JP4835997B2 - High temperature filtration method, filtration container and high temperature filtration device - Google Patents

Description

  The present invention relates to a high temperature filtration method, a filtration container, and a high temperature filtration apparatus. In particular, when a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at this heating temperature is filtered, the solvent remains until the solute material dissolves in the solvent. The present invention relates to a high-temperature filtration method that prevents permeation through a filter.

  In recent years, considering the influence on the environment and ecosystem, most of the wire coating materials have been replaced from polyvinyl chloride to polyolefin resins. In most cases, polyolefin resins are blended with inorganic fillers and multiple resins to provide functionality such as flame retardancy, flexibility, and abrasion. Generally, quantitative analysis is performed on these resins. In this case, it is necessary to separate and remove the inorganic filler with good reproducibility.

  As an apparatus for performing such separation, an apparatus described in Non-Patent Document 1 is known. This apparatus includes a heating block and a test tube set in the heating block. The heating block has a test tube and a loading hole for a sample bottle, which will be described later, and can be adjusted to a predetermined temperature by a heater. The test tube is a stainless steel container in which a sample to be separated is placed, and a filter is provided in the container. In addition, a syringe mounting portion is formed on the top of the test tube, and a syringe for pressurizing the inside of the test tube can be mounted on the mounting portion.

  For example, when a mixture of block-polypropylene (b-PP) and magnesium hydroxide is used as a sample, first, the sample and the solvent are put in a test tube. On the other hand, the heating block is heated to a predetermined temperature in advance. A sample bottle that receives the filtrate is set in the heating block, and a test tube is set on the bottle. Subsequently, the test tube containing the sample and the solvent is heated, and the sample is stirred and dissolved in a state where the sample is easily dissolved to some extent. The dissolved sample is pressurized with a syringe from the top of the test tube and filtered through a filter, and only the dissolved resin is dropped into the sample bottle. And a sample bottle is collect | recovered and the inside filtrate is analyzed using a gel permeation chromatography (GPC apparatus) etc.

Senshu Science Co., Ltd. Home Page <URL> http://www.ssc-jp.com/products/28.html <Search Date> November 20, 2006

  However, the above-described conventional apparatus has a problem that the solvent passes through the filter before the sample is dissolved in the solvent.

  B-PP in the sample is heated to a predetermined temperature and dissolved in the solvent. However, in general, the solvent has a low viscosity, and only the solvent passes through the filter before the sample is heated to the predetermined temperature. In that case, the solvent in a state in which b-PP is hardly dissolved is collected in the sample bottle, and an appropriate sample cannot be analyzed.

  Here, if a filter having a small opening (pore diameter) is used, it can be improved to some extent that only the solvent is first filtered by the filter. However, in that case, problems such as a long time for filtration and clogging of the filter in a relatively short time occur.

  For this reason, it has been desired to establish a technique that enables filtration after the sample is reliably dissolved in a solvent, even if a filter having a large opening is used.

  The present invention has been made in view of the above circumstances, and one of its purposes is a high-temperature filtration method, a filtration container, and a high-temperature filtration device capable of filtering a sample after reliably dissolving a solute material in a solvent. Is to provide.

  Another object of the present invention is to provide a high-temperature filtration method, a filtration container, and a high-temperature filtration device that can dissolve the solute material in a solvent without fail and can perform more efficient filtration.

[High-temperature filtration method]
The high temperature filtration method of the present invention includes the following steps.
A preparation step of preparing a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature.
A sample loading step of putting the mixed sample into a filtration container equipped with a filter.
A dissolution step of heating the mixed sample in the container to the heating temperature to dissolve the solute material in a solvent.
A filtration step of separating the insoluble material and the solute material by filtering the mixed sample in which the solute material is dissolved with a filter.
The method of the present invention is characterized in that, in the dissolution step, the solvent is not discharged out of the container until at least the solute material is dissolved in the solvent.

  According to the method of the present invention, since the solvent is not discharged outside the container until the solute material is dissolved in the solvent in the dissolving step, the solute material is surely dissolved in the solvent in the container and then filtered. It can be performed.

[Container for filtration]
On the other hand, the container for filtration of the present invention filters a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature, thereby filtering the insoluble material and the solute. It is the container for filtration for isolate | separating a material. The container includes an intake port for taking outside air into the container, a filter for filtering the sample, a discharge port for the filtrate that has passed through the filter, and an intake port until at least the solute material is dissolved in the solvent. And an inlet closing means for closing the air intake.

  According to this filtration container, it is possible to avoid the introduction of outside air into the container by closing the intake port until the solute material is dissolved in the solvent by the intake port closing means. Therefore, the mixed sample containing the solvent in the container is pressed at atmospheric pressure from the outlet side of the container, and the solvent is prevented from falling and passing through the filter. As a result, the solute material can be reliably dissolved in a solvent and then filtered.

  Another filtration container of the present invention is a non-dissolvable material obtained by filtering a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature. It is the container for filtration for isolate | separating a solute material. The container includes an intake port for taking outside air into the container, a filter for filtering the sample, a discharge port for the filtrate that has passed through the filter, and a discharge port until at least the solute material is dissolved in the solvent. And a discharge port closing means for closing.

  According to this filtration container, the solvent can be prevented from being discharged out of the container by the discharge port closing means. Therefore, if the discharge port is closed by the discharge port closing means until the solute material is dissolved in the solvent, the solute material can be reliably dissolved in the solvent during that time.

[High temperature filtration equipment]
Further, the high-temperature filtration device of the present invention filters an insoluble material and a solute by filtering a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature. It is a high temperature filtration apparatus provided with the container for filtration for isolate | separating a material, and the heating means which heats up the mixed sample in this container to the said heating temperature. Here, the container includes a suction port for taking outside air into the container, a filter for filtering the sample, a discharge port for the filtrate that has passed through the filter, and at least until the solute material is dissolved in the solvent. And an intake port closing means for closing the intake port.

  According to this high-temperature filtration device, it is possible to avoid the introduction of outside air into the container by using the container provided with the intake port closing means as the filtration container. Therefore, the mixed sample containing the solvent in the container is pressed at atmospheric pressure from the outlet side of the container, and the solvent is prevented from falling and passing through the filter. As a result, the solute material can be reliably dissolved in a solvent and then filtered.

  Furthermore, another high-temperature filtration device of the present invention filters an insoluble material by filtering a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature. And a heating container for heating the mixed sample in the container to the heating temperature. Here, the container includes a suction port for taking outside air into the container, a filter for filtering the sample, a discharge port for the filtrate that has passed through the filter, and at least until the solute material is dissolved in the solvent. And a discharge port closing means for closing the discharge port.

  According to this high-temperature filtration device, by using a container having a discharge port closing means as a filtration container, the closing means can prevent the solvent from being discharged out of the container. Therefore, if the discharge port is closed by the discharge port closing means until the solute material is dissolved in the solvent, the solute material can be reliably dissolved in the solvent during that time.

  According to the high temperature filtration method, the filtration container, and the high temperature filtration apparatus of the present invention, the sample can be filtered after the solute material is reliably dissolved in the solvent.

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

[Mixed sample]
<Solvent>
The solvent is a liquid used for dissolving the solute material at a predetermined temperature. The material is not particularly limited as long as it can dissolve a solute material described later. Specific examples of the solvent include tetrahydrofuran, nitrobenzene, dioxane, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, isopropyl alcohol, n-butanol, n-butyl acetate, cyclohexanone, propylene glycol monomethyl ether, ethyl-3-ethoxypropionate. , Ethylene glycol monoethyl ether, ethylene glycol monoethyl acetate, ethylene glycol monobutyl ether, isophorone, methyl amyl ketone, n-propyl alcohol, propylene glycol monomethyl ether acetate, toluene, xylene, 2-ethoxyethanol, 2-methoxyethanol, 2 -Butoxyethanol, chlorobenzene, acetone, methylene chloride, ethylene dichloride, trichrene, Chloroform, such as acetaldehyde, and the like.

  As a solvent for polypropylene, ortho-dichlorobenzene (o-DCB) is preferred. Xylene is preferred as the solvent for polyethylene. Examples of the polyvinyl chloride solvent include tetrahydrofuran, cyclohexanone, nitrobenzene, methyl ethyl ketone, and dioxane.

<Solute material>
The solute material is a material mixed with the insoluble material described below, and is a material that is dissolved in the solvent at a predetermined temperature. Various resins are suitable for the solute material. Specific examples of the resin include thermoplastic resins. Thermoplastic resins include crystalline resins and amorphous resins. Crystalline resins include polyethylene, polypropylene, polyamide, polyacetal, and polyester. Amorphous resins include polystyrene, polyvinyl chloride, ABS resin, acrylic resin, polycarbonate, polyurethane, polyvinyl acetate, and polyvinyl alcohol.

  In particular, polyolefins that are attracting attention as substitutes for polyvinyl chloride are suitable as solute materials. Polyolefin includes polyethylene, polypropylene, polypropylene copolymer, polybutene, polymethylpentene and the like.

  Other examples of the solute material include resin additives. In general, many resin additives have a low melting point, and the resin often becomes an insoluble material and the additive often becomes a solute material. These additives include heat stabilizers, light stabilizers, flame retardants, fluorescent brighteners, hydrophilicity imparting additives, antistatic agents, fungicides, foaming agents, crosslinking agents, crosslinking aids, plasticizers, copper Examples include harm prevention agents. Heat resistance stabilizers include hindered phenol antioxidants, phosphorus processing heat stabilizers, hydroxylamine processing heat stabilizers, vitamin E processing heat stabilizers, wire coating antioxidants, metal deactivators, And sulfur-based heat stabilizers. Examples of the light-resistant stabilizer include benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, benzoate-based UV absorbers, and hindered amine-based light stabilizers. Examples of the flame retardant include a melamine flame retardant. Examples of plasticizers include phthalate esters, adipate ester plasticizers, phosphate ester plasticizers, trimellitic ester plasticizers, citrate ester plasticizers, epoxy plasticizers, and polyester plasticizers. It is done. Examples of the phthalic acid ester include diethyl phthalate, dimethyl phthalate, dibutyl phthalate, dinormal octyl phthalate, dinonyl phthalate, and diisodecyl phthalate. Examples of the crosslinking agent include organic peroxides such as dicumyl peroxide, peroxyketal, diacyl peroxide, dialkyl peroxide, and peroxy ester. Copper damage inhibitors include N, N′-di-2-naphthyl-p-phenylenediamine. Even with these additives, depending on the resin to be combined, the additive may become an insoluble material and the resin may become a solute material.

<Insoluble material>
An insoluble material is a material that is mixed with a solute material, and is a material that does not dissolve in a solvent under the conditions even when the temperature reaches a predetermined temperature at which the solute material dissolves in the solvent. The insoluble material may be an organic material or an inorganic material. A typical example of the organic material is a resin, and a typical example of the inorganic material is glass, metal, or a metal carbide, nitride, oxide, hydroxide, or the like.

When the resin becomes an insoluble material, examples of the resin include a thermosetting resin and a crosslinked resin. Thermosetting resins include epoxy resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, polyimide resins, and the like. Examples of the crosslinked resin include crosslinked polyethylene, crosslinked polypropylene, and crosslinked epoxy resin. Further, in the case of a sample in which a plurality of types of resin materials are mixed, there is a case where one of the resins is a solute material and the other resin is an insoluble material. In this case, the thermoplastic resin can also be an insoluble material depending on the combination of resins to be mixed. In particular, highly crystalline polymers tend to be insoluble materials. Specific examples of a mixture of resins and a combination of “solute material / insoluble material” include the following.
(1) Ethylene-propylene copolymer / isotactic-polypropylene
(2) Ethylene-vinyl acetate copolymer / polyethylene (high density polyethylene)
(3) Ethylene-methyl acrylate copolymer / polyethylene (high density polyethylene)

  Other specific examples of the insoluble material include various fillers contained in the resin. As filler, glass fiber, glass powder, carbon fiber, potassium titanate, calcium silicate, calcium carbonate, talc, mica, clay, kaolin, carbon black, metal fiber, metal powder, ferrite, aluminum hydroxide, magnesium silicate , Magnesium hydroxide, antimony oxide and the like.

[Container for filtration]
The filtration container usually includes a mixed sample filling chamber, a filter for filtering the mixed sample, an intake port for introducing outside air into the filling chamber, and a discharge port for discharging the filtrate.

(Filling chamber)
The filling chamber is a space in which the mixed sample is filled. This filling chamber is preferably made of a material having high thermal conductivity so that when heated from the outside when the mixed sample is melted, the temperature can be quickly raised to a predetermined temperature. As a constituent material of the filling chamber, a metal material is preferable, and stainless steel having excellent corrosion resistance is particularly preferable. The filling chamber is usually provided with an openable / detachable lid so that the mixed sample can be easily introduced. An air inlet is formed in the lid, and the bottom surface of the filling chamber is constituted by a filter.

(filter)
The filter filters the solute material dissolved in the solvent in the mixed sample. What is necessary is just to select the kind of this filter suitably according to the kind and size of the insoluble material which are filtered. For example, examples of the filter include a thread wound filter, a nonwoven fabric / fiber laminated filter, and a nonwoven fabric pleated filter. The aperture (pore diameter) of the filter may be appropriately selected according to the size of the insoluble material. If the opening is large, relatively efficient filtration can be performed, and if the opening is small, an insoluble material having a small size can be separated by filtration.

(Intake port)
The intake port is an opening for introducing outside air into the filling chamber. By introducing outside air into the filling chamber from the intake port, the mixed sample is pressed and smoothly passes through the filter. Outside air can be introduced simply by having an opening through which the outside air can be introduced into the filling chamber, but by attaching a pressurizing means such as a syringe to the intake port, filtration can be performed while the inside of the filling chamber is pressurized. Also good.

(Vent)
The discharge port is an opening for discharging the filtrate to the outside of the filtration container. The outlet is provided on the filtrate discharge side of the filter. Usually, an outlet is formed below the filter. It is preferable that the filter and the outlet are formed in a funnel shape so that the filtrate is collected at the outlet after leaving the filter.

(Air intake closing means)
The intake port closing means closes the intake port described above. In order to block the introduction of outside air into the filling chamber, it is preferable that the closing means be configured so that the air inlet can be hermetically sealed. For example, a syringe can be attached to the intake port so as to pressurize the filling chamber, and an intake port closing means having the same structure as the distal end portion (connecting mechanism portion with the intake port) of the syringe is provided. preferable. With this configuration, the intake port can be reliably sealed.

(Discharge port closing means)
The outlet closing means closes the aforementioned outlet. This discharge port also preferably has a structure that can be sealed liquid-tight or air-tight so as to reliably prevent the discharge of the filtrate. The discharge port closing means preferably includes a sealing portion that seals / opens the discharge port and a drive mechanism for the sealing portion that drives the sealing portion. Furthermore, it is preferable to provide a timer means so that the discharge port can be closed by the sealing portion for a predetermined set time. The time to close the outlet is to know in advance the relationship between concentration and time that can be dissolved from the type of solute material and solvent, how long it takes after the mixed sample is introduced and the temperature is reached. It can be determined by counting the number of times.

[High temperature filtration equipment]
The high-temperature filtration device includes a heating unit that heats the mixed sample in the filtration container. In addition, a loading hole for loading a filtration container is also provided. In addition, usually, stirring means for mixing and stirring the mixed sample in the container is also provided.

(Heating means)
It is preferable that the heating means includes a heating block heated by a heater or the like. A loading hole is formed in the heating block, and a filtration container is loaded therein. If the filtrate discharged from the filtration container is received below the container, the loading hole is loaded with a sample bottle at the bottom and a filtration container at the top of the bottle. Good.

(Stirring means)
If the mixed sample is heated to a predetermined temperature in the filtration container, the solute material is dissolved in the solvent, but it is preferable to dissolve the solute material more uniformly. For this reason, it is preferable to provide a means for stirring the sample in the container. Examples of the agitation means include a mechanism for applying vibration to the heating block by utilizing rotation of a motor or the like.

  The filtration method of the present invention will be described using the filtration container of the present invention provided with an inlet closing means. First, the container of the present invention will be described based on FIG.

[Container for filtration]
The container 1 is a cylindrical container made of stainless steel, and can be divided into three parts, that is, an upper part 11, a middle part 12, and a lower part 13, a filter 20 attached to the inside of the body 10, and the container And a lid part 30 (intake port closing means) attached to the upper stage part 11. The space above the filter 20 in the container is a sample filling chamber 16.

  The upper stage portion 11 includes a cylindrical side wall 11W and an upper surface portion 11T, and an intake port 15 protruding upward is formed at the center of the upper surface portion 11T. The intake port 15 is an opening for introducing outside air into a sample filling chamber 16 formed inside the upper stage portion 11 and the middle stage portion 12. A female screw 15t is formed on the inner periphery of the opening, and is configured to be attached to the intake port 15 by screwing a lid 30 to be described later. Further, a male screw 11t is formed at the lower end of the upper step portion 11 (on the side opposite to the intake port 15), and is configured to be screwed to the middle step portion 12.

  The middle stage portion 12 is a short cylindrical member having a side wall portion 12W having the same inner and outer diameter as the side wall 11W of the upper stage portion. An inner peripheral projection 12p for supporting the filter 20 is formed on the inner surface of the middle step portion 12. The filter 20 is supported in the middle portion by being placed on the inner peripheral projection 12p. Further, female screws are respectively formed in the upper and lower openings of the middle step portion 12, and the upper female screw 12tu is screw-connected to the upper step portion 11 and the lower female screw 12tl is connected to the lower step portion 13.

  The lower step portion 13 is a cylindrical member that has an outer diameter that is the same as that of the sidewalls of the upper step portion 11 and the middle step portion 12, and that has a funnel shape that decreases as the inner diameter decreases downward. A discharge port 17 protruding downward is formed at the lower end of the funnel portion 13c. The filtrate that has passed through the filter 20 is collected by the funnel portion 13c and discharged from the discharge port 17 to the outside of the container. Further, the upper opening of the lower step portion 13 is provided with a male screw 13t that is screw-coupled with the female screw 12tl of the middle step portion.

  On the other hand, the filter 20 is a disk-like member having an outer diameter that can be placed on the inner circumferential protrusion. Although shown in a simplified manner in the figure, in practice, a frame part and a filter main body held inside the frame part are provided, and a net-like strainer for holding the filter main body is also provided.

  The lid 30 is a member configured to be detachable from the intake port 15, and a cylindrical portion 31 formed with a male screw 30t screwed to the female screw 15t of the intake port on the lower side and the upper portion of the cylindrical portion 31 are closed. And a knob portion 32. When the sample is filtered, if the lid 30 is attached to the intake port 15, the intake port 15 can be hermetically sealed.

[High temperature filtration equipment]
The above container 1 is set in the high-temperature filtration apparatus shown in FIG. The apparatus 100 includes a heating block 110, a heater 120 for the block 110, and stirring means (not shown) for applying vibration to the block 110.

  The heating block 110 includes a loading hole 111 for a filtration container. The loading hole 111 is loaded with not only the filtration container 1 but also the sample bottle 2 that receives the filtrate. That is, the sample bottle 2 is loaded in the lower stage of the loading hole 111, and the filtration container 1 is loaded on the bottle 2. In this state, the periphery of the filling chamber 16 of the filtration container is surrounded by the heating block 110. Therefore, if the heating block 110 is heated by the heater 120, the filtration container 1 is also heated by heat conduction, and the sample in the filling chamber 16 can be heated to a predetermined temperature.

  The sample in the filling chamber 16 is partially dissolved by heating at a predetermined temperature. At this time, the heating block 110 is vibrated by the stirring means so that it can be dissolved more uniformly. The stirring means is configured to convert the rotational movement of the motor as vibration to the heating block 110 and transmit it.

[Filtration method]
In order to perform filtration using the above filtration container and high-temperature filtration device, a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined temperature, and an insoluble material that does not dissolve in the solvent at the predetermined temperature is obtained in advance. The sample is prepared and placed in the filling chamber 16.

  After the sample is placed in the filling chamber 16, the inlet 15 is sealed with the lid 30. This prevents outside air from being introduced into the filling chamber 16 from the intake port 15.

  On the other hand, the heating block 110 is heated to a predetermined set temperature.

  First, the sample bottle 2 is first loaded into the loading hole 111 of the heating block heated to a predetermined temperature. Subsequently, the filtration container 1 is loaded on the sample bottle 2.

  This state is maintained until the solute material in the mixed sample is dissolved in the solvent. That is, a state in which outside air is not introduced into the filling chamber 16 from the intake port 15 is maintained. In the meantime, the sample in the filling chamber 16 is pushed by the atmospheric pressure from the discharge port 17 side, so that it does not pass through the filter 20 and fall. Therefore, the solute material can be reliably dissolved in the solvent.

  When the solute material is sufficiently dissolved in the solvent, the lid 30 is removed, and if necessary, a syringe (not shown) is attached to the intake port 15 and the mixed sample is filtered while pressurizing the filling chamber 16 .

[Test example]
The mixed sample is filtered using the filtration container and high-temperature filtration device of Example 1. A standard sample included in the mixed sample is a compounding material of a resin material and an inorganic filler. As the resin material, block-polypropylene (b-PP) in which polyethylene and rubber were added to isotactic-polypropylene was used. Magnesium hydroxide was used as the inorganic filler. The compounding amount of the inorganic filler in the compounding material is 50% by mass. Magnesium hydroxide is manufactured by Kyowa Chemical Industry Co., Ltd., Kisuma 5, and has an average particle size of 0.8 μm. This standard sample was subjected to a high-temperature filtration device after freeze-grinding. The freeze pulverization was performed by using JFC-300 (Nippon Analytical Industrial Co., Ltd.) and pre-cooling about 1 g of the sample in liquid nitrogen for 10 minutes and then pulverizing for 12 minutes.

  SSC-9300 manufactured by Senshu Scientific Co., Ltd. was used as the high-temperature filtration device. However, the filtration using this apparatus is performed when the filtration container is replaced with the one having the lid portion shown in FIG. 1 and the filling chamber is filtered without pressurizing, and the syringe is not replaced. In both cases, filtration was carried out while pressurizing the filling chamber. The filter was a polytetrafluoroethylene membrane filter. A standard sample and a solvent are placed in this filtration container and heated to a predetermined temperature. At that temperature, b-PP is dissolved in the solvent and filtered through a filter to separate b-PP and magnesium hydroxide. The heatable temperature range is room temperature + 10 ° C to 350 ° C, and the temperature control accuracy is ± 0.5 ° C. The capacity of the filtration container is 5 ml, and eight of these containers can be set simultaneously in the high-temperature filtration device.

  First, as a preliminary test for comparison, filtration was performed while pressurizing the filling chamber with a syringe as before, and the kind of solvent, the amount of sample, and the filter pore diameter were examined. Ortho-dichlorobenzene (o-DCB) and xylene were selected as the solvent. The dissolution and filtration temperature was set to 175 ° C. for o-DCB (boiling point: about 182 ° C.) and 130 ° C. for xylene (boiling point: about 144 ° C.). Moreover, four types of filter pore diameters having an average pore diameter of 0.5, 1.0, 5.0, and 10 μm were used. The residue after filtration was pre-dried at 175 ° C. for 1 hour, and the filtrate was concentrated and dried at 175 ° C. for 1 hour and then vacuum-dried at 60 ° C. for 16 hours. The amount was determined. The recovery rate ((Wf / Wo) × 100) was determined from the b-PP amount (Wo) blended in preparing the standard sample and the b-PP amount (Wf) recovered from the filtrate.

  FIG. 3 shows the relationship between the amount of b-PP mixed in the standard sample and the recovery rate for o-DCB and xylene. This graph shows the case of filtering with a filter having an average pore diameter of 0.5 μm. When the amount of b-PP was 90 mg or less, the b-PP recovery rate after dissolution for 30 minutes was 98% or more with o-DCB, whereas with xylene, the b-PP amount was 92% even with 10 mg. As the amount of PP increased, the recovery rate decreased to about 75% (see ○). On the other hand, when the amount of b-PP is 120 mg, even if o-DCB is used as the solvent, the recovery rate after one filtration (see ◇) is about 70%, and dissolution and filtration are repeated twice (see ◆). As a result, it was confirmed that the recovery rate could be improved to 95% or more. This is presumably because the solubility of b-PP in the solvent and the solvent temperature affected the recovery rate. Therefore, in order to separate b-PP and magnesium hydroxide at a recovery rate of 95% or more in a single filtration, the solvent is o-DCB, the temperature is 175 ° C, and the amount of b-PP per filtration container is 90 mg or less was judged appropriate.

  Next, the relationship between the filter pore diameter and the recovery rate of b-PP was examined with the solvent: o-DCB, temperature: 175 ° C., and b-PP amount per filtration container: 90 mg or less. The result is shown in FIG. Normally, in filtration, as the filter pore size increases, components that are insoluble in the solvent pass through the filter and are recovered along with the filtrate, and the recovery rate of b-PP is expected to exceed 100%. The However, the recovery rate of b-PP was 98% or more when the filter pore size was 1 μm or less, but the recovery rate was found to decrease to 59% at 5 μm and 10 μm (see ◇ in FIG. 4).

  As a result of investigating the cause, it was confirmed that when the filter pore size was 5 μm and 10 μm, the solvent gradually permeated through the filter during sample dissolution, and the solvent disappeared from the filling chamber before completely dissolving b-PP. Further, the disappearance of the solvent was judged to be because the filling chamber was in a pressurized state during filtration, and the speed at which the solvent permeated the filter was accelerated.

  Therefore, in this test, the filtration container shown in FIG. 1 was used, and the inlet was sealed with a lid so that the inside of the filling chamber was not pressurized during sample dissolution, and b-PP was dissolved. Also in this test, the solvent is o-DCB, the dissolution / filtration temperature is 175 ° C, and the amount of b-PP per filtration container is 90 mg or less. Further, after dissolution of b-PP (30 minutes after the start of heating), the lid was removed, and a syringe was attached instead, and the inside of the filling chamber was pressurized and filtered. As a result, it was found that b-PP and magnesium hydroxide can be separated in a high yield of 98% with a single filtration even with filter pore sizes of 5 μm and 10 μm (see ◆ in FIG. 4). Furthermore, this same test was repeated 5 times, and the relative standard deviation (RSD) of b-PP recovery rate in all tests was determined to be 2% or less and within the targeted 5%. Was confirmed.

  From these results, if b-PP is dissolved in o-DCB and the air inlet is sealed and filtered, only o-DCB is in b-PP even if the filter pore size is large. It was found that b-PP and magnesium hydroxide can be separated with a high recovery rate without passing through the filter before dissolution.

Furthermore, the inlet is sealed between the ¹ H-NMR spectrum of the mixed sample (b-PP, magnesium hydroxide, o-DCB) before hot filtration and until b-PP is dissolved in o-DCB. The ¹ H-NMR spectrum of the filtrate after filtration was examined. The measurement conditions of this spectrum are as follows: Device: A400 type FT-NMR manufactured by JEOL Ltd., observation nucleus: ¹ H (resonance frequency 399.65 MHz), solvent: o-DCB, internal standard: tetramethylsilane (TMS), temperature: 175 ° C., concentration (concentration of sample (b-PP + magnesium hydroxide) with respect to solvent): 10% by mass. FIG. 5 shows the spectrum of b-PP before hot filtration, and FIG. 6 shows the spectrum of b-PP after hot filtration.

  It can be seen that the spectrum before high-temperature filtration has a wide peak line width, so that adjacent peaks overlap with each other, and it is difficult to obtain each peak area value. In this case, the resolution using the half width of the TMS peak was 18 Hz.

In contrast, the spectrum after high-temperature filtration was improved in resolution, and it was confirmed that adjacent peaks can be separated even in a ¹ H-NMR spectrum with a small chemical shift. In this case, the resolution employing the half width of the TMS peak was 0.5 Hz. This is presumably because the broadening and distortion of the line width caused when magnesium hydroxide that does not dissolve in o-DCB floats in the solution and the magnetic field strength becomes non-uniform can be eliminated. From the above, it was confirmed that separation of b-PP and magnesium hydroxide improved the resolution of the NMR spectrum, and in particular, adjacent peaks could be separated even in a ¹ H-NMR spectrum with a small chemical shift.

  Next, the filtration container of the present invention provided with the discharge port closing means will be described with reference to FIG.

  The container of this example is different from the container of FIG. 1 in that the container 1 has a structure for closing the discharge port 17 instead of a structure for closing the intake port 15. In other words, the container 1 includes the upper step portion 11, the middle step portion 12, and the lower step portion 13 as in the first embodiment. A shielding plate 40 serving as a discharge port closing means is provided below the discharge port 17 provided in the lower stage portion 13.

  The shielding plate 40 is configured to be slidable in the horizontal direction, and closes / opens the discharge port 17. The shielding plate 40 is connected to a drive mechanism (not shown), and controls the drive mechanism to open and close the discharge port. For example, if the types and amounts of the solute material and the solvent are specified, the relationship between how much time the solute material will melt at a predetermined temperature is examined in advance, and the shielding plate 40 determines from the correlation. What is necessary is just to set the time which closes the discharge port 17. FIG. The drive mechanism may be controlled so that the shielding plate 17 slides in accordance with the set time. Since the other configurations of the container 1 are the same as those in the first embodiment, the description thereof is omitted.

  The container of Example 2 is also applied to the high temperature filtration apparatus shown in FIG. That is, the container 1 is accommodated in the filling hole of the heating block, and the outlet 17 (FIG. 2) is sealed with the shielding plate 40 (FIG. 7) until the solute material in the container is dissolved in the solvent. After dissolving in the solvent, the shielding plate 40 is retracted to open the discharge port 17. Thereafter, if necessary, a syringe is attached to the intake port, and the inside of the filling chamber 16 is pressurized to perform filtration.

  In the second embodiment, a funnel portion is provided directly below the filter, a discharge port is provided below the funnel portion, and a discharge port closing means is further provided below the discharge port. If the outlet is closed, the filtrate is not discharged from the outlet, but the mixed sample is filtered to some extent by the filter, and the filtrate may accumulate in the funnel. Therefore, it is preferable to provide the outlet closing means directly below the filter, that is, above the funnel. For example, a slit communicating with the inside and outside of the container is provided below the filter on the side wall of the middle stage, and a movable plate that can be inserted into and pulled out from the slit is provided as the closing means. In that case, while the lower surface of the filter is closed by the closing means, the mixed sample does not pass through the filter, and as a result, the filtrate can be prevented from being discharged from the discharge port.

In addition, the above Example 1 and Example 2 are only illustrations, and the range of this invention is not necessarily limited to the Example mentioned above. In addition to the above embodiments, various modifications may be made within the scope of the present invention. For example, the following combinations of “solute material / insoluble material / solvent” that can be used in the method of the present invention are considered.
(1) Ethylene-vinyl acetate copolymer / polypropylene / chloroform
(2) Ethylene-vinyl acetate copolymer / polyethylene / chloroform
(3) Ethylene-vinyl acetate copolymer / polyethylene terephthalate / chloroform
(4) Ethylene-vinyl acetate copolymer / polybutylene terephthalate / chloroform
(5) Ethylene-vinyl acetate copolymer / polyphenylene sulfide / chloroform
(6) Ethylene-vinyl acetate copolymer / inorganic filler (magnesium silicate, aluminum hydroxide, carbon black, etc.) / Chloroform
(7) Acrylic resin (ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc.) / Polypropylene / chloroform
(8) Acrylic resin (ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc.) / Polyethylene / chloroform
(9) Acrylic resin (ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc.) / Polyethylene terephthalate / chloroform
(10) Acrylic resin (ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc.) / Polybutylene terephthalate / chloroform
(11) Acrylic resin (ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc.) / Polyphenylene sulfide / chloroform
(12) Acrylic resin (ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc.) / Inorganic filler (magnesium silicate, aluminum hydroxide, carbon black, etc.) / Chloroform
(13) Polyphenylene sulfide / inorganic filler (magnesium silicate, aluminum hydroxide, carbon black, etc.) / 1-chloronaphthalene

  The method, container and apparatus of the present invention can be suitably used for separating a solute material and an insoluble material when component analysis of a wire coating material or the like is performed.

The container for filtration of this invention of Example 1 is shown, (A) is sectional drawing of the cover part of a container, (B) is sectional drawing which shows the container of the state which mounted | wore the cover part. It is sectional drawing which shows an example of this invention high temperature filtration apparatus. It is a graph which shows the relationship between the mixing amount and recovery rate of b-PP in a standard sample at the time of filtering with the filter of average pore diameter of 0.5 micrometer. It is a graph which shows the relationship between the average hole diameter of a filter, and the recovery rate of b-PP. It is a graph showing ¹ H-NMR spectrum of the filtered hot prior to b-PP. It is a graph showing ¹ H-NMR spectrum of b-PP after the high-temperature filtration. 6 is a cross-sectional view of the inventive filtration container of Example 2. FIG.

Explanation of symbols

1 container 10 container body
11 Upper step 11W Side wall 11T Top surface 11t Male thread 15t Female thread
12 Middle section 12W Side wall 12p Inner protrusion 12tu, 12tl Female thread
13 Lower part 13c Funnel part
15 Inlet 16 Filling chamber 17 Outlet
20 Filter
30 Lid 30t Male thread 31 Cylindrical part 32 Knob part
40 Shield plate
2 Sample bottle
100 high temperature filtration equipment
110 Heating block 111 Loading hole 120 Heater for heating

Claims (5)

Preparing a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature;
A sample loading step of placing the mixed sample in a filtration container equipped with a filter;
A dissolution step of heating the mixed sample in the container to the heating temperature to dissolve the solute material in a solvent;
Filtering the mixed sample in which the solute material is dissolved with a filter, and separating the insoluble material and the solute material,
The high-temperature filtration method is characterized in that the dissolution step is performed so that the solvent is not discharged out of the container at least until the solute material is dissolved in the solvent. A filtration container for separating a non-soluble material and a solute material by filtering a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature Because
An intake port for taking outside air into the container;
A filter for filtering the sample;
An outlet for the filtrate that has passed through the filter;
An air inlet closing means for closing the air inlet until at least the solute material is dissolved in the solvent. A filtration container for separating a non-soluble material and a solute material by filtering a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature Because
An intake port for taking outside air into the container;
A filter for filtering the sample;
An outlet for the filtrate that has passed through the filter;
A filtration container comprising: a discharge port closing means for closing the discharge port until at least the solute material is dissolved in the solvent. A filtration container for separating a non-soluble material and a solute material by filtering a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature And a high temperature filtration device comprising heating means for raising the temperature of the mixed sample in the container to the heating temperature,
The container is
An intake port for taking outside air into the container;
A filter for filtering the sample;
An outlet for the filtrate that has passed through the filter;
An air inlet closing means for closing the air inlet until at least the solute material is dissolved in the solvent. A filtration container for separating a non-soluble material and a solute material by filtering a mixed sample of a solvent, a solute material that dissolves in the solvent at a predetermined heating temperature, and an insoluble material that does not dissolve in the solvent at the heating temperature And a high temperature filtration device comprising heating means for raising the temperature of the mixed sample in the container to the heating temperature,
The container is
An intake port for taking outside air into the container;
A filter for filtering the sample;
An outlet for the filtrate that has passed through the filter;
A high-temperature filtration device comprising: an outlet closing means for closing the outlet until at least the solute material is dissolved in the solvent.

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