epoxy-functionalized polyhedral oligomeric silsesquioxane/cyanate ester resin organic-inorganic...

Research ArticleReceived: 31 October 2012 Revised: 12 March 2013 Accepted: 28 April 2013 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/pi.4557

Epoxy-functionalized polyhedral oligomericsilsesquioxane/cyanate ester resinorganic–inorganic hybrids with enhancedmechanical and thermal propertiesZengping Zhang,a∗ Guozheng Liangb and Xiaolei Wangc

Abstract

A series of cyanate ester resin (CE) based organic–inorganic hybrids containing different contents (0, 5, 10, 15 and 20 wt%) ofepoxy-functionalized polyhedral oligomeric silsesquioxane (POSS-Ep) were prepared by casting and curing. The hybrid resinsystems were studied by the gel time test to evaluate the effect of POSS-Ep on the curing reactivity of CE. The impact andflexural strengths of the hybrids were investigated. The micromorphological, dynamic mechanical and thermal properties ofthe hybrids were studied by SEM, dynamic mechanical analysis (DMA) and TGA, respectively. Results showed that POSS-Epprolonged the gel time of CE. CE10 containing 10 wt% POSS-Ep displayed not only the optimum impact strength but theoptimum flexural strength. SEM results revealed that the improvement of mechanical properties was attributed to the largeamount of tough whirls and fiber-like pull-outs observed on the fracture surfaces of CE10. DMA results indicated that POSS-CEtended to decrease E′ of the hybrids in the glassy state but to increase E′ of the hybrids in the rubbery state. TGA results showedthat CE10 also possesses the best thermal stability. The initial temperature of decomposition (T i) of CE10 is 426 ◦C, 44 ◦C higherthan that of pristine CE.c© 2013 Society of Chemical Industry

Keywords: polyhedral oligomeric silsesquioxane (POSS); cyanate ester resin; hybrid materials; mechanical properties

INTRODUCTIONCyanate ester resins (CEs) are an important kind of hightemperature thermosetting polymers, the monomer of whichcontains two or more cyanate ester groups (−OCN) and is curedto a crosslinked network structure after triazine polymerization.1,2

They have received much attention because of their outstandingphysical properties including low water absorption and lowoutgassing.3 It is well known that CE monomers can be thermallycured to a highly crosslinked network. The structural characteristicsof the cured network of CE endow the resin with excellent overallproperties including high mechanical strength, high thermalstability, low water absorption and excellent dielectric properties.They include a high crosslinking density, the existence of ethergroups and a relatively high free volume in the cured CEs. The lowdielectric constant and loss of CEs (ε 2.64−3.11; tan δ 0.001−0.008)are attributed to the weak dipole effect and large free volume ofthe polycyanate network.4 As a result, CEs are widely used as thestructural or functional materials in aeronautics, space, printedcircuit boards, adhesives etc.

However, like most thermosets their main drawback isbrittleness, although CEs have relatively higher toughness than theothers.1 Their fracture toughness and the interlaminar shearingstrength of the corresponding polymer based composites are notenough under certain severe conditions.5,6 So modification of CEshas been attractive during the past decade and is still of greatinterest. CEs have been modified by many different additives,such as thermoplastic polymers,7,8 thermosetting polymers,9,10

elastomers11,12 and nanoparticles.13–16 Among these additives,nanoparticles are particularly fascinating. For example, Ganguliet al. dispersed 2.5 wt% of organic layered silicates (OLS) intoCE to increase the modulus toughness by 30%.3 Dominguezet al. showed that the storage modulus of multi-walled carbonnanotubes/CE nanocomposites with 1 wt% multi-walled carbonnanotubes was nearly 60% and 600% higher than the neatpolymer at 100 and 200 ◦C, respectively.15 Our group adoptednanostructured aluminium borate and ZnO whiskers to improvethe impact strength of CE and the interlaminar shearing strengthof the corresponding graphite fiber reinforced composites.14,17

Polyhedral oligomeric silsesquioxane (POSS) emerges as anew nanostructured material owing to its excellent mechanical,electrical and thermal properties and good compatibility with

∗ Correspondence to: Zengping Zhang, Key Laboratory for Special Area HighwayEngineering of Ministry of Education, Chang’an University, Xi’an, Shaanxi710064, PR China.E-mails: [email protected]; [email protected]

a Key Laboratory for Special Area Highway Engineering of Ministry of Education,Chang’an University, Xi’an, Shaanxi 710064, PR China

b Department of Polymer Engineering, Materials Engineering Institute, SoochowUniversity, Suzhou, Jiangsu 215021, PR China

c Institute of Dongguan-Sun Yat-Sen University, Dongguan, Guangdong 523808,PR China

Polym Int (2013) www.soci.org c© 2013 Society of Chemical Industry

www.soci.org Z Zhang, G Liang, X Wang

OCCO C

CH3

CH3

NN

(I)

Si

O

O Si

Si

O

O Si

CH2CH2CH2OCH2R

RRSi

O

O Si

SiO

O SiR R

RR

OO

O O

CH2CH2CH2OCH2 CH

O

CH2R:

CH

O

CH2

(II)

Si CH2CH2CH2OCH2 CH

O

CH2

CH3O

CH3O

CH3O

(III)

Figure 1. Chemical structures of BADCy (I), octaepoxysilsesquioxane (II)and KH-560 (III).

polymers. It has been added to different polymers to obtainnanocomposites, such as polyethylene,18 polypropylene,19

polysilicone20 etc. Recently, it has been used to modify CEs.21,22

The POSS-containing polymers displayed enhanced mechanical,thermal and dielectric properties etc. Our group synthesizedseveral kinds of POSS monomers and incorporated them into

epoxy.23–25 Recently, we reported the synthesis and curing of anepoxy-functionalized POSS monomer octaepoxysilsesquioxane(POSS-Ep).26 Considering that POSS-Ep possesses not onlygood compatibility but also reactivity with many thermosettingpolymers, POSS-Ep/CE hybrids are expected to have excellentmechanical, dielectric and thermal properties.

In this paper, POSS-Ep was incorporated into bisphenyl A typecyanate ester resin (BADCy) to prepare POSS-Ep/CE hybrids bycasting and curing. We aim to obtain a modified CE with highperformance and widen the application of CE. The curing reactivityand mechanical and thermal properties of the POSS-Ep/CE hybridswere studied. Micromorphologies were observed to elucidate theeffect of POSS on the mechanical properties of CE. The resultsshowed that an appropriate amount of POSS (10 wt%) led toa POSS-Ep/CE hybrid with optimum thermal and mechanicalproperties.

EXPERIMENTALMaterialsBisphenol A dicyanate (2,2′-bis(4-cyanatophenyl)isopropylidene)(BADCy) with purity > 99.5 wt%, white granular crystal, waspurchased from Shanghai Huifeng Kemao Ltd (Shanghai,China). Octaepoxysilsesquioxane was synthesized in our lab-oratory using the procedure described in the literature.26

γ -[(2,3)-epoxypropoxy]- propyltrimethoxysilane (KH-560) washydrolyzed and condensed at 55 ◦C for 72 h to synthesize POSS-Ep.Ethanol and HCl were used as the co-solvent and catalyst, respec-tively. The synthesized POSS-Ep is a transparent, viscous andflowable liquid at room temperature. The chemical structures ofBADCy, octaepoxysilsesquioxane and KH-560 are shown in Fig. 1.

Table 1. Compositions of different CE systems

Samples CE (wt%) POSS-Ep (wt%)

CE 100 0

CE5 95 5

CE10 90 10

CE15 85 15

CE20 80 20

180 190 200 210 2200

5

10

15

20

Gel

tim

e (m

in)

Temperature (°C)

CECE5CE10CE15CE20

Figure 2. The gelation curves of POSS-Ep/CE systems.

3200 2800 2400 2000 1600 1200 800 400

O1370

(c)

(b)

(a)

1750

910,

Si-O-Si

Abs

orba

nce

Wavenumber (cm-1)

2270,-OCN

Figure 3. FTIR monitoring of the curing behavior of system CE10 at differentcuring stages: curve (a), original; curve (b), 150 ◦C/60 min; curve (c), 180◦C/120 min + 200 ◦C/120 min.

Preparation of the POSS-Ep/CE hybridsBADCy was melted at 100 ◦C in an oil bath and different amountsof POSS-Ep were added under mechanical stirring. The blend waspre-cured at this temperature for 30 min and then transferred to astainless steel mould which was coated with release agent on theinner walls and preheated at 110 ◦C. The mold containing the resinblend was degassed at 100 ◦C for 30 min in a digital vacuum oven.The following cure procedures were then carried out: 150 ◦C for 1 hplus 180 ◦C for 2 h plus 200 ◦C for 2 h. Finally it was cooled naturallyto room temperature. The cured specimens were removed from

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Epoxy functionalized POSS/cyanate ester resin hybrids www.soci.org

the mold and cut with a water coolant to the required sizes: 15mm × 10 mm × 4 mm (type I) and 27 mm × 27 mm × 4 mm (typeII). The specimens were post-cured at 220 ◦C for 2 h.

Different hybrid resin systems containing 0, 5, 10, 15 and 20 wt%of POSS-Ep were prepared. They are designated as CE, CE5, CE10,CE15 and CE20, respectively. The compositions for the variousresin systems are listed in Table 1.

Instruments and testingThe gel time of the resins was determined with a standard hot-plate with a temperature controller. The resin was spread on thesurface of the hot-plate preheated to different temperatures. The

time required for the resin to stop legging and become elastic iscalled the gel time.

Dynamic mechanical analysis (DMA) was performed on a DMAQ800 instrument (TA Instrument Co., New Castle, DE, USA) ata frequency of 3 Hz. Ten specimens of type I without obviousflaws were tested according to ASTM D790 to obtain the flexuralstrength, and another 10 specimens of type II were testedaccording to ASTM D4812 to obtain the impact strength.

The micromorphology of the cured POSS-Ep was observedby SEM using a Hitachi S-570 scanning electron microscope(Chiyoda-ku, Tokyo, Japan). The fracture surface of the materialswas sputtered with a thin layer (about 10 nm) of gold by vapor

O C N3RTrimerization N

N

N

O O

O

R R

R

N

N

N

O O

O

R R

R

O CH2 CH CH2

O

3R'Insertion N

N

N

O O

O

Alk Alk

AlkAryl Cyanurate

Alkyl Cyanurate

N

N

N

O O

O

Alk Alk

Alk

RearrangementN

N

N

O O

O

Alk

AlkAlk

Alkyl Isocyanurate

N

N

N+

O

OO

AlK

AlKAlK

H2C CH CH2 O R'

O

R' O CH2 CH CH2

NC

O AlK

O

Si O Si

Si Si

SiSi

O

OO

O

O

O

SiSi

O

O

O

O

OR

R

(CH2)3

(CH2)3

(CH2)3

(CH2)3

(CH2)3

(CH2)3

R':

R:C

CH3

CH3

AIK: CH2 CH

O R

CH2 O R'

Figure 4. Reaction mechanisms between POSS-Ep and CE.

Polym Int (2013) c© 2013 Society of Chemical Industry wileyonlinelibrary.com/journal/pi


deposition on a stainless steel stub using a Polaron SC502 vacuumsputter coater before the SEM observation.

TGA was performed using a Perkin Elmer TGA-7 microbalancecoupled with a 1022 Perkin Elmer microprocessor. Themicrobalance was calibrated making use of the Curie points ofperk alloy and nickel.

RESULTS AND DISCUSSIONCuring reactivity of the POSS-Ep/CE hybrid resinsGel time testing is an important method for evaluating the curingreactivity of thermosetting polymers. It is important for the deter-mination of the curing technique. Gelation behavior is dependenton many factors including temperature, pressure and time etc.It will influence the phase structure and mechanical propertiesof cured resins as well as the corresponding composites.27,28

Consequently, investigation of the gelation characteristics of thethermosetting polymers is of great interest for the determinationof curing techniques and molding conditions.

Figure 2 shows the gelation curves of various POSS-Ep/CEsystems. As can be seen from the figure, for all resin systems thegel time was shortened with increase in temperature, showing theincrease of the curing reactivity of the resin. This is the case formost thermosetting polymers. Besides, the addition of POSS-Epprolonged the gel time at a given curing temperature and thegel time increased with increase in the content of POSS-Ep. Forexample, gel times for CE, CE5, CE10, CE15 and CE20 cured at 190 ◦Care 6.7 min, 7.6 min, 8.5 min, 9.1 min and 9.9 min, respectively.The increase of gel time is probably caused by the low reactivityof epoxy groups on POSS-Ep molecules. The POSS-Ep diluted thesystem and slowed down the reaction, leading to an increase in geltime. As far as practical production is concerned, prolonging thegel time is favorable for the determination of the curing technique.

FTIR was used to elucidate the co-curing reaction of the POSS-Ep/CE system (Fig. 3). The absorptions at 2270 cm−1 and 910 cm−1

are attributed to the cyanate ester and epoxy groups, respectively.The disappearance of the two groups shows that the curing iscomplete. The absorption at 1370 cm−1 indicates formation ofthe triazine groups, and the increase of the peak at 1750 cm−1

proves the production of oxazolidinone. It accords well with thereported reaction between CE and epoxy groups.1,5 The chemicalreactions occurring in the POSS-Ep/CE hybrid resin system areshown schematically in Fig. 4. As can be seen, covalent bondingbetween the polymeric matrix of CE (organic) and the Si−O−Si core(inorganic) of POSS-Ep occurs in the hybrid systems. Besides, thePOSS cages are homogeneously dispersed in the hybrid materialssince POSS-Ep is flowable and the organic groups in the POSS-Epmolecule can promote its compatibility with the resin matrix.

Mechanical propertiesFigure 5 shows the mechanical properties of the POSS-Ep/CEhybrids as a function of the content of POSS-Ep. The impactstrength of the POSS-Ep/CE hybrids is increased with increasingPOSS-Ep content when the POSS-Ep content is not more than 10wt%. The impact strength of the pristine CE is only 15.6 kJ m−2.When the content of POSS-Ep is 10 wt%, the impact strength isas high as 18.4 kJ m−2, increasing by 17.9%. However, when thecontent of POSS-Ep is more than 10 wt% the impact strengthdecreases with increase in POSS content. The impact strengthof the system CE20 which contains 20 wt% of POSS-Ep is only12.8 MPa. The improvement in impact resistance is attributed

0 5 10 15 2010

12

14

16

18

20

Content of POSS-Ep (wt%)

Impa

ct s

tren

gth/

kJ/m

2

45

50

55

60

65

70

75

80

85

90

Fle

xura

l str

engt

h/M

Pa

Figure 5. Mechanical properties of POSS-Ep/CE hybrid systems as a functionof POSS content.

Figure 6. SEM images of pristine CE, showing river-like fracture surfaces.



Tough whirl

Fiber-like fracture

(a) (b)

(c) (d)

Figure 7. SEM images of (a), (b) CE5 and (c), (d) CE10 display coarser fracture surfaces than CE. Tough whirls and fiber-like pull-outs can be observed onthe fracture surfaces of CE10.

Stress concentration

(a) (b)

(c) (d)

Figure 8. SEM images of (a), (b) CE15 and (c), (d) CE20. The fracture surfaces are not as tough as CE10. A local stress concentration is observed for CE20,probably caused by agglomeration of POSS.



to the toughening effect of the uniformly dispersed nanosizePOSS-Ep. The toughening effect of POSS can be explained bythe toughening mechanism of nanoparticles. The nanoparticlesbasically respond to impact in two ways. On the one hand, theycan distribute the stresses concentrated on the tip of the cracks,resulting in the break mode called multicracks. On the otherhand, they can exist in the way of cracks so as to prevent theirdevelopment.14 However, excessive POSS-Ep will lead to seriousagglomeration of POSS, leading to the formation of a great amountof POSS clusters.17,29 Therefore, the impact strength drops whenthe content of POSS is more than 10 wt%. Based on the discussionabove, the distribution state of POSS-Ep in CE will determine thefinal mechanical properties of the hybrids.

The flexural strength of the POSS-Ep/CE hybrids can also beseen from Fig. 5. Its changes as a function of POSS content is similarto that of impact strength. The maximum value (68.5 MPa), 14.4%higher than that of the pristine CE, is obtained when the POSS con-tent is 10 wt%. However, a further increase of the POSS-Ep contentleads to a decrease of flexural strength. The increase of the flexuralstrength is attributed to two factors. One is the reinforcing effectof the nano-sized POSS-Ep on the molecular chains. The otheris the increase of crosslinking density caused by the co-curing ofPOSS-Ep with CE.24 These two factors can enhance the flexuralstrength. However, the decrease of flexural strength at higherPOSS content may be explained as follows. POSS-Ep monomersare cage-like nano-structured particles with hard cores. They actas lubricants for the stiff polymeric chains in the glassy state.30

They are able to weaken the strength of intermolecular bonding,enhancing the movability of molecular chains. Accordingly, theflexural strength of the cured resin is reduced. In addition, theflexural strength is also related to the distribution of POSS. Actuallythe agglomerated nanoparticles at higher POSS content do notact as reinforcement but as deficiencies in the cured resin. Alarge amount of these agglomerated nanoparticles will inevitablyaffect the flexural strength of the cured resin. It is assumed thatthe agglomeration of POSS-Ep is negligible when the content ofPOSS-Ep is low. So at higher POSS content both the lubricant effectand the agglomeration of POSS will affect the flexural strengthof the hybrids, leading to a significant decrease of the flexuralstrength.

Micromorphologies of the POSS-Ep/CE hybridsIn order to elucidate the influence of POSS-Ep on the mechanicalproperties of POSS-Ep/CE hybrids, the microstructure of theimpact-induced fracture surface of the specimens was investigatedby SEM. CE displays a river-like fracture surface, suggesting thatthe material is relatively brittle (Fig. 6).24 With the addition of POSS-Ep, the fracture surfaces become coarse (Fig. 7). When the POSScontent is increased from 5 wt% (CE5) to 10 wt% (CE10), the fracturesurface is coarser and two characteristics can be found. First, CE10shows a large amount of tough whirls (Fig. 7(c)). Second, its fracturedisplays the characteristics of fiber-like pull-out (Fig. 7(d)). Thesetough whirls and fiber-like pull-outs can absorb great energydue to the fracture of materials, to improve the toughness ofthe POSS-Ep/CE hybrids.24 However, the fracture surfaces of CE15and CE20 are not so tough (Fig. 8). In particular, a local stressconcentration is observed for CE20. It is probably caused by theagglomeration of POSS (Fig. 8(c)). So the impact strength of CE20is significantly decreased. The features of the fracture surfaces ofPOSS-Ep/CE hybrids accord well with the mechanical propertiesdiscussed above.

0 50 100 150 200 250 300 350

0

500

1000

1500

2000

2500

3000

3500(a)

(b)

(c)

308°C

270°C

62°C

E'(M

Pa)

Temperature (°C)

CECE5CE10CE15CE20

0 50 100 150 200 250 300 350 400

0

50

100

150

200

250

300

Temperature (°C)

Temperature (°C)

CECE5CE10CE15CE20

Loss

mod

ulus

(M

Pa)

Tan

δ

100 150 200 250 300 350

0.0

0.2

0.4

0.6

0.8

1.0

CECE5CE10CE15CE20

Figure 9. DMA curves of various systems. Storage modulus (a), loss modulus(b) and tan δ (c) as a function of temperature.

Dynamic mechanical analysisDMA is carried out under given heating programs at fixed orvaried frequencies. It tests the mechanical properties such asstorage modulus, loss modulus and dynamic viscosity as a functionof temperature and frequency.30 Figure 9 displays the storagemodulus, loss modulus and tan δ with respect to temperature.Figure 9(b) shows that the glass transition temperature (Tg) isaround 270 ◦C, although it is not the same for different hybrids.Figure 9(a) shows that the incorporation of POSS-Ep into CE haschanged the storage modulus (E′) of the POSS-Ep/CE hybrids inthe glassy state (T < Tg). The initial E′ of CE10 (3.004 GPa) is higher



0 100 200 300Temperature /°C Temperature /°C

400 500 600 700 800 90030

40

50

60

70

80

Wei

ght (

%)

90

100

360 380 400 420 440 460 48080

82

84

86

88

90

92

94

96

98

100

CECE5CE10CE15CE20

CECE5CE10CE15CE20

Figure 10. TGA curves of various resin systems. The right plot shows the enlarged view of the TGA curves in the dashed frame on the left plot.

than that of CE (2.875 GPa). But the other three hybrids (CE5, CE15and CE20) show lower E′ than that of CE. When the temperatureis between 62 ◦C and 270 ◦C, both CE10 and CE15 display higherE′ than that of CE. The other two hybrids show lower E′ than CE(i.e. the storage modulus of CE15 is close to that of CE at lowertemperature, but it displays a higher value than that of CE whenthe temperature is higher than 62 ◦C). It is worth noting that allthe hybrids containing POSS-Ep display higher E′ than pristineCE at the high temperature plateau (>308 ◦C). The different andrelatively complex DMA behavior of the hybrids may be caused bythe two contrary effects of POSS on CE. One effect is strengthening.Massive units of the relatively rigid POSS along the chain segmenttend to retard and restrict that segment’s motions in CE. Another islubricating, which may be attributed to the increased free volumecaused by not packing as well overall with the segments of thecrosslinked resin.31

The loss modulus measures the energy dissipated as heat,representing the viscous portion in the material. A lower lossmodulus means that the material behaves more like a rubber.32

Figure 9(b) shows that at higher temperature (>200 ◦C) all thehybrids show lower loss modulus than CE. This confirms thatPOSS-Ep is able to increase the crosslinking density and impedemolecular movement at high temperature. As a result, the lossmodulus is reduced with the addition of POSS-Ep, i.e. POSS-Ep canreinforce CE to make the hybrids behave more elastically at hightemperature.

Tg can be determined from Figs 9(b) and 9(c). All the hybridsshow a Tg higher than that of pristine CE. The single peak on eachcurve in Fig. 9(c) provides evidence of the homogeneous structureof the POSS-Ep/CE co-cured system.24

Thermal stability of the POSS-Ep/CE hybridsSilsesquioxanes possess a particular organic–inorganic hybridstructure. This hybrid structure endows them with excellentthermal stability. For example, the initial temperature ofdecomposition (T i) of polyphenylsilsesquioxane in air is ashigh as 525 ◦C.29 Recently, it was reported that POSS is ableto improve the thermal stability of various polymers, such as

polypropylene,19,33 polyethylene34,35 and epoxy.36–38 Our groupreported the enhancement of the thermal stability and hot/wetresistance of CEs by using POSS.29 In general, the thermalproperties (e.g. glass transition temperature and T i) of polymersare elevated with the addition of POSS. Figure 10 shows the

TGA curves of the POSS-Ep/CE hybrids.39 T i is defined as thetemperature at which the weight loss is 5%. It can be seen that T i

for CE, CE5, CE10, CE15 and CE20 is 382 ◦C, 412 ◦C, 426 ◦C, 382 ◦Cand 368 ◦C, respectively. The corresponding char residues at 800◦C (�W) are 36.5%, 38%, 40%, 36.4% and 36.1%, respectively. CE5and CE10 show superior thermal stability to CE with respect to T i.As is interpreted in our previous work, POSS-Ep introduces a largeamount of Si−O and Si−C bonds, which possess large bondingenergies. This is favorable for increasing the thermal stability ofthe hybrids.

It is worth noting that both T i and �W rise significantly withthe increase of POSS content for POSS content <10 wt%. But theydrop for POSS >10 wt%. This can be explained as follows. The�W at 800 ◦C depends on the content of inorganic POSS phaseand the quality of the inorganic protecting layer on the organicnetwork. The excessive POSS aggregation at a high POSS content(>10 wt%) results in a larger amount of unprotected CE matrix anda lower char yield. The TGA data indicate that CE10 also possessesthe best thermal stability.

CONCLUSIONSA series of POSS-Ep/CE organic–inorganic hybrids were prepared.The effect of POSS-Ep on the properties of the POSS-Ep/CE hybridswas investigated. It is concluded that POSS-Ep is able to prolongthe gel time of CE. Mechanical, micromorphological and thermalstudies show that incorporation of an appropriate amount ofPOSS-Ep can effectively improve the overall properties of CE.System CE10 which contains 10 wt% of POSS-Ep shows the bestmechanical properties and thermal stability.

ACKNOWLEDGEMENTSThis work was supported by the National Natural ScienceFoundation of China (NSFC) (Grant No. 51208043), the ChinaPostdoctoral Science Foundation funded.

Project (No. 201003661), the Special Fund for Basic ScientificResearch of Central Colleges and the Basic Research SupportProject of Chang’an University (CHD2012JC025).

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