KR100543127B1 - Complex adsorbing agent and preparation method of the same - Google Patents

Abstract

The present invention relates to a composite adsorbent and a method for preparing the same, and more particularly, an organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbide] of formula 3 is applied to a support body. It relates to a composite adsorbent and a method for producing the same.

[O _0.15 Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) ₃ Si _1.5 ] _n

(Wherein

n is 2 to 1500 as the degree of polymerization.)

The composite adsorbent of the present invention has excellent adsorptivity to carcinogens such as tar, nicotine, formaldehyde, hydrogen cyanide, acetone, benzopyrene, and the like, and the filter including the composite adsorbent may be preferably used as a tobacco filter.

 3-aminopropyltrialkylsilane, N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide, N, N'-bis (3-trialkylsilylpropyl) thiocarbamide, poly [1,3- Bis (silsesquioxypropyl) thiocarbamide], tobacco filter

Description

COMPOSITE ADDRESS AND MANUFACTURING METHOD THEREOF {COMPLEX ADSORBING AGENT AND PREPARATION METHOD OF THE SAME}

[TECHNICAL FIELD OF THE INVENTION]

The present invention relates to a composite adsorbent and a method for preparing the same, and more particularly, to a composite adsorbent having excellent adsorptive power to carcinogens such as tar, nicotine, formaldehyde, hydrogen cyanide, acetone, benzopyrene, and the like.

[Private Technology]

The present invention relates to a method for manufacturing a composite filter adsorbent for tobacco filters having an effective adsorption characteristic for the purpose of removing and reducing vapor and gaseous substances classified as harmful components in tobacco smoke.

Tobacco smoke consists of particulates such as gaseous substances such as carbon monoxide and hydrogen cyanide, vaporous substances such as acrolein, acetaldehyde, formaldehyde and acetonitrile, and polycyclic aromatic hydrocarbons with the inherent flavor of tobacco such as nicotine or tar. They can be classified as substances, which differ in their removal or reduction depending on their component groups.

As far as is reported, particulate matters are known to be filtered by fibrous filters or air dilution methods, and vapor or gaseous substances are known to be effective by air dilution or diffusion adsorption methods. Conventional fibrous filters are used for the purpose of filtration of nicotine, tar and the like, its filtration rate is about 20 to 40% and there is still a strong smell inherent in tobacco by nicotine or tar when smoking. In addition, these harmful components are scattered in the room may cause discoloration or discomfort in the room.

On the other hand, in order to remove or reduce gaseous or vaporous components, an adsorbent having selective adsorption capacity is used in addition to a fibrous filter. Depending on the type or method of adding these adsorbents, some harmful components in the smoke components may be selectively removed. Can be.

To date, the adsorbents added to tobacco filters for the purpose of removing or reducing harmful substances in tobacco are hydrophobic activated carbons made from vegetable raw materials such as palm shells, oaks and pines or lignite and hydrophilic zeolites which are mineral adsorbents. The complex adsorbent etc. which couple | bonded with the appropriate method are known. Activated carbon has a very large specific surface area due to the development of micropores and strong adsorption power to nonpolar molecules, which is excellent in exhaust gas removal, odor removal, and decolorization, while zeolite is a hydrophilic adsorbent having a pore diameter of about 3 to 10 Å. Carbon dioxide and moisture adsorption characteristics are strong.

Adsorbents used in conventional tobacco filters are activated carbon or a composite of activated carbon and zeolite, and are deposited in a fibrous filter in the form of fine activated carbon particles, and then used as a single or double filter or processed into a relatively large particle size. It is used in the form of a triple filter which is located between the fibrous filters.

According to Japanese Patent Laid-Open No. 59-69146, Japanese Patent Laid-Open No. 4-04039, Korean Patent No. 031709, and Korean Patent No. 0193377, various inorganic and organic binders are used for the purpose of complementing the adsorption characteristics of the two materials. A method for preparing a composite adsorbent in which two materials are mixed is described. However, activated carbon and zeolite have different physical properties, and due to pore closure of activated carbon and zeolite by inorganic and organic binders, there is a problem of lowering lipophilic and hydrophilic adsorption capacity due to molecular sieve effect.

Many types of additives have been applied to filters to reduce or eliminate certain harmful components of tobacco more effectively.

According to German Patent No. 1300854, German Patent No. 4320348, and Japanese Patent Laid-Open No. Hei 5-23159, it is known that nicotine can be reduced by using an organic acid or an ester compound thereof as a filter additive, and Japanese Patent Application Laid-Open No. 50-125100. , SO 51-32799, and German Patent No. 2527234, it is known that the addition of cyclic dextrin directly to the fibrous filter or the addition of 30 to 80 mg per filter in the form of granules provides excellent nicotine adsorption capacity, but removes other harmful components. Is not known.

U.S. Patent No. 5,409,021 discloses that the addition of 22 to 66 mg of lignin as a 20 to 50% of the filter weight to a double or triple filter can relatively reduce nicotine, benzopyrene, carbon monoxide, metals and nitroamines.

European Patent Publication No. 0246330 claims that the activated cellulose powder, etc., in the form of a triple filter of 15% or more of the filter weight has an effect of reducing harmful components, which can also be applied to the fibrous filter in powder form. Specific data are insufficient.

Silica surface treatment using organoalkoxysilanes has been widely known for the purpose of modifying the fixed phase of liquid chromatography. N, N'-bis (3-triethoxysilylpropyl) thio synthesized for the first time by Vlasova et al. (Bull. Acad. Sci. USSR Div. Chem. Sci., Vol. 28, pp. 1938-1940, 1979). The carbamide compound shows excellent ion exchange performance and complex formation ability when treated on a surface such as silica, especially the results of the experiments of Voronkov et al. (Russian Journal of General Chemistry, Vol. 68, pp. 770-774, 1998). According to the present invention, gold, silver, platinum, copper, zinc, cadmium, mercury, selenium, fluorine and bromine are known to exhibit excellent adsorption performance.

In European Patent Publication No. 0493026 and Russian Patent No. 2010546, a method for supporting 6 to 15.3 wt% of N, N'-bis (3-triethoxysilylpropyl) thiocarbamide in a fibrous filter is known, and US Patent No. 6,145,511 The method describes a method for manufacturing a filter using the various additives described above, and specific data on the removal and reduction of harmful tobacco components by additives are not provided.

Meanwhile, as a method for synthesizing N, N'-bis (3-triethoxysilylpropyl) thiocarbamide, 3-aminopropyltriethoxysilane and thiocarbamide are heated to 170 to 180 ° C under an ammonium sulfate catalyst. Although introduced in this document, the reaction conditions are intense, ammonia is generated as a by-product, purification is necessary to remove unreacted thiocarbamide and ammonium sulfate, so the yield is low and the process is complicated.

In order to solve the problems of the prior art, it is an object of the present invention to provide a composite adsorbent having excellent adsorptivity to carcinogens such as tar, nicotine, formaldehyde, hydrogen cyanide, acetone, benzopyrene and the like.

It is another object of the present invention to provide a filter comprising the composite adsorbent.

The present invention also provides a simple process for preparing N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thio, which does not require a separate complicated purification process. It is an object to provide a method for producing carbamide.

It is another object of the present invention to provide a method for producing a composite adsorbent having excellent adsorption capacity to carcinogens such as tar, nicotine, formaldehyde, hydrogen cyanide, acetone, benzopyrene and the like.

In order to achieve the above object, the present invention provides a composite adsorbent in which an organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] of Formula 3 is applied to a support.

[Formula 3]

[O _0.15 Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) ₃ Si _1.5 ] _n

(Wherein

n is 2 to 15 as the degree of polymerization.)

The present invention also provides a filter comprising the composite adsorbent.

The present invention also provides

3-aminopropyltrialkylsilane of the following Chemical Formula 1 in a nitrogen gas atmosphere was added to the reactor, and the reactor was stirred, carbon disulfide was added dropwise, followed by heating and refluxing. Provided are 3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide.

H ₂ NCH ₂ CH ₂ SiR ₃

(Wherein

R is C ₂ H ₅ , OCH ₃ or OC ₂ H _5. )

R ₃ Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) SiR ₃

(Wherein

R is C ₂ H ₅ , OCH ₃ or OC ₂ H _5. )

The present invention also provides

(a) Injecting 3-aminopropyltrialkylsilane of the following Chemical Formula 1 into the reactor under a nitrogen gas atmosphere, stirring the reactor, dropwise adding carbon disulfide, and heating and refluxing the mixture to form N, N'-bis (3). Preparing -trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide;

(b) N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide is dissolved in a solvent and N, N'-bis Preparing a (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide solution;

(c) the solution is mixed with the support to carry N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide Preparing a retard; And

(d) condensation polymerization of the carrier in a basic aqueous solution

It provides a method for producing a composite adsorbent in which an organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] of Formula 3 is coated on a carrier.

[Formula 1]

H ₂ NCH ₂ CH ₂ SiR ₃

(Wherein

R is C ₂ H ₅ , OCH ₃ or OC ₂ H _5. )

[Formula 2]

R ₃ Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) SiR ₃

(Wherein

R is C ₂ H ₅ , OCH ₃ or OC ₂ H _5. )

[Formula 3]

[O _0.15 Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) ₃ Si _1.5 ] _n

(Wherein

n is 2 to 1500 as the degree of polymerization.)

Hereinafter, the present invention will be described in detail.

The present inventors have confirmed that the organic silicone polymer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] of Formula 3 is excellent in adsorption capacity for gaseous organic materials and metal components, The present invention was completed.

[Formula 3]

[O _1.5 Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) ₃ SiO _1.5 ] _n

(Wherein

n is 2 to 1500 as the degree of polymerization.)

Therefore, the composite adsorbent in which the organic silicon polymer layer of the poly [1,3-bis (silsesquioxypropyl) thiocarbamide] of the formula 3 of the present invention is applied to the carrier, tar, nicotine, aldehyde, hydrogen cyanide, benzopyrene Excellent adsorption to carcinogens such as can be used as a filter and can be preferably used as a cigarette filter.

As the carrier on which the organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] of Formula 3 is applied, zeolite having an appropriate size and specific surface area or activated carbon is preferable. In addition, the particle size of the zeolite or activated char is preferably 30 to 80 mesh.

In addition, the composite adsorbent preferably further comprises 0.1 to 1.0 wt% of fullerene (C ₆₀ ). Fullerenes have a structure in which 60 carbons are bonded in the shape of a soccer ball and correspond to nano size, and are known to have anticancer effects as the longest and most powerful antioxidant known to date. The fullerene which can be used in the present invention may be a fullerene further added with boron in addition to a fullerene composed of pure carbon only.

The present invention also relates to the N, N'-bis (3-trialkoxysilyl) of formula (2), which is an intermediate for the preparation of the organosilicon polymer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] of formula (3). Propyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide.

The method for preparing N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide of Chemical Formula 2 may be carried out under a nitrogen gas atmosphere. Of 3-aminopropyltrialkylsilane was added to the reactor, followed by stirring the reactor, dropwise addition of carbon disulfide, followed by heating and refluxing.

Hydrogen sulfide is generated through the reflux process, a yellow viscous solution is generated, and reflux is stopped when hydrogen sulfide is no longer generated.

The conventional method for synthesizing N, N'-bis (3-triethoxysilylpropyl) thiocarbamide was a method in which 3-aminopropyltriethoxysilane and thiocarbamide were heated to 170 to 180 ° C under an ammonium sulfate catalyst. However, the conventional method has a problem that the reaction conditions are violent and ammonia is generated as a by-product, and a purification process for removing unreacted thiocarbamide and ammonium sulfate is essential, so the yield is low and the process is complicated.

However, in the present invention, hydrogen sulfide is refluxed to produce N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide. In addition, since ammonia is not generated as a by-product, high reactivity, there is a small amount of unreacted thiocarbamide, and an ammonium sulfate removal process is not necessary, so the manufacturing method is simple and the yield is high.

The present invention also provides the above formula (3) from N, N'-bis (3-trialkylsilylpropyl) thiocarbamide or N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide prepared above. Provided is a method for producing a composite adsorbent in which an organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] is coated on a support.

First, when the 3-aminopropyltrialkylsilane of Chemical Formula 1 reacts with carbon disulfide, hydrogen sulfide is generated, and N, N'-bis (3-trialkylsilylpropyl) thiocarbamide of Chemical Formula 2 or N, N'- Bis (3-trialkoxysilylpropyl) thiocarbamide is obtained in quantitative yield (step (a)).

By adopting the reaction process of step (a), 3-aminopropyltriethoxysilane and thiocarbamide, which are conventional methods for synthesizing N, N'-bis (3-triethoxysilylpropyl) thiocarbamide, are prepared by ammonium sulfate. Reaction conditions, which are disadvantages of the method of heating to 170 to 180 DEG C under a catalyst, are violently generated, ammonia is generated as a by-product, and a purification process for removing unreacted thiocarbamide and ammonium sulfate is essential, resulting in a low yield and a complicated process. Problem does not occur.

Thus, as described in the method for preparing N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide of Formula 2, heating and refluxing Since only the reaction proceeds, the reaction process is simple and the yield is high, and thus the yield of the final product is expected to be high.

Then dilute the N, N'-bis (3-trialkylsilylpropyl) thiocarbamide or N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide of Formula 2 obtained through the reaction in a solvent. To prepare a solution of 5 to 20% by weight (step (b)). As the diluting solvent, a water-soluble solvent such as water or alcohol is preferable.

The content of N, N'-bis (3-trialkylsilylpropyl) thiocarbamide or N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide of Formula 2 is less than 5% by weight in the diluting solvent. In this case, it is difficult to coat a sufficient amount of N, N'-bis (3-trialkylsilylpropyl) thiocarbamide monomer on the carrier, and if it exceeds 20% by weight, there is a problem that a uniform coating is not formed. .

The solution is then mixed with the carrier to form N, N'-bis (3-trialkylsilylpropyl) thiocarbamide or N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide To prepare a supported carrier (step (c)).

As the carrier, zeolite or activated carbon having a suitable size and specific surface area is preferable. In this case, N-N'-bis (3-trialkylsilylpropyl) thiocarbamide or N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide in an appropriate ratio of 30 to 80 mesh activated carbon or zeolite And then stirred at 30 to 40 ° C. for 1 hour, filtered and dried at 110 ° C. to form N, N′-bis (3-trialkylsilylpropyl) thiocarbamide or N, N′- A carrier having 5 to 40% by weight of bis (3-trialkoxysilylpropyl) thiocarbamide was prepared.

Condensation polymerization when the supported amount of N, N'-bis (3-trialkylsilylpropyl) thiocarbamide or N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide of Formula 2 is less than 5% by weight After the adsorption capacity of the resulting organic silicon polymer layer is not sufficient, N, N'-bis (3-trialkylsilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) If the supported amount of thiocarbamide exceeds 40% by weight, the specific surface area is remarkably reduced due to pore closure of activated carbon and zeolite during the polymerization reaction, and the adsorption capacity per unit weight decreases, which is not preferable.

Then, the carrier was polycondensed in a basic aqueous solution to prepare a composite adsorbent in which an organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] of Formula 3 was applied to the carrier. (Step (d)).

The composite adsorbent obtained by the above series of processes is used for the tobacco filter to remove and reduce not only harmful gaseous and vaporous substances, but also particulate matter among the smoke components of tobacco, in addition to the treatment agent for purification, air purifier, deodorant and various It may be used as a support for the catalyst.

Hereinafter, preferred examples and comparative examples of the present invention are described. The following examples are described for the purpose of more clearly expressing the contents of the present invention, but the contents of the present invention are not limited to the following examples.

Preparation of N, N'-bis (3-trialkylsilylpropyl) thiocarbamide or N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide

Example 1

347 g of 3-aminopropyltriethylsilane were placed in a 1 L reactor under a nitrogen atmosphere, and 300 g of carbon disulfide was slowly added dropwise at room temperature over 1 hour while stirring at 400 rpm. Subsequently, when the reaction mixture is heated and refluxed for 3 hours, hydrogen sulfide is generated to change into a light yellow viscous solution. When hydrogen sulfide no longer occurred, a distillation apparatus was attached to separate excess carbon disulfide to give 385 g of N, N'-bis (3-triethylsilylpropyl) thiocarbamide.

Example 2

482 g of N, N'-bis (3-triethoxysilylpropyl) thiocarbamide was prepared in the same manner as in Example 1 except that 443 g of 3-aminopropyltriethoxysilane and 300 g of carbon disulfide were used. Prepared.

Example 3

Except that 359 g of 3-aminopropyltrimethoxysilane and 300 g of carbon disulfide were used in the same manner as in Example 1, 400 g of N, N'-bis (3-trimethoxysilylpropyl) thiocarbamide was prepared. Prepared.

The samples prepared in Examples 1 to 3 were analyzed using infrared spectroscopy and nuclear magnetic resonance spectroscopy to find no impurities.

Preparation of a carrier on which N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide is supported

Example 4

N, N'-bis (3-triethylsilylpropyl) thiocarbamide prepared in Example 1 was mixed with isopropyl alcohol to prepare a 20% by weight solution. Next, 50 g of activated carbon powder (apparent specific gravity of 0.59 g / cc, specific surface area of 1,000 m 2 / g) and 300 g of N, N'-bis (3-triethylsilylpropyl) thiocarbamide solution were used in a 1 L reactor. The mixture was stirred at 35 ° C. for 1 hour, filtered and dried at 110 ° C. to obtain 62 g of a complex having 20% by weight of N, N′-bis (3-triethylsilylpropyl) thiocarbamide. The filtrate was stored separately because it is reusable.

Preparation of composite adsorbent in which organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] was applied to a support

Example 5

50 g of the composite prepared in Example 4 and 100 mL of a 3 wt% NaOH aqueous solution were placed in a 500 mL reactor, heated at reflux for 1 hour with stirring at 600 rpm, and hydrolyzed to generate a poly [1, 3-bis (silsesquioxypropyl) thiocarbamide] was produced.

After the condensation polymerization was completed, the mixture was cooled to room temperature, the coated composite composition was filtered, washed with distilled water until the filtrate was neutral, and dried at 120 ° C. to obtain 46.3 g of a composite adsorbent. The apparent specific gravity of the obtained adsorbent was 0.49 g / cc, and the specific surface area was 380 m <2> / g.

Example 6

Examples 4 and 5 were carried out under the same conditions except that 50 g of 5 Å synthetic zeolite (25 mesh) was used instead of the activated carbon powder. The coating amount of the organosilicon polymer of the obtained zeolite was measured at 16.8 wt%, the apparent specific gravity was 0.74 g / cc, and the specific surface area was 410 m 2 / g.

[Comparative Examples 1 and 2]

Zeolite and activated carbon which did not form an organosilicon polymer membrane of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] were used as the adsorbent.

Adsorption Performance Evaluation

The adsorbents prepared in Examples 5 and 6 and Comparative Examples 1 and 2 were used to prepare tobacco for analyzing the adsorption performance of tobacco smoke.

First, a commercial cigarette filter was used for the manufacture of tobacco, and the composition prepared in the present invention was filled in the existing adsorbent space between the acetate and the paper filter in the triple filter to 70% of the cavity volume. At this time, the suction resistance of the triple filter was 90 ± 5 mmH ₂ O, the suction resistance of the manufactured cigarette was 135 ± 5 mmH ₂ O. The adsorption performance of the adsorbent obtained in the present invention is shown in Table 1 below.

                                             Adsorption performance of harmful components in tobacco smoke Item Zeolite use Activated Carbon Use Example 5 Comparative Example 1 Example 6 Comparative Example 2 Tar (mg / cig) 6.2 8.46 7.30 10.12 Nicotine (mg / cig) 0.46 1.09 0.43 0.84 Formaldehyde (mg / cig) 3.0 16.4 1.9 2.8 Hydrogen cyanide (µg / cig) 35.1 71.2 2.6 12.0 Acetone (µg / cig) 75.4 242.6 70.5 224.6 Benzopyrene (ng / cig) 8.9 30.5 9.3 38.2

As shown in Table 1, a cigarette filter was prepared using a zeolite or activated carbon on which an organic silicon polymer film of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] was formed as a support material, and tar, nicotine, and formaldehyde were prepared. It can be seen that the content of the harmful components passing through the filter is significantly reduced because of excellent adsorption performance of harmful components such as hydrogen cyanide, acetone, benzopyrene and the like.

The composite adsorbent of the present invention has excellent adsorptivity to carcinogens such as tar, nicotine, formaldehyde, hydrogen cyanide, acetone, benzopyrene, and the like, and the filter containing the composite adsorbent may be preferably used as a cigarette filter.

Claims (12)

3 to 25% by weight of the organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] represented by the following Chemical Formula 3 is applied to one carrier selected from zeolite and activated carbon : [Formula 3] [O _0.15 Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) ₃ Si _1.5 ] _n (Wherein n is 2 to 1500 as the degree of polymerization.) delete The method of claim 1, The composite adsorbent is characterized in that it further comprises 0.1 to 1.0% by weight of fullerene composite adsorbent. A filter comprising a composite adsorbent according to any one of claims 1 and 3. The method of claim 4, wherein The filter is characterized in that the cigarette filter. 3-aminopropyltrialkylsilane of the following Chemical Formula 1 in a nitrogen gas atmosphere was added to the reactor, and the reactor was stirred, carbon disulfide was added dropwise, followed by heating and refluxing. Process for preparing 3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide: [Formula 1] H ₂ NCH ₂ CH ₂ SiR ₃ (Wherein R is C ₂ H ₅ , OCH ₃ or OC ₂ H _5. ) [Formula 2] R ₃ Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) SiR ₃ (Wherein R is C ₂ H ₅ , OCH ₃ or OC ₂ H _5. ) (a) Injecting 3-aminopropyltrialkylsilane of the following Chemical Formula 1 into the reactor under a nitrogen gas atmosphere, stirring the reactor, dropwise adding carbon disulfide, and heating and refluxing the mixture to form N, N'-bis (3). Preparing -trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide; (b) the N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide selected from water, alcohols and mixtures thereof Dissolving in a water-soluble solvent of the species to prepare a N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide solution; (c) the solution is mixed with the support to carry N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide or N, N'-bis (3-trialkylsilylpropyl) thiocarbamide Preparing a retard; And (d) condensation polymerization of the carrier in a basic aqueous solution Method for preparing a composite adsorbent, wherein the organosilicon polymer layer of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] of Formula 3 is coated on a carrier, comprising: [Formula 1] H ₂ NCH ₂ CH ₂ SiR ₃ (Wherein R is C ₂ H ₅ , OCH ₃ or OC ₂ H _5. ) [Formula 2] R ₃ Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) SiR ₃ (Wherein R is C ₂ H ₅ , OCH ₃ or OC ₂ H _5. ) [Formula 3] [O _0.15 Si (CH ₂ ) ₃ NHC (S) NH (CH ₂ ) ₃ Si _1.5 ] _n (Wherein n is 2 to 1500 as the degree of polymerization.) The method of claim 7, wherein N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide in the solution of step (b) is 5 to 20% by weight of N, N'-bis (3-trialkylsilylpropyl) thiocarbamide Composite adsorbent manufacturing method characterized in that. The method of claim 7, wherein N, N'-bis (3-trialkoxysilylpropyl) thiocarbamide in the carrier of step (c) is 5 to 40% by weight of N, N'-bis (3-trialkylsilylpropyl) thiocarbamide Composite adsorbent manufacturing method, characterized in that%. The method of claim 7, wherein The carrier of step (c) is a composite adsorbent production method, characterized in that the zeolite or activated carbon. The method of claim 10, Particle size of the zeolite or activated carbon is a composite adsorbent manufacturing method, characterized in that 30 to 80 mesh. The method of claim 7, wherein Method of producing a composite adsorbent, characterized in that the content of poly [1,3-bis (silsesquioxypropyl) thiocarbamide] in the composite adsorbent prepared in step (d) is 3 to 25% by weight.