Highly functional Unsaturated Ester Macromonomer Derived from ...
Supporting Information (SI)
Highly functional Unsaturated Ester Macromonomer Derived from Soybean Oil: Synthesis and Copolymerization with Styrene Chengguo Liu, *,†,‡ Yan Dai,† Yun Hu,† Qianqian Shang,† Guodong Feng,† Jing Zhou,† Yonghong Zhou,*,†
†
Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry
(CAF); National Engineering Lab for Biomass Chemical Utilization; Key Lab on Forest Chemical Engineering, State Forestry Administration; and Key Lab of Biomass Energy and Material, Jiangsu Province, 16 Suojin North Road, Nanjing 210042, P. R. China ‡
Institute of Forest New Technology, Chinese Academy of Forestry, Dongxiaofu-1
Xiangshan Road, Beijing 100091, P.R. China
The supporting information included 9 pages, 6 figures, and 3 tables.
S1
Variation of Acid Value with Reaction Time for the Synthesis of HEAMA. Figure S1 shows the variation of acid value with reaction time during the synthesis of HEAMA.
Figure S1. Variation of detected acid value with reaction time during the synthesis of HEAMA precursor.
Effect of Catalysts on Conversion of HEAMA for Synthesis of ESO-HEAMA. Table S1 shows the effect of several catalysts on conversion of HEAMA for the synthesis of ESO-HEAMA. Although triphenyl phosphine was more efficient than N,N-dimethyl benzyl amine and tetrabutyl titanate, the conversion didn’t reached a stable value before gelation. Under the effects of acidic catalysts such as phosphoric acid (liquid, moderate strong acid) and p-toluenesulfonic acid monohydrate (solid, strong acid), reaction systems rapidly reached a gelation state in less than 1 h. Two major reasons may cause the problem. First, a little of unreacted MA which remained in HEAMA precursor would result in the crosslinking of epoxy groups. Second, the hydroxyl groups from the residual unreacted HEA and the ring opening reaction of S2
epoxy groups may result in formation of polyether oligomers; because the hydroxyl groups was not in a stoichiometric excess amount over epoxy compounds, this oligomerization probably occurred and caused the gelation.1 Hence, N,N-dimethyl benzyl amine was selected for synthesis of ESO-HEAMA because under this catalyst the conversion approached a stable value at the reaction time of 4 h and the system didn’t form gelation. Table S1 Effect of catalysts on conversion of HEAMA for the synthesis of ESO-HEAMA Molar ratio
Temp.
Entry
Catalyst o
(ESO/HEAMA)
C
1h
3h
4h
1
1.00/3.84
Triphenyl phosphine
100
66.2
74.7
Gel.
2
1.00/3.84
N,N-Dimethyl benzyl amine
100
65.9
73.9
74.9
3
1.00/3.84
Tetrabutyl titanate
100
64.3
71.2
71.8
4
1.00/3.84
Phosphoric acida
100
Gel.
/
/
5
1.00/3.84
p-Toluenesulfonic acid monohydrateb
100
Gel.
/
/
a
1
Conversionc %
Liquid state. b Solid state. c Conversion of HEAMA.
H-NMR Spectrum of HEAMA and ESO. Figure S2 shows the 1H-NMR spectrum
of HEAMA and ESO. The chemical protons of them and the corresponding peaks were indicated clearly.
S3
Figure S2. 1H-NMR spectra of (a) HEAMA precusor and (b) ESO.
FT-IR Spectra of Free Maleic Anhydride during Maleinization Reaction of ESO-HEAMA. Figure S3 shows the FT-IR spectra of free maleic anhydride (in the shadow area) during maleinization reaction of ESO-HEAMA.
Figure S3. FT-IR spectra of free maleic anhydride during maleinization reaction of ESO-HEAMA: (a) initial reaction and (b) final reaction.
S4
Dynamic Mechanical Analysis of Cured ESO-HEAMA-MA Resins. Figure S4 shows the temperature dependence of storage modulus (E′) and loss factor (tan δ) for the cured bio-resins with different feed ratio of ESO/MA and the related results are listed in Table S2. The received biomaterials exhibited a very broad transition from glassy to rubbery state. As the increase of the amounts of MA modifier, the E′ at 25 °C (E′25) increased from 1.83 GPa to 2.27 GPa, and Tg (determined from the maximum of tan δ) increased from 86.7 °C to 116.8 °C. However, with the ratio of 1/3, the Vs value reached 2325 mPa·s, which was obviously larger than the reported suitable range (200–1000 mPa·s) for liquid modeling resins.2 Hence, the ratio of 1/2 with a viscosity of 530 mPa·s may be more appropriate for the synthesis of ESO-HEAMA-MA resins than the ratio of 1/3. The νe values for the ESO-HEAMA-MA resin with the ESO/MA ratio of 1/2 reached 7.71×103 mol/m3, which was very high in all the reported oil-based UE resins.3-5 The reason for this lies in that ESO-HEAMA-MA monomer had a high C═C functionality.
S5
Figure S4. Storage modulus (a) and loss factor (b) of the cured ESO-HEAMA-MA resins with different feed ratio of ESO/MA (40% styrene and 3% t-BPB).
Table S2. Physical and dynamic mechanical properties of the ESO-HEAMA-MA resins with different feed ratio
a
Molar ratio
Vsa
E′25b
Tg c
ν ed
(ESO/MA)
(mPa·s)
(GPa)
(°C)
(103mol/m3)
1/1
330
1.83
86.7
6.24
1/2
530
2.12
96.4
7.71
1/3
2325
2.27
116.8
6.60
Viscosity. b Storage modulus at 25 °C. c Glass transition temperature. d Crosslink density.
Figure S5 demonstrates the temperature dependence of E′ and tan δ for the ESO-HEAMA-MA resins with different concentration of t-BPB initiator and the corresponding DMA data are listed in Table S3. When the initiator concentration rose from 2% to 4%, the E′25 increased firstly from 1.68 GPa to 2.12 GPa then decreased to 1.93 GPa. The Tg value increased from 86.4 °C to 98.6 °C. Considering the two values, 3% of t-BPB concentration might be an optimal value for the balance of storage modulus and Tg.
S6
Figure S5. Storage modulus (a) and loss factor (b) of the cured ESO-HEAMA-MA resins with different concentration of t-BPB initiator (ESO/HEAMA/MA=1/3.85/2 and 40% styrene).
Table S3. Dynamic mechanical properties of the ESO-HEAMA-MA resins with different concentration of t-BPB initiator
a
Initiator concentration
E′25a
Tg b
ν ec
(wt%)
(GPa)
(°C)
(103mol/m3)
2
1.68
86.4
5.85
3
2.12
96.4
7.71
4
1.93
98.6
6.37
Storage modulus at 25 °C. b Glass transition temperature. c Crosslink density.
S7
Differential Scanning Analysis of Cured ESO-HEAMA-MA Resins. Figure S6 provides the DSC curves of the cured ESO-HEAMAMA resins with different styrene concentration.
Figure S6. DSC curves of the cured ESO-HEAMA-MA resins with different styrene concentration.
References 1.
Rengasamy, S.; Mannari, V. Development of soy-based UV-curable acrylate
oligomers and study of their film properties. Prog. Org. Coat. 2013, 76 (1), 78-85. 2.
Can, E.; Wool, R. P.; Kusefoglu, S. Soybean and castor oil based monomers:
Synthesis and copolymerization with styrene. J. Appl. Polym. Sci. 2006, 102(3), 2433-2447. 3.
Can, E.; Wool, R. P.; Küsefoğlu, S. Soybean- and castor-oil-based thermosetting
polymers: Mechanical properties. J. Appl. Polym. Sci. 2006, 102(2), 1497-1504. 4.
Lu, J.; Khot, S.; Wool, R. P. New sheet molding compound resins from soybean
oil. I. Synthesis and characterization. Polymer 2005, 46(1), 71-80. S8
5.
Liu, C. G.; Dai, Y.; Wang, C. S.; Xie, H. F.; Zhou, Y. H.; Lin, X. Y.; Zhang, L. Y.
Phase-separation dominating mechanical properties of a novel tung-oil-based thermosetting polymer. Ind. Crop. Prod. 2013, 43, 677-683.
S9
Highly functional Unsaturated Ester Macromonomer Derived from Soybean Oil: Synthesis and Copolymerization with Styrene Chengguo Liu, *,†,‡ Yan Dai,† Yun Hu,† Qianqian Shang,† Guodong Feng,† Jing Zhou,† Yonghong Zhou,*,†
†
Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry
(CAF); National Engineering Lab for Biomass Chemical Utilization; Key Lab on Forest Chemical Engineering, State Forestry Administration; and Key Lab of Biomass Energy and Material, Jiangsu Province, 16 Suojin North Road, Nanjing 210042, P. R. China ‡
Institute of Forest New Technology, Chinese Academy of Forestry, Dongxiaofu-1
Xiangshan Road, Beijing 100091, P.R. China
The supporting information included 9 pages, 6 figures, and 3 tables.
S1
Variation of Acid Value with Reaction Time for the Synthesis of HEAMA. Figure S1 shows the variation of acid value with reaction time during the synthesis of HEAMA.
Figure S1. Variation of detected acid value with reaction time during the synthesis of HEAMA precursor.
Effect of Catalysts on Conversion of HEAMA for Synthesis of ESO-HEAMA. Table S1 shows the effect of several catalysts on conversion of HEAMA for the synthesis of ESO-HEAMA. Although triphenyl phosphine was more efficient than N,N-dimethyl benzyl amine and tetrabutyl titanate, the conversion didn’t reached a stable value before gelation. Under the effects of acidic catalysts such as phosphoric acid (liquid, moderate strong acid) and p-toluenesulfonic acid monohydrate (solid, strong acid), reaction systems rapidly reached a gelation state in less than 1 h. Two major reasons may cause the problem. First, a little of unreacted MA which remained in HEAMA precursor would result in the crosslinking of epoxy groups. Second, the hydroxyl groups from the residual unreacted HEA and the ring opening reaction of S2
epoxy groups may result in formation of polyether oligomers; because the hydroxyl groups was not in a stoichiometric excess amount over epoxy compounds, this oligomerization probably occurred and caused the gelation.1 Hence, N,N-dimethyl benzyl amine was selected for synthesis of ESO-HEAMA because under this catalyst the conversion approached a stable value at the reaction time of 4 h and the system didn’t form gelation. Table S1 Effect of catalysts on conversion of HEAMA for the synthesis of ESO-HEAMA Molar ratio
Temp.
Entry
Catalyst o
(ESO/HEAMA)
C
1h
3h
4h
1
1.00/3.84
Triphenyl phosphine
100
66.2
74.7
Gel.
2
1.00/3.84
N,N-Dimethyl benzyl amine
100
65.9
73.9
74.9
3
1.00/3.84
Tetrabutyl titanate
100
64.3
71.2
71.8
4
1.00/3.84
Phosphoric acida
100
Gel.
/
/
5
1.00/3.84
p-Toluenesulfonic acid monohydrateb
100
Gel.
/
/
a
1
Conversionc %
Liquid state. b Solid state. c Conversion of HEAMA.
H-NMR Spectrum of HEAMA and ESO. Figure S2 shows the 1H-NMR spectrum
of HEAMA and ESO. The chemical protons of them and the corresponding peaks were indicated clearly.
S3
Figure S2. 1H-NMR spectra of (a) HEAMA precusor and (b) ESO.
FT-IR Spectra of Free Maleic Anhydride during Maleinization Reaction of ESO-HEAMA. Figure S3 shows the FT-IR spectra of free maleic anhydride (in the shadow area) during maleinization reaction of ESO-HEAMA.
Figure S3. FT-IR spectra of free maleic anhydride during maleinization reaction of ESO-HEAMA: (a) initial reaction and (b) final reaction.
S4
Dynamic Mechanical Analysis of Cured ESO-HEAMA-MA Resins. Figure S4 shows the temperature dependence of storage modulus (E′) and loss factor (tan δ) for the cured bio-resins with different feed ratio of ESO/MA and the related results are listed in Table S2. The received biomaterials exhibited a very broad transition from glassy to rubbery state. As the increase of the amounts of MA modifier, the E′ at 25 °C (E′25) increased from 1.83 GPa to 2.27 GPa, and Tg (determined from the maximum of tan δ) increased from 86.7 °C to 116.8 °C. However, with the ratio of 1/3, the Vs value reached 2325 mPa·s, which was obviously larger than the reported suitable range (200–1000 mPa·s) for liquid modeling resins.2 Hence, the ratio of 1/2 with a viscosity of 530 mPa·s may be more appropriate for the synthesis of ESO-HEAMA-MA resins than the ratio of 1/3. The νe values for the ESO-HEAMA-MA resin with the ESO/MA ratio of 1/2 reached 7.71×103 mol/m3, which was very high in all the reported oil-based UE resins.3-5 The reason for this lies in that ESO-HEAMA-MA monomer had a high C═C functionality.
S5
Figure S4. Storage modulus (a) and loss factor (b) of the cured ESO-HEAMA-MA resins with different feed ratio of ESO/MA (40% styrene and 3% t-BPB).
Table S2. Physical and dynamic mechanical properties of the ESO-HEAMA-MA resins with different feed ratio
a
Molar ratio
Vsa
E′25b
Tg c
ν ed
(ESO/MA)
(mPa·s)
(GPa)
(°C)
(103mol/m3)
1/1
330
1.83
86.7
6.24
1/2
530
2.12
96.4
7.71
1/3
2325
2.27
116.8
6.60
Viscosity. b Storage modulus at 25 °C. c Glass transition temperature. d Crosslink density.
Figure S5 demonstrates the temperature dependence of E′ and tan δ for the ESO-HEAMA-MA resins with different concentration of t-BPB initiator and the corresponding DMA data are listed in Table S3. When the initiator concentration rose from 2% to 4%, the E′25 increased firstly from 1.68 GPa to 2.12 GPa then decreased to 1.93 GPa. The Tg value increased from 86.4 °C to 98.6 °C. Considering the two values, 3% of t-BPB concentration might be an optimal value for the balance of storage modulus and Tg.
S6
Figure S5. Storage modulus (a) and loss factor (b) of the cured ESO-HEAMA-MA resins with different concentration of t-BPB initiator (ESO/HEAMA/MA=1/3.85/2 and 40% styrene).
Table S3. Dynamic mechanical properties of the ESO-HEAMA-MA resins with different concentration of t-BPB initiator
a
Initiator concentration
E′25a
Tg b
ν ec
(wt%)
(GPa)
(°C)
(103mol/m3)
2
1.68
86.4
5.85
3
2.12
96.4
7.71
4
1.93
98.6
6.37
Storage modulus at 25 °C. b Glass transition temperature. c Crosslink density.
S7
Differential Scanning Analysis of Cured ESO-HEAMA-MA Resins. Figure S6 provides the DSC curves of the cured ESO-HEAMAMA resins with different styrene concentration.
Figure S6. DSC curves of the cured ESO-HEAMA-MA resins with different styrene concentration.
References 1.
Rengasamy, S.; Mannari, V. Development of soy-based UV-curable acrylate
oligomers and study of their film properties. Prog. Org. Coat. 2013, 76 (1), 78-85. 2.
Can, E.; Wool, R. P.; Kusefoglu, S. Soybean and castor oil based monomers:
Synthesis and copolymerization with styrene. J. Appl. Polym. Sci. 2006, 102(3), 2433-2447. 3.
Can, E.; Wool, R. P.; Küsefoğlu, S. Soybean- and castor-oil-based thermosetting
polymers: Mechanical properties. J. Appl. Polym. Sci. 2006, 102(2), 1497-1504. 4.
Lu, J.; Khot, S.; Wool, R. P. New sheet molding compound resins from soybean
oil. I. Synthesis and characterization. Polymer 2005, 46(1), 71-80. S8
5.
Liu, C. G.; Dai, Y.; Wang, C. S.; Xie, H. F.; Zhou, Y. H.; Lin, X. Y.; Zhang, L. Y.
Phase-separation dominating mechanical properties of a novel tung-oil-based thermosetting polymer. Ind. Crop. Prod. 2013, 43, 677-683.
S9
