KR20140004276A - Cycloolefin polymers and method for preparing the same - Google Patents

Abstract

The present invention relates to a cycloolefin polymer compound and a production method of the same, more specifically to a production method of a cycloolefin polymer compound which selectively removes a double bond contained in a hexagon ring of dicyclopentadiene and tricyclopentadiene, and polymerizes the same for preventing the side reaction and gellation generated from producing the cycloolefin polymer compound; and the cycloolefin polymer compound obtained by the production method.

Description

Cycloolefin polymer compound and its manufacturing method {Cycloolefin Polymers and Method for Preparing the Same}

The present invention relates to a cyclic olefin polymer compound and a method for preparing the same, and more particularly, to a cyclic olefin by selectively removing a double bond contained in a hexagonal ring portion of dicyclopentadiene and tricyclopentadiene and polymerizing the same. The present invention relates to a method for producing a cyclic olefin polymer compound capable of preventing side reactions and gelling occurring during the production of a polymer compound and a cyclic olefin polymer compound produced by the method.

Among the products of naphtha cracking, the carbon number of 4 or less is separated and refined to be useful for the petrochemical industry, but most of the C5 oil having 5 carbon atoms is burned and used as fuel, and only some of them are separated and refined and used industrially. Therefore, efforts have been made to produce high value-added chemicals by separating and refining C5-oil.

For example, in the case of the norbornene-based monomer, as shown in Scheme 1, a resin may be prepared by hydrogenation after a ring opening metathesis polymerization (ROMP) reaction (Masahiro Yamazaki, Journal of Molecular Catalysis A: Chemical , 213: 81-87, 2004). The polymer thus obtained is called a cycloolefin polymer (COP). In terms of physical properties, there is a high transparency and a small double cut ratio, and thus, the development of applications for food and pharmaceutical packaging, DVD materials, and optical films for displays is progressing.

[Reaction Scheme 1]

As another example, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro obtained by diels-alder reaction of cyclopentadiene once more with norbornene Large cyclic olefin compounds such as naphthalene (1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphtalene, hereinafter abbreviated as 'DMON') are monomers. Efforts to produce resins by ROMP and hydrogenation are significant (Masahiro Yamazaki, Journal of Molecular Catalysis A: Chemical, 213: 81-87, 2004). However, as shown in Scheme 2, DMON is prepared from dicyclopentadiene in two steps, and the manufacturing process is not easy, so it is very expensive to use as a polymer monomer. Therefore, at present, manufacturing DMON economically is an important factor for commercializing resins based on DMON. The polymer material of Scheme 2 was commercialized by Zeon.

[Reaction Scheme 2]

Zeon, Japan, has produced a linear polymer through a ring opening metathesis polymerization (ROMP) reaction of a 5-6 carbon olefin group of dicyclopentadiene and hydrogenated it, as shown in Scheme 3 below. (Masahiro Yamazaki, Journal of Molecular Catalysis A: Chemical , 213: 81-87, 2004). In this case, it is essential to completely remove the double bond in the resin through a hydrogenation reaction. This resin has the disadvantage that the glass transition temperature is not high.

Scheme 3

Accordingly, in order to solve the problem of low glass transition temperature of the cyclic olefin polymer compound obtained only from the conventional dicyclopentadiene in Korean Patent No. 1135291, dicyclopentadiene and tricyclopentadiene were polymerized. Next, although a cyclic olefin polymer compound has been disclosed through a hydrogenation reaction (Scheme 4), the dicyclopentadiene and tricyclopentadiene are gelled during ring-opening polymerization due to two double bonds of each monomer. Or a side reaction such as in Scheme 5 occurred. This may not only stably proceed the polymerization reaction, but also has a problem that adversely affect the polymer properties (molecular weight, distribution, melt index, etc.).

[Reaction Scheme 4]

[Reaction Scheme 5]

Accordingly, the present inventors have made diligent efforts to solve the problems of the prior art, when selectively removing the double bonds contained in the hexagonal ring portion of dicyclopentadiene and tricyclopentadiene by hydrogenation, and then polymerizing them, It was confirmed that the cyclic olefin polymer compound having a high glass transition temperature could be stably produced without side reaction and gelation, and thus, the present invention was completed.

The main object of the present invention is to provide a cyclic olefin polymer compound that can solve the problem of low glass transition temperature of the cyclic olefin polymer compound obtained only from conventional dicyclopentadiene.

The present invention also provides a method for producing a cyclic olefin polymer compound capable of stably producing a cyclic olefin polymer compound having a high glass transition temperature without side reactions and gelling.

In order to achieve the above object, the present invention provides a cyclic olefin polymer compound comprising a repeating unit represented by the following formula (1).

[Formula 1]

In Formula 1, x: y is 1: 5 to 5: 1 on the basis of the molar ratio, n is an average value of 100 to 300.

The present invention also (a) in the presence of a catalyst to selectively hydrogenate the double bonds contained in the hexagonal ring portion of the dicyclopentadiene represented by the formula (2) and tricyclopentadiene represented by the formula (3) Generating a compound and a compound represented by Formula 5; And (b) polymerizing the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 to prepare a cyclic olefin polymer compound including a repeating unit represented by Chemical Formula 1 below. It provides a method for producing a cycloolefin-based polymer compound comprising a repeating unit represented.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Formula 1]

In Formula 1, x: y is 1: 5 to 5: 1 on the basis of the molar ratio, n is an average value of 100 to 300.

According to the present invention, by removing the double bonds contained in the hexagonal ring portions of dicyclopentadiene and tricyclopentadiene through selective addition reaction, respectively, not only side reactions and gelation occurring in the polymerization reaction can be prevented, By introducing tricyclopentadiene as a new cyclic olefin monomer, polymer properties superior to those of dicyclopentadiene polymers can be obtained, and polymer properties can be easily adjusted according to the degree of containing tricyclopentadiene monomers. The cyclic olefin polymer compound may be usefully used in various fields such as packaging materials, DVD materials, optical films, and the like.

1 is a gas chromatography measurement graph of a dicyclopentadiene and tricyclopentadiene mixture.
2 is a gas chromatography measurement graph of the tricyclopentadiene obtained in the Example.
3 is a graph of 1H-NMR measurement before (a) and after (b) hydrogenation of tricyclopentadiene obtained in Example 4. 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.

The present invention relates to a cyclic olefin polymer compound including a repeating unit represented by the following general formula (1) in one aspect.

[Formula 1]

In Formula 1, x: y is 1: 5 to 5: 1 on the basis of the molar ratio, n is an average value of 100 to 300.

More specifically, the cyclic olefin polymer compound including a repeating unit represented by the formula (1) according to the present invention, in the formula (1), x: y may be from 1: 5 to 5: 1 on a molar ratio basis. In terms of preparing a transparent amorphous resin, preferably x: y is 1: 3 to 3: 1, more preferably 1: 2 to 2: 1 on a molar ratio basis.

The x: y molar ratio in the polymer chain can be controlled by adjusting the molar ratio of the two monomers to the reactor. The average value of n which shows the degree of polymerization is 100-300, and is 150-200 from a viewpoint for having moderate mechanical strength.

In the cyclic olefin polymer compound including the repeating unit represented by Formula 1 according to the present invention, tricyclopentadiene having a larger monomer size than the polymer compound polymerized with conventional dicyclopentadiene is polymerized to increase the glass transition temperature of the polymer compound. It can increase, and also the glass transition temperature can be adjusted according to the content of tricyclopentadiene can further extend the range of use.

In another aspect, the present invention (a) in the presence of a catalyst selectively hydrogenated the double bonds contained in the hexagonal ring portion of the dicyclopentadiene represented by the formula (2) and tricyclopentadiene represented by the formula (3) to the formula Generating a compound represented by the compound represented by Formula 5; And (b) preparing a cyclic olefin polymer compound comprising a repeating unit represented by the following Formula 1 by ring opening metathesis polymerization of the compound represented by Formula 4 and the compound represented by Formula 5; It relates to a method for producing a cyclic olefin polymer compound comprising a repeating unit represented by the formula (1).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Formula 1]

In Formula 1, x: y is 1: 5 to 5: 1 on the basis of the molar ratio, n is an average value of 100 to 300.

More specifically, the present invention provides a cyclic olefin polymer compound including a repeating unit represented by Formula 1 in the hexagonal ring portion of the dicyclopentadiene represented by Formula 2 and tricyclopentadiene represented by Formula 3 in the presence of a catalyst. The contained double bonds are selectively hydrogenated to produce a compound represented by Formula 4 and a compound represented by Formula 5. The compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 generated as described above may be prepared by polymerization, which is summarized in the following Scheme 6.

[Reaction Scheme 6]

As shown in Scheme 7, tricyclopentadiene represented by Chemical Formula 3 generates a cyclopentadiene through a reverse Diels-Alder reaction of dicyclopentadiene represented by Chemical Formula 2, and generates the cyclopentadiene and the chemical formula. Dicyclopentadiene represented by 2 can be prepared by Diels-Alder reaction again.

[Reaction Scheme 7]

In this case, the reverse Diels-Alder reaction is carried out at 150 to 160 ° C. and 2 to 3 bar pressure for 20 to 30 minutes. If the reaction is out of the range, the reaction does not proceed or the pressure is increased due to the excessive generation of cyclopentadiene. Four or more cyclopentadienes can be synthesized to produce many byproducts. Meanwhile, the Diels-Alder reaction is carried out at 160 to 170 ° C. and 3 to 4 bar pressure for 100 to 120 minutes. If the reaction is out of the above range, the reaction does not proceed properly, or four or more of cyclopentadiene are synthesized. A lot of byproducts are produced.

The cyclopentadiene and dicyclopentadiene represented by the formula (2) and tricyclopentadiene represented by the formula (3) produced by this can be obtained by separating the vacuum distillation according to the temperature. In order to purely separate only the main isomers of tricyclopentadiene from the by-products, a recrystallization method may be introduced in which the by-products are dissolved in ethanol and separated by temperature solubility. This method of manufacturing and pure separation has been reported (Hyeong Cheol Park, Ahreum Kim and Bun Yeoul Lee, Journal of Polymer Science . Vol. 49: 938-944, 2011).

In the present invention, a side reaction generated during polymerization due to the double bond contained in the hexagonal ring portion of the tricyclopentadiene represented by the formula (3) and the dicyclopentadiene represented by the formula (2) obtained by the above method Compound represented by Formula 4 by removing the double bonds contained in the hexagonal ring portion of the tricyclopentadiene represented by the formula (3) and dicyclopentadiene represented by the formula (2) through selective hydrogenation to prevent gelation By producing a compound represented by the formula (5), and then polymerizing them to prepare a cyclic olefin polymer, tricyclopentadiene can increase the glass transition temperature than the polymer compound polymerized with dicyclopentadiene because of the large monomer size There is an advantage.

In the tricyclopentadiene compound represented by Formula 3, four isomers may exist due to endo and exo aromaticity. In addition, the dicyclopentadiene compound represented by the formula (2) is usually a mixture of endo-isomers and exo-isomers mixed at 9: 1 or more, and the norbornene-type olefin group and cyclopentadiene are Diels-Alder reaction. In addition, compounds can also be formed with endo and exo. Zhongqiang Xiong, Zhentao Mi, Xiangwen Zhang, React . Kinet . Catal . Lett . Vol. 85, 89-97 (2005) reported that only two compounds were formed at a ratio of about 5: 1.

The monomer used in the present invention is a pure tricyclopentadiene compound obtained by removing only a small amount of compounds in this mixture by recrystallization, thereby obtaining only one pure isomer. This is to closely analyze the newly prepared high molecular compound, it is also possible to prepare a polymer using a mixture without separating the isomers.

In the present invention, the compound represented by the formula (4) and the compound represented by the formula (4) by hydrogenating a double bond contained in the hexagonal ring portion of the dicyclopentadiene represented by the formula (2) and the tricyclopentadiene represented by the formula (3) in the presence of a catalyst Create each of them. At this time, the hydrogenation reaction is preferably carried out for 60 to 80 minutes at 80 ~ 110 ℃. When the reaction temperature is less than 80 ℃, the hydrogenation reaction hardly proceeds, if it exceeds 110 ℃ not only the hexagonal double bond of dicyclopentadiene represented by the formula (2) and tricyclopentadiene represented by the formula (3) In addition, hydrogenation proceeds to the double bond portions present in the pentagonal double bonds, thereby causing a problem of disappearing the polymerization site.

In addition, the pressure of the hydrogenation reaction hydrogen is preferably 8 to 15 kg / cm ² . When the pressure of the hydrogen is less than 8kg / cm ² , the rate of hydrogenation reaction is too slow, if more than 15kg / cm ² hydrogenation proceeds to the pentagonal double bond, the polymerization site (site) disappears at the same time occurs However, it is not economical because additional equipment is needed due to the high pressure reaction conditions.

The catalyst used for the hydrogenation reaction may be selected from the group consisting of Pd, Pd / C and Ni, preferably Pd / C.

In addition, the catalyst used for the hydrogenation reaction may be used in 0.5 to 0.7 parts by weight based on 100 parts by weight of the monomer. If it is added less than 0.5 parts by weight, the rate of the hydrogenation reaction is slowed, and when it exceeds 0.7 parts by weight, the rate of the hydrogenation reaction is no longer increased, which is meaningless.

As described above, the compound represented by the formula (4) and the compound represented by the formula (5) generated by the hydrogenation reaction, respectively, can be prepared by the polymerization of the cyclic olefin polymer compound according to the present invention.

In this case, the polymerization may be preferably performed at 10 to 40 ° C. for 120 to 180 minutes at normal pressure. If the temperature of the polymerization is less than 10 ℃, a problem that the polymerization power is lowered or polymerization is not generated, if the temperature exceeds 40 ℃, problems such as agglomeration of catalyst and yield decrease due to the increase of the initial reaction .

In addition, the catalyst used in the polymerization may be one or more catalysts selected from the group consisting of WCl ₆ , WOCl ₄ , Ru-based and Mo-based, molecular weight regulators such as 1-hexene, 1-Octene, etc. , Promoters such as triisobutylaluminum, diethylaluminum chloride, triehtylaluminum, etc., isobutylalcohol, butylalcohol, isopropylalcohol, etc. A polymerization regulator and the like can be further adjusted and added during the polymerization reaction.

In the method for preparing a cyclic olefin polymer compound according to the present invention, by removing the double bonds contained in the hexagonal ring portions of dicyclopentadiene and tricyclopentadiene, respectively, by selective addition reaction, side reactions and gelation occurring in the polymerization reaction. Not only prevents radically, but also introduces tricyclopentadiene as a new cyclic olefin monomer, thereby obtaining polymer properties superior to those of a dicyclopentadiene polymer and at the same time containing a tricyclopentadiene monomer. The physical properties of the polymer may also be easily adjusted, and thus the cyclic olefin polymer may be usefully used in various fields such as packaging materials, DVD materials, optical films, and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by these Examples.

< Example  1 to 6>

(1) Synthesis and Purification of Tricyclopentadiene Compound

1 kg of dicyclopentadiene was subjected to reverse Diels Alder reaction for 20 minutes at 155 ° C. under 2 bar pressure, and the mixture subjected to reverse Diels Alder reaction was subjected to Diels-Alder reaction for 120 minutes at 160 ° C. under 2 bar pressure. After 120 minutes, 750 g of dicyclopentadiene solution was separated through vacuum distillation (0.05 mbar) at 70 ° C., and 190 g of tricyclopentadiene solution was separated and purified at 130 ° C. After the separated tricyclopentadiene was cooled to room temperature and solidified, 500 ml of ethanol was added thereto, heated to 40 ° C. and dissolved therein, and then concentrated to 300 g using a vacuum distillation apparatus. After concentration was complete, the mixture was left for 4 h at -5 ° C to recrystallize and then filtered to obtain a white solid (160 g), and this recrystallization process was repeated three times, followed by filtration. The filtered white solid was dried under reduced pressure at 40 ° C. to finally obtain 140 g of pure tricyclopentadiene. The dicyclopentadiene used in the synthesis of tricyclopentadiene and tricyclopentadiene thus obtained was analyzed using gas chromatography (Aglient GC 7890).

As a result, as shown in Figure 1, the peak of the dicyclopentadiene used in the synthesis of tricyclopentadiene was confirmed to appear 11 to 12 minutes on the gas chromatography graph, as shown in Figure 2, Tricyclopentadiene obtained by the process was confirmed to appear around 25 ~ 26 minutes. In addition, as a result of analyzing the integral values of the peaks shown in FIGS. 1 and 2, it can be seen that 77% of dicyclopentadiene and 21% of tricyclopentadiene are produced. In the above synthesis conditions, when the temperature is increased to 180 ° C. for 16 hours, tricyclopentadiene has a high yield of up to 40%, but more than 20% of substances such as tetramers and pentamers, which are by-reactants, by weight. While produced and inferior in process efficiency, when synthesized under the above reaction conditions, the weight of the material was about 2%, indicating that the rich components that can be reused and used were as high as 98%.

(2) hydrogenation reaction

200 g of a solution in which the dicyclopentadiene and tricyclopentadiene monomers obtained in Example (1) were mixed at various molar ratios (described in Table 1 below) was added to a hydrogen reactor, and 100 ml of toluene was further added. Here, 1 g of Pd / C catalyst powder was mixed with 20 ml of toluene, added to the reactor, and heated to 90 ° C. to carry out the reaction. The reaction was carried out while adjusting the hydrogen pressure to 10 bar and adjusting with a mass flow controller to maintain the pressure for 1 hour. After 1 hour, the reaction was terminated, the temperature was lowered, the Pd / C catalyst was filtered off, and toluene was removed using a vacuum distillation apparatus. As described above, NMR (Nuclear Magnetic) was used to confirm that hydrogenation is performed on the dicyclopentadiene and the tricyclopentadiene of Example 4 having a molar ratio of dicyclopentadiene and tricyclopentadiene monomers among the hydrogenated compounds. Resonance, Bruker NMR 400 MHz) was measured.

As a result, as shown in Figure 3, the singlet peak appearing between 5 ~ 6ppm is a double bond peak (indicated by a red circle) included in the hexagon of tricyclopentadiene, the double bond disappeared after the hydrogenation reaction I could confirm it.

(3) Polymerization

12.1 g of dicyclopentadiene and 7.8 g of tricyclopentadiene obtained in Example (2) were dissolved in 150 ml of cyclohexane, and then 442 mg of 1-hexene was added thereto, followed by stirring at room temperature for 5 minutes. 137 mg of triisobutylaluminum (1M in hexane solution) was added to the mixture after stirring, and then stirred at room temperature for 15 minutes, and 4.8 mg of isobutyl alcohol was added thereto, followed by stirring for 15 minutes. After stirring was completed, 26 mg of WCl ₆ was added to conduct polymerization. The reaction proceeds in an environment in which oxygen and moisture are blocked below 1 ppm in a glove box and proceeds for 2 hours at room temperature to obtain a viscous light brown liquid cyclic olefin polymer compound (viscosity: 110 ~ 120cps / spidle 2 ).

< Comparative Example  1 to 2>

The reaction was carried out in the same manner as in Example 4 and Example 5, except for the hydrogenation reaction to prepare a cyclic olefin polymer compound.

< Experimental Example >

The glass transition temperature (Tg) was measured using a differential scanning calorimetry for the polymer material obtained from the examples and the comparative examples, and the molecular weight and the molecular weight distribution were measured using polystyrene as a standard through gel permeation chromatography. Table 1 summarizes the measurement results. At this time, the analysis temperature of the gel permeation chromatography (PL GPC-220) was 130 ° C and the mobile phase was analyzed using 1,2,4-trichlorobenzene. In addition, the rate of temperature increase of the differential scanning calorimeter was measured by raising the temperature to 250 ℃ to 10 ℃ / min, the process proceeds to analysis under N ₂ atmosphere was analyzed to 2nd scan.

division DCPD
(mol%) TCPD
(mol%) Hydrogenation
reaction
Time (h) polymerization
Time (h) Yield
(%) After polymerization
Tg (占 폚) Mw
(× 10 ³ ) PDI Example 1 100 0 One 2 90 110 78.2 2.8 Example 2 90 10 One 2 94 121 82.9 3.1 Example 3 80 20 One 2 95 130 77.1 2.6 Example 4 70 30 One 2 92 135 81.5 2.9 Example 5 60 40 One 2 98 142 81.3 2.9 Comparative Example 1 70 30 - 2 68 133 232.1 5.1 Comparative Example 2 60 40 - 2 52 139 192.2 4.6

As shown in Table 1, the yield of the cyclic olefin polymer compound of Comparative Example 1 and Comparative Example 2 is 68% or less, while Examples 1 to 5 can obtain a cyclic olefin polymer compound with a high yield of 90% or more. It was confirmed that, the molecular weight of Examples 1 to 5D was measured stably between 70,000 to 80,000, the number average molecular weight (PDI) was measured to 2.7 to 3.0. In particular, it was confirmed that the higher the mixing ratio of tricyclopentadiene (Example 4 and Example 5), the higher the glass transition temperature (Tg). As a result, the cyclic olefin polymer compound according to the present invention is expected to be used in a wide range of fields because of excellent thermal stability.

Having described specific portions of the invention in detail, those skilled in the art will appreciate that these specific embodiments are merely preferred embodiments and that the scope of the invention is not limited thereby will be. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (10)

The cyclic olefin polymer compound comprising a repeating unit represented by the following formula (1):
[Chemical Formula 1]

In Formula 1, x: y is 1: 5 to 5: 1 on the basis of molar ratio, n is an average value of 100 to 300.
The cyclic olefin polymer compound of claim 1, wherein x: y is 1: 2 to 2: 1 on the basis of molar ratio, and n has an average value of 150 to 200. 3.
Method for producing a cyclic olefin polymer compound comprising a repeating unit represented by the formula (1) comprising the following steps:
(a) a compound represented by the following formula (4) by selectively hydrogenating a double bond contained in the hexagonal ring portion included in the dicyclopentadiene represented by the formula (2) and the tricyclopentadiene represented by the formula (3) in the presence of a catalyst Producing a compound represented by 5; And
(b) preparing a cyclic olefin polymer compound comprising a repeating unit represented by Formula 1 by polymerizing the compound represented by Formula 4 and the compound represented by Formula 5;
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 1]

In Formula 1, x: y is 1: 5 to 5: 1 on the basis of molar ratio, n is an average value of 100 to 300.
The method of claim 3, wherein the catalyst of step (a) is at least one selected from the group consisting of Pd, Pd / C and Ni.
The method of claim 3, wherein step (a) is performed at 80 to 110 ° C. for 60 to 80 minutes.
The method of claim 3, wherein the hydrogenation pressure of the step (a) is 8 ~ 15kg / cm ² method for producing a cyclic olefin polymer compound.
The method according to claim 3, wherein the polymerization in step (b) is performed at 10 to 40 ° C. for 120 to 180 minutes under normal pressure.
According to claim 3, wherein the tricyclopentadiene represented by the formula (3) is obtained from the cyclopentadiene represented by the formula (2) through a reverse Diels-Alder reaction to obtain a cyclopentadiene, the cyclopentadiene and the obtained di Cyclopentadiene is produced by Diels-Alder reaction.
The method of claim 8, wherein the reverse Diels-Alder reaction is performed at 150 to 160 ° C. and 2 to 3 bar pressure for 20 to 30 minutes.
The method of claim 8, wherein the Diels-Alder reaction is performed at 160 to 170 ° C. and 3 to 4 bar pressure for 100 to 120 minutes.

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