具有高力学性能的可降解芳香/脂肪共聚酯的合成及其性能
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摘要
为了得到具有良好的热性能,更高的伸长率和弹性模量的可降解聚合物材料,本文通过熔融缩聚法合成了一系列的芳香/脂肪共聚酯,并通过核磁共振(~1HNMR),差示扫描量热法(DSC),热重分析法(TG)和X射线衍射(XRD)技术对共聚酯进行了表征,得到了它们的熔融温度(T_m),熔融热(△H_m),玻璃化转变温度(T_g)和热分解温度(T_d)。
首先利用对苯二甲酸二甲酯(DMT),1,6-己醇(HDO)和低聚乳酸(OLA)在钛酸四丁酯催化下合成了聚(对苯二甲酸己二醇酯-co-乳酸)(PHTL)共聚酯。通过对共聚酯PHTL核磁共振谱图分析得到,共聚酯中对苯二甲酸己二醇酯(n_(HT))的序列长度为3.5;DSC结果表明所有的共聚酯只显示一个玻璃化转变温度(T_g)和两个熔融温度(T_m),而且T_gs和T_ms都随乳酸含量增加而降低;水解降解实验证明PHTL共聚酯具有很好的水解降解性,通过对降解在缓冲液的成分萃取并进行~1H NMR分析得出,溶液中的主要成分为乳酸和对苯二甲酸己二醇链段。
为了提高PHTL共聚酯的热学性能和力学性能,我们在PHTL共聚酯中引入了1,4-环己烷二甲醇(CHDM),同样方法合成了共聚酯PHCTL。共聚酯PHCTL中,随着CHDM含量的增加,共聚酯PHCTL刚性增加,熔点(T_m),热分解温度(T_d)也都明显增加,当环己烷二甲醇在二元醇投料中占50%时,T_m和T_d分别由未含环己烷二甲醇的129℃和361℃上升至219℃和383℃;PHCTL在37℃,磷酸缓冲液中发生了明显的降解,降解速率的大小与共聚酯的亲水性有关。
为了进一步改善共聚酯的力学性能,我们在PHTL共聚酯中引入了自己合成的单体对苯二甲酸二(4-甲氧酰基苯基)酯(BMT),四元共聚合成了具有液晶性能的共聚酯PHBTL。DSC研究表明,随着BMT含量的增加,PHBTL共聚酯的熔点(T_m)降低,玻璃化转变温度(T_g)升高;XRD和偏光显微镜(POM)结果均表明共聚酯PHBTL为向列型液晶。
To obtain a biodegradable polymer material with satisfactory thermal properties, higher elongation and modulus of elasticity, a series of biodegradable aliphatic/aromatic copolyesters were synthesized via melt polycondensation. The resulting copolyesters were characterized by proton nuclear magnetic resonance (~1H NMR), differential scanning calorimetry (DSC), thermogravimetry (TG) and X-ray diffraction (XRD), and their melting temperature (T_m), melting heat of fusion (△H_m), glass-transition temperature (T_g), and thermal decomposition temperature (T_d) were obtained.
In the first, poly (hexylene terephthalate-co-lactide) (PHTL) was synthesized from dimethyl terephthalate (DMT), 1, 6-hexanediol (HDO), and oligo(lactic acid) (OLA) in the presence of titanium (Ⅳ) butoxide. By using the relative integral areas of the dyad peaks in 'H NMR spectrum of copolyesters PHTL, the sequence lengths of the hexylene terephthalate (n_(HT)) units in the resultant copolyesters were 3.5. Only one T_g and two T_m's were observed for all samples, and were found to go down gradually with increasing of lactide moieties. The PHTL copolyesters exhibited a pronounced hydrolytic degradability, which increased with the content of lactide units. ~1H NMR analysis of the residue left by evaporation of the mother solution after hydrolytic degradation revealed that the degradation products consisted mostly of lactide and hexylene terephthalate blocks.
To improve the thermal and mechanical properties of PHTL, 1, 4-cyclohexanedimethanol (CHDM) was introduced into the PHTL copolyester chains. The rigidity, melting temperature (T_m) and thermal decomposition temperature (T_d) of the PHCTL copolyesters increased obviously with increasing content of CHDM. With comparison to the copolyester without CHDM involving, T_m and T_d of the copolyesters with 50/50 of feeding ratio CHDM/HDO increased to 219℃and 383℃from 129℃and 361℃, respectively. Copolyester PHCTL exhibited a pronounced hydrolytic degradability, and the degradation rates of copolyesters were dependent on their hydrophilicity.
To further increase the mechanical properties of PHTL, monomer bis(4-methoxycarbonyl phenyl) terephthalate (BMT) was synthesized, and melt polycondensation from DMT, HDO, OLA and BMT in the presence of titanium (Ⅳ) butoxide was adopted. The melting temperature (T_m) of PHBTL copolyesters decreased but glass-transition temperature (T_g) increased with increasing content of BMT. XRD and POM results of PHBTL polymers indicated that all PHBTL polymers were nematic liquid crystalline polymers.
首先利用对苯二甲酸二甲酯(DMT),1,6-己醇(HDO)和低聚乳酸(OLA)在钛酸四丁酯催化下合成了聚(对苯二甲酸己二醇酯-co-乳酸)(PHTL)共聚酯。通过对共聚酯PHTL核磁共振谱图分析得到,共聚酯中对苯二甲酸己二醇酯(n_(HT))的序列长度为3.5;DSC结果表明所有的共聚酯只显示一个玻璃化转变温度(T_g)和两个熔融温度(T_m),而且T_gs和T_ms都随乳酸含量增加而降低;水解降解实验证明PHTL共聚酯具有很好的水解降解性,通过对降解在缓冲液的成分萃取并进行~1H NMR分析得出,溶液中的主要成分为乳酸和对苯二甲酸己二醇链段。
为了提高PHTL共聚酯的热学性能和力学性能,我们在PHTL共聚酯中引入了1,4-环己烷二甲醇(CHDM),同样方法合成了共聚酯PHCTL。共聚酯PHCTL中,随着CHDM含量的增加,共聚酯PHCTL刚性增加,熔点(T_m),热分解温度(T_d)也都明显增加,当环己烷二甲醇在二元醇投料中占50%时,T_m和T_d分别由未含环己烷二甲醇的129℃和361℃上升至219℃和383℃;PHCTL在37℃,磷酸缓冲液中发生了明显的降解,降解速率的大小与共聚酯的亲水性有关。
为了进一步改善共聚酯的力学性能,我们在PHTL共聚酯中引入了自己合成的单体对苯二甲酸二(4-甲氧酰基苯基)酯(BMT),四元共聚合成了具有液晶性能的共聚酯PHBTL。DSC研究表明,随着BMT含量的增加,PHBTL共聚酯的熔点(T_m)降低,玻璃化转变温度(T_g)升高;XRD和偏光显微镜(POM)结果均表明共聚酯PHBTL为向列型液晶。
To obtain a biodegradable polymer material with satisfactory thermal properties, higher elongation and modulus of elasticity, a series of biodegradable aliphatic/aromatic copolyesters were synthesized via melt polycondensation. The resulting copolyesters were characterized by proton nuclear magnetic resonance (~1H NMR), differential scanning calorimetry (DSC), thermogravimetry (TG) and X-ray diffraction (XRD), and their melting temperature (T_m), melting heat of fusion (△H_m), glass-transition temperature (T_g), and thermal decomposition temperature (T_d) were obtained.
In the first, poly (hexylene terephthalate-co-lactide) (PHTL) was synthesized from dimethyl terephthalate (DMT), 1, 6-hexanediol (HDO), and oligo(lactic acid) (OLA) in the presence of titanium (Ⅳ) butoxide. By using the relative integral areas of the dyad peaks in 'H NMR spectrum of copolyesters PHTL, the sequence lengths of the hexylene terephthalate (n_(HT)) units in the resultant copolyesters were 3.5. Only one T_g and two T_m's were observed for all samples, and were found to go down gradually with increasing of lactide moieties. The PHTL copolyesters exhibited a pronounced hydrolytic degradability, which increased with the content of lactide units. ~1H NMR analysis of the residue left by evaporation of the mother solution after hydrolytic degradation revealed that the degradation products consisted mostly of lactide and hexylene terephthalate blocks.
To improve the thermal and mechanical properties of PHTL, 1, 4-cyclohexanedimethanol (CHDM) was introduced into the PHTL copolyester chains. The rigidity, melting temperature (T_m) and thermal decomposition temperature (T_d) of the PHCTL copolyesters increased obviously with increasing content of CHDM. With comparison to the copolyester without CHDM involving, T_m and T_d of the copolyesters with 50/50 of feeding ratio CHDM/HDO increased to 219℃and 383℃from 129℃and 361℃, respectively. Copolyester PHCTL exhibited a pronounced hydrolytic degradability, and the degradation rates of copolyesters were dependent on their hydrophilicity.
To further increase the mechanical properties of PHTL, monomer bis(4-methoxycarbonyl phenyl) terephthalate (BMT) was synthesized, and melt polycondensation from DMT, HDO, OLA and BMT in the presence of titanium (Ⅳ) butoxide was adopted. The melting temperature (T_m) of PHBTL copolyesters decreased but glass-transition temperature (T_g) increased with increasing content of BMT. XRD and POM results of PHBTL polymers indicated that all PHBTL polymers were nematic liquid crystalline polymers.
引文
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