CN111269079B - A preparation system and preparation method of perfluoro-1,3-butadiene - Google Patents
A preparation system and preparation method of perfluoro-1,3-butadiene Download PDFInfo
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- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 49
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 24
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 claims abstract description 21
- PRJQLUNGZQZONS-UHFFFAOYSA-N chloro(diethyl)borane Chemical compound CCB(Cl)CC PRJQLUNGZQZONS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000007246 mechanism Effects 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 13
- 238000010926 purge Methods 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 8
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 4
- 229960003750 ethyl chloride Drugs 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- HYDZYXLZFSZQLP-UHFFFAOYSA-N C(C)BCC.[Cl] Chemical compound C(C)BCC.[Cl] HYDZYXLZFSZQLP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 12
- 239000000376 reactant Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 54
- 239000000047 product Substances 0.000 description 34
- 239000006227 byproduct Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- QVHWOZCZUNPZPW-UHFFFAOYSA-N 1,2,3,3,4,4-hexafluorocyclobutene Chemical compound FC1=C(F)C(F)(F)C1(F)F QVHWOZCZUNPZPW-UHFFFAOYSA-N 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 2
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920006926 PFC Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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Abstract
Description
技术领域Technical Field
本发明属于微流体及有机合成技术领域，具体涉及一种全氟1,3- 丁二烯的制备系统及其制备方法。The invention belongs to the technical field of microfluids and organic synthesis, and specifically relates to a preparation system and a preparation method of perfluoro-1,3-butadiene.
背景技术Background technique
全氟1,3-丁二烯(CF2＝CF-CF＝CF2，简称C4F6)是一种含有二个双键的液化气体。分子量162，熔点-132℃，沸点6℃，临界温度140℃，相对空气的气相密度6.79(1.4g/mL，15℃)，燃烧范围7％～73％。全氟丁二烯的GWP值只有290，在大气中的寿命小于2天，对环境基本不产生影响。Perfluoro-1,3-butadiene (CF 2 =CF-CF=CF 2 , abbreviated as C 4 F 6 ) is a liquefied gas containing two double bonds. Molecular weight is 162, melting point is -132°C, boiling point is 6°C, critical temperature is 140°C, gas phase density relative to air is 6.79 (1.4g/mL, 15°C), and combustion range is 7% to 73%. The GWP value of perfluorobutadiene is only 290, and its life in the atmosphere is less than 2 days, which has little impact on the environment.
全氟1,3-丁二烯在工业上有多方面的应用，不仅是制备多种含氟高分子弹性材料聚全氟丁二烯的单体，还是一种温室效应极低、绿色环保的高效干蚀刻气体。全氟丁二烯作为具有双官能团的单体适用于全氟化弹性体的制备与交联，可以制成聚全氟丁二烯，也可以与其他单体合成含氟弹性体和电性能优良的树脂。全氟1,3-丁二烯是一个优良的集成线路干蚀气体，它不仅可以对小于90nm甚至更窄宽度的超大型集成线路进行干蚀刻，具有高选择性和高精确性，更适合于高深宽比的蚀刻工艺。全氟丁二烯在0.13μm技术层面有许多蚀刻上的优点，它比C4F8有更高的对光阻和氮化硅选择比，在使用时可以提高蚀刻的稳定性，提高蚀刻速率和均匀度，从而提高产品优良率。全氟丁二烯具有各向异性，在硅和氧化硅蚀刻中能产生理想的高宽比，在蚀刻形成聚合物薄膜(光刻胶)时对侧壁起保护作用。全氟1,3-丁二烯不仅可以使用在更高要求的电子线路的蚀刻，而且可以取代目前正在电子线路干蚀刻中使用的PFCs。全氟1,3-丁二烯温室效应和对臭氧层的危害性很小，是一种环境友好型干蚀刻气体，有着广阔的市场前景。Perfluoro-1,3-butadiene has many industrial applications. It is not only a monomer for preparing various fluorinated polymer elastic materials, polyperfluorobutadiene, but also a highly efficient dry etching gas with extremely low greenhouse effect and green environmental protection. Perfluorobutadiene, as a monomer with bifunctional groups, is suitable for the preparation and cross-linking of perfluorinated elastomers. It can be made into polyperfluorobutadiene, and can also be used with other monomers to synthesize fluorinated elastomers and resins with excellent electrical properties. Perfluoro-1,3-butadiene is an excellent integrated circuit dry etching gas. It can not only dry etch ultra-large integrated circuits with a width of less than 90nm or even narrower, but also has high selectivity and high precision, and is more suitable for etching processes with high aspect ratios. Perfluorobutadiene has many advantages in etching at the 0.13μm technical level. It has a higher selectivity to photoresist and silicon nitride than C 4 F 8. When used, it can improve the stability of etching, the etching rate and uniformity, thereby improving the product quality rate. Perfluorobutadiene is anisotropic and can produce an ideal aspect ratio in silicon and silicon oxide etching, and protects the sidewalls when etching to form polymer films (photoresists). Perfluoro 1,3-butadiene can not only be used in etching of electronic circuits with higher requirements, but also can replace PFCs currently used in dry etching of electronic circuits. Perfluoro 1,3-butadiene has little greenhouse effect and harm to the ozone layer. It is an environmentally friendly dry etching gas with broad market prospects.
目前，全氟1,3-丁二烯的制备方法普遍存在副产物较多、反应生成收率不高的问题，这主要是1,4-二卤全氟丁烷脱氟化卤生成目标产物全氟1,3-丁二烯的过程中，易生成副产物全氟环丁烯，两者沸点仅相差0.8℃，给分离带来很大困难，同时溶解在溶剂中的全氟环丁烯较难提取，造成产品收率的下降。At present, the preparation methods of perfluoro-1,3-butadiene generally have the problems of more by-products and low reaction yield. This is mainly because the by-product perfluorocyclobutene is easily generated during the defluorination of 1,4-dihaloperfluorobutane to generate the target product perfluoro-1,3-butadiene. The boiling points of the two differ by only 0.8°C, which brings great difficulties to separation. At the same time, the perfluorocyclobutene dissolved in the solvent is difficult to extract, resulting in a decrease in the product yield.
发明内容Summary of the invention
为克服以上技术缺陷，本发明采用了以下技术方案：In order to overcome the above technical defects, the present invention adopts the following technical solutions:
本发明一方面提供了一种全氟1,3-丁二烯制备系统，包括通过管路依次连接的反应机构、纯化机构和收集机构；其中，In one aspect, the present invention provides a system for preparing perfluoro-1,3-butadiene, comprising a reaction mechanism, a purification mechanism and a collection mechanism connected in sequence through pipelines; wherein:
所述反应机构包括由下至上连通设置的微反应器、第一精馏塔和第一冷凝器，所述微反应器的两个原料入口分别连接溶解于四氢呋喃的氯-二乙基-硼烷储存罐和溶解于四氢呋喃的1，4-二碘八氟丁烷储存罐，所述第一冷凝器尾气出口连接至尾气罐，产物出口连接至所述纯化机构，所述纯化机构将产物纯化后输送至所述收集机构收集；The reaction mechanism comprises a microreactor, a first distillation tower and a first condenser which are connected from bottom to top, two raw material inlets of the microreactor are respectively connected to a storage tank of chloro-diethyl-borane dissolved in tetrahydrofuran and a storage tank of 1,4-diiodooctafluorobutane dissolved in tetrahydrofuran, the tail gas outlet of the first condenser is connected to a tail gas tank, and the product outlet is connected to the purification mechanism, and the purification mechanism purifies the product and transports it to the collection mechanism for collection;
所述纯化机构包括第二精馏塔和第二冷凝器，所述第一冷凝器的产物出口连接至所述第二精馏塔，所述第二精馏塔的蒸汽出口通过第二冷凝器连接至尾气罐，所述第二精馏塔的产物出口连接至所述收集机构；进一步优选的，所述纯化机构还包括第三精馏塔和第三冷凝器，所述第二精馏塔的产物出口连接至所述第三精馏塔，所述第三精馏塔的蒸汽出口连接至第三冷凝器，所述第三冷凝器的出口连接所述第三精馏塔和所述收集机构；The purification mechanism comprises a second distillation tower and a second condenser, the product outlet of the first condenser is connected to the second distillation tower, the steam outlet of the second distillation tower is connected to the tail gas tank through the second condenser, and the product outlet of the second distillation tower is connected to the collection mechanism; further preferably, the purification mechanism further comprises a third distillation tower and a third condenser, the product outlet of the second distillation tower is connected to the third distillation tower, the steam outlet of the third distillation tower is connected to the third condenser, and the outlet of the third condenser is connected to the third distillation tower and the collection mechanism;
进一步的，所述全氟1,3-丁二烯的制备系统，还包括真空机构或惰性气体吹扫机构；Furthermore, the system for preparing perfluoro-1,3-butadiene further includes a vacuum mechanism or an inert gas purge mechanism;
进一步优选的，所述真空机构连接至管路保持内部真空；Further preferably, the vacuum mechanism is connected to a pipeline to maintain an internal vacuum;
进一步优选的，所述惰性气体吹扫机构连接至管路沿产物输出方向吹送惰性气体；通过采用上述方案，在惰性气体吹扫情况下能够有效提高第一精馏塔内含全氟丁二烯混合体系与溶剂的分离速度，从而减少了它在溶剂中存留和自聚的机会。Further preferably, the inert gas purge mechanism is connected to a pipeline to blow inert gas along the product output direction; by adopting the above scheme, the separation rate of the perfluorobutadiene mixed system and the solvent in the first distillation tower can be effectively improved under the condition of inert gas purge, thereby reducing the chance of its retention and self-polymerization in the solvent.
本发明的第二方面还提供了一种采用上述全氟1,3-丁二烯制备系统连续合成全氟1,3-丁二烯的方法，包括以下步骤:在溶剂四氢呋喃中，以1，4-二碘八氟丁烷与氯-二乙基-硼烷在所述制备系统内反应，即得；The second aspect of the present invention also provides a method for continuously synthesizing perfluoro-1,3-butadiene using the above-mentioned perfluoro-1,3-butadiene preparation system, comprising the following steps: reacting 1,4-diiodooctafluorobutane with chloro-diethyl-borane in the preparation system in a solvent of tetrahydrofuran to obtain;
进一步的，所述1，4-二碘八氟丁烷与氯-二乙基-硼烷的摩尔用量比为1:0.5～2；优选的，1，4-二碘八氟丁烷与氯-二乙基-硼烷的摩尔用量比为1:1；Further, the molar ratio of 1,4-diiodooctafluorobutane to chloro-diethyl-borane is 1:0.5-2; preferably, the molar ratio of 1,4-diiodooctafluorobutane to chloro-diethyl-borane is 1:1;
进一步的，所述反应温度为10～25℃；优选的，所述反应温度为 20℃；Further, the reaction temperature is 10-25°C; preferably, the reaction temperature is 20°C;
进一步的，所述反应在真空条件或常压伴有惰性气体吹扫条件下进行的；进一步优选的，所述真空度为13.33～40kPa；或进一步优选的，所述惰性气体为N2，其流速为0.5～1.0L/h；更优选的，所述N2的流速为0.75L/h；Further, the reaction is carried out under vacuum conditions or atmospheric pressure accompanied by inert gas purging conditions; further preferably, the vacuum degree is 13.33-40 kPa; or further preferably, the inert gas is N 2 , and its flow rate is 0.5-1.0 L/h; more preferably, the flow rate of N 2 is 0.75 L/h;
进一步的，所述连续合成全氟1,3-丁二烯的方法的具体步骤包括：Furthermore, the specific steps of the method for continuously synthesizing perfluoro-1,3-butadiene include:
S1：将1，4-二碘八氟丁烷的四氢呋喃溶液和氯-二乙基-硼烷的四氢呋喃溶液混合滴加入连通第一精馏塔的微反应器中，在所述微反应器内充分混合反应，形成包括1，4-二碘八氟丁烷、氯-二乙基-硼烷、氯乙烷、目标产物全氟1,3-丁二烯以及四氢呋喃在内的混合体系A；S1: a tetrahydrofuran solution of 1,4-diiodooctafluorobutane and a tetrahydrofuran solution of chloro-diethyl-borane are mixed and added dropwise to a microreactor connected to a first distillation tower, and the mixture is fully mixed and reacted in the microreactor to form a mixed system A including 1,4-diiodooctafluorobutane, chloro-diethyl-borane, ethyl chloride, the target product perfluoro-1,3-butadiene and tetrahydrofuran;
S2：将上述混合体系A引入第一冷凝器内部，在继续反应的同时进行精馏冷凝操作，除去四氢呋喃后形成混合体系B；S2: introducing the mixed system A into the first condenser, performing rectification and condensation operations while continuing the reaction, and removing tetrahydrofuran to form a mixed system B;
S3：将所述混合体系B引入第二精馏塔和第二冷凝器进行精馏，所述精馏温度低于目标产物全氟1,3-丁二烯的沸点，以除去沸点低于全氟1,3-丁二烯的部分杂质而形成混合体系C；S3: introducing the mixed system B into a second distillation tower and a second condenser for distillation, wherein the distillation temperature is lower than the boiling point of the target product perfluoro-1,3-butadiene, so as to remove some impurities having a boiling point lower than that of perfluoro-1,3-butadiene to form a mixed system C;
S4：将所述混合体系C引入第三精馏塔和第三冷凝器进行精馏，所述精馏温度高于目标产物全氟1,3-丁二烯的沸点，反复精馏以除去沸点高于全氟1,3-丁二烯的杂质后，即得。S4: introducing the mixed system C into a third distillation tower and a third condenser for distillation, wherein the distillation temperature is higher than the boiling point of the target product perfluoro-1,3-butadiene, and repeatedly distilling to remove impurities having a boiling point higher than that of perfluoro-1,3-butadiene to obtain the product.
进一步的，S1中所述的微反应器为微通道式、毛细管式、降膜式、多股并流式、微孔列阵式或膜分散式微反应器；优选的，S1中所述的微反应器为微通道式微反应器。Furthermore, the microreactor described in S1 is a microchannel type, a capillary type, a falling film type, a multi-stream parallel flow type, a micropore array type or a membrane dispersed type microreactor; preferably, the microreactor described in S1 is a microchannel type microreactor.
有益效果：Beneficial effects:
本发明相对于现有技术具有的有益效果：The present invention has the following beneficial effects compared with the prior art:
1.本发明中采用的微型反应器通常是指其内部流体通道或分散空间尺度在微米量级的微结构化学反应器。在这种反应器中，由于反应体系的传质和传热过程获得极大改进，有效解决反应的传热和传质问题，有效减少副产物全氟环丁烯的产生。1. The microreactor used in the present invention generally refers to a microstructured chemical reactor whose internal fluid channel or dispersed space scale is in the micrometer level. In such a reactor, the mass transfer and heat transfer process of the reaction system are greatly improved, the heat transfer and mass transfer problems of the reaction are effectively solved, and the generation of the by-product perfluorocyclobutene is effectively reduced.
2.多次分步循环精馏，能够有效除去副产物，显著提高产物纯度。2. Multiple step-by-step cyclic distillation can effectively remove by-products and significantly improve product purity.
3.采用惰性气体吹扫情况下能够有效提高第一冷凝器内内含全氟丁二烯的混合体系与与溶剂的分离速度，从而减少了它在溶剂中存留和自聚的机会，以降低副产物的产生。3. The use of inert gas purging can effectively increase the separation rate of the mixed system containing perfluorobutadiene and the solvent in the first condenser, thereby reducing the chance of its retention and self-polymerization in the solvent, thereby reducing the generation of by-products.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍。在所有附图中，类似的元件或部分一般由类似的附图标记标识。附图中，各元件或部分并不一定按照实际的比例绘制。In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for the specific embodiments or the description of the prior art. In all the drawings, similar elements or parts are generally identified by similar reference numerals. In the drawings, the elements or parts are not necessarily drawn according to the actual scale.
图1是本发明的实施例1的结构示意图。FIG1 is a schematic structural diagram of embodiment 1 of the present invention.
图2是本发明的实施例2的结构示意图。FIG. 2 is a schematic structural diagram of embodiment 2 of the present invention.
图中所示：As shown in the figure:
1、微反应器；1. Microreactor;
2、第一精馏塔；2. The first distillation tower;
3、第一冷凝器；3. The first condenser;
4、氯-二乙基-硼烷储存罐；4. Chloro-diethyl-borane storage tank;
5、1，4-二碘八氟丁烷储存罐；5. 1,4-diiodooctafluorobutane storage tank;
6、尾气罐；6. Exhaust tank;
7、第二精馏塔；7. Second distillation tower;
8、第二冷凝器；8. Second condenser;
9、第三精馏塔；9. The third distillation tower;
10、第三冷凝器；10. The third condenser;
11、充装器；11. Filler;
12、预处理钢瓶；12. Pre-treat cylinders;
13、真空泵；13. Vacuum pump;
14、惰性气体储存罐；14. Inert gas storage tank;
15、鼓风机。15. Blower.
具体实施方式Detailed ways
下面将对本发明技术方案的实施例进行详细的描述。以下实施例仅用于更加清楚地说明本发明的技术方案，因此只是作为示例，而不能以此来限制本发明的保护范围。需要注意的是，除非另有说明，本申请使用的技术术语或者科学术语应当为本发明所属领域技术人员所理解的通常意义。The embodiments of the technical solution of the present invention are described in detail below. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present invention. It should be noted that, unless otherwise specified, the technical terms or scientific terms used in this application should be the usual meanings understood by those skilled in the art to which the present invention belongs.
实施例1：Embodiment 1:
如图1所示，本实施例提供的一种全氟丁二烯的制备系统，包括通过管路依次连接的反应机构、纯化机构、收集机构和真空机构。As shown in FIG1 , a system for preparing perfluorobutadiene provided in this embodiment includes a reaction mechanism, a purification mechanism, a collection mechanism, and a vacuum mechanism which are sequentially connected through pipelines.
反应机构包括由下至上连通设置的微反应器1、第一精馏塔2和第一冷凝器3，微反应器1的两个原料入口分别连接溶于四氢呋喃的氯- 二乙基-硼烷储存罐4和溶于四氢呋喃的1，4-二碘八氟丁烷储存罐5，第一冷凝器3尾气出口连接至尾气罐6，产物出口连接至纯化机构。The reaction mechanism includes a microreactor 1, a first distillation tower 2 and a first condenser 3 which are connected from bottom to top. The two raw material inlets of the microreactor 1 are respectively connected to a chloro-diethyl-borane storage tank 4 dissolved in tetrahydrofuran and a 1,4-diiodooctafluorobutane storage tank 5 dissolved in tetrahydrofuran. The tail gas outlet of the first condenser 3 is connected to a tail gas tank 6, and the product outlet is connected to a purification mechanism.
微反应器1与第一精馏塔2一体化设置，溶于四氢呋喃的氯-二乙基-硼烷和溶于四氢呋喃的1，4-二碘八氟丁烷滴加到微反应器1中，两者在微反应器1中微通道内充分混合反应，有效解决反应的传热和传质问题，有效解决副反应问题，同时两者和反应产物进入第一精馏塔2和第一冷凝器3的内部，在反应的同时进行精馏操作，将反应生成的混合体系(含目标产物全氟丁二烯)与溶剂迅速分离，有效减少副产物全氟环丁烯的产生，之后对产物进行进一步纯化操作，有效提高产物的反应收率和选择率。The microreactor 1 is integrated with the first distillation tower 2. Chloro-diethyl-borane dissolved in tetrahydrofuran and 1,4-diiodooctafluorobutane dissolved in tetrahydrofuran are dripped into the microreactor 1. The two are fully mixed and reacted in the microchannel of the microreactor 1, effectively solving the heat transfer and mass transfer problems of the reaction and the side reaction problems. At the same time, the two and the reaction product enter the first distillation tower 2 and the first condenser 3, and the distillation operation is carried out while the reaction is taking place. The mixed system (including the target product perfluorobutadiene) generated by the reaction is quickly separated from the solvent, effectively reducing the generation of the byproduct perfluorocyclobutene. After that, the product is further purified, effectively improving the reaction yield and selectivity of the product.
纯化机构包括第二精馏塔7、第二冷凝器8、第三精馏塔9和第三冷凝器10，第一冷凝器3的产物出口连接至第二精馏塔7，第二精馏塔7的蒸汽出口通过第二冷凝器8连接至尾气罐6，第二精馏塔7的产物出口连接至第三精馏塔9。The purification mechanism includes a second distillation tower 7, a second condenser 8, a third distillation tower 9 and a third condenser 10. The product outlet of the first condenser 3 is connected to the second distillation tower 7, the steam outlet of the second distillation tower 7 is connected to the tail gas tank 6 through the second condenser 8, and the product outlet of the second distillation tower 7 is connected to the third distillation tower 9.
第二精馏塔7内部进行低温精馏，精馏温度低于目标产物全氟丁二烯的沸点，从而进一步去除产物内部的反应生成的氯乙烷等尾气，提高纯度。Low-temperature distillation is performed inside the second distillation tower 7, and the distillation temperature is lower than the boiling point of the target product perfluorobutadiene, so as to further remove tail gas such as ethyl chloride generated by the reaction inside the product and improve the purity.
第三精馏塔9的蒸汽出口连接至第三冷凝器10，第三冷凝器10 的出口连接第三精馏塔9和收集机构。The steam outlet of the third distillation tower 9 is connected to the third condenser 10, and the outlet of the third condenser 10 is connected to the third distillation tower 9 and the collecting mechanism.
第三精馏塔9内部进行低温精馏，精馏温度稍高于目标产物全氟丁二烯的沸点，从而去除其他沸点较高的反应副产物；第三精馏塔9 的蒸汽出口连接至第三冷凝器10，第三冷凝器10的出口部分回流至第三精馏塔9形成循环，部分输送至收集机构收集，提高产物纯度。Low-temperature distillation is carried out inside the third distillation tower 9, and the distillation temperature is slightly higher than the boiling point of the target product perfluorobutadiene, so as to remove other reaction by-products with higher boiling points; the steam outlet of the third distillation tower 9 is connected to the third condenser 10, and part of the outlet of the third condenser 10 is refluxed to the third distillation tower 9 to form a cycle, and part is transported to the collection mechanism for collection, so as to improve the purity of the product.
收集机构包括充装器11和预处理钢瓶12。The collecting mechanism includes a filler 11 and a pre-treatment cylinder 12 .
真空机构包括真空泵13，真空泵13连接至管路保持内部真空，能够有效提高第一冷凝器3内含全氟丁二烯的混合体系与溶剂分离的速度，从而减少了它在溶剂中存留和自聚的机会。The vacuum mechanism includes a vacuum pump 13, which is connected to a pipeline to maintain internal vacuum, and can effectively increase the separation rate of the mixed system containing perfluorobutadiene in the first condenser 3 from the solvent, thereby reducing the chance of its retention and self-polymerization in the solvent.
实施例2：Embodiment 2:
本实施例与实施例一基本相同，不同之处在于本实施例并没有采用真空机构，而是通过惰性气体吹扫机构来夹块全氟丁二烯的分离速度，惰性气体吹扫机构包括相连的惰性气体储存罐14和鼓风机15，本实施例中的惰性气体采用氮气，沿产物输出方向吹送氮气能够有效提高第一冷凝器3内含全氟丁二烯的混合体系与溶剂的分离速度，从而减少了它在溶剂中存留和自聚的机会。This embodiment is basically the same as the first embodiment, except that this embodiment does not use a vacuum mechanism, but uses an inert gas purge mechanism to control the separation speed of the perfluorobutadiene. The inert gas purge mechanism includes a connected inert gas storage tank 14 and a blower 15. The inert gas in this embodiment is nitrogen. Blowing nitrogen along the product output direction can effectively increase the separation speed of the mixed system containing perfluorobutadiene in the first condenser 3 and the solvent, thereby reducing the chance of its retention and self-polymerization in the solvent.
实施例3：Embodiment 3:
一种采用实施例1的制备系统述连续合成全氟1,3-丁二烯的方法，包括以下步骤:连续合成全氟1,3-丁二烯的方法的具体步骤包括：A method for continuously synthesizing perfluoro-1,3-butadiene using the preparation system of Example 1 comprises the following steps: The specific steps of the method for continuously synthesizing perfluoro-1,3-butadiene include:
S1：在20℃下，真空度20kPa下，将1，4-二碘八氟丁烷的四氢呋喃溶液和氯-二乙基-硼烷的四氢呋喃溶液混合滴加入连通第一精馏塔的微反应器中，在所述微反应器内充分混合反应，形成包括1，4- 二碘八氟丁烷、氯-二乙基-硼烷、氯乙烷、目标产物全氟1,3-丁二烯以及四氢呋喃在内的混合体系A；其中，所述1，4-二碘八氟丁烷与氯 -二乙基-硼烷的摩尔用量比为1:1；S1: at 20°C and under a vacuum degree of 20 kPa, a tetrahydrofuran solution of 1,4-diiodooctafluorobutane and a tetrahydrofuran solution of chloro-diethyl-borane are mixed and dropwise added into a microreactor connected to a first distillation tower, and the mixture is fully mixed and reacted in the microreactor to form a mixed system A including 1,4-diiodooctafluorobutane, chloro-diethyl-borane, ethyl chloride, the target product perfluoro-1,3-butadiene and tetrahydrofuran; wherein the molar ratio of 1,4-diiodooctafluorobutane to chloro-diethyl-borane is 1:1;
S2：将上述混合体系A引入第一冷凝器内部，在继续反应的同时进行精馏冷凝操作，除去四氢呋喃后形成混合体系B；S2: introducing the mixed system A into the first condenser, performing rectification and condensation operations while continuing the reaction, and removing tetrahydrofuran to form a mixed system B;
S3：将所述混合体系B引入第二精馏塔和第二冷凝器进行精馏，所述精馏温度低于目标产物全氟1,3-丁二烯的沸点，以除去沸点低于全氟1,3-丁二烯的部分杂质而形成混合体系C；S3: introducing the mixed system B into a second distillation tower and a second condenser for distillation, wherein the distillation temperature is lower than the boiling point of the target product perfluoro-1,3-butadiene, so as to remove some impurities having a boiling point lower than that of perfluoro-1,3-butadiene to form a mixed system C;
S4：将所述混合体系C引入第三精馏塔和第三冷凝器进行精馏，所述精馏温度高于目标产物全氟1,3-丁二烯的沸点，反复精馏以除去沸点高于全氟1,3-丁二烯的杂质后，即得；经检测，获得的目标产物的全氟1,3-丁二烯的纯度为99.2％，收率为95.0％。S4: introducing the mixed system C into a third distillation tower and a third condenser for distillation, wherein the distillation temperature is higher than the boiling point of the target product perfluoro-1,3-butadiene, and repeatedly distilling to remove impurities having a boiling point higher than that of perfluoro-1,3-butadiene, to obtain the target product perfluoro-1,3-butadiene; after testing, the purity of the obtained target product perfluoro-1,3-butadiene is 99.2%, and the yield is 95.0%.
实施例4Example 4
一种采用实施例1的制备系统述连续合成全氟1,3-丁二烯的方法，包括以下步骤:连续合成全氟1,3-丁二烯的方法的具体步骤包括：A method for continuously synthesizing perfluoro-1,3-butadiene using the preparation system of Example 1 comprises the following steps: The specific steps of the method for continuously synthesizing perfluoro-1,3-butadiene include:
S1：在20℃下，流速为0.75L/h的N2吹扫下，将1，4-二碘八氟丁烷的四氢呋喃溶液和氯-二乙基-硼烷的四氢呋喃溶液混合滴加入连通第一精馏塔的微反应器中，形成包括1，4-二碘八氟丁烷的四氢呋喃溶液、氯-二乙基-硼烷以及目标产物全氟1,3-丁二烯在内的混合体系A；其中，所述1，4-二碘八氟丁烷与氯-二乙基-硼烷的摩尔用量比为1： 1；S1: at 20°C and under N2 purge at a flow rate of 0.75 L/h, a tetrahydrofuran solution of 1,4-diiodooctafluorobutane and a tetrahydrofuran solution of chloro-diethyl-borane are mixed and dropwise added into a microreactor connected to a first distillation tower to form a mixed system A including a tetrahydrofuran solution of 1,4-diiodooctafluorobutane, chloro-diethyl-borane and a target product, perfluoro-1,3-butadiene; wherein the molar ratio of the 1,4-diiodooctafluorobutane to the chloro-diethyl-borane is 1:1;
S2：将上述混合体系A引入第一冷凝器内部，在继续反应的同时进行精馏冷凝操作，除去四氢呋喃后形成混合体系B；S2: introducing the mixed system A into the first condenser, performing rectification and condensation operations while continuing the reaction, and removing tetrahydrofuran to form a mixed system B;
S3：将所述混合体系B引入第二精馏塔和第二冷凝器进行精馏，所述精馏温度低于目标产物全氟1,3-丁二烯的沸点，以除去沸点低于全氟1,3-丁二烯的部分杂质而形成混合体系C；S3: introducing the mixed system B into a second distillation tower and a second condenser for distillation, wherein the distillation temperature is lower than the boiling point of the target product perfluoro-1,3-butadiene, so as to remove some impurities having a boiling point lower than that of perfluoro-1,3-butadiene to form a mixed system C;
S4：将所述混合体系C引入第三精馏塔和第三冷凝器进行精馏，所述精馏温度高于目标产物全氟1,3-丁二烯的沸点，反复精馏以除去沸点高于全氟1,3-丁二烯的杂质后，即得；经检测，获得的目标产物的全氟1,3-丁二烯的纯度为99.4％，收率为95.5％。S4: introducing the mixed system C into a third distillation tower and a third condenser for distillation, wherein the distillation temperature is higher than the boiling point of the target product perfluoro-1,3-butadiene, and repeatedly distilling to remove impurities having a boiling point higher than that of perfluoro-1,3-butadiene, to obtain the target product; after testing, the purity of the obtained perfluoro-1,3-butadiene is 99.4%, and the yield is 95.5%.
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围，其均应涵盖在本发明的权利要求和说明书的范围当中。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.
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