CN114015041B - 一种用于聚苯醚合成的催化剂 - Google Patents
一种用于聚苯醚合成的催化剂 Download PDFInfo
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- CN114015041B CN114015041B CN202111606238.5A CN202111606238A CN114015041B CN 114015041 B CN114015041 B CN 114015041B CN 202111606238 A CN202111606238 A CN 202111606238A CN 114015041 B CN114015041 B CN 114015041B
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- polyphenyl ether
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- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 9
- 239000013084 copper-based metal-organic framework Substances 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- -1 imidazole compounds Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000350481 Pterogyne nitens Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000012869 ethanol precipitation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G65/44—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 by oxidation of phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
本发明涉及一种用于聚苯醚合成的催化剂体系，该催化剂是由基于铜的金属有机框架结构化合物与有机胺组成。这种催化剂对氧化偶合反应具有很好的催化活性，而且金属有机框架结构化合物在聚合后容易回收再利用，产物中金属残留量极低，大大降低了生产成本，减小环境污染，提高了产品品质。
Description
技术领域
本发明涉及一种用于聚苯醚合成的催化剂。
背景技术
聚芳醚，是一种通用工程塑料。具有具有优良的综合性能，最大的特点是在长期负荷下，具有优良的尺寸稳定性和突出的电绝缘性，使用温度范围广。具有自熄性。具有优良的耐水、耐蒸汽性能，制品具较高的拉伸强度和抗冲强度，抗蠕变性也好。此外，有较好的耐磨性和电性能。
聚苯醚的是由酚类化合物在金属/有机胺类或金属/咪唑类化合物的存在下与氧气发生氧化偶合聚合反应得到。该反应通常是在有机溶液中进行，催化剂和反应物均溶于有机溶剂，在聚合完成后，产物与催化剂混合在一起，需通过复杂的工艺进行分离。而且催化剂很难回收再利用，通常作为废渣排放，造成极大的浪费和环境污染。USP 3972851，USP3306874等公开的聚苯醚制备方法均采用上述催化剂体系，均存在催化剂回收困难，产物中金属离子去除困难等问题。
发明内容
本发明提供了一种用于聚苯醚合成的催化剂，具有反应活性高，易回收的特点。
为实现上述目的，本发明提供了一种用于聚苯醚合成的催化剂，其特征在于，由基于铜的金属有机框架结构化合物与有机胺复合得到。
基于铜的金属有机框架结构化合物是由铜盐与有机配合物制备的金属有机框架结构化合物。铜盐，如硝酸铜、氯化铜、硫酸铜、硝酸亚铜等，但不限于上述化合物。有机配合物是指有机胺类配合物，如H3BTP，DTOA，TIPA等，但不限于上述化合物。制备方法如下，将适量的铜盐与有机胺类配合物溶于有机溶剂，在一定温度下反应一定时间后，过滤洗涤所得晶体即为基于铜的金属有机框架结构化合物。
有机胺是指碳数为2-20的有机一元胺、二元胺或多元胺的一种或多种的混合物，如乙二胺、苯胺、环己胺等，但不限于上述化合物。
将基于铜的金属有机框架结构化合物与一定量有机胺在氮气保护条件下，混合一定时间即得。
聚苯醚的合成过程如下：将一定量的取代酚化合物（2，6-二甲基苯酚，2，3-二甲基苯酚等）溶于有机溶剂中，同时加入一定量的有基于铜的金属有机框架结构化合物与有机胺的复合物，在搅拌的条件下，通入氧气，在氧气的作用下，酚化合物发生氧化偶合反应，进过一定时间后得到聚苯醚，通过过滤、洗涤等操作可对铜-金属有机框架结构化合物金属快速回收。聚苯醚产物中金属残留量极低。
具体实施方式：
本发明提供了一种用于聚苯醚合成的催化剂，其特征在于，由基于铜的金属有机框架结构化合物与有机胺复合得到。
实施例1
将2.8g的 DTOA溶于50ml的DMSO，40℃下搅拌0.5h，然后向溶液中加入3.2g的硝酸铜，体系升温至85℃。48h后，过滤、洗涤得到蓝色晶体2.5g，即为基于Cu-DTOA的金属有机框架结构化合物。
将上述2g的Cu-DTOA化合物与30g的环己胺混合，在40℃，氮气保护下，搅拌5h，即得到用于聚苯醚合成的催化剂A。
实施例2
将30g的2，6-二甲基苯酚溶于100ml的二甲苯中，然后向溶液中加入0.5g的催化剂A，在搅拌条件下升温至50℃，然后向溶液中通入氧气，通入速度20ml/min。随着反应的进行，溶液粘度逐渐变大，3h后停止通氧，40-50℃条件下过滤，将Cu-DTOA分离出来，并用二甲苯洗涤三次后备用。聚苯醚的二甲苯溶液经乙醇沉淀析出后分离得到。所得聚苯醚重均分子量为19000，收率为92%，金属杂质含量低于0.5ppm。
应理解，本实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明的内容后，本领域技术人员可以对本发明做各种改动或修改，这些等价形式同样在本申请所附权利要求书所限定的范围。
Claims (1)
1. 一种用于聚苯醚合成的催化剂，其特征在于，通过以下方法制备得到，将2.8g的DTOA溶于50ml的DMSO，40℃下搅拌0.5h，然后向溶液中加入3.2g的硝酸铜，体系升温至85℃，48h后，过滤、洗涤得到蓝色晶体2.5g，即为基于Cu-DTOA的金属有机框架结构化合物；将上述2g的Cu-DTOA化合物与30g的环己胺混合，在40℃，氮气保护下，搅拌5h，即得到用于聚苯醚合成的催化剂。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5214128A (en) * | 1990-05-21 | 1993-05-25 | Koichi Horiguchi | Method for purifying a polyphenylene ether with amino carboxylic acid derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW200619267A (en) * | 2004-09-13 | 2006-06-16 | Univ Waseda | The manufacting method for polyphenylene ether |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5214128A (en) * | 1990-05-21 | 1993-05-25 | Koichi Horiguchi | Method for purifying a polyphenylene ether with amino carboxylic acid derivative |
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