CN108602057B - 用于生产双酚的离子交换树脂 - Google Patents
用于生产双酚的离子交换树脂 Download PDFInfo
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- CN108602057B CN108602057B CN201680072694.7A CN201680072694A CN108602057B CN 108602057 B CN108602057 B CN 108602057B CN 201680072694 A CN201680072694 A CN 201680072694A CN 108602057 B CN108602057 B CN 108602057B
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- Prior art keywords
- ion exchange
- exchange resin
- sulfonic acid
- amine salt
- promoter
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- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 69
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- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 34
- 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 abstract description 33
- -1 amine salts Chemical class 0.000 claims abstract description 44
- 125000000542 sulfonic acid group Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
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- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
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- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical group Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 claims description 8
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
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- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims description 3
- BZFGKBQHQJVAHS-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C(F)(F)F)=C1 BZFGKBQHQJVAHS-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Natural products OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
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- 150000002763 monocarboxylic acids Chemical class 0.000 claims 3
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- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
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- 238000000034 method Methods 0.000 description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
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- 239000003960 organic solvent Substances 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
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- 229910021641 deionized water Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 229940005605 valeric acid Drugs 0.000 description 1
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Abstract
本发明涉及用于以高转化百分比和高双酚选择性百分比生产双酚(特别是4,4′‑异亚丙基二苯酚)的离子交换树脂,其中所述离子交换树脂包含具有磺酸基的芳族聚合物,所述磺酸基用选自如结构(I)、(II)、(III)、(IV)所示的化合物或其胺盐的至少一种促进剂改性:
Description
技术领域
本发明涉及用于生产双酚的离子交换树脂和使用所述离子交换树脂生产双酚的方法,其中所述离子交换树脂包含具有磺酸基的芳族聚合物,所述磺酸基用选自结构(I)、(II)、(III)、(IV)所示化合物或其胺盐的至少一种促进剂改性:
其中,
R表示具有1-6个碳原子的烃单元,选自烷基、烯基、炔基、苯基或任选的含有具有1-6个碳原子的羰基的烃;
x表示杂原子;
n是从1到4的整数。
背景技术
公知的是,由苯酚和酮缩合得到的化合物双酚主要用于生产工程热塑性塑料,特别是用于聚碳酸酯制备的4,4′-异亚丙基二苯酚(4,4′-BPA)。所述反应需要酸性化合物作为催化剂。
无机酸如硫酸或盐酸可用作双酚制备的催化剂。但是,使用无机酸需要额外的手段来中和这些酸,以防止该过程中设备的腐蚀。而且,所述酸引起不良的产物,导致产物的分离和纯化困难,这限制了工业规模生产。
已经报道,在双酚制备中使用离子交换树脂作为催化剂可以克服上述问题。但是,所述离子交换树脂总是提供低的活性、反应速率和产品选择性。因此,需要具有促进剂的离子交换树脂,作为共进料促进剂或通过离子键或化学键固定化。与共进料促进剂相比,由于在生产过程中促进剂的暴露和污染较少,并且不需要进一步将促进剂与所得产物分离的过程,所以固定化已经广泛应用于工业规模。
迄今为止,已经广泛报道硫醇化合物适合作为离子交换树脂的促进剂。尽管开发包含所述促进剂的离子交换树脂已被广泛研究,但该催化剂导致一些不良的性质,如催化剂储存期限、对双酚特别是4,4′-异亚丙基二苯酚的选择性、活性和转化率(percentconversion)。
US3394089公开了利用巯基胺化合物部分中和离子交换树脂来改进用于双酚制备的催化剂。发现所述巯基胺化合物改善了转化率和催化剂稳定性。
US4584416公开了在用选自N-烷氨基烷基硫醇的促进剂改性的离子交换树脂以25-35摩尔%存在下的双酚制备。发现所述改性离子交换树脂与通用促进剂乙硫醇相比提供了更高的转化率和稳定性。
EP0676237公开了在用具有2个取代基的促进剂N,N-二取代巯基烷基胺改性的离子交换树脂的存在下的双酚制备。发现所述促进剂对双酚提供了较高的转化率和选择性,其中4-(二丁基氨基)丁烷-1-硫醇提供了94%的最高的双酚选择性。
US5075511公开了在用选自含有至少2个烷基硫醇分支的烷基巯基胺的促进剂改性的离子交换树脂的存在下的双酚制备。发现与含有1个烷基硫醇分支的烷基巯基胺即半胱胺相比,双-2-(巯基乙基)胺提供了更高的4,4′-异亚丙基二苯酚选择性。
US6534686公开了在用促进剂改性的离子交换树脂的存在下的双酚制备,所述促进剂选自包含吡啶和由选自叔烷基、酯基和苄基的官能团进行硫保护的基团的硫醇。发现硫保护基团可以增加4,4′-异亚丙基二苯酚的选择性。然而,所得4,4′-异亚丙基二苯酚的收益率(percent yield)相对较低。
WO2004078345公开了在用含有至少2个硫基的促进剂改性的离子交换树脂的存在下的双酚制备。发现含有至少2个硫基的促进剂可以增加4,4′-异亚丙基二苯酚的选择性。然而,所得4,4′-异亚丙基二苯酚的收益率相对较低。
US6825386公开了一种用于双酚制备的能够耐受甲醇的离子交换树脂。根据所述发明的离子交换树脂通过包含吡啶烷硫醇、氨基烷硫醇和/或噻唑烷的促进剂进行改性。发现所述混合促进剂可以增加甲醇的耐受性。然而,由根据所述发明的离子交换树脂获得的转化率相对较低。
本发明的目的是制备用于以高转化百分比和高双酚选择性百分比生产双酚特别是4,4′-异亚丙基二苯酚的离子交换树脂。
发明内容
本发明涉及用于以高转化百分比和高双酚选择性百分比生产双酚特别是4,4′-异亚丙基二苯酚的离子交换树脂,其中所述离子交换树脂包含具有磺酸基的芳族聚合物,所述磺酸基用选自如结构(I)、(II)、(III)、(IV)所示的化合物或其胺盐的至少一种促进剂改性:
其中,
R表示具有1-6个碳原子的烃单元,选自烷基、烯基、炔基、苯基或任选的含有具有1-6个碳原子的羰基的烃;
x表示杂原子;
n是从1到4的整数。
具体实施方式
定义
除非另有说明,否则本文使用的技术术语或科学术语具有本领域普通技术人员理解的定义。
本文提及的任何工具、设备、方法或化学物质是指本领域技术人员通常操作或使用的工具、设备、方法或化学物质,除非另外说明它们是特定用于本发明的工具、设备、方法或化学物质。
权利要求或说明书中单数名词或单数代词与“包含”一同使用是指“一个”以及“一个或多个”、“至少一个”和“一个或多于一个”。
在本发明中公开和要求保护的所有组合物和/或方法旨在涵盖来自任何行为、性能、修改或调整的实施方案,而不进行与本发明显著不同的实验,以根据本领域普通技术人员获得与本实施方案相同的结果,即使在权利要求中没有具体说明。因此,包括本领域技术人员显而易见的轻微修改或调整的对本实施方案的可替代或类似的细节将被解释为在本发明的范围和概念中。
在整个申请中,术语“约”用于表示在本文中提出或显示的任何值可能会变化或有偏差。这种变化或偏差可能是由设备、方法的误差引起的,包括由于不可控因素如湿度和温度的反应条件的变化而产生的变化或偏差。
杂原子是指非碳原子,包括但不限于氮、硫和氧。
本发明的一个目的是包含用新型促进剂改性的含有磺酸基的芳族聚合物的离子交换树脂,以用作生产双酚的催化剂。
本发明的另一个目的是使用本发明的离子交换树脂由苯酚和酮生产双酚,提供了高转化率以及对双酚特别是4,4′-异亚丙基二苯酚的高选择性。
以下细节描述了本发明的详述,并不旨在限制本发明的范围。
本发明涉及一种用于生产双酚的离子交换树脂,其中所述离子交换树脂包含具有用选自结构(I)、(II)、(III)、(IV)所示化合物或其胺盐的至少一种促进剂改性的磺酸基的芳族聚合物:
其中,
R表示具有1-6个碳原子的烃单元,选自烷基、烯基、炔基、苯基或任选的含有具有1-6个碳原子的羰基的烃;
x表示杂原子;
n是从1到4的整数。
优选地,根据本发明的离子交换树脂包含用选自结构(V)、(VI)、(VII)、(VIII)、(IX)、(X)所示的化合物或其胺盐的至少一种促进剂改性的磺酸基的芳族聚合物:
更优选地,促进剂是如结构(V)所示的化合物或其胺盐
在一个实施方案中,所述促进剂还包含氨烷基硫醇,其可以选自半胱胺、2-氨基-1-丙硫醇和3-巯基丙胺或它们的胺盐。优选地,氨烷基硫醇是半胱胺。
最优选地,促进剂是根据结构(V)的化合物的胺盐和半胱胺的胺盐的混合物。
通常,使用作为胺盐形式的促进剂可以增加芳族聚合物中磺基(sulfonic group)的改性期间促进剂的溶解度,其中胺盐可以选自但不限于盐酸盐、氢溴酸盐、乙酸盐、甲酸盐、硝酸盐、磷酸盐和高氯酸盐,优选盐酸盐。
在一个实施方案中,氨烷基硫醇或其胺盐的用量为总促进剂的10-90摩尔%,优选为总促进剂的30-70摩尔%。
在一个实施方案中,用促进剂改性的磺酸基(sulfonic acid group)占总磺酸基的5-30%,优选总磺酸基的10-20%。
在一个实施方案中,磺酸基通过离子键用促进剂改性,所述离子键可以通过所述促进剂的氮原子和芳族聚合物的磺酸基形成。
通常,所述改性可以通过混合含有磺酸基的芳族聚合物和促进剂来进行,其中使用水或芳族羟基化合物作为溶剂。
在一个实施方案中,含磺酸基的芳族聚合物可选自具有磺酸基的聚苯乙烯或具有磺酸基的苯乙烯-二乙烯基苯共聚物,优选具有磺酸基的苯乙烯-二乙烯基苯共聚物。
在一个实施方案中,所述含磺酸基的苯乙烯-二乙烯基苯共聚物可具有1-10%的量的二乙烯基苯,优选其量为1-4%。
在一个实施方案中,所述含磺酸基的芳族聚合物具有500-1500微米,优选850-1400微米的粒度。
在一个实施方案中,根据结构(I)、(II)、(III)的化合物或其胺盐可以通过以下步骤制备:
(a)将单羧酸与巯基化合物以1∶1至1∶2的单羧酸与巯基化合物的摩尔比混合;并且
(b)向从步骤(a)获得的混合物中加入碳二亚胺和碱性溶液。
在一个实施方案中,步骤(a)中的单羧酸可以选自2-吡啶羧酸、3-吡啶羧酸、4-吡啶羧酸、6-甲基-2-吡啶羧酸、5-甲基-2-吡啶羧酸、4-甲基-2-吡啶羧酸、3-甲基-2-吡啶羧酸、3-乙基-2-吡啶羧酸、丙酸、丁酸、戊酸、乙酰丙酸和己酸,优选2-吡啶羧酸(2-pyridinecarboxylic acid)、4-吡啶羧酸(4-pyridinecarboxylic acid)或乙酰丙酸(1evulinic acid)。
在一个实施方案中,步骤(a)中的巯基化合物是巯基胺或巯基醇。
在一个实施方案中,巯基胺可以选自半胱胺盐酸盐、2-氨基-1-丙硫醇、2-氨基-1-丙硫醇盐酸盐、3-巯基丙胺盐酸盐、3-氨基-2-甲基-1-丙硫醇、3-氨基-1-丁硫醇、3-氨基-2-丁硫醇、4-氨基-2-丁硫醇盐酸盐、3-氨基-1-丁硫醇盐酸盐、3-氨基-2,2-二甲基-1-丙硫醇、3-氨基-1-戊硫醇、3-氨基-1-戊硫醇盐酸盐、3-氨基-3-甲基-1-丁硫醇和3-氨基-3-甲基-1-丁硫醇盐酸盐,优选半胱胺盐酸盐。
在一个实施方案中,巯基醇可选自巯基乙醇、3-巯基丙醇、4-巯基丁醇、2,3-巯基丙醇、2-巯基丁醇、3-巯基丁醇或3-巯基-2-丁醇,优选巯基乙醇。
在一个实施方案中,步骤(b)中的碳二亚胺可以选自N,N′-二环己基碳二亚胺、N,N′-二异丙基碳二亚胺、N-(3-二甲基氨基丙基)-N′-乙基碳二亚胺盐酸盐、N-甲基-N′-叔丁基碳二亚胺,N-乙基-N′-叔丁基碳二亚胺、N-环己基-N′-叔丁基碳二亚胺和1,3-双(2,2-二甲基-1,3-二氧戊环-4-基甲基)碳二亚胺,优选N,N′-二环己基碳二亚胺。
在一个实施方案中,步骤(b)中的碱性溶液可选自吡啶、4-二甲基氨基吡啶、2,4,6-三甲基吡啶、二异丙基乙胺、N-甲基吗啉、三甲胺和N,N-二甲基苯胺,优选4-二甲基氨基吡啶。
在一个实施方案中,根据结构(III)的化合物或其胺盐可以通过以下步骤制备:
(a)将氯化剂与具有1-4个碳原子的醇混合,其中氯化剂与醇的体积比为1∶5至1∶20;和
(b)将半胱氨酸或其盐加入步骤(a)获得的混合物中,其中氯化剂与半胱氨酸或其盐的摩尔比为5∶1至10∶1。
在一个实施方案中,步骤(a)中的氯化剂可选自亚硫酰氯、乙酰氯、盐酸和三甲基甲硅烷基氯(trimethylsilyl chloride),优选亚硫酰氯。
在一个实施方案中,步骤(a)中的醇可以选自甲醇、乙醇、丙醇或丁醇。
在另一个实施方案中,本发明涉及使用本发明的离子交换树脂作为催化剂由苯酚和酮生产双酚的方法。
在一个实施方案中,酮可以选自但不限于丙酮、二乙基酮、甲基乙基酮、乙基甲基酮、异丁基甲基酮、环己酮和苯乙酮。
在一个实施方案中,苯酚可以选自但不限于未取代的苯酚、烷基酚、烷氧基酚、萘酚、烷基萘酚和烷氧基萘酚。
优选地,根据本发明的离子交换树脂用作通过缩合反应由未取代苯酚和丙酮生产双酚A中的催化剂。
在一个实施方案中,可以调节反应条件以适合反应。通常,反应中使用的双酚与丙酮的摩尔比可以为5至30。反应温度可以在40-120℃,优选60-80℃下进行。反应通常在大气压力下进行。
在一个实施方案中,根据本发明的离子交换树脂可以根据反应体系以几种形式用作催化剂。它可以作为间歇***(batch system)中的浆液或作为连续***中的固定床使用。
在一个实施方案中,对于间歇***和连续***,反应时间可以在0.5至20小时的范围内。液时空速(liquid hourly space velocity,LHSV)可以在0.5至10小时-1(hour-1)的范围内。
在一个实施方案中,从反应中获得的产物将与催化剂分离,并且双酚可以通过常规方法如蒸馏、重结晶或溶剂洗涤来分离和纯化。
给出以下实施例以进一步说明本发明,而没有限制本发明范围的任何目的。
用于制备根据本发明的离子交换树脂的促进剂的制备
如结构(V)所示的化合物的盐酸盐
在氩气氛下,将约5g 2-吡啶羧酸和约5.54g半胱胺盐酸盐溶于约50mL二氯甲烷溶剂中。然后,将约16.7g N,N′-二环己基碳二亚胺和约0.99g 4-二甲基氨基吡啶的混合溶液缓慢加入到约20mL二氯甲烷溶剂中。所述混合物在室温下在氩气氛下搅拌约24小时。从所得混合物中过滤所获得的白色固体。然后,真空蒸发过滤的液体。然后,将其在二氯甲烷和己烷的混合有机溶剂中结晶或通过硅胶柱纯化。将所得固体分离并在真空下干燥。
如结构(VI)所示的化合物的盐酸盐
在氩气氛下,将约5g 2-吡啶羧酸和约3.43g巯基乙醇溶于约50mL二氯甲烷溶剂中。然后,将约16.7g N,N′-二环己基碳二亚胺和约0.99g 4-二甲基氨基吡啶的混合溶液缓慢加入约20mL二氯甲烷溶剂中。所述混合物在室温下在氩气氛下搅拌约24小时。从获得的混合物中过滤所获得的白色固体。然后,将过滤的液体在真空下蒸发,并在二氯甲烷和己烷的混合有机溶剂中结晶或通过硅胶柱纯化。将所得固体分离并在真空下干燥。然后,将约5mL去离子水加入到约1g所述获得的固体中。之后,将约0.6mL约37%的盐酸溶液缓慢加入到所述混合物中,并在室温下搅拌约30分钟。然后,真空蒸发溶剂并将固体产物真空干燥。
如结构(VII)所示的化合物的盐酸盐
在氩气氛下,将约2g丙酸和约3.68g半胱胺盐酸盐溶于约15mL二氯甲烷溶剂中。然后,将约11.4g N,N′-二环己基碳二亚胺和约0.66g 4-二甲基氨基吡啶的混合溶液缓慢加入到约15mL二氯甲烷溶剂中。所述混合物在室温下在氩气氛下搅拌约24小时。从获得的混合物中过滤所获得的白色固体。然后,将过滤的液体在真空下蒸发,并在二氯甲烷和己烷的混合有机溶剂中结晶或通过硅胶柱纯化。将所得固体分离并在真空下干燥。
如结构(VIII)所示的化合物的盐酸盐
在氩气氛下,将约5g乙酰丙酸和约5.87g半胱胺盐酸盐溶于约20mL二氯甲烷溶剂中。然后,将约17.8g N,N′-二环己基碳二亚胺和约1.05g 4-二甲基氨基吡啶的混合溶液缓慢加入到约20mL二氯甲烷溶剂中。所述混合物在室温下在氩气氛下搅拌约24小时。从获得的混合物中过滤所获得的白色固体。然后,将过滤的液体在真空下蒸发,并在二氯甲烷和己烷的混合有机溶剂中结晶或通过硅胶柱纯化。将所得固体分离并在真空下干燥。
如结构(IX)所示的化合物的盐酸盐
在约0℃的温度和氩气氛下,将约3mL亚硫酰氯缓慢加入到约35mL甲醇中。将所述混合物搅拌约1小时。然后,加入约1g半胱胺盐酸盐。将所述混合物搅拌约3小时并回流约1小时。然后,真空蒸发有机溶剂。所得产物在二氯甲烷和甲醇的混合有机溶剂中结晶。将所得固体分离并在真空下干燥。
如结构(X)所示的化合物的盐酸盐
在氩气氛下,将约1.04g结构(X)所示化合物和约0.48g巯基丙酸溶于约5mL N,N-二甲基甲酰胺中。然后,将约1.25g N,N′-二环己基碳二亚胺和约0.81g 4-二甲基氨基吡啶的混合溶液缓慢加入约10mL二氯甲烷溶剂中。所述混合物在室温下在氩气氛下搅拌约24小时。从获得的混合物中过滤所获得的白色固体。然后,将过滤的液体在真空下蒸发,并在二氯甲烷和己烷的混合有机溶剂中结晶或通过硅胶柱纯化。将所得固体分离并在真空下干燥。
制备根据本发明的离子交换树脂
具有磺酸基的苯乙烯-二乙烯基苯共聚物型芳族聚合物,来自漂莱特有限公司(Pulorite Co.,Ltd.)的粒度为850-1400微米的Purolite122(Pu122)和来自罗门哈斯化工有限公司(Rohm and Haas Chemical Co.)的粒度为550-700微米的Amberlyst36(Am36),用于制备根据本发明的离子交换树脂。
通过以下方法制备具有用根据表1的量和百分比的各种促进剂改性的磺酸基的芳族聚合物。
将促进剂溶于约20mL去离子水中(量如表1所示)。然后,将所述溶液加入到约20g悬浮于约40mL去离子水中的苯乙烯-二乙烯基苯共聚物中。将混合物在室温下搅拌约1小时。搅拌后,将得到的混合物装入柱中,用去离子水以约1mL/min的流速洗涤直到洗液的pH约为6.5。为了测量芳族聚合物改性前后的磺酸基(SO3H),用氢氧化钠溶液通过滴定法测试所得固体的残余磺酸基。用促进剂改性的磺酸基的百分比可以由下面的等式计算。
双酚生产测试
根据本发明的离子交换树脂用作催化剂以通过以下方法测试双酚生产性能。
在使用之前,通过在约60-70℃的温度下使约10g离子交换树脂与约100g苯酚接触约15分钟(min)使离子交换树脂脱水。该方法进行3次。将约3g所得的离子交换树脂加入装有冷凝器的250mL三颈烧瓶中。然后,加入约90g苯酚并在约70℃的温度下加热。然后,加入约4.27g丙酮。反应进行到约1小时。
以下是用于测试从根据本发明的离子交换树脂获得的产品组合物的实例,其中测试方法和设备是通用方法和设备,并且不旨在限制本发明的范围。
通过配备有HP-PLOT/Al2O3“S”失活毛细管柱的气相色谱仪(岛津(Shimadzu)17A-GC)测试来自反应的剩余丙酮。设定柱温以分离组合物。开始时将温度设定在约40℃约10分钟。然后,温度以线性速率升高至约195℃并维持约30分钟。
通过配备有菲罗门(Phenomenex)Gemini-NX 5u C18柱的高效液相色谱(岛津LC-20AD)测试产品组合物。使用1∶1体积比的水和乙腈作为流动相,流速为1mL/min。
由以下等式计算丙酮转化率%和4,4′-异亚丙基二苯酚(4,4′BPA)的选择性%。
表1显示离子交换树脂的丙酮转化率%和4,4′异亚丙基二苯酚的选择性%
根据表1,当对比所述比较样品和制备中使用1种促进剂的根据本发明的样品A1至A3和B至F时,可以发现具有通过根据结构(V)、(VI)、(VII)、(VIII)、(IX)、(X)的化合物的盐酸盐改性的磺酸基的根据本发明的离子交换树脂,具有较高的丙酮转化率和4,4′异亚丙基二苯酚的选择性百分比。具有根据结构(V)的化合物的盐酸盐改性的磺酸基的离子交换树脂导致4,4′异亚丙基二苯酚的选择性百分比最高。
另外,当对比所述比较例、含有1种促进剂的样品A1、以及样品G1-G3时,所述样品G1-G3具有由促进剂改性的相同百分比的磺酸基的含有根据结构(V)的化合物的盐酸盐和半胱胺盐酸盐,可以发现,所述2种促进剂的使用产生了明显较高的丙酮转化率。
根据以上结果,可以说根据本发明的离子交换树脂给出了如本发明目的中所述的高转化率和对双酚特别是4,4′异亚丙基二苯酚的高选择性。
本发明的最佳方式
本发明的最佳方式如本发明的描述中所提供的。
Claims (26)
4.根据权利要求1或2所述的离子交换树脂,其中所述促进剂还包含氨烷基硫醇或其胺盐。
5.根据权利要求4所述的离子交换树脂,其中氨烷基硫醇是半胱胺。
6.根据权利要求3所述的离子交换树脂,其中所述促进剂还包含氨烷基硫醇或其胺盐。
7.根据权利要求6所述的离子交换树脂,其中氨烷基硫醇是半胱胺。
8.根据权利要求4所述的离子交换树脂,其中氨烷基硫醇或其胺盐的用量为总促进剂的30-70摩尔%。
9.根据权利要求5所述的离子交换树脂,其中氨烷基硫醇或其胺盐的用量为总促进剂的30-70摩尔%。
10.根据权利要求6所述的离子交换树脂,其中氨烷基硫醇或其胺盐的用量为总促进剂的30-70摩尔%。
11.根据权利要求7所述的离子交换树脂,其中氨烷基硫醇或其胺盐的用量为总促进剂的30-70摩尔%。
12.根据权利要求1所述的离子交换树脂,其中用促进剂改性的磺酸基占总磺酸基的10-20%。
13.根据权利要求1或12中任一项所述的离子交换树脂,其中所述磺酸基通过离子键被促进剂改性。
14.根据权利要求1所述的离子交换树脂,其中所述含磺酸基的芳族聚合物为具有磺酸基的苯乙烯-二乙烯基苯共聚物。
15.根据权利要求14所述的离子交换树脂,其中所述含磺酸基的苯乙烯-二乙烯基苯共聚物具有1-4%的量的二乙烯基苯。
16.根据权利要求1或14所述的离子交换树脂,其中所述含磺酸基的芳族聚合物具有850-1400微米的粒度。
17.根据权利要求1所述的离子交换树脂,其中通过以下步骤制备根据结构(I)、(III)的化合物或所述化合物的胺盐:
(a)将单羧酸与巯基化合物以1:1至1:2的单羧酸与巯基化合物的摩尔比混合;并且
(b)向从步骤(a)获得的混合物中加入碳二亚胺和碱性溶液。
18.根据权利要求17所述的离子交换树脂,其中步骤(a)中的所述单羧酸为2-吡啶羧酸、4-吡啶羧酸或乙酰丙酸。
19.根据权利要求17所述的离子交换树脂,其中步骤(a)中的巯基化合物是巯基胺或巯基醇。
20.根据权利要求19所述的离子交换树脂,其中所述巯基胺是半胱胺盐酸盐。
21.根据权利要求19所述的离子交换树脂,其中所述巯基醇是巯基乙醇。
22.根据权利要求17所述的离子交换树脂,其中所述碳二亚胺为N,N'-二环己基碳二亚胺。
23.根据权利要求17所述的离子交换树脂,其中步骤(b)中的所述碱性溶液是4-二甲基氨基吡啶。
24.根据权利要求1所述的离子交换树脂,其中根据结构(III)的化合物或其胺盐通过以下步骤制备:
(a)将氯化剂与具有1-4个碳原子的醇混合,其中氯化剂与醇的体积比为1:5至1:20;和
(b)将半胱氨酸或其盐加入步骤(a)获得的混合物中,其中氯化剂与半胱氨酸或其盐的摩尔比为5:1至10:1。
25.根据权利要求24所述的离子交换树脂,其中步骤(a)中的所述氯化剂是亚硫酰氯。
26.根据权利要求24所述的离子交换树脂,其中步骤(a)中的所述醇选自甲醇、乙醇、丙醇或丁醇。
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Application Number | Priority Date | Filing Date | Title |
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TH1501007417 | 2015-12-09 | ||
TH1501007417A TH158279A (th) | 2015-12-09 | เรซินแลกเปลี่ยนไอออน (ion exchange resin) สำหรับผลิตบิสฟีนอล (bisphenol) และวิธีผลิตบิสฟีนอลโดยใช้เรซินแลกเปลี่ยนไอออนดังกล่าว | |
PCT/TH2016/000088 WO2017099674A2 (en) | 2015-12-09 | 2016-10-31 | Ion exchange resin for producing bisphenol, and a method for producing bisphenol using said ion exchange resin |
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CN108602057B true CN108602057B (zh) | 2022-01-18 |
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US (1) | US10851230B2 (zh) |
EP (1) | EP3386634B1 (zh) |
JP (1) | JP6806383B2 (zh) |
KR (1) | KR102113706B1 (zh) |
CN (1) | CN108602057B (zh) |
PL (1) | PL3386634T3 (zh) |
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US20220363620A1 (en) * | 2019-06-28 | 2022-11-17 | Ptt Global Chemical Public Company Limited | An isomerization process of product obtained from bisphenol preparation from a condensation reaction of ketone and phenol |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2597438A (en) * | 1951-05-12 | 1952-05-20 | Rohm & Haas | Cation-exchange polymers of the sulfonic type |
US3394089A (en) * | 1964-12-02 | 1968-07-23 | Dow Chemical Co | Ion exchange catalyst for the preparation of bisphenols |
US4595704A (en) * | 1984-08-13 | 1986-06-17 | The Dow Chemical Company | Preparation of ion-exchange catalysts |
CN1121442A (zh) * | 1994-10-25 | 1996-05-01 | 中国石油化工总公司 | 合成双酚用离子交换树脂催化剂及其制备 |
US6492562B1 (en) * | 1999-01-27 | 2002-12-10 | Kosan Biosciences, Inc. | Racemic thioesters for production of polyketides |
CN101585849A (zh) * | 2009-07-03 | 2009-11-25 | 南京理工大学 | 联二硫基取代次卟啉及其金属络合物、制备方法和应用 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1183564A (en) | 1968-05-29 | 1970-03-11 | Dow Chemical Co | An Ion Catalyst for the Manufacture of Bisphenols |
US4584416A (en) | 1983-11-14 | 1986-04-22 | General Electric Company | Method and catalyst for making bisphenol |
US5075511A (en) | 1986-10-30 | 1991-12-24 | Shell Oil Company | Process and alkylmercaptoamine catalyst for production of bisphenol-A |
US5589517A (en) | 1994-04-08 | 1996-12-31 | Mitsubishi Chemical Corporation | Modified ion exchange resins and use thereof |
DE19919336A1 (de) * | 1999-04-27 | 2000-11-16 | Consortium Elektrochem Ind | Verfahren zur Ringspaltung von Thiazolidinderivaten |
US6534686B1 (en) | 2001-09-18 | 2003-03-18 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
JP4050053B2 (ja) | 2001-12-27 | 2008-02-20 | 出光興産株式会社 | ビスフェノール類製造用触媒及び該触媒を用いるビスフェノール類の製造方法 |
US7112702B2 (en) | 2002-12-12 | 2006-09-26 | General Electric Company | Process for the synthesis of bisphenol |
CN100551532C (zh) | 2003-03-03 | 2009-10-21 | 沙伯基础创新塑料知识产权有限公司 | 制备双酚催化剂和双酚的方法 |
KR101491874B1 (ko) * | 2007-06-14 | 2015-02-09 | 다우 글로벌 테크놀로지스 엘엘씨 | 비스페놀 제조용 촉매의 제조 방법 |
TWI494163B (zh) * | 2011-12-28 | 2015-08-01 | Rohm & Haas | 經處理、促進之離子交換樹脂觸媒之用途及製造方法 |
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2016
- 2016-10-31 JP JP2018529637A patent/JP6806383B2/ja active Active
- 2016-10-31 KR KR1020187019003A patent/KR102113706B1/ko active IP Right Grant
- 2016-10-31 EP EP16873478.8A patent/EP3386634B1/en active Active
- 2016-10-31 PL PL16873478.8T patent/PL3386634T3/pl unknown
- 2016-10-31 SG SG11201804797WA patent/SG11201804797WA/en unknown
- 2016-10-31 US US16/060,162 patent/US10851230B2/en active Active
- 2016-10-31 WO PCT/TH2016/000088 patent/WO2017099674A2/en active Application Filing
- 2016-10-31 CN CN201680072694.7A patent/CN108602057B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2597438A (en) * | 1951-05-12 | 1952-05-20 | Rohm & Haas | Cation-exchange polymers of the sulfonic type |
US3394089A (en) * | 1964-12-02 | 1968-07-23 | Dow Chemical Co | Ion exchange catalyst for the preparation of bisphenols |
US4595704A (en) * | 1984-08-13 | 1986-06-17 | The Dow Chemical Company | Preparation of ion-exchange catalysts |
CN1121442A (zh) * | 1994-10-25 | 1996-05-01 | 中国石油化工总公司 | 合成双酚用离子交换树脂催化剂及其制备 |
CN1038395C (zh) * | 1994-10-25 | 1998-05-20 | 中国石油化工总公司 | 合成双酚用离子交换树脂催化剂及其制备 |
US6492562B1 (en) * | 1999-01-27 | 2002-12-10 | Kosan Biosciences, Inc. | Racemic thioesters for production of polyketides |
CN101585849A (zh) * | 2009-07-03 | 2009-11-25 | 南京理工大学 | 联二硫基取代次卟啉及其金属络合物、制备方法和应用 |
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EP3386634B1 (en) | 2022-08-24 |
US10851230B2 (en) | 2020-12-01 |
KR102113706B1 (ko) | 2020-05-22 |
EP3386634A2 (en) | 2018-10-17 |
SG11201804797WA (en) | 2018-07-30 |
KR20180104288A (ko) | 2018-09-20 |
US20180355159A1 (en) | 2018-12-13 |
JP2019501015A (ja) | 2019-01-17 |
EP3386634A4 (en) | 2019-08-28 |
JP6806383B2 (ja) | 2021-01-06 |
WO2017099674A3 (en) | 2017-12-07 |
WO2017099674A2 (en) | 2017-06-15 |
CN108602057A (zh) | 2018-09-28 |
PL3386634T3 (pl) | 2022-11-07 |
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