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Progress in Organic Coatings 78 (2015) 49–54

Contents lists available at ScienceDirect

Progress in Organic Coatings

j o ur na l ho me pa ge: www.elsev ier .com/ locate /porgcoat

ynthesis of bio-based unsaturated polyester resins and theirpplication in waterborne UV-curable coatings

inyue Daia,b, Songqi Mab,∗, Xiaoqing Liub, Lijing Hanb, Yonggang Wua,∗∗,inyan Daib, Jin Zhub

College of Chemistry and Environmental Sciences, Hebei University, Baoding 071002, PR ChinaNingbo Key Laboratory of Polymer Materials, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, PRhina

r t i c l e i n f o

rticle history:eceived 16 May 2014eceived in revised form7 September 2014ccepted 8 October 2014

a b s t r a c t

In this paper, three bio-based unsaturated polyesters were synthesized from itaconic acid and differentdiols which could be derived from renewable resources. Their chemical structures were confirmed byFT-IR, 1H NMR and acid value as well as hydroxyl value. Waterborne UV curable networks based on thesepolyesters were manufactured and their mechanical properties, thermal stability and coating propertiesincluding pencil hardness, flexibility, adhesion, water resistance and solvent resistance were investigated.

vailable online 27 October 2014

eywords:io-basednsaturated polyesters

taconic acid

Results showed that the UV-cured polyester coatings exhibited high hardness, good water resistanceand solvent resistance. The coatings reported in this paper combined the merits of bio-based materials,UV-curing process and water distribution.

© 2014 Elsevier B.V. All rights reserved.

aterborne UV-curable coatings

. Introduction

Fossil fuel reserve is expected to deplete around the year 2050f the present consumption rate continues [1,2]. For this reason,eplacement of petroleum-based polymeric materials by bio-basednes has gained growing interest both by industry and academia3–5]. In the past decade, the global paints and coatings demandncreased rapidly with an average rise of 5.4% annually. In 2013,he global sales of coatings reached 41.75 million tons and withales value as high as $ 127.3 billion [6]. Due to the environmentaloncern and legislation constraint [7] as well as the rising pricef petroleum-based raw materials, more bio-based feedstock andnvironmentally friendly curing process have being employed inhe coating industry.

UV curing has the capability to produce high-performanceoatings with high productivity, low energy consumption and

xtremely low volatile organic compounds (VOC) emissions [8–11].ecently, its combination with renewable materials has drawnuch more attention in coating industry. For example, Cai et al. [12]

∗ Corresponding author. Tel.: +86 057486685120.∗∗ Corresponding author.

E-mail addresses: masongqi@nimte.ac.cn (S. Ma), wuyonggang@hbu.edu.cnY. Wu).

ttp://dx.doi.org/10.1016/j.porgcoat.2014.10.007300-9440/© 2014 Elsevier B.V. All rights reserved.

reported the bio-based films with good coating properties, whichwere prepared by the UV copolymerization from acrylated epoxi-dized soybean oil (AESO) and reactive diluents. Mahmoud [13] andAng and Gan [14] synthesized several UV curable resins for coat-ing applications from palm oil and its derivatives. Chen and Patel[15] produced three UV-cured coatings derived from norbornylepoxidized linseed oil and three different divinyl ether reactivediluents. However, it is easy to notice that the reactive diluentsor organic solvents, which are VOC, are necessary for the abovementioned coating systems to obtain the satisfied properties. Inorder to reduce the VOC emission in coatings industry, water sol-uble materials or water distribution systems were introduced inrecent decades. The replacement of organic solvents or diluents bywater has the advantage of decreasing air pollution, reducing therisk of fire, improving the aspects of occupational health and safetyas well as lower energy consumption. Additionally, the viscosity ofwaterborne coating is easy to be controlled and adjusted [16–18].

Itaconic acid (IA), one of the top 12 potential bio-based platformchemicals selected by the U.S. Department of Energy [19], pos-sesses two carboxyl groups and one carbon–carbon double bond.It has been proved to be suitable for the synthesis of unsaturated

polyesters [20–26]. The pendant carbon–carbon double bonds inthe polyesters showed high reactivity during the radial polymer-ization [21,22]. To the best of our knowledge, unsaturated polyesterhas been widely applied in coatings industry due to its high gloss,

5 ganic Coatings 78 (2015) 49–54

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ardness, impact resistance as well as fast cure characteristics27–29]. In this paper, several bio-based unsaturated polyestersere synthesized from itaconic acid and different diols (ethylene

lycol (EG), 1,4-butanediol (BDO) and 1,6-hexandiol (HDO)) to pro-uce bio-based waterborne UV-curable coatings. Their mechanicalroperties, thermal stability and coating properties including pen-il hardness, flexibility, adhesion, water resistance and solventesistance were carefully investigated.

. Experimental

.1. Raw materials

Itaconic acids (IA), sodium hydrogen carbonate (NaHCO3) andriethanol amine were purchased from Zhejiang Guoguang Bio-hemistry Co., Ltd, China. Ethylene glycol (EG), 1,4-butanediolBDO), 1,6-hexanediol (HDO), 4-methoxyphenol (MEHQ), p-oluenesulfonic acid monohydrate and ditin butyl dilaurateDBTL) were obtained from Aladdin Reagent, China. 2-Hydroxy-4-2-hydroxyethoxy)-2-methylpropiophenone (Irgacure2959) wasurchased from Heowns Biochem Technologies LLC. All chemicalsere used as received without further purification.

.2. Measurements

1H NMR was performed on a 400 MHz AVANCE III Bruker NMRpectrometer (Bruker, Switzerland) with acetone-d6 as a solvent.he infrared spectrum (FT-IR) was recorded with NICOLET 6700TIR (NICOLET, America).

The hydroxyl value (OHV) was defined as the number of mil-igrams of potassium hydroxide needed to neutralize the aceticcid formed in the acetylation of 1 g of sample. It was determinedccording to ASTM D1957-86. The specified method involvedcetylating hydroxyl groups with acetic anhydride in pyridine con-aining 4-dimethylaminopyridine as catalyst. After the reaction, thexcess amounts of acetic anhydride was hydrolyzed with waternd titrated with an aqueous solution of potassium hydroxide0.5 mol/L). The difference between the volumes of base neededo neutralize the sample and a blank provides the hydroxyl value.

The acid value (AV) was defined as the number of milligramsf potassium hydroxide required to neutralize 1 g of sample andas determined according to ASTM D465-01 by titrating the non-

olatile acid fraction of the sample with a potassium hydroxideolution in ethanol (0.1 mol/L).

Dynamic mechanical analysis (DMA) was carried out on Mettler-oledo DMA/SDTA861e using a tension fixture. All the samples withhe dimension of 20 mm × 7 mm × 0.5 mm were tested from −40 ◦Co 200 ◦C at a heating rate of 3 ◦C min−1 and a frequency of 1 Hz.

Thermogravimetric analysis (TGA) was performed on a Mettler-oledo TGA/DSC1 Thermogravimetric Analyzer (METTLER TOLEDO,witzerland) with high purity nitrogen or air as purge gas at acanning rate of 20 ◦C min−1 from 50 ◦C to 600 ◦C.

The pencil hardness of coatings with the thickness of about0 �m on the tinplate was measured according to ASTM D3363-00.

The water resistance of coatings was measured according toSTM D870-02. After soaking in water at 38 ◦C, the cured coatingsere wiped dry, changes in color, blistering, etc. of the coatingsere recorded.

The solvent resistance of coatings was determined by the dou-le rub method according to the modified ASTM D5402-06 [30].he UV-cured films were rubbed with a cotton gauze using ethanol

s solvent. The results were reported as the minimum number ofouble rubs at which the films were observed to fail or “>250” (ifo change happened for the UV-cured film after 250 double rubshich was the maximum number of double rubs in the test).

Scheme 1. Synthesis of bio-based unsaturated polyester resins.

The flexibility of the coatings was measured by T-Bend Testaccording to ASTM D4145-10. The adhesion of the UV-cured filmson tinplate was evaluated using the ASTM D3359-09 crosshatchadhesion method.

2.3. Preparation of unsaturated polyester resins

Poly(itaconic acid-ethylene glycol) (IA-EG):The reaction mixture with itaconic acid (20 g, 154 mmol) and

ethylene glycol (7.76 g, 0.125 mol) in the molar ratio of 1.2:1,p-toluenesulfonic acid monohydrate (0.146 g, 0.5 mol% based onitaconic acid) as the catalyst for pre-polymerization, and 4-methoxyphenol (0.139 g, 0.5 wt.% relative to the total weight ofitaconic acid and diols) as the free radical polymerization inhibitorwere charged into a four-necked round-bottom flask equippedwith a mechanical stirrer, a thermometer, a reflux condenser anda nitrogen inlet. The mixture was kept at 160 ◦C for 2 h for the pre-polymerization to form the oligomer. Then 0.028 g of ditin butyldilaurate (1 wt.% relative to the total weight of reactants) was addedas the polycondensation catalyst. After the oligomer was kept at160 ◦C for 6 h under the vacuum of 0.09–0.095 MPa, it was cooledto 100 ◦C and the target resin was obtained. The synthetic route isshown in Scheme 1.

The similar procedures were also employed for the synthesisof Poly(itaconic acid-1,4-butanediol) (IA-BDO) and Poly(itaconicacid-1,6-hexanediol) (IA-HDO). For the case of Poly(itaconic acid-1,4-butanediol), 11.27 g 1,4-butanediol (0.125 mol) was added. And14.77 g 1,6-hexanediol (0.125 mol) was charged for the synthesis ofPoly(itaconic acid-1,6-hexanediol).

Poly(itaconic acid-ethylene glycol) (IA-EG): 1H NMR (400 MHz,Acetone-d6), ı (ppm): 4.30–4.43 (t, 4H, O CH2 CH2 O ), 5.85(s, H, CH2), 6.32 (s, H, CH2), 3.39–3.42 (d, J = 11.50 Hz, 2H,

O CO CH2 ). FT-IR (KBr, �/cm−1): 3258 ( OH), 2937 ( CH2 ),1730 (C O), 818 and 1639 (C CH2), 1383 (C O).

Poly(itaconic acid-1,4-butanediol) (IA-BDO): 1H NMR (400 MHz,Acetone-d6), � (ppm): 1.71–1.80 (t, 4H, CH2 CH2 ), 5.81–5.82 (d,J = 7.54 Hz, H, CH2), 6.28–6.30 (d, J = 5.66 Hz H, CH2), 3.37–3.40(d, J = 10.75 Hz, 2H, O CO CH2 ), 4.12–4.13 (d, J = 4.41 Hz, 2H,

CO CH2 CH2 ), 4.20–4.21 (d, J = 5.80 Hz, 2H, CH2 CH2 OC ).FT-IR (KBr, �/cm−1): 3254 ( OH), 2939 ( CH2 ), 1728 (C O), 819and 1638 (C CH2).

1

Poly(itaconic acid-1,6-hexanediol) (IA-HDO): H NMR(400 MHz, Acetone-d6), ı (ppm): 1.42 (s, 4H, CH2 CH2 ),5.79–5.82 (d, J = 12.21 Hz, 2H, CH2), 6.27–6.29 (d, J = 5.82 Hz,2H, CH2), 3.36–3.38 (d, J = 8.08 Hz, 2H, O CO CH2 ), 4.08 (t,

J. Dai et al. / Progress in Organic Coatings 78 (2015) 49–54 51

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The viscoelastic characteristics of the UV-cured polyesters wereevaluated by dynamic mechanical analysis (DMA). Fig. 4 shows the

Fig. 1. Process of UV curing waterborne coatings.

H, CO CH2 CH2 ), 4.15 (t, 2H, CH2 CH2 OC ), 1.66–1.69 (d, = 15.03 Hz, 2H, CO CH2 CH2 CH2 ), 1.43–144 (d, J = 6.80 Hz,H, CH2 CH2 CH2 OC ). FT-IR (KBr, �/cm−1): 3254 ( OH),939 ( CH2 ), 1728 (C O), 819 and 1638 (C CH2).

.4. Preparation of the waterborne UV-cured coatings

In order to get the stable emulsion, the synthesized resins andeionized water mixture were stirred vigorously for 5 min, fol-

owed by slow addition of sodium hydrogen carbonate (NaHCO3)o partly neutralize the carboxylic acid groups of the resins at0 ◦C. After it was stirred with an agitation speed of 1500 rpmor another 30 min, the emulsions with 40% solid content werebtained. Then 3 wt.% waterborne photoinitiator Irgacure 2959nd 2 wt.% curing promoter triethanol amine (on the base of theesins’ weight) were added into the system. Finally, the emulsionsere poured into a stainless steel mold (with the grooves’ size of

0 mm × 8 mm × 0.5 mm) and coated on the tinplate, followed byrying at 80 ◦C in the vacuum oven for 8 h to reach a constant weightnd cured at room temperature for 30 min using a high-pressureercury lamp (500 W) at 365 nm. The distance from the lamp to

he surface of samples was 15 cm. The thickness of the obtainedoatings on the tinplate was about 40 �m (Fig. 1).

. Results and discussion

.1. Chemical characterization of the bio-based unsaturatedolyester resins

The chemical structures of the synthesized resins were deter-ined by FT-IR and 1H NMR. Fig. 2 represents the FT-IR spectra of

oly(IA-EG), poly(IA-BDO) and poly(IA-HDO). The broad adsorptionand centered at 3193 cm−1 corresponded to the OH stretchingibration of the carboxylic acids. The strong absorption peak at728 cm−1 was assigned to the C O stretching of ester units andhe peaks at 819 and 1638 cm−1 belonged to the C CH2 stretch-ng. As could be seen in Fig. 3, the peaks for the protons were all inccordance with the characteristic peaks of target polyester resins’rotons. These results demonstrated that the target compounds

ere synthesized successfully. To further identify the chemical

tructures, their hydroxyl values (OHV) and the acid values (AV)ere also examined by titration. In Table 1, all the polyester

esins exhibited high acid value and relatively low hydroxyl value,hich was in agreement with the feed composition. The Mn of theolyesters calculated from the AV and OHV was 748 for poly(IA-EG),144 for poly(IA-BDO) and 1247 for poly(IA-HDO), respectively.

Fig. 2. FT-IR spectra of poly(IA-EG), poly(IA-BDO), and poly(IA-HDO).

3.2. Dynamic mechanical properties of the cured polyesters

Fig. 3. 1H NMR spectra of poly(IA-EG), poly(IA-BDO), and poly(IA-HDO).

52 J. Dai et al. / Progress in Organic Coatings 78 (2015) 49–54

Table 1The acid value (AV) and hydroxyl value (OHV) of the prepolymers.

Value Poly(IA-EG) Poly(IA-BDO) Poly(IA-HDO)

AV (mg KOH/g) 119 85 81OHV (mg KOH/g) 31 13 9

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a Mn = 56.1 × 1000 × f/(AV + OHV), f is the functionality of the polyesters [31].

emperature dependence of storage modulus (E′) and loss factortan ı) of the UV-cured polyesters.

In general, the cross-link density (�e: the number of moles oflastically effective chains per cubic centimeter of the film) of theV-cured polyesters was calculated by the equation derived from

he theory of rubber elasticity [32,33]:

e = E′

3RT

here E′ is the storage modulus after Tg in the rubbery plateauegion (The storage modulus (E′) in the rubbery plateau region wasetermined at 150 ◦C for all the samples), R is the gas constant and

is the absolute temperature.Based on Fig. 4 and Table 2, the cured poly(IA-EG) showed the

ighest E′ at 25 ◦C but the lowest �e. This might be due to the

act that poly(IA-EG) had the more rigid aliphatic chain and thetrongest intermolecular force because of the more number ofster bonds. Although poly(IA-EG) owned the highest number ofeactive double bonds, the molecular chains of poly(IA-EG) was

Fig. 4. DMA curves of the three UV-cured polyesters.

Fig. 5. TGA curves of the three UV-cured polyesters under nitrogen (a) and air (b).

fixed earlier during the curing process because of the rigidity andstrong intermolecular force of poly(IA-EG). And a part of doublebonds of poly(IA-EG) were remained and could not be furthercured at room temperature. As a result, the UV-cured poly(IA-EG)exhibited the lowest �e and E′ in the rubbery plateau. With theincrease of the aliphatic chain length of polyesters, the molecularmotion became easier and the E′ at 25 ◦C decreased. For poly(IA-BDO), its molecular motion was easier than that of poly(IA-EG), andits aliphatic chain length was shorter than that of poly(IA-HDO),resulting in the highest �e of the UV-cured poly(IA-BDO).

3.3. Thermal properties

The TGA curves of the UV-cured polyesters under nitrogen andair atmosphere are shown in Fig. 5 and the data are listed in Table 2.As could be seen from Table 2, both in nitrogen and air atmosphere,the degradation temperature for 10% weight loss (Td10%) of the UV-cured polyesters increased with the length of diol’s aliphatic chain,while the char yield at 700 ◦C (R700) were decreased, and the UV-cured poly(IA-EG) exhibited the lowest Td10% and highest R700. Thelowest Td10% of the UV-cured poly(IA-EG) was due to its highestvalue of OHV and AV (the intermolecular elimination first happenamong the hydroxyl and carboxyl group [9,34]) and the most num-

ber of easily cleavable ester linkages [35,36]. Especially, in theair atmosphere, due to the dehydration reaction of the hydroxylwhich promoted the char formation, the UV-cured poly(IA-EG)

J. Dai et al. / Progress in Organic Coatings 78 (2015) 49–54 53

Table 2The thermal properties of the three UV-cured polyesters.

Samples E′ at 25 ◦C (MPa) E′ at 150 ◦C (MPa) �e (×103 mol m−3) Td10% (◦C) R700 (%)

In N2 In air In N2 In air

UV-cured poly(IA-EG) 1885 60 5.7 256 251 24.1 16.6UV-cured poly(IA-BDO) 1268 150 14.2 285 279 21.6 4.9UV-cured poly(IA-HDO) 338 111 10.5 295 293 17.5 2.4

Table 3The coating performances of the three UV-cured polyesters.

Samples Pencil hardness Flexibility Adhesion Water resistance Solvent resistance

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ave the highest R700. The more number of hydroxyl groups, theore amount of char yield [37–40].

.4. Coating properties

The properties such as pencil hardness, flexibility, adhesion,ater resistance and solvent resistance of the UV-cured coatings

n tinplate sheet were measured and shown in Table 3. The hard-ess of the coatings depends not only on the cross-linking densityf networks but also on the chemical structure of the prepolymers41]. From Table 3, it can be seen that the pencil hardness (at 25 ◦C)ecreased with the increase of diol’s aliphatic chain length in theV-cured polyesters. The reason might be that the rigidity and the

ntermolecular force of the UV-cured polyesters decreased withhe increasing diol’s aliphatic chain length [42]. The T-bend testndicated that the UV-cured poly(IA-HDO) was more flexible thanhe cured poly(IA-EG) and poly(IA-BDO) due to its longer aliphatichain and less polar groups. The tape test was applied to deter-ine the adhesion properties of the different coatings. Obviously,

he adhesion (at 25 ◦C) of the coatings on tinplate substrate alsoncreased with the increasing aliphatic chain length of polyesters.t is well known that when the unsaturated polyester is changedrom liquid to solid during the curing process, the internal stressould be developed to reduce its adhesive strength [43,44]. With theecrease of the aliphatic chain length, the increasing rigidity and

ntermolecular force will lead to the increasing internal stress. As result, the UV-cured poly(IA-EG) presented the lowest adhesionnd the UV-cured poly(IA-HDO) showed the highest one.

The water and solvent resistance of coatings are also importantactors to determine their application. The water based coatingsre expected to be more sensitive to moisture because of theydrophilic polar groups. When they are placed in a humid atmo-phere, their properties will be affected by the absorbed moisturend so as to restrict their end use in humid environments [45].owever, as shown in Table 3, the UV-cured poly(IA-EG) exhib-

ted excellent water resistance without change after being soakedn 38 ◦C water for 48 h. This was due to the reason that the wateresistance not only has a relationship with the crosslink densityf the network, it also has close ties with the chemical structuref the network. Although the poly(IA-EG) system has the lowestross-linking density compared with the UV-cured poly(IA-BDO)nd poly (IA-HDO), it owns the strongest intermolecular force fromhe most number of ester bonds, corresponding to the compactetwork and good water resistance. From Table 3, we can also

otice that the UV-cured poly(IA-EG) and poly(IA-BDO) showedood solvent resistance after alcohol double rubs for 250 times onhe surfaces. However, the UV-cured poly(IA-HDO) exhibited rel-tively poor solvent resistance due to its lower cross-link density

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50%) No effect on surface >25020%) Blurred surface, slight blistering >25010%) Whitened surface, a few blistering 175

than the UV-cured poly(IA-BDO) and weaker intermolecular forcerelative to the UV-cured poly(IA-EG).

4. Conclusions

Three bio-based unsaturated polyesters were synthesized suc-cessfully from itaconic acid and diols (EG, BDO and HDO). Basedon these polyesters, the bio-based waterborne UV-cured coatingswere prepared. The coatings exhibited good properties such aswater resistance, solvent resistance and hardness. This work pro-vided us the potential possibility to manufacture the coatingscombining the merits of bio-based materials, UV-curing processand water distribution.

Acknowledgment

The authors greatly thank the financial support from theResearch Project of Technology Application for Public Welfare ofZhejiang Province (No. 2014C31143).

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