CN102115430A - Bisphenol A simulated ether-bond-containing model compound of cured epoxy resin and preparation method thereof - Google Patents
Bisphenol A simulated ether-bond-containing model compound of cured epoxy resin and preparation method thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 69
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims 19
- 238000000354 decomposition reaction Methods 0.000 abstract description 21
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- 229910052739 hydrogen Inorganic materials 0.000 description 9
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
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Abstract
一种模拟双酚A环氧树脂固化物的含醚键的模型化合物及其制备方法，它涉及环氧树脂固化物的模型化合物及其制备方法。本发明解决了现有的研究环氧树脂固化物的分解规律的方法繁杂的问题。本发明的模型化合物的结构式为：
Description
技术领域technical field
本发明涉及环氧树脂固化物的模型化合物及其制备方法。The invention relates to a model compound of cured epoxy resin and a preparation method thereof.
背景技术Background technique
由于环氧树脂固化物具有交联结构，难以分解，且其不能熔融、不能溶解、也不能被微生物分解的特性使得废弃物的处理非常困难，无法采用通常热塑性塑料的回收方法来回收。另外，环氧复合材料中基体与纤维的分离技术也是难以解决的问题，而复合材料中的纤维增强材料(如碳纤维)回收利用价值极大。寻找一种有效的热固性环氧树脂的分解方法已成为人们关注的焦点。但是交联环氧树脂的分解过程非常复杂，产物种类繁多，且其为空间三维网状结构，分子结构复杂，分解过程更为复杂，难以找出环氧树脂固化物的分解规律。目前还没有一种分子结构与环氧树脂结构相似、但结构简单的低分子模型化合物，通过研究低分子模型化合物在不同反应条件下的分解特性和分解产物，为揭示环氧树脂的分解规律提供依据。Since the cured epoxy resin has a cross-linked structure, it is difficult to decompose, and it cannot be melted, dissolved, or decomposed by microorganisms, which makes waste treatment very difficult and cannot be recycled by the usual thermoplastic recycling methods. In addition, the separation technology of the matrix and fibers in epoxy composite materials is also a difficult problem to solve, and the fiber-reinforced materials (such as carbon fibers) in composite materials are of great value for recycling. Finding an effective decomposition method of thermosetting epoxy resin has become the focus of attention. However, the decomposition process of cross-linked epoxy resin is very complicated, and there are many kinds of products, and it has a three-dimensional network structure in space. The molecular structure is complex, and the decomposition process is more complicated. It is difficult to find out the decomposition law of cured epoxy resin. At present, there is no low-molecular-weight model compound with a molecular structure similar to that of epoxy resin, but with a simple structure. By studying the decomposition characteristics and decomposition products of low-molecular-weight model compounds under different reaction conditions, it provides a basis for revealing the decomposition rules of epoxy resin. in accordance with.
发明内容Contents of the invention
本发明是为了解决现有的研究环氧树脂固化物的分解规律的方法繁杂的问题，而提供一种模拟双酚A环氧树脂固化物的含醚键的模型化合物及其制备方法。The present invention aims to solve the complicated problem of existing methods for studying the decomposition rules of cured epoxy resins, and provides a model compound containing ether bonds for simulating cured bisphenol A epoxy resins and a preparation method thereof.
本发明的一种模拟双酚A环氧树脂固化物的含醚键的模型化合物的结构式为：The structural formula of a model compound containing ether bonds that simulates bisphenol A epoxy resin cured product of the present invention is:
本发明的一种模拟双酚A环氧树脂固化物的含醚键的模型化合物的制备方法按以下步骤进行：按双酚A与苯基缩水甘油醚的质量比为1∶1.3～1.5称取双酚A与苯基缩水甘油醚后混合，然后再加入占双酚A质量35％～53％的氢氧化钠，在95℃～105℃的恒温水浴条件下，搅拌3h～4h，然后用热水洗涤5～6次，得到模拟双酚A环氧树脂固化物的含醚键的模型化合物。A kind of preparation method of the model compound containing ether bond that simulates bisphenol A epoxy resin cured product of the present invention is carried out according to the following steps: be 1: 1.3～1.5 by weighing the mass ratio of bisphenol A and phenyl glycidyl ether Mix bisphenol A with phenyl glycidyl ether, then add sodium hydroxide accounting for 35% to 53% of the mass of bisphenol A, stir for 3h to 4h in a constant temperature water bath at 95°C to 105°C, and then heat After washing with water for 5-6 times, the ether bond-containing model compound simulating the cured product of bisphenol A epoxy resin is obtained.
本发明的模拟双酚A环氧树脂固化物的含醚键的模型化合物的结构式为：The structural formula of the model compound containing the ether bond of the simulated bisphenol A epoxy resin cured product of the present invention is:
其合成原理如下：Its synthesis principle is as follows:
双酚A环氧E-44/甲基四氢邻苯二甲酸酐MeTHPA树脂体系的分子结构为：The molecular structure of bisphenol A epoxy E-44/methyltetrahydrophthalic anhydride MeTHPA resin system is:
双酚A环氧E-44/异佛尔酮二胺IPDA树脂体系的分子结构为The molecular structure of bisphenol A epoxy E-44/isophorone diamine IPDA resin system is
从以上两个双酚A环氧固化体系固化后的交联结构可以看出交联中含有典型的双酚A结构和醚键结构，本发明制备的模型化合物的结构式中同样具有双酚A结构和醚键结构，所以可以通过研究模型化合物在不同反应条件下的分解特性和分解产物，为揭示环氧树脂的分解规律提供依据。From the cross-linked structure after curing of the above two bisphenol A epoxy curing systems, it can be seen that the cross-link contains a typical bisphenol A structure and an ether bond structure, and the structural formula of the model compound prepared by the present invention also has a bisphenol A structure Therefore, by studying the decomposition characteristics and decomposition products of model compounds under different reaction conditions, it can provide a basis for revealing the decomposition rules of epoxy resins.
附图说明Description of drawings
图1是具体实施方式十一制备的模拟双酚A环氧树脂固化物的含醚键的模型化合物的色谱图；图2是具体实施方式十一制备的模拟双酚A环氧树脂固化物的含醚键的模型化合物的质谱图；图3是具体实施方式十一制备的模拟双酚A环氧树脂固化物的含醚键的模型化合物的傅立叶红外光谱图；图4是具体实施方式十一制备的模拟双酚A环氧树脂固化物的含醚键的模型化合物的核磁共振氢谱图；图5是具体实施方式十一制备的模拟双酚A环氧树脂固化物的含醚键的模型化合物的核磁共振碳谱图。Fig. 1 is the chromatogram of the model compound containing the ether bond of the simulated bisphenol A epoxy resin cured product prepared in the eleventh embodiment; Fig. 2 is the chromatogram of the simulated bisphenol A epoxy resin cured product prepared in the eleventh specific embodiment The mass spectrogram of the model compound containing ether bond; Fig. 3 is the Fourier infrared spectrogram of the model compound containing ether bond of the simulated bisphenol A epoxy resin cured product prepared in the eleventh embodiment; Fig. 4 is the eleventh embodiment The hydrogen nuclear magnetic resonance spectrogram of the ether bond-containing model compound of the simulated bisphenol A epoxy resin cured product prepared; Fig. 5 is the ether bond-containing model of the simulated bisphenol A epoxy resin cured product prepared in specific embodiment eleven C NMR spectrum of the compound.
具体实施方式Detailed ways
具体实施方式一：本实施方式的一种模拟双酚A环氧树脂固化物的含醚键的模型化合物的结构式为：Specific embodiment one: the structural formula of a model compound containing ether bonds that simulates bisphenol A epoxy resin cured product in this embodiment is:
本实施方式的模型化合物的结构式中具有双酚A结构和醚键结构，双酚A结构和醚键结构是环氧树脂交联后的典型结构，所以可以通过研究模型化合物在不同反应条件下的分解特性和分解产物，为揭示环氧树脂的分解规律提供依据。The structural formula of the model compound of the present embodiment has a bisphenol A structure and an ether bond structure, and the bisphenol A structure and the ether bond structure are typical structures after crosslinking of epoxy resins, so it is possible to study the model compounds under different reaction conditions. The decomposition characteristics and decomposition products provide a basis for revealing the decomposition law of epoxy resin.
具体实施方式二：本实施方式的一种模拟双酚A环氧树脂固化物的含醚键的模型化合物的制备方法按以下步骤进行：按双酚A与苯基缩水甘油醚的质量比为1∶1.3～1.5称取双酚A与苯基缩水甘油醚后混合，然后再加入占双酚A质量35％～53％的氢氧化钠，在95℃～105℃的恒温水浴条件下，搅拌3h～4h，然后用热水洗涤5～6次，得到模拟双酚A环氧树脂固化物的模型化合物。Specific embodiment two: the preparation method of the model compound containing ether bond of a kind of simulation bisphenol A epoxy resin cured product of the present embodiment is carried out according to the following steps: be 1 by the mass ratio of bisphenol A and phenyl glycidyl ether : 1.3 to 1.5 Weigh bisphenol A and phenyl glycidyl ether and mix them, then add sodium hydroxide accounting for 35% to 53% of the mass of bisphenol A, and stir for 3 hours at a constant temperature of 95°C to 105°C in a water bath ~4h, and then washed with hot water for 5-6 times to obtain a model compound that simulates the cured product of bisphenol A epoxy resin.
本实施方式制备的模型化合物的结构式为：The structural formula of the model compound prepared in this embodiment is:
本实施方式的模型化合物的结构式中具有双酚A结构和醚键结构，双酚A结构和醚键结构是环氧树脂交联后的典型结构，所以可以通过研究模型化合物在不同反应条件下的分解特性和分解产物，为揭示环氧树脂的分解规律提供依据。The structural formula of the model compound of the present embodiment has a bisphenol A structure and an ether bond structure, and the bisphenol A structure and the ether bond structure are typical structures after crosslinking of epoxy resins, so it is possible to study the model compounds under different reaction conditions. The decomposition characteristics and decomposition products provide a basis for revealing the decomposition law of epoxy resin.
具体实施方式三：本实施方式与具体实施方式二不同的是：双酚A与苯基缩水甘油醚的质量比为1∶1.35～1.45。其它与具体实施方式二相同。Embodiment 3: This embodiment is different from Embodiment 2 in that the mass ratio of bisphenol A to phenyl glycidyl ether is 1:1.35-1.45. Others are the same as in the second embodiment.
具体实施方式四：本实施方式与具体实施方式二不同的是：双酚A与苯基缩水甘油醚的质量比为1∶1.40。其它与具体实施方式二相同。Embodiment 4: This embodiment is different from Embodiment 2 in that the mass ratio of bisphenol A to phenyl glycidyl ether is 1:1.40. Others are the same as in the second embodiment.
具体实施方式五：本实施方式与具体实施方式二至四之一不同的是：氢氧化钠的加入量为双酚A质量的40％～50％。其它与具体实施方式二至四之一相同。Embodiment 5: This embodiment differs from Embodiment 2 to Embodiment 4 in that the amount of sodium hydroxide added is 40% to 50% of the mass of bisphenol A. Others are the same as one of the second to fourth specific embodiments.
具体实施方式六：本实施方式与具体实施方式二至四之一不同的是：氢氧化钠的加入量为双酚A质量的45％。其它与具体实施方式二至四之一相同。Embodiment 6: This embodiment differs from Embodiment 2 to Embodiment 4 in that the amount of sodium hydroxide added is 45% of the mass of bisphenol A. Others are the same as one of the second to fourth specific embodiments.
具体实施方式七：本实施方式与具体实施方式二至六之一不同的是：水浴的温度为97℃～103℃。其它与具体实施方式二至六之一相同。Embodiment 7: This embodiment differs from Embodiment 2 to
具体实施方式八：本实施方式与具体实施方式二至六之一不同的是：水浴的温度为100℃。其它与具体实施方式二至六之一相同。Embodiment 8: This embodiment is different from Embodiment 2 to
具体实施方式九：本实施方式与具体实施方式二至八之一不同的是：洗涤用的热水的温度为80℃～100℃。其它与具体实施方式二至八之一相同。Embodiment 9: This embodiment is different from Embodiment 2 to Embodiment 8 in that: the temperature of the hot water for washing is 80°C-100°C. Others are the same as one of the second to eighth specific embodiments.
本实施方式以热水洗涤来除去化合物中的氢氧化钠催化剂和多余的苯基缩水甘油醚反应物。In this embodiment, the sodium hydroxide catalyst and excess phenyl glycidyl ether reactants in the compound are removed by washing with hot water.
具体实施方式十：本实施方式与具体实施方式二至八之一不同的是：洗涤用的热水的温度为90℃。其它与具体实施方式二至八之一相同。Embodiment 10: This embodiment is different from Embodiment 2 to Embodiment 8 in that: the temperature of the hot water for washing is 90°C. Others are the same as one of the second to eighth specific embodiments.
具体实施方式十一：本实施方式的一种模拟双酚A环氧树脂固化物的含醚键的模型化合物的制备方法按以下步骤进行：按双酚A与苯基缩水甘油醚的质量比为1∶1.3称取双酚A与苯基缩水甘油醚并加入到容器中，然后再加入占双酚A质量48％的氢氧化钠，在100℃的恒温水浴条件下，搅拌3h，得到模拟双酚A环氧树脂固化物的含醚键的模型化合物。Specific embodiment eleven: the preparation method of the model compound containing ether bond of a kind of imitation bisphenol A epoxy resin cured product of the present embodiment is carried out according to the following steps: by the mass ratio of bisphenol A and phenyl glycidyl ether: 1:1.3 Weigh bisphenol A and phenyl glycidyl ether and add them into the container, then add sodium hydroxide accounting for 48% of the mass of bisphenol A, and stir for 3 hours in a constant temperature water bath at 100°C to obtain simulated bisphenol A Ether bond-containing model compound of cured phenol A epoxy resin.
本实施方式得到的模拟双酚A环氧树脂固化物的含醚键的模型化合物的结构式为：The structural formula of the ether bond-containing model compound that simulates the bisphenol A epoxy resin cured product obtained in this embodiment is:
将本实施方式得到的模拟双酚A环氧树脂固化物的含醚键的模型化合物用色谱柱分离法提纯，然后将样品溶于甲醇中，配成浓度为500ppm的溶液，设定以甲醇与水体积比为10∶1为流动相，流速为0.7mL/min，紫外检测器检测波长为278nm，进行气质联用分析，得到模型化合物的色谱图如图1所示，从图1可以看出，苯基缩水甘油醚的峰较明显，说明经过提纯处理的模型化合物中仅含有苯基缩水甘油醚，并且基本没有其它副产物峰出现，说明经过提纯处理后的模型化合物的纯度较高，从而可以满足本实验的使用要求。Purify the ether bond-containing model compound of the simulated bisphenol A epoxy resin cured product obtained in the present embodiment with a chromatographic column separation method, then dissolve the sample in methanol to form a solution with a concentration of 500ppm, and set the mixture of methanol and The water volume ratio is 10:1 as the mobile phase, the flow rate is 0.7mL/min, and the detection wavelength of the ultraviolet detector is 278nm, and the gas chromatography-mass spectrometry analysis is carried out to obtain the chromatogram of the model compound as shown in Figure 1, as can be seen from Figure 1 , the peak of phenyl glycidyl ether is more obvious, indicating that the purified model compound only contains phenyl glycidyl ether, and basically no other by-product peaks appear, indicating that the purified model compound has a higher purity, thus It can meet the requirements of this experiment.
本实施方式采用ESI源质谱进行分析，在负离子模式下，只进行一级电离分析，得到模型化合物的质谱图如图2所示，从图2可以看出，在m/z为526.8处对应模型化合物的分子离子峰，因此确定所合成的模型化合物的分子量为527.8(约为528)，m/z为377.3处对应模型化合物的碎片离子峰，此峰较强，是模型化合物通过断键产生的主要离子碎片峰，其断键位置如下式所示。In this embodiment, ESI source mass spectrometry is used for analysis. In the negative ion mode, only the first-order ionization analysis is performed, and the mass spectrogram of the model compound is obtained as shown in Figure 2. It can be seen from Figure 2 that the corresponding model at m/z is 526.8 The molecular ion peak of the compound, so it is determined that the molecular weight of the synthesized model compound is 527.8 (about 528), and the m/z is 377.3 corresponding to the fragment ion peak of the model compound. This peak is stronger and is produced by the model compound through bond breaking The main ion fragment peak, its bond breaking position is shown in the following formula.
从以上谱图信息中可以初步确定，所合成模型化合物的分子量为528，即为目标合成产物的分子量。此外，还可以从离子碎片峰中初步验证出目标产物的结构。From the above spectral information, it can be preliminarily determined that the molecular weight of the synthesized model compound is 528, which is the molecular weight of the target synthetic product. In addition, the structure of the target product can also be preliminarily verified from the ion fragment peaks.
用KBr压片法，对本实施方式得到的模拟双酚A环氧树脂固化物的含醚键的模型化合物经用色谱柱分离法提纯后进行红外光谱分析，得到的模型化合物的傅立叶红外光谱图如图3所示，从图3可看出，3398cm-1为羟基的伸缩振动吸收峰，3052cm-1为苯环的碳氢伸缩振动吸收峰，2931cm-1、2876cm-1为亚甲基、甲基的伸缩振动吸收峰，1602cm-1、1505cm-1为苯环碳碳骨架的振动吸收峰，1245cm-1、1044cm-1为脂肪芳香醚的反对称、对称伸缩振动吸收峰，831cm-1为对位取代苯环的变形振动吸收峰，735cm-1、692cm-1为单取代苯环的变形振动吸收峰。由红外谱图的测试结果可知，本实验合成的模型化合物结构中含有苯环、羟基、醚键等基团，可满足本实验对模型化合物的结构要求。With the KBr tablet method, the ether bond-containing model compound of the simulated bisphenol A epoxy resin cured product obtained in the present embodiment is purified by a chromatographic column separation method and then subjected to infrared spectrum analysis. The Fourier infrared spectrum of the obtained model compound is as follows As shown in Figure 3, it can be seen from Figure 3 that 3398cm -1 is the stretching vibration absorption peak of the hydroxyl group, 3052cm -1 is the hydrocarbon stretching vibration absorption peak of the benzene ring, and 2931cm -1 and 2876cm -1 are the methylene, formazan 1602cm -1 and 1505cm -1 are the vibration absorption peaks of the carbon-carbon skeleton of the benzene ring, 1245cm -1 and 1044cm -1 are the antisymmetric and symmetric stretching vibration absorption peaks of the aliphatic aromatic ether, and 831cm -1 is the The deformation vibration absorption peak of the para-substituted benzene ring, 735cm -1 and 692cm -1 are the deformation vibration absorption peaks of the mono-substituted benzene ring. From the test results of infrared spectrum, it can be seen that the structure of the model compound synthesized in this experiment contains groups such as benzene ring, hydroxyl group, and ether bond, which can meet the structural requirements of the model compound in this experiment.
以丙酮为溶剂，对本实施方式得到的模拟双酚A环氧树脂固化物的含醚键的模型化合物进行用核磁共振仪进行氢谱分析，得到的模型化合物的核磁共振氢谱如图4所示，氢谱中2.05ppm是溶剂峰，δ值为1.607ppm处的单峰对应甲基上的氢，δ值在3.983ppm-4.183ppm范围内的峰对应亚甲基上的氢，δ值在6.855ppm-7.269ppm范围内的峰对应苯环上的氢，δ值为3.967ppm处的峰对应次甲基上的氢，δ值为4.314ppm处的峰对应羟基上的氢。各峰的指认见表1。Using acetone as a solvent, the model compound containing ether bonds of the simulated bisphenol A epoxy resin cured product obtained in the present embodiment is carried out with a nuclear magnetic resonance instrument for hydrogen spectrum analysis, and the hydrogen nuclear magnetic resonance spectrum of the model compound obtained is as shown in Figure 4 , 2.05ppm in the hydrogen spectrum is the solvent peak, the single peak at δ value of 1.607ppm corresponds to the hydrogen on the methyl group, the peak with the δ value in the range of 3.983ppm-4.183ppm corresponds to the hydrogen on the methylene group, and the δ value is 6.855 The peak in the range of ppm-7.269ppm corresponds to the hydrogen on the benzene ring, the peak at the δ value of 3.967ppm corresponds to the hydrogen on the methine, and the peak at the δ value of 4.314ppm corresponds to the hydrogen on the hydroxyl group. The identification of each peak is shown in Table 1.
表1模型化合物的1H谱峰的化字位移Table 1 The displacement of the 1 H spectral peaks of the model compounds
以丙酮为溶剂，对本实施方式得到的模拟双酚A环氧树脂固化物的含醚键的模型化合物进行用核磁共振仪进行碳谱分析，得到的模型化合物的核磁共振碳谱如图5所示，从图5可以看出，δ值为42.2ppm处的单峰对应连接两个苯环的季碳原子，δ值在31.4ppm处的峰对应甲基上的碳原子，δ值在114.7ppm～157.7ppm范围内的峰对应苯环上的碳原子。各峰的指认见表2。Using acetone as a solvent, the ether bond-containing model compound of the simulated bisphenol A epoxy resin cured product obtained in the present embodiment is carried out with a nuclear magnetic resonance instrument for carbon spectrum analysis, and the carbon nuclear magnetic resonance spectrum of the model compound obtained is shown in Figure 5 , as can be seen from Figure 5, the single peak at the δ value of 42.2ppm corresponds to the quaternary carbon atom connecting the two benzene rings, the peak at the δ value at 31.4ppm corresponds to the carbon atom on the methyl group, and the δ value is between 114.7ppm and The peaks in the range of 157.7 ppm correspond to the carbon atoms on the benzene ring. The identification of each peak is shown in Table 2.
表2模型化合物的13C谱峰的化学位移Table 2 Chemical shifts of 13 C peaks of model compounds
利用红外光谱、核磁共振等分析可知，模型化合物含有所需的醚键、羟基等官能团以及特定的苯环结构等，从而证明本实验按照拟定合成路线成功合成出所需结构的模型化合物。Analysis by infrared spectroscopy and nuclear magnetic resonance shows that the model compound contains the required functional groups such as ether bonds, hydroxyl groups, and specific benzene ring structures, etc., which proves that this experiment successfully synthesized the model compound with the required structure according to the proposed synthesis route.
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| JP2009276633A (en) * | 2008-05-15 | 2009-11-26 | Toppan Printing Co Ltd | Colored alkali-developable photosensitive resin composition, color filter and substrate with protrusion for control of liquid crystal segmentation alignment using the same, and liquid crystal display device with the substrate |
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| JP2009276633A (en) * | 2008-05-15 | 2009-11-26 | Toppan Printing Co Ltd | Colored alkali-developable photosensitive resin composition, color filter and substrate with protrusion for control of liquid crystal segmentation alignment using the same, and liquid crystal display device with the substrate |
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