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  • 1 Department of Polymer Chemistry, Maria Curie-Skłodowska University, Gliniana 33 str, 20-614, Lublin, Poland
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Abstract

This article presents the studies on the thermal and viscoelastic properties of novel epoxy-dicyclopentadiene-terminated polyesters-styrene copolymers. The novel materials were prepared during a three step process including the addition reaction of maleic acid to norbonenyl double bond of dicyclopentadiene; polycondensation of acidic ester of dicyclopentadiene, cyclohex-4-ene-dicarboxylic anhydride, maleic anhydride, and suitable glycol: ethylene, diethylene, or triethylene glycol; and the epoxidation process of prepared polyesters. It allowed obtaining novel epoxy-dicyclopentadiene-terminated polyesters which were successfully used as a component of different styrene content (10–80 mass%) copolymers. The influence of the structures of polyester and styrene content on the cross-linking density (ve), tgδmax, tgδmax height, storage modulus (E′20 °C), FWHM values as well as the thermal stability of copolymers was evaluated by TG, DSC, and DMA analyses and discussed.

Abstract

This article presents the studies on the thermal and viscoelastic properties of novel epoxy-dicyclopentadiene-terminated polyesters-styrene copolymers. The novel materials were prepared during a three step process including the addition reaction of maleic acid to norbonenyl double bond of dicyclopentadiene; polycondensation of acidic ester of dicyclopentadiene, cyclohex-4-ene-dicarboxylic anhydride, maleic anhydride, and suitable glycol: ethylene, diethylene, or triethylene glycol; and the epoxidation process of prepared polyesters. It allowed obtaining novel epoxy-dicyclopentadiene-terminated polyesters which were successfully used as a component of different styrene content (10–80 mass%) copolymers. The influence of the structures of polyester and styrene content on the cross-linking density (ve), tgδmax, tgδmax height, storage modulus (E′20 °C), FWHM values as well as the thermal stability of copolymers was evaluated by TG, DSC, and DMA analyses and discussed.

Introduction

The chemical structure of the starting polymer, the type of monovinyl monomer and the polymer/monovinyl monomer ratio significantly influences the thermal and mechanical properties of manufactured copolymers. The suitable selection of the individual components during the synthesis of polymers leads to the preparation of different materials suitable for many applications [1, 2]. The presence of aromatic units in the structure of polymer allows the formation of materials with higher glass transition temperature, hardness, and chemical resistance comparing to those aliphatic based [3, 4]. The incorporation of cycloaliphatic rings into polymer backbone surely improves the thermal stability, transparency, glass transition temperature, and the flexibility of prepared copolymers [57]. In addition, the presence of a rigid structure in the polymer skeleton, e.g., bisphenyl or dicyclopentadiene, influences on the improving mechanical elongation and toughness of the products [8, 9]. Dicyclopentadiene is one of the most popular reagents used for synthesis because of its reactivity, accessibility, and low cost. It is utilized for the preparation of, e.g., acidic esters, secondary alcohols which serves as intermediate compounds for polymer preparation [1012]. The chemical modification of dicyclopentadiene-based products with organic peracids allows obtaining high reactive epoxy derivatives during cure due to the high ring strain of epoxycyclopentenyl groups. Consequently, the materials with excellent rigidity, thermal and dimensional stability, and good mechanical properties suitable for many applications are formed [13, 14].

Those studies are a part of general work connecting with the preparation of new epoxy polyester materials. This paper presents the studies on the thermal and viscoelastic properties of novel epoxy-dicyclopentadiene-terminated polyesters-styrene copolymers. The influence of the structure of polyester and styrene content on the cross-linking density (ve), tgδmax, tgδmax height, storage modulus (E′20 °C), FWHM values as well as the thermal stability of prepared copolymers was evaluated by TG, DSC, and DMA analyses and discussed.

Experimental

Materials

Dicyclopentadiene (DCPD), maleic acid (MA), cyclohex-4-ene-1,2-dicarboxylic anhydride (THPA), maleic anhydride (BM), hexahydrophthalic anhydride (HHPA), and 40% peracetic acid were supplied by Merck-Schuchardt, Germany. Ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), and benzoyl peroxide (BPO) were obtained from Fluka, Buchs, Switzerland. Styrene, hydroquinone, and xylene were delivered by POCh, Poland. Butylstannoic acid (catalyst) was delivered by Alkema Inc., USA. All the reagents were used without further purification.

Synthesis of novel epoxy-dicyclopentadiene-terminated polyesters

DCPD (1.07 mol), maleic acid (1 mol), and hydroquinone (0.035 mass%) were placed into a 500 ml three-neck flask equipped with a mechanical stirrer, a thermometer, and a condenser. The mixture was heated to 135 °C, and stirred for 2.5 h. In this stage, the acidic ester of DCPD was prepared. Then, the polycondensation process of the acidic ester of DCPD, cyclohex-4-ene-1,2-dicarboxylic anhydride (0.5 mol), catalyst (0.01 mass%), maleic anhydride (0.5 mol), and suitable glycol: ethylene glycol (EG), diethylene glycol (DEG) or triethylene glycol (TEG) was performed. The reaction mixture was heated at 150 °C for 1 h and then at 180 °C, until the drop of an acid value below 3 mgKOH g−1 was observed. The reaction water was removed by azeotropic distillation with xylene. After completion, xylene was removed by distillation under reduced pressure. Then, the obtained product was chemically modified with 40% peracetic acid according to the procedure described in Ref. [1517]. In this way, novel epoxy-dicyclopentadiene-terminated polyesters were obtained, Scheme 1.

Scheme 1
Scheme 1

The theoretical structure of novel epoxy-dicyclopentadiene-terminated polyesters

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2327-1

Characterization of novel epoxy-dicyclopentadiene-terminated polyesters

Proton nuclear magnetic resonance (1H NMR) spectra were recorded on an NMR Brucker-Avance 300 MSL (Germany) spectrometer at 300 MHz with deuterated chloroform (CDCl3) as the solvent. 1H-NMR chemical shifts in parts per million (ppm) were reported downfield from 0.00 ppm using tetramethylsilane (TMS) as an internal reference.

Fourier transform infrared (FTIR) spectra were obtained using a Perkin-Elmer 1725 × FTIR spectrophotometer in the 400–4000-cm−1 wavenumber range.

Characterization of styrene copolymers

The calorimetric measurements were carried out in the Netzsch DSC 204 calorimeter (Germany). The dynamic scans were performed at a heating rate of 10 °C min−1 under nitrogen atmosphere (40 mL min−1). The copolymers were heated from room temperature to 500 °C. As a reference, an empty aluminum crucible was used. The characteristic maximum temperatures during degradation (T) were evaluated.

Thermogravimetric (TG) experiments were carried out on a STA 449 Jupiter F1, Netzsch (Germany). The conditions were as follows: heating rate 10 °C min−1, a helium atmosphere (40 mL/min), the temperature range of 30–800 °C, and sample mass ∼10 mg. Empty Al2O3 crucible was used as a reference. The temperatures of 5, 10, and 50% of mass loss (T5%, T10%, and T50%) and the temperatures of the maximum rate of mass loss (Tmax) were determined.

Dynamic mechanical analysis (DMA) was performed using Dynamic Mechanical Analyzer Q 800 TA Instruments (USA). Tests were conducted using a double Cantilever device with a support span of 35 mm. Apparatus was calibrated according to the producer's instruction. The rectangular profiles of the samples 10-mm wide and 4-mm thick were applied The measurements were made from room temperature to the temperatures at which the sample was too soft to be tested at a constant heating rate of 4 °C min−1 and an oscillation frequency of 10 Hz. The storage modulus (E′20 °C), glass transition temperature (α-relaxation) identified as a maximum of the tgδ (tgδmax), tgδmax height, cross-linking density (ve), and FWHM values were determined. Cross-linking density was calculated based on the equation: E′ = 3veRT, where E′ is the storage modulus in the rubbery plateau region, R is the gas constant, T is the absolute temperature at which the experimental modulus was determined (T = Tg + 50 °C) [18, 19].

Curing procedure

The polyesters were dissolved in styrene to prepare the resins containing 10, 20, 40, 60, and 80 mass% of monovinyl monomer. The curing system: the mixture of stoichiometric amount of hexahydrophthalic anhydride and 1.0 mass% of benzoyl peroxide was applied. The compositions after degassing were placed in a glass mold, conditioned in the temperature range of 60–120 °C, and then post-cured at 160–180 °C, until no additional exothermic peak was seen from DSC curves.

Results and discussion

Characterization of novel epoxy-dicyclopentadiene-terminated polyesters

The structure of prepared materials was confirmed based on spectroscopic methods. The analysis of 1HNMR spectra of polyesters shows the presence of the characteristic resonance signals for protons at the epoxide groups (2.8–3.2 ppm) and for protons attributed to cistrans units of maleic residue, at 6.20–6.40 ppm (cis unit) and at 6.80–6.95 ppm (trans unit), respectively, as shown in Fig. 1. Figure 2 presents the example FTIR spectra of novel epoxy-dicyclopentadiene-terminated polyesters. The strong absorption bands at 783–880 cm−1 (oxirane ring vibration groups) and the absorption bands at 1,646 cm−1 (C=C stretching vibration bonds) are visible, which confirms the formation of desirable product.

Fig. 1
Fig. 1

Example 1H NMR spectra of novel epoxy-dicyclopentadiene-terminated polyesters

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2327-1

Fig. 2
Fig. 2

Example FTIR spectra of novel epoxy-dicyclopentadiene-terminated polyesters

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2327-1

Thermal and viscoelastic properties of styrene copolymers

The results obtained based on DMA analysis are summarized in Tables 1, 2, 3. Also, the representative DMA curves for copolymers containing different styrene content are presented in Fig. 3. The results show that the properties of copolymers strongly depended on the structure of polyesters and styrene content. In general, the decrease in molecular mobility of the polymer chains (tgδmax height) of each copolymer is determined by the cross-linking density (ve) [20, 21]. The copolymers prepared in the presence of polyesters based on diethylene or triethylene glycols exhibited lower values of cross-linking density (ve), glass transition temperature identified as a tgδmax, storage modulus (E′20 °C), and higher values of tgδmax height than those ethylene glycol-based copolymers. It indicated on formation of more flexible polymer networks for copolymers based on polyesters with longer glycol's chain length in their structure [22, 23].

Table 1

Viscoelastic properties of copolymers (based on ethylene glycol)

Styrene content/%E′20 °C/MPatgδmaxtgδmax/°Cve × 10−3/mol/cm3FWHM/°C
10 1,800 1.12374.50.39837 
20 2,700 0.306129.10.65245 
40 2,700 0.615128.50.51240 
60 2,700 0.795129.20.46938 
80 2,620 1.003131.50.45838 
Table 2

Viscoelastic properties of copolymers (based on diethylene glycol)

Styrene content/%E20°C/MPatgδmaxtgδmax/°Cve × 10−3/mol/cm3FWHM/°C
10 1,280 1.28042.20.38633 
20 2,300 0.61385.30.60240 
40 2,250 0.78484.50.49433 
60 2,245 0.94785.30.44832 
80 2,180 1.22586.70.42130 
Table 3

Viscoelastic properties of copolymers (based on triethylene glycol)

Styrene content/%E20°C/MPatgδmaxtgδmax/°Cve × 10−3/mol/cm3FWHM/°C
10 620 1.35432.00.39530 
20 1,250 0.72255.40.60038 
40 1,200 0.86556.80.50235 
60 1,180 1.14557.30.45034 
80 1,150 1.38456.50.43332 
Fig. 3
Fig. 3

Storage modulus (E′) and tgδ versus temperature for ethylene glycol based copolymers containing 10, 20, 40, 60, and 80 mass% of styrene

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2327-1

Moreover, as the styrene content in the copolymers is varied from 20 to 80 mass%, the significant increase in molecular mobility of the polymer chains (tmax height), decrease in cross-linking values (ve) and the storage modulus (E′20 °C) and almost constant tmax were observed. It was expected since reduced ve values usually lower E′20 °C of the materials. It suggests that less densely cross-linked networks are produced for copolymers containing lower polyester content, probably due to the plasticizing action of styrene monomer. Also, the heterogeneity of prepared copolymers was evaluated qualitatively by examining the width of the tangent delta peak (FWHM). Physically, the FWHM values provide a measure of the range of mobilities in the network. Their higher values imply better interactions between the phases and a more heterogeneous structure [2426]. The results clearly indicate that FWHM values slightly decreases as the styrene content increases from 20 to 80 mass%. It can be an indication on higher degree of structural heterogeneity of the copolymers containing higher content of polyester.

The TG and DSC data for prepared copolymers are shown in Tables 4, 5, and 6. The representative TG curves are presented in Fig. 4. The differences in the thermal behavior of copolymers are indicated. The ethylene glycol-based copolymers are characterized by a little higher thermal stability (higher values of T5%, T10%, and T50%) than those diethylene or triethylene glycols based. It was due to the formation of more rigid and cross-linked networks. In addition, the presence of two degradation peaks with Tmax1 at ∼362–371 °C and Tmax2 at ∼405–425 °C for all copolymers suggests that the degradation process run through at least two steps. The degradation of linkages present in the polyester structure and formed during the cure process is mainly expected [27].

Table 4

Thermal properties of copolymers (based on ethylene glycol)

Styrene content/%T5%/°CT10%/°CT50%/°CTmax1/°CTmax2/°CT1/°CT2/°C
10 255 277 363 368 412 366 410 
20 280 306 368 365 420 368 412 
40 295 320 372 368 425 363 415 
60 302 324 370 366 422 365 418 
80 308 325 365 365 423 363 422 
Table 5

Thermal properties of copolymers (based on diethylene glycol)

Styrene content/%T5%/°CT10%/°CT50%/°CTmax1/°CTmax2/°CT1/°CT2/°C
10 253 274 365 366 408 361 405 
20 280 305 368 370 412 365 408 
40 285 308 368 371 412 363 410 
60 292 315 370 368 420 360 418 
80 300 318 370 365 425 358 421 
Table 6

Thermal properties of copolymers (based on triethylene glycol)

Styrene content/%T5%/°CT10%/°CT50%/°CTmax1/°CTmax2/°CT1/°CT2/°C
10 238 254 365 365 405 358 401 
20 270 295 365 362 408 362 403 
40 274 298 368 371 410 360 405 
60 283 302 372 368 410 356 412 
80 285 310 370 369 420 359 418 
Fig. 4
Fig. 4

TG curves for ethylene glycol based copolymers containing 10, 20, 40, 60, and 80 mass% of styrene

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2327-1

Moreover, the increase of styrene content in copolymers causes an increase of the T5%, T10%, and T50% values. When the percentage of styrene is increased, the number of aromatic rings and new carbon–carbon linkages due to the homopolymerization of styrene increases, whereas the number of ester groups in the polymer network decreases. This is probably the reason that can be responsible for better thermal stability of higher styrene content. Besides, as was already discussed, the higher degree of cross-linking density should also increase the thermal stability of copolymers. However, in those studies copolymers with lower ve were characterized by better thermal stability. This observation confirms that the presence of higher content of styrene allows producing copolymers with lower E′20 °C, tgδmax, ve, and FWHM values due to the plasticizing effect of styrene but more thermally stable due to the presence of higher content of aromatic rings in prepared networks.

Conclusions

The performed analyses showed that the thermal and viscoelastic properties of copolymers strongly depended on the chemical structure of polyester as well as the styrene content. The ethylene glycol-based copolymers were generally more rigid and more thermally stable than those diethylene or triethylene glycols based. The increase in styrene content in copolymers resulted in obtaining less densely cross-linked networks probably due to the plasticizing action of monovinyl monomer but more thermally stable due to higher content of aromatic rings in the prepared polymer networks. Those studies confirmed that the novel epoxy-dicyclopentadiene-terminated polyesters can be successfully applied as components for the preparation of styrene copolymers and due to their properties are promising materials for practical applications.

References

  • 1. Harper, CA 1975 Handbook of plastics and elastomers Mc Graw-Hill Book Company New York.

  • 2. Martuscelli, E, Musto, P, Ragosta, G, Scarinzi, G 1996 A polymer network of unsaturated polyester and bismaleimide resins: 1. Kinetics, mechanism and molecular structure. Polymer 37:40254032 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3. Pilati, F, Toselli, M, Messori, M 1999 Principles of step polymerisation D Sanders eds. Waterborne and solvent based saturated polyesters and their applications Wiley New York.

    • Search Google Scholar
    • Export Citation
  • 4. Singh, D, Kumar Narula, A 2010 Studies on the curing and thermal behaviour of diglycidyl ether of bisphenol-A (DGEBA) in the presence of aromatic diamine-diacids. J Therm Anal Calorim 100:199205 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Ni, H, Daum, JL, Thiltgen, PR, Soucek, MD WJ Simonsick Jr 2002 Cycloaliphatic polyester-based high-solids polyurethane coatings: II. The effect of difunctional acid. Prog Org Coat 45:4958 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Jung, IK, Lee, KH, Chin, IJ, Yoon, JS, Kim, MN 1999 Properties of biodegradable copolyesters of succinic acid-1,4butanediol/succinic acid-1,4-cyclohexanedimethanol. J Appl Polym Sci 72:553561 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Tan, SG, Chow, WS 2010 Thermal properties of anhydride cured bio-based epoxy blends. J Therm Anal Calorim 101:10511058 .

  • 8. Ochi, M, Yamashita, K, Yoshizumi, M, Shimbo, M 1989 Internal stress in epoxide resin networks containing phenyl structure. J Appl Polym Sci 38:789799 .

    • Crossref
    • Search Google Scholar
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  • 9. Crivello, JV, Soyoung, S 2000 Synthesis and cationic photopolymerization of novel monomers based on dicyclopentadiene. Chem Mater 12:36743680 .

  • 10. Wang, T, Wan, PY, Yu, QP, Yu, M 2008 Synthesis and characterization of dicyclopentadiene- cresol epoxy resin. Polym Bull 59:787793 .

  • 11. Zhang, X, Zhang, Z, Xia, X, Zhang, Z, Xu, W, Xiong, Y 2007 Synthesis and characterization of a novel cycloaliphatic epoxy resin starting from dicyclopentadiene. Europ Polym J 43:21492154 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. Johnson, KG, Yang, LS 2003 Preparation, properties and applications of unsaturated polyesters J Scheirs TE Long eds. Modern polyesters: chemistry and technology of polyesters and copolyesters, Chap. 21 Wiley New York 699713.

    • Search Google Scholar
    • Export Citation
  • 13. McGary, CW, Patrick, CT, Smith, PL 1963 Resins from endo-dicyclopentadiene dioxide. J Appl Polym Sci 7:114 .

  • 14. Lee, SM 1988 Epoxy resins Mercel Dekker New York 860865.

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    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16. Worzakowska, M 2010 Succinic/or glutaric anhydride modified unsaturated (epoxy) polyesters. J Therm Anal Calorim 101:685693 .

  • 17. Worzakowska, M 2011 The influence of tertiary aromatic amines on the BPO initiated cure of unsaturated epoxy polyesters with styrene studied by non-isothermal DSC. J Therm Anal Calorim 105:987994 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Treloar, LRG 1958 The physics of rubber elasticity Oxford University Press London.

  • 19. Charlesworth, JM 1988 Effect of crosslink density on molecular relaxations in diepoxide-diamine network polymers. Part 2. The rubbery plateau region. Polym Eng Sci 28:230236 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Shibayama, K, Suzuki, Y 1965 Effect of crosslinking density on the viscoelastic properties of unsaturated polyesters. J Polym Sci Part A 3:26372651.

    • Search Google Scholar
    • Export Citation
  • 21. Nielsen, LJ 1969 Crosslinking effect on physical properties of polymers. Macromol Sci-Rev Macromol Chem C3 1 69103 .

  • 22. Worzakowska, M 2009 Chemical modification of unsaturated polyesters. Influence of polyester's structure on thermal and viscoelastic properties of low styrene content copolymers. J Appl Polym Sci 114:720731 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23. Worzakowska, M 2009 The influence of chemical modification of unsaturated polyesters on viscoelastic properties and thermal behavior of styrene copolymers. J Therm Anal Calorim 96:235241 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Manikandan Nair, KC, Sabu, T, Groeninckx, G 2001 Thermal and dynamic mechanical analysis of polystyrene composites reinforced with short sisal fibres. Comp Sci Technol 61:25192529 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25. Rana, AK, Mitra, BC, Banerjee, AN 1999 Short jute fibre-reinforced polypropylene composites: dynamic mechanical study. J Appl Polym Sci 71:531539 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Calvo, S, Escribano, J, Prolongo, MG, Masegosa, RM, Salom, C 2011 Thermomechanical properties of cured isophthalic polyester resin modified with poly(∊-caprolactone). J Therm Anal Calorim 103:195203 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Ellis, B 1993 Chemistry and technology of epoxy resins Chapman and Hall London.

  • 1. Harper, CA 1975 Handbook of plastics and elastomers Mc Graw-Hill Book Company New York.

  • 2. Martuscelli, E, Musto, P, Ragosta, G, Scarinzi, G 1996 A polymer network of unsaturated polyester and bismaleimide resins: 1. Kinetics, mechanism and molecular structure. Polymer 37:40254032 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3. Pilati, F, Toselli, M, Messori, M 1999 Principles of step polymerisation D Sanders eds. Waterborne and solvent based saturated polyesters and their applications Wiley New York.

    • Search Google Scholar
    • Export Citation
  • 4. Singh, D, Kumar Narula, A 2010 Studies on the curing and thermal behaviour of diglycidyl ether of bisphenol-A (DGEBA) in the presence of aromatic diamine-diacids. J Therm Anal Calorim 100:199205 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Ni, H, Daum, JL, Thiltgen, PR, Soucek, MD WJ Simonsick Jr 2002 Cycloaliphatic polyester-based high-solids polyurethane coatings: II. The effect of difunctional acid. Prog Org Coat 45:4958 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Jung, IK, Lee, KH, Chin, IJ, Yoon, JS, Kim, MN 1999 Properties of biodegradable copolyesters of succinic acid-1,4butanediol/succinic acid-1,4-cyclohexanedimethanol. J Appl Polym Sci 72:553561 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Tan, SG, Chow, WS 2010 Thermal properties of anhydride cured bio-based epoxy blends. J Therm Anal Calorim 101:10511058 .

  • 8. Ochi, M, Yamashita, K, Yoshizumi, M, Shimbo, M 1989 Internal stress in epoxide resin networks containing phenyl structure. J Appl Polym Sci 38:789799 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Crivello, JV, Soyoung, S 2000 Synthesis and cationic photopolymerization of novel monomers based on dicyclopentadiene. Chem Mater 12:36743680 .

  • 10. Wang, T, Wan, PY, Yu, QP, Yu, M 2008 Synthesis and characterization of dicyclopentadiene- cresol epoxy resin. Polym Bull 59:787793 .

  • 11. Zhang, X, Zhang, Z, Xia, X, Zhang, Z, Xu, W, Xiong, Y 2007 Synthesis and characterization of a novel cycloaliphatic epoxy resin starting from dicyclopentadiene. Europ Polym J 43:21492154 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. Johnson, KG, Yang, LS 2003 Preparation, properties and applications of unsaturated polyesters J Scheirs TE Long eds. Modern polyesters: chemistry and technology of polyesters and copolyesters, Chap. 21 Wiley New York 699713.

    • Search Google Scholar
    • Export Citation
  • 13. McGary, CW, Patrick, CT, Smith, PL 1963 Resins from endo-dicyclopentadiene dioxide. J Appl Polym Sci 7:114 .

  • 14. Lee, SM 1988 Epoxy resins Mercel Dekker New York 860865.

  • 15. Worzakowska, M 2010 Studies on the cure reaction and thermal properties of NADIC/or PA modified unsaturated (epoxy) polyesters. J Therm Anal Calorim 99:599608 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16. Worzakowska, M 2010 Succinic/or glutaric anhydride modified unsaturated (epoxy) polyesters. J Therm Anal Calorim 101:685693 .

  • 17. Worzakowska, M 2011 The influence of tertiary aromatic amines on the BPO initiated cure of unsaturated epoxy polyesters with styrene studied by non-isothermal DSC. J Therm Anal Calorim 105:987994 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Treloar, LRG 1958 The physics of rubber elasticity Oxford University Press London.

  • 19. Charlesworth, JM 1988 Effect of crosslink density on molecular relaxations in diepoxide-diamine network polymers. Part 2. The rubbery plateau region. Polym Eng Sci 28:230236 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Shibayama, K, Suzuki, Y 1965 Effect of crosslinking density on the viscoelastic properties of unsaturated polyesters. J Polym Sci Part A 3:26372651.

    • Search Google Scholar
    • Export Citation
  • 21. Nielsen, LJ 1969 Crosslinking effect on physical properties of polymers. Macromol Sci-Rev Macromol Chem C3 1 69103 .

  • 22. Worzakowska, M 2009 Chemical modification of unsaturated polyesters. Influence of polyester's structure on thermal and viscoelastic properties of low styrene content copolymers. J Appl Polym Sci 114:720731 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23. Worzakowska, M 2009 The influence of chemical modification of unsaturated polyesters on viscoelastic properties and thermal behavior of styrene copolymers. J Therm Anal Calorim 96:235241 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Manikandan Nair, KC, Sabu, T, Groeninckx, G 2001 Thermal and dynamic mechanical analysis of polystyrene composites reinforced with short sisal fibres. Comp Sci Technol 61:25192529 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25. Rana, AK, Mitra, BC, Banerjee, AN 1999 Short jute fibre-reinforced polypropylene composites: dynamic mechanical study. J Appl Polym Sci 71:531539 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Calvo, S, Escribano, J, Prolongo, MG, Masegosa, RM, Salom, C 2011 Thermomechanical properties of cured isophthalic polyester resin modified with poly(∊-caprolactone). J Therm Anal Calorim 103:195203 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Ellis, B 1993 Chemistry and technology of epoxy resins Chapman and Hall London.

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Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
Foundation
1969
Volumes
per Year
4
Issues
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24
Founder Akadémiai Kiadó
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Address
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Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
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Address
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ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)