新型含磷脂环族环氧化合物的合成及其性能研究
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摘要
脂环族环氧树脂含有刚性脂环结构且环氧基直接连接在脂环上,因此具备不同于双酚A型环氧树脂的特性,如粘度低、热稳定性好、膨胀系数低等优点,广泛用于活性稀释剂、电子封装料、涂料等领域,但脂环族环氧树脂合成工艺较为复杂、收率低,制造成本较高,品种较少。
本文研究利用廉价易得的石油工业副产品双环戊二烯和过量的乙二醇在强酸催化剂三氟化硼乙醚作用下,发生亲电加成反应得到乙二醇单双环戊二烯基醚(I);在以三乙胺作为缚酸剂的条件下,乙二醇单双环戊二烯基醚(I)与三氯氧磷低温反应得到磷酸酯型脂环烯烃(II);再经间氯过氧苯甲酸低温环氧化反应得到一种新型含磷的三官能团脂环族环氧化物(III)。所合成的含磷脂环族环氧树脂及其中间体经红外光谱、氢核磁共振谱、磷核磁共振谱、质谱、环氧当量测定等证实了其结构。新型环氧树脂的合成具有工艺简单、中间体及其产物产率高和成本低廉等特点。
采用非等温差示扫描量热分析(DSC)法测定磷酸酯型脂环族环氧化物酸酐固化反应动力学参数,确定其固化工艺;采用差示扫描量热分析(DSC)、热重分析(TGA)、热膨胀分析(DIL)、氧指数等测试手段研究了环氧树脂固化物的热稳定性、热膨胀性和阻燃性能。研究表明在相同失重条件下合成环氧树脂固化物起始热分解温度与ERL-4221相近,500℃时的热重残碳量高于ERL-4221,说明磷酸酯型脂环族环氧树脂热稳定性良好;膨胀系数与ERL-4221相近,膨胀系数低;且磷酸型脂环族环氧树脂固化物具有一定的阻燃性,在不添加任何阻燃剂的情况下,其极限氧指数(LOI)可达24.9。
通过凝胶率法研究阳离子光引发剂IHT-PI820 (二甲苯基碘鎓六氟磷酸盐)引发磷酸酯型脂环族环氧化物阳离子光聚合的活性,同时研究过氧化苯甲酰(BPO)对阳离子光引发剂IHT-PI820的增感作用,研究发现BPO具有显著的增感效应,添加有BPO的光固化体系曝光较短时间凝胶转化率即可达到相当高的程度,比没有加BPO的光固化体系需要的曝光时间短。光固化物热稳定性良好,最快分解温度在300℃以上,同时在700℃时其最终残留物高达30%。预计合成的新型含磷脂环族环氧化物在阻燃活性稀释剂、电子封装料以及光固化涂料等领域具有广泛应用前景。
Cycloaliphatic epoxides, which contain rigid cycloaliphatic rings and epoxide groups linked to the cycloaliphatic rings, exhibit different properties from BPA, such as low viscosity, good heat resistance, a low expansion coefficient and so on. They have been found to be useful in a wide variety of industrial applications, such as reactive diluents, encapsulating compounds, coatings. But, in generally, the synthesis process of cycloaliphatic epoxide is difficult with low yield and high cost. For these reason, the synthesis and application of novel cycloaliphatic epoxy resins are attracting more and more attention.
In this paper, dicyclopentadiene and ethylene glycol in mole ratio 2:3 with BF3·(C2H5)O as the catalyst (quantity of catalyst is 5% of the mole number of dicyclopentadiene) reacted at 100℃for 5h to give ethylene glycol monodicyclopentenyl ether (I) in 75.6% yield. Phosphation of I with phosphorus oxychloride was carried out with triethyl amine as an additive colligating acid and the yield of phosphate-type cycloalkene (II) was 95%. Then a novel phosphorus-containing trifuntional cycloaliphatic epoxide (III) was produced in 75% yield by epoxidation of II with m-chloroperoxybenzoic acid at 0℃for 10h. The structures of the epoxide (III) and its intermediates were determined by several methologies such as FTIR spectroscopy, 1H-NMR spectroscopy, 31P-NMR spectroscopy, Mass spectroscopy and epoxide equivalent.
The cure kinetics of phosphate-type cycloaliphatic epoxide/anhydride themosetting systems were studied under dynamic curing conditions by Differential Scanning Calorimetry (DSC) technique, which was helpful for determination of the curing process technology. The thermal properties and flame retardant properties of the cured epoxy systems were examined by Thermal Gravimetric Analysis (TGA), Dilatometer (DIL) and Limited Oxygen Index (LOI). The epoxide and hexahydrophthalic anhydride (or methyltetrahydrophthalic anhydride) as a hardener were mixed with a 1:0.8 equivalent ratio of epoxide to anhydride groups. The homogeneous mixture was cured first at 80℃for 6h, then at 150℃for 12h, and finally at 170℃for 6h. The cured epoxide showed a good thermal stability (the initial decomposition temperature was 285.8℃), a low coefficient of thermal expansion (7.31×10-5/℃), and a high flame retardance (the LOI value of 24.9 was achieved without any flame-retardant additive).
The photosensitivity of cationic polymerization of phosphate-type cycloaliphatic epoxide initiated by photointitiator IHT-PI820 (ditolyl iodonium hexafluorophosphate) was studied. The promotion of benzyol peroxide on polymerization of the cycloaliphatic epoxide which initiated by IHT-PI820 was also studied. The results showed that BPO could promote the initiation of IHT-PI820 significantly. The photoinitiated cured system with 4% of BPO got a 90.6% gel yield after 3min UV exposure, which was faster than the case without BPO. The photo-cured polymer exhibited a good thermal stability with a higher thermal decomposition temperature over 300℃and a char yield about 29.92% at 700℃.
The resultant novel phosphorous-containing cycloaliphatic epoxy resin was prospected to be used as flame-retardant reactive diluents, electronic encapsulating compounds or photoinitiated curing coatings.
本文研究利用廉价易得的石油工业副产品双环戊二烯和过量的乙二醇在强酸催化剂三氟化硼乙醚作用下,发生亲电加成反应得到乙二醇单双环戊二烯基醚(I);在以三乙胺作为缚酸剂的条件下,乙二醇单双环戊二烯基醚(I)与三氯氧磷低温反应得到磷酸酯型脂环烯烃(II);再经间氯过氧苯甲酸低温环氧化反应得到一种新型含磷的三官能团脂环族环氧化物(III)。所合成的含磷脂环族环氧树脂及其中间体经红外光谱、氢核磁共振谱、磷核磁共振谱、质谱、环氧当量测定等证实了其结构。新型环氧树脂的合成具有工艺简单、中间体及其产物产率高和成本低廉等特点。
采用非等温差示扫描量热分析(DSC)法测定磷酸酯型脂环族环氧化物酸酐固化反应动力学参数,确定其固化工艺;采用差示扫描量热分析(DSC)、热重分析(TGA)、热膨胀分析(DIL)、氧指数等测试手段研究了环氧树脂固化物的热稳定性、热膨胀性和阻燃性能。研究表明在相同失重条件下合成环氧树脂固化物起始热分解温度与ERL-4221相近,500℃时的热重残碳量高于ERL-4221,说明磷酸酯型脂环族环氧树脂热稳定性良好;膨胀系数与ERL-4221相近,膨胀系数低;且磷酸型脂环族环氧树脂固化物具有一定的阻燃性,在不添加任何阻燃剂的情况下,其极限氧指数(LOI)可达24.9。
通过凝胶率法研究阳离子光引发剂IHT-PI820 (二甲苯基碘鎓六氟磷酸盐)引发磷酸酯型脂环族环氧化物阳离子光聚合的活性,同时研究过氧化苯甲酰(BPO)对阳离子光引发剂IHT-PI820的增感作用,研究发现BPO具有显著的增感效应,添加有BPO的光固化体系曝光较短时间凝胶转化率即可达到相当高的程度,比没有加BPO的光固化体系需要的曝光时间短。光固化物热稳定性良好,最快分解温度在300℃以上,同时在700℃时其最终残留物高达30%。预计合成的新型含磷脂环族环氧化物在阻燃活性稀释剂、电子封装料以及光固化涂料等领域具有广泛应用前景。
Cycloaliphatic epoxides, which contain rigid cycloaliphatic rings and epoxide groups linked to the cycloaliphatic rings, exhibit different properties from BPA, such as low viscosity, good heat resistance, a low expansion coefficient and so on. They have been found to be useful in a wide variety of industrial applications, such as reactive diluents, encapsulating compounds, coatings. But, in generally, the synthesis process of cycloaliphatic epoxide is difficult with low yield and high cost. For these reason, the synthesis and application of novel cycloaliphatic epoxy resins are attracting more and more attention.
In this paper, dicyclopentadiene and ethylene glycol in mole ratio 2:3 with BF3·(C2H5)O as the catalyst (quantity of catalyst is 5% of the mole number of dicyclopentadiene) reacted at 100℃for 5h to give ethylene glycol monodicyclopentenyl ether (I) in 75.6% yield. Phosphation of I with phosphorus oxychloride was carried out with triethyl amine as an additive colligating acid and the yield of phosphate-type cycloalkene (II) was 95%. Then a novel phosphorus-containing trifuntional cycloaliphatic epoxide (III) was produced in 75% yield by epoxidation of II with m-chloroperoxybenzoic acid at 0℃for 10h. The structures of the epoxide (III) and its intermediates were determined by several methologies such as FTIR spectroscopy, 1H-NMR spectroscopy, 31P-NMR spectroscopy, Mass spectroscopy and epoxide equivalent.
The cure kinetics of phosphate-type cycloaliphatic epoxide/anhydride themosetting systems were studied under dynamic curing conditions by Differential Scanning Calorimetry (DSC) technique, which was helpful for determination of the curing process technology. The thermal properties and flame retardant properties of the cured epoxy systems were examined by Thermal Gravimetric Analysis (TGA), Dilatometer (DIL) and Limited Oxygen Index (LOI). The epoxide and hexahydrophthalic anhydride (or methyltetrahydrophthalic anhydride) as a hardener were mixed with a 1:0.8 equivalent ratio of epoxide to anhydride groups. The homogeneous mixture was cured first at 80℃for 6h, then at 150℃for 12h, and finally at 170℃for 6h. The cured epoxide showed a good thermal stability (the initial decomposition temperature was 285.8℃), a low coefficient of thermal expansion (7.31×10-5/℃), and a high flame retardance (the LOI value of 24.9 was achieved without any flame-retardant additive).
The photosensitivity of cationic polymerization of phosphate-type cycloaliphatic epoxide initiated by photointitiator IHT-PI820 (ditolyl iodonium hexafluorophosphate) was studied. The promotion of benzyol peroxide on polymerization of the cycloaliphatic epoxide which initiated by IHT-PI820 was also studied. The results showed that BPO could promote the initiation of IHT-PI820 significantly. The photoinitiated cured system with 4% of BPO got a 90.6% gel yield after 3min UV exposure, which was faster than the case without BPO. The photo-cured polymer exhibited a good thermal stability with a higher thermal decomposition temperature over 300℃and a char yield about 29.92% at 700℃.
The resultant novel phosphorous-containing cycloaliphatic epoxy resin was prospected to be used as flame-retardant reactive diluents, electronic encapsulating compounds or photoinitiated curing coatings.
引文
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