KR20150144650A - Pure Tricyclopentadiene and Method of Preparing the Same - Google Patents

Abstract

The present invention relates to pure tricyclopentadiene and a method for preparing the same. More specifically, the present invention relates to pure tricyclopentadiene which can be effectively used in various fields, such as a packaging material, a DVD material, an optical film, a copper clad laminate, etc., by preventing a side reaction and gelation generated during polymerization by easily removing pentacyclo[9.2.1.1^(4,7.)0^(2,10).0^(3,8)]pentadecane-5,12-diene, which generates the side reaction and gelation during the polymerization, with a simple method using fractional distillation; and by manufacturing a cycloolefin polymer compound having excellent dielectric properties and a high heat resisting property by introducing the pure tricyclopentadiene, from which pentacyclo[9.2.1.1^(4,7).0^(2,10).0^(3,8)]pentadecane-5,12-diene is removed, into a cycloolefin monomer. The present invention also relates to a method for preparing the pure tricyclopentadiene.

Description

Pure tricyclopentadiene and a process for producing the same are disclosed.

The present invention relates to a pure tricyclopentadiene and a process for producing the same, and more particularly, to a process for producing a cyclic olefin-based polymer compound by reacting pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component is removed, and to a process for producing the tricyclopentadiene.

Among the products of naphtha cracking, those having less than 4 carbon atoms are separated and purified and used for the petrochemical industry. However, C5 oil with 5 carbon atoms is mainly used as fuel for combustion, and only a part of it is separated and purified from some companies and used industrially. Efforts to isolate and refine C5 oil to produce high value-added chemicals have been made.

In particular, tricyclopentadiene (TCPD) can be prepared by heating a dicyclopentadiene (DCPD) (A), which accounts for a large portion of the C5 fraction of naphtha cracking, as shown in Scheme 1 below, The cyclopentadiene (B) is produced by the Alder reaction and the cyclopentadiene (B) and the dicyclopentadiene (A) can easily be obtained by the Diels-Alder reaction. The tricyclopentadiene tricyclopentadiene (TCPD) has high heat resistance due to its high glass transition temperature and low dielectric constant.

[Reaction Scheme 1]

However, despite such a high interest and possibility, tricyclopentadiene is produced by cyclopentadiene (B) reacting with a double bond of a dicyclopentadiene (A) hexagonal double bond, while cyclopentadiene ) Is subjected to a Diels-Alder reaction with a double bond of a dicyclopentadiene (A) pentagon to obtain a pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component (D ) Are produced and cause gelation and side reaction in the polymerization process. Is about 20 to 30% by weight. Therefore, the application of tricyclopentadiene is limited and it has not been applied to the commercialization process.

Accordingly, pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene components causing gelling and side reactions from the tricyclopentadiene isomer mixture are removed at present and pure Is an important factor in the commercialization of tricyclopentadiene.

In recent years, a recrystallization method has been introduced in which tricyclopentadiene prepared to purely isolate only the main isomer of tricyclopentadiene is dissolved in ethanol and then separated into solubility differences according to temperature (Hyeong Cheol Park, Ahreum Kim and Bun Yeoul Lee, Journal of Polymer Science . Vol. 49, 938-944 (2011)), there is a problem in that a large amount of ethanol solvent should be used in comparison with the product, and the efficiency is low due to the drawback that the yield is greatly decreased and the facility investment is too much to be applied to the commercialization process.

The main object of the present invention is to provide a process for producing a cyclic olefin-based polymer compound, which comprises reacting a pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecen-5,12- The diene component is removed or a pure tricyclopenta [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component containing less than 10% by weight of pentacyclo [ Diene, and pure tricyclopentadiene produced by the above-mentioned production method.

The present invention also provides a process for producing a cyclic olefin-based polymer compound capable of stably producing a cyclic olefin-based polymer compound through ring-opening polymerization of the produced pure tricyclopentadiene without side reaction and gelation.

The present invention also provides a ring-opening polymer containing tricyclopentadiene, which has excellent dielectric properties and high heat resistance and is useful for electronic materials, and a copper-clad laminate using the same.

In order to accomplish the above object, an embodiment of the present invention is a method for producing a cyclopentadiene, comprising: (a) obtaining a cyclopentadiene by a dicyclopentadiene through a reverse-Diels-Alder reaction and then reacting the obtained cyclopentadiene and dicyclopentadiene To obtain a tricyclopentadiene isomer mixture containing pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecen-5,12-diene via a Diels-Alder reaction; And (b) a tricyclopentadiene isomer mixture containing the obtained pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene was subjected to fractional distillation under reduced pressure to give tri ^{Wherein at} least 90% by weight of pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene is removed in an amount of at least 90% by weight based on the total weight of the cyclopentadiene isomer mixture. Tricyclopentadiene. ≪ / RTI >

In a preferred embodiment of the present invention, in the step (b), the tricyclopentadiene isomer mixture is injected into the distillation column, and then the lowermost temperature of the distillation column is adjusted to 150 to 200 ° C, the uppermost temperature of the distillation column And the distillation column is controlled to have a pressure of 5 to 20 mmHg.

In one preferred embodiment of the present invention, the reflux ratio of the reduced pressure fractionation in the step (b) is 2 to 8. [

In a preferred embodiment of the present invention, the step (b) may further include the step of further distilling the obtained fraction in one or more additional distillation columns after the fractional distillation under reduced pressure.

Another embodiment of the present invention provides pure tricyclopentadiene prepared by the above process.

Another embodiment of the present invention provides a process for producing a cyclic olefinic high molecular compound, which comprises ring-opening polymerization of a cyclic olefin monomer containing the pure tricyclopentadiene.

Another embodiment of the present invention provides a cyclic olefin-based polymer compound produced by the above process.

In still another embodiment of the present invention, the cyclic olefin-based polymer compound has a weight average molecular weight of 1,000 to 15,000 g / mol and a glass transition temperature of 160 ° C or more.

In another preferred embodiment of the present invention, the cyclic olefin-based polymer compound has a dielectric constant of 4.0 or less and a dielectric loss tangent of 0.002 or less at 1 GHz.

Another embodiment of the present invention provides a copper-clad laminate comprising the cyclic olefin-based polymer compound.

According to the present invention, the pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component which causes gelation and side reactions in the polymerization process using fractional distillation can be obtained by a simple method by easily removed, as well as to avoid side reactions and gelation is caused in the polymerization reaction, penta-cyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8] penta-decene -5,12- diene It is possible to produce a cyclic olefinic polymer compound having excellent dielectric properties and high heat resistance by introducing the pure tricyclopentadiene from which the component has been removed as a cyclic olefin monomer so as to produce a cyclic olefin polymer compound having various properties such as a packaging material, Can be usefully used in the field.

1 is a schematic view showing a process for producing pure tricyclopentadiene according to an embodiment of the present invention.
2 is a graph of gas chromatography measurement of the tricyclopentadiene isomer mixture before (a) and (b) after reduced pressure fractional distillation.
3 is a ¹ H-NMR measurement graph of pure tricyclopentadiene obtained in Example 1. Fig.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

Throughout the specification, 'pure tricyclopentadiene' does not contain pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene, or contains 10% Means a tricyclopentadiene containing pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecen-5,12-diene at a level of less than about ¹⁰ %

According to one aspect of the present invention, there is provided a process for producing a cyclopentadiene, which comprises: (a) obtaining a cyclopentadiene from a dicyclopentadiene through a reverse-Diels-Alder reaction and then reacting the obtained cyclopentadiene and a dicyclopentadiene with a pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecen-5,12-diene to obtain a tricyclopentadiene isomer mixture; And (b) subjecting the resulting tricyclopentadiene isomer mixture to reduced pressure fractional distillation to obtain a mixture of pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] penta Decene-5,12-diene is removed in an amount of 90% by weight or more based on the total amount of the tricyclopentadiene.

More specifically, the present invention relates to a process for the preparation of pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5 from a tricyclopentadiene isomer mixture prepared from dicyclopentadiene (DCPD) , The isomer of the 12-diene component was easily removed using reduced pressure fractional distillation and the pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecen-5,12-diene was removed When ring-opening olefinic monomers are ring-opened with pure tricyclopentadiene, cyclic olefinic polymer compounds can be stably produced without gelation and side reactions, and pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^{3 , 8} ] cyclic olefin-based polymer having excellent dielectric properties and high heat resistance can be produced by using pure tricyclopentadiene from which the pentadecene-5,12-diene component has been removed as a cyclic olefin-based monomer.

The process for producing pure tricyclopentadiene according to the present invention is a process for producing cyclopentadiene (B) by reacting dicyclopentadiene (A) with cyclopentadiene (B) through dicyclo- The pentadiene (A) is subjected to a Diels-Alder reaction to obtain a tricyclopentadiene isomer mixture [(C) and (D)], and then the tricyclopentadiene isomer mixture is reacted with pentacyclo [9.2. 1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene (D) was removed to give pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] (C) component is contained in an amount of 90 wt% or more based on the total weight of the tricyclopentadiene isomer mixture (Scheme 2).

[Reaction Scheme 2]

At this time, the Inverse Diels-Alder reaction and the Diels-Alder reaction can be carried out at a temperature of 150 to 200 ° C and 1 to 4 bar for 10 minutes to 24 hours. When the amount is less than the above-mentioned range, the cyclic pentadienes are cracked with cyclopentadiene The reaction does not proceed. If the above conditions are exceeded, the Diels-Alder reaction proceeds continuously, and four or more cyclopentadiene may be synthesized to produce a large number of by-products.

The reaction product produced by such a reaction includes not only a tricyclopentadiene isomer mixture but also unreacted materials such as cyclopentadiene and dicyclopentadiene and side products (byproducts) of heavy materials. As a method for separating the tricyclopentadiene isomer mixture as a target material, a method commonly used in the art can be used, but it is preferable to use the following fractional distillation under reduced pressure.

Decompression fractionation of the reaction product may be carried out by first recovering unreacted materials such as cyclopentadiene and dicyclopentadiene from the reaction product, and then separating and purifying the mixture of the side reaction product and the tricyclopentadiene isomer.

In the reduced pressure fractional distillation method for recovering unreacted products in the reaction product, a reaction product is injected into a first distillation column, and the injected reaction product is distilled at a temperature of 50 to 80 DEG C at the uppermost (low boiling point) High boiling point) temperature and a pressure of 40 to 80 mmHg to recover unreacted cyclopentadiene and dicyclopentadiene through a condenser at the top of the first distillation column, and the unreacted tricyclopentadiene isomer mixture and the unreacted The reactants can be recovered from the bottom of the first distillation column. The recovered unreacted material can be reused or discarded in the Reverse Diels-Alder and Diels-Alder reactions described above. At this time, the reflux ratio in the distillation column (that is, the amount of reflux of distillate in the column / amount of distillate removed) is preferably 1 to 3.

The reaction product from which the unreacted material has been removed by the reduced pressure fractionation distillation is supplied to the second distillation column again, and the supplied reaction product is distilled at a temperature of 140 to 150 ° C (low boiling point), 180-220 ° C And distillation under a pressure of 5 to 15 mm Hg to recover the tricyclopentadiene isomer mixture in the condenser above the second distillation column and the side reaction can be recovered from the bottom of the second distillation column. At this time, the reflux ratio in the distillation column is preferably 1 to 3.

If the temperature is outside the range of the reduced pressure fractionation distillation conditions, separation purification may not be performed properly, or a large amount of by-products may be generated during purification for a long time, resulting in a problem of hardening at room temperature.

The recovered tricyclopentadiene isomer mixture is a mixture of pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecen-5,12-diene and pentacyclo [6.5.1.1 ^3,6 .0 ^2,7. 0 ^9,13 ] ^pentadecene -4,10-diene in a weight ratio of 20-30: ^80-70 , with the tricyclopentadiene isomer mixture recovered without isolation of the isomers thereof When polymerizing with a cyclic olefin-based polymer compound, the polymerization is properly performed due to the pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component which causes gelation and side reactions , The pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component which causes gelation and side reactions is completely removed, or at a level of less than 10% by weight ^Pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component is required to be separated and purified.

However, the penta-cyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene and pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7. 0 ^9,13 ] Since ^pentadecene -4,10-diene is a structural isomer, it is difficult to separate efficiently when purified in simple complete vacuum (0 mmHg).

Therefore, in the present invention, in order to purely separate only pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] ^pentadecene -4,10-diene of tricyclopentadiene from the tricyclopentadiene isomer mixture The reduced pressure fractional distillation method is applied considering the economic aspect.

The pressure-fractionated distillation according to the present invention is characterized in that the tricyclopentadiene isomer mixture is fed to the third distillation column, and then the tricyclopentadiene isomer mixture is fed to the third distillation column in the third distillation column fed with the tricyclopentadiene isomer mixture, (Low boiling point) temperature is controlled to 50 to 100 ° C, preferably 60 to 80 ° C, and the pressure is adjusted to 5 to 20 mmHg, Preferably 10 to 15 mmHg, to recover the pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component in the upper portion of the third distillation column, [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] The ^pentadecene -4,10-diene component can be recovered from the bottom of the third distillation column. At this time, the reflux ratio in the third distillation column is preferably 2 to 8.

If the temperature is outside the range of the reduced pressure fractionation distillation conditions, the purification may not be performed properly, or a large amount of by-products may be generated at the time of refining for a long period of time to cause hardening at room temperature. If the reflux ratio is more than 8, the reflux time is prolonged because of the increase of the reflux liquid, which may result in a problem that the purification efficiency is lowered.

Hereinafter, in order to facilitate understanding of the production process of the pure tricyclopentadiene, a process for producing pure tricyclopentadiene according to an embodiment of the present invention will be described in detail, but the present invention is not limited thereto.

As shown in Figure 1, dicyclopentadiene is fed to the reactor 10 via a feeder 1, and in the reactor 10, the inverse Diels-Alder and Diels-Alder reactions of dicyclopentadiene as described above To produce and discharge reaction products such as unreacted materials, by-products, tricyclopentadiene isomer mixtures, and the like. The discharged reaction product is injected into the first distillation column 20 through the reactant recovery conveyor 2 and the reaction product injected into the first distillation column is subjected to the reduced pressure fractional distillation under the above- Unreacted materials such as dicyclopentadiene, cyclopentadiene and the like are recovered through the unreacted material recovery conveyor 4 in the first distillation column 21 and recovered through the product recovery conveyor 3 in the lower part 22 of the first distillation column The by-product and tricyclopentadiene isomer mixture is recovered.

The thus-recovered by-product and the tricyclopentadiene isomer mixture are injected again into the second column 30, and the mixture of the injected by-product and the tricyclopentadiene isomer is subjected to the pressure fractionation distillation under the above- Product recovery conveyor 6 at the second distillation column top 32 and recover the tricyclopentadiene isomer mixture through the isomeric mixture recycle conveyor 5 of the second distillation column top 31 do.

The recovered tricyclopentadiene isomer mixture is injected again into the third distillation column 40 and the injected tricyclopentadiene isomer mixture is subjected to the reduced pressure fractional distillation under the conditions described above to produce the first The pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component is recovered via the isomer transporter 7 and the lower portion of the third distillation column 42 The pure isomer is recovered via the second isomer feeder (8).

In the present invention, the first, second, and third distillation columns may use columns filled with dividing walls, trays and / or fillers, and the dividing walls are designed to be thermally insulated, The zones can be different depending on the location and structure of the divided zones, and the temperature and pressure can be different from the operating temperature and pressure of the conventionally used distillation column and it is also possible to adjust them appropriately according to the design. In addition, the tray may be provided in the distillation column at 2 to 30 stages in consideration of an efficient aspect. The filler may be a filler commonly used in the art, for example, glass beads, .

In addition, the fraction distilled by the above-described method may be distilled in one or more, preferably 2 to 30, additional distillation columns to increase the purity of the fractions.

The pure tricyclopentadiene thus prepared contains 90% by weight or more of pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] ^pentadecene -4,10-diene in the total isomer weight And the like.

In another aspect of the present invention, there is provided a method for producing a cyclic olefin-based polymer compound and a cyclic olefin-based polymer compound produced by the above-described method, characterized in that the cyclic olefin-based monomer containing the pure tricyclopentadiene is ring- .

The present invention relates to a pure tree containing more than 90% by weight of pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] ^pentadecene -4,10-diene component based on the total weight of isomers as described above Cyclopentadiene is used as a cyclic olefin-based monomer to prepare a cyclic olefin-based polymer compound, it is possible to stably produce a cyclic olefin-based polymer compound having a high glass transition temperature and excellent dielectric properties without side reactions and gelation during ring- have.

At this time, the ring-opening polymerization can be carried out for 30 minutes to 5 hours by introducing a molecular weight regulator, a polymerization catalyst, etc., after preparing a homogeneous solution by dissolving the cyclic olefin monomer in a solvent under inert conditions. The ring-opening polymerization temperature is not particularly limited and may be -10 to 100 ° C, preferably 20 to 80 ° C.

As the cyclic olefin-based monomer, a monomer represented by the formula (1) may be used in addition to pure tricyclopentadiene .

≪ Formula 1 >

In formula (1), R ₅ to R ₈ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, an amine group or -COOR To 20 carbon atoms).

The solvent, the polymerization catalyst, and the molecular weight regulator can be used without restriction as long as they can be used for ring opening metathesis polymerization, a molecular weight regulator and a solvent. . Examples that, polymerization catalyst _{WCl 6, WOCl 4, W (} CO) 6, W (OC 6 H 5) 6, WCl 2 (OC 6 H 5) 4, a tungsten-based compound such as W (CO) _3, ruthenium An organoaluminum compound such as triisobutylaluminum, triethylaluminum, isobutylaluminum dichloride and the like can be used as a co-catalyst for activating the tungsten compound, and as the molecular weight regulator, 1- Butene, 1-hexene, 1-pentene, and the like.

The cyclic olefin polymer thus prepared had a weight average molecular weight of 1,000 to 15,000 g / mol, a glass transition temperature of 160 ° C or more, a dielectric constant of 4.0 or less at 1 GHz and a dielectric loss tangent of 0.002 or less, , It is possible to increase the glass transition temperature of a polymer prepared by polymerizing pure tricyclopentadiene having a large molecular weight and a void volume in the interior of the polymer compound and lower the dielectric constant The use range can be expanded for electronic materials such as a copper-clad laminate.

In another aspect, the present invention relates to a copper-clad laminate comprising the cyclic olefin-based polymer compound.

The copper clad laminate according to the present invention includes the above-mentioned cyclic olefin-based polymer compound in the form of a varnish, which is then impregnated with glass fiber and then dried at 100 to 200 ° C to form a B- Prepregs are produced. At this time, drying means removal of the solvent.

In addition, the present invention is characterized in that a desired number of prepregs are formed into a composite body which overlaps with each other, and then at least one kind of metal foil (preferably copper foil) is stacked and laminated on one or both sides thereof, cm < ^{2 &} gt ;, so that a copper clad laminate for a printed circuit board can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples. It should be noted, however, that the examples are for illustrative purposes only and are not intended to limit the scope of the invention.

< Example  1>

1-1: pure water Tricyclopentadiene  Produce

1 kg of dicyclopentadiene was subjected to a reverse-Diels-Alder reaction at 155 ° C under a pressure of 2 bar for 20 minutes, and the mixture subjected to the reverse-Diels-Alder reaction was subjected to a Diels-Alder reaction at 160 ° C under a pressure of 2 bar for 10 hours To give the reaction product. The obtained reaction product was fed to a first distillation column and subjected to fractional distillation under reduced pressure to collect the unreacted dicyclopentadiene and cyclopentadiene at the top of the first distillation column and recovered by condensation in a condenser operated at -2 ° C , The reaction product from which the dicyclopentadiene and cyclopentadiene had been removed was recovered at the bottom of the first distillation column. At this time, the recovered dicyclopentadiene and cyclopentadiene were analyzed by gas chromatography (Aglient GC 7890A) and found to be 65.6 wt% and 7.1 wt%, respectively, based on the total weight of the reaction products.

The reaction product thus recovered from the dicyclopentadiene and the cyclopentadiene is fed to a second distillation column, and the tricyclopentadiene isomer mixture is collected at the top of the second distillation column by reduced pressure fractional distillation, The reaction product (non-reactant) from which the tricyclopentadiene isomer mixture was removed was collected at the bottom of the second distillation column. At this time, the recovered heavy material and tricyclopentadiene isomer mixture were analyzed by gas chromatography (Aglient GC 7890A) and found to be 4.6 wt% and 22.7 wt%, respectively, based on the total weight of the reaction products.

Further, the recovered tricyclopentadiene isomer mixture was analyzed using gas chromatography (Aglient GC 7890A). As a result, it was found that pentacyclo [9.2.1.1 ^{4.7 2,10.} 0 ^3,8 ] pentadecene-5,12-diene and pure tricyclopentadiene (tricyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] ^pentadecene -4 , 10-diene), respectively.

The recovered tricyclopentadiene isomer mixture is fed to a third distillation column (10-stage tray) and subjected to reduced pressure fractional distillation to obtain pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^{3, 8} ] pentadecene-5,12-diene was collected and recovered by condensation in a condenser operated at 20 ° C, and the remaining tricyclopentadiene was collected at the bottom of the distillation column and recovered. At this time, the recovered pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecen-5,12-diene and pure tricyclopentadiene (tricyclo [6.5.1.1 ^{3,6 2,7.} 0 ^9,13 ] ^pentadecene -4,10-diene) was analyzed by gas chromatography (Aglient GC 7890A), and found to be 90.1% by weight based on the total weight of the tricyclopentadiene isomer mixture, 9.9% by weight.

The pure tricyclopentadiene recovered was analyzed by gas chromatography (Aglient GC 7890A). As a result, as shown in FIG. 2B, pure tricyclopentadiene (tricyclo [6.5.1.1 ^{3 , 6,0 2,7} .0 ^9,13 ] ^pentadecene -4,10-diene).

Details of the size, distillation conditions, etc. corresponding to the first to third distillation columns are shown in Table 1.

The first distillation column Second distillation column Third distillation column Distillation column inner diameter (inch) One One One Height of distillation column (cm) 80 80 30 The first bead filler of the distillation column Filler diameter: 5 mm
Filling height: 5cm Filler diameter: 5 mm
Filling height: 5cm Filler diameter: 5 mm
Filling height: 2cm The second bead filler of the distillation column Filler diameter: 3 mm
Filling height: 15cm Filler diameter: 3 mm
Filling height: 15cm Filler diameter: 3 mm
Filling height: 5cm The third bead filler of the distillation column Filler diameter: 1 mm
Filling height: 40cm Filler diameter: 1 mm
Filling height: 40cm Filler diameter: 1 mm
Filling height: 16cm The fourth bead filler of the distillation column Filler diameter: 3 mm
Filling height: 15cm Filler diameter: 3 mm
Filling height: 15cm Filler diameter: 3 mm
Filling height: 5cm The fifth bead filler of the distillation column Filler diameter: 5 mm
Filling height: 5cm Filler diameter: 5 mm
Filling height: 5cm Filler diameter: 5 mm
Filling height: 2cm tray - - 10 steps The pressure inside the distillation column (mmHg) 60 10 15 Top temperature of distillation column (℃) 60 140 76 The lowest temperature of the distillation column (℃) 150 200 168 Condenser temperature (℃) -2 10 20 Refund Ratio ^* One One 5 Distillation time (hr) 4 6 10

* Reflux ratio = (amount of reflux in purified distillate on top) / (amount released)

For example, if the reflux ratio is 1, 1L of the distillate is refined in the top of the purification tower. 500mL of the purified distillate is refluxed to the refining tower, and the remaining 500mL is discharged to obtain the product.

1-2: Preparation of cyclic olefin-based polymer compound

In Example 1-1, 9.98 g of the pure tricyclopentadiene obtained in the third distillation column and 26.62 g of dicyclopentadiene were dissolved in 330 ml of cyclohexane. Then, 1.27 g of 1-hexene was added thereto, Lt; / RTI &gt; 0.37 ml of 1 M in hexane solution was added to the mixture which had been stirred, stirred for 15 minutes at room temperature, 28 mg of isobutyl alcohol was added, and the mixture was stirred for 15 minutes. After completion of the stirring, 50 mg of WCl ₆ was added to carry out the polymerization. The reaction proceeded in an environment where oxygen and moisture were blocked to less than 1 ppm in the glove box and proceeded for 3 hours at room temperature to obtain 36 g of viscous, light brown liquid oleophilic polymer compound.

< Comparative Example  1>

A cyclic olefin polymer was prepared in the same manner as in Example 1, and a cyclic olefin polymer was prepared using the recovered tricyclopentadiene isomer mixture.

< Example  2 to 3 and Comparative Example  2 to 5>

Cycloolefin-based polymer was prepared in the same manner as in Example 1 except that the cyclic olefin polymer compound was prepared by changing the distillation conditions for the reduced pressure fractionation of the third distillation column as shown in Table 2.

The lowest temperature of the distillation column (℃) Top temperature of distillation column (℃) Distillation column pressure (mmHg) Refund ratio Purity (% by weight) ^Pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene ^Pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] ^pentadecene -4,10-diene Example 1 168 76 15 5 9.9 90.1 Example 2 175 75 10 5 7.0 93.0 Example 3 180 76 10 5 4.8 95.2 Comparative Example 1 - - - - 26.8 73.2 Comparative Example 2 205 112 10 5 18.8 81.2 Comparative Example 3 174 74 40 5 24.2 75.8 Comparative Example 4 169 77 10 One 26.8 73.2 Comparative Example 5 139 45 10 0 26.8 73.2

As shown in Table 2, the purity of the pure tricyclopentadiene obtained in Examples 1 to 3 was 90 wt% or more, while in Comparative Examples 1 to 5, the purity of the pure tricyclopentadiene was less than 82 wt% It was confirmed that the isolation of pure tricyclopentadiene from the tricyclopentadiene isomer mixture was not properly performed.

The following physical properties of the cyclic olefin-based polymer compounds prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were measured and are shown in Table 3.

(1) Measurement of molecular weight and molecular weight distribution

The polystyrene reduced weight average molecular weight, number average molecular weight and z-average molecular weight were measured by gel permeation chromatography (GPC) (PL GPC-220). The cyclic olefin-based polymer to be measured was dissolved in 1,2,4-trichlorobenzene so as to have a concentration of 0.34% by weight, and 200 μl was injected into GPC. The mobile phase of GPC was loaded with 1, 2, 4-trichlorobenzene at a flow rate of 1 mL / min and analysis was performed at 130 ° C. The column was connected in series with one guard column and two PL 5 μm mixed-D columns. The detector was analyzed using a refractive index detector.

(2) Measurement of glass transition temperature (Tg)

And the temperature was raised to 250 ° C in a nitrogen atmosphere at a rate of 10 ° C / min using a differential scanning calorimetry (DSC) apparatus.

(3) Measurement of permittivity

 The dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product were measured under the following conditions using an Agilent impedance analyzer (Agilent E4991A 1 MHz to 3GHz).

Measuring frequency: 1GHz

Measuring temperature: 25 ~ 27 ℃

Measuring humidity: 45 ~ 55%

Measurement sample: thickness 1.5 mm (1.3-1.7 mm)

Mw PDI Tg (占 폚) Dk Df Example 1 10,100 2.0 181 3.48 0.0018 Example 2 11,400 2.1 182 3.61 0.0017 Example 3 10,400 2.1 181 3.54 0.0019 Comparative Example 1 Not measurable Not measurable Not measurable Not measurable Not measurable Comparative Example 2 Not measurable Not measurable Not measurable Not measurable Not measurable Comparative Example 3 Not measurable Not measurable Not measurable Not measurable Not measurable Comparative Example 4 Not measurable Not measurable Not measurable Not measurable Not measurable Comparative Example 5 Not measurable Not measurable Not measurable Not measurable Not measurable

As shown in Table 3, in Examples 1 to 3, the glass transition temperature (Tg) was 181 ° C or more, the dielectric constant (Dk) was 3.61 or less and the dielectric loss tangent (Df) In case of 1 ~ 5, measurement was impossible as gelation occurred in the manufacturing process.

Thus, according to the present invention, the pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component which causes gelation and side reactions in the polymerization process can be easily removed Side reaction and gelation generated in the polymerization reaction can be prevented, and at the same time, the pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene component is removed By introducing the pure tricyclopentadiene as a cyclic olefin monomer, it is possible to produce a cyclic olefin-based polymer compound having excellent dielectric properties and high heat resistance, which is useful for various fields such as packaging materials, DVD materials, optical films, Can be used.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

1: feeder, 2: reactant recovery conveyor, 3: product recovery conveyor, 4: unreacted material recovery conveyor, 5: isomer mixture recovery conveyor, 6: 1 isomer feeder, 8: second isomer feeder, 10: reactor, 20: first distillation column, 21: first distillation column upper portion, 22: first distillation column bottom, 30: second distillation column, 31: 2 upper portion of the distillation column, 32 lower portion of the second distillation column, 40: third distillation column, 41: upper portion of the third distillation column, 42:

Claims (10)

(a) dicyclopentadiene is obtained by cyclodextrin-alder reaction to obtain cyclopentadiene, and then the obtained cyclopentadiene and dicyclopentadiene are reacted with each other to obtain pentacyclo [9.2.1.1 ^4.7 &^Lt; / RTI &gt; ^2,10. 0 ^3,8 ] pentadecen-5,12-diene, to obtain a tricyclopentadiene isomer mixture; And
(b) a tricyclopentadiene isomer mixture containing the obtained pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene is subjected to reduced pressure fractional distillation to obtain tricyclo ^{Wherein at} least 90% by weight of pentacyclo [9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ] pentadecene-5,12-diene is removed in an amount of at least 90% by weight based on the total weight of the pentadiene isomer mixture. &Lt; / RTI &gt; cyclopentadiene.
The method according to claim 1, wherein the decompression fractionation in step (b) is carried out by introducing a tricyclopentadiene isomer mixture into a distillation column, then distilling the mixture at a lowermost temperature of 150-200 ° C, Lt; 0 &gt; C, and the pressure of the distillation column is adjusted to 5 to 20 mmHg, followed by distillation.
The process for producing pure tricyclopentadiene according to claim 2, wherein the reflux ratio of the reduced pressure fractionation is 2 to 8 in the step (b).
The process for producing pure tricyclopentadiene according to claim 2, further comprising the step of further distilling the obtained fraction in the one or more additional distillation columns after the reduced pressure fractional distillation in the step (b) .
A pure tricyclopentadiene produced by the process of any one of claims 1 to 4.
A process for producing a cyclic olefin-based polymer compound, which comprises ring-opening polymerization of a cyclic olefin monomer containing the pure tricyclopentadiene of claim 5.
A cyclic olefin-based polymer compound produced by the production method of claim 6.
The cycloolefin-based polymer compound according to claim 7, wherein the cyclic olefin-based polymer compound has a weight-average molecular weight of 1,000 to 15,000 g / mol and a glass transition temperature of 160 ° C or more.
The cyclic olefin-based polymer compound according to claim 7, wherein the cyclic olefin-based polymer compound has a dielectric constant of 4.0 or less at 1 GHz and a dielectric loss tangent of 0.002 or less.
A copper-clad laminate comprising the cyclic olefin-based polymer compound of claim 7.

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