Synthesis of tung oil based triglycidyl ester plasticizer and its effects on

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Synthesis of tung oil based triglycidyl ester plasticizer and its effects on poly(vinyl chloride) soft films Jie Chen, yigang wang, Jinrui Huang, Ke Li, and Xiaoan Nie ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b02989 • Publication Date (Web): 07 Nov 2017 Downloaded from http://pubs.acs.org on November 13, 2017

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ACS Sustainable Chemistry & Engineering

Synthesis of tung oil based triglycidyl ester plasticizer and its effects on poly(vinyl chloride) soft films

Jie Chen a, Yigang Wang a, Jinrui Huang a, Ke Li a, Xiaoan Nie a, b* a

Institute of Chemical Industry of Forestry Products, Chinese Academy of Forestry;

National Engineering Laboratory for Biomass Chemical Utilization; Key Laboratory of Biomass Energy and Material, Nanjing, Jiangsu 210042, China b

Institute of New Technology of Forestry, Chinese Academy of Forestry, Beijing

100091, China *Correspondence: Xiaoan Nie, Institute of Chemical Industry of Forestry Products, Chinese Academy of Forestry, Suojin Wucun 16#, Nanjing, 210042, China; Fax: +86 025 85482454; E-mail: [email protected], [email protected].

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ABSTRACT: A tung oil derived renewable plasticizer, tung-maleic triglycidyl esters (TMTE), was prepared and incorporated into Poly(vinyl chloride) (PVC) for the first time. The chemical structure was studied by FTIR, 1H-NMR and 13C-NMR. The plasticizing effects of TMTE replacement of dioctyl phthalate (DOP) in soft PVC films were researched. Thermal stability, thermal degradation performance, dynamic mechanical property and mechanical properties of pure PVC and PVC films were investigated with TGA, TGA-FTIR, TGA-MS, DMA and mechanical test. The results showed that PVC films plasticized with the TMTE exhibited increased thermal stability, plasticizing effect, compatibility and flexibility. When 30 phr DOP was substituted with TMTE in PVC blends, glass transition temperature (Tg) dropped from 41.46 °C to 40.18 °C, the initial decomposition temperature (Ti), 10 % and 50 % mass loss temperatures (T10 and T50) had maximum increases of 8.0 °C, 20.0, 27.5 °C, respectively. The interaction between TMTE and PVC molecule was also discussed. Furthermore, the extraction, exudation and volatility resistance of plasticizers were carried out and analyzed by solubility parameters, which results revealed the migration stabilities of PVC films were promoted with the increasing amount of TMTE. KEYWORDS: plasticizer, Poly(vinyl chloride) (PVC), tung oil, thermal stability

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INTRODUCTION A plasticizer is a substance added in a resin to increase its flexibility or workability.1 Large amount of plasticizers are applied in Poly(vinyl chloride) (PVC) processing as additive to obtain the desired flexible PVC products, which can be used in a wide application area, such as packaging, medical devices, coatings, films etc..2-7 1

Over 500 kinds of plasticizers have become commercialized. Phthalates for example

dioctyl phthalate (DOP), are the most important commercial plasticizers for PVC and occupy for more than 80% of the total plasticizer consumption, attributing to their outstanding plasticizing effect and relatively low price.8, 9 However, it is reported that phthalates have high risk of toxic and biological effects on human,10-14 which limits their application, particularly in the field with high requirements of health sensible application or environmental such as children toys and medical devices.15-20 In addition, phthalates have environmental impact for easily diffusing to surrounding from PVC matrix, which also reduce durable performance of PVC products.21-26 Moreover, petroleum shortages have aroused comprehensive researches on chemicals obtained from renewable resources,27-33 such as plant oils.24-36 Many alternative plasticizers based on plant oil have been reported and used in environmental PVC materials.37-39 Tung oil contains about 80% α-eleostearic (9,11,13-octadecatrienoic) acid which make it is easy to react with dienophile through the Diels-Alder reaction.40, 41 It is known that the tung oil is a kind of very promising renewable resource to develop environmentally friendly materials, such as coatings, varnishes, inks, resins etc..40-47 Although some kinds of tung oil derived plasticizers for rubber have been reported,48 there are few researches on the plasticizers based on tung oil for PVC. Li et al. 49 have prepared a tung oil derived epoxidized dicarboxylic acid dimethyl ester which has

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good potential as a primary PVC plasticizer. Therefore, in order to make available a promising renewable resource and to extend the utilization of tung oil, this research has been directed toward the development of new derivatives of tung oil which was suitable as plastieizers for PVC. Tung-maleic anhydride (TMA) can be obtained from eleostearic acid methyl ester and maleic anhydride through Diels-Alder reaction. It could be expected that the substitution of carboxylic acid groups in TMA with three glycidyl ethers might lead to a new plasticizer for PVC. Since it contain a number of esters, epoxy groups, flexible alkyl chains and hexatomic ring, this new tung oil based plasticizer is tend to enhance the compatibility and thermal stability of plasticizer with PVC. In this work, a partially novel renewable plasticizer derived from tung oil, tungmaleic triglycidyl esters (TMTE) has been synthesized (scheme 1).The obtained plasticizer was incorporated into PVC as a main or secondary plasticizer for DOP. A wide range of plasticizing characteristics, such as thermal stability, thermal degradation behavior, mechanical properties, dynamic mechanical property and migration stabilities of PVC films were researched. Results indicated that TMTE was an efficient alternative renewable plasticizer and had potential to manufacture PVC products to satisfy the health and environmental demands.

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Scheme 1.The synthesis routes of TMTE and the commercial plasticizer used in this study. EXPERIMENTAL SECTION Materials. TMA (acid value of 269 mg/ g) was purchased from Institute of Chemical Industry of Forestry Products Co., Ltd., (Nanjing, China). Ethyl alcohol (99.5%), hydrochloric acid (37%), benzyltriethylammonium chloride (97%), sodium

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hydroxide (97+%), epichlorohydrin (99%), dioctyl phthalate (99.5%) were supplied by Aladdin Chemical Reagent Co., Ltd.(Shanghai, China). Calcium stearate and zinc stearate were purchased from Changzhou Huaren Chemical Co., Ltd., (Changzhou, China). PVC (S-1000) was supplied by the Sinopec Qilu Co., Ltd., (Zibo, China). Preparation of TMTA. To a 1000 ml three- neck flask with a magnetic stirrer, reflux condenser and thermometer, ethyl alcohol (100.0mL), distilled water (100.0 mL) and sodium hydroxide (30.0 g) were charged. When the temperature reached 70°C, 78.0 g TMA was charged. Then the reaction was continued at 70°C for 2h. After cooling, 5 mol/ L hydrochloric acid was dropped into the mixture until the PH decreased to 2-3. The mixture was separated from the aqueous phase and was washed to neutral with distilled water. Finally, the water was removed through distillation under vacuum. Preparation of TMTE. TMTA (63.5 g) was stirred with 450.0 g of epichlorohydrin and 1.11 g benzyltriethyl ammonium chloride at 117° C for 2 h. Then 19.6 g sodium hydroxide was added when the temperature of mixture was decreased to 60 °C. Then the reaction continued for 3 h at 60 °C. After that, the solids were filtered and the excess epichlorophydrin in the filter liquor was recycled. Then the TMTE was obtained, which has a acid value of 0.69 mg/ g and epoxy value of 5.21 %. Preparation of PVC films. For comparison, pure PVC and plasticized PVC films with different plasticizers were prepared. Thermal stabilizers (Casalts/ Zn salts= 3/1), plasticizers and PVC were mixed by a mechanical mixer for 5 min at room temperature. Then the blends was continuing mixed by double-roller blending rolls (Zhenggong Co., China) at 165 °C for 3 min. The PVC films with a thickness of 2 mm were obtained. The formulations are shown in Table 1.

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Table 1. Formulation for the pure PVC and PVC films Component (phr)

F0

F1

F2

F3

F4

pure PVC

Total plasticizer content

40.0

40.0

40.0

40.0

40.0

0.0

TMTE content

0.0

10.0

20.0

30.0

40.0

0.0

DOP content

40.0

30.0

20.0

10.0

0.0

0.0

Thermal stabilizers content

2.0

2.0

2.0

2.0

2.0

0.0

Characterizations. Fourier transform infrared (FTIR) spectra was confirmed by a Nicolet IS10 instrument (Thermo Fisher Scientific Inc., USA) in a range of 4000 cm-500 cm−1 by an attenuated total reflectance method.

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1

H and 13C NMR spectra of the plasticizer were recorded in deuterated chloroform

(CDCl3) using a Bruker ARX 300 spectrometer (Bruker Co., Germany). Dynamic mechanical analysis (DMA) of the plasticizer was performed using a DMA Q800 (TA Instruments, New Castle, DE) with a frequency of 1 Hz in a dual cantilever mode. The testing was swept at a heating rate of 3 °C/min from -60 to 80 °C. In order to ensure the reproducibility of data, replicated tests were carried out for each sample. Thermogravimetric analysis (TGA) was performed using a 409PC thermogravimetric analyzer (Netzsch Co., Germany). Samples were scanned at a rate of 10 °C / min from ambient temperature to 600 °C under a nitrogen atmosphere. The TGA-FTIR measurement was recorded on a NicoletiS10 FT-IR (Nicolet Instrument Crop., USA) coupled with a 409PC thermal analyzer (Netzsch, Germany). Each sample was heated from 40 to 600 °C under N2 atmosphere at a rate of 10 °C /min. The spectra were acquired at a resolution of 4 cm-1 in the range of 4000 cm-1-

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500 cm-1. The TGA-MS measurement was performed by a QMS403C instrument (Netzsch Co., Germany) coupled with a 409PC thermal analyzer (Netzsch Co., Germany). Each sample was heated under N2 atmosphere from 40 to 600 °C at a rate of 10 °C /min. Mass scanning was performed over the range m/v 2–200. Tensile properties were measured through a SANS CMT-4303 universal testing machine (Shenzhen Xinsansi Jiliang Instrument Co., China) with cross-head speed of 10 mm/min, according to ISO 527-2: 1993. Each specimen was conditioned at 50% humidity and 23 °C for 1 day prior to tensile testing. To obtain an average value, five samples were tested for each group. Extraction tests were according to ASTMD 1239-98. The PVC film was immersed in soybean oil, petroleum ether, distilled water, 10 % (w/w) sodium hydroxide and 30 % (w/v) acetic acid at 23 ±1 °C and 50 ±5 % relative humidity. The extracted PVC film was rinsed by distilled water and wiped up after 24 h. Then, each film was dried in a convection oven (Shanghai Suopu Instrument Co., China) for 24 h at 30 °C and reweighed. The weight loss before and after the immersing was measured. Three samples were tested to get an average value. Exudation of the plasticizer was studied by placing a PVC film between two pieces of filter paper. The system was then placed in a convection oven (Shanghai Suopu Instrument Co., China) for 48 h at 60 °C. The weight increments of the filter papers were measured. To obtain an average value, three samples were tested. Volatility tests were according to ISO 176:2005. The film with 120 cm3 of activated carbon spreading over it was placed on the bottom of a metal container with lid. Then the container was placed in the convection oven (Shanghai Suopu Instrument Co., China) at 70 °C ± 1 °C. The container was removed from the oven and cooled in a

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desiccator after 24 h. The film was brushed and reweighed. The weight loss was measured before and after the heating. To obtain an average value, three samples were tested. Solubility parameter. Solubility parameters of plasticizer and PVC were studied by the Small equation (1).50 Furthermore, the solubility parameter of mixed plasticizer was calculated in terms of the additivity rule equation (2) and (3).51 1/2

δ=

( CED )

1/ 2

 ∆E  ∑ F i = ρ ∑ F i = x1∑ F 1 + x 2∑ F 2 + ...x n ∑ F n  = M Vi x1V 1+ x 2V 2+...x nV n  Vi 

=

(1)

n

δ mix = ∑ Φ i,2δ i,2 i =1

(2)

n

∑ Φ i,2 = 1 i=1

(3)

where δ is the solubility parameter, Vi is molar volume, ∆E is energy of vaporization and Fi is the molar attraction constant. M and ρ are the molecular weight and density of the plasticizer or chain unit of the polymer, respectively. Φi,2 is the volume fraction of the component i , δi, 2 is the solubility parameter of the component

i. RESULTS AND DISCUSSION Synthesis and characterization. Figure1displayed the FTIR spectra of TMTA and TMTE. In the spectrum of TMTA, the broad peak at around 3500-2500 cm-1 was on account of the presence of C-H and O-H stretching vibrations. The absorption at 2853 cm-1 and 2925 cm-1 were corresponded to the methylene and methyl groups. The peak at around 928cm-1 was attributed to O-H stretching of carboxy groups. For TMTE, the broadband around 3500-2500 cm-1 had disappeared, as well as the peak at around 928 cm-1, which indicated the ester groups were obtained. Furthermore, characteristic features of glycidyl esters group were found at 910, 847 and 731cm−1. The

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characteristic peaks implied the TMTE had been obtained.

Figure 1. FTIR spectra of TMTA and TMTE. Figure 2 and Figure 3 display the 1NMR and 13C NMR spectrum of TMTA and TMTE, respectively. It could be seen from Figure 2 (a) that the peak at 0.90 ppm was the sign of methyl ( peak 18). The peaks at around 1.32-2.91 ppm (peak 2-8, 11 and 14-17) were the signs of methylene and methyne. The chemical shifts around 3.67 ppm (peak19, 20) corresponded to the methine protons attached to the-COOH groups. The multi peaks at around 5.09-5.68 ppm were attributed to hydrogens of CH=CH of number 9, 10, 12 and 13 carbon. In Figure 2 (b), the new peaks at 2.54-4.35 ppm (peak 23-31) attributing to the protons of the glycidyl ester group appeared, indicating that esterification reaction of TMTA with epichlorohydrin occurred. This result was in accordance with the previous report by Serra.52 Figure 3 displays the 13C NMR spectra of TMTA and TMTE. In Figure 3(a), the chemical shifts at 178-180 ppm were assigned to the carbons of carboxyl. The chemical shifts around 127-131 ppm were attributed to the carbons of double bond. In Figure 3(b), the new peaks at 44-50 and 64-70 ppm were the signs of the glycidyl ester groups carbons, which implied the TMTA transferred into TMTE. 10


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Figure 2. 1H NMR spectra of (a) TMTA and (b) TMTE.

Figure 3. 13C NMR spectra of (a) TMTA and (b) TMTE. Thermal stability. Figure 4(a) shows the TGA results of DOP and TMTE heated at the rate of 10 °C/min in nitrogen. Furthermore, the thermal degradation data, 11



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including 10 % and 50 % mass loss temperatures (T10 and T50), initial decomposition temperature (Ti) and residual of the plasticizers are summarizes in Table 2. Compared with DOP, Ti, T10 and T50 of TMTE increased 116.2 °C, 55.3 °C and 135.1 °C, respectively. In addition, the residuals of DOP and TMTE were 0.4 % and 5.5 %, respectively. In conclusion, the TMTE shows higher thermal stability due to the high stability glycidyl esters groups.

Figure 4. TGA curves of (a) plasticizers and (b) pure PVC and PVC films with different plasticizers. Figure 4 (b) presents the thermogravimetric results of pure PVC and PVC films with different content of TMTE. Table 2 summarizes the thermal degradation data of Ti, T10, T50, weight loss at different time and residual. Two main degradation steps could be observed from all of the TGA curves, which was well coincident with reports.10, 53-62 A largest weight loss of 69.9 % at 210-350 °C occurred in the first stage. The second degradation step of PVC films which was connected with the formation of aromatic compounds took place at 400-520 °C, attributing to the largest 12


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weight loss of 22.4 %.63 It was shown that the Ti, T10 and T50 for pure PVC were 272.8 °C, 269.2°C and 294.2°C , respectively. When DOP cooperated with PVC, degradation temperature decreased significantly from 272.8 °C to 262.1 °C. However, the Ti, T10 and T50 increased when DOP was gradually substituted with TMTE. When 30 phr DOP was replaced with TMTE, the Ti, T10 and T50 reached to 270.1°C, 275.5 °C, 328.0 °C, respectively. It is mainly attributed to the multi glycidyl esters group of TMTE which can scavenge HCl and retard the thermal decomposition.64-66 Furthermore, the byproduct of eleostearic acid methyl ester with a conjugated double bond may be formed by reversible process of Diels- Alder reaction, which might inhibit the degrading of PVC. 67,68 However, compared with film F0, the films F4 modified by 40 phr TMTE had maximum increase of 5.4 °C, 19.8 °C and 37.5 °C in Ti, T10 and T50 respectively. Hence, TMTE can improve the thermal stability of PVC matrix more effectively. Table 2. Thermal properties of pure PVC and PVC films with different plasticizers Weight loss (wt%) Sample

Tg (℃)

Ti(℃)

T10(℃)

T50(℃) 210-350(℃)

400-520(℃)

DOP

-

224.3

223.1

263.3

-

-

TMTE

-

340.5

278.4

398.4

-

-

F0

41.46

262.1

255.5

300.5

69.9

16.2

F1

39.65

264.9

265.8

308.3

65.2

15.3

F2

40.27

266.6

270.4

317.9

61.3

20.1

F3

40.18

270.1

275.5

328.0

56.6

20.9

F4

44.30

267.5

275.3

338.0

52.3

22.4

pure PVC

92.29

272.8

269.2

294.2

59.0

19.4

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TGA-FTIR analysis. The TGA-FTIR spectra were performed to disclose the contents of gas products of pyrolysis and the thermal degradation processes of PVC blends. Figure 5 presents the 3D FTIR spectrum of gaseous products of pure PVC, film F0, F2 and F4, respectively. The constituents of pyrolysis gas products of pure PVC, film F0, F2 and F4 are similar, which were hydrogen chloride (HCl), water (H2O),carbon monoxide (CO), carbon dioxide (CO2) and benzene (C6H6). At the first fastest degradation stage around 210-350 °C, CO (2181 cm-1), CO2 (2318 cm-1), H2O (3613 cm-1), HCl (2864 cm-1), and C6H6 (3085 and 1540 cm-1) were all released. 69,70 Figure 5 (b) and (c) showed that glycidyl esters(1715, 1216, 688 and 672 cm-1) were released due to the addition of TMTE with PVC. The absorbance of pure PVC, film F0, F2 and F4 at maximum mass loss rates was similar to each other. However, the intensity of absorption band of HCl of film F0 at around 210-350°C was higher than that of film F2 and F4, which implied more amount of HCl were released in the decomposition process. The results was agreed with the previous TGA results.

Figure 5. 3D FTIR spectra of pyrolysis gas products of (a) pure PVC, (b) F0, (c) F2 and (d) F4. 14


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Figure 6. MS spectra of the main pyrolysis products of PVC films: (a) HCl, (b) C6H6, (c) CO2, (d) CO. TGA-MS analysis. Figure 6 shows the curves for the temperature dependence of ion current variation of PVC films. The signals at m/z 36, 78, 44 and 28 were shown. The MS spectra presented peaks at m/z 36 and 78 at the first fastest degradation step around210-350°C, which could be due to HCl and C6H6 respectively.55-58,60,63 Figure 6 (a) revealed that the lease temperature of the maximum HCl concentration was delayed as the addition of TMTE, and the HCl concentration decreased with the increase of TMTE. This result was consistent with previous studies 50-52 that indicated the epoxy groups could scavenge HCl gas and retard degradation events. Moreover, a small quantity of benzene was revealed. Curves of m/ z 44 and m/ z 28 were the results of CO and CO2, respectively, which were reported that mainly attributed to the second degradation step.71 It was obviously that the CO2 and CO outputs by film F4 were less than those of film F0 and F2, which suggested more residues formed when TMTE was incorporated into PVC. The reason could be

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explained that the esters and long carbon chains of TMTE were quite thermal stable, which might not decompose until charring. These results were in accordance with the well known two-step degradation mechanism of PVC blends. That is the first degradation step mainly involve dehydrochlorination with simultaneous formation of reactive conjugated double bond containing sequences (polyenes)72 in the PVC chain and the second step refer to the macromolecules degradation. 73, 74 Consequently, thermal stability performance of PVC films plasticized with TMTE was enhanced. Dynamic mechanical analysis. DMA technology was adopted to research the dynamic mechanical properties of PVC blends. Figure 7 shows the loss factor (tan δ) dependence of temperature of the PVC films with different plasticizers. It could be seen that all the blends are homogenous materials due to the single peak of tan δ for each PVC film.75 In addition, Table 2 presents the data of glass transition temperature (Tg). The Tg values for pure PVC and films F0-F4 are 92.29, 41.46, 39.65, 40.27, 40.18 and 44.30 °C, respectively, which were far below the 92.29°C of pure PVC. The long alkyl chain and polar groups of the plasticizer interacted with the polar fraction of the PVC molecule and lubricated, decreasing the polymer-polymer interaction, and increasing the free volume between polymer molecules (as shown in Figure 8). This result suggested the plasticizer could decrease the Tg of PVC films when DOP was partly replaced by TMTE, indicating the compatibility between PVC and the mixed plasticizers increased with the amount of TMTE increasing. However, Tg value increased from 41.46°C to 44.30°C when DOP was fully substituted with TMTE in film F4. This was might due to the higher molecule weight (about 582) of TMTE comparing with DOP (391), which relatively reduced the polar groups content, thereby decreased its plasticity on PVC.

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Figure 7. DMA curves for the pure PVC and PVC films with different plasticizers.

Figure 8. Possible interaction between TMTE and PVC molecule.

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Mechanical properties. The results of tensile test of PVC films are presented in Table 3. It could be observed that PVC films plasticized with TMTE (F0-F4) had better elongation at break, similar tensile strength and higher modulus of elasticity properties compared with film F0. After adding 0 to 30 phr TMTE, the elongation at break of film F0-F3 could generally increased from 301.2 to 358.4 %, indicating that TMTE had higher plasticizing effect than DOP. However, when the concentration of TMTE increased up to 30 and 40 phr, the elongation at break decreased to 338.3%. The result is in accordance with the DMA result. All the results indicate that TMTE could enhance the flexibility of PVC resin. Table 3. Results obtained from tensile measurements Film

Tensile strength

Elongation at break

Modulus of elasticity

(MPa)

(%)

(MPa)

F0

5.4±1.69

301.2±15.96

2.40±0.82

F1

5.8±0.15

331.2±10.87

4.20±1.10

F2

6.1±1.14

340.5±6.75

7.93±0.98

F3

6.4±0.78

358.4±6.02

9.05±2.01

F4

6.7±0.59

338.3±14.03

42.3±5.23

Extraction, exudation and Volatility resistance. The weight losses of the PVC films by extraction in petroleum ether, soybean oil, distill water, 10% (w/w) NaOH and 30% (w/w) acetic acid are shown in Figure 9, as well as the performance of extraction resistance and volatilization resistance. It could be seen that the films showed poor exudation resistance in soybean oil and petroleum ether than in distill water, acid and alkali. This mainly due to the plasticizers was organic solvents. In addition, the weight loss of films after exudation testing mainly followed the order of

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F0﹥F1﹥F2﹥F3﹥F4, which implied the resistance of migration was enhanced with the replacement of TMTE into DOP. The exudation resistances of films F1-F4were similar to film F0.The volatilization loss decreased mainly with the increased of TMTE content. These results could be due to structure of the plasticizers, the compatibility and the intermolecular interaction between plasticizers and PVC, which could be inferred from the solubility parameter theory.

Figure 9. Weight losses of extraction, exudation and volatilization testing. The solubility parameters for different plasticizers were calculated using to Equations (1) and (2) and shown in Table 4. When the difference of the solubility parameter value is as small as possible, the good solubility occurs between polymer and plasticizers.51 The difference in the solubility parameter value was measured by equation 4. DS = δ

pvc

− δ Plasticizer

(4)

Where δPVC and δPlasticizer denote the solubility parameter of the plasticizer and polymer, respectively.

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As shown in Table 4, the DS of TMTE was the lowest during these plasticizers, implying a good miscibility of TMTE with PVC matrix. The substitution of DOP with TMTE results in a reduction in the contribution of polar group. Hence, the complex plasticizers caused lower solubility parameters than TMTE but higher solubility parameters than DOP. There results were consistent with previous results of DMA, tensile and migration test. Table 4. Solubility parameters for plasticizers and PVC Items

δ (J/cm3)1/2

DS (J/cm3)1/2

PVC

9.6651

-

TMTE

9.07

0.59

DOP

8.89

0.77

Complex plasticizer of F1

8.90

0.76


8.92

0.74


8.94

0.72

CONCLUSIONS TMTE was synthesized and added into PVC blends to analysis its effects on thermal, mechanical properties and migration stabilities of PVC films. The effects of TMTE partially or completely substituting commercial plasticizer DOP in soft PVC films were investigated. The results of DMA showed the compatibility between the mixed plasticizers and PVC increased with the addition amount of TMTE. The thermal performances were examined by TGA, TGA-FTIR and TGA-MS, which suggested the addition of TMTE could endow PVC films with higher thermal stabilities. When DOP was completely replaced with TMTE, Ti, T10 and T50 of PVC film increased to 267.5 °C, 275.3 °C, 338.0 °C, respectively. The tensile test was carried out and the results suggested TMTE had higher plasticizing effect than DOP.

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Furthermore, with the substitution of TMTE into DOP, PVC films exhibited better migration stability. Consequently, this plasticizer derived from tung oil is a potentially secondary or main plasticizer in environmental plastic materials. ACKNOWLEDGMENTS The authors are grateful for the financial support from The Science and technology plan projects in Jiangsu Province (grant number: BK20160149) and The Key laboratory of biomass energy and materials of Jiangsu province (grant number: JSBEM-S-201604). SUPPORTING INFORMATION SEM microphotographs of fractured surface of PVC films with different plasticizers.

Reference (1) Vieira, M. G. A.; Silva, M. A. D.; Santos, L. O. D.; Beppu, M. M. Natural-based plasticizers and biopolymer films: A review. Eur. Polym. J. 2011, 47, DOI 10.1016/j.eurpolymj.2010.12.011. (2) Choi, J. S.; Park, W. H. Effect of biodegradable plasticizers on thermal and mechanical properties of poly(3-hydroxybutyrate). Polym. Test. 2004, 23, 455460. (3) Ito, M.; Nagai, K. Analysis of degradation mechanism of plasticized PVC under artificial

aging

conditions.

Polym.

Degrad.

Stab.

2007,

92,

DOI

10.1016/j.polymdegradstab.2006.11.003. (4) Zhou, Y.; Yang, N.; Hu, S. Industrial metabolism of PVC in China: A dynamic material

flow

analysis.

Resour.

Conserv.

Recy.

2013,

73,

DOI

10.1016/j.resconrec.2012.12.016. (5) Starnes Jr, W. H. Structural and mechanistic aspects of the thermal degradation of

21



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 33

poly(vinyl chloride). Prog. Polym. Sci. 2002, 27, DOI 10.1016/S00796700(02)00063-1. (6) Qiu, Z.; Zhou, P. Effect of biodegradable poly(ethylene adipate) with low molecule weight as an efficient plasticizer on the significantly enhanced crystallization rate and mechanical properties of poly(L-lactide). Rsc Advances 2014, 4, 51411-51417. (7) Sejidov, F. T.; Mansoori, Y.; Goodarzi, N. Esterification reaction using solid heterogeneous acid catalysts under solvent-less condition. J. Mol. Catal. A Chem. 2005, 240, DOI 10.1016/j.molcata.2005.06.048. (8) Rahman, M.; Brazel, C. S. The plasticizer market: an assessment of traditional plasticizers and research trends to meet new challenges. Prog. Polym. Sci. 2004, 29, DOI 10.1016/j.progpolymsci.2004.10.001. (9) Vieira, M. G. A.; Silva, M. A. D.; Maçumoto, A. C. G.; Santos, L. O. D.; Beppu, M. M. Synthesis and application of natural polymeric plasticizer obtained through polyesterification of rice fatty acid. Materials Research 2014, 17, DOI 10.1590/S1516-14392014005000017. (10) Szarka, G.; Iván, B. Thermal Properties, Degradation and Stability of Poly(vinyl chloride) Predegraded Thermooxidatively in the Presence of Dioctyl Phthalate Plasticizer.

J.

Macromol.

Sci.

A.

2013,

50,

DOI

10.1080/10601325.2013.742804C. (11) Szarka, G.; Domján, A.; Szakács, T.; Iván, B. Oil from poly(vinyl chloride): Unprecedented degradative chain scission under mild thermooxidative conditions.

Polym.

Degrad.

Stab.

2012,

97,

DOI

10.1016/j.polymdegradstab.2012.06.005. (12) Szarka, G.; Iván, B. Degradative Transformation of Poly(vinyl chloride) under

22


Page 23 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Mild Oxidative Conditions. ACS Symp. Ser. 2009, 1004, 219-226. (13) Szakacs, T.; Ivan, B.; Szesztay, M., Chain scission in thermooxidative degradation of PVC in dioctylphthalate. Polym. Prepr. 1998, 39, 372-373. (14) Szarka G.; Ivan B.. Environmentally benign mild degradative transformation of poly (vinyl chloride) into useful products. Polym. Prepr. 2007, 48, 584-585. (15) Hill, S. S.; Shaw, B. R.; Wu, A. H. The clinical effects of plasticizers, antioxidants, and other contaminants in medical polyvinylchloride tubing during respiratory and non-respiratory exposure. Clin. Chim. Acta 2001, 304, DOI 10.1016/S0009-8981(00)00411-3. (16) Chiellini, F.; Ferri, M.; Morelli, A.; Dipaola, L.; Latini, G. Perspectives on alternatives to phthalate plasticized poly(vinyl chloride) in medical devices applications.

Prog.

Polym.

Sci.

2013,

38,

DOI

10.1016/j.progpolymsci.2013.03.001. (17) Chiellini, F.; Ferri, M.; Latini, G. Physical-chemical assessment of di-(2ethylhexyl)-phthalate leakage from poly(vinyl chloride) endotracheal tubes after application in high risk newborns. Int. J. Pharm. 2011, 409, DOI 10.1016/j.ijpharm.2011.02.024. (18) Benjamin, S.; Masai, E.; Kamimura, N.; Takahashi, K.; Anderson, R. C.; Faisal, P. A. Phthalates impact human health: Epidemiological evidences and plausible mechanism

of

action.

J.

Hazard.

Mater.

2017,

340,

DOI

10.1016/j.jhazmat.2017.06.036. (19) Lessmann, F.; Correia-Sá, L.; Calhau, C.; Domingues, V. F.; Weiss, T.; Brüning, T.; Koch, H. M. Exposure to the plasticizer di(2-ethylhexyl) terephthalate (DEHTP) in Portuguese children - Urinary metabolite levels and estimated daily intakes. Environ. Int. 2017, 104, DOI 10.1016/j.envint.2017.03.028.

23



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(20) Perez, A. L.; Liong, M.; Plotkin, K.; Rickabaugh, K. P.; Paustenbach, D. J. Health risk assessment of exposures to a high molecule weight plasticizer present in automobile interiors. Chemosphere 2017, 167, 541-550. (21) Albar, H. M. S. A.; Ali, N.; Shahzad, K.; Ismail, I. M. I.; Rashid, M. I.; Wang, W.; Ali, L. N. Phthalate esters in settled dust of different indoor microenvironments; source of non-dietary human exposure. Microchem. J. 2017, 132, DOI 10.1016/j.microc.2017.02.008. (22) Swan, S. H. Environmental phthalate exposure in relation to reproductive outcomes and other health endpoints in humans. Environ. Res. 2008, 108, DOI 10.1016/j.envres.2008.08.007. (23) Lithner, D.; Larsson, A.; Dave, G. Environmental and health hazard ranking and assessment of plastic polymers based on chemical composition. Sci. Total. Environ. 2011, 409, DOI 10.1016/j.scitotenv.2011.04.038. (24) Staples, C. A.; Peterson, D. R.; Parkerton, T. F.; Adams, W. J. The environmental fate of phthalate esters: A literature review. Chemosphere 1997, 35, 667-749. (25) Gani, K. M.; Tyagi, V. K.; Kazmi, A. A. Occurrence of phthalates in aquatic environment and their removal during wastewater treatment processes: a review. Environ. Sci. Pollut. R. 2017, DOI 10.1007/s11356-017-9182-3. (26) Kasza, G.; Stumphauser, T.; Nádor, A.; Osváth, Z.; Szarka, G.; Domján, A.; Mosnáček, J.; Iván, B. Hyperbranched polyglycerol nanoparticles based multifunctional, nonmigrating hindered phenolic macromolecular antioxidants: Synthesis, characterization and its stabilization effect on poly(vinyl chloride). Polymer 2017, 124, DOI 10.1016/j.polymer.2017.07.061. (27) Noel, A.; Borguet, Y. P.; Wooley, K. L. Self-Reporting Degradable Fluorescent Grafted Copolymer Micelles Derived from Biorenewable Resources. Acs Macro

24


Page 24 of 33

Page 25 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Lett. 2015, 4, DOI 10.1021/acsmacrolett.5b00227. (28) Bakare, I. O.; Pavithran, C.; Okieimen, F. E.; Pillai, C. K. S. Polyesters from renewable resources: Preparation and characterization. J. Appl. Polym. Sci. 2010, 100, 3748-3755. (29) Uyama, H.; Kuwabara, M.; Tsujimoto, T.; Kobayashi, S. Enzymatic synthesis and curing of biodegradable epoxide-containing polyesters from renewable resources. Biomacromolecules 2003, 4, DOI 10.1021/bm0256092. (30) Papageorgiou, G. Z.; Tsanaktsis, V.; Papageorgiou, D. G.; Chrissafis, K.; Exarhopoulos, S.; Bikiaris, D. N. Furan-based polyesters from renewable resources:

Crystallization

and

thermal

degradation

behavior

of

poly(hexamethylene 2,5-furan-dicarboxylate). Eur. Polym. J. 2015, 67, DOI 10.1016/j.eurpolymj.2014.08.031. (31) Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.; Lindner, F. Improved Utilization of Renewable Resources: New Important Derivatives of Glycerol. Green Chem. 2008, 10, DOI 10.1039/b710561d. (32) Caes, B. R.; Teixeira, R. E.; Knapp, K. G.; Raines, R. T. Biomass to furanics: Renewable routes to chemicals and fuels. ACS Sustain. Chem. Eng. 2015, 3, DOI 10.1021/acssuschemeng.5b00473. (33) Sulmonetti, T.; Hu, B.; Lee, S.; Agrawal, P. K.; Jones, C. W. Reduced Cu-Co-Al Mixed Metal Oxides for the Ring-Opening of Furfuryl Alcohol to Produce Renewable

Diols.

ACS

Sustain.

Chem.

Eng.

2017,

5,

DOI 10.1021/acssuschemeng.7b01769. (34) Aydın, R. S. T.; Akyol, E.; Hazer, B. Influence of Soybean Oil Blending with Polylactic Acid (PLA) Films: In Vitro and In Vivo Evaluation. J. Am. Oil Chem. Soc. 2017, DOI 10.1007/s11746-017-2954-6.

25



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 33

(35) Patil, C. K.; Rajput, S. D.; Marathe, R. J.; Kulkarni, R. D.; Phadnis, H.; Sohn, D.; Mahulikar, P. P.; Gite, V. V. Synthesis of bio-based polyurethane coatings from vegetable oil and dicarboxylic acids. Prog. Org. Coat. 2017, 106, DOI 10.1016/j.porgcoat.2016.11.024. (36) Meier, M. A. R.; Metzger, J. O.; Schubert, U. S. Plant Oil Renewable Resources as Green Alternatives in Polymer Science. Chem. Soc. Rev. 2008, 39, DOI 10.1039/b703294c. (37) Fernandez, S. S.; Kunchandy, S.; Ghosh, S. Linseed Oil Plasticizer Based Natural Rubber/Expandable Graphite Vulcanizates: Synthesis and Characterizations. J. Polym. Environ. 2015, 23, DOI 10.1007/s10924-015-0721-z. (38) Chavan, A. P.; Gogate, P. R. Ultrasound assisted synthesis of epoxidized sunflower oil and application as plasticizer. J. Ind. Eng. Chem. 2015, 21, DOI 10.1016/j.jiec.2014.04.021. (39) Yang, D.; Peng, X.; Zhong, L.; Cao, X.; Chen, W.; Zhang, X.; Liu, S.; Sun, R. "Green" films from renewable resources: properties of epoxidized soybean oil plasticized ethyl cellulose films. Carbohydr. Polym. 2014, 103, DOI 10.1016/j.carbpol.2013.12.043. (40) Trumbo, D. L.; Mote, B. E. Synthesis of tung oil–diacrylate copolymers via the Diels-Alder reaction and properties of films from the copolymers. J. Appl. Polym. Sci. 2010, 80, DOI 10.1002/app.1343. (41) Li, F.; Larock, R. C. Synthesis, structure and properties of new tung oil-styrenedivinylbenzene

copolymers

prepared

by

thermal

polymerization.

Biomacromolecules 2003, 4, DOI 10.1021/bm034049j. (42) Macchi, C.; Meiorin, C.; Mosiewicki, M. A.; Aranguren, M. I.; Somoza, A. Effect of the composition and chemical aging in tung oil-styrene networks: Free

26


Page 27 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


volume and dynamic-mechanical properties. Eur. Polym. J. 2016, 87, DOI 10.1016/j.eurpolymj.2016.12.016. (43) Cao, M.; Wang, H.; Cai, R.; Ge, Q.; Jiang, S.; Zhai, L.; Jiang, S. Preparation and properties of epoxy-modified tung oil waterborne insulation varnish. J. Appl. Polym. Sci. 2015, 132, DOI 10.1002/app.42755. (44) Wang, C.; Jones, F. N. Stability and film properties of tung oil modified soybean alkyd emulsion. J. Appl. Polym. Sci. 2015, 78, DOI 10.1002/10974628(20001128)78:93.0.CO;2-J. (45) Samadzadeh, M.; Boura, S. H.; Peikari, M.; Ashrafi, A.; Kasiriha, M. Tung oil: An autonomous repairing agent for self-healing epoxy coatings. Prog. Org. Coat. 2011, 70, DOI 10.1016/j.porgcoat.2010.08.017. (46) Liu, C.; Shang, Q.; Jia, P.; Dai, Y.; Zhou, Y.; Liu, Z. Tung oil-based unsaturated co-ester macromonomer for thermosetting polymers: synergetic synthesis and copolymerization with styrene. ACS Sustain. Chem. Eng.

2016, 4, DOI

10.1021/acssuschemeng.6b00466. (47) Xin, J.; Li, M.; Li, R.; Wolcott, M. P.; Zhang, J. Green epoxy resin system based on lignin and tung oil and its application in epoxy asphalt. ACS Sustain. Chem. Eng. 2016, 4, DOI 10.1021/acssuschemeng.6b00256. (48) Placek, L. L.; Pastor, H. P.; Hughes, J. P.; Bickford, W. G. Tung oil derivatives as plasticizers for buna-N rubber. J. Am. Oil Chem. Soc. 1960, 37, DOI 10.1007/BF02631775. (49) Li, M.; Li, S.; Xia, J.; Ding, C.; Wang, M.; Xu, L.; Yang, X.; Huang, K. Tung oil based plasticizer and auxiliary stabilizer for poly(vinyl chloride). Materials & Design 2017, 122, DOI 10.1016/j.matdes.2017.03.025. (50) Small, P. Some factors affecting the solubility of polymers. J. Chem. Technol.

27



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 33

Biotechnol. 1953, 3, 71-80. (51) Van Krevelen, D. W.; Te Nijenhuis, K. Properties of polymers: their correlation with chemical structure; their numerical estimation and prediction from additive group contributions. Elsevier: 2009. (52) Serra, A.; Cádiz, V.; Martínez, P.; Mantecón, A. Preparation and reactivity of new 3,3',4,4'-tetracarboxybenzophenone dianhydride glycidyl ester derivatives. Angew. Makromol. Chem. 1986, 140, 113-125. (53) Chen, J.; Li, X.; Wang, Y.; Li, K.; Huang, J.; Jiang, J.; Nie, X. Synthesis and application of a novel environmental plasticizer based on cardanol for poly (vinyl

chloride).

J.

Taiwan

Inst.

Chem.

Eng.

2016,

65,

DOI

10.1016/j.jtice.2016.05.025. (54) Jimenez, A.; Berenguer, V.; Lopez, J.; Sanchez, A. Thermal degradation study of poly (vinyl chloride): kinetic analysis of thermogravimetric data. J. Appl. Polym. Sci. 1993, 50, 1565-1573. (55) Iván, B., The stability of poly(vinyl chloride). J. Vinyl Addit. Technol. 2003, 9, 1– 3. (56) Iván, B., Thermal Stability, Degradation, and Stabilization Mechanisms of Poly(vinyl chloride). Advances in Chemistry 1996, 249,19-32. (57) Iván, B.; Turcsányi, B.; Kelen, T.; Tüdős, F., Thermooxidative degradation of PVC in solution in the presence of metal stearate stabilizers. Angew. Makromol. Chem. 1991, 189, DOI 10.1002/apmc.1991.051890104. (58) Iván, B.; Turcsányi, B.; Kelen, T.; Tüdös, F., Effect of metal stearate stabilizers on the thermal degradation of PVC in solution: The reversible blocking mechanism of stabilization. J. Vinyl Technol. 1990, 12, 126-135. (59) Iván, B.; Kelen, T.; Tüdös, F., The main elementary events of degradation and

28


Page 29 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


stabilization of PVC. Macromol. Symp. 1989, 29, 59-72. (60) Szakács, T.; Iván, B.; Kupai, J., Thermal stability of cationically allylated poly(vinyl chloride) and poly(vinyl chloride- co -2-chloropropene) copolymer. Polym. Degrad. Stab. 2004, 85, DOI 10.1016/j.polymdegradstab.2003.04.004. (61) Iván, B.; Kennedy, J. P.; Kelen, T.; Tüdõs, F.; Nagy, T. T.; Turcsányi, B., Degradation of PVCs obtained by controlled chemical dehydrochlorination. J. Polym. Sci. Pol. Che. 1983, 21, DOI 10.1002/pol.1983.170210802. (62) Iván, B.; Kennedy, J. P.; Kende, I.; Kelen, T.; Tüdős, F. Degradation, Cyclopentadienylation, and Grafting of Vinyl Chloride/2-Chloropropene Copolymers.

J.

Macromol.

Sci.

Chem.

1981,

A16,

DOI

10.1080/00222338108063249. (63) Iván B.; Kelen, T.; Tüdős F. Degradation and Stabilization of Poly(vinyl chloride) in “Degradation and Stabilization of Polymers”, Vol. 2., eds., H. H. G. Jellinek, H. Kachi, Elsevier Sci. Publ. Co.: Amsterdam, New York, 1989, pp. 483-714. (64) Ayrey, G.; Man, F.; Poller, R. Mechanism of thermal stabilization of PVC by organotin compounds: scavenging of chlorine atoms. J. Organomet. Chem. 1979, 173, DOI 10.1016/S0022-328X(00)81286-3. (65) Tüzüm Demir, A. P.; Ulutan, S. Degradation kinetics of PVC plasticized with different plasticizers under isothermal conditions. J. Appl. Polym. Sci. 2015, 132, DOI 10.1002/app.41579. (66) Nagy, T. T.; Iván, B.; Turcsányi, B.; Kelen, T.; Tüdös, F. Crosslinking, scission and benzene formation during PVC degradation under various conditions. Polym. Bull. 1980, 3, DOI 10.1007/BF01135332. (67) Iván, B.; Nagy, T. T.; Kelen, T.; Turcsányi, B.; Tüdös, F. Crosslinking and scission in thermooxidative degradation of PVC. Polym. Bull. (Berlin) 1980, 2,

29



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 33

DOI 10.1007/BF00275558. (68) Kelen, T.; Iván, B.; Nagy, T. T.; Turcsányi, B.; Tűdős, F.; Kennedy, J. P. Reversible crosslinking during thermal degradation of PVC. Polym. Bull. (Berlin) 1978, 1, DOI 10.1007/BF00255718. (69) Qu, H.; Liu, X.; Xu, J.; Ma, H.; Jiao, Y.; Xie, J. Investigation on Thermal Degradation of Poly (1, 4-butylene terephthalate) Filled with Aluminum Hypophosphite and Trimer by Thermogravimetric Analysis–Fourier Transform Infrared Spectroscopy and Thermogravimetric Analysis–Mass Spectrometry. Ind. Eng. Chem. Res. 2014, 53, DOI 10.1021/ie404297r.. (70) Botelho, G.; Queirós, A.; Liberal, S.; Gijsman, P. Studies on thermal and thermooxidative degradation of poly (ethylene terephthalate) and poly (butylene terephthalate).

Polym.

Degrad.

Stab.

2001,

74,

DOI

10.1016/S0141-

3910(01)00088-X. (71) Jia, P.; Zhang, M.; Liu, C.; Hu, L.; Feng, G.; Bo, C.; Zhou, Y. Effect of chlorinated phosphate ester based on castor oil on thermal degradation of poly (vinyl chloride) blends and its flame retardant mechanism as secondary plasticizer. RSC Advances 2015, 5, DOI 10.1039/c5ra05784a. (72) Szakács, T.; Iván, B. Epoxidation of thermally degraded poly(vinyl chloride). Polym. Degrad. Stab. 2004, 85, DOI 10.1016/j.polymdegradstab.2003.04.003. (73)

Grossman,

R.

F.

Mixed

metal

vinyl

stabilizer

synergism.

V:

Dehydrochlorinations reactions of model compounds. J. Vinyl Addit. Techn. 1993, 15, 25-28. (74) Lerke, I.; Szymański, W. Radiation yield of hydrogen chloride in gammairradiated poly (vinyl chloride) stabilized by epoxy compounds. J. Appl. Polym. Sci. 1977, 21, 2067-2075.

30


Page 31 of 33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(75) Greco, A.; Brunetti, D.; Renna, G.; Mele, G.; Maffezzoli, A. Plasticizer for poly (vinyl chloride) from cardanol as a renewable resource material. Polym. Degrad. Stab. 2010, 95, 2169-2174.

31



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

For Table of Contents Use Only

Graphic abstract

synopsis A novel renewable plasticizer, tung oil based triglycidyl ester, was successfully prepared and applied as an alternative plasticizer for Poly(vinyl chloride).

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254x190mm (96 x 96 DPI)


Synthesis of tung oil based triglycidyl ester plasticizer and its effects on

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