TW201402802A - A method is provided for preparing hydrogenated C5 aliphatic petroleum resins by adopting C5 aliphatic petroleum resins as feed and was prepared by - Google Patents

Abstract

A method is provided for preparing hydrogenated C5 aliphatic petroleum resins by adopting C5 aliphatic petroleum resins as feed, hydrogenating the C5 aliphatic petroleum resins by one stage hydrogenation and sole catalyst being used in the one stage hydrogenation. C5 aliphatic petroleum resins are polymerized from at least two alkenes wherein the alkene is selected from the group consisting of long chain and aliphatic mono-olefin of 4 to 8 carbon numbers and long chain and aliphatic diene of 4 to 8 carbon numbers. This invention also provides a hydrogenated C5 aliphatic petroleum resins. The present invention provides a simpler and low-cost method and thus increases industrial applicability.

Description

Hydrogenation method of aliphatic five-carbon series petroleum resin and preparation thereof

The invention provides a hydrogenated aliphatic five-carbon series petroleum resin and a hydrogenation method thereof, in particular to a hydrogenation method of an aliphatic five-carbon series petroleum resin which is simple in process and is used for an aliphatic five-carbon series petroleum resin.

Petroleum resin products can be used for medium or low grade paints, inks or rubber products due to their special water resistance, acid resistance and good adhesion. The advanced petroleum resin products are mainly petroleum resin hydrogenated products, which have the advantages of good weather resistance, good heat stability and light color. They can be added to advanced products of adhesives, road marking paints, advanced paints, inks or Rubber products, etc., for surface coating.

Generally, petroleum resins can be classified into different types according to raw materials and characteristics, among which are five-carbon series petroleum resins, nine-carbon series petroleum resins, five-carbon series and nine-carbon series copolymer resins, dicyclopentadiene resins and hydrogenated petroleum resins. The five-carbon series petroleum resin is obtained by polymerizing a C ₅ fraction of petroleum cracking, such as isoprene, cyclopentadiene, 1-pentene, etc., and the nine-carbon series petroleum resin is a C ₉ fraction of petroleum cracking, such as It is obtained by polymerization of hydrazine, methyl styrene, divinylbenzene and the like.

In recent years, there have been many studies on hydrogenation of nine-carbon series petroleum resins and five-carbon series (especially cyclopentadiene-based compounds) and nine-carbon series copolymer resins. For example, TW No. I237033 discloses a kind of ruthenium and vinyl toluene. The hydrogenation method of the nine-carbon series petroleum resin formed, and the invention of TW No. 200406428 discloses a five-carbon series and a nine-carbon series copolymer resin mainly composed of a cyclopentadiene compound and a vinyl aromatic compound. Hydrogen method, which uses palladium and platinum as a specific ratio of bimetallic catalyst to maintain The life of the catalyst. And TW No. I237033 discloses a modified hydrogenated copolymer synthesized from a conjugated diene and a vinyl aromatic monomer, the copolymer having a weight average molecular weight of 100,000 to 1,000,000, and the copolymer is used for Building materials, shock-proof and sound-insulating materials or wire coating materials, etc., because the weight average molecular weight of the copolymer is much larger than the weight average molecular weight of the general petroleum resin, and cannot be used for blending in paint or hot melt adhesive.

The invention of the TW200404822 discloses a method for hydrogenating a petroleum resin, which aims to prevent the metal which is a catalyst from being inactivated due to poisoning, so a two-stage hydrogenation procedure is used to hydrogenate the petroleum resin. In the two-stage hydrogenation process, different catalysts are used. The hydrogenation process in the previous stage uses a palladium catalyst, and the hydrogenation process in the latter stage uses a nickel-based catalyst to carry out hydrogenation and desulfurization reactions. The hydrogenation process of the segment type and the use of different catalysts in each hydrogenation process are a complicated procedure, thereby reducing the industrial applicability.

However, the above-mentioned prior art is mostly a study on the hydrogenation method of a nine-carbon series petroleum resin and a five-carbon series (especially a cyclopentadiene-based compound) and a nine-carbon series copolymer resin, and few of the five-carbon series petroleum resins are added. Research on hydrogen methods. In addition, the hydrogenation method provided by the prior art is a two-stage hydrogenation process and requires the use of different catalysts or the use of a bimetallic catalyst, which is a complicated process in the process and cannot reduce the cost. Thereby reducing its industrial utilization.

In order to provide a hydrogenation method for a five-carbon series petroleum resin which is simple in process and greatly reduced in cost, the present invention provides a method for hydrogenating an aliphatic five-carbon series petroleum resin, wherein an aliphatic five-carbon series petroleum resin is used as a And hydrogenating in a one-stage hydrogenation process to obtain a hydrogenated aliphatic five-carbon series petroleum resin, and the one-stage hydrogenation process uses a single catalyst, and the one-stage hydrogenation process refers to the aliphatic The five-carbon series petroleum resin and the single catalyst are reacted by hydrogen in a reactor, wherein the aliphatic five-carbon series petroleum resin is formed by polymerizing two or more kinds of the olefinic compounds, and the olefinic compound is selected from the following The group formed is an aliphatic monoolefin having a long chain and a carbon number of 4 to 8 and an aliphatic diolefin having a long chain and a carbon number of 4 to 8.

According to the present invention, the number average molecular weight of the aliphatic five-carbon series petroleum resin of the present invention is, but not limited to, between 800 and 1,500.

According to the present invention, the polymerization according to the present invention is, for example, but not limited to, the raw material used is mainly a by-product from the pyrolysis of petroleum brain, and the by-product contains an unsaturated compound, and the unsaturated compound is long. An aliphatic monoolefin having a carbon number of 4 to 8 and an aliphatic diolefin having a long chain and a carbon number of 4 to 8. These unsaturated compounds are polymerized by Friedel-Crafts catalyst such as aluminum chloride or boron trifluoride, or polymerized by heating to obtain aliphatic petroleum resins or aliphatic and aromatic Copolymerized petroleum resin. The solvent used in the polymerization process includes, but is not limited to, benzene, toluene, xylene, cyclohexane, dimethylcyclohexane or ethylcyclohexane, and more preferably, the solvent is xylene; polymerization process Wherein the solvent is based on the starting monomer (i.e., the aforementioned unsaturated compound), preferably between 10 and 60 wt%, more preferably between 20 and 50 wt%; The temperature is between 100 and 350 ° C, more preferably between 220 and 300 ° C; the polymerization pressure is between 0 MPa (Mpa) and 3 Mpa, more preferably, the system is between 0 Mpa to 2 Mpa The petroleum resin polymerized by the aforementioned polymerization conditions contains an unsaturated bond.

According to the present invention, the aliphatic monoolefin having a long chain and having a carbon number of 4 to 8 according to the present invention comprises an aliphatic monoolefin having a linear chain and a carbon number of 4 to 8 and a branched chain and having a carbon number of An aliphatic monoolefin of between 4 and 8.

According to the present invention, the aliphatic monoolefins having a long chain and having a carbon number of 4 to 8 according to the present invention include, but are not limited to, butene, pentene, isopentene, hexene or heptene.

According to the present invention, the aliphatic diolefin having a long chain and having a carbon number of 4 to 8 according to the present invention comprises an aliphatic diolefin having a linear chain and a carbon number of 4 to 8 and a branched chain having a carbon number of An aliphatic diolefin between 4 and 8.

According to the present invention, the aliphatic diolefins having a long chain and having a carbon number of 4 to 8 according to the present invention include, but are not limited to, butadiene, pentadiene, isoprene or methylpentadiene. .

Preferably, the single catalyst is a precious metal catalyst.

According to the present invention, the noble metal catalyst of the present invention includes, but is not limited to, a palladium catalyst or a platinum catalyst.

Preferably, the single catalyst is a nickel catalyst.

Preferably, the one-stage hydrogenation process is continuous.

According to the present invention, the continuous hydrogenation according to the present invention refers to the feed and the aliphatic five-carbon series petroleum resin which continuously enters the reactor for reaction and continuously obtains hydrogenation.

Preferably, the one-stage hydrogenation process is batch type.

According to the present invention, the batch type according to the present invention means that the feed and the hydrogen are fed into the reactor for reaction. At this time, the feed is not added, but the hydrogen can be supplemented. After the reaction is completed, the hydrogenation is obtained once. Aliphatic five carbon system Column petroleum resin.

Preferably, the hydrogenation of an aliphatic five-carbon series petroleum resin in a one-stage hydrogenation process further comprises first dissolving the aliphatic five-carbon series petroleum resin by using a hydrocarbon solvent of a saturated hydrocarbon to obtain an aliphatic five carbon. The series of petroleum resin solutions are used as feeds and then hydrogenated in a one-stage hydrogenation process.

According to the present invention, the hydrocarbon solvent of the saturated hydrocarbon according to the present invention includes, but is not limited to, an n-heptane solvent or a cyclohexane solvent.

Preferably, the aliphatic five-carbon series petroleum resin is 10% by weight (wt%) to 50% by weight of the aliphatic five-carbon series petroleum resin solution.

Preferably, the hydrogenation pressure in the one-stage hydrogenation process is between 4 MPa and 10.0 MPa.

Preferably, the reaction temperature in the one-stage hydrogenation process is from 150 ° C to 320 ° C.

Preferably, the volume ratio of hydrogen to feed in the one-stage hydrogenation process is from 200 to 1600.

Preferably, the flow rate of the reaction liquid in the one-stage hydrogenation process is from 0.1 to 10 hours per hour (hr ^-1 ).

The invention also provides a hydrogenated aliphatic five-carbon series petroleum resin obtained by the hydrogenation method of the foregoing aliphatic five-carbon series petroleum resin, the hydrogenated aliphatic five-carbon series petroleum resin by gel The number average molecular weight measured by permeation chromatography (GPC) is between 240 and 8000.

The invention has the advantages that hydrogenation of an aliphatic five-carbon series petroleum resin by using a one-stage hydrogenation process and using only a single catalyst can obtain a good saturation rate compared to the two-stage hydrogenation process and For each hydrogenation process Different catalysts need to be used in the sequence, and the process of the invention is simple and the cost is greatly reduced, thereby increasing the industrial utilization.

Further, the present invention utilizes a design in which the olefinic compound is limited to an aliphatic olefin having a long chain and a carbon number of 4 to 8, and the hydrogenated aliphatic group of the present invention is used since no aromatic compound is used. The five-carbon series petroleum resin can increase the weather resistance, thermal stability and chromaticity of the petroleum resin because of its low unsaturated bond ratio, and since the number average molecular weight is between 240 and 8000, it is available. It is used for surface coating in paints, hot melt adhesives or adhesives with low blending.

In order to understand the technical features and practical effects of the present invention in detail, and in accordance with the description of the present invention, reference should be made to the preferred embodiments.

The source and composition ratios of the samples described in the experimental preparation process of the present invention are as follows:

One-drop fixed bed reactor: manufactured by Xytel, model: 316 stainless steel (USA).

Methylcyclohexane: Purity: 99.9%, manufactured by TEDIA (USA).

Aliphatic five-carbon series petroleum resin: purchased from Sino-German Petroleum Resin Co., Ltd., the model: FR (Fuyang City, China), the raw materials of the product are four carbon and five carbon aliphatic monoolefins and four carbon and five The carbon aliphatic diolefin is polymerized, and the number average molecular weight after polymerization is 1,254.

Diatomaceous earth: The surface area is 256 m ^ 2 /g (m ² /g), and the pore volume is 0.31 per ml / g (mL / g).

Aliphatic five-carbon series petroleum resin and hydrogenated aliphatic five-carbon series stone Analysis and testing of oleoresin:

Color identification: The color of the aliphatic five-carbon series petroleum resin is regarded as brownish yellow, and the color of the hydrogenated aliphatic five-carbon series petroleum resin is water white and transparent.

Degree of saturation: According to the ASTM D5776 titration method, the bromine index indicates the content of the unsaturated bond of the sample, and therefore, the magnitude of the bromine index indicates the degree of saturation of the hydrogenated petroleum resin. The bromine index of the generally unhydrogenated petroleum resin is 10,000 mg bromine/100 g (mgBr/100 g) or more, and the hydrogenated petroleum resin has a bromine index of 1,000 mgBr/100 g or less.

Saturation rate (%): 100 × (bromine index of aliphatic five-carbon series petroleum resin, bromine index of hydrogenated aliphatic five-carbon series petroleum resin petroleum resin) / bromine index of aliphatic five-carbon series petroleum resin.

Molecular weight: The molecular weight was determined by gel permeation chromatography (GPC).

Embodiment 1 Hydrogenation method of aliphatic five-carbon series petroleum resin of the present invention and preparation thereof

The hydrogenation process of one stage of the present invention is as follows: first prepare an aliphatic five-carbon series petroleum resin having a bromine index of 13467 mgBr/100g and a color of brownish yellow, and dissolving the fat with methylcyclohexane. a five-carbon series petroleum resin, which is obtained by feeding an aliphatic five-carbon series petroleum resin solution, wherein the aliphatic five-carbon series petroleum resin is 10 wt% of the aliphatic five-carbon series petroleum resin solution; By pumping into the pipeline, hydrogen is added to the pipeline and mixed with the feed, and pumped into a one-drop fixed bed reactor to carry out the reaction, wherein the feed, hydrogen mixing, and reaction are continuous. The condition for hydrogenation is: the volume of the catalyst used is 50 mL, and the catalyst comprises nickel metal and diatomaceous earth as a nickel metal carrier, wherein diatomaceous earth is used. Base, containing 55 wt% nickel metal, with a reaction temperature of 180 ° C, a hydrogenation pressure of 5.5 MPa, a hydrogen to feed volume ratio of 600:1, and a liquid hourly space velocity (LHSV) of 0.5 hr -1, wherein the periphery of the one-drop fixed bed reactor is an electrically heated heating hood, the heating hood being divided into three sections for respectively heating the upper, middle and lower sections of the one-drop fixed bed reactor, The heating temperature can be set freely in each section; finally, the hydrogenated aliphatic five-carbon series petroleum resin is obtained.

After obtaining the hydrogenated aliphatic five-carbon series petroleum resin, the hydrogenated aliphatic five-carbon series petroleum resin flows into the gas-liquid separator for gas-liquid separation, and the gas flows through the wet flow meter to calculate the gas flow rate, and the liquid Then, the flow controller maintains the liquid level of the gas-liquid separator and discharges the amount of the aliphatic five-carbon series petroleum resin which is subjected to the hydrogenation, and finally enters the liquid product tank. The hydrogenated aliphatic five-carbon series petroleum resin has a bromine index of 3194 mgBr/100 g, a color of pale yellow, a saturation ratio of 76.3%, and a number average molecular weight of 900.

Example 2 Hydrogenation method of aliphatic five carbon series petroleum resin of the present invention and preparation thereof

This example differs from Example 1 in that the reaction temperature is 190 ° C and the volume ratio of hydrogen to feed is 360:1. The hydrogenated aliphatic five-carbon series petroleum resin prepared in this example has a bromine index of 1917 mgBr/100 g, a saturation ratio of 85.8%, and a number average molecular weight of 826.

Examples 3 to 8 hydrogenation method of aliphatic five carbon series petroleum resin of the present invention and preparation thereof

In Examples 3 to 8, the difference from Example 1 is that the catalyst used has a volume of 30 mL, an LHSV of 1.0 hr ^-1 , and the reaction temperatures of Examples 3 to 8 and the respective additions. The saturation ratio and number average molecular weight of the aliphatic five-carbon series petroleum resin of hydrogen are shown in Table 1 below.

It can be seen from Table 1 that when the reaction temperature is increased from 200 ° C to 280 ° C, that is, in Examples 3 to 7, the saturation ratio of the hydrogenated aliphatic five-carbon series petroleum resin is increased from 99.4% to 100%, so It is known that the heating effect increases the hydrogenation effect, and the petroleum resin cracking situation is less. However, when the reaction temperature was further raised to 290 ° C, that is, in Example 8, the number average molecular weight of the hydrogenated aliphatic five-carbon series petroleum resin was also significantly lowered to 243, and the saturation rate was also lowered to 95%, so that it was known. At high temperature, the hydrogenation of the aliphatic five-carbon series petroleum resin is severely cracked, and the hydrogenation process cannot make up the olefins produced by the cracking, so the saturation rate decreases.

Embodiments 9 to 11 hydrogenation method of aliphatic five-carbon series petroleum resin of the present invention and preparation thereof

In Examples 9-11, the difference from Example 1 is that the reaction temperature is 200 ° C, and the liquid space flow rates of Examples 9 to 11 and the saturation ratio of each of the prepared hydrogenated aliphatic five-carbon series petroleum resins are obtained. And the number average molecular weight is shown in Table 2 below.

Table 2. Liquid space flow rates of Examples 9 to 11 and the saturation ratio and number average molecular weight of each of the prepared hydrogenated five-carbon series petroleum resins

As shown in Table 2, when the LHSV decreased from 0.7 hr ^-1 to 0.2 hr ^-1 , that is, in Examples 9 to 11, the saturation rate decreased from 99.8% to 99.2%, and the saturation rate of the falling pair of LHSV was known. The impact is small. The LHSV decreased from 0.7 hr ^-1 to 0.2 hr ^-1 , and the number average molecular weight decreased from 1130 to 955. It can be seen that a small amount of cleavage occurred.

Embodiment 12 Hydrogenation method of aliphatic five-carbon series petroleum resin of the present invention and preparation thereof

In the embodiment 12, the difference from the first embodiment is that the reaction temperature is 200 ° C, the volume ratio of hydrogen to the feed is 360:1, and the hydrogenated aliphatic five-carbon series petroleum resin obtained in the present embodiment is The saturation ratio was 99.2%, and the number average molecular weight was 955.

Embodiment 13 Hydrogenation method of aliphatic five-carbon series petroleum resin of the present invention and preparation thereof

In Example 13, the difference from Example 1 is that the reaction temperature is 200 ° C, the volume ratio of hydrogen to the feed is 860:1, and the LHSV is 0.2 hr-1. The hydrogenated fat obtained in the present example. The five-carbon series petroleum resin has a saturation ratio of 99.0% and a number average molecular weight of 905.

Claims (18)

A method for hydrogenating an aliphatic five-carbon series petroleum resin, wherein an aliphatic five-carbon series petroleum resin is used as a feed and hydrogenated by a one-stage hydrogenation process to obtain a hydrogenated aliphatic five-carbon series petroleum resin. And the one-stage hydrogenation process uses a single catalyst, and the one-stage hydrogenation process refers to the aliphatic five-carbon series petroleum resin and the single catalyst reacted with hydrogen in a reactor, wherein the aliphatic The five-carbon series petroleum resin is obtained by polymerizing two or more kinds of olefinic compounds selected from the group consisting of long chain and aliphatic monoolefins having a carbon number of 4 to 8 and long An aliphatic diolefin having a chain and a carbon number of between 4 and 8. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 1, wherein the single catalyst is a noble metal catalyst. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 1, wherein the single catalyst is a nickel catalyst. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to any one of claims 1 to 3, wherein the one-stage hydrogenation process is continuous. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to any one of claims 1 to 3, wherein the one-stage hydrogenation process is batch type. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 4, wherein the hydrogenation of an aliphatic five-carbon series petroleum resin in a one-stage hydrogenation process further comprises first dissolving a hydrocarbon solvent using a saturated hydrocarbon. The aliphatic five-carbon series petroleum resin is obtained by feeding an aliphatic five-carbon series petroleum resin solution as a feed, and then hydrogenating in a one-stage hydrogenation process. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 6, wherein the aliphatic five-carbon series petroleum resin is the aliphatic five-carbon 10 parts by weight (wt%) to 50 wt% of the series petroleum resin solution. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 4, wherein the hydrogenation pressure in the one-stage hydrogenation process is from 4 MPa to 10.0 MPa. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 4, wherein the reaction temperature in the one-stage hydrogenation process is from 150 ° C to 320 ° C. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 4, wherein a volume ratio of hydrogen to a feed in the one-stage hydrogenation process is from 200 to 1600. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 4, wherein the liquid flow rate of the reaction liquid in the one-stage hydrogenation process is from 0.1 to 10 hr ^-1 . The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 5, wherein the hydrogenation of an aliphatic five-carbon series petroleum resin in a one-stage hydrogenation process further comprises first dissolving a hydrocarbon solvent using a saturated hydrocarbon. The aliphatic five-carbon series petroleum resin is obtained by feeding an aliphatic five-carbon series petroleum resin solution as a feed, and then hydrogenating in a one-stage hydrogenation process. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 12, wherein the aliphatic five-carbon series petroleum resin is 10% by weight (wt%) to 50 wt% of the aliphatic five-carbon series petroleum resin solution. %. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 5, wherein the hydrogenation pressure in the one-stage hydrogenation process is from 4 MPa to 10.0 MPa. Hydrogenation of aliphatic five-carbon series petroleum resin as described in claim 5 The method wherein the reaction temperature in the one-stage hydrogenation process is from 150 ° C to 320 ° C. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 5, wherein a volume ratio of hydrogen to a feed in the one-stage hydrogenation process is from 200 to 1600. The method for hydrogenating an aliphatic five-carbon series petroleum resin according to claim 5, wherein the liquid flow rate of the reaction liquid in the one-stage hydrogenation process is from 0.1 to 10 hr ^-1 . A hydrogenated aliphatic five-carbon series petroleum resin obtained by the hydrogenation method of an aliphatic five-carbon series petroleum resin according to any one of claims 1 to 17, the hydrogenated aliphatic five-carbon series The number average molecular weight of the petroleum resin as measured by gel permeation chromatography (GPC) is between 240 and 8,000.