CN108084429B - 含羧基侧基超支化聚芳醚共聚物及其制备方法和应用 - Google Patents
含羧基侧基超支化聚芳醚共聚物及其制备方法和应用 Download PDFInfo
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- 229920000090 poly(aryl ether) Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 32
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical class C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 12
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 10
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 5
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 239000012024 dehydrating agents Substances 0.000 claims description 12
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
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- -1 acyl benzene Chemical compound 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical class C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 claims description 3
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
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- 229920005989 resin Polymers 0.000 abstract description 4
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- 238000005815 base catalysis Methods 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000010792 warming Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 9
- 229960001553 phloroglucinol Drugs 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229920006260 polyaryletherketone Polymers 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
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- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 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 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000012869 ethanol precipitation Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
- C08G65/405—(I) or (II) containing oxygen other than as phenol or carbonyl group in ring structure, e.g. phenolphtalein
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Abstract
本发明提供了一种含羧基侧基超支化聚芳醚共聚物及其制备方法和应用。该共聚物是以酚酞啉及其含取代基衍生物与多酚单体在极性溶剂中、碱催化下、与双卤单体进行共聚反应制得。本发明提供的制备方法可以通过多酚单体与双酚单体的比例调节含羧基侧基超支化聚芳醚的支化度，有利于在改性环氧树脂过程中调控交联密度，不仅可应用与环氧树脂和氰酸酯树脂的增强增韧，而且在膜分离材料，涂料，绝缘漆材料以及键合型稀土配位荧光材料的制备等方面都具有重要的实用价值和开发价值。
Description
技术领域
本发明属于高分子材料领域，涉及一种含羧基侧基超支化聚芳醚酮共聚物及其制备方法和应用。
背景技术
聚芳醚(聚芳醚酮，聚芳醚酮酮，聚芳醚砜)是一种具有优良综合性能的工程塑料材料，在航空航天，机械电子，电子电器，核能工业以及民用高技术领域有着广泛的应用，但是随着人们对材料使用和加工性能的要求越来越高，传统的聚芳醚材料已经不能满足科学技术发展的需要，传统的双酚A型聚芳醚砜和聚芳醚酮具有完全无定形结构，在常用的有机溶剂中可溶解，但其玻璃化转变温度较低，造成了其使用温度较低。聚醚酮酮于1980年首次在英国ICI公司合成，它是一种半结晶聚合物，使用温度在200℃以上，但其在有机溶剂中溶解性较差，给溶液浸渍法或者灌注法制备复合材料带来了困难。可溶性聚芳醚材料虽然为复合材料的制备提供了可能，但其耐溶剂差应用受限。因此，本领域亟需一种具有良好加工性能和溶解性的聚芳醚。
发明内容
为了解决现有技术中聚芳醚耐溶剂性差、加工性能不好等问题，本发明提供了一种含羧基侧基超支化聚芳醚酮共聚物的制备方法。通过多酚单体与双酚单体的比例调节超支化聚芳醚共聚物的支化度，从而可以调节羧基侧基的含量，该超支化聚芳醚共聚物可与环氧树脂中的环氧基发生固化反应，形成三维交联的网状结构，得到一种兼具热塑性材料和热固性材料优点的交联树脂。
为实现上述目的，本发明提供一种含羧基侧基超支化聚芳醚的共聚物，具有式(Ⅰ)的结构：
其中，A为
B为
C为
中的一种。
本发明还提供了上述含羧基侧基超支化聚芳醚共聚物的制备方法，包括：
(1)将多酚单体，酚酞啉单体、双卤单体、碱催化剂、有机溶剂和脱水剂依次加入到反应釜中，在温度为120℃～160℃下脱水1～8小时，蒸出脱水剂；
(2)蒸出脱水剂后在温度为160℃～210℃下反应1～10小时；
(3)加入N,N-二甲基甲酰胺稀释，冷却后过滤，在沉淀剂中沉降，水洗，干燥后得到产品。
优选的，所述酚酞啉单体为酚酞啉，2’,2”-二甲基酚酞啉，2’,2”-二异丙基-5’,5”-二甲基酚酞啉中的一种或一种以上；所述酚酞啉单体与多酚单体的摩尔比为1：(0.05～0.42)。
优选的，所述双卤单体可以是4,4’-二氟二苯酮，4,4’-二氟二苯砜，4,4’-二氯二苯砜，2,6-二氟苯腈，1,4-二-4-氟苯酰基苯中的一种或几种的混合物；所述多酚单体、酚酞啉单体的羟基之和与双卤单体中卤原子的摩尔比为1：1。
优选的，所述有机溶剂为二甲基亚砜，环丁砜，N,N-二甲基甲酰胺，N-甲基吡咯烷酮，二苯砜中的一种或一种以上；所述有机溶剂与双卤单体的体积质量比为(0.4～5.5)：1(mL/g)。
优选的，所述的脱水剂为苯，甲苯，二甲苯或氯苯中的一种或几种的混合物，所述脱水剂与所述有机溶剂的体积比为1：(0.3～2.5)。
优选的，碱催化剂为氢化钠，氢化钾，氢氧化钠，氢氧化钾，碳酸钠或碳酸钾中的一种或一种以上，所述碱催化剂与酚酞啉单体的摩尔比为(2～5)：1。
优选的，步骤(2)为蒸出脱水剂后在165℃～185℃反应2～6小时。
优选的，步骤(3)所述N,N-二甲基甲酰胺与步骤(1)所述有机溶剂物质的量比为(1.5～2)：1。
优选的，步骤(3)所述沉淀剂为乙醇，甲醇或水中的一种或一种以上；所述沉淀剂的用量为0.25～1L。
本发明另一个目的请求保护上述含羧基侧基超支化聚芳醚共聚物在环氧树脂改性中的应用。
通过在聚合物的主链的侧基上引入可以与环氧基团反应的羧基侧基，使羧基侧基与环氧基发生固化反应，形成三维交联的网状结构，可以同时改善环氧树脂材料的强度，韧性以及耐溶剂性。
本发明所制备的系列含羧基侧基超支化聚芳醚共聚物具有如下优点：
(1)、所制备的为系列芳香聚合物，活性羧基基团连接在苯环侧基上，具有较大的刚性，所制备聚合物用DSC法测定玻璃化转变温度在186-200℃之间有较好的耐热性。
(2)、本发明的含羧基侧基超支化聚芳醚酮的化学结构经傅立叶红外光谱(FTIR)和核磁共振分析(NMR)方法得到了证实。凝胶渗透色谱(GPC)法测定得到的数均分子量在两万以上，可知，本发明聚合反应较为完全，并且所合成的共聚物具有一定的强度。
(3)、本发明制备的含羧基侧基超支化聚芳醚共聚物不仅具有线性聚芳醚的性质，即机械强度高和稳定性好等，而且具有超支化聚合物的性质，如低的熔融黏度、良好的溶解性能、无链缠结和非晶性等，使超支化聚芳醚的加工性能和溶解性都得到提高。
(4)、本发明提供的制备方法可以通过多酚单体与双酚单体的比例调节含羧基侧基超支化聚芳醚的支化度，有利于在改性环氧树脂过程中调控交联密度，不仅可应用与环氧树脂和氰酸酯树脂的增强增韧，而且在膜分离材料，涂料，绝缘漆材料以及键合型稀土配位荧光材料的制备等方面都具有重要的实用价值和开发价值。
附图说明
图1为本发明制备的含羧基侧基超支化聚芳醚共聚物红外谱图；
图2为本发明制备的含羧基侧基超支化聚芳醚共聚物核磁谱图；
图3为本发明制备的含羧基侧基超支化聚芳醚共聚物GPC谱图。
具体实施方式
下面通过具体实施例详述本发明，但不限制本发明的保护范围。
实施例1
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，5.8623g(0.0183mol)酚酞啉，6.546g(0.03mol)4,4’-二氟二苯酮，12.4389g(0.09mol)无水碳酸钾，19ml二甲基亚砜和21ml甲苯，升温至140℃，2小时后，继续升温到175℃反应4小时。用N,N-二甲基甲酰胺稀释，在乙醇中沉淀，用蒸馏水反复煮洗除去无机盐，干燥后得到絮状产物。所得产物红外谱图见图1；所得产物核磁谱图见图2；所得产物GPC谱图见图3。
实施例2
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，6.3388g(0.0183mol)2’,2”-二甲基酚酞啉，6.546g(0.03mol)4,4’-二氟二苯酮，6.9105g(0.05mol)无水碳酸钾，19ml二甲基亚砜和21ml甲苯，升温至125℃，共沸脱水，4小时后，继续升温到210℃反应4小时。用N,N-二甲基甲酰胺稀释，在乙醇中沉淀，洗涤除去无机盐，干燥后得到絮状产物。
实施例3
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，7.9158g(0.0183mol)2’,2”-二异丙基-5’,5”-二甲基酚酞啉，6.546g(0.03mol)4,4’-二氟二苯酮，12.4389g(0.09mol)无水碳酸钾，22ml二甲基亚砜和24ml甲苯，升温至150℃，2小时后，继续升温到180℃反应7小时。用N,N-二甲基甲酰胺稀释，在乙醇中沉淀，用蒸馏水反复煮洗除去无机盐，干燥后得到絮状产物。
实施例4
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，5.8623g(0.0183mol)酚酞啉，7.6275g(0.03mol)4,4’-二氟二苯砜，3.6g(0.09mol)氢氧化钠，40ml二甲基亚砜和22ml甲苯，升温至120℃，8小时后，继续升温到170℃反应9小时。用N,N-二甲基甲酰胺稀释，用600mL乙醇沉淀，用蒸馏水反复煮洗除去无机盐，干燥后得到絮状产物。
实施例5
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，6.3388g(0.0183mol)2’,2”-二甲基酚酞啉，7.6275g(0.03mol)4,4’-二氟二苯砜，12.4389g(0.09mol)无水碳酸钾，8ml二甲基亚砜和23ml甲苯，升温至140℃，6小时后，继续升温到190℃反应7小时。用N,N-二甲基甲酰胺稀释，在乙醇中沉淀，用蒸馏水反复煮洗除去无机盐，干燥后得到絮状产物。
实施例6
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，7.9158g(0.0183mol)2’,2”-二异丙基-5’,5”-二甲基酚酞啉，7.6275g(0.03mol)4,4’-二氟二苯砜，12.4389g(0.09mol)无水碳酸钾，25ml二甲基亚砜和25ml甲苯，升温至160℃，1小时后，继续升温到200℃反应3小时。用N,N-二甲基甲酰胺稀释，在乙醇中沉淀，用蒸馏水反复煮洗除去无机盐，干燥后得到絮状产物。
实施例7
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，5.8623g(0.0183mol)酚酞啉，4.1733g(0.03mol)2,6-二氟苯腈，3.6099g(0.09mol)氢化钾，42ml二甲基亚砜和17ml甲苯，升温至145℃，2小时后，继续升温到185℃反应5小时。用N,N-二甲基甲酰胺稀释，在乙醇中沉淀，用蒸馏水反复煮洗除去无机盐，干燥后得到絮状产物。
实施例8
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，6.3388g(0.0183mol)2’,2”-二甲基酚酞啉，4.1733g(0.03mol)2,6-二氟苯腈，5.5284g(0.04mol)无水碳酸钾，13ml二甲基亚砜和18ml甲苯，升温至140℃，3小时后，继续升温到175℃反应4小时。用N,N-二甲基甲酰胺稀释，在乙醇中沉淀，用蒸馏水反复煮洗除去无机盐，干燥后得到絮状产物。
实施例9
往装有氮气导管，冷凝管，分水器，温度计和机械搅拌器的三口瓶中依次加入0.9837g(0.0078mol)间苯三酚，7.9158g(0.0183mol)2’,2”-二异丙基-5’,5”-二甲基酚酞啉，4.1733g(0.03mol)2,6-二氟苯腈，12.4389g(0.09mol)无水碳酸钾，18ml二甲基亚砜和20ml甲苯，升温至130℃，3小时后，继续升温到155℃反应4小时。N,N-二甲基甲酰胺稀释，在乙醇中沉淀，用蒸馏水反复煮洗，干燥后得到絮状产物。
以上所述，仅为本发明创造较佳的具体实施方式，但本发明创造的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明创造披露的技术范围内，根据本发明创造的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明创造的保护范围之内。
Claims (10)
1.一种含羧基侧基超支化聚芳醚的共聚物，其特征在于，具有式(Ⅰ)的结构：
其中，A为
B为
C为
中的一种。
2.一种如权利要求1所述含羧基侧基超支化聚芳醚共聚物的制备方法，其特征在于，包括：
(1)将多酚单体，酚酞啉单体、双卤单体、碱催化剂、有机溶剂和脱水剂依次加入到反应釜中，在温度为120℃～160℃下脱水1～8小时，蒸出脱水剂；
(2)蒸出脱水剂后在温度为160℃～210℃下反应1～10小时；
(3)加入N,N-二甲基甲酰胺稀释，冷却后过滤，在沉淀剂中沉降，水洗，干燥后得到产品；N,N-二甲基甲酰胺与步骤(1)所述有机溶剂物质的量比为(1.5～2)：1；
所述酚酞啉单体与多酚单体的摩尔比为1：(0.05～0.42)；所述多酚单体、酚酞啉单体的羟基之和与双卤单体中卤原子的摩尔比为1：1；所述有机溶剂与双卤单体的体积质量比为(0.4～5.5)mL：1g；所述脱水剂与有机溶剂的体积比为1：(0.3～2.5)；所述碱催化剂与酚酞啉单体的摩尔比为(2～5)：1。
3.根据权利要求2所述的方法，其特征在于，所述酚酞啉单体为酚酞啉、2’,2”-二甲基酚酞啉或2’,2”-二异丙基-5’,5”-二甲基酚酞啉中的一种或一种以上。
4.根据权利要求2所述的方法，其特征在于，所述双卤单体为4,4’-二氟二苯酮，4,4’-二氟二苯砜，4,4’-二氯二苯砜，2,6-二氟苯腈或1,4-二-4-氟苯酰基苯中的一种或多种。
5.根据权利要求2所述的方法，其特征在于，所述有机溶剂为二甲基亚砜，环丁砜，N,N-二甲基甲酰胺，N-甲基吡咯烷酮或二苯砜中的一种或多种。
6.根据权利要求2所述的方法，其特征在于，所述的脱水剂为苯，甲苯，二甲苯或氯苯中的一种或多种。
7.根据权利要求2所述的方法，其特征在于，碱催化剂为氢化钠，氢化钾，氢氧化钠，氢氧化钾，碳酸钠或碳酸钾中的一种或多种。
8.根据权利要求2所述的方法，其特征在于，步骤(2)为蒸出脱水剂后在165℃～185℃反应2～6小时。
9.根据权利要求2所述的方法，其特征在于，步骤(3)所述沉淀剂为乙醇，甲醇或水中的一种或多种。
10.如权利要求1所述含羧基侧基超支化聚芳醚共聚物在环氧树脂改性中的应用。
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