JP2007204519A - Petroleum resin and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a petroleum resin which reduces the components capable of affecting the living environment, and a manufacturing method which stabilizes the quality of the petroleum resin and improves the productivity. <P>SOLUTION: The petroleum resin has not more than 0.5 wt.% components having a weight average molecular weight of 300 or less, a hue measured by a Gardner color difference meter of 8 or less, and not more than 500 nL/g volatile organic compound components. The method for manufacturing the petroleum resin is disclosed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a petroleum resin having a small amount of volatile organic compound components and a method for producing the same, and more specifically, a petroleum resin having a small amount of volatile organic compound components and a low environmental load, and a desolvation step when producing the petroleum resin. It is related with the method of manufacturing efficiently by managing by the measured value obtained by the liquid chromatograph apparatus.

  Conventionally, petroleum resins are free of aromatic trichloride, boron trifluoride, etc. in reactive aromatic compounds and / or reactive aliphatic compounds that are polymerizable unsaturated hydrocarbon-containing fractions obtained by thermal decomposition of petroleum. It is manufactured by adding a Del Crafts type catalyst and carrying out a polymerization reaction.

  In general, fractions containing polymerizable unsaturated hydrocarbons obtained by thermal cracking of petroleum also contain low-reactive hydrocarbons that do not show a polymerization reaction with Friedel-Crafts catalysts. Hydrogen contains an aromatic organic solvent such as toluene and xylene. It is known that the composition of fractions containing polymerizable unsaturated hydrocarbons obtained by petroleum pyrolysis, etc., changes depending on the country of origin of petroleum, the pyrolysis process of petroleum, and the pressure and temperature of pyrolysis. Because of the nature that fractions containing polymerizable unsaturated hydrocarbons obtained by pyrolysis of petroleum etc. are by-products when petroleum is pyrolyzed, etc. It is difficult to obtain a fraction containing a polymerizable unsaturated hydrocarbon obtained by thermal decomposition or the like.

  For this reason, a polymerization reaction product obtained by polymerization is obtained as a mixture with a low-reactivity hydrocarbon solvent, and the polymerization reaction product obtained by polymerization with the low-reactivity hydrocarbon solvent by the solvent removal step. Is separated to obtain a petroleum resin. As the solvent removal step, stripping by heating, heating, vacuum distillation by a vacuum pump or an ejector, bubbling by circulation of an inert gas such as nitrogen, and the like are performed.

  In the solvent removal step, heating is generally performed as described above, and it is effective to increase the heating temperature in order to increase the solvent removal efficiency. Therefore, it is desirable that the heating is minimal.

  On the other hand, at the study meeting of the Ministry of Health and Welfare, it was pointed out that volatile organic compounds (hereinafter sometimes referred to as VOC) are the causative substances of the sick house (indoor environmental pollution) problem. A guideline value for the indoor concentration is determined, and a sample sample collection method and a measurement method are prepared (see Non-Patent Document 1). In the study group, substances contained in the polymerizable unsaturated hydrocarbon-containing fraction obtained by pyrolysis of petroleum such as toluene and xylene have been taken up as substances subject to formulation of VOC guideline values from the beginning of the study. In addition, since the guideline value established by the study group covers the indoor concentration of VOCs when products used for indoor construction are used, the manufacturer of products used for indoor constructions Inquiries about requests for measurement and reduction of VOC concentration contained in the sap are increasing. However, the study group is intended to cover all indoor spaces in principle with the scope of application of the guideline values, and the sampling and measurement methods for sample samples related to the raw materials of products used for indoor construction have been studied. Yes.

  In order to respond to requests and inquiries from manufacturers of products used for indoor construction, there are many examples of measuring the VOC of raw materials of products used for indoor construction in accordance with the guidelines established by the study group. As an example of the measurement method, a sample sample is placed in a heating sealed container and heated at a constant temperature for 5 hours or more, whereby VOC in the sample sample is gasified and the gas in the sealed container is analyzed by GC-MS. The method is taken.

  In recent years, in order to satisfy the guideline values prepared by the study group, manufacturers of products used for indoor construction have set management values for VOCs derived from raw materials for products used for indoor construction. An example of requesting reduction of VOC contained in the raw material of a product used for the construction of the construction has been recognized.

  For this reason, VOC reduction is also required for petroleum resins used as raw materials for products used in indoor construction, but the measurement method is unsuitable for continuous measurement, so representative samples are measured according to the measurement method. However, it is necessary to control the manufacturing process based on the results, but since the measurement takes a long time, the quality of the petroleum resin is deteriorated and the production efficiency of the petroleum resin is remarkably deteriorated. ing.

Study Meeting on Sick House (Indoor Air Pollution) Issue, “Interim Report-Summary of the 1st to 3rd Report”, [online], June 29, 2000, Ministry of Health and Welfare, [January 26, 2006] Search], Internet (URL: http://www1.mhlw.go.jp/houdou/1206/h0629-2_13.html)

  The VOC measurement method in accordance with the guidelines established by the Ministry of Health and Welfare Study Group is for grasping the impact on the actual living environment. The measurement method is used to produce raw materials for products used for indoor construction. By applying it sometimes, the productivity of petroleum resin, which is one of the raw materials of products used for indoor construction, is deteriorated.

  Accordingly, the present invention provides a stable quality petroleum resin in which the VOC concentration contained in the petroleum resin is reduced and the components that can affect the living environment are reduced, and a method for producing the petroleum resin with high production efficiency. It is.

  Therefore, the inventors of the present invention measured the VOC concentration contained in the petroleum resin in a short time during the production of the above-described petroleum resin, and fed back the measurement result to the desolvation step of the petroleum resin production step, so that appropriate desorption was performed. By carrying out the solvent treatment, the present inventors have completed the present invention by finding a petroleum resin with reduced components that can affect the living environment, a production method that stabilizes the quality of the petroleum resin, and improves productivity.

  That is, a petroleum resin characterized in that a component having a weight average molecular weight of 300 or less is 0.5% by weight or less, a hue measured by a Gardner colorimeter is 8 or less, and a volatile organic compound component is 500 nL / g or less, and A reactive aromatic compound and / or a reactive aliphatic compound, which is a polymerizable unsaturated hydrocarbon-containing fraction obtained by thermal decomposition of petroleum or the like, is subjected to a polymerization reaction in the presence of a catalyst, and then in a solvent removal step. A method for producing a petroleum resin in which unreacted oil is distilled off by heating, and the solvent removal process is controlled by measuring the weight fraction of a component having a weight average molecular weight of 300 or less in the petroleum resin using a liquid chromatograph apparatus. This is a method for producing a petroleum resin.

  The present invention will be described in detail below.

  In the petroleum resin in the present invention, a component having a weight average molecular weight of 300 or less is 0.5% by weight or less. When the component having a weight average molecular weight of 300 or less exceeds 0.5% by weight, it becomes a petroleum resin having a lot of VOC and having a problem in environmental load. In order to further reduce the environmental load, the content is preferably 0.4% by weight or less, and more preferably 0.3% by weight or less. Here, the component having a weight average molecular weight of 300 or less is obtained by polymerizing a fraction containing an unsaturated hydrocarbon having a boiling point in the range of −20 ° C. to 280 ° C. obtained in the case of pyrolysis of petroleums. It is a component contained in the polymer, and examples thereof include toluene, xylene and styrene. The weight average molecular weight here is measured by a liquid chromatograph.

  In order to reduce VOC and reduce the environmental burden, it is particularly preferable that the petroleum resin in the present invention contains 0.2% by weight or less of a component having a weight average molecular weight of 150 or less.

  The petroleum resin in the present invention has a hue measured by a Gardner color difference meter of 8 or less. When the hue measured by the Gardner color difference meter exceeds 8, the petroleum resin is inferior in color tone and has a reduced commercial value. In order to reduce the effect of adding yellowishness to the color tone of the final product containing the petroleum resin, it is preferably 7 or less, and more preferably 6 or less.

  The petroleum resin in the present invention has a volatile organic compound component of 500 nL / g or less. When the volatile organic compound component exceeds 500 nL / g, the VOC is large and the petroleum resin has a problem in environmental load. In order to further reduce the environmental load, it is preferably 500 to 200 nL / g, and more preferably less than 200 nL / g.

  The petroleum resin of the present invention polymerizes a reactive aromatic compound and / or a reactive aliphatic compound, which is a polymerizable unsaturated hydrocarbon-containing fraction obtained by thermal decomposition of petroleum, in the presence of a catalyst. Then, a method for producing a petroleum resin in which unreacted oil is distilled off by heating in a desolvation step, and the weight fraction of a component having a weight average molecular weight of 300 or less in the petroleum resin is measured using a liquid chromatograph device. By managing the desolvation process according to the measurement result, it can be obtained with high productivity as a petroleum resin having high quality.

  Here, the reactive aromatic compound and / or the reactive aliphatic compound which is a raw material of petroleum resin is, for example, unsaturated carbonization having a boiling point of −20 ° C. to 280 ° C. obtained at the time of thermal decomposition of petroleum. Any fraction of fractions containing hydrogen. In addition, the catalyst for polymerizing the fraction is not particularly limited as long as it is an acidic substance, and examples thereof include a Friedel-Crafts type catalyst and a protonic acid. Examples of the Friedel-Crafts type catalyst include aluminum halides such as anhydrous aluminum trichloride or complexes thereof, boron trifluoride or complexes thereof, tin halides such as tin tetrachloride, etc. Among them, anhydrous aluminum trichloride Boron trifluoride or a complex thereof is preferable.

  Moreover, conditions, such as superposition | polymerization temperature, superposition | polymerization time, and the catalyst amount used for superposition | polymerization, are arbitrary, and are the conditions used for superposition | polymerization of a normal petroleum resin, ie, superposition | polymerization temperature 10-100 degreeC, superposition | polymerization time 0.5-6 hours. The catalyst concentration may be 0.1 to 1 wt% with respect to the raw material.

  And when manufacturing petroleum resin, in order to distill off an unreacted component after completion | finish of a polymerization reaction, performing the desolvation process by heating etc. is generally performed. The purpose of the heating or the like in the desolvation step is to separate the polymerization reaction product from a low-reactivity hydrocarbon or the like that does not show a polymerization reaction with a catalyst after the completion of the polymerization reaction. Specific heating can be exemplified by solvent removal only by heating, solvent removal using both heating and decompression, and solvent removal using heating and bubbling with an inert gas.

  Here, the petroleum resin obtained by the solvent removal step is collected, dissolved in a solvent such as THF or dichlorobenzene, and the weight fraction of components having a weight average molecular weight of 300 or less in the petroleum resin by a liquid chromatograph apparatus. And the solvent removal process is managed based on the measurement result. In addition, the liquid chromatograph apparatus in that case can be utilized without limitation especially if a weight average molecular weight can be measured. In addition, adjustment with a standard substance is performed in order to improve the measurement accuracy of the measurement method using a liquid chromatograph. However, measurement can be performed according to a normal adjustment method, and the accuracy is preferably high in the region of several hundred molecular weights. It is desirable to adjust so that it becomes.

  Furthermore, since the time required for sample preparation can be shortened and the measurement result of the sample can be reflected in the petroleum resin production conditions at an early stage, the content of volatile organic compounds in the petroleum resin can be achieved by using a liquid chromatograph. It is preferable to manage. Here, as a result of GPC analysis using a liquid chromatograph apparatus, when the weight fraction of the component having a weight average molecular weight of 300 or less is high, the content of the volatile organic compound is estimated to be high. . For this reason, in this case, the content of the volatile organic compound in the petroleum resin can be managed by further distilling off the unreacted oil.

  By adopting a measurement method using a liquid chromatograph apparatus, the present inventors appropriately adjust the desolvation treatment conditions such as the heating temperature and the heating time, avoid excessive heating, and reduce the polymerization reaction product It was found that the VOC concentration in the polymerization reaction product can be suppressed while suppressing the deterioration of color.

  From the above results, according to the present invention, the deterioration of the color of the petroleum resin is suppressed, the petroleum resin in which components that can affect the living environment are reduced, the quality of the petroleum resin is stabilized, and the product is manufactured with high productivity. It becomes possible to do.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

  In Examples and Comparative Examples, measurement was performed using the following apparatus.

Liquid chromatograph apparatus: High-speed GPC apparatus (manufactured by Tosoh Corporation, model HLC-8220GPC)
GC-MS: Gas chromatograph mass spectrometer (manufactured by PerkinElmer, model turbo MS)
Softening point: Softening point tester [Ring and ball method (ring and ball automatic softening point tester, model ASP-MK2 manufactured by Meitec Co., Ltd.)]
Hue: Hue measuring device [Gardner color difference meter (Nippon Denshoku Co., Ltd. color difference / turbidity measuring device, model ND-300A)]
Example 1
Nitrogen was passed through a 4 liter flask equipped with a stirrer and a heater to replace the gas inside the flask. 2 liters of a fraction containing unsaturated hydrocarbons having a boiling point of −20 ° C. to 280 ° C. and 22 g of boron trifluoride phenol complex obtained in the pyrolysis of petroleum are added to the reactor, and the temperature is 60 ° C. The polymerization reaction was carried out by maintaining for 2 hours. After washing the reaction solution with a 1% aqueous caustic solution, the unreacted oil in the oil phase was distilled off by heating with a heater. At the time of distilling off the unreacted oil in the oil phase, the contents are collected in a timely manner and subjected to GPC analysis using a liquid chromatograph, and the content of the weight average molecular weight of 300 or less is 0.5% by weight. The temperature and time of unreacted oil distillation were adjusted so that the heating temperature was 215 ° C. to 221 ° C., and the heating time was 120 minutes.

  As a result, 780 g of a resin having a softening point of 120 ° C., a hue of 7, and a weight average molecular weight of 1550 was obtained.

  The obtained petroleum resin was heated at 50 ° C. for 24 hours in an airtight container for heating, and as a result of GC-MS analysis of the generated vapor, the volatile organic compound (total of toluene, xylene and styrene) was 400 nL / g. It was.

Example 2
In GPC analysis using a liquid chromatograph of the contents collected in a timely manner when distilling off the unreacted oil in the oil phase, the content of the contents having a weight average molecular weight of 300 or less is 0.4% by weight. The same procedure as in Example 1 was performed except that the temperature and time for distilling off the unreacted oil were adjusted, the heating temperature was 218 ° C. to 224 ° C., and the heating time was 120 minutes.

  As a result, 790 g of a resin having a softening point of 120 ° C., a hue of 7, and a weight average molecular weight of 1530 was obtained.

  The volatile organic compound of the obtained petroleum resin was 360 nL / g.

Example 3
In GPC analysis using a liquid chromatograph of the contents collected at the time of removal of unreacted oil in the oil phase, the content of the contents having a weight average molecular weight of 300 or less is 0.3% by weight. The same procedure as in Example 1 was performed except that the temperature and time for distilling off the unreacted oil were adjusted, the heating temperature was 220 ° C. to 228 ° C., and the heating time was 140 minutes.

  As a result, 750 g of a resin having a softening point of 120 ° C., a hue of 8, and a weight average molecular weight of 1560 was obtained.

  The volatile organic compound of the obtained petroleum resin was 300 nL / g.

Example 4
In GPC analysis using a liquid chromatograph of the contents collected in a timely manner when distilling off the unreacted oil in the oil phase, the content of the contents having a weight average molecular weight of 150 or less is 0.2% by weight. The same procedure as in Example 1 was conducted except that the temperature and time for distilling off the unreacted oil were adjusted, the heating temperature was 222 ° C. to 228 ° C., and the heating time was 160 minutes.

  As a result, 750 g of a resin having a softening point of 122 ° C., a hue of 8, and a weight average molecular weight of 1570 was obtained.

  The volatile organic compound of the obtained petroleum resin was 200 nL / g.

Example 5
Except that the unreacted oil in the oil phase was distilled off at 210 ° C. for 120 minutes and the contents collected were subjected to GPC analysis using a liquid chromatograph, the same as in Example 1. As a result of GPC analysis, the content of the weight average molecular weight of 300 or less of the content was 0.6% by weight. Therefore, unreacted oil was further distilled off at 225 ° C. for 60 minutes.

  As a result, 760 g of a resin having a weight average molecular weight of 300 or less of 0.3% by weight, a softening point of 121 ° C., a hue of 8, and a weight average molecular weight of 1570 was obtained.

  The volatile organic compound of the obtained petroleum resin was 380 nL / g.

Comparative Example 1
The same procedure as in Example 1 was performed except that the GPC analysis of the contents was not performed when the unreacted oil in the oil phase was distilled off, the heating temperature was 199 to 201 ° C., and the heating time was 120 minutes.

  As a result, 780 g of a petroleum resin having a softening point of 120 ° C., a hue of 7, and a weight average molecular weight of 1550 was obtained.

  The volatile organic compound of the obtained petroleum resin was 2000 nL / g.

Comparative Example 2
The same procedure as in Example 1 was performed except that the GPC analysis of the contents was not performed when the unreacted oil in the oil phase was distilled off, the heating temperature was 259 to 261 ° C., and the heating time was 120 minutes.

  As a result, 700 g of a resin having a softening point of 126 ° C., a hue of 11, and a weight average molecular weight of 1650 was obtained.

  When 5 parts by weight of unreacted oil distilled off was added to the obtained resin and the softening point was adjusted to 120 ° C., 735 g of a resin having a softening point of 120 ° C., a hue of 11, and a weight average molecular weight of 1580 was obtained. .

  The volatile organic compound of the petroleum resin, in which the softening point was adjusted by adding unreacted oil, was at least the upper limit of measurement (3000 nL / g or more).

Comparative Example 3
The same procedure as in Example 1 was performed except that the GPC analysis of the contents was not performed when the unreacted oil in the oil phase was distilled off, the heating temperature was 199 to 201 ° C., and the heating time was 240 minutes.

  As a result, 770 g of a petroleum resin having a softening point of 123 ° C., a hue of 8, and a weight average molecular weight of 1590 was obtained.

  By adding 2 parts by weight of unreacted oil distilled off to the obtained petroleum resin and adjusting the softening point to 120 ° C., 785 g of a resin having a softening point of 120 ° C., a hue of 11 and a weight average molecular weight of 1560 was obtained. It was.

The volatile organic compound of the petroleum resin, in which the softening point was adjusted by adding unreacted oil, was at least the upper limit of measurement (3000 nL / g or more).

Claims (4)

A petroleum resin, wherein a component having a weight average molecular weight of 300 or less is 0.5% by weight or less, a hue measured by a Gardner color difference meter is 8 or less, and a volatile organic compound component is 500 nL / g or less. The petroleum resin according to claim 1, wherein a component having a weight average molecular weight of 150 or less is 0.2% by weight or less. A reactive aromatic compound and / or a reactive aliphatic compound, which is a polymerizable unsaturated hydrocarbon-containing fraction obtained by thermal decomposition of petroleum or the like, is subjected to a polymerization reaction in the presence of a catalyst, and then in a solvent removal step. A method for producing a petroleum resin in which unreacted oil is distilled off by heating, wherein a solvent removal process is controlled by measuring a weight fraction of a component having a weight average molecular weight of 300 or less in the petroleum resin using a liquid chromatograph apparatus. The method for producing a petroleum resin according to claim 1, wherein: The method for producing a petroleum resin according to claim 3, wherein the content of the volatile organic compound in the petroleum resin is managed by using a liquid chromatograph.