carbohy-drate Research vol 84 no 2 pp 287ndash295 1980

[7] S C Moldovenau Analytical Pyrolysis of Natural OrganicPolymers vol 20 Brown ampWilliamson Tobacco Corp MaconGa USA 1998 p 510

[8] T V Travinskaya A N Brykova I K Kurdish A V Chevy-chalova and Y V Savelyev ldquoDegradable ionomer polyurethaneon the basis of xanthanrdquo Reports of the Academy of Sciences vol7 pp 132ndash139 2014

[9] Y V Savelyev T V Travinskaya L A Markovskaya and AN Brykova ldquoThe method of obtain of degradable polymercompositionrdquo Pat No 93372 Ukraine Publ 25092014 Bull no18 2014

[10] Q B Meng S-I Lee C Nah and Y-S Lee ldquoPreparationof waterborne polyurethanes using an amphiphilic diol forbreathable waterproof textile coatingsrdquo Progress in OrganicCoatings vol 66 no 4 pp 382ndash386 2009

[11] V Sriram S Sundar A Dattathereyan and G RadhakrishnanldquoSynthesis and characterization of cationomeric AB crosslinkedpolyurethane polymers based on different chain extendersrdquoReactive and Functional Polymers vol 64 no 1 pp 25ndash34 2005

[12] J Bullermann S Friebel T Salthammer and R SpohnholzldquoNovel polyurethane dispersions based on renewable rawmaterialsmdashStability studies by variations of DMPA content anddegree of neutralisationrdquo Progress in Organic Coatings vol 76no 4 pp 609ndash615 2013

[13] T Travinskaya Y Savelyev and E Mishchuk ldquoWaterbornepolyurethane based starch containing materials preparationproperties and study of degradabilityrdquo PolymerDegradation andStability vol 101 no 1 pp 102ndash108 2014

[14] S J Lee and B K Kim ldquoCovalent incorporation of starchderivative into waterborne polyurethane for biodegradabilityrdquoCarbohydrate Polymers vol 87 no 2 pp 1803ndash1809 2012

[15] Y V Savelyev T V Travinskaya L P Robota et al ldquoBiodegrad-able polyurethane materials of different origin based on nat-ural componentsrdquo Austin Journal of Biomedical Engineeringvol 2 no 1 article 1030 2015 httpwwwaustinpublishing-groupcom

[16] ASTM D2572-03 ldquoStandard test method for isocyanate groupsin urethane materials or prepolymersrdquo ASTM West Con-shohocken Pa USA 2003

[17] S Y Shegolev and V I Klenin ldquoDetermination of parameters ofcomplicated disperse polymer system from turbidity spectrumrdquoVysokomolekulyarnye Soedineniya B vol 13 no 12 pp 2809ndash2815 1971

[18] T V Travinskaya A N Brykova V I Bortnitskiy and YuV Savelyev ldquoPreparation and Properties of (bio)degradable


ionomer polyurethanes based on xanthanrdquo Polymernyj Journalvol 36 no 4 pp 393ndash400 2014

[19] N I Levchenko S A Sukhorukova and T V TravinskayaldquoAqueous anionactive polyurethanes for highmdashquality coat-ingsrdquo in Proceedings of the Partnership in Polymers the Cam-bridge Polymer Conference pp 195ndash200 Cambridge UK 1996Special conference issue of full papers

[20] B S Lee M Vert and E Holler Water-Soluble AliphaticPolyesters Poly(malic acid)s Wiley-VCH Verlag Gmbh Wein-heim Germany Polyester 1st edition 2002

[21] I P Babaeva and G M Zenova Biology of Soils MoscowUniversity Moscow Russia 1989

[22] V A Zaikin Mass Spectroscopy of Synthetic Polymers All-Russian Mass Spectrometric Society Moscow Russia 2009

[23] V V Boyko L V Kobrina S V Riabov and R L GaidukldquoInvestigation of biodegradable properties of polyurethanecompositions filled by chitosanrdquo Polymernyj Journal vol 26 no4 pp 235ndash238 2004

[24] J L Matthews H S Peiser and R B Richards ldquoThe X-raymeasurement of the amorphous content of polythene samplesrdquoActa Crystallographica vol 2 no 2 pp 85ndash90 1949

[25] A Guiner Radiography of CrystalsTheory And Practice NaukaMoscow Russia 1961 p 604

[26] V I Shtompel and Y Y Kercha Structure of Linear Polyur-ethanes Nauka Moscow Russia 2008 Kiev p 248

[27] G Porod in General Theory Small-Angle X-Ray ScatteringO Glatter and O Kratky Eds pp 17ndash51 Academic PressCambridge Mass USA 1982 London

[28] R Perret and W Ruland ldquoEine verbesserte Auswertungsmeth-ode fur die Rontgenkleinwinkelstreuung von HochpolymerenrdquoKolloid-Zeitschrift amp Zeitschrift fur Polymere vol 247 no 1-2pp 835ndash843 1971

Submit your manuscripts athttpswwwhindawicom

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



the necessary operational parameters during the time oftheir use in combination with accelerated degradation underthe influence of various natural factors after the expira-tion Microorganisms are the main biological systems whichdestroy the polymeric compounds The ability of polymersto degrade and be assimilated by microorganisms dependson a number of their characteristics the chemical structureof the polymer molecular weight branching of macrochainand supramolecular structure [15] The aim of the latestdevelopments in the field of degradable polymers is toestablish the common principles in selecting the componentsfor synthesis of polymer which combine a high level ofperformance with the (bio)degradation ability and knack ofadjusting the (bio)degradation processes to ensure fast andsafe (bio)degradation of polymer materials at the expirationof their working time The paper considers the synthesis andcomplex study of ldquocomposition structure properties and(bio)degradation abilityrdquo relationship of structurally modi-fied polymeric materials based on polyurethane ionomer andmicrobial exopolysaccharide xanthan

2 Experimental

21 Materials Hexamethylene diisocyanate (HMDI)(Merck) polyoxytetramethylene glycol (POTMG 1000)dimethylolpropionic acid (DMPA) triethylamine (TEA)and Xa in the form of powder (Brookfield viscosity of1 solution according to Certificate of analysis amounts959 cps) were purchased from Aldrich and used as receivedacetone was purchased from Fluka

22 Preparation of Xanthan Containing Ionomer Polyure-thane Xanthan containing ionomer polyurethanes (IPUXa)in the form of aqueous dispersions was prepared by the reac-tion of an isocyanate precursor based on POTMG andHMDIwith DMPA as ion centers carrier taken in a molar ratioof 1 2 06 The reaction time for the isocyanate precursorformation was 2 h at 80∘C until the NCO content reached thetheoretical value to produce NCO-terminated prepolymerThe content of NCO groups was controlled according to[16] Then DMPA was added and reacted with prepolymerat 80∘C for 1 h Suitable amount of acetone was added tothe system to decrease the viscosity of reaction mixtureXa (C35H49O29)119899 was added to the reaction mixture in aform of dry powder (the reaction time was 1 h at 56∘C)Neutralization of the DMPA fragmentsrsquo carboxyl groups ofobtained IPUXa hard block was performed with TEA (themolar ratio of TEA DMPA = 1 1) Next a simultaneouselongation and water dispersion were carried out followedby removal of acetone Film-forming opalescent dispersionswere then obtained by phase inversion Polymer films wereformed at room temperature on a Teflon disk followed bydrying in an oven at 65∘C and in a vacuum oven at 55∘C toconstant weight

IPUXa systems with different Xa weight concentrations5 10 and 30 (IPU5Xa IPU10Xa IPU30Xa) wereprepared IPU matrix was synthesized similar to IPUXa(using water as chain extender without addition of Xa) andhas been selected as an object of comparison

23 Characterization

231 pHValues pH values were determined using pH-meterldquopH-150 Mrdquo (Russia)

232 Particle Size Particle size measurements were deter-mined from the turbidity spectrum using FEK-56M accord-ing to [17]

233 Mechanical Properties Measurements were performedusing a tensile testing machine FU-1000 (VEB MWK ldquoFritzHeckertrdquo Germany) at a tensile speed of 100mmmin andtemperature 25∘C The number of samples used in eachmeasurement was three Samples were prepared in a form ofstrips (width 4mm operating length 2mm) Measurementswere carried out in accordance with standard 14236-81allowed error is 3

234 Water Absorption Preliminary weighed dry films ofIPU matrix IPUXa were immersed in water for 24 hwhereupon the excess water was removed with filter paperand samples were weighed Water absorption (119882H2O wt)was calculated according to 119882H2O() = [(119882119908 minus 119882119889)119882119889] sdot100 where 119882119908 and 119882119889 are weight of the films in a wet anddry state correspondingly

235 Degree ofHydrolysis inAcid andAlkaliMedium Degreeof hydrolysis in acid and alkali medium was determinedby evaluation of the weight change and physic-mechanicalcharacteristics of the samples after hydrolysis Preweighedsamples were immersed in 01 N solution of KOH and HCland kept in a thermostat for 30 days at 119879 = 25∘C afterwardsthe films were dried to constant weight with following weightcontrol and tensile test

236 IR Measurements IR measurements were performedon Bruker ldquoTensor-37rdquo Fourier transform infrared spectrom-eter in the region of wave numbers of 4500 cmminus1ndash500 cmminus1Samplesrsquo surfaces were studied by attenuated total internalreflection infrared spectroscopy

237 Thermodestruction of Xa-Containing IPU Thermode-struction of Xa-containing IPU was studied by pyrolyticmass spectrometry (PVS) A device consisting of a massspectrometer MX-1321 for determination of the componentsof gasmixtures in the range ofmass numbers of 1ndash4000 and ofcells for linearly programmable pyrolysis in the temperaturerange 25ndash400∘b was used The sample was placed into thecell which was evacuated (133 sdot 10minus4 Pa) for 30 minutesat 25∘C The same pressure was maintained during theexperimentThe heating rate was (6plusmn 1)∘bminThe accuracyof determining the temperature of the sample was plusmn1∘C Theionization energy in the chamber of the mass spectrometerwas 70 eV

238 The X-Ray Diffraction Patterns The wide-angleX-ray diffraction patterns (WAXS) were recorded with






Contact angledegree



0 71 784 26 68 73 110050 176 755 23 50 81 742100300

272 717 65 45 169 530504 682 405 29 364 360















(1)

(2)(3)3533

1031

1720

3375

00

02

04

06

08

10

Inte

nsity

(rel

uni

t)


(a)

1400 1350 1300

(2)

(1)

reactive

1298 cmminus1

1334 cmminus1

free CH2OH

CH 2OH

(cmminus1 )

(b)








tan 120575max1198641015840VP1(25∘b )




(4)

(1)

(3)(2)

01

02

03

04

05

06

07ＮＨ

1500 50 100 200 250minus50minus100T (∘C)

(a)

(4)

(2)

(1)

(3)

1

10

100

1000

E

(MPa

)

1500 50 100 200 250minus50minus100T (∘C)

(b)








Inte

nsity

(rel

uni

t)

3522

0

02

04

06

12

10

14

083232

17171698 1683

1045

(2)(1)













0

50

100

150

200

(1)

(2)

I

50 100 150 200 250 300 350 400 4500

T (∘C)

(a)

(1)

(2)

(3)

50 100 150 200 250 300 350 400 4500

T (∘C)

0

50

100

150

200

250

300

I

(1)

(2)

(b)




Xa content 0 50 100 300







15

30

45

(2)

(3)

20 3010

I(r

el u

nit)

2 (degree)

(1)(1)

(2)

(a)

10 20 30

15

30

I(r

el u

nit)

2 (degree)

(1)

(2)

(3)

(3)

(b)













1 2

12

24

(1)(2)

(3)(4)

2 (degree)

I(r

el u

nit)

(a)

1 2

12

24

(3)

2 (degree)

I(r

el u

nit)

(1)(2)

(b)




1198761015840 = intinfin

0119902119868 (119902) 119889119902 (1)










4 Conclusions




References






































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of







Contact angledegree



0 71 784 26 68 73 110050 176 755 23 50 81 742100300

272 717 65 45 169 530504 682 405 29 364 360















(1)

(2)(3)3533

1031

1720

3375

00

02

04

06

08

10

Inte

nsity

(rel

uni

t)


(a)

1400 1350 1300

(2)

(1)

reactive

1298 cmminus1

1334 cmminus1

free CH2OH

CH 2OH

(cmminus1 )

(b)








tan 120575max1198641015840VP1(25∘b )




(4)

(1)

(3)(2)

01

02

03

04

05

06

07ＮＨ

1500 50 100 200 250minus50minus100T (∘C)

(a)

(4)

(2)

(1)

(3)

1

10

100

1000

E

(MPa

)

1500 50 100 200 250minus50minus100T (∘C)

(b)








Inte

nsity

(rel

uni

t)

3522

0

02

04

06

12

10

14

083232

17171698 1683

1045

(2)(1)













0

50

100

150

200

(1)

(2)

I

50 100 150 200 250 300 350 400 4500

T (∘C)

(a)

(1)

(2)

(3)

50 100 150 200 250 300 350 400 4500

T (∘C)

0

50

100

150

200

250

300

I

(1)

(2)

(b)




Xa content 0 50 100 300







15

30

45

(2)

(3)

20 3010

I(r

el u

nit)

2 (degree)

(1)(1)

(2)

(a)

10 20 30

15

30

I(r

el u

nit)

2 (degree)

(1)

(2)

(3)

(3)

(b)













1 2

12

24

(1)(2)

(3)(4)

2 (degree)

I(r

el u

nit)

(a)

1 2

12

24

(3)

2 (degree)

I(r

el u

nit)

(1)(2)

(b)




1198761015840 = intinfin

0119902119868 (119902) 119889119902 (1)










4 Conclusions




References






































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of



(1)

(2)(3)3533

1031

1720

3375

00

02

04

06

08

10

Inte

nsity

(rel

uni

t)


(a)

1400 1350 1300

(2)

(1)

reactive

1298 cmminus1

1334 cmminus1

free CH2OH

CH 2OH

(cmminus1 )

(b)








tan 120575max1198641015840VP1(25∘b )




(4)

(1)

(3)(2)

01

02

03

04

05

06

07ＮＨ

1500 50 100 200 250minus50minus100T (∘C)

(a)

(4)

(2)

(1)

(3)

1

10

100

1000

E

(MPa

)

1500 50 100 200 250minus50minus100T (∘C)

(b)








Inte

nsity

(rel

uni

t)

3522

0

02

04

06

12

10

14

083232

17171698 1683

1045

(2)(1)













0

50

100

150

200

(1)

(2)

I

50 100 150 200 250 300 350 400 4500

T (∘C)

(a)

(1)

(2)

(3)

50 100 150 200 250 300 350 400 4500

T (∘C)

0

50

100

150

200

250

300

I

(1)

(2)

(b)




Xa content 0 50 100 300







15

30

45

(2)

(3)

20 3010

I(r

el u

nit)

2 (degree)

(1)(1)

(2)

(a)

10 20 30

15

30

I(r

el u

nit)

2 (degree)

(1)

(2)

(3)

(3)

(b)













1 2

12

24

(1)(2)

(3)(4)

2 (degree)

I(r

el u

nit)

(a)

1 2

12

24

(3)

2 (degree)

I(r

el u

nit)

(1)(2)

(b)




1198761015840 = intinfin

0119902119868 (119902) 119889119902 (1)










4 Conclusions




References






































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of



(4)

(1)

(3)(2)

01

02

03

04

05

06

07ＮＨ

1500 50 100 200 250minus50minus100T (∘C)

(a)

(4)

(2)

(1)

(3)

1

10

100

1000

E

(MPa

)

1500 50 100 200 250minus50minus100T (∘C)

(b)








Inte

nsity

(rel

uni

t)

3522

0

02

04

06

12

10

14

083232

17171698 1683

1045

(2)(1)













0

50

100

150

200

(1)

(2)

I

50 100 150 200 250 300 350 400 4500

T (∘C)

(a)

(1)

(2)

(3)

50 100 150 200 250 300 350 400 4500

T (∘C)

0

50

100

150

200

250

300

I

(1)

(2)

(b)




Xa content 0 50 100 300







15

30

45

(2)

(3)

20 3010

I(r

el u

nit)

2 (degree)

(1)(1)

(2)

(a)

10 20 30

15

30

I(r

el u

nit)

2 (degree)

(1)

(2)

(3)

(3)

(b)













1 2

12

24

(1)(2)

(3)(4)

2 (degree)

I(r

el u

nit)

(a)

1 2

12

24

(3)

2 (degree)

I(r

el u

nit)

(1)(2)

(b)




1198761015840 = intinfin

0119902119868 (119902) 119889119902 (1)










4 Conclusions




References






































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of









0

50

100

150

200

(1)

(2)

I

50 100 150 200 250 300 350 400 4500

T (∘C)

(a)

(1)

(2)

(3)

50 100 150 200 250 300 350 400 4500

T (∘C)

0

50

100

150

200

250

300

I

(1)

(2)

(b)




Xa content 0 50 100 300







15

30

45

(2)

(3)

20 3010

I(r

el u

nit)

2 (degree)

(1)(1)

(2)

(a)

10 20 30

15

30

I(r

el u

nit)

2 (degree)

(1)

(2)

(3)

(3)

(b)













1 2

12

24

(1)(2)

(3)(4)

2 (degree)

I(r

el u

nit)

(a)

1 2

12

24

(3)

2 (degree)

I(r

el u

nit)

(1)(2)

(b)




1198761015840 = intinfin

0119902119868 (119902) 119889119902 (1)










4 Conclusions




References






































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of



15

30

45

(2)

(3)

20 3010

I(r

el u

nit)

2 (degree)

(1)(1)

(2)

(a)

10 20 30

15

30

I(r

el u

nit)

2 (degree)

(1)

(2)

(3)

(3)

(b)













1 2

12

24

(1)(2)

(3)(4)

2 (degree)

I(r

el u

nit)

(a)

1 2

12

24

(3)

2 (degree)

I(r

el u

nit)

(1)(2)

(b)




1198761015840 = intinfin

0119902119868 (119902) 119889119902 (1)










4 Conclusions




References






































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of



1 2

12

24

(1)(2)

(3)(4)

2 (degree)

I(r

el u

nit)

(a)

1 2

12

24

(3)

2 (degree)

I(r

el u

nit)

(1)(2)

(b)




1198761015840 = intinfin

0119902119868 (119902) 119889119902 (1)










4 Conclusions




References






































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of




4 Conclusions




References






































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of





















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


(bio)degradable ionomeric polyurethanes based on xanthan: … · 2019. 7. 30. · as packaging,...

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