KR20170038313A - Method for Manufacturing Petroleum Resin - Google Patents

Abstract

The present invention relates to a petroleum resin, and a production method thereof. More specifically, provided is a petroleum resin which brings reduction in costs required in production processes, since a polymerization regulator used in the petroleum resin production can be recycled, while regulating physical properties of the petroleum resin. Moreover, provided is a production method thereof. To this end, the production method includes: a step (S1) of producing a raw polymerization material; a step (S2) of producing a catalyst dispersion solution; and a step (S3) of carrying out a polymerization.

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing a petroleum resin,

The present invention relates to a process for producing a petroleum resin which can regulate the physical properties of a petroleum resin and can recycle the polymerization regulator used in the production of petroleum resin, thereby reducing the manufacturing process cost.

The C5-based petroleum resin is produced using a mixture of various kinds of conjugated dienes and monoenes. The physical properties of the petroleum resin obtained vary greatly depending on the kind of the conjugated diene and the type of the monoene used at this time, and the economic efficiency and quality depend greatly on the method of obtaining these raw materials.

Unsaturated hydrocarbon oil fractions having a boiling point range of 20 to 60 占 폚 obtained at the time of thermal decomposition of petroleum such as naphtha are generally used in combination with cyclic conjugated diene compounds such as cyclopentadiene and methyl cyclopentadiene and 1,3- 1,3-pentadiene, isoprene, and the like. Methods for producing a kind of petroleum resin by contacting an oil containing these components with a Friedel-Craft type catalyst are well known.

When oil containing a large amount of these conjugated dienes is directly used, a large amount of insoluble gel is generated, which causes many problems in the process such as plugging of the reactor pipe and the recovery and purification apparatus. In addition, since the resultant petroleum resin has an unfavorable phenomenon in terms of physical properties such as a poor heat resistance and a high melt viscosity, it is practically not used because of its great disadvantage in terms of practical use.

Among the above-mentioned conjugated diene compounds, there is a large gel-forming effect by cyclic conjugated diene compounds such as cyclopentadiene and methylcyclopentadiene. Therefore, there are many methods for eliminating these cyclic conjugated diene compounds to prevent gel formation However, these methods also fail to prevent the formation of gels generated by the chain conjugated dienes such as isoprene and 1,3-pentadiene (piperylene), and therefore, it is difficult to say that the effect is sufficient.

On the other hand, many attempts have been made to suppress the formation of gel by polymerization method without removing the conjugated cyclodiene compound in the polymerization raw material. For example, in JP-A-47-45833, gel formation is prevented by a method of polymerizing an anhydrous aluminum chloride powder in powder form with an aromatic solvent as a catalyst. However, in this method, since the effect of inhibiting gel formation is not large, a large amount of aromatic solvent should be used. In this case, addition of an aromatic solvent, addition of recovery facilities, and lowered softening point of the resin to be produced cause problems.

Since such gel formation is generated by the above-mentioned conjugated dienes, methods of obtaining a high quality petroleum resin by suppressing gel formation by adding an appropriate amount of monoene components such as isobutene, diisobutene and the like Has been proposed, but the effect of suppressing gel formation by isoprene is not sufficient.

Accordingly, in U.S. Patent No. 4,403,080, a conjugated diene compound in a depentanizer tower top component is separated by extractive distillation, and 2-methyl- It is disclosed that when 1-butene is isomerized into 2-methyl-2-butene by a solid acid catalyst and mixed with 1,3-pentadiene concentrated oil, a petroleum resin having a low molecular weight and a high softening point is produced have. However, this method can not be an economical method unless isoprene is used for other purposes simultaneously because it removes a large amount of isoprene contained in the raw material and produces a petroleum resin.

In addition, in Korean Patent No. 0533906, in order to solve the problems of the above-mentioned U.S. Patent No. 4,403,080, an oil fraction having a weight ratio of 1,3-pentadiene to 1,3-pentadiene of 1/3 or less in an oil fraction from which a cyclic conjugated diene compound has been removed ) And the remaining isoprene (oil B) are separated and concentrated, and then the separated oil A is partially hydrogenated to produce oil C, and the oil C is cationically polymerized with oil B to produce a petroleum resin / RTI > However, the manufacturing method of the above document has a problem in that it is difficult to put the separating step and the concentrating step into practical use, because the entire process is complicated and the manufacturing facility is expensive.

The main object of the present invention is to increase the concentration of the polymerization controlling agent (TCDE) by introducing cyclohexane as a catalyst dispersing agent, and it is possible to recycle the catalyst, thereby reducing the manufacturing cost. In addition, when the cyclohexane is used as tertiary butyryl chloride as a promoter, the softening point and the molecular weight of the petroleum resin tend to be prevented from being increased and controlled.

Accordingly, the present invention provides, as a first preferred embodiment, a method of mixing a mixed C5 oil fraction and at least one polymerization regulator selected from cyclopentene, methylcyclopentene, dihydro dicyclopentadiene or dihydrodicyclopentadiene derivatives (S1) of producing a polymerization raw material; Comprising: a mixture of cyclohexane and AlF _3, AlCl _3, 1 jong or more catalyst selected from the group consisting of BF ₃ and BCl ₃ to prepare a catalyst dispersion solution (S2); And a step (S3) of adding a polymerization raw material prepared in the step S1, a catalyst dispersion solution prepared in the step S2 and tert-butyl chloride to a polymerization reaction (S3). .

In the step S1, the polymerization regulator is added in an amount of 40 to 65 parts by weight based on 100 parts by weight of the mixed C5 oil.

And the cyclohexane and the catalyst are mixed in a weight ratio of 1: 0.1 to 2 in the step S2.

And the catalyst dispersion solution is added to the polymerization raw material in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polymerization raw material in the step S3.

In step S3, the tertiary butyl chloride is mixed in an amount of 0.1 to 1.5 parts by weight based on 1 part by weight of the catalyst.

The step of conducting the polymerization reaction in step S3 is performed at a temperature of 50 to 75 ° C for 1 to 3 hours.

The present invention provides, as a second preferred embodiment, a petroleum resin having a weight average molecular weight (Mw) of 1,000 to 3,000 g / mol and a molecular weight distribution of 2.5 or less.

The petroleum resin according to the above embodiment is characterized in that it is produced by the above-mentioned production method.

The method for producing a petroleum resin according to the present invention is a method for producing a petroleum resin by using cyclohexane alone as a catalyst dispersing solvent and petroleum resin using tert-butyl chloride as a cocatalyst, The recycle efficiency of the polymerization regulator used in the production of the petroleum resin is improved compared to the method of producing the petroleum resin, and the manufacturing process cost is reduced.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a process for producing a polymerization raw material by mixing a mixed C5 oil fraction and at least one polymerization regulator selected from cyclopentene, methylcyclopentene, dihydro dicyclopentadiene or dihydrodicyclopentadiene derivative S1); Comprising: a mixture of cyclohexane and AlF _3, AlCl _3, 1 jong or more catalyst selected from the group consisting of BF ₃ and BCl ₃ to prepare a catalyst dispersion solution (S2); And a step (S3) of adding a catalyst dispersing solution prepared in the step S2 to the polymerization starting material prepared in the step S1 and then adding tertiary butyl chloride to perform a polymerization reaction And a manufacturing method thereof.

First, a mixed raw material is prepared by mixing mixed C5 oil and a polymerization regulator (S1).

The mixed C5 oil fraction is an initial raw material obtained by separating unsaturated hydrocarbons having 4 to 6 carbon atoms in a boiling point range of 20 to 60 DEG C in oil fractions obtained by pyrolyzing petroleum such as naphtha and the like and is used as cyclopentadiene and methylcyclopentadiene And a chain conjugated diene compound such as isoprene and 1,3-pentadiene. In addition, it is preferable that the cyclic conjugated diene compounds not only cause gel formation but also have a high molecular weight and deteriorate color, so that the content thereof is reduced to about 3% by weight or less in the initial raw material.

In order to remove the cyclic conjugated diene compound in the initial raw material, the initial raw material is heated. The heat treatment may be carried out at 100 to 200 ° C for 2 to 20 hours, preferably at 110 to 180 ° C for 4 to 8 hours in view of increasing the productivity while reducing the color deterioration factor. At this time, the cyclic conjugated diene compound is dimerized and the cyclized conjugated diene compound is a high boiling compound. Therefore, the cyclic conjugated diene compound is easily removed as a tower bottom component through a distillation process.

As described above, the mixed C5 oil obtained by removing the dimer with the column bottom component and obtained from the column top is obtained by reacting a chain conjugated diene compound such as 1,3-pentadiene, isoprene and the like with a mono Yen. At this time, the content of the chain conjugated diene is about 20 to 40% by weight based on the total oil fraction. Particularly 10 to 20 parts by weight of 1,3-pentadiene, 10 to 20 parts by weight of isoprene, 5 to 10 parts by weight of pentene and 5 to 10 parts by weight of 2-methyl-2-butene.

In the mixed C5 oil fraction, the cyclic conjugated diene compound was removed from the components causing gel formation, but the chain conjugated diene compound such as isoprene and 1,3-pentadiene still remained. In this chain conjugated diene, gel production by isoprene is much larger than that by 1,3-pentadiene, and the increase of the average molecular weight and the molecular weight distribution is also significantly increased by isoprene. Therefore, among the chain conjugated diene compounds, The content should be as low as possible. However, since isoprene content is the most abundant in oil A, simply removing isoprene is not economical because the raw material loss is excessive.

In the present invention, the mixed C5 fraction is subjected to a partial hydrogenation reaction without any additional treatment to produce a molecular weight regulator capable of suppressing the formation of a gel during petroleum resin production and appropriately controlling the molecular weight. At this time, the partial hydrogenation reaction of mixed C5 oil is brought into contact with hydrogen while maintaining the total pressure and temperature in the presence of the hydrogenation catalyst.

That is, in the present invention, the polymerization regulator is produced by adding a hydrogenation catalyst to a mixed C5 oil fraction and performing a partial hydrogenation reaction. Partially hydrogenated polymerization modifiers economically reduce the content of isoprene causing gel formation, so that when the petroleum resin is mixed with the mixed C5 oil, the gel formation is prevented, and the molecular weight distribution is narrowed and the color and specific gravity An improved petroleum resin can be produced.

As such a polymerization modifier, at least one selected from cyclopentene, methylcyclopentene, dihydro dicyclopentadiene and dihydrodicyclopentadiene derivatives can be mentioned.

The polymerization regulator is preferably added in an amount of 40 to 65 parts by weight based on 100 parts by weight of the mixed C5 oil. When the content of the polymerization regulator is within the above range, a petroleum resin having an appropriate softening point and molecular weight can be produced.

Subsequently, a catalyst dispersion solution is prepared by mixing cyclohexane and at least one catalyst selected from the group consisting of AlF ₃ , AlCl ₃ , BF ₃ and BCl ₃ (S 2).

In the present invention, by applying cyclohexane as a catalyst dispersing solvent, the recycle efficiency is increased by increasing the concentration of the polymerization controlling agent, thereby reducing the cost of the manufacturing process.

Specifically, since cyclohexane has a lower boiling point than xylene, the concentration of the polymerization regulator can be increased during distillation. If the concentration of the polymerization regulator is increased by such action, the polymerization regulator used in the preparation of the petroleum resin can be used to produce the petroleum resin again, so that the manufacturing cost can be reduced.

The cyclohexane and the catalyst are preferably mixed in a weight ratio of 1: 0.1 to 2 in the color of the petroleum resin to be produced.

Then, the polymerization raw material, the prepared catalyst dispersion solution, and tert-butyl chloride as a cocatalyst are added to perform the polymerization reaction (S3).

It is preferable that the tertiary butyl chloride is mixed in an amount of 0.1 to 1.5 parts by weight based on 1 part by weight of the catalyst in the range of appropriate softening point and molecular weight of the petroleum resin finally produced.

As described above, in the present invention, cyclohexane is used instead of xylene as a catalyst dispersing solvent to increase the recycle efficiency of the polymerization controlling agent, thereby reducing manufacturing process cost. (TCDE) concentration in the distillation process due to boiling point difference. However, when cyclohexane is used, there is a problem that the softening point and the molecular weight of the produced petroleum resin increase, so it is necessary to secure the technology capable of controlling the softening point and the molecular weight of the petroleum resin. Accordingly, the present invention has an advantage in that physical properties can be controlled by introducing tert-butyl chloride as a cocatalyst and lowering the softening point and molecular weight of the petroleum resin prepared from cyclohexane.

The polymerization reaction is carried out at a temperature of 50 to 75 ° C for 1 to 3 hours, and is appropriate for the appropriate softening point and molecular weight range of the petroleum resin finally produced.

The present invention provides a petroleum resin produced by the above-described production method.

The petroleum resin produced by the above process has a weight average molecular weight (Mw) of 1,000 to 3,000 g / mol and a molecular weight distribution of 2.5 or less.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments.

Example 1

With respect to the mixed C5 fraction in a stainless steel pressure reactor 100 parts by weight, was added to the polymerization regulator dihydro-dicyclopentadiene (dicyclopentadiene) 55 parts by weight, and kept at the same temperature under a pressure of 1.6kgf / cm ² to 60 ℃ and then mixed . On the other hand, solid AlCl ₃ powder was mixed with cyclohexane at a weight ratio of 1: 0.5 by weight of catalyst to cyclohexane to prepare a catalyst dispersion solution. The polymerization raw material and catalyst dispersion solution thus prepared were mixed with tert-butyl chloride.

At this time, 0.3 parts by weight of a cocatalyst was added to and mixed with 3 parts by weight of the catalyst dispersion solution and 1 part by weight of the catalyst (solid AlCl ₃ powder) relative to 100 parts by weight of the polymerization raw material. An average residence time of about 2 hours was obtained by injecting the polymerization raw material at a rate of 200 ml per minute. The reaction temperature was maintained within ± 1 ° C using a heat exchanger. After about 6 hours from the start of the continuous reaction, the polymerization solution in the reactor was extracted, and the catalyst component in the reaction product was neutralized with the same amount of water as the polymerization solution. After washing with water, the oil layer was separated and the oil layer was stripped at 5 mmHg for 10 minutes Followed by stripping to remove the remaining low boiling point components to prepare a petroleum resin.

Example 2

A petroleum resin was prepared in the same manner as in Example 1, except that 1 part by weight of the cocatalyst was added to 1 part by weight of the catalyst (solid AlCl ₃ powder).

Comparative Example 1

A petroleum resin was prepared in the same manner as in Example 1, except that xylene was used as a catalyst dispersing agent.

Comparative Example 2

A petroleum resin was prepared in the same manner as in Example 1, except that tert-butyl chloride was not added.

≪ Property evaluation method &

(1) Measurement of softening point

The softening point was measured by raising the temperature by 5 ° C / minute using an automatic softening point measuring machine (model: ASPT-S2-01, manufactured by Oh Sung Machinery Co., Ltd.).

(2) Measurement of molecular weight and molecular weight distribution

The polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (product of Hewlett Packard Co., model name HP-1100). The polymer to be measured was dissolved in tetrahydrofuran so as to have a concentration of 4000 ppm and 100 μl was injected into GPC. The mobile phase of GPC was run at a flow rate of 1.0 mL / min using tetrahydrofuran and the assay was performed at 30 < 0 > C. The column was connected in series with three Agilent Plgel (1,000 + 500 + 100A). The detector was measured at 30 DEG C using an RI detector (HP-1047A, manufactured by Hewlett-Packard). At this time, PDI (molecular weight distribution) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.

(3) Measurement of polymerization modifier concentration

Based on the actual tower spec and material balance of T-401, each Aspen Simulation was performed when the catalyst dispersion solvent was Xylene and Cyclohexane.

The physical properties measured by the above-mentioned method are shown in Tables 1 and 2 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Polymerization modifier concentration 82.3 82.3 65.6 82.3

Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Softening point (℃) 99.8 96.6 92.2 102.7 Molecular Weight Mn 768 678 861 874 Mw 1622 1242 1688 1918 Mz 9310 6872 3666 12932 MWD 2.11 1.83 1.96 2.19

As shown in Table 1, when the cyclohexane is used instead of xylene as the catalyst dispersant, the recycle polymerization regulator (TCDE) concentration is increased.

As shown in Table 2, Comparative Example 2 shows a softening point and a molecular weight of a petroleum resin when cyclohexane is used as a catalyst dispersing solvent. The softening point and the molecular weight of the petroleum resin are increased as compared with Comparative Example 1. However, as in Examples 1 and 2, the softening point and the molecular weight were lowered by using tert-butyl chloride, so that it was confirmed that the physical properties of the petroleum resin can be controlled.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

(S1) mixing a mixed C5 fraction and at least one polymerization regulator selected from cyclopentene, methylcyclopentene, dihydro dicyclopentadiene or dihydrodicyclopentadiene derivative to prepare a polymerization raw material;
Comprising: a mixture of cyclohexane and AlF _3, AlCl _3, 1 jong or more catalyst selected from the group consisting of BF ₃ and BCl ₃ to prepare a catalyst dispersion solution (S2); And
And a step (S3) of adding the polymerization raw material prepared in the step S1, the catalyst dispersion solution prepared in the step S2, and tert-butyl chloride to perform a polymerization reaction. The method for producing a petroleum resin according to claim 1, wherein the polymerization regulator is added in an amount of 40 to 65 parts by weight based on 100 parts by weight of the mixed C5 oil. The method of claim 1, wherein the cyclohexane and the catalyst are mixed in a weight ratio of 1: 0.1 to 2 in the step S2. The method for producing a petroleum resin according to claim 1, wherein the catalyst dispersion solution is added to the polymerization starting material in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polymerization starting material. The method of claim 1, wherein the tertiary butyl chloride is mixed in an amount of 0.1 to 1.5 parts by weight based on 1 part by weight of the catalyst in the step S3. The method for producing a petroleum resin according to claim 1, wherein the step of carrying out the polymerization reaction in step S3 is carried out at a temperature of 50 to 75 캜 for 1 to 3 hours. Wherein the weight average molecular weight (Mw) is 1,000 to 3,000 g / mol and the molecular weight distribution is 2.5 or less. 8. The petroleum resin as claimed in claim 7, wherein the petroleum resin is produced according to any one of claims 1 to 6.