METHOD FOR PRODUCING DICYCLOPENTADIENE-BASED RESIN

Abstract

The present invention relates to a method for producing a dicyclopentadiene-based resin and a dicyclopentadiene-based resin produced thereby, the method comprising thermal polymerizing under non-catalyst, non-initiator conditions, thereby enabling not only excellent yield, but also, by a low polydispersity index, a narrow molecular weight distribution and the realization of uniform physical properties.

Claims

1. A method for producing a dicyclopentadiene-based resin, the method comprising: a) a primary thermal polymerization step of thermally polymerizing a monomer composition in a continuous stirred tank reactor (CSTR) under non-catalytic conditions, the monomer composition containing a mixed monomer of dicyclopentadiene and a C.sub.2-C.sub.20 olefin-based monomer, or a mixed monomer of dicyclopentadiene, a C.sub.2-C.sub.20 olefin-based monomer, and an aromatic vinyl-based monomer; and b) a secondary thermal polymerization step of thermally polymerizing a reaction product obtained by the primary thermal polymerization in a plug flow reactor (PFR) under non-catalytic conditions.

2. The method of claim 1, wherein the mixed monomer of the dicyclopentadiene and the C.sub.2-C.sub.20 olefin-based monomer includes the dicyclopentadiene and the C.sub.2-C.sub.20 olefin-based monomer in a weight ratio of 50:50 to 99:1.

3. The method of claim 1, wherein the olefin-based monomer is any one or a mixture of two or more selected from the group consisting of piperylene, isoprene, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and mixed C5 fractions.

4. The method of claim 1, wherein the aromatic vinyl-based monomer is any one or a mixture of two or more selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, indene, methyl indene, vinyltoluene, mixed C9 fractions, and derivatives thereof.

5. The method of claim 1, wherein a reaction temperature (T.sub.1) in the step a) is 210 to 270° C., and a reaction temperature (T.sub.2) in the step b) is 180 to 300° C.

6. The method of claim 1, wherein a reaction time in the step a) is 10 to 180 minutes, and a reaction time in the step b) is 10 to 360 minutes.

7. The method of claim 1, wherein the dicyclopentadiene-based resin has a polydispersity index (PDI) of 2.5 or less.

8. The method of claim 1, further comprising, after the step b), performing a hydrogenation process.

9. A dicyclopentadiene-based resin obtained by thermally polymerizing a monomer composition containing a mixed monomer of dicyclopentadiene and a C.sub.2-C.sub.20 olefin-based monomer, or a mixed monomer of dicyclopentadiene, a C.sub.2-C.sub.20 olefin-based monomer, and an aromatic vinyl-based monomer under non-catalytic and non-initiator conditions.

10. The dicyclopentadiene-based resin of claim 9, wherein the dicyclopentadiene-based resin is produced with continuous polymerization by performing primary thermal polymerization on the monomer composition in a continuous stirred tank reactor (CSTR), and then performing secondary thermal polymerization on the resulting polymer in a plug flow reactor (PFR).

11. The dicyclopentadiene-based resin of claim 9, wherein the dicyclopentadiene-based resin has a number average molecular weight of 200 to 1,200 g/mol, a weight average molecular weight of 250 to 4,000 g/mol, and a Z-average molecular weight (Mz) of 300 to 5,000 g/mol.

12. The dicyclopentadiene-based resin of claim 9, wherein the dicyclopentadiene-based resin has a polydispersity index (PDI) of 2.5 or less.

Description

EXAMPLE 1

[0091] 970 g of dicyclopentadiene and 30 g of piperylene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into a continuous stirred tank reactor (CSTR) having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 30 minutes.

[0092] The primary polymer thus produced was polymerized under the conditions of a temperature of 272° C. and a pressure of 25 bar for 45 minutes, while continuously supplying the primary polymer into a plug flow reactor (PFR) having an internal volume of 0.590 L connected to a continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

EXAMPLE 2

[0093] 950 g of dicyclopentadiene and 50 g of piperylene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 30 minutes.

[0094] The primary polymer thus produced was polymerized under the conditions of a temperature of 272° C. and a pressure of 25 bar for 45 minutes, while continuously supplying the primary polymer into the plug flow reactor having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

EXAMPLE 3

[0095] 900 g of dicyclopentadiene and 100 g of piperylene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 30 minutes.

[0096] The primary polymer thus produced was polymerized under the conditions of a temperature of 272° C. and a pressure of 25 bar for 45 minutes, while continuously supplying the primary polymer into the plug flow reactor having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

EXAMPLE 4

[0097] 750 g of dicyclopentadiene, 50 g of piperylene, and 250 g of styrene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 34 minutes.

[0098] The primary polymer thus produced was polymerized under the conditions of a temperature of 278° C. and a pressure of 25 bar for 51 minutes, while continuously supplying the primary polymer into the plug flow reactor having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

EXAMPLE 5

[0099] 650 g of dicyclopentadiene, 100 g of piperylene, and 250 g of styrene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 34 minutes.

[0100] The primary polymer thus produced was polymerized under the conditions of a temperature of 278° C. and a pressure of 25 bar for 51 minutes, while continuously supplying the primary polymer into the plug flow reactor having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

EXAMPLE 6

[0101] 600 g of dicyclopentadiene, 150 g of piperylene, and 250 g of styrene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 34 minutes.

[0102] The primary polymer thus produced was polymerized under the conditions of a temperature of 278° C. and a pressure of 25 bar for 51 minutes, while continuously supplying the primary polymer into the plug flow reactor having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

EXAMPLE 7

[0103] 600 g of dicyclopentadiene, 100 g of piperylene, and 300 g of styrene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 36 minutes.

[0104] The primary polymer thus produced was polymerized under the conditions of a temperature of 278° C. and a pressure of 25 bar for 54 minutes, while continuously supplying the primary polymer into the plug flow reactor having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

COMPARATIVE EXAMPLE 1

[0105] 1,000 g of dicyclopentadiene was mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 30 minutes.

[0106] The primary polymer thus produced was polymerized under the conditions of a temperature of 272° C. and a pressure of 25 bar for 45 minutes, while continuously supplying the primary polymer into the plug flow reactor (PFR) having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

COMPARATIVE EXAMPLE 2

[0107] 1,000 g of dicyclopentadiene was mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor (PFR) having an internal volume of 0.590 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 30 minutes.

[0108] The primary polymer thus produced was polymerized under the conditions of a temperature of 272° C. and a pressure of 25 bar for 45 minutes, while continuously supplying the primary polymer into the plug flow reactor (PFR) having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

COMPARATIVE EXAMPLE 3

[0109] 1,000 g of dicyclopentadiene was mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor (CSTR) having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 30 minutes.

[0110] The primary polymer thus produced was polymerized under the conditions of a temperature of 272° C. and a pressure of 25 bar for 45 minutes, while continuously supplying the primary polymer into the continuous stirred tank reactor (CSTR) having an internal volume of 0.416 L. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

COMPARATIVE EXAMPLE 4

[0111] 750 g of dicyclopentadiene and 250 g of styrene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 34 minutes.

[0112] The primary polymer thus produced was polymerized under the conditions of a temperature of 278° C. and a pressure of 25 bar for 51 minutes, while continuously supplying the primary polymer into the plug flow reactor having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

COMPARATIVE EXAMPLE 5

[0113] 700 g of dicyclopentadiene and 300 g of styrene were mixed in 1,000 g of a xylene solvent to prepare a monomer composition. A primary polymer was produced by reacting the monomer composition while continuously supplying the monomer composition into the continuous stirred tank reactor having an internal volume of 0.416 L with stirring under the conditions of a temperature of 260° C. and a pressure of 25 bar for 34 minutes.

[0114] The primary polymer thus produced was polymerized under the conditions of a temperature of 278° C. and a pressure of 25 bar for 51 minutes, while continuously supplying the primary polymer into the plug flow reactor having an internal volume of 0.590 L connected to the continuous stirred tank reactor. A product in which polymerization was completed was depressurized at 200° C. for 30 minutes to recover a dicyclopentadiene-based resin.

[0115] The reaction conditions of the Examples and Comparative Examples are shown in the following Table 1.

TABLE-US-00001 TABLE 1 Reaction condition Reaction condition of first step of second step Reaction Reaction Weight temperature temperature ratio (n) of Reactor and time Reactor and time comonomer Example 1 CSTR 260° C., PFR 272° C., 0.03 30 min 45 min Example 2 CSTR 260° C., PFR 272° C., 0.05 30 min 45 min Example 3 CSTR 260° C., PFR 272° C., 0.10 30 min 45 min Example 4 CSTR 260° C., PFR 278° C., 0.30 34 min 51 min Example 5 CSTR 260° C., PFR 278° C., 0.35 34 min 51 min Example 6 CSTR 260° C., PFR 278° C., 0.40 34 min 51 min Example 7 CSTR 260° C., PFR 278° C., 0.40 36 min 54 min Comparative CSTR 260° C., PFR 272° C., — Example 1 30 min 45 min Comparative PFR 260° C., PFR 272° C., — Example 2 30 min 45 min Comparative CSTR 260° C., CSTR 272° C., — Example 3 30 min 45 min Comparative CSTR 260° C., PFR 278° C., 0.25 Example 4 34 min 51 min Comparative CSTR 260° C., PFR 278° C., 0.30 Example 5 36 min 54 min

EXPERIMENTAL EXAMPLE

[0116] The molecular weights (Mn, Mw, Mz) and the polydispersity index (PDI, Mw/Mn) of the dicyclopentadiene-based resin produced from the Examples and the Comparative Examples were measured and are shown in the following Table 2.

TABLE-US-00002 TABLE 2 Weight Mw Mn Mz ratio (n) (g/ (g/ (g/ of PDI- Yield mol) mol) mol) PDI comonomer 1.45 × n (%) Example 1 484 318 3557 1.52 0.03 1.477 65 Example 2 494 320 3353 1.54 0.05 1.458 63 Example 3 493 318 3388 1.55 0.10 1.405 61 Example 4 650 406 1363 1.60 0.30 1.165 60 Example 5 686 426 1474 1.61 0.35 1.103 61 Example 6 713 437 1537 1.63 0.40 1.050 58 Example 7 753 461 1625 1.63 0.40 1.050 65 Compar- 475 269 3762 1.76 — — 55 ative Example 1 Compar- 537 285 3875 1.88 — — 54 ative Example 2 Compar- 521 280 3672 1.86 — — 52 ative Example 3 Compar- 645 343 1371 1.88 0.25 1.518 56 ative Example 4 Compar- 712 365 1502 1.95 0.30 1.515 50 ative Example 5

[0117] As shown in Table 2, it was confirmed that the dicyclopentadiene-based resin according to the Examples of the present invention has a high yield and a narrow molecular weight distribution as compared to the Comparative Examples.

[0118] Furthermore, for Comparative Examples 2 and 3, it was confirmed that the molecular weight distribution was broad and the yield was low by setting the reactor configurations in the primary and secondary polymerization to be the same. Thus, it was confirmed that the reactor was configured differently during the primary and secondary polymerization, and during the primary polymerization, the polymerization was performed while stirring in the continuous stirred tank reactor and during the secondary polymerization, the polymerization was performed in the plug flow reactor, thereby implementing an excellent yield and narrow molecular weight distribution of the dicyclopentadiene-based resin.

[0119] Moreover, it was confirmed that the dicyclopentadiene-based resin produced by a production method according to the embodiment of the present invention may be subjected to the thermal polymerization under the non-catalytic conditions, thereby having the narrow molecular weight distribution and implementing uniform physical properties.

EXAMPLE 8

[0120] The hydrogenation was performed twice under the conditions of a temperature of 260° C. and a pressure of 100 bar using 0.5 wt % of palladium catalyst based on the total weight of the dicyclopentadiene-based resin in Example 1 and 4 NL/min of hydrogen.

COMPARATIVE EXAMPLE 6

[0121] The dicyclopentadiene-based resin in Comparative Example 1 was subjected to the hydrogenation in the same manner as in Example 8.

COMPARATIVE EXAMPLE 7

[0122] The dicyclopentadiene-based resin in Comparative Example 2 was subjected to the hydrogenation in the same manner as in Example 8.

COMPARATIVE EXAMPLE 8

[0123] The dicyclopentadiene-based resin in Comparative Example 3 was subjected to the hydrogenation in the same manner as in Example 8.

[0124] In order to evaluate adhesion of the dicyclopentadiene based hydrogenated resin produced from Example 8, and Comparative Examples 6, 7, and 8, the adhesive composition was produced by adding 25 parts by weight of styrene-butadiene-styrene copolymers, 57 parts by weight of a dicyclopentadiene based hydrogenated resin, 18 parts by weight of a paraffin oil plasticizer, and 0.5 parts by weight of an antioxidant.

[0125] The adhesive composition thus produced was applied to a 100 μm PET film whose cross section was corona treated at a wet thickness of 36 μm using an automatic film applicator. The applied film was dried at 100° C. for 30 minutes to remove the solvent, and a peel strength at 180° and a loop tack test were measured using an FT-1 universal material testing machine (manufactured by LLOYD). The results are shown in Table 3.

TABLE-US-00003 TABLE 3 Peel strength at Tack force Softening point 180° (kgf/25 mm) (kgf) (° C.) Example 8 0.72 1.08 103 Comparative 0.48 0.96 106 Example 6 Comparative 0.44 0.90 103 Example 7 Comparative 0.42 0.91 104 Example 8

[0126] As shown in Table 3, it was confirmed that the dicyclopentadiene based hydrogenated resin in Example 8 has a significantly improved peel strength and a tack force as compared to the hydrogenated resin produced as the Comparative Examples, thereby having excellent adhesion.

[0127] In addition, it was confirmed that the dicyclopentadiene based hydrogenated resin in Example 8 did not cause contamination of the bonding surface or contamination of surrounding devices, even with an increase in implementation with long-term use, and thus exhibited excellent adhesion and holding ability over a long period of time.

[0128] The present invention described above is only an example, and it may be appreciated by those skilled in the art to which the present invention pertains that various modifications and equivalent other exemplary embodiments may be made from the exemplary embodiment. It may be thus understood well that the present invention is not limited to only a form mentioned in the above detailed description. Accordingly, the true scope of technical protection of the present invention is to be determined by the technical spirit of the appended claims.

[0129] Therefore, the spirit of the present invention should not be limited to these exemplary embodiments, but the claims and all of the modifications equal or equivalent to the claims are intended to fall within the scopes and spirits of the present invention.