WO2020085282A1 - Procédé de production d'une résine phénolique - Google Patents

Procédé de production d'une résine phénolique Download PDF

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Publication number
WO2020085282A1
WO2020085282A1 PCT/JP2019/041266 JP2019041266W WO2020085282A1 WO 2020085282 A1 WO2020085282 A1 WO 2020085282A1 JP 2019041266 W JP2019041266 W JP 2019041266W WO 2020085282 A1 WO2020085282 A1 WO 2020085282A1
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activated carbon
resin
nylon
carbon adsorbent
phenol
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PCT/JP2019/041266
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English (en)
Japanese (ja)
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亮介 浅原
秀治 西垣
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フタムラ化学株式会社
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Priority claimed from JP2019191035A external-priority patent/JP7228498B2/ja
Application filed by フタムラ化学株式会社 filed Critical フタムラ化学株式会社
Priority to KR1020217011989A priority Critical patent/KR20210080389A/ko
Priority to CN201980070219.XA priority patent/CN112867761B/zh
Publication of WO2020085282A1 publication Critical patent/WO2020085282A1/fr
Priority to PH12021550649A priority patent/PH12021550649A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a method for producing a phenolic resin, and in particular, by improving the composition of the phenolic resin for producing an activated carbon adsorbent, carbonizing the phenolic resin to improve the performance of the activated carbon adsorbent obtained by activation. And a method for producing a phenol resin capable of
  • activated carbon is highly hydrophobic and is not suitable for adsorbing low molecular weight ionic organic compounds such as indoxyl sulfate, DL- ⁇ -aminoisobutyric acid and tryptophan, which are represented by uremic causative substances and their precursors. The problem is included.
  • an anti-nephrotic agent composed of activated carbon obtained by forming a spherical resin compound by using wood, petroleum-based or coal-based pitches etc. as a raw material Syndrome agents have been reported (see, for example, Patent Document 3).
  • the above-mentioned activated carbon is prepared by carbonizing and activating the petroleum hydrocarbon (pitch) or the like as a raw material to have a relatively uniform particle size.
  • an adsorbent for oral administration has been reported in which the particle size of activated carbon itself is made relatively uniform and the distribution of pore volume and the like in the activated carbon is attempted to be adjusted (see Patent Document 4).
  • the medicinal activated carbon has a relatively uniform particle size, which improves the fluidity in the intestine, and at the same time, the pores are adjusted to improve the adsorption performance of the activated carbon. Therefore, it is taken in many patients with mild chronic renal failure.
  • Medicinal activated carbon is required to adsorb substances that cause uremia and its precursors quickly and efficiently.
  • the adjustment of the pores in the conventional medicinal activated carbon was not said to be good, and the adsorption performance was not stable. Therefore, the daily dose should be increased.
  • chronic renal failure patients have limited water intake, swallowing with a small amount of water has been a great pain for patients.
  • the gastrointestinal tract such as the stomach and small intestine, it is an environment in which various substances such as sugars, proteins and other compounds essential for physiological functions and enzymes secreted from the intestinal wall are mixed.
  • a medicinal activated carbon adsorbent that rapidly adsorbs a toxic substance causing uremia and the like, particularly a nitrogen-containing compound, and excretes it out of the body with feces as it is has been desired.
  • the inventor scrutinized the raw material of activated carbon adsorbent before carbonization and the development of pores.
  • a phenol resin as a resin component that is a raw material of activated carbon and devising the composition of the resin, the pores of the activated carbon derived from resin carbide are suitably controlled, and the nitrogen-containing compound of low molecular weight can be quickly and We have found an activated carbon with a pore distribution suitable for efficient adsorption.
  • the present invention has been made in view of the above points, in the phenol resin used for the production of the activated carbon adsorbent, by improving the composition of the phenol resin, to increase the proportion of macropores in the pores generated in the resin carbide.
  • a method for producing a phenol resin for producing an activated carbon adsorbent capable of quickly and efficiently adsorbing a nitrogen-containing low molecular weight compound is provided.
  • the first invention is a phenolic resin for activated carbon adsorbent production which is activated by carbonization to be an activated carbon adsorbent, and water-soluble nylon is added to phenol and melted to prepare a raw material.
  • a phenol resin characterized by comprising a raw material preparing step and a resole adjusting step of preparing a nylon-containing resole resin containing nylon by heating while mixing formaldehyde, a basic catalyst and an emulsifier in the raw material. It relates to the manufacturing method.
  • a second invention is a phenolic resin for producing an activated carbon adsorbent which is carbonized and activated to be an activated carbon adsorbent, wherein a raw material preparation step of adding nylon to phenol and melting it to prepare a raw material, Formaldehyde and a basic catalyst are added to a novolak resin synthesizing step of preparing a novolak resin component by heating formaldehyde, an acidic catalyst and an emulsifier while mixing the raw material, and formaldehyde and a basic catalyst in the solution obtained by the novolak resin synthesizing step. And a composite phenol resin adjusting step of adjusting the nylon-containing composite phenol resin also containing the novolak resin component by heating while mixing to synthesize a resol resin component, and a method for producing a phenol resin.
  • a third invention relates to the method for producing a phenol resin according to the first or second invention, wherein the amount of the nylon added is 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol.
  • a fourth invention is an activated carbon adsorbent obtained from the nylon-containing resole resin of the first invention, which has a mercury pore volume (V1 M ) (g / mL) at 50 to 1000 nm represented by the following formula (i). ) mercury pore volume in the 7.5 ⁇ 1000nm (V2 M) ( g / mL) and the ratio of (R V) is, according to the activated carbon adsorbent, characterized in that 0.3 to 0.6.
  • a fifth invention is a second activated carbon adsorbent obtained from the nylon-containing composite phenolic resin of the present invention, mercury pore volume (V1 M) in 50 ⁇ 1000 nm represented by the above formula (i) (g / (mL) and the mercury pore volume (V 2 M ) (g / mL) at 7.5 to 1000 nm (R V ) is 0.3 to 0.8. .
  • a sixth invention is the oral method according to any one of the first to fifth inventions, wherein the activated carbon adsorbent is a therapeutic or prophylactic agent for orally administered renal disease or orally administered liver disease. It concerns adsorbents for administration.
  • a phenol resin for producing an activated carbon adsorbent which is activated by carbonization to be an activated carbon adsorbent, wherein water-soluble nylon is applied to phenol and melted.
  • a raw material preparing step of preparing a raw material and a resol adjusting step of preparing a nylon-containing resole resin containing nylon by heating while mixing the raw material with formaldehyde, a basic catalyst, and an emulsifier.
  • the ratio of macropores in the pores generated in resin carbide can be increased by improving the resin composition in phenolic resin, and nitrogen-containing low molecular weight compounds can be quickly and efficiently prepared.
  • a phenolic resin for producing an adsorbable activated carbon adsorbent can be obtained.
  • a phenol resin for producing an activated carbon adsorbent which is activated by carbonization to be an activated carbon adsorbent.
  • a novolak resin synthesis step of preparing a novolak resin component by heating formaldehyde to the raw material, while mixing an acidic catalyst and an emulsifier in the solution obtained by the novolak resin synthesis step, Formaldehyde and a basic catalyst are mixed and heated to synthesize a resole resin component and to have a composite phenol resin adjustment step of adjusting a nylon-containing composite phenol resin that also contains the novolac resin component.
  • the carbonization of the resin is improved by improving the resin composition in the phenol resin. It is possible to increase the ratio of macropores in the pores occurring, nitrogen can be obtained phenolic resin to produce a rapidly adsorbable activated carbon adsorbent low molecular compound containing.
  • the amount of the nylon added is 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol.
  • the resin is used as the activated carbon adsorbent, it is possible to prevent a decrease in packing density while increasing the ratio of macropores in the pores generated in the resin carbide.
  • the activated carbon adsorbent obtained from the nylon-containing resole resin according to the first aspect of the invention has a mercury pore volume (50 to 1000 nm in formula (i)) V1 M) (g / mL) and the proportion of the mercury pore volume in the 7.5 ⁇ 1000nm (V2 M) ( g / mL) (R V) is from 0.3 to 0.6 nitrogen It is possible to make an activated carbon adsorbent capable of rapidly adsorbing a low molecular weight compound containing a.
  • the activated carbon adsorbent obtained from the nylon-containing composite phenolic resin according to the second aspect has a mercury pore volume at 50 to 1000 nm represented by the formula (i). Since the ratio (R V ) of (V1 M ) (g / mL) and mercury pore volume (V2 M ) (g / mL) at 7.5 to 1000 nm is 0.3 to 0.8, A low-molecular compound containing nitrogen can be used as an activated carbon adsorbent capable of rapidly adsorbing.
  • the adsorbent for activated carbon is a therapeutic or prophylactic agent for renal disease for oral administration or liver disease for oral administration. Therefore, it has a high effect of selectively adsorbing a causative substance of renal disease or liver disease, and is suitable as a therapeutic agent or preventive agent.
  • the phenolic resin produced by the production method of the present invention is a phenolic resin used for producing an activated carbon adsorbent, and particularly a phenolic resin containing nylon.
  • nylon By including nylon in the phenol resin, it is possible to obtain an activated carbon adsorbent capable of adsorbing nitrogen-containing low molecular weight compounds quickly and efficiently by increasing the ratio of macropores in the pores generated in resin carbide. .
  • a process for synthesizing a phenol resin, particularly a resole resin, which is a starting material for an activated carbon adsorbent will be described with reference to the process chart of FIG.
  • nylon is added to and mixed with phenol, which is the raw material for the phenolic resin, and dissolved in phenol to prepare it as the raw material (“raw material preparation process”).
  • phenol resin to be subjected to the condensation reaction a novolac resin or a resole resin can be used, and it is preferable to use the resole resin from the viewpoint of moldability, hardness, and pore preparation.
  • the resole resin has a higher packing density than the novolac resin, the use of an activated carbon adsorbent as a medicinal adsorbent reduces the dose volume and is useful because the burden on the patient can be reduced.
  • a composite phenol resin in which a novolac resin and a resole resin are compounded is adopted.
  • a composite phenol resin is useful because it improves the adsorption performance of the activated carbon adsorbent.
  • nylon is preferably water-soluble nylon.
  • the addition amount of nylon is preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol.
  • the carbonization step and the activation step if the amount is too small, the proportion of macropores in the pores generated in the resin carbide cannot be increased.
  • an aromatic compound having a hydroxyl group is also used.
  • aromatic compound having a hydroxyl group examples thereof include cresol (o-, m-, p-positions), p-phenylphenol, xylenol (2,5-, 3,5-), resorcinol and various bisphenols.
  • aldehyde compounds are used instead of the formaldehyde used in the above process.
  • examples include acetaldehyde, benzaldehyde, glyoxal, furfural and the like.
  • An amine compound is used as the basic catalyst used in the synthesis of the resole resin.
  • Amine compounds are often used in the synthesis of resole resin components and are suitable for obtaining a stable reaction.
  • hexamethylenetetramine hexamine, 1,3,5,7-tetraazaadamantane
  • triethylenetetramine N, N'-di (2-aminoethyl) ethylenediamine
  • sodium hydroxide, magnesium hydroxide, sodium carbonate, ammonia and the like can be mentioned as the basic catalyst.
  • the amount of basic catalyst added in the resol resin preparation step is 1 to 10% by weight based on the total amount charged in the step. The amount of addition depends on the type of basic catalyst.
  • the activated carbon adsorbent adsorbs causative substances such as uremia while smoothly flowing in the oral cavity, esophagus, stomach, duodenum, small intestine and large intestine, and is excreted from the anus along with feces. Then, a particle size or spherical shape with less resistance is a desirable shape for the convenience of smooth flow in various digestive tracts. In view of this point, it is desirable that the resin is a granular material or a spherical material from the stage of resin before carbonization.
  • an emulsifier is added in the resol resin preparation process.
  • the resole resin prepared in the same step becomes a granular material or a spherical material due to dispersion by the action of the emulsifier.
  • the emulsifier water-soluble polysaccharides such as hydroxyethyl cellulose and gum arabic (gum arabic) are used.
  • the amount of the emulsifier added is 0.1 to 5% by weight based on the total amount charged in the resol resin preparation step. The amount may be adjusted depending on the type of emulsifier and the reaction conditions.
  • emulsification progresses through heating and stirring during the resol resin preparation process, resulting in a granular or spherical resol (phenol) resin (phenol resin particles) in the reaction liquid. It is considered that the addition of the emulsifier increases the surface tension of the reaction liquid containing phenol and the like, and minute droplets are generated to promote spheroidization.
  • the desired size of the phenolic resin is a granular or spherical material having an average particle diameter of 200 to 700 ⁇ m. The particle size in this range is a size that allows for the volume reduction associated with the firing of carbonization described below.
  • the resulting activated carbon adsorbent has a size suitable for oral administration.
  • the nylon-containing composite phenol resin is a composite phenol resin composed of a novolak resin containing nylon and a resole resin.
  • nylon is applied to and mixed with granular phenol, which is a raw material of a phenol resin, and the nylon is dissolved in phenol to be prepared as a raw material (“raw material preparation step”). It is considered that the addition amount of nylon is preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol as in the resol resin adjusting step according to FIG.
  • nylon having water solubility was adopted, but the nylon in the raw material adjusting step for nylon-containing composite phenol resin shown in FIG. 2 was water-soluble nylon. Not limited to This is because nylon is dissolved in the generated novolac resin described later. Also in the prototype example described below, when normal (non-water-soluble) nylon was used, most of the nylon did not precipitate in the reaction medium water and the like, and the phenol resin contained nylon. .
  • the phenols, alternative aromatic compounds, and alternative aldehyde compounds for formaldehyde used are the same as those described in the resole resin preparation step according to the process chart shown in FIG.
  • An inorganic acid and an organic acid are used as the acidic catalyst.
  • Oxalic acid was used in the prototype.
  • Other examples of the acidic catalyst include carboxylic acids such as formic acid, dicarboxylic acids such as malonic acid, hydrochloric acid, sulfuric acid, phosphoric acid and the like.
  • the phenol resin (nylon-containing resole resin and nylon-containing composite phenol resin) prepared from a series of steps becomes a resin carbide through the steps shown in the process chart of FIG. 3 after appropriate washing and drying.
  • the phenol resin is stored in a firing furnace such as a cylindrical retort electric furnace, and the inside of the furnace is kept under an inert atmosphere of nitrogen, argon, helium or the like at 300 to 1000 ° C., preferably 450 to 700 ° C. for 1 to 20 hours.
  • a firing furnace such as a cylindrical retort electric furnace
  • nitrogen, argon, helium or the like at 300 to 1000 ° C., preferably 450 to 700 ° C. for 1 to 20 hours.
  • carbonization step When it is carbonized, it becomes a resin carbide (“carbonization step”).
  • the resin carbide is stored in a heating furnace such as a rotary type external heating furnace and steam activated at 750 to 1000 ° C., preferably 800 to 1000 ° C., and further 850 to 950 ° C. (“activation step”). )).
  • the activation time is 0.5 to 50 hours, depending on the production scale, equipment, etc. Alternatively, activation of gas such as carbon dioxide is also used.
  • the activated carbon adsorbent after activation is washed with dilute hydrochloric acid.
  • the activated carbon adsorbent that has been washed with dilute hydrochloric acid is washed with water until the pH reaches 5 to 7, for example, by measuring the pH according to JIS K 1474 (2014).
  • the activated carbon adsorbent After washing with dilute hydrochloric acid, the activated carbon adsorbent is heat-treated in a mixed gas of oxygen and nitrogen and washed with water, if necessary, to remove impurities such as ash. The residual hydrochloric acid and the like are removed by the heat treatment. Then, the amount of surface oxide of the activated carbon adsorbent is adjusted through each treatment. After the acid cleaning, the amount of surface oxides of the activated carbon adsorbent increases through the heat treatment of the activated resin carbide. The oxygen concentration during the treatment is 0.1 to 21% by volume. The heating temperature is 150 to 1000 ° C., preferably 400 to 800 ° C., and 15 minutes to 2 hours.
  • the resin carbide (activated carbon adsorbent) after the activation treatment or after the heat treatment subsequent to the activation treatment is preferably selected by sieving into granular or spherical activated carbon having an average particle diameter of 150 to 500 ⁇ m.
  • the adsorption rate of the activated carbon adsorbent can be made constant and the adsorption capacity can be stabilized.
  • the range of particle diameter is not particularly limited, but if it is within the above range, swallowing by the patient (administrator) can be made smooth and the surface area of the activated carbon adsorbent can be secured.
  • the particle diameters are made uniform, the adsorption performance in the digestive tract can be stabilized.
  • the shape of the activated carbon of the adsorbent for oral administration is preferably spherical.
  • granularity is also included because variations in sphericity due to manufacturing are also allowed.
  • the phenol resin (resole resin) prepared through the raw material preparation step and the resole resin preparation step in the step shown in FIG. 1 contains nylon.
  • Nylon is a thermoplastic resin and resol resin is a thermosetting resin. Therefore, when the phenol resin particles are exposed to the heating temperature in the carbonization step, the heat resistance, the melting temperature, the volatilization amount, etc. of the nylon and the resole resin in the phenol resin particles are different from each other. Then, it is considered that the carbonization of the phenol resin particles proceeds inhomogeneously rather than becoming uniform during the firing.
  • the resin component is volatilized from the phenol resin particles by heating and baking during carbonization. It is expected that cracks, cracks, etc. will occur in the resin carbide through this volatilization. Therefore, it is considered that macropores (about 50 nm or more) relatively easily develop in the activated carbon adsorbent derived from the resin carbide of the phenol resin.
  • the weight of volatile components is reduced, obviously. Therefore, the smaller the amount of volatile components, the more the amount of carbon in the activated carbon adsorbent increases, and more dense activated carbon can be obtained. Therefore, the volatile content of the nylon-containing phenol resin is suppressed to 50% or less.
  • the nylon-containing composite phenol resin prepared through the novolak resin synthesis step and the composite phenol resin preparation step is combined with the phenol resin having different traits in both the novolac resin content and the resole resin content.
  • the novolac resin is a thermoplastic resin and the resol resin is a thermosetting resin. Therefore, when the composite phenol resin particles are exposed to the heating temperature in the carbonization step, the novolac resin content, the resole resin content, and the nylon in the composite phenol resin particles differ from each other in heat resistance, melting temperature, volatilization amount, and the like.
  • the ratio of the novolac resin component (former) and the resole resin component (latter) in the composite phenol resin (composite phenol resin particles) is 9: 1 to 5: 5.
  • the proportion of macropores in the pores generated in the resin carbide can be increased. Further, by changing the ratio depending on the target substance to be adsorbed, it is possible to produce activated carbon having an arbitrary adsorption performance.
  • the weight of the volatiles is reduced in the process of carbonization from the composite phenol resin (composite phenol resin particles) to a resin carbide, and further activation to the activated carbon adsorbent. Therefore, the smaller the amount of volatile components, the more the amount of carbon in the activated carbon adsorbent increases, and more dense activated carbon can be obtained. Therefore, the volatile content of the composite phenol resin (composite phenol resin particles) is suppressed to 60% or less.
  • the nylon-containing resole resin and nylon-containing composite phenol resin have an aromatic ring structure in the molecule, so the carbonization rate increases. Furthermore, activation produces an activated carbon adsorbent having a large surface area.
  • the activated carbon adsorbent after activation has a small pore size and a high packing density as compared with conventional activated carbon such as wood, coconut shell, and petroleum pitch. Therefore, it is suitable for adsorbing an ionic organic compound having a relatively small molecular weight (molecular weight in the range of several tens to several hundreds).
  • both phenolic resins containing nylon have less ash content such as nitrogen, phosphorus, sodium, magnesium and the like, and a higher carbon ratio per unit mass than conventional activated carbon raw materials such as wood. Therefore, an activated carbon adsorbent containing few impurities can be obtained.
  • the adsorption target can easily penetrate into the activated carbon adsorbent. Then, the adsorption target is captured by the mesopores and the micropores connected to the macropores, and the adsorption proceeds rapidly.
  • the time taken for food to be decomposed by digestion and flow in the small intestine is considered to be about 3 to 5 hours. That is, it is necessary for the adsorbent for oral administration (activated carbon adsorbent) to adsorb the nitrogen-containing low molecule that is the target of adsorption while flowing in the small intestine. Therefore, in consideration of efficient adsorption in the intestinal tract, it can be said that adsorption in a short time is desirable. From this, it is meaningful to develop many macropores of the activated carbon adsorbent.
  • the activated carbon adsorbent obtained from the above-mentioned production method should adsorb the causative agent of liver dysfunction and renal dysfunction listed in the prototypes described below as quickly as possible, and have sufficient adsorption performance with a relatively small dose. It is required to demonstrate.
  • the activated carbon adsorbent is defined by the index of the volume ratio of the mercury pore volume value. Then, as is clear from the tendency of the prototype example described below, the suitable range value of each index is derived. The method of measuring the physical properties and the like of the activated carbon and various conditions described below will be described in detail in a prototype example.
  • the activated carbon adsorbent is a granular or spherical substance, and its average particle size is not particularly specified, but it is preferably 150 to 400 ⁇ m.
  • the size of the particles themselves is within the above range, pores such as macropores are appropriately developed, which is preferable in terms of selective adsorption. Further, since the surface area becomes appropriate, it is also preferable in terms of adsorption rate and strength.
  • the average particle size of the activated carbon adsorbents in the present specification and prototype examples is the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.
  • Mercury pore volume (V M) is an index for evaluating the large pores of mesopores or macropores of the activated carbon. Therefore, we determined the so-called mesopores ⁇ macropores ranging mercury pore volume of a pore diameter range of 7.5 - 1000 nm and (V2 M). Further, it is considered that the range of the pore diameter of 50 to 1000 nm is the effective pore size when adsorbing the adsorption target, and therefore the mercury pore volume (V1 M ) in this range, so-called macropore range was also calculated.
  • volume ratio (R V) the volume ratio in the activated carbon adsorbent consisting of nylon-containing resole resin represented by to equation (i) (R V) is defined to 0.3 to 0.6.
  • the volume ratio (R V ) of the formula (i) is such that the nitrogen pore volume (V1 M ) in the pore diameter range of 50 to 1000 nm (macropore) is equivalent to the nitrogen pore volume range of 7.5 to 1000 nm (mesopore). Is the quotient divided by the mercury pore volume (V2 M ) of macropores.
  • the volume ratio (R V ) is specified to be 0.3 to 0.8.
  • the volume ratio (R V ) is an index showing that the ratio of macropores is high in the range of mesopores to macropores.
  • an adsorbent such as activated carbon
  • micropores, mesopores, and macropores are all present.
  • the adsorption target and performance of the activated carbon adsorbent change depending on which range of pores is developed more.
  • the activated carbon adsorbent desired in the present invention is assumed to adsorb nitrogen-containing low molecular weight ionic organic compounds such as indoxyl sulfate, aminoisobutyric acid and tryptophan, which are represented by uremia-causing substances and precursors thereof.
  • the activated carbon adsorbent of the present invention is to adsorb the molecule to be adsorbed faster than the conventional activated carbon adsorbent.
  • the adsorbent for oral administration contains nitrogen, which is the target of adsorption, in a short time. It is necessary to adsorb small molecules that do. From this, it is meaningful to develop many macropores of the activated carbon adsorbent. As disclosed in a prototype example described below, the adsorption rate increases as the numerical value of the volume ratio (R V ) increases.
  • the packing density of activated carbon should be 0.3 to 0.6 g / mL. If the packing density is less than 0.3 g / mL, the dose increases and it becomes difficult to swallow upon oral administration. If the packing density exceeds 0.6 g / mL, there is a risk that selective adsorption as activated carbon derived from phenol resin may not be accompanied. Therefore, the packing density is preferably in the above range.
  • Such an activated carbon adsorbent is a drug intended for oral administration and is a therapeutic or prophylactic agent for renal disease or liver disease.
  • the causative substances of diseases and chronic symptoms are adsorbed and retained in the pores developed on the surface of the activated carbon adsorbent and discharged to the outside of the body, whereby the deterioration of symptoms is relieved and the pathological condition is improved.
  • the in-vivo concentration of the causative substance of a disease or chronic symptom can be lowered by taking an activated carbon adsorbent in advance. Therefore, it may be taken as a preventive measure to prevent the deterioration of symptoms.
  • renal diseases include chronic renal failure, acute renal failure, chronic pyelonephritis, acute pyelonephritis, chronic nephritis, acute nephritis syndrome, acute progressive nephritis syndrome, chronic nephritis syndrome, nephrotic syndrome, nephrosclerosis, interstitial nephritis.
  • Renal tubular disease lipoid nephrosis, diabetic nephropathy, renovascular hypertension, hypertension syndrome, secondary renal diseases associated with the above-mentioned underlying diseases, and mild renal failure before dialysis.
  • liver diseases include fulminant hepatitis, chronic hepatitis, viral hepatitis, alcoholic hepatitis, liver fibrosis, liver cirrhosis, liver cancer, autoimmune hepatitis, drug allergic liver injury, primary biliary cirrhosis, and tremor (shinshin). ), Encephalopathy, metabolic disorders, and functional disorders.
  • an activated carbon adsorbent as an adsorbent for oral administration, because it is affected by age, sex, physique, or medical condition. However, in general, when it is intended for humans, it is expected that 1 to 20 g of the activated carbon adsorbent will be taken 2 to 4 times a day.
  • the adsorbent for oral administration of the activated carbon adsorbent is administered in the form or dosage form of powder, granules, tablets, dragees, capsules, suspensions, sticks, sachets, emulsions or the like.
  • N6 Six types of nylon were used. ⁇ Toray Industries, Inc. AQ nylon "A-90” (water-soluble nylon) (Hereinafter, referred to as N1.) ⁇ Toray Industries, Inc. AQ nylon “P-70” (water-soluble nylon) (Hereinafter, referred to as N2.) ⁇ Ube Industries, Ltd. 6-nylon “1011FB” (Hereafter referred to as N3.) ⁇ Ube Industries, Ltd. 6-nylon “1022B” (Hereinafter referred to as N4.) ⁇ 6-Nylon “1030B” manufactured by Ube Industries, Ltd. (Hereinafter referred to as N5.) ⁇ Ube Industries, Ltd. polyamide elastomer "9040X1" (Hereinafter referred to as N6.)
  • formalin formaldehyde
  • 1.6 parts by weight of gum arabic as an emulsifier 21.6 parts by weight of triethylenetetramine as a basic catalyst
  • 166 parts by weight of water were charged into a separable
  • the amount of raw material is defined by the equivalence ratio (molar conversion amount).
  • the relationship of the equivalent ratio (R1 1 ) between the equivalent of phenol (P1 R ) and the equivalent of formaldehyde (F1 R ) during the synthesis of the resole resin component was 1.3, which was derived from the formula (ii).
  • the equivalent ratio (R1 1 ) is in the range of 1.1 to 1.8, and more preferably in the range of 1.1 to 1.6, the ratio between the amount of resole resin and the amount of novolac resin becomes preferable.
  • the range of the equivalent ratio (R1 1 ) is a range in which suitable emulsion formation and the like are taken into consideration.
  • the equivalence ratio (R1 1 ) of prototype 1 was 1.3.
  • a nylon-containing resol resin of Prototype Example 3 was prepared in the same manner as in Prototype Example 2 except that the amount of nylon (N2) was 1.35 parts by weight.
  • the equivalence ratio (R1 1 ) of Prototype Example 3 was 1.3.
  • a nylon-containing resole resin of Prototype Example 4 was prepared in the same manner as in Prototype Example 2 except that the amount of nylon (N2) was 8.1 parts by weight.
  • the equivalence ratio (R1 1 ) of Prototype Example 4 was 1.3.
  • the raw material amount is also defined by the equivalence ratio (molar conversion amount) because of promotion of synthesis of the novolac resin component and reduction of unreacted substances.
  • the relationship of the equivalent ratio (R2 1 ) between the equivalent of phenol (P2 N ) and the equivalent of formaldehyde (F2 N ) at the time of synthesis of the novolac resin component was derived from the formula (iii) and was 0.9 in the prototype example 6. Met.
  • Equivalent ratio (R2 1) is conveniently in the synthesis of the novolak resin content be in the range of 0.9 to 0.5.
  • the equivalent ratio (R2 1 ) range is also a range in which suitable emulsion formation and the like are taken into consideration as in the equivalent ratio (R1 1 ).
  • the table below shows the types of phenolic resin, equivalent ratio (R1 1 ), equivalent ratio (R2 1 ), nylon type, and nylon content (%) in the nylon-containing resole resin and nylon-containing composite phenolic resin of each prototype and comparative example. 1 and Table 2.
  • the nylon content represents the ratio of nylon amount to phenol resin amount.
  • the pH was measured by the method described in JIS K 1474 (2014), and the adsorbent was washed with water until the pH was roughly 5 to 7.
  • the activated carbon adsorbent after washing with water was heated in a nitrogen atmosphere in a nitrogen atmosphere at 600 ° C. for 1 hour to obtain an activated carbon adsorbent corresponding to the prototype.
  • the yield (%) was obtained by measuring the weight of the resin stage before carbonization and the weight of the activated carbon adsorbent finally collected after carbonization, activation, washing and sieving to determine the amount of reduction. Then, the ratio from the initial resin weight was used.
  • V M Mercury pore volume
  • Mercury pore volume of the activated carbon adsorbent of each prototype example and comparative examples (V M) is manufactured by Shimadzu Corporation, using Autopore 9500, contact angle 130 °, surface tension 484 dynes /cm(4.84mN/m set), pore volume value by mercury porosimetry pore diameter 7.5 ⁇ 1000nm (V2 M) ( mL / g) and pore diameter 50 to pore volume value by mercury porosimetry of 1000 nm (V1 M ) (ML / g).
  • the volume ratio (R V ) is, as shown in the above formula (i), the nitrogen pore volume (V1 M ) in the pore diameter range of 50 to 1000 nm (macropore), and the pore diameter of 7.5 to. The quotient was divided by the mercury pore volume (V2 M ) of 1000 nm.
  • the average particle diameter ( ⁇ m) of the activated carbon adsorbents of the prototype and comparative examples was measured by using a laser light scattering particle size distribution measuring device (SALD3000S) manufactured by Shimadzu Corporation, and determined by a laser diffraction / scattering method.
  • SALD3000S laser light scattering particle size distribution measuring device manufactured by Shimadzu Corporation.
  • the particle size was defined as the particle size distribution with an integrated value of 50%.
  • Nylon containing Prototype Examples 1-4 is activated carbon adsorbent consisting resole resin
  • mercury porosimetry range comparison to mesopores ⁇ macropores in Comparative Example 1 is activated carbon adsorbent consisting resole resin volume (V2 M) Is large, and the mercury pore volume (V1 M ) in the macropore range is also large.
  • V2 M resole resin volume
  • V1 M mercury pore volume
  • the volume ratio (R V ) also increased. That is, it was confirmed that many macropores were developed and the ratio was high. From the measurement of the nitrogen pore volume ( VH ), it was also confirmed that the micropores themselves also developed a lot.
  • Nylon containing composite phenolic made of a resin activated carbon adsorbent Prototype Example 5-7 is, as compared to Comparative Example 2 is activated carbon adsorbent consisting composite phenolic resin, mercury pore volume (V1 M), (V2 M ) It was confirmed that they both increased, and it was also confirmed that the prototype example 8 was almost the same. As for the volume ratio (R V ) in all of Prototype Examples 5 to 8, it was confirmed that many macropores developed and the ratio increased. From the measurement of the nitrogen pore volume ( VH ), it was also confirmed that the micropores themselves also developed a lot.
  • the activated carbon adsorbent made of the composite phenol resin of Comparative Example 2 had a large mercury pore volume (V1 M ) and (V2 M ) and a high volume ratio (R V ). It was shown that the ratio of macropores can be further increased by incorporating nylon into the composite phenolic resin, which is a raw material for the activated carbon adsorbent, as in Examples 1 to 8.
  • macropores due to the thermal expansion (difference in expansion coefficient) of resin components, the difference in volatilization conditions, etc., which are compounded and overlapped during the carbonization and firing of the phenol resin, and the macropores are not limited to the pores on the surface of the activated carbon, It can be inferred that the cause is the formation of pores with a depth that penetrates into.
  • the path leading to the micropores that have adsorption capacity is expanded, and it is considered that the toxin can be easily introduced into the micropores, so the toxin can be adsorbed quickly.
  • each spherical activated carbon of each prototype and comparative example was added to 50 mL of a standard solution of indole acetic acid, and contact shaking was performed at a temperature of 37 ° C. for 3 hours. 0.01 g of each spherical activated carbon of each prototype and comparative example was added to 50 mL of a standard solution of indoxyl sulfuric acid, and contact shaking was performed at a temperature of 37 ° C. for 3 hours.
  • the filtrate obtained after filtration after 3 hours and 24 hours was measured for absorbance at 279 nm by an absorptiometry method using a spectrophotometer (UVmini-1240, manufactured by Shimadzu Corporation).
  • Tables 5 and 6 show the adsorption rates (%) of the above four kinds of substances as the adsorption performance experiment 1 after 3 hours and the indole as the adsorption performance experiment 2 for 3 hours for the activated carbon adsorbents of the prototypes and the comparative examples adsorption rate after (Ar 1) (%) and the adsorption ratio after 24 hours (Ar 2) (%), and the proportion of (Ar 1) adsorption rate after 3 hours divided by the (Ar 2) (As) (%)showed that.
  • the activated carbon adsorbents made of the nylon-containing resole resins of Prototype Examples 1 to 4 were equal to or less than the activated carbon adsorbents made of the resole resin of Comparative Example 1 with respect to any of the four types of nitrogen-containing compounds of the toxic substances used for the adsorption performance evaluation.
  • Exhibited high adsorption performance Regarding the ratio (As) of the adsorption rate after 3 hours obtained by dividing (Ar 1 ) by (Ar 2 ) as an index of the adsorption rate of indole, the activated carbon adsorbents of Prototype Examples 1 to 4 were compared with Comparative Example 1. Also demonstrated high performance.
  • the activated carbon adsorbents made of the nylon-containing composite phenol resins of Prototype Examples 5 to 8 exhibited higher adsorption performance than the activated carbon adsorbents made of the composite phenol resin of Comparative Example 2.
  • the adsorption rate of indole was equivalent or high. From this result, rapid and efficient adsorption proceeds even in the digestive tract after actual administration, and excretion to the outside of the body can be expected. Therefore, the activated carbon adsorbent made of the phenol resin produced according to the present invention can be an adsorbent for oral administration which is effective for the treatment and prevention of renal function, liver dysfunction and the like.
  • the activated carbon adsorbent produced from the phenolic resin by the production method of the present invention reaches the digestive organs by oral administration, and can rapidly adsorb nitrogen-containing compounds that cause uremia, renal function, liver dysfunction, etc. , As a therapeutic or preventive agent. Further, in the method for producing a phenol resin for producing an activated carbon adsorbent of the present invention, macropores in the activated carbon adsorbent can be efficiently developed, so that an activated carbon adsorbent having a high toxic substance adsorption performance and a high adsorption rate can be obtained.

Abstract

Le problème selon la présente invention est de fournir un procédé de production d'une résine phénolique, ladite résine phénolique étant destinée à être utilisée pour la formation d'un adsorbant à base de charbon actif, le rapport des macropores dans les pores formés dans un carbure de résine étant augmenté par l'amélioration de la composition de la résine phénolique de façon à former un adsorbant à base de charbon actif qui soit apte à adsorber rapidement et efficacement un composé de faible poids moléculaire contenant de l'azote. La solution selon l'invention porte sur un procédé de production d'une résine phénolique permettant de former un adsorbant à base de charbon actif, ladite résine phénolique étant destinée à être carbonisée et activée afin de former un adsorbant à base de charbon actif. Ce procédé comprend une étape de préparation de matériau de départ consistant à mélanger du phénol avec un nylon soluble dans l'eau et à les faire fondre afin de donner un matériau de départ, et une étape de préparation de résol consistant à mélanger la matière de départ avec du formaldéhyde, un catalyseur basique et un émulsifiant sous chauffage afin de donner une résine de résol contenant du nylon.
PCT/JP2019/041266 2018-10-24 2019-10-21 Procédé de production d'une résine phénolique WO2020085282A1 (fr)

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CN201980070219.XA CN112867761B (zh) 2018-10-24 2019-10-21 酚醛树脂的制造方法
PH12021550649A PH12021550649A1 (en) 2018-10-24 2021-03-22 Method for producing phenolic resin

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JPH0649161A (ja) * 1992-08-04 1994-02-22 Sumitomo Durez Co Ltd 炭素繊維強化複合材用フェノール樹脂組成物
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Publication number Priority date Publication date Assignee Title
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