阅读说明：本技术 制备基于二环戊二烯的树脂的方法以及基于二环戊二烯的树脂 (Method for preparing dicyclopentadiene-based resin and dicyclopentadiene-based resin ) 是由 姜炫旭 成必济 尹景俊 张稀晋 于 2017-12-11 设计创作，主要内容包括：本发明涉及一种制备基于二环戊二烯的树脂的方法以及基于二环戊二烯的树脂。根据本发明,可以提供一种基于二环戊二烯的树脂,其通过包含基于芳香族烯烃的共聚单体作为共聚单体而具有改善的产品质量,包括高的相容性、良好的颜色特性和低的软化点,并且由于低的分子量和分子量分布而具有改善的粘合强度。(The present invention relates to a method for preparing dicyclopentadiene based resin and to dicyclopentadiene based resin. According to the present invention, it is possible to provide a dicyclopentadiene based resin having improved product quality including high compatibility, good color characteristics and a low softening point by including an aromatic olefin based comonomer as a comonomer, and having improved adhesive strength due to low molecular weight and molecular weight distribution.)

1. A dicyclopentadiene-based resin prepared by polymerization of a monomer composition comprising dicyclopentadiene and an aromatic olefin-based comonomer in a weight ratio of 90:10 to 10:90 and satisfying the following formula 1,

[ formula 1]

0.1<PDI-1.45*n<1.3

Wherein PDI represents a molecular weight distribution of the dicyclopentadiene based resin, and

n represents the weight ratio of aromatic olefin-based comonomer in the monomer composition (weight of the aromatic olefin-based comonomer/total weight of the monomer composition).

2. The dicyclopentadiene based resin of claim 1, wherein the Z-average molecular weight (Mz) is from 100g/mol to 5,000g/mol, the weight-average molecular weight (Mw) is from 100g/mol to 3,000g/mol, and the number-average molecular weight (Mn) is from 100g/mol to 1,200 g/mol.

3. The dicyclopentadiene-based resin according to claim 1, wherein a molecular weight distribution (PDI, Mw/Mn) is 2.5 or less.

Technical Field

This application is based on and claims priority from korean patent application No. 10-2016-.

The present invention relates to a method for preparing dicyclopentadiene based resin and to dicyclopentadiene based resin.

Background

Dicyclopentadiene (DCPD) resin is a resin prepared by thermal polymerization, which can be mixed with various polymers such as Amorphous Polyalphaolefin (APAO), ethylene-vinyl acetate (EVA), Styrene Block Copolymer (SBC), etc. to be used as a tackifying resin for adhesives/stickers. In this regard, depending on the kind and use of adhesives/stickers, dicyclopentadiene resins are required to have various physical properties, and in order to satisfy these physical properties, many studies have been actively conducted to improve the compatibility thereof with polymers and to improve the adhesive strength.

For example, U.S. Pat. nos. 5,502,140 and 5,739,239 disclose a copolymer prepared by thermal polymerization of styrene and/or α -methylstyrene (AMS) as a comonomer, and a method of hydrogenating the copolymer. In the examples of these patents, the use of higher levels of styrene produces resin products having undesirably high molecular weights, and it is considered desirable to employ AMS instead of styrene. However, due to the relatively low reactivity of AMS with respect to other vinyl aromatic compounds such as styrene, only about 50% of AMS in the initial charge is consumed during the thermal reaction, showing low yields below 50%. Therefore, a method of extending the reaction time, a method of increasing the reaction temperature, or a method of recycling the unreacted residue back into the process may be employed. These methods can improve the yield, but have problems of broadening the molecular weight distribution or lowering the productivity.

In addition, the color of resins produced from DCPD and AMS is often undesirably dark. Hydrogenation of the DCPD resin is performed to saturate the olefinic unsaturation and improve the color characteristics. However, there are problems in that the demand for hydrogen consumption is high and excessive hydrogenation time is required.

Therefore, there is a need to produce DCPD resins having aromatic comonomer content suitable for improving resin compatibility and having improved color characteristics and productivity.

JP 3934053 discloses a DCPD resin containing 5 to 23 wt% of styrene and having improved color characteristics by controlling the feed rate and reaction rate of DCPD and styrene, and a method for preparing the same. However, this method is also disadvantageous in that it requires control of complicated process conditions, productivity is low, and DCPD resins having a broad molecular weight distribution of 2.3 or more are produced with low adhesive strength.

Disclosure of Invention

[ problem ] to

In order to solve the above problems, the present invention provides a method for preparing a dicyclopentadiene based resin containing an appropriate amount of an aromatic olefin based comonomer, which suppresses an excessive crosslinking reaction and exhibits high productivity.

Further, the present invention provides a dicyclopentadiene-based resin, which contains an aromatic olefin-based comonomer as a comonomer, to have improved qualities including high compatibility, good color characteristics, thermal stability and a low softening point, and also to have improved adhesive strength due to a low molecular weight and a narrow molecular weight distribution.

[ solution ]

In order to solve the above-mentioned problems, according to an embodiment of the present invention, there is provided a method for preparing a dicyclopentadiene based resin, the method comprising:

a first polymerization step of performing a polymerization process of a monomer composition under stirring, wherein the monomer composition comprises dicyclopentadiene and an aromatic olefin-based comonomer in a weight ratio of 90:10 to 10: 90; and

a second polymerization step of performing a polymerization process of the reaction product of the first polymerization step without stirring.

According to another embodiment of the present invention, there is provided a dicyclopentadiene-based resin prepared by polymerization of a monomer composition and satisfying the following formula 1, wherein the monomer composition comprises dicyclopentadiene and an aromatic olefin-based comonomer in a weight ratio of 90:10 to 10:90,

[ formula 1]

0.1<PDI-1.45*n<1.3

Wherein PDI represents a molecular weight distribution of the dicyclopentadiene based resin, and

n represents the weight ratio of aromatic olefin-based comonomer in the monomer composition (weight of the aromatic olefin-based comonomer/total weight of the monomer composition).

[ advantageous effects ]

According to the method for preparing dicyclopentadiene based resin of the present invention, polymerization of dicyclopentadiene and aromatic olefin based comonomers is carried out in two stages. In the first polymerization step, continuous mixing and reaction of monomers are performed, and in the second polymerization step, polymerization is continued while inhibiting a crosslinking reaction, thereby preparing a dicyclopentadiene-based resin having high productivity and a lower molecular weight and a narrower molecular weight distribution than known dicyclopentadiene-based resins.

In addition, the dicyclopentadiene-based resin prepared by the above-described polymerization process has a relatively low molecular weight and a narrow molecular weight distribution, compared to known dicyclopentadiene-based resins having a similar content of an aromatic olefin-based comonomer, and thus, the dicyclopentadiene-based resin may exhibit excellent adhesive strength while maintaining thermal stability and compatibility, and may exhibit a low softening point and good color characteristics.

Detailed Description

As used herein, the term "dicyclopentadiene-based resin" refers to a resin polymerized by using dicyclopentadiene as a monomer or together with other comonomers, and also includes a hydrogenated resin obtained by hydrogenation of the resin.

In the present invention, the terms "first", "second", and the like are used to describe various components, and these terms are used only to distinguish one component from other components.

Furthermore, the terms used in the present specification are used only for explaining exemplary embodiments, and are not intended to limit the present invention. Singular expressions may include plural expressions unless the context is differently expressed. It must be understood that the terms "comprises", "comprising", "includes" and "including" in this specification are only used for indicating the presence of the stated features, steps, components or their combinations, and do not preclude the presence or addition of one or more other features, steps, components or their combinations in advance.

The present invention is susceptible to various modifications and forms, and specific embodiments thereof have been described in the specification. However, it is not intended to limit the present invention to the specific embodiments, and it must be understood that the present invention includes various modifications, equivalents, and alternatives included in the spirit and technical scope of the present invention.

Hereinafter, the method for preparing dicyclopentadiene based resin and the dicyclopentadiene based resin of the present invention will be described in more detail.

A method of preparing a dicyclopentadiene-based resin according to an embodiment of the present invention may include a first polymerization step of performing a polymerization process of a monomer composition under stirring, wherein the monomer composition includes dicyclopentadiene and an aromatic olefin-based comonomer in a weight ratio of 90:10 to 10: 90; and a second polymerization step of carrying out a polymerization process of the reaction product of the first polymerization step without stirring.

Further, a dicyclopentadiene based resin according to another embodiment of the present invention may be prepared by polymerization of a monomer composition comprising dicyclopentadiene and an aromatic olefin-based comonomer in a weight ratio of 90:10 to 10:90, and may satisfy the following formula 1,

[ formula 1]

0.1<PDI-1.45*n<1.3

Wherein PDI represents a molecular weight distribution of the dicyclopentadiene based resin, and

n represents the weight ratio of aromatic olefin-based comonomer in the monomer composition (weight of the aromatic olefin-based comonomer/total weight of the monomer composition).

In formula 1, when PDI-1.45 × n is represented as z, it may satisfy 0.1< z <1.3, or 0.3< z <1.3, or 0.5< z <1.25, or 0.8< z <1.25, or 1.0< z < 1.25.

In the case where the dicyclopentadiene-based resin has the same weight ratio of the aromatic olefin-based comonomer, a smaller z-value of formula 1 means a narrower molecular weight distribution. The dicyclopentadiene-based resin prepared by the preparation method of the present invention has a narrow molecular weight distribution, compared to known dicyclopentadiene-based resins having the same content of the aromatic olefin-based comonomer, thereby exhibiting excellent adhesive strength while maintaining high compatibility.

Dicyclopentadiene resins are mixed with various polymers to be widely used as tackifying resins for adhesives/stickers. In this regard, the dicyclopentadiene resin is required to have various physical properties according to the kind and use of the adhesive/sticker, and a copolymerized resin obtained by using an aromatic olefin-based comonomer compound as a comonomer is proposed to improve compatibility with a polymer and improve adhesive strength.

However, it is not easy to prepare a resin having a low molecular weight and a narrow molecular weight distribution, which is advantageous for adhesive strength, by copolymerizing dicyclopentadiene together with the aromatic olefin-based comonomer at high productivity.

Accordingly, the present inventors have found that, during the preparation of a dicyclopentadiene-based resin comprising the aromatic olefin-based comonomer as a comonomer, polymerization is carried out in two stages, and stirring is controlled at each stage, thereby preparing a high-quality dicyclopentadiene-based resin with high yield, resulting in the present invention.

More specifically, in the first polymerization step, the first polymerization is performed by feeding and mixing the monomer composition until the conversion of dicyclopentadiene reaches a predetermined level. Subsequently, in the second polymerization step, the reaction product of the first polymerization step is subjected to second polymerization without stirring. As a result, side reactions such as homopolymer generation are prevented, and a high-quality dicyclopentadiene based resin having a narrow molecular weight distribution is produced. That is, in the first polymerization step, side reactions such as the production of polystyrene can be prevented by effective mixing of polymerization raw materials, and in the second polymerization, the reaction rate can be increased, thereby preventing overall side reactions and increasing the reaction rate of dicyclopentadiene and aromatic olefin-based comonomers.

In the method of preparing a dicyclopentadiene based resin according to the present invention, the monomer composition as a raw material may include dicyclopentadiene and an aromatic olefin-based comonomer in a weight ratio of 90:10 to 10:90, 80:20 to 20:80, 70:30 to 30:70, or 50:50 to 30: 70.

In order to provide a dicyclopentadiene resin having thermal stability, compatibility with other resins, and color characteristics, copolymerization with a comonomer is widely employed.

Aromatic olefin-based comonomers useful in the present invention may include styrene; styrene derivatives such as α -methylstyrene (AMS), p-methylstyrene, etc.; indene; indene derivatives such as methylindene and the like; toluene; toluene derivatives such as vinyl toluene and the like; c9-based monomers produced by thermal cracking of naphtha; or mixtures thereof, but the invention is not limited thereto.

Since the dicyclopentadiene-based resin has a high content of the aromatic olefin-based comonomer, compatibility with other base resins may be improved, but molecular weight distribution may be broadened, which may reduce adhesive strength of the resin. For this reason, it is necessary to control the molecular weight distribution below a predetermined level.

According to the method of preparing dicyclopentadiene based resin of the present invention, it is possible to prepare dicyclopentadiene based resin having a low molecular weight and a narrow molecular weight distribution by suppressing a crosslinking reaction while having a high content of an aromatic olefin based comonomer.

According to an embodiment of the present invention, in the first polymerization step, the monomer composition comprising dicyclopentadiene and an aromatic olefin-based comonomer may be at a reaction temperature (t) of 210 ℃ to 270 ℃₁) The polymerization reaction is carried out.

In this regard, the weight ratio of dicyclopentadiene to aromatic olefin-based comonomer in the monomer composition may be from 90:10 to 10:90, or from 80:20 to 20:80, or from 70:30 to 30:70, or from 50:50 to 30: 70. If the amount of the aromatic olefin-based comonomer is too small, the quality improvement of the resin may not be satisfactory, and if the amount of the aromatic olefin-based comonomer is too large, the cost required for the hydrogenation process may be increased, and the adhesive properties may be reduced due to homopolymer generation during polymerization. Therefore, the content of the aromatic olefin-based comonomer may be controlled by controlling the range of the weight ratio depending on the desired dicyclopentadiene-based resin.

The monomer composition may be used in a state that the monomer composition is dissolved in a solvent, which may be any solvent commonly used in the art to which the present invention pertains. For example, a solvent such as pentane, hexane, heptane, nonane, decane, benzene, toluene, xylene, etc., may be used, but the present invention is not limited thereto.

The monomer composition may further include additives commonly used in the art to which the present invention pertains, such as antioxidants and polymerization inhibitors.

The first polymerization step may be carried out at a reaction temperature (t) of 210 ℃ to 270 ℃ while stirring the monomer composition₁) The process is carried out as follows.

According to one embodiment of the present invention, the first polymerization step may be carried out in a Continuous Stirred Tank Reactor (CSTR). A CSTR is a type of continuous reactor that is advantageous in that it can continuously inject reactants to provide a mixing effect during the reaction, to keep the temperature constant during the reaction, and to reduce the possibility of local hot spots. However, the CSTR has disadvantages in that the conversion of reactants per reactor volume is low and the molecular weight distribution of the resin is widened since the remaining polymer is not discharged during the residence time.

In addition, the Plug Flow Reactor (PFR), which is another continuous reactor, has advantages in that the reactor has no stirrer, so that maintenance and management of the reactor are relatively easy, and the conversion rate per reactor volume is high. However, the reactor has disadvantages in that it is difficult to control the temperature in the reactor, and when the reaction is exothermic, there is a high possibility of local hot spots.

According to one embodiment of the present invention, the polymerization of dicyclopentadiene and aromatic olefin-based comonomers can be carried out in two stages, the first polymerization step can be carried out in a CSTR and the second polymerization step described below can be carried out in a PFR. Through each step of the polymerization, a high-quality dicyclopentadiene based resin can be produced by suppressing broadening of the molecular weight distribution while maintaining high productivity.

The CSTR used in the first polymerization step may be any CSTR commonly used in the art to which the present invention pertains, and the polymerization may be performed while continuously injecting and mixing the monomer composition.

According to one embodiment of the invention, the reaction temperature (t) of the first polymerization step₁) Can be controlled at 210 ℃ to 270 ℃ or 220 ℃ to 270 ℃.

If the reaction temperature is too low, the reaction may not sufficiently occur, and if the reaction temperature is too high, side reactions such as a crosslinking reaction may occur. From this viewpoint, the reaction temperature is preferably controlled within the above-described range.

Further, the reaction pressure of the first polymerization step may be from 1 bar to 40 bar, or from 5 bar to 35 bar, or from 10 bar to 30 bar. If the reaction pressure is too low, the evaporated monomer may decrease reactivity, while if the reaction pressure is too high, there is a high risk of accident. From this viewpoint, the reaction pressure is preferably controlled within the above-mentioned range.

Further, the reaction time of the first polymerization step may be 10 minutes to 90 minutes, or 20 minutes to 80 minutes, or 30 minutes to 70 minutes. If the reaction time is too short, it may be insufficient to suppress side reactions by mixing raw materials, whereas if the reaction time is too long, the productivity of the final resin may be reduced, and the molecular weight distribution may be broadened. From this viewpoint, the reaction time is preferably controlled within the above-mentioned range.

The first polymerization step may be carried out until a conversion of dicyclopentadiene in the monomer composition reaches 5% to 70%, or 10% to 60%, or 15% to 50%. The conversion of dicyclopentadiene can be calculated as a percentage of the amount of dicyclopentadiene consumed per unit time to the amount injected and can be determined by measuring the dry weight of the resin produced relative to the weight of the feedstock injected.

If the conversion of dicyclopentadiene in the first polymerization step is too low, the subsequent second polymerization step may be burdened and a resin having a sufficient degree of polymerization may not be produced. If the conversion is too high, the molecular weight and molecular weight distribution of the dicyclopentadiene based resin may be greatly increased, which is undesirable. From this point of view, the first polymerization step may be carried out only before the conversion of dicyclopentadiene reaches the above-mentioned range.

Next, the reaction product of the first polymerization step may be subjected to the second polymerization in a separate reactor connected to the reactor used in the first polymerization step.

According to one embodiment of the invention, the second polymerization may be carried out in a Plug Flow Reactor (PFR). The PFR may be connected to a CSTR wherein said first polymerization step is carried out. Thus, the reaction product of the first polymerization step can be injected into the PFR, whereby a continuous polymerization can take place.

As mentioned above, PFR is a reactor without internal stirrer and has the advantage of high monomer conversion per reactor volume. However, the stirring is insufficient, and thus there is a possibility that local hot spots are generated and side reactions are caused thereby.

However, in the present invention, the polymerization of the monomer composition is not carried out from the PFR, but the second polymerization step is carried out with the reaction product polymerized at a predetermined degree of polymerization by the first polymerization step. Therefore, the generation of local hot spots can be prevented due to the reduction of the heat of polymerization, and as a result, a dicyclopentadiene resin having a narrow molecular weight distribution can be prepared.

The PFR used in the second polymerization may be any PFR commonly used in the art to which the present invention pertains. In the PFR, polymerization may be carried out while continuously providing the reaction product of the first polymerization.

According to one embodiment of the invention, the reaction temperature (t) of the second polymerization₂) Can be at the reaction temperature (t) of the first polymerization₁) In the range of + -30 ℃, i.e. at t₁-30 ℃ to t₁+30 ℃ or t₁-20 ℃ to t₁+20 ℃ or t₁-15 to t₁+15 ℃, or t₁-10 to t₁Within a range of +10 ℃.

Reaction temperature (t) of the second polymerization₂) May be within the above rangeAnd an inner limit, thereby suppressing side reactions and obtaining the effect of high productivity. That is, if t₂And t₁If the difference is too large, the productivity may be lowered. Thus, the t₂And t₁The difference is preferably controlled within the above-described range.

More preferably, the reaction temperature (t) of the second polymerization₂) Can be controlled at t₁To t₁+20 ℃ or t₁To t₁Within +15 ℃. When the reaction temperature of the second polymerization is controlled as above, the generation of unreacted oligomers is minimized, thereby obtaining a dicyclopentadiene based resin having a high softening point and a narrow molecular weight distribution.

Further, the reaction pressure of the second polymerization may be 1 bar to 40 bar, or 5 bar to 35 bar, or 10 bar to 30 bar. If the reaction pressure is too low, the generation of dead zones or the change in residence time may occur due to the evaporated monomer. If the reaction pressure is too high, safety issues may arise in the process. From this viewpoint, the reaction pressure is preferably controlled within the above-mentioned range.

Further, the reaction time of the second polymerization may be 1 to 4 times, 1 to 3 times, or 1 to 2 times that of the first polymerization. If the reaction time is too short, the reaction may not sufficiently occur compared to the reaction time of the first polymerization, and if the reaction time is too long, side reactions may occur. From this viewpoint, the reaction time is preferably controlled within the above-mentioned range.

Further, the internal volume of the PFR used in the second polymerization may be 1 to 3 times, or 1 to 2.5 times, or 1 to 2 times the internal volume of the CSTR used in the first polymerization. If the internal volume of the PFR is too small, polymerization may not sufficiently occur in the PFR compared to the internal volume of the CSTR, and as a result, a large amount of impurities, such as wax, may remain therein. If the internal volume of the PFR is too large, the effect obtained with the CSTR reactor is unsatisfactory compared to the internal volume of the CSTR, and the control of the initial reaction heat is insufficient, thus making it difficult to control the reaction temperature. From this viewpoint, the internal volume of the PFR is preferably controlled within the range described above.

According to the method of preparing dicyclopentadiene-based resin of the present invention, a relatively high yield of about 50% or more, or about 60% or more, or about 65% or more can be achieved, and a narrow molecular weight distribution can also be achieved, although the reaction time is relatively short.

The dicyclopentadiene-based resin prepared as above may satisfy the following formula 1:

[ formula 1]

0.1<PDI-1.45*n<1.3

Wherein PDI represents a molecular weight distribution of the dicyclopentadiene based resin, and

n represents the weight ratio of aromatic olefin-based comonomer in the monomer composition (weight of the aromatic olefin-based comonomer/total weight of the monomer composition).

In formula 1, when PDI-1.45 × n is represented as z, it may satisfy 0.1< z <1.3, or 0.3< z <1.3, or 0.5< z <1.25, or 0.8< z <1.25, or 1.0< z < 1.25.

Further, the dicyclopentadiene based resin can have a Z average molecular weight (Mz) of 100g/mol to 5,000g/mol, or 300g/mol to 4,500g/mol, or 500g/mol to 4,000 g/mol.

Further, the dicyclopentadiene based resin can have a weight average molecular weight (Mw) of 100g/mol to 3,000g/mol, or 200g/mol to 2,500g/mol, or 300g/mol to 2,000 g/mol.

Further, the dicyclopentadiene based resin can have a number average molecular weight (Mn) of 100g/mol to 1,200g/mol, or 150g/mol to 1,000g/mol, or 200g/mol to 800 g/mol.

Further, the dicyclopentadiene based resin may have a molecular weight distribution (PDI, Mw/Mn) of 2.5 or less, more specifically, 1.0 or more, or 1.2 or more, or 1.4 or more and 2.5 or less, or 2.4 or less, or 2.2 or less, or 1.8 or less.

Due to these characteristics, the dicyclopentadiene based resin can be mixed with other polymers to provide a hot melt adhesive/sticker exhibiting excellent adhesive strength. In particular, the dicyclopentadiene based resin can be used as a tackifying resin for polymers having many different physical properties, and thus, it is expected that the dicyclopentadiene based resin can be used in a wide variety of fields.

The dicyclopentadiene-based resin obtained by the above-described method may be further subjected to hydrogenation reaction. The hydrogenation reaction may be carried out by a method known in the art to which the present invention pertains. For example, the dicyclopentadiene-based resin obtained by the first and second polymerization reactions may be fed to a continuous hydrogenation reactor containing a hydrogenation catalyst, and then the hydrogenation reaction may be carried out in the reactor.

Hereinafter, the action and effect of the present invention will be described in more detail with reference to specific examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not intended to be limited by these examples.

< example >

Example 1

750g of dicyclopentadiene and 750g of styrene were mixed in 1500g of a xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 42 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while the monomer composition was continuously fed to a CSTR (internal volume: 0.416L).

While the reaction product of the first polymerization step was continuously fed into a PFR (internal volume: 0.590L) connected to the CSTR, a second polymerization step was carried out under conditions of a temperature of 270 ℃ and a pressure of 25 bar (reaction time: 63 minutes).

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Example 2

1050g of dicyclopentadiene and 450g of styrene were mixed in 1500g of xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 36 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while the monomer composition was continuously fed to a CSTR (internal volume: 0.416L).

While the reaction product of the first polymerization step was continuously fed into a PFR (internal volume: 0.590L) connected to the CSTR, a second polymerization step was carried out under conditions of a temperature of 270 ℃ and a pressure of 25 bar (reaction time: 54 minutes).

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Example 3

450g of dicyclopentadiene and 1050g of styrene were mixed in 1500g of xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 42 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while the monomer composition was continuously fed to a CSTR (internal volume: 0.416L).

While the reaction product of the first polymerization step was continuously fed into a PFR (internal volume: 0.590L) connected to the CSTR, a second polymerization step was carried out under conditions of a temperature of 270 ℃ and a pressure of 25 bar (reaction time: 63 minutes).

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Examples 4 to 6

A dicyclopentadiene based resin was polymerized in the same manner as in example 1, except that the reaction temperature of the first polymerization step was different from that of the second polymerization step in example 1.

Example 7

A dicyclopentadiene based resin was polymerized in the same manner as in example 2, except that the reaction temperature of the second polymerization step was changed in example 2.

Example 8

The hydrogenation reaction was carried out twice using 0.5 wt% of Pd catalyst and 4NL/min of hydrogen at a temperature of 260 c and a pressure of 100 bar, relative to the total weight of the dicyclopentadiene based resin of example 1.

Example 9

750g of dicyclopentadiene and 750g of C9-based monomers (including 40% by weight, in total, of styrene, alpha-methylstyrene, vinyltoluene, indene and methylindene, and including the remaining amount of dicyclopentadiene) were mixed in 1500g of a xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 40 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while the monomer composition was continuously fed to a CSTR (internal volume: 0.416L).

While the reaction product of the first polymerization step was continuously fed into a PFR (internal volume: 0.590L) connected to the CSTR, a second polymerization step was carried out under conditions of a temperature of 270 ℃ and a pressure of 25 bar (reaction time: 60 minutes).

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Comparative example 1

750g of dicyclopentadiene and 750g of styrene were mixed in 1500g of a xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 52 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while continuously feeding the monomer composition to a PFR (internal volume: 0.295L).

The reaction product of the first polymerization step was subjected to a second polymerization step (reaction time: 53 minutes) in the same PFR (internal volume: 0.295L) connected to the PFR at a temperature of 270 ℃ and a pressure of 25 bar.

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Comparative example 2

1050g of dicyclopentadiene and 450g of styrene were mixed in 1500g of xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 45 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while continuously feeding the monomer composition to a PFR (internal volume: 0.295L).

The reaction product of the first polymerization step was subjected to a second polymerization step (reaction time: 45 min) in the same PFR (internal volume: 0.295L) connected to the PFR at a temperature of 270 ℃ and a pressure of 25 bar.

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Comparative example 3

1050g of dicyclopentadiene and 450g of styrene were mixed in 1500g of xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 40 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while continuously feeding the monomer composition to a PFR (internal volume: 0.295L).

The reaction product of the first polymerization step was subjected to a second polymerization step (reaction time: 40 min) in the same PFR (internal volume: 0.295L) connected to the PFR at a temperature of 270 ℃ and a pressure of 25 bar.

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Comparative example 4

450g of dicyclopentadiene and 1050g of styrene were mixed in 1500g of xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 45 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while continuously feeding the monomer composition to a PFR (internal volume: 0.295L).

The reaction product of the first polymerization step was subjected to a second polymerization step (reaction time: 45 min) in the same PFR (internal volume: 0.295L) connected to the PFR at a temperature of 270 ℃ and a pressure of 25 bar.

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Comparative example 5

750g of dicyclopentadiene (available from Baorun chemistry) and 750g of styrene were mixed in 1500g of xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 48 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while the monomer composition was continuously fed to a CSTR (internal volume: 0.416L).

The reaction product of the first polymerization step was subjected to a second polymerization step (reaction time: 72 minutes) in the same CSTR connected to the CSTR, at a temperature of 270 ℃ and a pressure of 25 bar.

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

Comparative example 6

The dicyclopentadiene based resin of comparative example 1 was subjected to hydrogenation reaction in the same manner as in example 8.

Comparative example 7

The dicyclopentadiene based resin of comparative example 5 was subjected to hydrogenation reaction in the same manner as in example 8.

Comparative example 8

750g of dicyclopentadiene and 750g of the same C9-based monomer as in example 9 were mixed in 1500g of xylene solvent to prepare a monomer composition.

The first polymerization step (reaction time: 45 minutes) was carried out under conditions of a temperature of 260 ℃ and a pressure of 25 bar while the monomer composition was continuously fed to a CSTR (internal volume: 0.416L).

While the reaction product of the first polymerization step was continuously fed to a CSTR (internal volume: 0.416L) connected to the CSTR, the second polymerization step was carried out under conditions of a temperature of 270 ℃ and a pressure of 25 bar (reaction time: 45 minutes).

After completion of the polymerization, the product was decompressed at 200 ℃ for 30 minutes to recover a dicyclopentadiene based resin.

The reaction conditions of the examples and comparative examples are summarized in the following table 1.

[ Table 1]

< Experimental example >

Evaluation of physical Properties of resin

The Z-average molecular weight (Mz), weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (PDI, Mw/Mn) of the dicyclopentadiene based resins prepared in examples and comparative examples were measured and are shown in table 2 below.

[ Table 2]

Referring to table 1, it can be seen that the dicyclopentadiene based resin of the example of the present invention shows a narrow molecular weight distribution and a high yield as compared to the dicyclopentadiene based resin of the comparative example having the same weight ratio of the aromatic olefin based comonomer.

In particular, as for comparative examples 1 and 5 (in which the reaction temperature and the weight ratio of the aromatic olefin-based comonomer during the first and second reaction steps are the same as in example 1, but the reactor configuration is different from example 1), the dicyclopentadiene-based resin of example 1 has a molecular weight distribution of 1.88, while comparative examples 1 and 5 have a molecular weight distribution of 2 or more, indicating that whether stirring is performed in the first and second reaction steps can greatly affect the molecular weight distribution.

In example 9, when a C9-based monomer having lower reactivity than the aromatic olefin-based monomer was used, the dicyclopentadiene-based resin also showed a very narrow molecular weight distribution of less than 1.5 and a high yield of 58%. However, despite the same C9-based monomer used in comparative example 8, the dicyclopentadiene-based resin showed a molecular weight distribution of greater than 1.5, and a lower yield than example 9.

In addition, the dicyclopentadiene based resins of the examples exhibited PDI-1.45 × (n represents the weight ratio of the aromatic olefin-based comonomer in the monomer composition (weight of the aromatic olefin-based comonomer/total weight of the monomer composition)) of less than 1.3, while the dicyclopentadiene based resins of the comparative examples exhibited PDI-1.45 × (1.3).

Evaluation of adhesive Strength of resin

In order to evaluate the adhesive strength of the dicyclopentadiene based hydrogenated resin prepared in example 8 and comparative examples 6 and 7, 25 parts by weight of SBS (styrene/butadiene/styrene) resin, 57 parts by weight of dicyclopentadiene based hydrogenated resin, and 18 parts by weight of paraffin oil plasticizer were mixed, and 0.5 parts by weight of antioxidant was added thereto to prepare an adhesive composition.

The adhesive composition was applied to a 100 μm PET film, the surface of which had been subjected to corona treatment, in a wet thickness of about 36 μm with an automatic coater. The coated film was dried at 100 ℃ for 30 minutes to remove the solvent and tested for 180 ° peel strength and loop tack using a general purpose material tester (FT-1 of LLOYD).

The results of measuring the adhesive strength and softening point of each hydrogenated resin are shown in table 3 below.

[ Table 3]

Referring to table 3, the dicyclopentadiene based hydrogenated resin of example 8 shows improved adhesive strength as compared with the dicyclopentadiene based hydrogenated resins of comparative examples 6 and 7.