Aromatic petroleum resin with reduced ratio of low molecular weight oligomer and method for preparing same

Abstract

The method for preparing an aromatic petroleum resin according to the present invention comprises the step of thermally polymerizing a monomer including an aromatic vinyl-based monomer in the absence of a catalyst, wherein the thermal polymerization is carried out only in one step in a single reactor, and the single reactor is a continuous stirred-tank reactor (CSTR).

Description

Aromatic petroleum resin with reduced proportion of low molecular weight oligomers and method for producing the same

[0001] The present invention relates to an aromatic petroleum resin and a method for producing the same. More specifically, the present invention relates to an aromatic petroleum resin with a significantly reduced proportion of low-molecular-weight oligomers and a method for producing the same.

[0002]

[0003] Pure monomer resin (PMR) is a aromatic petroleum resin that exhibits low volatility (low VOC), a light color (water white), and excellent thermal stability compared to other aromatic resins. PMR is used in applications such as electric vehicle tire additives and adhesives, and is recognized as a high-value-added product.

[0004] Currently commercially manufactured PMRs are typically polymerized using Friedel-Crafts catalysts, Lewis acid catalysts, etc. However, these methods pose problems such as resin decomposition and contamination due to residual halides caused by the use of catalysts, and the inherent need for a neutralization process, which can lead to wastewater generation.

[0005] The inventors of the present invention have developed a method for polymerizing aromatic petroleum resins without using a catalyst. However, this method has the problem of generating large amounts of low-molecular-weight oligomers as byproducts. Low-molecular-weight oligomers broaden the molecular weight distribution, cause deviations in product properties, and lower the softening point. Therefore, to control the softening point, low-molecular-weight oligomers must be removed. However, these removed low-molecular-weight oligomers have low thermal polymerization reactivity, making it difficult to reintroduce them as raw materials and thus impossible to commercialize them into petroleum resins. Therefore, even when producing aromatic petroleum resins without a catalyst, there is a need to minimize the generation of low-molecular-weight oligomers as byproducts.

[0006] Related prior art includes US patent US332332.

[0007]

[0008] The purpose of the present invention is to provide an aromatic petroleum resin and a method for producing the same, which can minimize the production of low-molecular-weight oligomers as by-products.

[0009] Another object of the present invention is to provide an aromatic petroleum resin having an increased softening point and a narrow molecular weight distribution and a method for producing the same.

[0010] Another object of the present invention is to provide an aromatic petroleum resin having excellent physical properties and a method for producing the same without using a catalyst and without causing resin decomposition or contamination by residual halides.

[0011] Another object of the present invention is to provide an aromatic petroleum resin and a method for producing the same, which do not require a separation process for removing a catalyst and thus do not generate waste water generated in a neutralization process of a polymer resin.

[0012] Another object of the present invention is to provide an aromatic petroleum resin and a method for producing the same, which can reduce catalyst costs and process costs incurred by using a catalyst and reduce process management points.

[0013] Another object of the present invention is to provide an aromatic petroleum resin and a method for producing the same, which are easy to recover and separate from solvent and unreacted monomer and are easy to reuse.

[0014] Another object of the present invention is to provide an aromatic petroleum resin whose physical properties are easy to control and a method for producing the same.

[0015] Another object of the present invention is to provide an environmentally friendly aromatic petroleum resin and a method for producing the same by reducing VOC and wastewater generation.

[0016] The above and other objects of the present invention can all be achieved by the present invention described below.

[0017]

[0018] 1. One aspect of the present invention relates to a method for producing an aromatic petroleum resin having a reduced proportion of low-molecular-weight oligomers. The method comprises a step of thermally polymerizing a monomer including an aromatic vinyl monomer in the absence of a catalyst, wherein the thermal polymerization is carried out in a single reactor in a single-stage polymerization, and the single reactor is characterized in that it is a continuous stirred tank reactor (CSTR).

[0019] 2. In the above 1 specific example, the monomer comprises about 60 to 100 wt% of an aromatic vinyl monomer and about 0 to 40 wt% of a comonomer, and the comonomer may comprise a hydrogenated aromatic vinyl monomer, a C4-C10 olefin monomer, or a combination thereof.

[0020] 3. In the above 1 to 2 specific examples, the aromatic vinyl monomer may be selected from styrene, alkyl styrene, divinylbenzene, indene, alkyl indene, vinyltoluene, mixed C9 oils and derivatives thereof.

[0021] 4. In the above 1 to 3 specific examples, the monomer and the solvent are continuously introduced into the reactor, and the monomer may be about 20 to 100 wt% and the solvent may be about 0 to 80 wt%.

[0022] 5. In the above specific examples 1 to 4, the thermal polymerization can be performed at a temperature of about 150 to about 300° C. and a pressure of about 5 to about 30 bar.

[0023] 6. In the above 1 to 5 specific examples, the thermal polymerization is completed in only one stage of polymerization in a continuous stirred tank reactor (CSTR), and the thermally polymerized polymer is not subjected to a second thermal polymerization in a plug flow reactor (PFR).

[0024] 7. In the above 1 to 5 specific examples, the method can satisfy the following equation 1:

[0025] [Formula 1]

[0026] 100 * [(A1-A2) / A1] ≥10%

[0027] (In the above equation 1, A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the first stage of thermal polymerization in a CSTR-only reactor, and A1 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the second stage of thermal polymerization).

[0028] 8. Another aspect of the present invention relates to an aromatic petroleum resin. The aromatic petroleum resin is produced by the above production method, and has a weight average molecular weight (Mw) of about 300 g / mol to about 10,000 g / mol, a z-average molecular weight (Mz) of about 1,000 to about 20,000 g / mol, a molecular weight distribution (PDI) of about 1 to about 3, and a softening point of about 0 to 150°C.

[0029] 9. In the above 8 specific examples, the aromatic petroleum resin may have a residual halide of less than about 100 ppm.

[0030] 10. In the above 8 to 9 specific examples, the aromatic petroleum resin may satisfy the following equation 2:

[0031] [Formula 2]

[0032] I O = O A * A2 < 35

[0033] (In the above equation 2, I O is the low molecular weight oligomer index, and O A is the ratio (%) of the total peak area occupied by the olefin region (4.0 to 6.5 ppm region) calculated through integration in the graph obtained as a result of 1H-NMR analysis, and A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) in the total polymer area in GPC analysis of the polymer.

[0034] 11. In the above 8 to 10 specific examples, the aromatic petroleum resin may have a ratio of the z-average molecular weight to the weight-average molecular weight (Mz / Mw) of less than about 2.5.

[0035] 12. In the above 8 to 11 specific examples, the aromatic petroleum resin may have an aromatic hydrogen ratio of about 40 to 62.5%, an aliphatic ratio of about 35 to 60%, and an olefin ratio of about 5% or less among the entire polymer.

[0036] 13. Another aspect of the present invention relates to an adhesive. The adhesive may include an aromatic petroleum resin of any of the above 8 to 12 specific examples.

[0037] 14 Another aspect of the present invention relates to a method for reducing the proportion of low molecular weight oligomers in an aromatic petroleum resin. The method is characterized in that only a single reactor is used during the polymerization of an aromatic vinyl monomer, and the single reactor is a continuous stirred tank reactor (CSTR).

[0038] 15. In the above 14 specific examples, the method can satisfy the following equation 1:

[0039] [Formula 1]

[0040] 100 * [(A1-A2) / A1] ≥10%

[0041] (In the above equation 1, A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the first stage of thermal polymerization in a CSTR-only reactor, and A1 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the second stage of thermal polymerization).

[0042]

[0043] The present invention has the effects of providing an aromatic petroleum resin and a method for manufacturing the same, which can minimize the production of low-molecular-weight oligomers as products, increase the softening point and have a narrow molecular weight distribution, do not use a catalyst and thus do not cause resin decomposition and contamination by residual halides, have excellent physical properties, do not require a separation process to remove the catalyst, and thus do not generate wastewater generated in the neutralization treatment process of the polymerized resin, reduce catalyst costs and process costs generated by using a catalyst, reduce process management points, and are easy to recover and separate solvents and unreacted monomers, are easy to reuse, and are easy to control physical properties, and reduce VOC and wastewater generation, thereby being environmentally friendly.

[0044]

[0045] Figure 1 is a reaction process diagram according to one specific embodiment of the present invention.

[0046] Figure 2 compares the gel permeation chromatography (GPC) results of Example 1 and Comparative Example 1.

[0047] Figure 3 compares the gel permeation chromatography (GPC) results of Example 2 and Comparative Example 2.

[0048]

[0049] Hereinafter, the present invention will be described in more detail. In the present specification, where the terms "includes," "has," and "consists of," are used, other parts may be added, unless "only" is used. When a component is expressed in the singular, it also includes the plural, unless otherwise explicitly stated.

[0050] When interpreting components, it is interpreted to include an error range of approximately 5% even if there is no separate explicit description.

[0051] In this specification, 'low molecular weight oligomer' means an aromatic vinyl oligomer having a weight average molecular weight of less than 700 g / mol.

[0052]

[0053] Aromatic petroleum resin (PMR)

[0054] The above aromatic petroleum resin comprises an aromatic vinyl polymer. In a specific example, the aromatic petroleum resin is produced by thermal polymerization without using a catalyst.

[0055] Figure 1 is a reaction process diagram according to one specific embodiment of the present invention.

[0056] As illustrated in Fig. 1, one specific example can be produced by including a step of thermally polymerizing a monomer solution in a single reactor. In this case, the thermal polymerization is performed in a continuous stirred tank reactor (CSTR) (1) in a single-stage polymerization without using any catalyst.

[0057] In the present invention, the first stage polymerization in a single reactor means that the polymerization reaction is completed in one reactor, and secondary polymerization is not performed in a subsequent reactor.

[0058] The continuous stirred tank reactor (1) described above is not particularly limited as long as it is one commonly used in the technical field to which the present invention pertains, and a polymerization reaction can be carried out with continuous input and mixing of monomers. By performing thermal polymerization in the continuous stirred tank reactor described above, the temperature is maintained uniformly during the reaction, thereby reducing the probability of occurrence of local hot spots and allowing for a narrow molecular weight distribution.

[0059] In a specific example, the monomer is mixed with a solvent and introduced into the reactor, and the mixing ratio may be about 20 to 100 wt% of the monomer and about 0 to 80 wt% of the solvent.

[0060] The above monomer may include about 60 to 100 wt% of an aromatic vinyl monomer and about 0 to 40 wt% of a comonomer.

[0061] The aromatic vinyl monomer may be selected from styrene, alkyl styrene, divinylbenzene, indene, alkyl indene, vinyltoluene, mixed C9 oils, and derivatives thereof. For example, the aromatic vinyl monomer may include about 30 to 100 wt% of styrene monomer and about 0 to 70 wt% of alkyl styrene monomer.

[0062] In a specific example, a comonomer may also be introduced together with the aromatic vinyl monomer. The comonomer may include a hydrogenated aromatic vinyl monomer in which hydrogen is added to an aromatic group, a C4-C10 olefin monomer, or a combination thereof. In a specific example, the comonomer may include vinyl cyclohexane, vinyl cyclohexene, piperylene, isoprene, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or a combination thereof. When the comonomer is further included, the compatibility of the polymer and additives in the pressure-sensitive adhesive composition can be increased by changing the resin structure.

[0063] The above solvent may be one or a mixed solvent of two or more selected from benzene, toluene, and xylene, but is not limited thereto.

[0064] Additionally, in one embodiment, a radical initiator may be added to control reactivity. Such initiators may include, but are not limited to, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, t-butyl 4,4-di(t-butylperoxy)valerate, and the like.

[0065] The above thermal polymerization can be performed at a temperature of about 150 to about 300°C, for example, about 200 to about 295°C, and in a specific example, about 250 to about 290°C. In the above range, the conversion rate or polymerization rate of the monomer is excellent, the occurrence of side reactions is suppressed, and uniform physical properties can be realized with a narrow molecular weight distribution.

[0066] The reaction pressure of the above thermal polymerization can be performed at about 5 to about 30 bar, for example, about 10 to about 25 bar. In the above range, the reaction stability is excellent and the reactivity of the monomer can be increased.

[0067] The above thermal polymerization can be performed for a period of about 5 to about 180 minutes, for example, about 20 to about 120 minutes, and in specific examples, about 30 to about 60 minutes. In this period, side reactions can be suppressed and a narrow molecular weight distribution can be provided.

[0068] Since the above thermal polymerization is completed in a single polymerization step in a continuous stirred tank reactor (CSTR), the proportion of low-molecular-weight oligomers can be significantly reduced. In a specific example, the low-molecular-weight oligomers can be reduced by about 10% or more, preferably about 20% or more, compared to an aromatic petroleum resin that has been first thermally polymerized in a continuous stirred tank reactor (CSTR) and then second thermally polymerized in a plug flow reactor (PFR).

[0069] In a specific example, the method of the present invention can satisfy the following equation 1:

[0070] [Formula 1]

[0071] 100 * [(A1-A2) / A1] ≥ 10%

[0072] (In the above equation 1, A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the first stage of thermal polymerization in a CSTR-only reactor, and A1 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the second stage of thermal polymerization.)

[0073] According to the present invention, by controlling the reaction temperature, monomer concentration or reaction time, the low molecular oligomer ratio, weight average molecular weight, molecular weight distribution (PDI) or softening point of the aromatic petroleum resin can be controlled.

[0074] In a specific example, the outlet of the continuous stirred tank reactor (CSTR) may be equipped with a filter (not shown). The filter may be made of one or a mixture of two or more materials selected from metals, polymers, and ceramics, and may have a pore size of about 100 nm to about 10 μm, preferably about 100 nm to about 1 μm. There are no particular limitations on the filter as long as it can filter out foreign substances.

[0075] The product, after the polymerization is completed, can be subjected to a solvent separation process to recover the aromatic petroleum resin. During the solvent separation process, the solvent and some of the low-molecular-weight oligomers can be separated. The solvent separation process can be performed using a thin film evaporator.

[0076] In one specific example, a hydrogenation reaction may be further performed. For example, the obtained aromatic petroleum resin may be introduced into a continuous hydrogenation reactor packed with a hydrogenation catalyst to perform the hydrogenation reaction. The hydrogenation reaction may be performed at a pressure of about 50 to about 150 bar and a temperature of about 150 to about 300°C, but is not limited thereto. When performed at the above pressure and temperature, destruction of the molecular structure can be prevented. The hydrogenation catalyst is not particularly limited, but any known hydrogenation catalyst may be used. For example, it may be one or a mixture of two or more selected from Ni, Fe, Cu, Co, Mo, Pd, Rh, Pt, Nb, Au, Rd, and Raney Ni. The hydrogenation catalyst may be included in a molar ratio of about 0.001 to about 0.5, preferably about 0.05 to about 0.2, per 1 mol of the petroleum resin monomer to improve reactivity, but is not limited thereto.

[0077] The aromatic petroleum resin according to the present invention is manufactured without using a catalyst, and therefore has a residual halide content of less than about 100 ppm, an aromatic hydrogen content of about 40 to 62.5% of the entire polymer, an aliphatic content of about 35 to 60%, and an olefin content of about 5% or less, preferably about 2% or less, and more preferably about 1.7% or less.

[0078] In a specific example, the aromatic petroleum resin, when polymerized only with aromatic vinyl monomers, has a low molecular weight oligomer index (I) represented by the following formula 2 O ) can satisfy less than about 35:

[0079] [Formula 2]

[0080] I O = O A * A2 < 35

[0081] (In the above equation 2, IO is the low molecular weight oligomer index, and O A is the ratio (%) of the total peak area occupied by the olefin region (4.0 to 6.5 ppm region) calculated through integration in the graph obtained as a result of 1H-NMR analysis, and A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) in the total polymer area in GPC analysis of the polymer.

[0082] In a specific example, the low molecular weight oligomer index (I O ) is less than about 35, for example, about 1 to 24.5, and specifically, about 10 to 20. In the above range, uniform properties can be secured, VOC generation can be reduced, and excellent adhesive strength can be achieved when manufacturing an adhesive.

[0083] The above aromatic petroleum resin may have a softening point of about 0 to 150°C, for example, about 70 to 130°C.

[0084] The aromatic petroleum resin may have a weight average molecular weight (Mw) of about 300 g / mol to about 10,000 g / mol, in specific examples, about 1,000 g / mol to about 7,000 g / mol, preferably about 1,350 g / mol to about 7,000 g / mol, a z average molecular weight (Mz) of about 1,000 g / mol to about 20,000 g / mol, in specific examples, about 1,500 g / mol to about 15,000 g / mol, preferably about 2,000 g / mol to about 15,000 g / mol, and a molecular weight distribution (PDI) of about 1 to about 3, for example, about 1 to about 2.7, specifically, about 1.1 to about 2.65.

[0085] In addition, the aromatic petroleum resin may have a ratio of z-average molecular weight to weight-average molecular weight (Mz / Mw) of less than about 2.5, in specific examples, 2.0 or less, for example, about 1.84 or less, specifically, about 1.6 to about 1.835. It may have uniform physical properties within the above range.

[0086] In a specific example, the aromatic petroleum resin has low VOC and low yellow index, and excellent thermal stability.

[0087] The aromatic petroleum resin according to the present invention has no problems of resin decomposition or contamination and has excellent physical properties, so it can be used for purposes such as adhesives and electric vehicle tire additives.

[0088] Another aspect of the present invention is a method for controlling the properties of an aromatic petroleum resin. The method comprises controlling the reaction temperature, monomer concentration, and reaction time in a single-stage thermal polymerization step of a monomer solution in a continuous stirred tank reactor (CSTR) in the absence of a catalyst. In one specific example, the molecular weight distribution (PDI) can be narrowly controlled by lowering the concentration of the aromatic vinyl monomer fed into the continuous stirred tank reactor. In another specific example, lowering the reaction temperature in the continuous stirred tank reactor can reduce the production of low-molecular-weight oligomers.

[0089] In a specific example, the method may satisfy the following equation 1:

[0090] [Formula 1]

[0091] 100 * [(A1-A2) / A1] ≥10%

[0092] (In the above equation 1, A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the first stage of thermal polymerization in a CSTR-only reactor, and A1 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the second stage of thermal polymerization.)

[0093]

[0094] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0095]

[0096] Example

[0097] Example 1

[0098] A monomer solution was prepared by mixing 1350 g of styrene and 150 g of alpha methyl styrene in 1500 g of xylene solvent. The monomer solution was continuously supplied to a CSTR (internal volume: 400 ml) and polymerization was performed (reaction time: 80 min) under conditions of 270°C and 25 bar. The polymerized product was separated from the solvent and some of the low-molecular-weight oligomers in a thin film evaporator (TFE) at 230°C and 2 mbar to recover the aromatic petroleum resin.

[0099]

[0100] Comparative Example 1

[0101] A monomer solution was prepared by mixing 1350 g of styrene and 150 g of alpha methyl styrene in 1500 g of xylene solvent. The monomer solution was continuously supplied to a CSTR (internal volume: 400 ml) and the first stage polymerization (reaction time: 40 minutes) was performed under the conditions of 280°C and 25 bar of pressure. The reaction product from the first stage polymerization was continuously supplied to a PFR (internal volume: 600 ml) connected to the CSTR and the second stage polymerization (reaction time: 60 minutes) was performed under the conditions of 280°C and 25 bar of pressure. The polymerized product was separated from the solvent and some of the low-molecular-weight oligomers in a thin film evaporator at 230°C and 2 mbar to recover the aromatic petroleum resin.

[0102] The results of GPC analysis of the aromatic petroleum resin polymerized in Example 1 and Comparative Example 1 before being introduced into the thin film evaporator are shown in Fig. 2.

[0103] The reaction conditions are shown in Table 1, and the physical property evaluation results are shown in Table 2:

[0104] Monomer solution (styrene: alpha-methylstyrene: solvent) Polymerization conditions Example 145: 5: 50 CSTR (270℃, 80min) Comparative example 145: 5: 50 CSTR (280℃, 40min) - PFR (280℃, 60min)

[0105]

[0106] MwMnMzPDI Low molecular weight oligomer % * Softening point (℃) Aromatic ratio (%) Olefin ratio (%) Aliphatic ratio (%) Example 1149385226211.75217860.011.6238.37 Comparative example 1148077729251.91267259.501.8638.64

[0107] As confirmed in the above examples and comparative examples, the aromatic petroleum resin manufactured according to the method of the present invention has a 19.23% decrease in the proportion of low-molecular-weight oligomers according to Equation 1 and an increase in the softening point. In addition, the aromatic petroleum resin exhibits a narrow molecular weight distribution and a significantly reduced olefin content.

[0108]

[0109] Example 2

[0110] The same procedure as Example 1 was followed except that the polymerization temperature was changed to 260°C.

[0111]

[0112] Comparative Example 2

[0113] The same procedure as Example 2 was performed except that the polymerization conditions were changed to those in Table 3 below.

[0114] The results of GPC analysis of the aromatic petroleum resin polymerized in Example 2 and Comparative Example 2 before being introduced into the thin film evaporator are shown in Fig. 3.

[0115] The reaction conditions are shown in Table 3, and the physical property evaluation results are shown in Table 4:

[0116]

[0117] Monomer solution (styrene: alpha-methylstyrene: solvent) Polymerization conditions Example 245: 5: 50 CSTR (260℃, 80min) Comparative example 245: 5: 50 CSTR (270℃, 40min) - PFR (270℃, 60min)

[0118]

[0119] MwMnMzPDI Low molecular weight oligomer % * Softening point (℃) Aromatic ratio (%) Olefin ratio (%) Aliphatic ratio (%) Example 22515129744441.94169061.021.5237.46 Comparative example 22441121545232.0188560.302.3237.39

[0120] As confirmed in the above examples and comparative examples, the aromatic petroleum resin manufactured according to the method of the present invention has a reduced proportion of low molecular weight oligomers according to Equation 1 by 11.1% and an increased softening point. In addition, the aromatic petroleum resin exhibits a narrow molecular weight distribution and a significantly reduced olefin content.

[0121]

[0122] Example 3

[0123] The same procedure as Example 1 was followed, except that only styrene was used as a monomer and the polymerization conditions were changed to those in Table 5 below.

[0124]

[0125] Comparative Example 3

[0126] The same procedure as Example 3 was performed except that the polymerization conditions were changed to Table 5 below.

[0127] The reaction conditions are shown in Table 5, and the physical property evaluation results are shown in Table 6:

[0128]

[0129] Monomer solution (styrene: solvent) Polymerization conditions Example 350: 50 CSTR (260℃, 80min) Comparative example 350: 50 CSTR (270℃, 40min) - PFR (270℃, 60min)

[0130]

[0131] MwMnMzPDI Low molecular weight oligomer % * Softening point (℃) Aromatic ratio (%) Olefin ratio (%) Aliphatic ratio (%) Example 33239153956542.10129861.691.2037.11 Comparative example 32974134955722.20169061.161.8936.95

[0132] As confirmed in the above examples and comparative examples, the aromatic petroleum resin manufactured according to the method of the present invention has a 25% reduction in the proportion of low-molecular-weight oligomers according to Equation 1 and an increased softening point. In addition, the aromatic petroleum resin exhibits a narrow molecular weight distribution and a significantly reduced olefin content.

[0133]

[0134] Example 4

[0135] A monomer solution was prepared by mixing 2430 g of styrene and 270 g of piperylene with 300 g of xylene solvent. The monomer solution was continuously supplied to a CSTR (internal volume: 400 ml) and polymerization was performed (reaction time: 80 min) under conditions of 270°C and 25 bar. The polymerized product was separated from the solvent and some of the low-molecular-weight oligomers in a thin film evaporator (TFE) at 230°C and 2 mbar to recover the aromatic petroleum resin.

[0136]

[0137] Example 5

[0138] A monomer solution was prepared by mixing 2160 g of styrene and 540 g of piperylene with 300 g of xylene solvent. The monomer solution was continuously supplied to a CSTR (internal volume: 400 ml) and polymerization was performed (reaction time: 80 min) under conditions of 270°C and 25 bar. The polymerized product was separated from the solvent and some of the low-molecular-weight oligomers in a thin film evaporator (TFE) at 230°C and 2 mbar to recover the aromatic petroleum resin.

[0139]

[0140] Monomer solution (styrene: piperylene: solvent) Polymerization conditions Example 48 1: 9: 10 CSTR (270℃ 40min) Example 57 2: 18: 10 CSTR (270℃ 40min)

[0141]

[0142] MwMnMzPDI Low molecular weight oligomer % * Softening point (℃) Aromatic. (%) Olefin (%) Aliphatic (%) Example 4 4 ​​4 3 4 1 6 8 8 1 4 3 2.6 3 1 0 1 0 2 5 5.7 4 2.0 8 4 2.1 8 Example 5 3 9 7 5 1 5 0 4 7 4 7 0 2.6 4 1 2.5 9 4 5 0.5 3 3.6 1 4 5.8 6

[0143] As confirmed in the above examples, the aromatic petroleum resin manufactured according to the method of the present invention had a low molecular weight oligomer content of 12.5% ​​or less, a softening point of 90°C or higher, and a narrow molecular weight distribution.

[0144]

[0145] Physical property evaluation method

[0146] (1) Molecular weight

[0147] Polystyrene-converted weight-average molecular weight (Mw), number-average molecular weight (Mn), and Z-average molecular weight (Mz) were determined by gel permeation chromatography (GPC) (Viscotek TDA302 and Agilent 1200 series (Pump)).

[0148] The resin to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm and 100 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and the flow rate was 1.0 mL / min. The analysis was performed at 35°C. The column was (Agilent PL Mixed C 2 set + PL 50 Å). An RI detector (Viscotek RI) was used for the measurement at 35°C. The Mw, Mn, and Mz values ​​were derived using the calibration curve formed after measuring the polystyrene standard. The molecular weights of the polystyrene standard were 12 types: 104 / 118 / 236 / 580 / 1480 / 2340 / 2970 / 5030 / 8450 / 10850 / 20650 / 24600.

[0149] At this time, the polydispersity index (PDI) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.

[0150]

[0151] (2) Low molecular weight oligomer %

[0152] GPC analysis was performed before the polymer solution was introduced into the thin-film evaporator, and the area of ​​low-molecular-weight oligomers (retention time 21.6–24.1 min) was calculated from the proportion of the total polymer.

[0153]

[0154] (3) Softening point

[0155] The softening point of the resin was measured twice according to ASTM E 28 using an Anton Paar RKA5 instrument, and the average value was calculated and reported.

[0156]

[0157] (4) NMR analysis

[0158] Nuclear magnetic resonance (1H-NMR) analysis was performed on the aromatic petroleum resins manufactured in the examples and comparative examples.

[0159] ​Specifically, the aromatic petroleum resins manufactured in the above examples and comparative examples were each dissolved in the solvent CDCl3 at a concentration of 2.5 wt% to manufacture a sample, and then analyzed using a nuclear magnetic resonance spectrometer (Bruker 600NMR, 14.1 telsa) under the conditions of 600 MHz, acquisition time 2.75 s, delay time 1 s, number of scans 128, pulse 30°, and solvent CDCl3.

[0160] From the above 1H-NMR analysis results, the aromaticity (Aromaticity, %) of the aromatic petroleum resin was calculated according to the following mathematical formula 1.

[0161] [Mathematical Formula 1]

[0162] Aromaticity(%) = [Ar A / (Ar A + O A + Al A )] * 100

[0163]

[0164] In the above mathematical formula 1, Ar A is a value calculated as the area ratio of the hydrogen peak bonded to aromatic hydrocarbons, which appears in the aromatic region, specifically in the region of 6.5 to 8.5 ppm, based on the total peak area in the graph obtained as a result of 1H-NMR analysis, and O A is a value calculated as the area ratio of the hydrogen peak appearing in the olefin region, specifically in the 4.0 to 6.5 ppm region, based on the total peak area, and Al A is a value obtained from the area ratio of the hydrogen peak bonded to aliphatic hydrocarbons, which appears in the aliphatic region, specifically in the region of 0.1 to 4.0 ppm, based on the total peak area. The peak area was calculated through integration.

[0165]

[0166] Simple modifications or changes of the present invention can be easily implemented by a person having ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims

1. A method for producing an aromatic petroleum resin having a reduced proportion of low molecular oligomers, the method comprising: A step of thermally polymerizing a monomer including an aromatic vinyl monomer in the absence of a catalyst, The above thermal polymerization is carried out in a single reactor in only one stage. A method for producing an aromatic petroleum resin, characterized in that the single reactor is a continuous stirred tank reactor (CSTR).

2. A method for producing an aromatic petroleum resin according to claim 1, wherein the monomer comprises 60 to 100 wt% of an aromatic vinyl monomer and 0 to 40 wt% of a comonomer, and the comonomer comprises a hydrogenated aromatic vinyl monomer, a C4-C10 olefin monomer, or a combination thereof.

3. A method for producing an aromatic petroleum resin in the first paragraph, wherein the aromatic vinyl monomer is selected from styrene, alkyl styrene, divinylbenzene, indene, alkyl indene, vinyltoluene, mixed C9 oil and derivatives thereof.

4. A method for producing an aromatic petroleum resin, wherein in paragraph 1, the monomer and solvent are continuously fed into the reactor, and the monomer is 20 to 100 wt% and the solvent is 0 to 80 wt%.

5. A method for producing an aromatic petroleum resin, wherein the thermal polymerization in the first paragraph is performed at a temperature of 150 to 300°C and a pressure of 5 to 30 bar.

6. In the first paragraph, the thermal polymerization It is completed in one stage of polymerization in a continuous stirred tank reactor (CSTR). A method for producing an aromatic petroleum resin, wherein a thermally polymerized polymer is not subjected to a second thermal polymerization in a plug flow reactor (PFR).

7. In the first paragraph, the method is a method for producing an aromatic petroleum resin that satisfies the following formula 1: [Formula 1] 100 * [(A1-A2) / A1] ≥ 10% (In the above equation 1, A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the first stage of thermal polymerization in a CSTR-only reactor, and A1 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the second stage of thermal polymerization.) 8. Manufactured by any one of the manufacturing methods of clauses 1 to 7, The weight average molecular weight (Mw) is 300 g / mol to 10,000 g / mol, z The average molecular weight (Mz) is 1,000 to 20,000 g / mol, The molecular weight distribution (PDI) is 1 to 3, Aromatic petroleum resin with a softening point of 0 to 150 ℃.

9. In paragraph 8, the aromatic petroleum resin is an aromatic petroleum resin having a residual halide of less than 100 ppm.

10. In the 8th paragraph, the aromatic petroleum resin is an aromatic petroleum resin that satisfies the following formula 2: [Formula 2] I O = O A * A2 < 35 (In the above equation 2, I O is the low molecular weight oligomer index, and O A is the ratio (%) of the total peak area occupied by the olefin region (4.0 to 6.5 ppm region) calculated through integration in the graph obtained as a result of 1H-NMR analysis, and A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) in the total polymer area in GPC analysis of the polymer.

11. In the 8th paragraph, the aromatic petroleum resin is an aromatic petroleum resin having a ratio of the z-average molecular weight to the weight-average molecular weight (Mz / Mw) of less than 2.

5.

12. In the 8th paragraph, the aromatic petroleum resin is an aromatic petroleum resin having an aromatic hydrogen ratio of 40 to 62.5%, an aliphatic ratio of 35 to 60%, and an olefin ratio of 5% or less among the entire polymer.

13. Adhesive containing the aromatic petroleum resin of Article 9.

14. A method for reducing the low molecular weight oligomer ratio of aromatic petroleum resin, wherein the method comprises: When polymerizing aromatic vinyl monomers, only a single reactor is used. A method wherein the single reactor is a continuous stirred tank reactor (CSTR).

15. In the 14th paragraph, the method is a method for reducing the low molecular weight oligomer ratio of an aromatic petroleum resin, which satisfies the following formula 1: [Formula 1] 100 * [(A1-A2) / A1] ≥10% (In the above equation 1, A2 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the first stage of thermal polymerization in a CSTR-only reactor, and A1 is the ratio (%) of the area of ​​low molecular weight oligomers (retention time 21.6 to 24.1 minutes) to the total polymer area in the GPC analysis of the polymer polymerized in the second stage of thermal polymerization).

Images