Two-step process for synthesizing polycarbonate from isosorbide and dimethyl carbonate

doi:10.16085/j.issn.1000-6613.2018-2444

Abstract

Abstract:

Polycarbonate (PC） is synthesized from isosorbide (IS） and dimethyl carbonate (DMC）through transesterification and polycondensation reactions catalyzed by rubidium carbonate (Rb₂CO₃）and lithium acetylacetonate (LiAcac）. The reaction conditions in both steps were fully optimized including the amount of the catalysts, ratio of the raw materials, polycondensation temperature, and the polycondensation residence time. Moreover, FTIR, ¹H NMR, ¹³C NMR, and TGA technologies were used to characterize both transesterification and polycarbonate products. The optimum conditions were obtained as follows: the amount of Rb₂CO₃ 1×10^-3mol/mol_IS, the molar ratio of DMC/IS 14, the amount of LiAcac 2×10^-3mol/mol_IS, polycondensation temperature of 225℃ and polycondensation retention time of 4h. And the intrinsic viscosity, chromatic aberration, T_g of polymer PC could be up to 36.55mL/g, 6.92, 155.6℃, respectively. The M_n of PC is 30659 and M_w is 42551 with M_w/M_n of 1.39, respectively.

Key words: catalyst, diol, polymer, synthesis, optimization

摘要：

研究了以碳酸铷（Rb₂CO₃）和乙酰丙酮锂（LiAcac）为催化剂，异山梨醇（IS）和碳酸二甲酯（DMC）为原料合成聚碳酸酯（PC）的工艺过程。优化了酯交换反应催化剂用量、原料配比、缩聚反应催化剂用量、缩聚反应温度以及缩聚反应停留时间，并对酯交换产物和聚碳酸酯产品进行了红外光谱、核磁氢谱、核磁碳谱和热重分析，得到较优工艺条件为：Rb₂CO₃用量1×10^-3mol/mol_IS、原料配比n(DMC)/n(IS)=14、LiAcac用量2×10^-3mol/mol_IS、缩聚温度225℃、缩聚停留时间4h，所得的PC产品特性黏数可达36.55mL/g，数均分子量（M_n）为30659，重均分子量（M_w）为42551，M_w/M_n为1.39，色差为6.92，玻璃化转变温度（T_g）为155.6℃。

关键词: 催化剂, 二元醇, 聚合物, 合成, 优化

CLC Number:

TQ323.4

Guohang TAO,Jintao YU,Yongmei WEI,Tao WANG,Hengshui TIAN. Two-step process for synthesizing polycarbonate from isosorbide and dimethyl carbonate[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4632-4638.

陶国行,余锦涛,魏永梅,王涛,田恒水. 异山梨醇与碳酸二甲酯两步法合成聚碳酸酯的工艺[J]. 化工进展, 2019, 38(10): 4632-4638.

Figures/Tables 12

References 14

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催化剂名称	甲醇产率^①/%	H_—OH/H_—C(O)—^②	甲基化产率^③/%
Li₂CO₃	—^④	—	—
Na₂CO₃	—	—	—
K₂CO₃	78.35	0.69	1.15
Rb₂CO₃	85.34	0.19	0.64
Cs₂CO₃	80.27	0.32	1.08
CH₃ONa	45.61	0.85	2.50
LiAcac	52.04	0.76	1.16

催化剂名称	甲醇产率^①/%	H_—OH/H_—C(O)—^②	甲基化产率^③/%
Li₂CO₃	—^④	—	—
Na₂CO₃	—	—	—
K₂CO₃	78.35	0.69	1.15
Rb₂CO₃	85.34	0.19	0.64
Cs₂CO₃	80.27	0.32	1.08
CH₃ONa	45.61	0.85	2.50
LiAcac	52.04	0.76	1.16

催化剂名称	特性黏数/mL·g^-1	色差
无	—	—
钛酸丁酯	14.17	7.61
TEAH	12.95	9.69
Li₂CO₃	11.77	9.00
K₂CO₃	14.07	11.10
Ca(Acac)₂	23.86	7.60
LiAcac	29.42	5.61

催化剂名称	特性黏数/mL·g^-1	色差
无	—	—
钛酸丁酯	14.17	7.61
TEAH	12.95	9.69
Li₂CO₃	11.77	9.00
K₂CO₃	14.07	11.10
Ca(Acac)₂	23.86	7.60
LiAcac	29.42	5.61

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