KR102393363B1 - Petroleum resin and preparation method thereof - Google Patents

Abstract

The present invention relates to a petroleum resin and a method for manufacturing the same, and more particularly, the use of dicyclopentadiene, C9 monomer, and C5 monomer is maintained as it is, but by changing the mixing ratio and polymerization conditions of raw materials, the physical properties as a petroleum resin are It relates to a petroleum resin capable of securing and minimizing the generation of volatile organic compounds without an increase in manufacturing cost and a method for manufacturing the same.

Description

Petroleum resin and preparation method thereof

The present invention relates to a petroleum resin for reducing the generation of volatile organic compounds and a method for manufacturing the same.

Petroleum resin is polymerized using by-products generated during the naphtha cracking process as a raw material, and is mainly used to impart adhesiveness to polymers or rubbers. Currently, it is widely used in various applications such as adhesives, coatings, inks, and rubber compounds that require adhesive properties.

Petroleum resins are generally prepared through thermal polymerization using a solvent. When a petroleum resin manufactured through thermal polymerization is melted at a high temperature, a large amount of volatile organic compounds (VOC) are generated by unreacted raw materials, solvents, and low molecular weight oligomers present in the petroleum resin, which is harmful to the working environment. It has adverse effects and is released into the atmosphere, causing environmental pollution.

Volatile organic compounds are chemical substances that pose a risk to the human body and the environment in various aspects, such as carcinogenic potential, tropospheric ozone formation, photochemical smog formation, and explosiveness.

For example, in the case of benzene, it is closely related to a decrease in central nervous system activity and an increase in the carcinogenic rate of workers exposed to large amounts for a long period of time. aplastic anemia).

Accordingly, it is possible to minimize the generation of the volatile organic compounds through the removal of unreacted raw materials, solvents, low molecular weight oligomers, etc. present in the petroleum resin. Removal of the unreacted raw material, solvent, and low molecular weight oligomer may be performed through a conventional purification process such as fractional distillation or chromatography, but this additional purification process causes another problem of increased cost. In particular, the removal of unreacted raw materials or solvents is possible through simple heat treatment such as degassing, but the removal of low molecular weight oligomers is very difficult because they are directly involved in the physical properties of petroleum resins.

Accordingly, rather than suppressing the generation of the volatile organic compound through the removal of the material, a technique for effectively treating the already generated volatile organic compound before discharging it to the atmosphere has been proposed.

The treatment technology for volatile organic compounds is largely divided into destruction technology and recovery technology. A combustion technique such as oxidation or incineration is used to destroy the volatile organic compound, and these techniques include a thermal oxidation method including radiant heat and a regenerative heat recovery device and a catalytic oxidation method. The recovery technology for collecting volatile organic compounds before final treatment includes adsorption, absorption, and condensation. In addition, prevention technologies using various new technologies using biological treatment methods or adsorption/catalytic oxidation methods have been developed and utilized.

The above methods are a technology for treating volatile organic compounds that have already been generated, and an increase in cost is inevitably followed by various devices and facilities for this.

Therefore, it is better to design to minimize the generation of substances causing the volatile organic compounds in the production of petroleum resin than to remove the substances causing the generation of volatile organic compounds or to process the previously generated volatile organic compounds without increasing the cost. It can be the most effective way to solve the problem caused by volatile organic compounds.

Accordingly, the present inventors tried to solve this problem by adding a new monomer or adjusting the process conditions during polymerization of petroleum resin, but this control rather lowers the physical properties of the petroleum resin itself, revealing another problem in the field of application caused

Korean Patent Laid-Open Patent No. 2016-0002273 (Jan. 7, 2016), Manufacturing method of petroleum resin with improved odor

In order to solve the above problem, the present inventors prepared a petroleum resin by polymerizing dicyclopentadiene and C9 and C5 monomers, but as a result of polymerization by controlling the content of the monomer and setting only the polymerization temperature upward, the physical properties of the petroleum resin It was possible to effectively reduce only the generation of low molecular weight oligomers that cause the generation of volatile organic compounds without degradation, and thereby completed the present invention by confirming that the generation of volatile organic compounds during high-temperature melting of the petroleum resin for manufacturing an adhesive is minimized. .

Accordingly, an object of the present invention is to provide a petroleum resin capable of significantly lowering the amount of volatile organic compounds generated from the petroleum resin while maintaining the physical properties of the petroleum resin and a method for manufacturing the same.

In order to achieve the above object, the present invention is a petroleum resin in which dicyclopentadiene and C9 monomer are copolymerized, and the content of volatile organic compounds (VOC) generated from the petroleum resin when the petroleum resin is left at 200° C. for 90 minutes It provides a petroleum resin, characterized in that less than 2% by weight relative to the initial weight of the petroleum resin.

In addition, the present invention is a petroleum resin in which dicyclopentadiene, a C9 monomer and a C5 monomer are copolymerized, and the content of volatile organic compounds (VOC) generated from the petroleum resin when the petroleum resin is left at 200° C. for 90 minutes. It provides a petroleum resin, characterized in that not more than 2% by weight relative to the initial weight of the petroleum resin.

In this case, the petroleum resin has a weight average molecular weight of 500 to 1000 g/mol, and a softening point of 100 to 120°C.

In addition, the present invention comprises the steps of mixing 25 to 50 parts by weight of a C9 monomer with respect to 100 parts by weight of dicyclopentadiene; and

It provides a method for producing a petroleum resin, characterized in that it comprises the step of thermal polymerization at a temperature of 275 to 280 ℃.

In addition, the present invention comprises the steps of mixing 10 to 20 parts by weight of a C9 monomer and 40 to 60 parts by weight of a C5 monomer based on 100 parts by weight of dicyclopentadiene; and

It provides a method for producing a petroleum resin, characterized in that it comprises the step of thermal polymerization at a temperature of 275 to 280 ℃.

According to the present invention, the physical properties of the petroleum resin are maintained through establishment of optimal conditions for suppressing the generation of volatile organic compounds, and at the same time, the volatile organic compounds generated from the petroleum resin in the manufacturing process of the adhesive using the petroleum resin are maximized. There is an effect that can increase the efficiency of the work by suppressing the problem that had a bad influence on the prior work environment.

1 is a gel chromatography of the petroleum resin prepared in Example 1 and Comparative Example 1.
Figure 2 is a gel chromatography of the petroleum resin prepared in Example 2 and Comparative Example 3.

The present invention provides a petroleum resin capable of minimizing the generation of volatile organic compounds and a method for manufacturing the same.

The term "volatile organic compound" as used herein is a generic term for numerous organic compounds, including benzene, butadiene, gasoline, hexane, butane, propane, olefin, acrolein, acrylonitrile, 1-butene, 2-butene, carbon tetrachloride, chloroform, Cyclohexane, 1,2-dichloromethane, ethylene, formaldehyde, isopropyl alcohol, methanol, methyl ethyl ketone, methylene chloride, MTB (methyl tertiary butyl ether), propylene, propylene oxide, 1,1,1-trichloro Ethane, trichloroethylene, gasoline, naphtha, crude oil, acetic acid, ethylbenzene, nitrobenzene, toluene, tetrachloroethylene, xylene, styrene, etc. are substances that have a harmful effect on the human body. The volatile organic compound is easily evaporated and exists in a gaseous state in the atmosphere, and is not only an air pollutant but also a substance that causes global warming, and has carcinogenicity.

Volatile organic compounds are classified into volatile (Volatile), semi-volatile (Semi-Volatile), and non-volatile (Non-Volatile) according to the form of the material phase. VOCs are classified according to their boiling points, high volatility (VVOCs) when boiling point is 0℃~(50-100℃), volatile (VOCs), (240~260) (50-100℃)~(240-260℃) ℃)~(380-400℃) are classified as semi-volatile (SVOCs), and those above 380℃ are classified as solid (POM: Particle-bond Organic Compounds), and the Reid Vapor Pressure (RVP) among hydrocarbons is 10.3 kPa ( 1.5 psia) or higher is defined as petrochemical products, organic solvents, or other substances.

Among them, the volatile organic compounds to be removed in the present invention refer to highly volatile (VVOCs) and volatile (VOCs) organic compounds having a boiling point of 0 to 200°C.

The petroleum resin presented in the present invention is characterized in that the content of volatile organic compounds (VOC) generated from the petroleum resin is 2% by weight or less based on the weight of the initial petroleum resin when the petroleum resin is left at 200° C. for 90 minutes. If it is out of the above range, a separate treatment device for removing the volatile organic compound is required, and without such a device, it may adversely affect workers and the environment.

Generation of volatile organic compounds of 2 wt % or less can be achieved by designing a petroleum resin manufacturing process by fundamentally reducing the generation of substances that cause its occurrence, ie, low molecular weight oligomers that are difficult to remove in petroleum resin.

A general petroleum resin is made by copolymerizing dicyclopentadiene with C9 monomer or additional C5 monomer, which is an aromatic oil, and usually 80 to 90% of dicyclopentadiene is used, and C9 monomer and/or C5 monomer is 10 to Use 20%. The petroleum resin of this composition has a weight average molecular weight of 500 to 1000 g/mol, and a softening point of 100 to 120° C., and when it is within the above range, it can be preferably applied to various uses such as adhesives. In particular, it is very important to secure the physical properties of petroleum resins with a softening point of 100°C or higher.

However, unreacted raw materials, solvents and low molecular weight oligomers are present in the petroleum resin after polymerization. Although the unreacted raw materials and solvents are simple, the removal of low molecular weight oligomers is not easy even through post-treatment, etc., which generates a large amount of volatile organic compounds in the adhesive manufacturing process at 150 to 200°C.

Therefore, in the present invention, by maintaining the monomer used as it is to secure the physical properties of the petroleum resin, but to fundamentally reduce the occurrence of low-molecular-weight oligomers that are difficult to remove, (i) the mixing ratio of the raw materials and (ii) the polymerization temperature during polymerization conditions are controlled. A petroleum resin with minimal generation of volatile organic compounds is manufactured without an increase in manufacturing cost.

(i) Control of the mixing ratio of raw materials

The adjustment of the raw material mixing ratio is performed in consideration of the physical properties of the finally obtained petroleum resin. The content of dicyclopentadiene affects basic properties such as molecular weight, softening point, and glass transition temperature (Tg) of the finally obtained petroleum resin, as well as application properties such as adhesive strength, compatibility, and color. At this time, the C9 monomer copolymerized together is used to increase the physical properties (eg, molecular weight, softening point, Tg) of the petroleum resin. If the content is too small or too large, the molecular weight and Tg of the petroleum resin increase but the softening point is lowered. Together with the above-mentioned application properties are affected and the yield is greatly reduced. Therefore, the design of the raw material mixing ratio is very important.

The petroleum resin according to the present invention is polymerized by lowering the content of dicyclopentadiene and increasing the content of the comonomer instead of using 80 to 90% of the petroleum resin. The comonomer may be a C9 monomer and a C5 monomer.

Specifically, the petroleum resin according to the first embodiment of the present invention is a petroleum resin in which dicyclopentadiene/C9 monomer is copolymerized, and the petroleum resin according to the second embodiment is copolymerized in dicyclopentadiene/C9 monomer/C5 monomer. It is an old petroleum resin.

These petroleum resins have the above-mentioned weight average molecular weight of 500 to 1000 g/mol, and limit the content of each monomer in order to achieve the physical properties of a softening point of 100 to 120°C.

The petroleum resin according to the first embodiment is copolymerized with 25 to 50 parts by weight of a C9 monomer based on 100 parts by weight of dicyclopentadiene to achieve the physical properties of the petroleum resin. If less than the above range is used, the generation of volatile organic compounds is increased, and on the contrary, when used in excess of the above range, the basic physical properties (eg, molecular weight, softening point, etc.) of the petroleum resin are lowered or the yield is greatly lowered, so the above range properly used within

The C9 monomer used is not particularly limited in the present invention, and a known aromatic monomer is used. Typically, the C9 monomer may be at least one selected from the group consisting of styrene, vinyltoluene, indene, alphamethylstyrene, and benzene/toluene/xylene (BTX), preferably styrene 10 to 20 wt%, vinyltoluene 10-20 wt%, indene 10-20 wt%, alpha methylstyrene 1-7 wt% and BTX 40-60 wt%, or styrene 10-30 wt%, indene 10 wt% A mixed oil containing 20% by weight, 1 to 7% by weight of alpha methylstyrene, and 50 to 80% by weight of BTX is used.

The petroleum resin according to the second embodiment is copolymerized with 10 to 20 parts by weight of a C9 monomer and 40 to 60 parts by weight of a C5 monomer based on 100 parts by weight of dicyclopentadiene to achieve the physical properties of the petroleum resin.

The C9 monomer is as mentioned above.

The C5 monomer may be at least one selected from the group consisting of isoprene, piperylene, cyclopentadiene, 1-pentene, 2-methyl-2-butene and n-pentane as an aliphatic monomer, preferably isoprene 10 to 20 wt%, piperylene 10-20 wt%, cyclopentadiene 0.5-1.5 wt%, 1-pentene 2-4 wt%, 2-methyl-2-butene 1-3 wt% and n-pentane 25-35 wt% A mixed C5 fraction containing

When the content of the C9 monomer and the C5 monomer is within the above ranges, the physical properties (eg, molecular weight, softening point) of the petroleum resin presented above can be achieved, and when it is out of this range, the physical properties of the softening point of 100° C. or higher cannot be secured.

(ii) control of polymerization conditions

The petroleum resin produced through the content of C9 monomer and C5 monomer has a lower content of dicyclopentadiene than that of the conventional petroleum resin when the content of each monomer is 100% compared to that of the conventional petroleum resin. This low content of dicyclopentadiene affects the yield along with the physical properties of the petroleum resin, as already mentioned. Dicyclopentadiene has excellent reactivity even at low temperatures and has a conversion rate of 99%, and the yield tends to increase as the temperature increases. However, deterioration of physical properties caused by a decrease in the content of dicyclopentadiene can be offset by designing the conditions for thermal polymerization.

Thermal polymerization is a polymerization through a radical or Diels-Alder reaction between dicyclopentadiene and a C9 monomer, preferably dicyclopentadiene and a C9 monomer, and further a C5 monomer. Thermal polymerization is preferred.

Thermal polymerization is carried out at a temperature at which the initiation and polymerization reaction of dicyclopentadiene and C9 monomer can sufficiently occur, and in particular, when carried out at 275 to 280 ° C. It is possible to solve the problem of low yield, and it is possible to increase the softening point of the petroleum resin by a fast reaction with such a high conversion rate. The temperature is 5 to 8°C higher than the conventional thermal polymerization temperature of dicyclopentadiene and C9 monomer. When polymerization is performed in the polymerization temperature range of the present invention with the existing composition ratio, decomposition of the monomer occurs, side reaction or gelation occurs. This is directly related to deterioration of physical properties and low yield, and the generation of volatile organic compounds may be more severe due to the monomer decomposition, side reactions, and gelation.

Preferably, the petroleum resin according to the first embodiment in which dicyclopentadiene and C9 monomers are copolymerized is prepared by mixing 25 to 50 parts by weight of a C9 monomer with respect to 100 parts by weight of dicyclopentadiene; And it is prepared including the step of thermal polymerization at a temperature of 275 to 280 ℃.

In addition, the petroleum resin according to the second embodiment in which dicyclopentadiene, C9 monomer and C5 monomer is copolymerized is 10 to 20 parts by weight of C9 monomer and 40 to 60 parts by weight of C5 monomer based on 100 parts by weight of dicyclopentadiene. step; And it is prepared including the step of thermal polymerization at a temperature of 275 to 280 ℃.

Thermal polymerization for preparing the petroleum resin according to the first and second embodiments is performed for 1 to 4 hours, preferably 1.5 to 2 hours. Thermal polymerization time is related to polymerization yield. Generally, the higher the polymerization time, the higher the yield. However, an unnecessarily long polymerization time causes unwanted side reactions to generate low molecular weight oligomers or by-products that are the source of volatile organic compounds, so it is preferable to carry out within the above time.

In this case, thermal polymerization is not particularly limited in the present invention, and bulk polymerization and solution polymerization methods may be used. Preferably solution polymerization can be used.

A solvent is used for solution polymerization, and when this step is performed by solution polymerization, a dicyclopentadiene solution is prepared by dissolving dicyclopentadiene in a solvent, and a C9 monomer, and additional After addition of the C5 monomer, thermal polymerization is performed.

In this case, the solvent may be any solvent capable of sufficiently dissolving the dicyclopentadiene presented above, and the present invention is not limited thereto. For example, toluene, methylene chloride, hexane, xylene, trichlorobenzene, alkylbenzene, acetonitrile, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, gamma-butyrolactone, furpral , one selected from the group consisting of acetone and a mixed solvent thereof is possible.

The content of the solvent is possible as long as it is at a level capable of sufficiently dissolving dicyclopentadiene, and for example, it is used in the range of 2 to 10 moles per 1 mole of dicyclopentadiene.

The petroleum resin according to the present invention is prepared by copolymerizing dicyclopentadiene, C9 monomer, and additionally C5 monomer, and minimizes the generation of volatile organic compounds by controlling the monomer content ratio and temperature conditions during thermal polymerization as described above. do. Specifically, as a result of measuring the amount of the volatile organic compound generated from the petroleum resin according to the preferred Experimental Example 1 of the present invention, it was confirmed that the amount was 2% by weight or less.

In particular, the production method of the petroleum resin of the present invention minimizes the generation of volatile organic compounds through the design of the monomer content and the polymerization temperature without the need for a conventional device for the refining process or a separate device for the removal or recovery of the volatile organic compound. The production process can be improved because it is more simplified and has the effect of reducing the equipment cost and the process cost.

The petroleum resin produced in the present invention can impart adhesive properties to hot melt adhesives, pressure-sensitive adhesives, inks, paints, road marking paints, etc., and can be used as an adhesive by mixing with various resins such as natural rubber and synthetic rubber. It can be usefully used.

In addition, the petroleum resin presented in the present invention; styrenic block copolymers such as styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, polyethylene, polypropylene, Polymers selected from at least one selected from ethylene based poly olefin block copolymers such as ethylene vinyl acetate and propylene-ethylene copolymer; and paraffin wax, synthetic wax such as microstalin wax, animal natural wax, vegetable natural wax, aromatic oil, naphthenic oil and paraffinic oil.

The softening point of the adhesive prepared from the adhesive composition is 50 to 150 ℃, the melt viscosity is 300 cps to 10,000 cps at 160 ℃, it is characterized in that 200 cps to 8,000 cps at 180 ℃.

If the softening point of the adhesive is less than 50° C., the adhesive strength may decrease, and if it exceeds 150, it is not preferable in terms of difficulty in applying the manufacturing process.

In addition, if the melt viscosity exceeds 10,000 cps at 160 ° C., the workability may be reduced, if it is less than 300 cps, the adhesion may be reduced, if it exceeds 8,000 cps at 180 ° C., the workability may be deteriorated, and if it is less than 200 ° C.

The adhesive prepared from the adhesive composition may be used as a hot melt adhesive (HMA) or a pressure sensitive adhesive (HMPSA).

In the case of hot melt adhesive, compatibility is 100 or less, Hardness is 30 or more and 90 or less, Open time is 5 seconds or more and less than 30 seconds, and Set time is 0.1 seconds or more and less than 5 seconds. can

In the case of pressure-sensitive adhesive, the initial 40 cm or less in the ball tack method and 40 cm or less after aging, the initial 500 gf/in or more in the peel strength method, and 500 gf/in or more after aging, and the initial 30 in the holding power method min or more and 30 min or more after aging, and showed an initial 40 or more and 40 or more after aging in the SAFT method, indicating that it has excellent physical properties as a pressure-sensitive adhesive.

The adhesive according to the present invention as described above, the hydrogenated petroleum resin does not have double bonds by hydrogenation reaction, and is produced by thermal polymerization, so the content of unreacted raw materials, solvents and low molecular weight oligomers is small, so that 100 to It minimizes the generation of volatile organic compounds that occur during high-temperature melting at 200°C.

These adhesives can be preferably used in all fields requiring the use of adhesives, especially hot melt pressure-sensitive adhesives or adhesives for hygiene products that come into contact with the human body, such as diapers, sanitary napkins, and adult diapers.

Hereinafter, the present invention will be described in more detail through examples, but the following examples are not intended to limit the scope of the present invention, which should be construed to aid understanding of the present invention.

[Example]

Examples 1 to 3 and Comparative Examples 1 to 6: Preparation of petroleum resin

With the composition shown in Table 1 below, a mixture of dicyclopentadiene (DCPD) dissolved in toluene as a solvent was prepared in a 1L autoclave, and C9 (styrene 20%, indene 15%, alpha methylstyrene 5.5%, BTX 59.5%), C5 (isoprene 20%, piperylene 17%, cyclopentadiene 1.2%, 1-pentene 3.2%, 2-methyl-2-butene 3%, n-pentane 55.6%) were added, and the reactor was closed. After that, the reaction temperature was raised to conduct a thermal polymerization reaction, and then the reaction was terminated. After completion of the reaction, the resulting petroleum resin was distilled at 240° C. for 5 minutes to recover unreacted fractions to obtain the remaining petroleum resin.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 monomer
mixing ratio
(%)
DCPD 32 35 33 39.2 32 40 25 35 33 C9 14 5 5 16.8 14 5 5 5 5 C5 0 15 17 0 0 5 20 15 17 menstruum 44 50 50 44 44 50 50 50 50 polymerization conditions
Polymerization temperature (℃) 277 275 278 269 269 270 278 270 270 polymerization time (h) 2 1.85 1.85 2 2 1.85 1.85 1.85 1.85

Experimental Example 1: Analysis of petroleum resin properties

(1) softening point

The softening point was measured using the Ring and ball softening method (ASTM E 28). Melt the resin in a ring-shaped mold, place it in a beaker containing glycerin, place the ball on the ring containing the resin, and increase the temperature by 2.5°C per minute to determine the temperature (softening point) when the resin melts and the balls fall It was measured and described in Table 2.

(2) Yield (%)

The yield was calculated|required by the following formula.

Yield (%) = resin obtained (g) / sum of monomers added (g) * 100

(3) weight average molecular weight

The polystyrene reduced weight average molecular weight and the number average molecular weight were measured by gel permeation chromatography (GPC) (PL GPC-220). The hydrogenated petroleum resin to be measured was dissolved in 1,2,4-trichlorobenzene to a concentration of 0.34 wt%, and 288 μl was injected into GPC. The mobile phase of GPC was 1,2,4-trichlorobenzene and was introduced at a flow rate of 1 mL/min, and the analysis was performed at 130°C. As a column, two Guard columns and one PL 5 μl mixed-D were connected in series. As a detector, the temperature was increased to 250 at 10/min using a differential scanning calorimeter, and the analysis was performed under N ₂ atmosphere to analyze up to the 2nd scan, and are described in Table 2. In Table 2 below, Mw means a weight average molecular weight, and MWD means Mw/Mn.

(4) Volatile organic compound (VOC) generation amount

An aluminum container having a diameter of 5 cm and a height of 2 cm was prepared. In this container, 10.500 g of the sample was weighed to the third decimal place. The container containing the sample was put into a rotary oven that is incubated at 200 °C. After 90 minutes, the container was taken out and the weight was again measured to the third decimal place, and the difference in weight before and after was compared. At this time, the reduced amount is volatile organic compounds (VOCs) blown into the atmosphere at high temperatures. [VOC/initial sample weight (10.500g) * 100] carried away is the amount (%) of VOC generated by the sample at high temperature.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Softening Point (℃) 101 101 100 101.5 83 101 77 85 67 transference number(%) 52 42 40 49 43 39 30 35 34 Mw 755 564 571 703 648 521 473 495 391 VOC generation (wt%) 1.40% 2.00% 1.98% 2.50% 2.51% 2.40% 2.61% 2.55% 2.51%

Referring to Table 2, in the case of the resins of Examples 1 to 3, in which the monomer content ratio and the thermal polymerization temperature were controlled according to the present invention, the amount of volatile organic compound generated was 2 wt% or less.

Comparing Example 1 and Comparative Example 1, the petroleum resin of Example 1 was able to secure the same softening point by increasing the polymerization temperature by 8° C. even if the content of dicyclopentadiene was lowered compared to the petroleum resin of Comparative Example 1. The petroleum resin of Comparative Example 2, performed under the same content conditions as in Example 1, had a very low softening point of 83° C., and a low yield. Moreover, both the petroleum resins of Comparative Examples 1 and 2 showed a higher value than Example 1 in the amount of volatile organic compounds generated.

Comparing the petroleum resins of Example 2 and Comparative Example 5, Example 3 and Comparative Example 6, even if the content ratio of the monomer was used the same, the polymerization temperature was performed at a low temperature of 5 ° C. As a result, the softening point of the finally obtained petroleum resin was It was as low as 85° C. and showed a lower value than that of the petroleum resin of Example 1, and it can be seen that the content of the volatile organic compound was as high as 2.55%.

Accordingly, when the petroleum resin of Example 2 and Comparative Example 3 was compared, the content of dicyclopentadiene was increased to secure the same level of softening point, but as a result of carrying out the polymerization temperature at a low temperature of 5° C., molecular weight and volatile organic compounds showed a difference in the amount of occurrence of

In addition, comparing the petroleum resin of Comparative Example 4 and the petroleum resin of Example 3, when less than 25 parts by weight of C9 monomer is used with respect to 100 parts by weight of dicyclopentadiene, the softening point and yield are significantly lowered, and the VOC content is It can be seen that an increase of about 20%

From these results, it can be seen that when the monomer content ratio and thermal polymerization temperature are controlled according to the present invention, basic physical properties such as softening point of petroleum resin can be secured and volatile organic compounds can be selectively reduced.

Experimental example 2: low molecular weight Oligomer content analysis

GPC analysis was performed to confirm the relationship between the volatile organic compounds and the low molecular weight oligomers of the petroleum resins prepared in Examples and Comparative Examples, and the results are shown in FIGS. 1 and 2 . At this time, the shift in the right direction in FIGS. 1 and 2 means that the molecular weight decreases.

1 is a gel chromatography of petroleum resins prepared in Example 1 and Comparative Example 1, a green region may be divided into a high molecular weight region, and a red region may be divided into a low molecular weight region. 1, it can be seen that the petroleum resin of Example 1 is shifted to a higher molecular weight side compared to the petroleum resin of Comparative Example 1, so that the content of low molecular weight oligomers in the petroleum resin is relatively small.

2 is a gel chromatography of the petroleum resin prepared in Example 2 and Comparative Example 3, which also showed the same trend as in FIG. 1 .

As shown in Table 2 of Experimental Example 1, the results of FIGS. 1 and 2 serve as data supporting the low generation amount of volatile organic compounds.

The petroleum resin according to the present invention can be used as an additive in various fields, including adhesives.

Claims (14)

As a petroleum resin copolymerized with dicyclopentadiene and C9 monomer,
When the petroleum resin is left at 200° C. for 90 minutes, the content of volatile organic compounds (VOC) generated from the petroleum resin is 2% by weight or less based on the weight of the initial petroleum resin,
wherein the C9 monomer comprises 10 to 30% by weight of styrene, 10 to 20% by weight of indene, 1 to 7% by weight of alpha methylstyrene, and 50 to 79% by weight of a mixture of benzene, toluene and xylene;
Petroleum resin, characterized in that the softening point of 100 to 120 ℃. According to claim 1,
The petroleum resin is a petroleum resin, characterized in that the weight average molecular weight is 500 to 1000 g / mol. According to claim 1,
The petroleum resin is a petroleum resin, characterized in that 25 to 50 parts by weight of the C9 monomer is copolymerized with respect to 100 parts by weight of dicyclopentadiene. delete According to claim 1,
The petroleum resin is a petroleum resin, characterized in that the thermal polymerization at a temperature of 275 to 280 ℃. As a petroleum resin copolymerized with dicyclopentadiene, C9 monomer and C5 monomer,
When the petroleum resin is left at 200° C. for 90 minutes, the content of volatile organic compounds (VOC) generated from the petroleum resin is 2% by weight or less based on the weight of the initial petroleum resin,
wherein the C9 monomer comprises 10 to 30% by weight of styrene, 10 to 20% by weight of indene, 1 to 7% by weight of alpha methylstyrene, and 50 to 79% by weight of a mixture of benzene, toluene and xylene;
Petroleum resin, characterized in that the softening point of 100 to 120 ℃. 7. The method of claim 6,
The petroleum resin is a petroleum resin, characterized in that the weight average molecular weight is 500 to 1000 g / mol. 7. The method of claim 6,
The petroleum resin is a petroleum resin, characterized in that 10 to 20 parts by weight of a C9 monomer and 40 to 60 parts by weight of a C5 monomer are copolymerized with respect to 100 parts by weight of dicyclopentadiene. 7. The method of claim 6,
The C5 monomer is a petroleum resin, characterized in that at least one selected from the group consisting of isoprene, piperylene, cyclopentadiene, 1-pentene, 2-methyl-2-butene and n-pentane. 7. The method of claim 6,
The petroleum resin is a petroleum resin, characterized in that the thermal polymerization at a temperature of 275 to 280 ℃. As a method for producing a petroleum resin according to any one of claims 1 to 3 and 5,
mixing 25 to 50 parts by weight of a C9 monomer with respect to 100 parts by weight of dicyclopentadiene; and
A method for producing a petroleum resin, characterized in that it comprises the step of thermal polymerization at a temperature of 275 to 280 ℃. 12. The method of claim 11,
The petroleum resin has a weight average molecular weight of 500 to 1000 g / mol, and a method for producing a petroleum resin, characterized in that the softening point is 100 to 120 ℃. As a method for producing a petroleum resin according to any one of claims 6 to 10,
mixing 10 to 20 parts by weight of a C9 monomer and 40 to 60 parts by weight of a C5 monomer based on 100 parts by weight of dicyclopentadiene; and
A method for producing a petroleum resin, characterized in that it comprises the step of thermal polymerization at a temperature of 275 to 280 ℃. 14. The method of claim 13,
The petroleum resin has a weight average molecular weight of 500 to 1000 g / mol, and a method for producing a petroleum resin, characterized in that the softening point is 100 to 120 ℃.

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