577870 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（） 發明領域 本發明係關於石油化學領域，更明確的說，係關於一 種高純度二環戊二烯（dicycolpentadiene，DCPD)的製造方 法，該高純度二環戊二烯係可供製造一種改良之乙烯-丙 烯共聚物、DCPD聚合物及正莰烯（norbornene)衍生物之 用。 發明背景： 德國專利第2,334,63 3號揭露了 一種藉由將内含環戊 二晞（cycolpentadiene，CPD)之 C5-邵分加以二聚化 (d i m e r i z a t i ο η)以製造純 D C P D、的方法。在此方法中，純 DCPD係先藉由二聚化反應，之後，再於甲苯中蒸餾去 除沸點較低的混合物而製造出來的。以此法所製造出來 的純DCPD，由於純度太低，因此若不進一步純化的話， 將無法被廣泛應用。只有沸點較低的混合物可藉蒸餾法 去除，但CPD與異-戊-間二烯或1，3-戊二烯（piperylene) 所形成之共-二聚物，則因彼此沸點太接近，因此很難藉 由蒸餾法將其——分離。以此法所製造出來的 DCPD， 最高純度只達8 5 %。由於供製造改良之乙烯-丙烯共聚 物、DCPD聚合物及正莰晞衍生物所需之DCPD純度高 達98.5%，因此以上述方法製作而成的DCPD將無法用 於此目的。 可藉由將純CPD進一步二聚化來提高其純度，其係 先將DCPD單聚化（monomerization)之後再加以蒸餘，此 第頂 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） ..............餐.........、可…·-.....----- (請先閲讀背面之注意事項再填寫本頁) 577870 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（） 係因C P D與異-戊-間二晞或1,3 -戊二烯間之共-二聚化反 應速率遠比C P D二聚化的速率來得低之故。美國專利第 3,772,3 96號揭露了以此方法製造出來的DCPD純度高達 9 9 °/〇。但疋’此方法在操作上有些困難，因為在將〇 c P D 裂解的蒸氣過程中’會產生大量會阻塞管線及冷卻器的 物質來。 俄國專利第2，0 5 9，5 9 5號揭露了由碳氫化物熱裂解後 之C5 -部分來製造純D C P D的方法。依據此方法，其包含 下列步驟。首先’將C5 -邵分二聚化後，以蒸館去除其中 沸點較低的碳氫化物部分。其次，將純D C P D裂解後再 進一步精餾以製造純C P D。最後，將第二步驟中產生的 純C P D再次二聚化形成D C P D，並將此二聚物混合物精 館以得到南純度的D C P D。在此方法中，該c 5 -部分係先 於1 10-13 5°C下二聚化，之後該DCPD則於0.16 MPa之 壓力，3 00-3 70 °C的水蒸氣下單聚化。將單聚化之產物以 兩隻精餾管柱’於140-300 °C下精餾分離出純CPD。經上 述方法所得產物之最高純度為9 4 %。亦有人報導說c 5 -部 分通常是在 135°C 下二聚化（Vostrikova V.N.，Chernikh S.P·，Grigoriev A. A.，“Petrochemical CPD and DCPD - perspective raw material for organic synthesis，，， CNnTENeftekhim，1 984, p.7)。上述方法之缺點如下：i) DCPD純度不夠；2)製程複雜；及3)需耗費相當高的 能源。 本發明則藉由採用新的最佳操作狀況，成功地克服了 第4頁 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐） .......................訂---------I I r (請先閲讀背面之注意事項再填寫本頁) 577870 A7 B7 五、發明説明（） 上述方法之所有缺點。 發明詳述： (請先閲讀背面之注意事項再填寫本頁) 本發明主要目的係為了提高DCPD純度，簡化其製程 並降低能源耗損率。 上述這些技術性問題，係藉由自碳氫化物熱裂解後之 (V部分來製造純DCPD的方法而加以克服：1)藉由加 熱將部分中的CPD二聚化；2)分餾去除低沸點之碳 氫化物以純化DCPD ; 3)將純化的DCPD單聚化；4)將 純化的CPD二聚化；5)將此二聚化後之混合物精餾， 以獲得高純度的D C P D。在上述方法中，C 5 -部分之二聚 化反應係在 5 0 -1 1 〇 t：下進行，直到轉換率達9 5 % ;且 DCPD單聚化反應係在高沸點溶劑下進行，較好是十七 烷，且在聚合抑制劑存在下，較好是氫醌，並於丨6 〇 _ 2 5 〇 °C下反應，較好是在180-2 10°C下反應。之後，所生成的 CPD則於50-1 l〇°C，較好是50-60°C時二聚化，直到轉 換率達90-99%。在此，若CPD二聚化時之溫度低於50 °C，反應速率太慢而降低其產率；但若溫度高於1 i(TC， 不純物的產生會增加，降低其產率與純度。 經濟部智慧財產局員工消費合作社印製 藉由本發明，可將DCPD純度提高到95- 1 00%，並降 低所需之製程數目及能源耗損率。 在此發明中，係使用沸點介於25-70°C且具下列組成 之C 5 -部分為進料。 第5頁 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 577870 A7 B7 五、發明説明（ 化合物 含量，重量％ 環戊烷 4.3-10.3 異戊烷 6.6-12.6 N-戊烷 5.9-15.9 1 -戊烯· 2.2-4.2 2-甲基-1-丁烯 3.9-7.9 2-甲基-2-丁埽 2.7-4.7 2-戊埽（順式_及反式―） 2.8-4.8 U-戊二缔(順式-及反式 12.8-20.8 異-戊-間二少希 10.9-22.9 DCPD/CPD 9.4-17.4 環戊缔 2.5-3.5 重碳氫化物，，（C6) 2.5-6.5 .............t C請先閱讀背面之法意事項存填寫本買) 經濟部智慧財產局員工消費合作社印製 實施例1577870 Printed by A7 B7, Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs. 5. Description of Invention () Field of the Invention The present invention relates to the field of petrochemicals, more specifically, to a high-purity dicycolpentadiene (DCPD). Manufacturing method: The high-purity dicyclopentadiene series can be used for manufacturing an improved ethylene-propylene copolymer, DCPD polymer, and norbornene derivative. BACKGROUND OF THE INVENTION: German Patent No. 2,334,63 3 discloses a method for producing pure D C P D, by dimerizing C5-shaft containing cycolpentadiene (CPD) to dimerize (d i m e r i z a t i ο η). In this method, pure DCPD is produced by dimerization first, followed by distillation in toluene to remove the mixture with a lower boiling point. The pure DCPD produced by this method is too low in purity and cannot be widely used without further purification. Only mixtures with lower boiling points can be removed by distillation. However, the co-dimers formed by CPD and iso-pentadiene or 1,3-pentadiene (piperylene) are too close to each other because of their boiling points. It is difficult to separate it by distillation. The highest purity of DCPD produced by this method is only 85%. Since the purity of DCPD required for the manufacture of improved ethylene-propylene copolymers, DCPD polymers, and n-fluorene derivatives is as high as 98.5%, DCPDs produced by the above methods cannot be used for this purpose. Pure CPD can be further dimerized to improve its purity. It is first monopolized DCPD (monomerization) and then steamed. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297). Li) .............. meal ........., but ... · -.....----- (Please read the precautions on the back first (Fill in this page) 577870 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Due to the co-dimerization reaction between CPD and iso-penta-dioxin or 1,3-pentadiene The rate is much lower than the rate of CPD dimerization. U.S. Patent No. 3,772,3 96 discloses that the purity of DCPD produced by this method is as high as 99 ° / °. However, this method is somewhat difficult to operate, because in the steam cracking process of 0 c P D, a large amount of material that can block the pipeline and the cooler is generated. Russian Patent No. 2,0 559, 5 9 5 discloses a method for producing pure D C P D from the C5 -part of a hydrocarbon after thermal cracking. According to this method, it includes the following steps. First, after dimerizing the C5 -Shao fraction, the lower boiling hydrocarbon portion is removed in a steaming chamber. Second, the pure DCP D is cracked and further rectified to produce pure CPD. Finally, the pure C P D produced in the second step is dimerized again to form D C P D, and this dimer mixture is refined to obtain D C P D of South purity. In this method, the c 5 -part is dimerized at 1 10-13 5 ° C, and then the DCPD is monomerized at a pressure of 0.16 MPa and water vapor at 3 00-3 70 ° C. The monomerized product was purified by two distillation columns' at 140-300 ° C to separate pure CPD. The highest purity of the product obtained by the above method was 94%. It has also been reported that c 5 -part is usually dimerized at 135 ° C (Vostrikova VN, Chernikh SP ·, Grigoriev AA, "Petrochemical CPD and DCPD-perspective raw material for organic synthesis,", CNnTENeftekhim, 1 984, p .7). The disadvantages of the above method are as follows: i) the purity of DCPD is not enough; 2) the process is complicated; and 3) the energy consumption is quite high. The present invention successfully overcomes the fourth problem by adopting a new optimal operating condition. The paper size of this page applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ............. Order -------- -II r (Please read the notes on the back before filling this page) 577870 A7 B7 V. Description of the invention () All the shortcomings of the above method. Detailed description of the invention: (Please read the notes on the back before filling this page) The present invention The main purpose is to improve the purity of DCPD, simplify its process and reduce the energy consumption rate. These technical problems are overcome by the method of manufacturing pure DCPD after pyrolysis of hydrocarbons (Part V): 1) By Dimerization of CPD in the part by heating; 2) Fractionation to remove low boiling 3) Monomerize the purified DCPD; 4) Dimerize the purified CPD; 5) Distill the dimerized mixture to obtain DCPD with high purity. In the method, the C 5 -partial dimerization reaction is carried out at 50 -1 10 t: until the conversion rate reaches 95%; and the DCPD monomerization reaction is carried out in a high boiling point solvent, preferably Heptadecane, and in the presence of a polymerization inhibitor, preferably hydroquinone, and reacted at 60 ° -25 ° C, preferably at 180-2 10 ° C. After that, the resulting CPD dimerizes at 50-1 l0 ° C, preferably 50-60 ° C, until the conversion rate reaches 90-99%. Here, if the temperature of CPD dimerization is lower than 50 ° C, The reaction rate is too slow to reduce its yield; but if the temperature is higher than 1 ° C, the production of impurities will increase, reducing its yield and purity. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The purity is increased to 95- 100%, and the required number of processes and energy consumption are reduced. In this invention, C 5-with a boiling point between 25-70 ° C and the following composition is used Divided into feed. Page 5 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 577870 A7 B7 V. Description of the invention (compound content, wt% cyclopentane 4.3-10.3 isopentane 6.6.6-12.6 N-pentane 5.9-15.9 1-pentene 2.2-4.2 2-methyl-1-butene 3.9-7.9 2-methyl-2-butane 2.7-4.7 2-pentamidine (cis_ and trans ―) 2.8-4.8 U-pentadiene (cis- and trans 12.8-20.8 iso-penta-metaschyl 10.9-22.9 DCPD / CPD 9.4-17.4 cyclopentyl 2.5-3.5 heavy hydrocarbon, ( C6) 2.5-6.5 ............. t C Please read the legal and legal matters on the back and fill in this purchase) Example 1 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
Cr部分中的CPD係於5(rc下的反應器内二聚化，直 到CPD轉換率達95%為止。之後，以兩個管柱將反應混 α物刀餾，自弟一管柱上邵將低滞點之礙氫化物分離， 並自第二管柱上部將純的DCPD分離。將製得之DCpD 於十七烷這樣的高沸點溶劑，及氫醌這樣的聚合抑制劑 及1 8 0 - 2 1 0 C之溫度下單聚化。之後，於5 〇 °C下將所製 成的C P D 一聚化，直到轉換率達9 9 °/〇為止。以兩根精餾 管柱將此二聚混合物精餾，可分離出高純度的DCPD。 將上述方法製成之DCPD純度高達99·5%以上，產率則 第6頁 本紙張尺度適用中國國家標準(CNS)A4規格(210X 297公釐) 577870 A7 B7 五、發明説明（） (請先閱讀背面之注意事項再填寫本頁) 高達77%。CPD與DCPD在反應物與產物中之含量係利 用氣相層析法（GC)測得，其中氣相層析管柱具有DB Wax 5 2。表1示出實施例1所得之結果。 表1 階段 溫度 °C 轉換率 % 含量，重量％ CPD DCPD C5-碳氮化 物 CPD與異-戊-間 二烯或1,3-戍二 烯所形成之共-二聚物 C5-部分 二聚化 50 95 0.55 10.45 87.67 1.33 分館 70 (20 mmHg) 90 - 88.8 - 11.2 DCPD 單聚化 180-210 90 99.26 0.44 0.304 - CPD 二聚化 50 99 1.16 98.84 - - DCPD 精餾 70 (20 mmHg) 94 - 99.5 - - 經濟部智慧財產局員工消費合作社印製 實施例2 C5-部分中的CPD係於110°C下的反應器内二聚化， 直到CPD轉換率達95%為止。之後，以兩個管柱將反應 混合物分餾，自第一管柱上部將低沸點之碳氫化物分離， 並自第二管柱上部將純的 DCPD分離。將製得之DCPD 於十七烷這樣的高沸點溶劑，及氫醌或苯醌這樣的聚合 第7頁 本紙張尺度適用中國國家標準(CNS)A4規格(210X 297公釐） 577870 A7 B7 五、發明説明（） 抑制劑及180-2 10 °C之溫度下單聚化。之後，於60 °C下 將所製成的CPD二聚化，直到轉換率達92%為止。以兩 根精餾管柱將此二聚混合物精餾，可分離出高純度的 DCPD。將上述方法製成之DCPD純度高達 100%以上， 產率則高達7 5 °/。。表2示出實施例2所得之結果。 經濟部智慧財產局員工消費合作社印製 表2 階段 溫度 °C 轉換率 % 含量，重量％ CPD DCPD C5-碳氮化 物 CPD與異-戊-間 二烯或1,3-戊二 烯所形成之共-二聚物 c5-部分 二聚化 110 95 0.72 13.66 81.40 4.22 分顧 70 (20 mmHg) 93.5 - 83.8 - 16.2 DCPD 單聚化 180-200 88 86.44 3.48 5.8 4.16 CPD 二聚化 60 92 3.36 96.21 0.33 - DCPD 精餾 70 (20 mmHg) 97 - 99.5 - - (請先閱讀背面之注意事項再填寫本頁) 第煩 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐)The CPD in the Cr part is dimerized in the reactor at 5 ° C. until the CPD conversion rate reaches 95%. After that, the reaction mixture α is knife-distilled with two columns, and it is on the column The low stagnation point hinders hydride separation, and pure DCPD is separated from the upper part of the second column. The obtained DCpD is in a high boiling point solvent such as heptadecane, and a polymerization inhibitor such as hydroquinone and 180 -Monomerization at a temperature of 2 1 0 C. After that, the prepared CPD was monomerized at 50 ° C until the conversion rate reached 99 ° / 〇. This was achieved by two distillation column columns. Dimerization of dimeric mixtures can separate high-purity DCPD. The purity of DCPD made by the above method is more than 99 · 5%, and the yield is page 6 This paper is in accordance with Chinese National Standard (CNS) A4 (210X 297) (Mm) 577870 A7 B7 V. Description of the invention () (Please read the notes on the back before filling this page) Up to 77%. The content of CPD and DCPD in the reactants and products is determined by gas chromatography (GC) It was measured that the gas chromatography column had DB Wax 5 2. Table 1 shows the results obtained in Example 1. Table 1 Stage temperature ° C Conversion rate% Content, wt% CPD DCPD C5-Carbonitride CPD Co-dimer formed by iso-penta-diene or 1,3-fluorene diene C5-partial dimerization 50 95 0.55 10.45 87.67 1.33 Branch 70 (20 mmHg) 90-88.8-11.2 DCPD Monomerization 180-210 90 99.26 0.44 0.304-CPD Dimerization 50 99 1.16 98.84--DCPD Distillation 70 (20 mmHg) 94-99.5--Employees of Intellectual Property Office, Ministry of Economic Affairs The Consumer Cooperative printed the CPD in Part C5- of Example 2 as a dimerization in the reactor at 110 ° C until the CPD conversion reached 95%. After that, the reaction mixture was fractionated with two columns. The upper part of one column separates the low-boiling hydrocarbons, and the pure DCPD is separated from the upper part of the second column. The obtained DCPD is used in a high-boiling point solvent such as heptadecane, and the polymerization of hydroquinone or benzoquinone. Page 7 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 577870 A7 B7 V. Description of the invention () Inhibitor and 180-2 Monomerization at a temperature of 10 ° C. After that, at 60 Dimerize the produced CPD at ° C until the conversion rate reaches 92%. Dimerization mixture was distilled to high purity DCPD separable. The above-described method of DCPD made up to 100% purity, the yield as high as 7 5 ° /. . Table 2 shows the results obtained in Example 2. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 2 Phase temperature ° C Conversion rate% Content, Weight% CPD DCPD C5-Carbonitride CPD and iso-pentadiene or 1,3-pentadiene Co-dimer c5-Partial dimerization 110 95 0.72 13.66 81.40 4.22 70 (20 mmHg) 93.5-83.8-16.2 DCPD Monomerization 180-200 88 86.44 3.48 5.8 4.16 CPD Dimerization 60 92 3.36 96.21 0.33 -DCPD Distillation 70 (20 mmHg) 97-99.5--(Please read the precautions on the back before filling this page) The paper size applies to China National Standard (CNS) A4 (210X297 mm)