JPH0663337A - Adsorbent material and sheetlike adsorbent material - Google Patents

Abstract

PURPOSE:To obtain the absorbent material and the sheetlike absorbent material which does not cause the generation of conductive dust as activated carbon, does not cause the elimination and flying of porous copolymer. CONSTITUTION:Porous copolymer is fixed on the surface of pulp or short fiber, and if nessesary, made more porously through swelling and cross-linking treatment. The material can be used as sheetlike absorbent material by wet or dry type sheet making or by making into nonwoven fabric. Thus, dropping out does not occur easily because the porous copolymer is fixed on the surface of pulp or short fiber like shish kebab. Moreover, handling property is improved by making into sheet, it becomes feasible for use in extensive absorption field.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbent obtained from a synthetic polymer and a sheet-shaped adsorbent having a high adsorption capacity comparable to that of activated carbon.

[0002]

2. Description of the Related Art Inorganic porous materials such as activated carbon and activated carbon fibers are used as adsorbents because of their high specific surface area. In particular, activated carbon fibers having a fiber form are used in many fields by being processed into a sheet-shaped material typified by paper and felt. However, it is known that activated carbon and activated carbon fibers have low strength and are powdered by vibration or the like to generate dust. In particular, since dust from activated carbon and activated carbon fiber has electrical conductivity, it may cause serious problems such as failure and malfunction when attached to electronic equipment. For this reason, inorganic porous materials such as activated carbon and activated carbon fibers cannot be conventionally used around precision instruments or in clean rooms. In addition, the amount of functional groups on the surface of activated carbon-based adsorbents is extremely small, and since it is chemically extremely stable, it was difficult to add functional groups afterwards, so even though it has a high specific surface area, it is ionic. The adsorption capacity of the substance was small. Further, in the adsorption of gas components in the gas phase, the activated carbon-based adsorbent exhibits high hygroscopicity when the relative humidity in the gas phase exceeds about 50%, and the adsorption performance of the gas components is improved because the activated carbon preferentially adsorbs water vapor. There was also a problem of significant decline.

On the other hand, a granular adsorbent made of a porous copolymer having a macroreticular structure, as represented by JP-A-61-69816, JP-A-55-18297, is known. And German patent D
In D249703, porous copolymer particles having a high specific surface area of more than 1500 m ² / g are synthesized. In addition, these porous copolymers have an advantage that the surface state can be controlled from hydrophilic to hydrophobic relatively easily by providing a surface functional group. However, since the above-mentioned porous copolymer is synthesized by the suspension polymerization method, only granular materials can be conventionally synthesized. Therefore, when the above-mentioned granular adsorbent is processed into a sheet-shaped adsorbent such as paper, felt, and non-woven fabric, the granular adsorbent comes off and its use is extremely difficult. Further, since the above-mentioned granular adsorbent has a crosslinked structure, it has the advantage of having relatively high strength and heat resistance, but it cannot be melted by heating and is insoluble in the solvent. Therefore, it has been extremely difficult to spin the above crosslinkable resin into fibers.

On the other hand, in Japanese Patent Laid-Open No. 2-84545, a linear polymer such as polystyrene is spun and then post-crosslinked to make it porous to obtain 642 m ² / g of porous resin fiber. However, its surface area is much inferior to that of the above-mentioned granular material. This shows that the granular porous resin that starts porosification from the polymerization step of the monomer is more advantageous in terms of specific surface area than the porous resin fiber that is crosslinked after the linear polymer is spun. There is. In addition, when fibers made from pure polystyrene are used as a starting material and made porous, the strength of polystyrene, which is a linear polymer, is extremely low, so sufficient agitation cannot be performed in its production, and the productivity is very low. there were. When polystyrene is reinforced with a substance such as polypropylene by composite spinning to secure practical strength, a large amount of reinforcing material equal to or more than 1/2 weight of polystyrene is required. This has caused a decrease in the relative adsorption performance of the material.

[0005]

In the conventional inorganic porous materials typified by activated carbon, the strength thereof is low and the powder is easily pulverized and the field of use thereof is limited. Further, it is not easy to add a functional group and it is a non-adsorbed substance. Is also limited. In addition, in the organic resin-based porous material, it is possible to synthesize a granular material having a relatively high specific surface area, but a fibrous material has low industrial productivity and only a low specific surface area was obtained. . Therefore, there is a need for organic resin-based adsorbents that have the form of pulp or fibers that can be easily processed into various shapes, and that have high strength and high specific surface area. Further, these adsorbents were used. A sheet of adsorbent was needed.

[0006]

According to the present invention, a copolymer having a macroreticular structure composed of monovinyl monomers and polyvinyl monomers is immobilized on the surface of pulp or short fibers. An adsorbent characterized by that.

Further, in the present invention, the adsorbent is used in an amount of 100 to 5
The sheet-shaped adsorbent is characterized by containing 0% by weight.

In the present invention, the macroreticular structure is a structure in which true pores are formed in the spaces between the microspheres, in contrast to the gel-type structure, and the microspheres have a diameter of 30 to 300Å. Have. The average pore diameter is 8 to 500Å, preferably 10 to 100Å, more preferably 15 to 50Å.

Since the adsorbent in the present invention has the advantages that it can be easily separated by filtration and the porous copolymer that serves as an adsorbing element is less likely to be scattered, it can be used as it is. is there. Furthermore, it can be used as a sheet-shaped adsorbent because it can be easily processed into a sheet by wet or dry papermaking, making it into a non-woven fabric, and the like. The sheet-shaped adsorbent has a high handling property and is characterized in that the adsorbent does not drop off, that is, the porous copolymer does not drop off. The sheet-shaped adsorbent can be used for a wide range of purposes by using it in a flat shape as it is or by processing it into various shapes such as a honeycomb shape.

The adsorbent and the sheet-shaped adsorbent can be used as filters for water purification and waste liquid treatment represented by household water purifiers to remove various organic substances and malodorous components. As an even more important application, there is little loss of powder,
It has very little water adsorption, it is easy to give functional groups chemically, it is easy to incinerate, it has a white or pale color and it has a clean appearance, and it has the catalytic activity shown by activated carbon and activated carbon fibers. It can be used as an adsorbent for various gas components in a gas phase system by utilizing the characteristics such as not having it. As a specific example of the application, it can be used as a gas adsorption mask, various filters for cleaning air in a clean room, an air conditioner, etc., and can be used for oxidation of vinyl compounds, ketone compounds represented by cyclohexanone, various alcohols, etc. It is possible to adsorb and recover a solvent gas that is easily decomposed without degrading it. In addition, activated carbon or activated carbon fiber can be used as a substitute for a wide range of gas-phase adsorption fields where conventionally used.

The pulp in the present invention is a fibrous material having a fibril structure. In the polymerization step, the surface of the pulp needs to be in a state in which it can be sufficiently adhered to the monovinyl polymer and the polyvinyl polymer, and it is important that the surface of the pulp has affinity with the monovinyl monomer and the polyvinyl monomer. Is. The pulp material is not particularly limited as long as it is a material having the above characteristics and sufficient mechanical strength, but a polyolefin resin such as polyethylene or polypropylene, an aromatic polyamide typified by Kevlar, or the like is particularly effective. However, pulp made of highly hydrophilic materials such as cellulose and polyvinyl alcohol is not suitable. As a measure of hydrophilicity, the oxygen / carbon ratio (O / C ratio) by ESCA is preferably 30 or less. O /
A material having a large C ratio is generally highly hydrophilic and not suitable for the present invention. The O / C ratio can be used at 5 or less for polyolefin-based materials and at 20 or less for aromatic polyamides, but it is difficult to use it at a value of 40 or more for polyvinyl alcohol-based materials.

The short fiber in the present invention is not particularly limited as to the material as long as it has the same characteristics as the above pulp, but the polyolefin resin such as polyethylene or polypropylene, and the aromatic represented by Kevlar. In addition to organic materials such as polyamide, hydrophobic inorganic fibers such as glass fiber and alumina fiber are also effective. Further, it is also very effective to use the above pulp and the above short fibers together, and there is an advantage that by using both of them having different forms, it is possible to process into a high density sheet or the like with few gaps.

If the fiber length of pulp and staple fibers is too short, the characteristics of the above-mentioned fiber form cannot be utilized. Therefore, it is desirable that the fiber length is 0.5 mm or more and 50 mm or less, preferably 1 mm or more and 10 mm or less, and the aspect ratio (fiber length / fiber diameter) is 3 or more. Further, in the case of processing into a sheet shape, if the fiber length is too long, the processability deteriorates. Therefore, in wet papermaking, 50 mm or less, 1 mm or more, and in dry papermaking or felting, 100 m
It is preferably m or less and 1 mm or more. The fiber length of pulp means the maximum length of pulp measured from the tip of fibrillated fiber.

In the present invention, the monovinyl monomer means
Styrene and styrene derivatives such as dialkylstyrenes such as chloromethylstyrene, methylstyrene, α-methylstyrene, ethylstyrene and dimethylstyrene are most suitable. In addition, acrylic acid ester, methacrylic acid ester and the like can be effectively used.

In the present invention, the polyvinyl monomer functions as a crosslinking agent during polymerization. Divinylbenzene (4
Commercially available divinylbenzenes containing less than 5% by weight of ethylvinylbenzene are most suitable, such as trivinylbenzene, diallyl phthalate, N, N'-methylenebisacrylamide, triallyl isocyanurate, alkylene glycol diacrylates, Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, alkylene glycol dimethacrylate, trimethylol alkant methacrylate, tetramethyl alkant methacrylate, polypropylene glycol dimethacrylate, alkylene glycol divinyl ether, polyethylene glycol, divinyl ether and the like can be effectively used.

The method of immobilizing the porous copolymer in the present invention is to polymerize with a mixture of a monovinyl monomer and a polyvinyl monomer attached to the surface of pulp or monofilament which is a base material. Therefore, the method of immobilizing on the substrate surface is the most excellent. In this case, the porous copolymer is
Since the pulp or short fibers have a shish-kebab structure, that is, the pulp or short fibers have a structure in which the porous copolymer is combed and stabbed, the degree of immobilization is high and the porous copolymer, which is an adsorption element, is extremely It has an excellent advantage that it is hard to fall off.

Further, it is possible to produce an adsorbent having a further increased surface area by immobilizing the pulp or short fibers on the surface and then swelling and post-crosslinking.
That is, after immobilizing the porous copolymer on the surface of pulp or short fibers, it is immersed in an organic solvent that swells the porous copolymer, and the post-crosslinking treatment fixes the swollen structure to increase the porosity and increase the surface area. Is a method of measuring. As the post-crosslinking treatment for fixing the swelling structure, a chloromethyl group (—CH ₂ Cl) that the porous copolymer has as a functional group is used, and a Friedel-Craft catalyst such as zinc chloride, tin chloride, or aluminum chloride is used. A method of performing post-crosslinking treatment by a nucleophilic reaction in the presence is effective. The chloromethyl group is introduced from the monomer stage by using chloromethylstyrene or the like, or after polymerization, JP-A-52-81395, JP-A-52-12.
Any method such as a method of introducing a chloromethyl group by the method shown in 1693 or a method of chlorinating a methyl group (—CH ₃ ) introduced as a functional group into the porous copolymer is effective. . Further, after performing the same swelling treatment as described above, the surface area can also be increased by carrying out a post-crosslinking treatment for fixing the swollen state by using formalin or pararumaldehyde by the method as disclosed in JP-A-2-84545. It is effective for Further, if a reaction for fixing a swelled state similar to the above, such as the use of a crosslinking agent such as sulfur or a sulfur homolog, or a reaction utilizing the functional group of the porous copolymer,
It can be used as the post-crosslinking treatment of the present invention.
The various post-crosslinking treatments are described in detail in "Crosslinking Agent Handbook" (Shinzo Yamashita, Taiseisha, 1981).

In the above-mentioned post-treatment, it is important to use pulp or short fibers having a material which is not soluble in the organic solvent used. When it is desired to use a material that is easily dissolved, it is necessary to previously perform a treatment for making the material insoluble in an organic solvent, that is, a treatment such as surface protection or crosslinking.

The specific surface area of the adsorbent in the present invention is not particularly limited, but if the specific surface area is too small, the adsorption capacity will be insufficient, so that it is preferably 300 m ² / g or more.
The average pore diameter is 8 to 500Å, preferably 10
˜100Å, more preferably 15 to 50Å. The pores of the adsorbent correspond to the pores of the immobilized porous copolymer or the porous copolymer whose porosity is increased by post-treatment. If the pore size is too small, the adsorption capacity will be reduced, and if it is too large, desorption from the adsorbent will be easy, and in this case as well, the adsorption capacity, that is, the equilibrium adsorption amount per unit weight of the adsorbent, will be reduced. Invite. The carrier fiber (pulp or short fiber) does not substantially have pores that contribute to adsorption, and the specific surface area and the average pore diameter mean the values of the carrier fiber dust.

In the present invention, when the amount of pulp or short fibers used is too small, unfixed porous copolymer is produced, which is not desirable. On the contrary, when the amount of pulp or short fibers used is too large, an adsorption effect is obtained. It is not desirable because the amount of non-existent components increases and the adsorption amount per unit weight decreases.
Proportion of the total amount of pulp and short fibers in the adsorbent, that is, [(pulp weight + short fiber weight) / total adsorbent weight] x 1
00 (%) is preferably in the range of 0.5% to 30%.

In the present invention, the polyvinyl monomer content (% by weight), which is the proportion of polyvinyl monomers in the total amount of monomers (monovinyl monomer + polyvinyl monomer), is
The following range is desirable. When the post-treatment in the range of claim 2 is performed and the proportion of the polyvinyl monomer is too high, the rate of increase in the surface area due to the post-treatment becomes small,
As a result, the surface area is relatively small, which is not desirable. Therefore, the polyvinyl monomer content is 0.1 to 50.
It is desirable to be in the range of%. When the content of the polyvinyl monomer is 0.1% or less, the porous copolymer is dissolved in the organic solvent during the swelling treatment, which is not desirable.

On the contrary, when the above-mentioned post-treatment is not carried out, it is advantageous in that the polyvinyl monomer content is relatively high in order to increase the surface area, but when it is more than necessary, the pore diameter becomes large. There is a problem that it becomes too large and deviates from the desired pore size. For this reason, it is desirable to be in the range of 30 to 85%.

In the sheet-shaped adsorbent according to claim 2 of the present invention, a copolymer having a macroreticular structure composed of a monovinyl monomer and a polyvinyl monomer is immobilized on the surface of a carrier fiber (pulp or short fiber). The sheet made of only the adsorbent according to claim 1, a sheet mixed with other fibers, and the sheet made of the adsorbent and the adhesive component. In the case of a sheet-shaped adsorbent comprising the adsorbent according to claim 1 of the present invention and another fiber or an adhesive component, the content of the adsorbent according to claim 1 of the present invention is up to 50% by weight, preferably up to 30% by weight. .
The adhesive component is polyvinyl alcohol fiber or thermoplastic resin having a low melting point, for example, fiber having hot melt property such as polyethylene, polypropylene or modified polyester, or powdered thermoplastic resin having hot melt property. A preferred embodiment of the sheet-shaped adsorbent is claim 1 of the present invention.
95-70% by weight of adsorbent and 5-30 adhesive fibers
It is a mixed sheet adhesive material with a weight percentage. As a method of forming a sheet, a wet papermaking method using water at the time of papermaking is most preferable, and a binder or a sticking agent is added as necessary to perform papermaking. Also, dry papermaking, which is a sheeting method that does not use water,
Non-woven fabric is also effective as a sheeting method.

If the basis weight or thickness of the sheet-shaped adsorbent of the present invention is too high, the proportion of the adsorbent that works effectively may decrease. Conversely, if the basis weight or thickness is too high, the strength The handling property is deteriorated due to the decrease of
For the above reasons, the basis weight is preferably 10 to 300 g / m ² and the thickness is preferably in the range of 0.1 to 2.5 mm. As a measure of strength that can be used without any problems in handling, the tensile strength is 0.1 kgf / cm.
The above is desirable.

The present invention will be described with reference to the following examples.

Example 1 A polypropylene made of polypropylene, which was previously washed with 10 times the amount of pure water and methanol and dried in a 2-liter four-necked flask equipped with a stirrer, a water-cooled reflux condenser, a thermometer, and a nitrogen inlet tube. Synthetic pulp (Dick Hercules Co., Ltd.-Palpex, fiber length 1.9 mm) 5 g, deionized water 750
g, polyvinyl alcohol as a dispersant (degree of polymerization n = 5
00, saponification degree 88 mol%) 1 g with stirring and dispersion. Further, in a state of flowing nitrogen gas, 10 g of styrene monomer (purity 97%), divinylbenzene (purity 55%, containing ethylvinylbenzene as an impurity) 90 g, and benzoyl peroxide as a polymerization initiator (purity 75%, 25% water content) 7 g of the product) and 150 g of toluene as a porosifying agent were added, and the mixture was stirred as it was for 20 minutes, and then heated in an agitated state using an oil bath so that the temperature inside the flask was 80 ° C. and kept as it was for 8 hours. After filtering, it was washed with 1000 cc of pure water and filtered again. The sample was transferred to the above-mentioned four-necked flask again, heated with 1000 cc of methanol, and refluxed at the reflux temperature of methanol for 5 hours to replace toluene as a porosifying agent with methanol. After separating the sample by filtration, 60 ℃, 10m
Methanol was removed by vacuum drying at mHg. In the obtained sample, the porous copolymer was fixed to the pulp in a shish-kebab shape in which the pulp fibers penetrated through the particles, and the porous copolymer particles as the adsorption element did not fall off. , Almost never. Specific surface area is 430m
² / g, the pore volume was 0.43 cc / g, and the average pore diameter was 40.0Å. The polyvinyl monomer content is
Pure divinylbenzene is 49.5g and total monomer amount is 100
Since it is g, it is 49.5%.

Example 2 5 g of polyethylene synthetic pulp (Mitsui Zeraback Co., Ltd.-SWP, fiber length 2.4 mm) as the pulp and glass fiber (fiber diameter 10 μm, fiber length 15) as the short fibers.
mm) was also used, and 100 g of divinylbenzene (purity 55%, containing ethylvinylbenzene as an impurity) was used as the monomer, and the synthesis was carried out in exactly the same manner as in Example 1. The obtained adsorbent was fixed in the form of shish-kebab in which pulp and short fibers penetrated through the particles as in Example 1, and the particles were hardly dropped. The specific surface area is 590 m ² / g and the pore volume is 0.
It was 70 cc / g and the average pore diameter was 47.5Å. The polyvinyl monomer content is 55.0%.

Example 3 In a reaction vessel similar to that of Example 1, 10 g of polypropylene synthetic pulp (Dick Hercules Co., Ltd.-Palpex, fiber length 1.9 mm), 750 g of deionized water,
As a dispersant, 1 g of polyvinyl alcohol is mixed by stirring to sufficiently disperse it. Furthermore, 90 g of chloromethylstyrene monomer (purity: 95%) with nitrogen gas flowing,
Divinylbenzene (purity 55%, containing ethylvinylbenzene as an impurity) 10 g, polymerization initiator benzoyl peroxide (purity 75%, 25% water content) 7 g, and porosifying agent 150 g were charged, and 20 After stirring for 1 minute, the temperature in the flask was adjusted to 8 using an oil bath.
The mixture was heated with stirring to 0 ° C. and kept as it was for 8 hours. It was refluxed with methanol under the same conditions as in Example 1 and dried under vacuum. Here, again using the same reaction vessel as in Example 1, 30 g of a part of the sample was put into the molecular sieve 4A.
It was placed in 350 cc of dehydrated dichloroethane and left to swell for 12 hours. After the swelling treatment, 50 g of tin chloride (SnCl ₄ ) was added, and the mixture was heated under stirring in a nitrogen atmosphere while heating at the reflux temperature of dichloroethane (80 to 82 ° C.).
Hold for 7 hours. 200cc while cooling the reaction vessel with ice
After acetone was added dropwise to decompose the catalyst, the sample was separated by filtration. The sample is pure water 1000 cc, 10% hydrochloric acid aqueous solution 1000 cc, pure water 1000 cc, acetone 500 cc
After washing in this order, it was dried at 120 ° C. The obtained adsorbent was fixed in the form of shish-kebab in which pulp penetrates through the particles, as in Example 1, and there was almost no dropout of the particles. The specific surface area was 1020 m ² / g, the pore volume was 0.66 cc / g, and the average pore diameter was 25.9Å. The polyvinyl monomer content is 5.5%.

Example 4 A synthetic container made of polyethylene was placed in a reaction vessel similar to that used in Example 1.
Pu (Mitsui Zeraback Co., Ltd.-SWP, fiber length 2.4 m
m) 5 g, deionized water 750 g, polyvinyl chloride as a dispersant
1 g of alcohol is mixed by stirring and sufficiently dispersed.
Chloromethylstyrene model with nitrogen gas flowing
95 g of Nomer (purity 95%), divinylbenzene (purity
55%, containing ethyl vinylbenzene as an impurity) 5
g, benzoyl peroxide 7g and toluene 150g
Then, stir for 20 minutes as it is, and then stir at 80 ° C for 8 hours.
It was heated in the state. With methanol under the same conditions as in Example 1.
Reflux and vacuum dry. Here, again, the same antithesis as in the first embodiment
Using a reaction container, a portion of 30 g of the sample is
Dichloroethane 350c dehydrated with sieve 4A
It was placed in c and left to swell for 12 hours. Swelling treatment
After that, tin chloride (SnCl 2 _Four) Add 50g, nitrogen atmosphere
While stirring under 50 ° C for 4 hours, 60 ° C, 70 ° C for each
Stir for 1 hour and 8 hours at the reflux temperature of dichloroethane
It was heated in the state. 200cc while cooling the reaction vessel with ice
After decomposing the catalyst by dropping acetone, the sample was filtered off.
It was The sample is pure water 1000 cc, 10% hydrochloric acid aqueous solution
1000 cc, pure water 1000 cc, acetone 500 cc
After washing in this order, it was dried at 120 ° C. The resulting adsorption
As for the material, most of the particles are pulverized in the same manner as in Example 1.
Fixed in a shish-kebab shape
Almost no particles fell out. Specific surface area is 1240m
²/ G, pore volume is 0.69 cc / g, average pore diameter is 2
It was 2.3Å. Polyvinyl monomer content is 2.8%
Is.

Example 5 In a reaction vessel similar to that in Example 1, synthetic polyethylene pulp (Mitsui Zeraback Co., Ltd.-SWP, fiber length 2.4 m) was used.
m) 10 g, deionized water 750 g, and polyvinyl alcohol 1 g are mixed with stirring to sufficiently disperse them. Furthermore, 80 g of p-methylstyrene monomer (purity 95%), 20 g of divinylbenzene, 7 g of benzoyl peroxide which is a polymerization initiator and 150 g of toluene were added in a state where nitrogen gas was flown, and the mixture was stirred for 20 minutes as it was, and then in the flask It was heated so that the temperature became 80 ° C. and kept as it was for 8 hours.
It was refluxed with methanol under the same conditions as in Example 1 and dried under vacuum. Here, again using the same reaction container as in Example 1, a part of 30 g of the sample was put into 350 cc of dichloroethane dehydrated with molecular sieve 4A and left to stand for 6 hours to be swollen. After the swelling treatment, 9 g of paraformaldehyde was added, and the mixture was stirred as it was for 20 minutes. Further, while stirring in a nitrogen atmosphere, concentrated sulfuric acid (97%) as a catalyst 1
After dropping 00 cc, the mixture was heated and kept at the reflux temperature of dichloroethane for 24 hours. After allowing to cool, 200 cc of pure water was added dropwise for dilution, and then the sample was filtered off. The sample was washed with 1000 cc of pure water and 500 cc of methanol in this order, and then dried at 120 ° C. The obtained adsorbent was obtained in Example 1
Like shish kebab (sh
It was fixed by (ish-kebab) and almost no particles fell out. Specific surface area is 320 m ² / g, pore volume is 0.30
It was cc / g, and the average pore diameter was 375Å. The polyvinyl monomer content is 11.0%.

Example 6 80% by weight of the adsorbent obtained in Example 3 and 20% by weight of ES fiber (manufactured by Chisso Co., Ltd.) having a core-sheath structure adhesive fiber and a sheath polyethylene part of which the core part is polypropylene Polyethylene oxide having an average molecular weight of 1,000,000 (1% by weight) was further added as a thickening agent. The above was dispersed in a large amount of water (10000% by weight) to prepare a stock solution for papermaking, which was made up with a papermaking net and dried by a dryer at 120 ° C to form a sheet. The physical properties of the sheet-shaped adsorbent made into paper are as follows. The areal weight was 40 g / m ² , the thickness was 0.35 mm, and the tensile strength was 2.5 kgf / cm. When the adsorption characteristic at 25 ° C. with respect to toluene gas was measured, 26.0 wt% (based on the dry weight of the sheet-shaped adsorbent) of toluene gas was adsorbed with respect to toluene gas having a saturation of 1/10.

Example 7 90% by weight of the adsorbent obtained in Example 4 and 10% by weight of ES fiber (made by Chisso Co., Ltd.), which is an adhesive fiber having a core-sheath structure and whose sheath part is polyethylene whose core part is polypropylene A sheet was formed in the same manner as in Example 6 using the same as the raw material. The physical properties of the sheet-shaped adsorbent made into paper are as follows. The areal weight was 50 g / m ² , the thickness was 0.64 mm, and the tensile strength was 2.0 kgf / cm. When the adsorption characteristic for toluene gas was measured, 30.5% by weight (based on the dry weight of the sheet-shaped adsorbent) of toluene gas was adsorbed with respect to the toluene gas of 1/10 saturation.

Example 8 70% by weight of the adsorbent obtained in Example 2 and 30% by weight of rayon staple (fiber length 40 mm, 2 denier) were thoroughly mixed and then sheeted by applying a needle punch machine. . The areal weight was 80 g / m ² , the thickness was 1.30 mm, and the tensile strength was 4.2 kgf / cm. When the adsorption characteristic for toluene gas was measured, 11.4% by weight (based on the dry weight of the sheet-shaped adsorbent) of toluene gas was adsorbed to the toluene gas having a saturation of 1/10.

Comparative Example 1 No pulp was used in Example 3, and the other examples were used.
The synthesis was carried out in exactly the same manner as in. The obtained sample had a specific surface area of 1100 m ² / g and a pore volume of 0.7.
The particles were 2 cc / g, the average pore diameter was 26.2Å, and the particles were microsphere-shaped porous particles having a diameter of 100 μm. Further, the above porous granular material was formed into a sheet by the same method as in Example 6. In the obtained sheet-like material, a large amount of the porous granular material fell off. When the adsorption characteristic to toluene gas at 25 ° C. was measured, it was 15.0% by weight to the toluene gas of 1/10 saturation (based on the dry weight of the sheet material).
Of toluene gas was adsorbed.

Comparative Example 2 Synthesis was carried out in the same manner as in Example 2 except that pulp and glass fiber were not used in Example 2.
The obtained sample was a fine spherical porous granular material having a specific surface area of 610 m ² / g, a pore volume of 0.76 cc / g, an average pore diameter of 49.8Å, and a diameter of 120 μm.
Further, the above porous granular material was formed into a sheet by the same method as in Example 8. In the obtained sheet-like material, an extremely large amount of the porous granular material was dropped off. When the adsorption characteristic to toluene gas at 25 ° C. was measured, 3.5% by weight (based on the dry weight of the sheet material) of toluene gas was adsorbed to the toluene gas of 1/10 saturation.

Comparative Example 3 The same treatment as in Example 3 was performed except that the post-treatment after the swelling treatment with dichloroethane in Example 3 was not performed. In the obtained sample, the copolymer particles were immobilized in a shish-kebab shape. The specific surface area is a small value of 100 m ² / g or less, which is outside the measuring range of the measuring device,
It could not be measured together with the pore volume. Comparative Example 4 Synthesis was carried out under exactly the same conditions as in Example 4, except that polyethylene synthetic pulp was not used. The obtained sample was in a powder state with a particle size of 100 to 120 microns. Specific surface area 1290 m ² / g, pore volume 0.7
It was 3 cc / g and the average pore diameter was 22.6Å. Comparative Example 5 86% by weight of the powdery sample obtained in Comparative Example 4 and 14% by weight of ES fiber (manufactured by Chisso Corporation) in which an adhesive fiber having a core-sheath structure and a sheath portion made of polypropylene is a polypropylene portion are used for papermaking. The raw material was formed into a sheet by the same method as in Example 6. The physical properties of the sheet-shaped adsorbent made into paper are as follows. Basis weight 50 g / m ² , thickness 0.60 mm,
The tensile strength was 1.1 kgf / cm. When the adsorption characteristics for toluene gas were measured, 29.9% by weight (based on the dry weight of the sheet-shaped adsorbent) of toluene gas was adsorbed with respect to the toluene gas of 1/10 saturation. In the above sheet-like material, immobilization of the powdery sample was not sufficient, and the powder easily fell off. Comparative Example 6 60% by weight of the powdery sample obtained in Comparative Example 4 and 40% by weight of ES fiber (manufactured by Chisso Co., Ltd.), which is an adhesive fiber having a core-sheath structure and whose sheath is polyethylene and whose core is polypropylene, is used as a raw material for papermaking. Then, a sheet was formed in the same manner as in Example 6. The physical properties of the sheet-shaped adsorbent made into paper are as follows. Basis weight 51 g / m ² , thickness 0.63 mm,
The tensile strength was 2.3 kgf / cm. When the adsorption characteristic for toluene gas was measured, 11.2% by weight (based on the dry weight of the sheet-shaped adsorbent) of toluene gas was adsorbed with respect to the toluene gas of 1/10 saturation.

The specific surface area (m ² / g) and pore volume (cc / g) in the present invention are measured by Carlo Elba Ltd.
Using a soapmatic, SSII-80, it was determined by the adsorption amount of nitrogen gas at the liquid nitrogen temperature. Further, the average pore diameter in the present invention is a cylindrical approximation of the pore shape (cylindrical
The model was calculated according to the following equation. Average pore diameter (Å) = (4 x pore volume / specific surface area) x 10
^Four

The surface element strengths of oxygen and carbon in the present invention were measured by ESCA-850 type manufactured by Shimadzu Corporation. Press the pulp or staple fibers to flatten them,
After drying for an hour, the sample was mounted on a sample table and deaerated under vacuum for 3 hours or more, and then measurement was performed using Mg Kα ray as an X-ray source.
The measurement was performed on the C1S and O1S peaks.

In the present invention, the basis weight of the sheet-like adsorbent is 24 after vacuum drying (5 to 10 mmHg) at 100 ° C.
The weight per unit area is shown based on the dry weight after the time.

In the present invention, the thickness of the sheet-shaped adsorbent is measured by a standard micrometer (manufactured by Mitutoyo Corporation,
It is an average value of the values measured by M110-25 type).

The tensile strength of the sheet-shaped adsorbent in the present invention was measured according to JIS-P8113, which was specified for the tensile strength test method for paper and paperboard.
The measurement was performed with a sample width of 15 mm.

The adsorption property of the gas substance of the sheet-shaped adsorbent in the present invention was determined according to the test method of JIS-K1474, and vacuum drying (5 to 10 mmHg) was performed at 100 ° C. for 24 hours and then the above. The measurement was performed.

[0042]

As described above, the adsorbent and the sheet-shaped adsorbent according to the present invention have the same excellent adsorbing characteristics as activated carbon, no generation of conductive dust, and the porous adsorbent which is an adsorbing element. It has the advantage of very little loss of polymer. Therefore, it can be usefully used in a wide range of adsorption applications, and can bring great industrial utility.

Claims (2)

[Claims] 1. An adsorbent characterized in that a copolymer having a macroreticular structure composed of a monovinyl monomer and a polyvinyl monomer is immobilized on the surface of pulp or short fibers. 2. 100 to 50% by weight of the adsorbent of claim 1.
A sheet-shaped adsorbent characterized by containing.