CN114621046B - 离子液体催化制备高纯度双环戊二烯的方法 - Google Patents
离子液体催化制备高纯度双环戊二烯的方法 Download PDFInfo
- Publication number
- CN114621046B CN114621046B CN202210351099.4A CN202210351099A CN114621046B CN 114621046 B CN114621046 B CN 114621046B CN 202210351099 A CN202210351099 A CN 202210351099A CN 114621046 B CN114621046 B CN 114621046B
- Authority
- CN
- China
- Prior art keywords
- dicyclopentadiene
- ionic liquid
- purity
- preparing high
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 title claims abstract description 63
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 8
- YMBWNYKEVPQWII-UHFFFAOYSA-N [Br].N1C=NC=C1 Chemical compound [Br].N1C=NC=C1 YMBWNYKEVPQWII-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- -1 benzene compound Chemical class 0.000 claims description 5
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- RIQKQQLKIBMABS-UHFFFAOYSA-M sodium;3,5-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC(C)=CC(S([O-])(=O)=O)=C1 RIQKQQLKIBMABS-UHFFFAOYSA-M 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 28
- 150000001450 anions Chemical group 0.000 abstract description 5
- 238000003776 cleavage reaction Methods 0.000 abstract description 5
- 230000007017 scission Effects 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- AUIXNZFZSGLHKP-UHFFFAOYSA-M sodium;2,3-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=CC(S([O-])(=O)=O)=C1C AUIXNZFZSGLHKP-UHFFFAOYSA-M 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/50—Diels-Alder conversion
- C07C2/52—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于化工技术领域，具体涉及一种离子液体催化制备高纯度双环戊二烯的方法。以双环戊二烯粗品作为原料，以离子液体作为催化剂和稀释剂，进行催化解聚反应、精馏得到环戊二烯；再将环戊二烯聚合得到双环戊二烯。本发明的离子液体催化剂/稀释剂采用酸性基团作为离子液体的阴离子结构，为其催化DCPD解聚提供催化作用，酸性基团能够产生活性H+，而H+对C‑C键的断裂至关重要，它可以进攻DCPD碳环上的桥键碳，从而导致C‑C键的断裂，为提高双环戊二烯裂解转化率及选择性提供重要保障，提高了双环戊二烯产品的收率。
Description
技术领域
本发明属于化工技术领域，具体涉及一种离子液体催化制备高纯度双环戊二烯的方法。
背景技术
双环戊二烯(DCPD)是重要的精细化工原料，主要来源于石油裂解制乙烯的副产物C5馏分，主要途径为C5馏分中的环戊二烯(CPD)经聚合后分离得到。由于聚合过程中存在着副反应，得到的粗双环戊二烯产品纯度为80％左右，通常用于生产树脂或代替部分苯酐生产不饱和聚酯，附加值不高；而超高纯度(大于99％)的双环可用于生产反应注射成型工程塑料聚双环戊二烯(PDCPD)，其产品可替代某些金属和工程塑料，广泛用于土木、建筑、车辆、船舶及机械方面，价值大大提高。
目前工业上主要以粗双环戊二烯为原料，通过解聚-再二聚法来获得高纯度(纯度>95％)双环戊二烯，而在优化的条件下可获得超高纯度的双环戊二烯(纯度>99％)。如中国专利CN102060649A公开一种制备高纯度双环戊二烯的方法，采用高温载体，双环戊二烯在其中解聚，但多聚物在其中聚集，容易结焦，在工业应用中装置无法长时间运行。美国专利US5321177A公开一种高纯度双环戊二烯生产过程，采用管式反应器解聚双环戊二烯，这种方式双环戊二烯裂解较完全，但同时杂质(其它二聚体)裂解，产品中含少量异戊二烯(IP)影响环戊二烯产品的纯度，与环戊二烯难以分离，故难以获得高纯度双环戊二烯。为了解决此类问题，中国专利CN105585415A开展了裂解C5馏分分离中反应精馏技术的开发研究，采用二个反应精馏塔将反应与精馏相结合，通过调节反应精馏塔的操作参数控制反应方向及反应深度，来提高产品双环戊二烯的纯度和收率。但由于CPD易发生聚合反应，且CPD二聚与IP和CPD的共聚速率差距不大，其反应深度很难控制，为保证双环戊二烯的纯度，会有较多的未聚合的IP和CPD从塔顶排出循环，影响收率且极大地增加了能耗。
中国专利CN103664472A公开一种制备高纯度双环戊二烯的方法，以粗双环戊二烯为原料，在解聚过程中加入稀释剂，双环戊二烯与稀释剂按0.5-5的比例混合后进入解聚精馏塔；在常压下，解聚温度为160℃-200℃，回流比为0.5-5，解聚时间为1-3h。塔顶获得高纯度的环戊二烯(CPD)，环戊二烯再经一管式反应器，反应温度为40-120℃，反应压力为0.1-1.5MPa，停留时间为4-10h，最终获得纯度99％以上的双环戊二烯。所述稀释剂为乙烯裂解装置副产C9-C10组分或芳烃重整装置副产C9-C10组分。该专利工业流程较为复杂，且反应过程中伴有高压反应，对设备的要求过高，且伴随有危险隐患。
中国专利CN112679307A公开一种以粗双环戊二烯为原料制备高纯度双环戊二烯的方法，步骤包括：①粗双环戊二烯原料进入固定床反应器进行选择加氢反应，催化剂为Pt和Pb改性的Pd系催化剂；②加氢后的物料送入解聚反应精馏塔，解聚生成环戊二烯，③环戊二烯经一段聚合反应器、二段聚合反应器和三段聚合反应器聚合得双环戊二烯。但该专利中Pt金属催化剂制备花费较大，并且催化加氢过程中存在一定的危险性，操作困难。
现有脱除环戊二烯中杂质的技术中还存在着明显的缺陷，解聚温度较高，无法同时满足产品双环戊二烯的高纯度和高收率，不利于工业化生产。
发明内容
本发明的目的在于提供一种离子液体催化制备高纯度双环戊二烯的方法，有效降低了结焦程度，并提高了解聚反应速率及选择性，提高了双环戊二烯产品的收率。
本发明解决其技术问题所采取的技术方案是：
本发明所述的离子液体催化制备高纯度双环戊二烯的方法：以双环戊二烯粗品作为原料，以离子液体作为催化剂和稀释剂，进行催化解聚反应、精馏得到环戊二烯；再将环戊二烯聚合得到双环戊二烯。
其中：
离子液体的结构式如下：
其中：R1为-CH3或-H，R2为-BF4 -、-PF6 -、-PO4 3-、-SO3 -或-H，R3为-BF4 -、-PF6 -、-PO4 3-、-SO3 -或-H，R4为-CH3或-H，R5为-CH3或-H，且R2与R3不能同时为-H；n为7-15。
优选地，R1为-CH3，R2为-SO3 -或-H，R3为-SO3 -或-H；R4为-CH3或-H，R5为-CH3或-H，且R2与R3不能同时为-H；n为7、9或11。
所述的离子液体与双环戊二烯粗品的质量比为1:10-1:0.1。
所述的催化解聚反应温度为145-148℃。
所述的聚合的温度为0-150℃。
所述的双环戊二烯粗品中双环戊二烯的含量为80-85wt.％。
本发明的催化解聚反应及聚合均在常压下进行。
所述的离子液体的制备方法为将咪唑溴盐与苯类化合物置于微波反应器中反应，经萃取、减压蒸馏、重结晶，得到离子液体。
咪唑溴盐与苯类化合物的摩尔比为1:1-1.1。
所述的咪唑溴盐为[C12mim][Br]、[C10mim][Br]或[C14mim][Br]；苯类化合物为苯磺酸钠或二甲基苯磺酸钠。
反应温度为100-105℃，反应时间为10-15min，微波反应器的功率为400-410W。
所述的离子液体的制备方法具体过程如下：
将咪唑溴盐与苯类化合物按照1:1-1.1的摩尔比例混合倒入250mL单口烧瓶中，再加入50-60mL蒸馏水，将烧瓶置于带有冷凝回流装置的微波反应器中，设定微波反应器的功率为400-410W，反应温度为100-105℃，反应时间为10-15min，反应结束后得到黄色透明粘稠液体(粗产品)。
待所得粗产品冷却至室温后，将其倒入分液漏斗中。量取30-40mL正戊烷，分成3次对粗产品进行萃取分离，待萃取结束后收集下层液体，重复上述操作3次。将萃取后所得产物在70-75℃条件下进行减压蒸馏，得到白色固体。然后采用环已烷/乙酸乙酯(体积比为2:1)混合溶剂对目标产品进行重结晶提纯3次，得到白色粉末状产物，最后将其于50-55℃条件下真空干燥4-5h后即得到纯度较高的离子液体。
本发明的有益效果如下：
本发明的离子液体催化剂/稀释剂采用酸性基团作为离子液体的阴离子结构，为其催化DCPD解聚提供催化作用，酸性基团能够产生活性H+，而H+对C-C键的断裂至关重要，它可以进攻DCPD碳环上的桥键碳，从而导致C-C键的断裂。并且离子液体中阴阳离子半径和体积差异大，互相的结构不对称性大，削弱了阴阳离子间的库仑力，导致离子结构失衡使熔点降低，阴阳离子结合得到室温离子液体，离子液体催化剂/稀释剂为提高双环戊二烯裂解转化率及选择性提供重要保障，提高了双环戊二烯产品的收率。
本发明制备高纯度双环戊二烯，采用离子液体催化剂和稀释剂，拥有热稳定性较高、化学稳定性优良、可忽略不计的蒸汽压、不易挥发、溶解性良好，在催化反应中作为有机溶剂的替代品，使反应过程反应条件趋于温和、绿色无污染。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1-8
离子液体催化制备高纯度双环戊二烯的方法：以1500g含量为83wt.％的双环戊二烯粗品作为原料，以离子液体作为催化剂和稀释剂，进行催化解聚反应、精馏得到环戊二烯；再将环戊二烯聚合得到双环戊二烯。
其中实施例1-4中的离子液体的结构式如下：
其制备方法为：
将[C12mim][Br]与苯磺酸钠按照1:1的摩尔比例混合倒入250mL单口烧瓶中，再加入55mL蒸馏水，将烧瓶置于带有冷凝回流装置的微波反应器中，设定微波反应器的功率为405W，反应温度为105℃，反应时间为10min，反应结束后得到黄色透明粘稠液体(粗产品)。
待所得粗产品冷却至室温后，将其倒入分液漏斗中。量取35mL正戊烷，分成3次对粗产品进行萃取分离，待萃取结束后收集下层液体，重复上述操作3次。将萃取后所得产物在75℃条件下进行减压蒸馏，得到白色固体。然后采用环已烷/乙酸乙酯(体积比为2:1)混合溶剂对目标产品进行重结晶提纯3次，得到白色粉末状产物，最后将其于50℃条件下真空干燥5h后即得到上述结构的离子液体。
实施例5-8中的离子液体的结构式如下：
其制备方法为：
将[C12mim][Br]与二甲基苯磺酸钠按照1:1的摩尔比例混合倒入250mL单口烧瓶中，再加入50mL蒸馏水，将烧瓶置于带有冷凝回流装置的微波反应器中，设定微波反应器的功率为4000W，反应温度为100℃，反应时间为15min，反应结束后得到黄色透明粘稠液体(粗产品)。
待所得粗产品冷却至室温后，将其倒入分液漏斗中。量取40mL正戊烷，分成3次对粗产品进行萃取分离，待萃取结束后收集下层液体，重复上述操作3次。将萃取后所得产物在70℃条件下进行减压蒸馏，得到白色固体。然后采用环已烷/乙酸乙酯(体积比为2:1)混合溶剂对目标产品进行重结晶提纯3次，得到白色粉末状产物，最后将其于55℃条件下真空干燥4h后即得到上述结构的离子液体。
实施例1-8中离子液体与双环戊二烯粗品的质量比、催化解聚反应温度、聚合的温度、产品收率及纯度如表1。
表1实施例1-8中操作条件及产品收率及纯度数据
对比例1
催化解聚过程中不添加离子液体催化剂，其余条件同实施例1；得到双环戊二烯产品的产品纯度为88.6％，产品收率80.4％。
对比例2
催化解聚过程中不添加离子液体催化剂，其余条件同实施例6；得到双环戊二烯产品的产品纯度为87.8％，产品收率81.9％。
Claims (6)
1.一种离子液体催化制备高纯度双环戊二烯的方法，其特征在于：以双环戊二烯粗品作为原料，以离子液体作为催化剂和稀释剂，进行催化解聚反应、精馏得到环戊二烯；再将环戊二烯聚合得到双环戊二烯；
离子液体的结构式如下：
或/>；
催化解聚反应温度为145-148℃。
2.根据权利要求1所述的离子液体催化制备高纯度双环戊二烯的方法，其特征在于：离子液体与双环戊二烯粗品的质量比为1:10-1:0.1。
3.根据权利要求1所述的离子液体催化制备高纯度双环戊二烯的方法，其特征在于：聚合的温度为0-150℃。
4.根据权利要求1所述的离子液体催化制备高纯度双环戊二烯的方法，其特征在于：离子液体的制备方法为将咪唑溴盐与苯类化合物置于微波反应器中反应，经萃取、减压蒸馏、重结晶，得到离子液体；所述的咪唑溴盐为[C12mim][Br]；苯类化合物为苯磺酸钠或3,5-二甲基苯磺酸钠。
5.根据权利要求4所述的离子液体催化制备高纯度双环戊二烯的方法，其特征在于：咪唑溴盐与苯类化合物的摩尔比为1:1-1.1。
6.根据权利要求4所述的离子液体催化制备高纯度双环戊二烯的方法，其特征在于：反应温度为100-105℃，反应时间为10-15min，微波反应器的功率为400-410W。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210351099.4A CN114621046B (zh) | 2022-04-02 | 2022-04-02 | 离子液体催化制备高纯度双环戊二烯的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210351099.4A CN114621046B (zh) | 2022-04-02 | 2022-04-02 | 离子液体催化制备高纯度双环戊二烯的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114621046A CN114621046A (zh) | 2022-06-14 |
| CN114621046B true CN114621046B (zh) | 2024-01-09 |
Family
ID=81905463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210351099.4A Active CN114621046B (zh) | 2022-04-02 | 2022-04-02 | 离子液体催化制备高纯度双环戊二烯的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114621046B (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664472A (zh) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | 一种制备高纯度双环戊二烯的方法 |
| KR20160071038A (ko) * | 2014-12-11 | 2016-06-21 | 국방과학연구소 | 이온성 액체 촉매를 이용한 트리시클로펜타디엔 제조방법 |
-
2022
- 2022-04-02 CN CN202210351099.4A patent/CN114621046B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664472A (zh) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | 一种制备高纯度双环戊二烯的方法 |
| KR20160071038A (ko) * | 2014-12-11 | 2016-06-21 | 국방과학연구소 | 이온성 액체 촉매를 이용한 트리시클로펜타디엔 제조방법 |
Non-Patent Citations (1)
| Title |
|---|
| "离子液体催化Ｃ5 馏分中二烯烃的聚合反应";陈晓伟 等;《石油化工》;第36卷(第3期);232-236 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114621046A (zh) | 2022-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109665934B (zh) | 一种制备双环戊二烯的方法 | |
| CN102452934B (zh) | 一种乙酸仲丁酯的制备方法 | |
| CN101450886A (zh) | 一种由碳五馏分生产双环戊二烯的方法 | |
| CN1117958A (zh) | 用于生产高纯度异丁烯的甲基叔丁基醚的制法 | |
| CN114621046B (zh) | 离子液体催化制备高纯度双环戊二烯的方法 | |
| CN102786984B (zh) | 一种利用中低温焦油制备针状焦原料的工艺 | |
| CN112679297A (zh) | 一种高纯度双环戊二烯的制备方法 | |
| CN101092319A (zh) | 一种分离环戊二烯的方法 | |
| TWI752212B (zh) | 二氫茚甲醛之製造方法 | |
| CN114436741B (zh) | 一种环戊烯的制备方法 | |
| CN114349603A (zh) | 一种由乙酸环戊酯制备环戊醇的方法 | |
| CN114751812A (zh) | 一种用多聚甲醛生产二乙氧基甲烷的方法 | |
| CN109988055A (zh) | 一种高纯度环戊二烯及甲基环戊二烯的制备方法 | |
| CN101805631B (zh) | 一种碳五馏分萃取溶剂的变压汽提方法 | |
| CN114105744A (zh) | 一种在较低温度下催化Claisen重排的方法 | |
| CN109337714B (zh) | 用于橡胶树脂增塑剂的低萘高沸点芳烃溶剂的制备方法 | |
| CN114656319B (zh) | 高纯度双环戊二烯的制备方法 | |
| CN107137948B (zh) | 一种从乙烯裂解碳九馏分中脱除双环戊二烯的方法 | |
| CN114436751A (zh) | 一种甲基环戊烯的制备方法 | |
| CN112759501A (zh) | 一种聚合级双环戊二烯的制备方法 | |
| CN111689893A (zh) | 一种2,2,6,6-四甲基-4-氨基哌啶的制备方法 | |
| CN110698318A (zh) | 一种高纯度环戊烯的生产方法 | |
| CN110066267B (zh) | 一种2，2-二甲基-4-羟甲基-1，3-二氧戊环的连续化生产工艺 | |
| CN114014739B (zh) | 一种固体酸催化提高二苄基甲苯选择性的制备方法 | |
| CN114773264B (zh) | 橡胶防老剂tmq的制备装置及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |