KR101512238B1 - A method for preparing pitch having high solubility - Google Patents

Abstract

(A) preparing a naphtha-decomposed residual oil having halogen substitution as a starting material; (b) adding a formaldehyde to the starting material, followed by a dehydration condensation reaction to obtain a first polymer; And (c) subjecting the primary polymer to a secondary polymerization by a halogenation condensation reaction, wherein the petroleum pitch produced by the process according to the present invention is characterized in that the fluidity of the polymer molecular chain mobility) and is capable of dissolving 70% to 100% in an organic solvent such as toluene, has a high molecular weight and a high softening point, and is useful as a precursor for producing high-function carbon fibers.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a solvent-

The present invention relates to a method for producing an emissive pitch.

Naphtha refers to the distillation of crude oil between LPG and kerosene oil, and is generally divided into light naphtha and heavy naphtha.

The heavy naphtha has a boiling point of 100 ° C or lower and the heavy naphtha has a boiling point of 100 ° C or higher. The light naphtha is mainly used as a raw material for solvents and petrochemicals. The heavy naphtha is produced by reforming, .

In this way, naphtha undergoes pyrolysis process to produce raw materials such as petrochemicals, and many undesired by-products are emitted in this process. Among them, C10 + (aromatic compounds with more than 10 carbon atoms), pyrolysed fuel oil (PFO) and pyrolysed gas oil (PGO) are examples of by-products discharged in the oil state.

As of 2003, domestic naphtha cracking companies produce about 5.7 million tons of ethylene per year. Of these, the amount of residues is treated confidentially by the company, so it is difficult to calculate the exact amount, but about 1.1 million tons of aromatic residues per year are produced as byproducts and are increasing every year.

On the other hand, carbon fiber began to become known in the 1880s when Thomas Edison first used carbon fibers in filaments of incandescent lamps. In recent years, carbon fiber reinforced composite products have been produced by improving mechanical, thermal and electrical properties by mixing chemical resins, cement, and ceramics. These composite materials have been widely used in the aerospace industry, the automobile industry, and the defense industry.

In order to produce a high-performance carbon fiber, a high softening point petroleum pitch, which is a precursor, is required to be homogeneous in a melting or dissolving process with respect to heat or solvent, and a single phase is required. Further, a high purity precursor petroleum pitch is required. Quinoline solubles and the like, and further studies for producing a high softening point petroleum pitch at a high yield by using a distillation fraction or an aromatic hydrocarbon monolith which does not contain impurities such as metals, In the prior art, when a high-softening point petroleum pitch is produced using a complex mixture such as coal-based residue and petroleum-based heavy oil as starting materials, excessive pyrolysis and condensation reactions tend to occur at the application stage such as the production of carbon fibers of the obtained petroleum pitch , Whereby gas and insoluble materials are generated to produce a predetermined carbon fiber There is a problem that carbon fibers having no or poor physical properties can be obtained.

(A) preparing a naphtha-decomposed residual oil having halogen substitution as a starting material; (b) adding a formaldehyde to the starting material, followed by a dehydration condensation reaction to obtain a first polymer; And (c) subjecting the primary polymer to a secondary condensation reaction by a halogenation condensation reaction.

However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

(A) preparing a naphtha-decomposed residual oil having halogen substitution as a starting material; (b) adding a formaldehyde to the starting material, followed by a dehydration condensation reaction to obtain a first polymer; And (c) subjecting the primary polymer to a secondary polymerization by a halogenation condensation reaction.

(d) evaporating and removing the unreacted material contained in the secondary polymer.

In (d), the unreacted material may include a low boiling point material at 400 ° C or lower.

In (a), the halogen may be bromine (Br), chlorine (Cl), or iodine (I).

In (a), the naphtha-decomposed residual oil may be a low boiling point material of 400 ° C or lower.

The naphtha-decomposed residual oil in (a) may contain a compound having two to ten aromatic rings.

In the above (b), the first polymerization may be carried out at 100 ° C to 180 ° C.

In (c), the secondary polymerization may be carried out at 180 ° C to 300 ° C.

In one embodiment of the present invention, there is provided an emissive petroleum pitch which is prepared by the process and which is dissolved in an organic solvent in an amount of 70% to 100%.

The organic solvent may be at least one selected from the group consisting of toluene, xylene, chloroform, dimethylsulfoxide, m-cresol, N-methylpyrrolidone, and combinations thereof.

The solubilized petroleum pitch may have a high softening point of 250 ° C to 350 ° C.

The solubilizable petroleum pitch may have a weight average molecular weight of from 1,000 g / mol to 10,000 g / mol.

(A) preparing a naphtha-decomposed residual oil having halogen substitution as a starting material; (b) adding a formaldehyde to the starting material, followed by a dehydration condensation reaction to obtain a first polymer; And (c) subjecting the primary polymer to a secondary polymerization by a halogenation condensation reaction, wherein the petroleum pitch produced by the process according to the present invention is characterized in that the fluidity of the polymer molecular chain mobility) and is capable of dissolving 70% to 100% in an organic solvent such as toluene, has a high molecular weight and a high softening point, and is useful as a precursor for producing high-function carbon fibers.

The present inventors have confirmed that petroleum pitch is prepared by adding formaldehyde to a halogen-substituted naphtha-decomposed residual oil and that the produced petroleum pitch has a high softening point and is highly soluble in an organic solvent such as toluene.

Specifically, the present invention provides

(a) preparing a halogen-substituted naphtha decomposition residue as a starting material;

(b) adding a formaldehyde to the starting material, followed by a dehydration condensation reaction to obtain a first polymer; And

(c) subjecting the primary polymer to a halogenation condensation reaction to obtain a second polymer.

In addition,

(a) preparing a halogen-substituted naphtha decomposition residue as a starting material;

(b) adding a formaldehyde to the starting material, followed by a dehydration condensation reaction to obtain a first polymer;

(c) subjecting the first polymer to a halogenation condensation reaction to form a second polymer; And

(d) evaporating and removing the unreacted material contained in the secondary polymer.

The step (a) is a step of preparing halogen-substituted naphtha decomposed residual oil as a starting material.

The naphtha-decomposed residual oil preferably contains a low-boiling point substance of 400 ° C or lower. The naphtha-decomposed residual oil may be composed of a low boiling point substance having a boiling point of 400 ° C or lower prepared by distillation of naphtha-decomposed residual oil at 400 ° C, Is more preferable. When the naphtha-decomposed residual oil is a low-boiling substance having a temperature of 400 ° C or less, there is an advantage that unreacted materials contained in the secondary polymer can be recovered as it is. In addition, since the number of aromatic rings is relatively small, a low boiling point material having a temperature of 400 ° C or less can perform the polymerization reaction under relatively mild conditions with less steric hindrance.

The naphtha-decomposed residual oil preferably contains a compound having two to ten aromatic rings. As the naphtha-decomposed residual oil, 1,3,6-trimethylnaphthalene (1,3,6-trimethylnaphthalene) , 1-methylnaphthalene, 2,3-dimethylanthracene, 1,4,6-trimethylpyrene and 1,3-diethyl- 1,3-diethyl-5-ethylpyrene, and the like, but is not limited thereto.

In the present invention, naphtha decomposed residual oil containing 1,3,6-trimethylnaphthalene having a boiling point of 284.137 ° C was used as an example.

That is, in the case where the naphtha-decomposed residual oil is a low-boiling substance having a temperature of 400 ° C or lower, it generally contains a compound having two to ten aromatic rings. Therefore, the petroleum pitch produced using a compound having two to ten aromatic rings The aromatic ring may form a relatively long chain because the steric hindrance of the aromatic ring is less than that of the molecules having a molecular weight of 10 or more in the crosslinking reaction of molecules having 2 to 10 aromatic rings, Is high. Therefore, even if the molecular weight of the polymer of the petroleum pitch is high, it is 100% soluble in an organic solvent such as toluene.

The halogen may be bromine (Br), chlorine (Cl), or iodine (I). Namely, naphtha decomposed residual oil substituted with bromine (Br), chlorine (Cl), or iodine (I) may be used as a starting material.

In the step (b), formaldehyde is added to the starting material, and a dehydration condensation reaction is carried out to perform the primary polymerization. At this time, the primary polymerization may be carried out at 100 ° C to 180 ° C.

A typical reaction of the above primary polymerization is represented by the following reaction formula (1).

[Reaction Scheme 1]

In the step (c), the primary polymer is subjected to a halogenation condensation reaction to carry out a secondary polymerization. At this time, the secondary polymerization may be carried out at 180 캜 to 300 캜.

A typical reaction of the secondary polymerization is represented by the following reaction formula (2).

[Reaction Scheme 2]

The step (d) is a step of removing the unreacted material contained in the secondary polymer by evaporation. In this case, the unreacted material is a low boiling point material at 400 ° C or lower. By evaporating the unreacted materials contained in the secondary polymer, the molecular weight of the polymer of the petroleum pitch can be increased to increase the softening point of the petroleum pitch.

The present invention provides an emissive petroleum pitch which is prepared by the above process and which is dissolved in an organic solvent in an amount of 70% to 100%.

The organic solvent is preferably at least one selected from the group consisting of toluene, xylene, chloroform, dimethylsulfoxide, m-cresol, N-methylpyrrolidone, and combinations thereof, but is not limited thereto. In the present invention, toluene was used as an organic solvent.

The solubilizable petroleum pitch may have a high softening point of 250 ° C to 350 ° C, and the solubilized petroleum pitch may have a weight average molecular weight of 1,000 g / mol to 10,000 g / mol. .

Accordingly, the petroleum pitch produced by the process according to the present invention has high mobility of the polymer molecular chain and is capable of dissolving 70% to 100% in an organic solvent such as toluene, has a high molecular weight and a high softening point, And is useful as a precursor for producing fibers.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the following examples.

Example  One

The naphtha-decomposed residue was distilled at 400 ° C to obtain 1,3,6-trimethylnaphthalene [boiling point: 284.137 ° C] corresponding to the low-boiling substance contained in the residual naphtha residue Prepared. Bromine was added to the prepared 1,3,6-trimethylnaphthalene to prepare 1-bromomethyl-3,6-dimethylnaphthalene as a starting material. Lt; / RTI >

50 g of formaldehyde was added to 1,000 g of the prepared starting material and subjected to a primary polymerization by dehydration condensation reaction at 120 DEG C for 3 hours, followed by secondary polymerization by halogenation condensation reaction at 180 DEG C for 2 hours. The unreacted material contained in the secondary polymer was removed by evaporation at 360 캜 to produce a petroleum pitch.

Example  2

Bromine was added to the naphtha-decomposed residual oil itself without distillation at 400 ° C to obtain a halogen containing 1-bromomethyl-3,6-dimethylnaphthalene Substituted naphtha decomposition residue was prepared as starting material.

50 g of formaldehyde was added to 1,000 g of the prepared starting material and subjected to a primary polymerization by dehydration condensation reaction at 120 DEG C for 3 hours, followed by secondary polymerization by halogenation condensation reaction at 180 DEG C for 2 hours. The unreacted material contained in the secondary polymer was removed by evaporation at 360 캜 to produce a petroleum pitch.

Comparative Example  One

The naphtha decomposition residue was polymerized by reacting 1,000 g of the residue at 360 ° C for 5 hours. The unreacted material contained in the polymer was removed by evaporation at 360 캜 to produce a petroleum pitch.

Comparative Example  2

The naphtha-decomposed residue was distilled at 400 ° C to obtain 1,3,6-trimethylnaphthalene (boiling point: 284.137 ° C) corresponding to the low-boiling substance contained in the residual naphtha oil, Were prepared. Bromomethyl-3,6-dimethylnaphthalene was added to the prepared 1,3,6-trimethylnaphthalene by adding bromine to the prepared 1,3,6-trimethylnaphthalene. Material.

1,000 g of the prepared starting material was polymerized by halogenation condensation reaction at 180 ° C for 2 hours. The unreacted material contained in the polymer was removed by evaporation at 360 캜 to produce a petroleum pitch.

Experimental Example

In order to measure the characteristics of the oil-soluble petroleum pitch according to the present invention, the following experiment was conducted. The results are shown in Table 1 below.

(1) Measurement of softening point

The softening points of the petroleum pitches prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by applying a Mettler cup and ball method according to ASTM D3461 under a nitrogen atmosphere.

(2) Measurement of weight average molecular weight

The petroleum pitches prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were dissolved in m-cresol and then subjected to gel permeation chromatography to obtain a mixture of the petroleum pitches obtained in Examples 1 and 2 and Comparative Examples 1 and 2 The weight average molecular weight (Mw) of the produced petroleum pitch was measured.

(3) Measurement of solubility in toluene

The petroleum pitches prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were dissolved in toluene and then the solubility of the petroleum pitch in toluene prepared in Examples 1 and 2 and Comparative Examples 1 and 2 was measured according to ASTM D3461 toluene soluble fraction).

Softening point
(softening point) Weight average molecular weight
(Mw) Solubility in toluene
Example 1 284 ° C 4,175 g / mol 100% Example 2 285 ℃ 5,912 g / mol 79% Comparative Example 1 283 DEG C 893 g / mol 32% Comparative Example 2 287 ° C 1,623 g / mol 52%

As a result, it was confirmed that the petroleum pitches according to Examples 1 and 2 have a high weight average molecular weight of the polymer and have a high softening point, and are highly soluble in toluene because of high mobility of the polymer molecular chain. In particular, it was confirmed that the petroleum pitch according to Example 1 was 100% soluble in toluene. On the other hand, the petroleum pitches according to Comparative Example 1 and Comparative Example 2 showed low mobility of the polymer molecular chains and low solubility in toluene.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (12)

(a) preparing a halogen-substituted naphtha decomposition residue as a starting material;
(b) adding a formaldehyde to the starting material, followed by a dehydration condensation reaction to obtain a first polymer; And
(c) subjecting the primary polymer to a second polymerization by halogenating a condensation reaction
A method for producing an oil - soluble petroleum pitch.
The method according to claim 1,
(d) evaporating and removing the unreacted material contained in the secondary polymer
A method for producing an oil - soluble petroleum pitch.
3. The method of claim 2,
In (d), the unreacted material is a low-boiling substance
A method for producing an oil - soluble petroleum pitch.
3. The method according to claim 1 or 2,
In the above (a), the halogen is bromine (Br), chlorine (Cl), or iodine (I)
A method for producing an oil - soluble petroleum pitch.
3. The method according to claim 1 or 2,
In (a), the naphtha-decomposed residual oil contains a low boiling point substance of 400 ° C or lower
A method for producing an oil - soluble petroleum pitch.
3. The method according to claim 1 or 2,
The naphtha-decomposed residual oil in (a) above contains a compound having 2 to 10 aromatic rings
A method for producing an oil - soluble petroleum pitch.
3. The method according to claim 1 or 2,
In the above (b), the primary polymerization is carried out at 100 ° C to 180 ° C
A method for producing an oil - soluble petroleum pitch.
3. The method according to claim 1 or 2,
In (c), the secondary polymerization is carried out at 180 ° C to 300 ° C
A method for producing an oil - soluble petroleum pitch.
3. The method according to claim 1 or 2,
Wherein the solvolytic petroleum pitch is dissolved in an organic solvent in an amount of 70% to 100%.
10. The method of claim 9,
Wherein the organic solvent is at least one selected from the group consisting of toluene, xylene, chloroform, dimethylsulfoxide, m-cresol, N-methylpyrrolidone, and combinations thereof.
3. The method according to claim 1 or 2,
Wherein the solvolytic petroleum pitch has a high softening point of 250 占 폚 to 350 占 폚.
3. The method according to claim 1 or 2,
Wherein the solvolytic petroleum pitch has a weight average molecular weight of 1,000 g / mol to 10,000 g / mol.