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KR20020034816A - Production method of a highly pure dicyclopentadiene - Google Patents

Production method of a highly pure dicyclopentadiene Download PDF

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KR20020034816A
KR20020034816A KR1020000078959A KR20000078959A KR20020034816A KR 20020034816 A KR20020034816 A KR 20020034816A KR 1020000078959 A KR1020000078959 A KR 1020000078959A KR 20000078959 A KR20000078959 A KR 20000078959A KR 20020034816 A KR20020034816 A KR 20020034816A
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dicyclopentadiene
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dcpd
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누룰리나엘레나발렌티노브나
솔로비바나탈리아보리스브나
사무일로브야코브드미트리비치
리아쿠모비치알렉산더그리고리비치
레카레바발렌티나스테파노브나
박윤석
이기화
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삼성종합화학주식회사
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
    • C07C13/15—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentadiene ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/605—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system
    • C07C13/61—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system with a bridged indene ring, e.g. dicyclopentadiene
    • 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
    • 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
    • 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

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Abstract

본 발명은 수지 및 노르보넨 유도체들의 제조에 사용될 수 있는, 탄화수소 열분해에 의해 생성되는 C5-유분으로부터 고순도 디시클로펜타디엔의 제조방법에 관한 것으로, 다음의 단계들을 포함한다: 탄화수소 열분해에 의해 생성되는 C5-유분을 50∼110℃의 온도로 가열하여, 상기 C5-유분에 포함되어 있는 시클로펜타디엔을 95%의 전환율로 다이머화하여, 다이머화 혼합물을 얻는 단계; 분별증류에 의해 상기 다이머화 혼합물로부터 순수한 디시클로펜타디엔을 분리하는 단계; 고비점 용매 및 중합방지제의 존재하에 180∼210℃의 온도에서 상기 순수한 디시클로펜타디엔을 모노머화하여, 모노머화된 혼합물을 얻는 단계; 분별증류에 의해 상기 모노머화된 혼합물로부터 순수한 시클로펜타디엔을 분리하는 단계; 상기 순수한 시클로펜타디엔을 50∼110℃의 온도로 가열하여, 90∼99%의 전환율로 다이머화하여, 디시클로펜타디엔이 풍부한 유출물을 형성하는 단계; 및 정류에 의해 상기 디시클로펜타디엔이 풍부한 유출물로부터 최소한 99.5% 의 고순도를 갖는 디시클로펜타디엔을 분리하는 단계.The present invention relates to a process for the preparation of high purity dicyclopentadiene from C 5 -oil produced by hydrocarbon pyrolysis, which can be used for the preparation of resins and norbornene derivatives, comprising the following steps: heating the oil to a temperature of 50~110 ℃, the C 5 - - C 5 is a cyclopentadienyl that is included in the oil by dimerization with 95% conversion, obtaining the dimerization mixture; Separating pure dicyclopentadiene from the dimerization mixture by fractional distillation; Monomerizing the pure dicyclopentadiene at a temperature of 180-210 ° C. in the presence of a high boiling point solvent and an antipolymerizing agent to obtain a monomerized mixture; Separating pure cyclopentadiene from the monomerized mixture by fractional distillation; Heating the pure cyclopentadiene to a temperature of 50-110 ° C. and dimerizing at a conversion of 90-99% to form a dicyclopentadiene-rich effluent; And separating dicyclopentadiene having a high purity of at least 99.5% from the dicyclopentadiene rich effluent by rectification.

Description

고순도 디시클로펜타디엔의 제조방법{Production method of a highly pure dicyclopentadiene}Production method of a highly pure dicyclopentadiene

본 발명은 석유화학 공정에서 얻어지는 탄화수소 열분해에 의해 생성되는 C5-유분으로부터 고순도 디시클로펜타디엔(이하, "DCPD"라 함)을 제조하는 방법에 관한 것으로, 보다 상세하게는 기능화된 에틸렌-프로필렌 공중합체, DCPD 중합체 및 노르보넨(norbornene) 유도체의 생산에 사용할 수 있는 98.5% 이상의 순도를 가지는 고순도 디시클로펜타디엔의 제조방법에 관한 것이다.The present invention relates to a process for producing high purity dicyclopentadiene (hereinafter referred to as "DCPD") from C 5 -oil produced by hydrocarbon pyrolysis obtained in petrochemical processes, more specifically functionalized ethylene-propylene A method for the preparation of high purity dicyclopentadiene having a purity of at least 98.5% which can be used for the production of copolymers, DCPD polymers and norbornene derivatives.

독일특허 제2,334,633호에는 시클로펜타디엔(CPD)을 포함하는 C5-유분의 다이머화(dimerization)에 의해 순수한 DCPD을 제조하는 방법이 개시되어 있다. 상기 방법에서, 순수한 DCPD는 CPD의 다이머화후 생성물중 저비점 혼합물을 톨루엔 존재하에 증류(distillation)에 의하여 제거하므로써 얻어진다. 그러나, 상기 방법에 의해 생산된 DCPD는 낮은 순도 때문에 추가적인 정제 없이는 사용이 제한적이다. 상기 방법에 의하면, 저비점 혼합물만이 분리되므로, DCPD의 끓는 점과 거의 유사한 끓는 점을 갖는 이소프렌(isoprene) 또는 피페릴렌(piperylene)과 CPD의 코다이머(co-dimer)를 분리하기는 어렵다. 따라서, 상기 방법으로 생산된 DCPD의 최대 순도는 겨우 85% 정도에 불과하다. 기능화된 에틸렌-프로필렌 공중합체, DCPD 중합체 및 노르보넨 유도체의 생산을 위해 사용되는 DCPD는 98.5% 이상의 순도가 요구되므로, 상기의 방법에 의해 생산된 DCPD는 상기 목적으로 사용될 수 없다.German Patent No. 2,334,633 discloses the preparation of pure DCPD by dimerization of a C 5 -oil comprising cyclopentadiene (CPD). In this method, pure DCPD is obtained by distillation of the low boiling mixture in the product after dimerization of CPD in the presence of toluene. However, the DCPD produced by this method is of limited use without further purification due to its low purity. According to this method, since only a low boiling point mixture is separated, it is difficult to separate isoprene or piperylene and co-dimer of CPD having a boiling point almost similar to that of DCPD. Thus, the maximum purity of the DCPD produced by this method is only about 85%. Since DCPD used for the production of functionalized ethylene-propylene copolymers, DCPD polymers and norbornene derivatives requires a purity of at least 98.5%, DCPD produced by the above method cannot be used for this purpose.

CPD와 이소프렌 또는 피페릴렌의 코다이머화 속도가 CPD의 다이머화 속도보다 상당히 느리기 때문에, 증류후의 DCPD의 모노머화(monomerization)에 의해 생산된 비교적 순수한 CPD를 다이머화하므로써 DCPD의 순도를 높일 수 있다. 미국특허 제3,772,396호에서는 상기 방법에 의해 DCPD의 순도를 99%까지 높일 수 있는 방법이 개시되어 있다. 그러나, 상기 방법은 DCPD의 증기 상(vapor phase) 크랙킹(cracking, 열분해)시에, 파이프 및 냉각기를 막는 많은 양의 코크스(coke) 물질이 생성되기 때문에 조작에 있어 문제점이 있다.Since the rate of codimerization of CPD and isoprene or piperylene is considerably slower than that of CPD, the purity of DCPD can be increased by dimerizing relatively pure CPD produced by monomerization of DCPD after distillation. US Patent No. 3,772, 396 discloses a method for increasing the purity of DCPD by 99% by the above method. However, the method is problematic in operation because a large amount of coke material is produced which blocks the pipes and the cooler during vapor phase cracking of the DCPD.

한편, 러시아 특허 제2,059,595호는 탄화수소 열분해에 의해 생산되는 C5-유분으로부터 순수한 DCPD를 생산하는 방법을 개시하고 있다. 상기 방법은 다음의 공정을 포함한다. 첫번째 단계에서, C5-유분의 다이머화에 의하여 DCPD를 생성한 후 생성물중 저비점의 탄화수소 화합물을 증류에 의해 제거하여 순순한 DCPD를 제조한다. 두번째 단계에서, 상기 순수한 DCPD의 크랙킹에 의해 CPD를 생산한 후 정류(rectification)에 의하여 순수한 CPD를 제조한다. 마지막 단계로, 두번째 단계에서 생성된 순수한 CPD를 다시 DCPD로 다이머화하고, 다이머화한 혼합물을 정류하여 고순도 DCPD를 제조한다. 상기 방법에서, C5-유분은 110∼135℃에서 다이머화하고, DCPD는 300∼370℃의 온도, 0.16MPa의 압력의 수증기의 매질내에서 모노머화한다. 상기 모노머화 생성물은 140∼300℃의 온도의 두개의 정류 컬럼을 통해 정류되어, 순수한 CPD를 분리하게 된다. 상기 방법으로 얻어진 CPD의 최대 순도는 94%이다.On the other hand, Russian Patent No. 2,059,595 discloses a process for producing pure DCPD from C 5 -oil produced by hydrocarbon pyrolysis. The method includes the following steps. In the first step, DCPD is generated by dimerization of the C 5 -oil, followed by distillation of the low boiling hydrocarbon compound in the product to produce a pure DCPD. In the second step, the CPD is produced by cracking the pure DCPD and then pure CPD is prepared by rectification. In the last step, the pure CPD generated in the second step is dimerized back to DCPD, and the dimerized mixture is rectified to prepare high purity DCPD. In this process, the C 5 -oil is dimerized at 110-135 ° C. and the DCPD is monomerized in a medium of steam at a temperature of 300-370 ° C. and a pressure of 0.16 MPa. The monomerization product is rectified through two rectification columns at a temperature of 140-300 ° C. to separate pure CPD. The maximum purity of CPD obtained by this method is 94%.

이상의 러시아 방법은 일반적인 문헌에 나타나 있는, C5-유분을 135℃에서 다이머화한다는 내용과 일치한다(Vostrikova V.N., Chernikh S.P., Grigoriev A.A., "석유화학으로부터 CPD 및 DCPD-유기합성을 위한 전망있는 원료물질", CNITENeftekhim, 1984, p.7), 그러나, 상기 방법은 1) DCPD의 낮은 순도, 2) 방법의 복잡성 및 3) 고 에너지 소비와 같은 문제점을 안고 있다.The above Russian method is consistent with the dimerization of C 5 -oil at 135 ° C., which is shown in the general literature (Vostrikova VN, Chernikh SP, Grigoriev AA, "Prospective Raw Materials for CPD and DCPD-Organic Synthesis from Petrochemicals) Material ", CNITENeftekhim, 1984, p. 7), however, the method suffers from problems such as 1) low purity of DCPD, 2) complexity of the method and 3) high energy consumption.

본 발명에서는 새로운 최적의 반응 조건의 적용에 의해서 상기의 종래기술이 안고 있는 문제점들을 모두 해결할 수 있었다. 본 발명의 목적은 DCPD의 순도를 증가시키며, 생산 공정을 단순화 할 수 있고, 에너지 소비를 감소시킬 수 있는, 고순도 디시클로펜타디엔의 제조방법을 제공하는 것이다.In the present invention, all of the problems of the prior art can be solved by applying a new optimal reaction condition. It is an object of the present invention to provide a process for the preparation of high purity dicyclopentadiene, which can increase the purity of DCPD, simplify the production process and reduce energy consumption.

본 발명의 고순도 DCPD의 제조방법은 다음의 단계들을 포함한다; 1) 탄화수소의 열분해에 의해 생산되는 C5-유분을 가열하므로써 상기 C5-유분내의 CPD를 다이머화하여 다이머화 혼합물을 형성하는 단계; 2) 분별증류(fractionation)에 의해 상기 다이머화 혼합물로부터 순수한 DCPD를 분리하는 단계; 3) 순수한 DCPD를 모노머화하여 모노머화된 혼합물을 형성하는 단계; 4) 분별증류에 의해 상기 모노머화된 혼합물로부터 순수한 CPD를 분리하는 단계; 5) 순수한 CPD를 다이머화하여 디시클로펜타디엔이 풍부한 유출물을 형성하는 단계; 6) 정류(rectification)에 의해 상기 디시클로펜타디엔이 풍부한 유출물로부터 고순도의 DCPD를 얻는 단계.The preparation method of high purity DCPD of the present invention includes the following steps; 1) C 5 which is produced by pyrolysis of hydrocarbons, wherein the C 5 by heating the oil-to the dimer in the CPD fraction screen forming a dimerization mixture; 2) separating pure DCPD from the dimerization mixture by fractionation; 3) monomerizing the pure DCPD to form a monomerized mixture; 4) separating pure CPD from the monomerized mixture by fractional distillation; 5) dimerizing pure CPD to form a dicyclopentadiene rich effluent; 6) obtaining high purity DCPD from the dicyclopentadiene rich effluent by rectification.

상기한 본 발명의 방법에서, 단계 1)의 C5-유분내의 CPD의 다이머화는 40∼150℃, 바람직하게는 50∼135℃, 더욱 바람직하게는 50∼110℃에서 전환율이 95%에 달할 때까지 수행되고, 단계 3)의 순수한 DCPD의 모노머화는 고비점 용매, 바람직하게는 헵타데칸(heptadecane) 및 중합방지제, 바람직하게는 하이드로퀴논 (hydroquinone) 또는 벤조퀴논 또는 이들의 혼합물의 존재하에 160∼250℃, 바람직하게는 180∼210℃에서 수행된다. 그리고, 단계 5)의 순수한 CPD의 다이머화는 40∼150℃, 바람직하게는 50∼135℃, 더욱 바람직하게는 50∼60℃에서 전환율이 90∼99%가 될때까지 수행된다.In the process of the present invention described above, the dimerization of CPD in the C 5 -oil in step 1) may reach 95% conversion at 40-150 ° C., preferably 50-135 ° C., more preferably 50-110 ° C. Monomeric polymerization of pure DCPD in step 3) is carried out in the presence of a high boiling point solvent, preferably heptadecane and an anti-polymerizing agent, preferably hydroquinone or benzoquinone or mixtures thereof. It is carried out at ˜250 ° C., preferably 180 to 210 ° C. The dimerization of the pure CPD in step 5) is carried out at 40 to 150 ° C, preferably 50 to 135 ° C, more preferably 50 to 60 ° C until the conversion is 90 to 99%.

본 발명에 의하면, DCPD의 순도 수준을 99.5∼100%까지 올릴수 있고, 공정 단계의 수가 적어지며, 에너지 소비가 낮아진다.According to the present invention, the purity level of DCPD can be raised from 99.5 to 100%, the number of process steps is reduced, and the energy consumption is low.

본 발명에서는, 25∼70℃의 끓는 점(boiling temperature)을 갖는 C5-유분 및 하기 표 1의 조성물이 원료로 사용된다.In the present invention, a C 5 -oil having a boiling temperature of 25 to 70 ° C. and the composition of Table 1 below are used as raw materials.

표 1Table 1

화합물compound 함량(중량%)Content (% by weight) 시클로펜탄Cyclopentane 4.3∼10.34.3-10.3 이소펜탄Isopentane 6.6∼12.66.6 to 12.6 N-펜탄N-pentane 5.9∼15.95.9 to 15.9 펜텐-1Pentene-1 2.2∼4.22.2 to 4.2 2-메틸부텐-12-methylbutene-1 3.9∼7.93.9 to 7.9 2-메틸부텐-22-methylbutene-2 2.7∼4.72.7 to 4.7 펜텐-2(시스- 및 트랜스-)Pentene-2 (cis- and trans-) 2.8∼4.82.8 to 4.8 피페릴렌(시스- 및 트랜스-)Piperylene (cis- and trans-) 12.8∼20.812.8-20.8 이소프렌Isoprene 10.9∼22.910.9 to 22.9 DCPD/CPDDCPD / CPD 9.4∼17.49.4 to 17.4 시클로펜텐Cyclopentene 2.5∼3.52.5 to 3.5 "고비점 혼합물"(C6이상)"High boiling point mixture" (C 6 or higher) 2.5∼6.52.5 to 6.5

이하 본 발명을 하기의 실시예를 통하여 상세히 설명한다. 그러나 하기 실시예는 본 발명을 설명하기 위하여 제공되는 것일 뿐, 본 발명의 기술적 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in detail through the following examples. However, the following examples are merely provided to illustrate the present invention, but do not limit the technical scope of the present invention.

실시예 1Example 1

CPD의 전환율이 약 95%에 도달할 때까지, 50℃의 반응기내에서 C5-유분내의 CPD를 다이머화하였다. 그 후, 반응혼합물을 두개의 컬럼으로 분별증류를 실시하여, 처음 컬럼의 윗부분으로부터 저비점의 탄화수소들을 분리하고, 둘째 컬럼의 윗부분으로부터는 순수한 DCPD를 분리하였다. 제조된 순수한 DCPD는 고비점 용매인 헵타데칸 존재하에 하이드로퀴논을 중합방지제로 사용하여 180∼210℃에서 모노머화 반응을 수행하였다. 모노머화 반응에 의하여 생성된 CPD를 전환율이 99%에 도달할 때까지 50℃에서 다이머화하였다. 다이머화된 혼합물을 정류 컬럼으로 정류하여, 고순도 DCPD를 분리하였다. 이와 같은 방법으로 99.5% 이상의 순도를 갖는 DCPD를 77%의 수득율로 제조하였다. 실시예 1의 결과를 표 2에 나타내었다.The CPD in the C 5 -oil was dimerized in the reactor at 50 ° C. until the conversion of CPD reached about 95%. The reaction mixture was then fractionally distilled into two columns to separate low boiling hydrocarbons from the top of the first column and pure DCPD from the top of the second column. The pure DCPD prepared was subjected to a monomerization reaction at 180 to 210 ° C. using hydroquinone as a polymerization inhibitor in the presence of a high boiling point heptadecane. CPD produced by the monomerization reaction was dimerized at 50 ° C. until the conversion reached 99%. The dimerized mixture was rectified with a rectification column to separate high purity DCPD. In this way DCPD having a purity of 99.5% or more was prepared in a yield of 77%. The results of Example 1 are shown in Table 2.

표 2TABLE 2

단계step 온도(℃)Temperature (℃) 전환율(%)% Conversion 함량(중량%)Content (% by weight) CPDCPD DCPDDCPD C5탄화수소C 5 hydrocarbon 이소프렌 및 피페릴렌과 DCPD의 코다이머Isoprene and Piperylene and Codomers of DCPD C5-유분 다이머화C 5 -oil dimerization 5050 9595 0.550.55 10.4510.45 87.6787.67 1.331.33 분별증류Fractional distillation 70(20mmHg)70 (20 mmHg) 9090 -- 88.888.8 -- 11.211.2 DCPD 모노머화DCPD Monomerization 180∼210180-210 9090 99.2699.26 0.440.44 0.3040.304 -- CPD 다이머화CPD Dimerization 5050 9999 1.161.16 98.8498.84 -- -- DCPD의 정류DCPD Rectification 70(20mmHg)70 (20 mmHg) 9494 -- 99.599.5 -- --

실시예 2Example 2

CPD의 전환율이 약 95%에 도달할 때까지, 110℃의 반응기내에서 C5-유분내의 CPD를 다이머화하였다. 그 후, 반응혼합물을 두개의 컬럼으로 분별증류를 실시하여,처음 컬럼의 윗부분으로부터 저비점의 탄화수소들을 분리하고, 둘째 컬럼의 윗부분으로부터는 순수한 DCPD를 분리하였다. 제조된 DCPD는 고비점 용매로서 헵타데칸 및 중합방지제로서 하이드로퀴논 또는 벤조퀴논의 존재하에 180∼210℃에서 모노머화 하였다. 그 후, 전환율이 92%에 도달할 때까지 60℃에서 제조된 CPD를 다이머화하였다. 다이머화된 혼합물을 정류 컬럼으로 정류하여, 고순도 DCPD를 분리하였다. 이와 같은 방법으로 거의 100%의 순도를 갖는 DCPD를 75%의 수득율로 제조하였다. 실시예 2의 결과를 표 3에 나타내었다.The CPD in the C 5 -oil was dimerized in a reactor at 110 ° C. until the conversion of CPD reached about 95%. The reaction mixture was then fractionally distilled into two columns to separate low boiling hydrocarbons from the top of the first column and pure DCPD from the top of the second column. The prepared DCPD was monomerized at 180 to 210 ° C in the presence of heptadecane as a high boiling point solvent and hydroquinone or benzoquinone as an polymerization inhibitor. Thereafter, the CPD prepared at 60 ° C. was dimerized until the conversion reached 92%. The dimerized mixture was rectified with a rectification column to separate high purity DCPD. In this way DCPD having a purity of nearly 100% was prepared at a yield of 75%. The results of Example 2 are shown in Table 3.

표 3TABLE 3

단계step 온도(℃)Temperature (℃) 전환율(%)% Conversion 함량(중량%)Content (% by weight) CPDCPD DCPDDCPD C5탄화수소C 5 hydrocarbon 이소프렌 및 피페릴렌과 DCPD의 코다이머Isoprene and Piperylene and Codomers of DCPD C5-유분 다이머화C 5 -oil dimerization 110110 9595 0.720.72 13.6613.66 81.4081.40 4.224.22 분별증류Fractional distillation 70(20mmHg)70 (20 mmHg) 93.593.5 -- 83.883.8 -- 16.216.2 DCPD 모노머화DCPD Monomerization 180∼210180-210 8888 86.4486.44 3.483.48 5.85.8 4.164.16 CPD 다이머화CPD Dimerization 6060 9292 3.363.36 96.2196.21 0.330.33 -- DCPD의 정류DCPD Rectification 70(20mmHg)70 (20 mmHg) 9797 -- 99.599.5 -- --

이상에서 알 수 있는 바와 같이, 본 발명의 방법에 의하면 간단한 공정에 의하여 고순도의 DCPD를 제조할 수 있으며, 에너지 소비를 줄일 수 있다.As can be seen from the above, according to the method of the present invention it is possible to manufacture a high purity DCPD by a simple process, it is possible to reduce the energy consumption.

Claims (6)

다음의 단계들을 포함하는 것을 특징으로 하는, 탄화수소 열분해에 의해 생성되는 C5-유분으로부터의 고순도 디시클로펜타디엔의 제조방법:A process for the preparation of high purity dicyclopentadiene from C 5 -oil produced by hydrocarbon pyrolysis, comprising the following steps: 1) 탄화수소 열분해에 의해 생성되는 C5-유분을 40∼150℃의 온도로 가열하여, 95%까지의 전환율에 도달시까지 C5-유분내에 포함되어 있는 시클로펜타디엔을 다이머화하여, 다이머화 혼합물을 형성하는 단계;1) The C 5 -oil produced by hydrocarbon pyrolysis is heated to a temperature of 40 to 150 ° C, and dimerization is carried out by dimerizing the cyclopentadiene contained in the C 5 -oil until the conversion rate reaches 95%. Forming a mixture; 2) 분별증류에 의해 상기 다이머화 혼합물로부터 순수한 디시클로펜타디엔을 분리하는 단계;2) separating pure dicyclopentadiene from the dimerization mixture by fractional distillation; 3) 상기 순수한 디시클로펜타디엔을 고비점 용매 및 중합방지제의 존재하에 160∼250℃의 온도에서 모노머화하여, 모노머화된 혼합물을 형성하는 단계;3) monomerizing the pure dicyclopentadiene at a temperature of 160-250 ° C. in the presence of a high boiling point solvent and an antipolymerizing agent to form a monomerized mixture; 4) 분별증류에 의해 상기 모노머화된 혼합물로부터 순수한 시클로펜타디엔을 분리하는 단계;4) separating pure cyclopentadiene from the monomerized mixture by fractional distillation; 5) 상기 순수한 시클로펜타디엔을 40∼150℃의 온도로 가열하여, 90∼99%의 전환율로 다이머화하여, 디시클로펜타디엔이 풍부한 유출물을 형성하는 단계; 및5) heating the pure cyclopentadiene to a temperature of 40-150 ° C., dimerizing at a conversion of 90-99% to form a dicyclopentadiene-rich effluent; And 6) 정류에 의해 상기 디시클로펜타디엔이 풍부한 유출물로부터 최소한 99.5%의 순도를 갖는 고순도 디시클로펜타디엔을 분리하는 단계.6) separating the high purity dicyclopentadiene having a purity of at least 99.5% from the dicyclopentadiene rich effluent by rectification. 제1항에 있어서, 상기 1) 단계의 다이머화는 50∼110℃의 온도에서 행하는것을 특징으로 하는 고순도 디시클로펜타디엔의 제조방법.The method for producing high purity dicyclopentadiene according to claim 1, wherein the dimerization of step 1) is performed at a temperature of 50 to 110 ° C. 제1항에 있어서, 상기 3) 단계의 모노머화는 180∼210℃의 온도에서 행하는 것을 특징으로 하는 고순도 디시클로펜타디엔의 제조방법.The method for producing high purity dicyclopentadiene according to claim 1, wherein the monomerization of step 3) is performed at a temperature of 180 to 210 ° C. 제1항에 있어서, 상기 3) 단계의 고비점 용매는 헵타데칸인 것을 특징으로 하는 고순도 디시클로펜타디엔의 제조방법.The method of claim 1, wherein the high boiling point solvent of step 3) is heptadecane. 제1항에 있어서, 상기 3) 단계의 중합방지제는 하이드로퀴논, 벤조퀴논 또는 이들의 혼합물인 것을 특징으로 하는 고순도 디시클로펜타디엔의 제조방법.The method of claim 1, wherein the polymerization inhibitor of step 3) is hydroquinone, benzoquinone or a mixture thereof. 제1항에 있어서, 상기 5) 단계의 다이머화는 50∼60℃의 온도에서 행하는 것을 특징으로 하는 고순도 디시클로펜타디엔의 제조방법.The method for producing high purity dicyclopentadiene according to claim 1, wherein the dimerization of step 5) is performed at a temperature of 50 to 60 ° C.
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