双酚芴双甲基丙烯酸酯的合成及性能研究
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摘要
甲基丙烯酸酯是一种应用十分广泛的功能性高分子聚合物单体,本文中在丙烯酸酯结构中引入刚性芴基,可以有效提高强度、耐热、耐湿等性能。可作为胶黏剂、涂料、牙科树脂等功能材料。
本论文合成了两种含芴结构的功能性丙烯酸酯单体,双酚芴双甲基丙烯酸酯(HPFDM)和双邻甲酚芴双甲基丙烯酸酯(MHPFDM)。HPFDM的合成采用双酚芴环氧树脂(DGEBF)和α-甲基丙烯酸合成单体的路线,以及双酚芴(BPF)和α-甲基丙烯酸环氧树脂合成单体的路线,通过对合成反应条件和两种合成路线的讨论,确定了最佳反应条件和反应路线。同时通过双邻甲酚芴环氧树脂(DGEMBF)和α-甲基丙烯酸合成MHPFDM,确定最佳反应条件。各产物分子结构均经傅立叶红外光谱(FTIR)和核磁共振波谱(NMR)确证。
实验结果表明：当n(DGEBF):n(α-甲基丙烯酸)=1：9,反应温度90℃,反应时间10h时,产物产率最高,可达78%。同时当n(BPF):n(甲基丙烯酸环氧丙酯)=1：2,反应温度80℃,反应时间8h,产品收率可达70%。通过对比可知使用双酚芴环氧树脂的路线合成单体更加可行。以DGEMBF和α-甲基丙烯酸为原料合成MHPFDM的合成工艺条件为n (DGEMBF):n(α-甲基丙烯酸)=1：12,反应时间为10h时反应产率为85%。
选用HPFDM和a-甲基丙烯酸共混制备聚合树脂,采用过氧化苯甲酰为固化剂所用的质量分数为2%,以及N,N-二甲基苯胺为固化促进剂所用的质量分数为1%,制备共混树脂体系。通过热重分析(TGA)进一步考察了共混树脂体系的热性能。
Methyl acrylates compound are widely used as functional polymer monomer. In this paper fluorene-containing methyl acrylate compounds were used extensively as functionality materials, e.g. as dope, adhesive and dental restorative materials, due to their high strength, good thermal stability and desirable moisture resistance.
In this article, two fluorene-containing methyl acrylate compounds, 9,9'-bis[4-(2'-hydroxy-3'-methacryloyloxypropoxy)phenyl]fluorene (HPFDM) and 9,9'-bis[3-methyl-4-(2'-hydroxy-3'-methacryloyloxypropoxy)phenyl]fluorene (MHPFDM) were synthesized. The HPFDM was prepared by fluorene-containing epoxy resins (DGEBF) and methacrylic acid, and the other process was used the epoxy acrylate resin and 9,9-bis(4-hydroxyphenyl)flourene (BPF). Making sure the synthetic process and synthetic conditions such as reagent formula, catalyst dosage, reaction temperature and reaction time were optimized. At the same time, MHPFDM was synthesized by 9,9'-bis (3-methyl-4-hydroxyphenyl)fluorene epoxy resin (DGEMBF) and methacrylic acid, and discussed the optimated synthetic conditions. The chemical structures of the obtained products were characterized by FTIR, NMR.
The results showed that, when n (DGEBF):n (methacrylic acid)=1:9, the reaction temperature was 90℃, The reaction time was 10h, the product of the highest yield was 78%. At one time, n (BPF):n (the epoxy acrylate resin)=1:2, the quality of the mixture solvent was ten times as the epoxy acrylate resin, the reaction temperature was 80℃, the reaction time was 8h, the product of the highest yield was 70%. The first process is the optimum one through the discussion. MHPFDM was synthesized by DGEMBF and methacrylic acid, and the best synthetic condition was:n (DGEMBF):n (methacrylic acid)=1:12, the reaction temperature was 90℃, The reaction time was 10h, the product of the highest yield was 85%.
Solidification resin was prepared with methacrylic acid and HPFDM, and then cured with benzoyl peroxide as curing agent, the quality content of curing agent is 2%, the 1% N,N-dimethylaniline was used as the accelerant.
The thermal properties of solidification resin was further evaluated by thermogravimetric analysis (TGA).
本论文合成了两种含芴结构的功能性丙烯酸酯单体,双酚芴双甲基丙烯酸酯(HPFDM)和双邻甲酚芴双甲基丙烯酸酯(MHPFDM)。HPFDM的合成采用双酚芴环氧树脂(DGEBF)和α-甲基丙烯酸合成单体的路线,以及双酚芴(BPF)和α-甲基丙烯酸环氧树脂合成单体的路线,通过对合成反应条件和两种合成路线的讨论,确定了最佳反应条件和反应路线。同时通过双邻甲酚芴环氧树脂(DGEMBF)和α-甲基丙烯酸合成MHPFDM,确定最佳反应条件。各产物分子结构均经傅立叶红外光谱(FTIR)和核磁共振波谱(NMR)确证。
实验结果表明：当n(DGEBF):n(α-甲基丙烯酸)=1：9,反应温度90℃,反应时间10h时,产物产率最高,可达78%。同时当n(BPF):n(甲基丙烯酸环氧丙酯)=1：2,反应温度80℃,反应时间8h,产品收率可达70%。通过对比可知使用双酚芴环氧树脂的路线合成单体更加可行。以DGEMBF和α-甲基丙烯酸为原料合成MHPFDM的合成工艺条件为n (DGEMBF):n(α-甲基丙烯酸)=1：12,反应时间为10h时反应产率为85%。
选用HPFDM和a-甲基丙烯酸共混制备聚合树脂,采用过氧化苯甲酰为固化剂所用的质量分数为2%,以及N,N-二甲基苯胺为固化促进剂所用的质量分数为1%,制备共混树脂体系。通过热重分析(TGA)进一步考察了共混树脂体系的热性能。
Methyl acrylates compound are widely used as functional polymer monomer. In this paper fluorene-containing methyl acrylate compounds were used extensively as functionality materials, e.g. as dope, adhesive and dental restorative materials, due to their high strength, good thermal stability and desirable moisture resistance.
In this article, two fluorene-containing methyl acrylate compounds, 9,9'-bis[4-(2'-hydroxy-3'-methacryloyloxypropoxy)phenyl]fluorene (HPFDM) and 9,9'-bis[3-methyl-4-(2'-hydroxy-3'-methacryloyloxypropoxy)phenyl]fluorene (MHPFDM) were synthesized. The HPFDM was prepared by fluorene-containing epoxy resins (DGEBF) and methacrylic acid, and the other process was used the epoxy acrylate resin and 9,9-bis(4-hydroxyphenyl)flourene (BPF). Making sure the synthetic process and synthetic conditions such as reagent formula, catalyst dosage, reaction temperature and reaction time were optimized. At the same time, MHPFDM was synthesized by 9,9'-bis (3-methyl-4-hydroxyphenyl)fluorene epoxy resin (DGEMBF) and methacrylic acid, and discussed the optimated synthetic conditions. The chemical structures of the obtained products were characterized by FTIR, NMR.
The results showed that, when n (DGEBF):n (methacrylic acid)=1:9, the reaction temperature was 90℃, The reaction time was 10h, the product of the highest yield was 78%. At one time, n (BPF):n (the epoxy acrylate resin)=1:2, the quality of the mixture solvent was ten times as the epoxy acrylate resin, the reaction temperature was 80℃, the reaction time was 8h, the product of the highest yield was 70%. The first process is the optimum one through the discussion. MHPFDM was synthesized by DGEMBF and methacrylic acid, and the best synthetic condition was:n (DGEMBF):n (methacrylic acid)=1:12, the reaction temperature was 90℃, The reaction time was 10h, the product of the highest yield was 85%.
Solidification resin was prepared with methacrylic acid and HPFDM, and then cured with benzoyl peroxide as curing agent, the quality content of curing agent is 2%, the 1% N,N-dimethylaniline was used as the accelerant.
The thermal properties of solidification resin was further evaluated by thermogravimetric analysis (TGA).
引文
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