KR20170049245A - Heat-decomposed compound and method for gasification using the same - Google Patents

Abstract

Disclosed are a heat decomposition compound and a gas generating method using the same capable of chemically transforming a structure of azodicarbonnamide. The heat decomposition compound is represented by below chemical formula 1 or chemical formula 2. R_1, R_2, R_4, and R_5 are respectively represented by a hydrocarbon group having 1 to 20 carbon atoms, an amine group, or a combination thereof in the chemical formula 1 and the chemical formula 2. The hydrocarbon group includes or excludes hydrogen and heteroatoms. R_3 is an alkyl group having the hydrogen or the 1 to 10 carbon atoms. X_1 and X_2 are oxygen, sulfur atoms, or imine. When the X_1 is the oxygen (O), one among the R_1 to the R_3 is not the hydrogen; and the R can be a single bond or a double bond.

Description

TECHNICAL FIELD The present invention relates to a heat decomposition compound and a gas generating method using the heat decomposition compound.

The present invention relates to a heat decomposition compound and a gas generating method using the same. More particularly, the present invention relates to a heat decomposition compound capable of preventing generation of harmful components at the time of foaming by chemically modifying the structure of azodicarbonamide, And a method of generating the same.

The blowing agent is a resin additive for blending with a resin to prepare a porous foam. Azodicarbonamide (ADCA) is used as a foaming agent for thermoplastic resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride, styrene-butadiene rubber, acrylonitrile- , p, p'-oxybis (benzenesulfonyl hydrazide), dinitroso pentamethylene tetramine (DPT), p-toluenesulfonyl hydrazide a variety of organic compound blowing agents such as ptoluenesulfonylhydrazide, benzenesulfonyl hydrazide and 5-phenyl tetrazole are known (Korean Patent Publication No. 2011-0061303, Korean Patent No. 1482749, Korean Patent Publication No. 2005-0023986, Japanese Patent No. 5212265, Japanese Patent No. 5300499, Japanese Patent No. 5649693, US Patent No. 2005-0222282, etc.).

Among the above blowing agents, azodicarbonamide (ADCA) is a general-purpose product because nitrogen gas is rapidly generated by heating, decomposition products are incombustible, and toxicity is low. However, when a foam is produced using azodicarbonamide, the azodicarbonamide is not completely decomposed and yellowish remnants remain, and the whiteness of the foam is lowered. Further, as shown in the following reaction formula (1), when azodicarbonamide is thermally decomposed, gases such as nitrogen, carbon-monoxide, ammonia, and carbondioxide are generated. Harmful gases such as formamide, which can react with carbon monoxide and ammonia under high temperature and high pressure, may cause reproductive toxicity.

[Reaction Scheme 1]

Accordingly, an object of the present invention is to provide a heat decomposition compound which does not generate harmful components such as formamide and ammonia by chemically modifying the structure of azodicarbonamide, and a method for producing a gas using the same. Another object of the present invention is to provide a heat decomposition compound which can be environmentally friendly and can avoid regulation of harmful substances, can be evenly dispersed at the time of production of the foam, can form a closed cell, And a gas generating method using the same.

The present invention provides a blowing agent represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

In the general formulas (1) and (2), each of R ₁ , R ₂ , R ₄ and R ₅ independently represents hydrogen, a hydrocarbon group having 1 to 20 carbon atoms with or without a hetero atom, , R ₃ is hydrogen or a C 1-10 alkyl group, X ₁ and X ₂ are each independently oxygen, sulfur or imine, provided that when X ₁ is oxygen (O), R ₁ to R ₃ is not hydrogen, and R is a single bond or a double bond.

The foaming agent according to the present invention is environmentally friendly and can avoid the regulation of harmful substances because it suppresses or reduces the generation of harmful components such as formamide and ammonia while maintaining a good expansion ratio and pyrolyzes to generate mainly nitrogen gas. Further, the foaming ratio can be uniformly dispersed in the production of the foam, and independent bubbles can be formed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the decomposition temperature and gas volume decomposition curves of conventional azodicarbonamide (a) and Example 16 (b); FIG.
2 is a photograph showing a polyvinyl chloride foaming state using Example 16. Fig.

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

The heat decomposition compound according to the present invention has a good foaming ability and is capable of preventing or minimizing the formation of formamide during thermal decomposition, and is represented by the following formula (1) or (2).

[Chemical Formula 1]

(2)

Wherein R ₁ , R ₂ , R ₄ and R ₅ each independently represent hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, which contains or does not contain a hetero atom, an amine group or a combination thereof, R ₃ is hydrogen or an alkyl group having 1 to 10 carbon atoms (specifically, 1 to 5 carbon atoms), X ₁ and X ₂ are each independently an oxygen, a sulfur atom or an imine (= NH) R is a single bond or a double bond. Provided that when X ₁ is oxygen (O), at least one of R ₁ to R ₃ is not hydrogen and the heteroatom may be nitrogen (N), oxygen (O), or sulfur (S).

Specifically, each of R ₁ , R ₂ , R ₄ and R ₅ is independently an iso branched or linear alkyl group having 1 to 10 carbon atoms (specifically having 1 to 6 carbon atoms), an alkyl group having 2 to 10 carbon atoms An alkynyl group having 2 to 10 carbon atoms (specifically 2 to 6 carbon atoms), a cycloalkyl group having 3 to 10 carbon atoms (specifically 5 to 7 carbon atoms), or an alkyl group having 3 to 10 carbon atoms An aryl group having 4 to 15 carbon atoms (specifically 6 to 10 carbon atoms), a cycloalkyl group having 1 to 5 (specifically 1 to 3) hetero atoms and 2 to 15 carbon atoms (Heteroaryl group, etc.) having 1 to 20 carbon atoms, an amine group (-NH ₂ ), an alkylamine or arylamine group having 1 to 20 carbon atoms (specifically, 1 to 10), and combinations thereof ≪ / RTI > When R ₁ , R ₂ , R ₄ and R ₅ each independently have an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or a cycloalkenyl group, they have a chemical structure different from that of azodicarbonamide (ADCA) Has similar performance to azodicarbonamide.

More specifically, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms (methyl, ethyl, butyl, isobutyl, pentyl, etc.), a cycloalkyl group having 5 to 7 carbon atoms (Such as cyclopentyl and the like), a cycloalkenyl group (cyclopentadienyl group and the like), an aryl group having 6 to 10 carbon atoms (such as a phenyl group) or a hydrazinecarbonyl group, R ₃ is an alkyl group having 1 to 6 carbon atoms, X ₁ is an oxygen or sulfur atom. More specifically, R ₁ and R ₂ are cycloalkyl groups having 5 to 7 carbon atoms, R ₃ is hydrogen, and X ₁ is oxygen.

More particularly, R ₄ and R ₅ is an amine group (-NH _2), C 1 -C 20 alkyl amine (methylamine, ethylamine of (more specifically, 1 to 10 carbon atoms, more specifically 1 to 5 carbon atoms) Etc.), a cycloalkylamine group (cyclopentylamine group, etc.) having 5 to 15 carbon atoms (specifically 5 to 10 carbon atoms), a carbon number 5 to 10 having a double bond of 1 or more (E.g., cyclopentadienylamine group) of 5 to 7 carbon atoms (e.g., cyclopentadienylamine group) and arylamine groups of 5 to 15 carbon atoms (specifically 6 to 10 carbon atoms) such as benzylamine, and X ₂ is oxygen, and R is a single bond or a double bond. More particularly, R ₄ and R ₅ are an amine group (-NH ₂ ), X ₂ is oxygen, and R is a single bond or a double bond. In this case, it is similar to the performance of azodicarbonamide, has excellent compatibility with various resins, and does not generate harmful substances such as ammonia and formamide upon thermal decomposition.

For example, R ₄ and R ₅ may be an amine group (-NH ₂ ), X ₂ may be oxygen, and R may be a single or double bond.

In the case of foaming using the foaming agent according to the present invention, decomposition temperature (DT) and gas volume (GV) are similar to azodicarbonamide, and harmful substances such as formamide are not generated.

Specific examples of the compound (blowing agent) represented by the above formula (1) include the compounds represented by the following compounds 1a to 1t.

[Compound 1a]

[Compound 1b]

[Compound 1c]

[Compound 1d]

[Compound 1e]

[Compound 1f]

[Compound 1g]

[Compound 1h]

[Compound 1i]

[Compound 1j]

[Compound 1k]

[Compound l]

[Compound 1m]

[Compound 1n]

[Compound 1o]

[Compound 1p]

[Compound 1q]

[Compound 1 r]

[Compound 1s]

[Compound 1t]

[Compound 1u]

[Chemical Formula 1v]

[Compound 1w]

Specific examples of the compound (blowing agent) represented by the above formula (2) include the compounds represented by the following compounds 2a to 2g.

[Compound 2a]

[Compound 2b]

[Compound 2c]

[Compound 2d]

[Compound 2e]

[Compound 2f]

[Compound 2g]

[Compound 2h]

The foaming agent of the present invention can be produced by replacing an amine which is a side group of an azodicarbonamide which is a general purpose foaming agent with a secondary amine in a primary amine or by changing the arrangement, Amide, and ammonia, and the generation of noxious gas is reduced, so that the regulation of harmful substances at high risk can be avoided. Further, the foaming agent of the present invention can form a closed cell in which the nitrogen gas generated at the time of foaming is uniformly distributed in the resin, and the expansion ratio is large and evenly dispersed.

The blowing agent according to the present invention can be produced by a variety of conventional organic synthesis methods. Specifically, as shown in the following examples, a biuret compound and an amine group-containing compound (for example, methylamine, ethylamine (E.g., butylamine, cyclohexylamine, etc.) and reacting the reacted compound under the conditions of hydrogen peroxide (H ₂ O ₂ ) and sulfuric acid (H ₂ SO ₄ ) Ethyl chloroformate, etc.) and hydrazine hydrate, evaporating the organic solvent using methyl chloride under sodium bicarbonate, and then reacting with an alkylamine solution, or preparing ammonium thiocyanate (NH ₄ SCN) With hydrazine hydrate and reacting the reacted compound under conditions of hydrogen peroxide (H ₂ O ₂ ) and sulfuric acid (H ₂ SO ₄ ). Also, a method of reacting sodium isocyanurate in the presence of an acid (for example, acetic acid, etc.) after reacting an alkylcarboxylate (for example, dimethylcarboxylate) with hydrazine hydrate in a nitrogen atmosphere It is possible. For example, it can be prepared by the following Reaction Schemes 2 to 6.

[Reaction Scheme 2]

[Reaction Scheme 3]

[Reaction Scheme 4]

[Reaction Scheme 5]

[Reaction Scheme 6]

The method for foaming a resin according to the present invention includes a step of mixing and heating the foaming agent of the present invention with a resin to be foamed. The foaming agent may be mixed with the resin to be foamed by a conventional resin mixing means such as a stirrer or a press roll. The heating may be carried out using a conventional resin such as an extruder, a press mold or a hot air circulating oven Heating means can be used. The operation conditions of the resin mixing means and the resin heating means can be appropriately operated according to the kind of the resin to be foamed, the type of the foaming agent, the kind of the additive, and the state. Typical operating conditions include the use of the foaming agent in the form of powder And master batch (master batch means that the foaming agent is concentrated and dispersed in the resin at a high concentration, for example, 10 to 55% by weight) The masterbatch may be prepared by mixing in a resin mixing means having a temperature of 90 to 120 캜 for 10 to 30 minutes and heating in a resin heating means having a temperature of 90 to 250 캜. The foamable resin and the foaming agent (in the form of a powder or a master batch) are mixed in a resin mixing means having a temperature of 25 to 120 DEG C for 1 to 30 minutes and heated at 150 to 250 DEG C (specifically, 170 to 230 DEG C ) And a resin heating means having a pressure of 100 to 160 kg / cm ² (specifically, 100 to 150 kg / cm ² ) for 20 seconds to 30 minutes. The amount of the blowing agent to be used may vary depending on the type of the resin to be foamed, the type of the blowing agent, the desired degree of foaming, etc. For example, the powdered blowing agent may be used in an amount of 1 to 40 parts by weight 1 to 20 parts by weight, more specifically, 1.5 to 10 parts by weight, and more specifically 2 to 6 parts by weight) of the blowing agent in the form of a master batch may be used in an amount of 10 to 100 parts by weight, 80 parts by weight (specifically, 20 to 70 parts by weight, more specifically 30 to 55 parts by weight) may be used.

Examples of the resin to be foamed in which the foaming agent of the present invention is used include polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), polyamide, acetal, styrene butadiene rubber (SBR), an ethylene vinyl acetate copolymer (EVA), an ethylene propylene rubber (EPDM), a thermoplastic elastomer (TPE), a thermoplastic polyurethane (TPU), a thermoplastic rubber Various synthetic or natural resins such as thermoplastic rubber (TPR), ABS resin (acrylonitrile butadiene styrene copolymer), rubber, epoxy resin and acrylic resin may be used. In the foaming step, various additives such as calcium carbonate, zinc oxide, stearic acid, and dicyclohexyl phthalate may be used.

The blowing agent according to the present invention can be applied to engineering plastics such as vehicle seat, tire and roof tec cover, garnish cover device, weather strip, air duct for air conditioner, automobile products such as interior / , Footwear products such as wallpaper, flooring, artificial leather, sneakers and slippers, infant and children's mats, household appliances such as TVs, PCs (personal computers), foam molding products such as sashes, sponges, , Children's products such as toys, synthetic wood, accessory ornaments, and other plastic containers.

Hereinafter, the present invention will be described in more detail by way of examples. The following examples are provided to illustrate the present invention, and the scope of the present invention is not limited by these examples.

Example 1 Preparation of N- methyl-1,2-hydrazine dicarboxy amine

(49.2 gr, 0.474 mol), sodium bromide (NaBr, 0.49 g, 0.005 mol) and distilled water (442.8 gr) were placed in a four-necked flask and cooled to below 5 ° C and stirred. Slowly drop the 12% sodium hypochlorite (NaOCl, 299.8 gr, 0.474 mol) and do not exceed the reactor temperature of 5 ° C. Methylamine-1,2-hydrazinedicarboxamide (41.9 g, yield: 97%) was obtained by pouring methylamine (147.2 g, 4.74 mol) and stirring at 55 ° C for 2 hours. 67.1%).

Example 2 Preparation of N- ethyl-1, 2-hydrazine dicarboxy amine

(49.2 gr, 0.474 mol), sodium bromide (NaBr, 0.49 g, 0.005 mol) and distilled water (442.8 gr) were placed in a four-necked flask and cooled to below 5 ° C and stirred. Slowly drop the 12% sodium hypochlorite (NaOCl, 299.8 gr, 0.474 mol) and do not exceed the reactor temperature of 5 ° C. Ethylamine (305.3 g, 4.74 mol) was poured into the flask and stirred at 55 ° C for 2 hours to obtain N-ethyl-1,2-hydrazinedicarboxamide (47.7 g, 69.1%).

Example 3 Preparation of N- butyl-1,2-hydrazine dicarboxy amine

(Biuret, 492 gr, 0.474 mol) and sodium bromide (NaBr, 0.49 g, 0.005 mol) were added to a four-necked flask and cooled to below 5 캜. Slowly drop the 12% sodium hypochlorite (NaOCl, 299.8 gr, 0.474 mol) and do not exceed the reactor temperature of 5 ° C. Butylamine (N-butyl-1,2-hydrazinedicarboxamide, 49.5 g, yield: 35%) was obtained by pouring butylamine (346.7 gr, 4.74 mol) 60%).

[Example 4] N -Cyclohexyl -1,2- hydrazinecarboxamidine

(Biuret, 492 gr, 0.474 mol) and sodium bromide (NaBr, 0.49 g, 0.005 mol) were added to a four-necked flask and cooled to below 5 캜. Slowly drop the 12% sodium hypochlorite (NaOCl, 299.8 gr, 0.474 mol) and do not exceed the reactor temperature of 5 ° C. Cyclohexylamine-1,2-hydrazinedicarboxamide (50.258 g, 4.74 mol) was added to the reaction mixture at 55 ° C for 2 hours. , Yield: 55%).

[Example 5] Production of foaming agent represented by compound 1a

(N-methyl-1,2-hydrazinedicarboxamide, 20 gr 0.152 mol), distilled water (113.3 gr), catalyst iodo-potassium (KI) and sodium bromide (NaBr) were placed in a four-necked reactor Stirring at room temperature. Dropping the 34% hydrogen peroxide (H ₂ O ₂ , 16.5 gr 0.167 mol) and dropping the 10% sulfuric acid (H ₂ SO ₄ ) solution to pH 3, Lt; / RTI > for 2 hours. The reaction solution was filtered and the filtrate was evaporated in a vacuum oven and washed with water to obtain an orange powder (N-methyl-1,2-azodicarboxamide, yield 9.6 g, 48.5% DT 136占 폚, GV: 124 ml / g).

[Example 6] Production of foaming agent represented by compound 1b

(N-ethyl-1,2-hydrazinedicarboxamide, 20 g 0.137 mol), distilled water (113.3 g), catalyst iodo potassium (KI) and sodium bromide (NaBr) were placed in a four-necked reactor Stirring at room temperature. After dropping 34% hydrogen peroxide (H ₂ O ₂ , 15.0 gr 0.151 mol) and dropping the 10% sulfuric acid (H ₂ SO ₄ ) solution to pH 3, Lt; / RTI > for 4 hours. The reaction solution was filtered, and the filtrate was evaporated in a vacuum oven and washed with water to obtain a yellow powder (N-ethyl-1,2-azodicarboxamide, 13.2 gr yield 67% DT 138占 폚, GV: 124 ml / g).

[Example 7] Production of foaming agent represented by Compound 1c

20 g of 0.114 mol of the compound prepared in Example 3 (N-butyl-1,2-hydrazinedicarboxamide, 20 gr, 0.1 g of distilled water, 0.38 g of potassium iodide (KI) 11.4 mmol, NaBr) was added to a four-neck reactor and stirred at room temperature. Dropping the 34% hydrogen peroxide (H ₂ O ₂ , 22.5 gr 0.299 mol) dropping and dropping the 10% sulfuric acid (H ₂ SO ₄ ) solution to pH 3, Lt; / RTI > for 4 hours. The reaction solution was filtered, and the filtrate was evaporated in a vacuum oven and washed with water to obtain a dark orange powder (N-butyl-1,2-azodicarboxamide, 13.8 g yield 75% DT 156 占 폚, GV: 92 ml / g).

[Example 8] Production of blowing agent represented by 1 g of a compound

(20 g, 0.102 mol), distilled water (200 g), catalyst iodo-potassium (0.34 g, 20.2 mmol, KI), sodium bromide (0.104 g, 10.2 mmol, NaBr) was added to a four-necked reactor and stirred at room temperature. Dropping the 34% hydrogen peroxide (H ₂ O ₂ , 11.06 gr 0.122 mol) dropping and dropping the 10% sulfuric acid (H ₂ SO ₄ ) solution to pH 3, Lt; / RTI > for 4 hours. The reaction solution was filtered and the filtrate was evaporated in a vacuum oven and washed with water to obtain N-cyclohexyl-1,2-azodicarboxamide (17.9 g yield: 91.4% DT 156 占 폚, GV: 128 ml / g).

[Example 9] Synthesis of diethyl -1,2- hydrazine Preparation of dicarboxylate

80 g of hydrazine hydrate (93.75 g, 1.5 mol) and 750 ml of ethanol were placed in a 2 L four-necked reactor and ethyl chloroformate (326 g, 3 mol) was added thereto at 10 ° C. Dropwise. The reaction temperature is sufficiently stirred while maintaining 15 to 20 占 폚. Sodium carbonate (Na ₂ CO ₃ , 159 gr 1.5 mol) is diluted in 750 ml of water and dropped into the reaction solution, and the temperature does not exceed 20 ° C. 200 ml of cold water is poured for 30 minutes, stirred at room temperature for 30 minutes, and dehydrated using a Buchner funnel. After drying for 24 hours, white powdery diethyl 1,2-hydrazine dicarboxylate (212.24 gr, 80.3%) was synthesized.

[Example 10] Diethyl Preparation of azodicarboxylate

In a 2 L reactor, the compound (Diethyl 1,2-hydrazine dicarboxylate, 52.8 g, 0.3 mol) and the catalyst sodium bromide (NaBr, 1.54 g, 15 mmol) prepared in Example 9 were placed in 200 ml of water, Stirring. Then, chlorine gas was introduced for about 1 hour until the powder completely disappeared and became a red liquid phase. The pH was adjusted to 7 by adding 10% sodium bicarbonate and the organic layer was separated by adding methyl chloride (200 ml), and the organic solvent was evaporated in a vacuum oven to obtain a red liquid Of diethyl azodicarboxylate (46.84 g, 89%).

[Example 11] Production of foaming agent represented by compound 1k

(Diethyl azodicarboxylate, 17.4 g, 0.1 mol) and methylene chloride (17.4 g) were added to a 2 L reactor and stirred at 8 to 10 ° C. When 40% methylamine solution (Methyl amine, 23.25 gr, 0.3 mol) is added, an orange powder is formed. (Dimethyl-azodicarboxamide, 8.64 gr, 60%, DT 178 deg. C, 84 ml / g, and the like) at a reaction temperature of 6 to 10 DEG C for about 30 minutes, ).

[Example 12] Production of foaming agent represented by compound 1m

(Diethyl azodicarboxylate, 17.4 g, 0.1 mol) and methylene chloride (17.4 g) were added to a 2 L reactor and stirred at 8 to 10 ° C. When 70% ethylamine solution (Ethyl amine, 19.28 gr, 0.3 mol) is added, orange powder is formed. (Diethyl-azodicarboxamide, 12.24 gr, 72%, DT 182 deg. C, 80 ml / g (1mol)) represented by the orange color was obtained by stirring and stirring at a reaction temperature of 6 to 10 ° C for about 30 minutes. ).

[Example 13] Preparation of foaming agent represented by Compound 1o

(Diethyl azodicarboxylate, 17.4 g, 0.1 mol) and methylene chloride (17.4 g) were added to a 2 L reactor and stirred at 8 to 10 ° C. When cyclohexylamine solution (29.75 gr, 0.3 mol) is added, an orange powder is formed. (Dicyclohexyl-azodicarboxamide, 19.6 gr, 70%, DT 212 ° C, 110 ml / g, and the like) was added to the reaction mixture at a reaction temperature of 6 to 10 ° C for about 30 minutes. ).

[Example 14] Preparation of foaming agent represented by compound 1u

2L reactor was charged with calcium cyanamide (16 g, 0.2 mol), amino-guanidine bicarbonate (27.22 g, 0.2 mol), hydroxyamine (NH ₄ OH, 0.7 g, 0.2 mol) (Ethyl alcohol, 160 ml), and the mixture is stirred at 15 to 20 ° C for 6 hours. Thereafter, a white powder (powder, hydrazo-diguanidine, 15 g, yield 72%) was obtained after filter purification. The prepared compound (Hydrazo-diguanidine, 20 g, 0.192 mol), 113.3 g of distilled water, catalyst iodo potassium (KI) and sodium bromide (NaBr) were put into a four-necked reactor and stirred at room temperature. After dropping 34% hydrogen peroxide (H ₂ O ₂ , 15.0 gr 0.151 mol) and dropping the 10% sulfuric acid (H ₂ SO ₄ ) solution to pH 3, Lt; / RTI > for 4 hours. The reaction solution was filtered, and the filtrate was evaporated in a vacuum oven and washed with water to obtain a foaming agent (azodiguanidine, 13.2 g, 69% DT 125 ° C, GV: 220 ml / g) .

[Example 15] Preparation of carbohydrazide

(255.95 gr 2.145 mol) and 80% hydrazine hydrate (128.75 gr, 2.06 mol) were placed in a four necked round bottom flask and heated at 65 ° C in a nitrogen atmosphere for 2 hours and 30 minutes Stirring. Thereafter, ethanol and residual diethyl carbonate produced during the reaction were removed through a vacuum evaporator to obtain ethyl carbazate. 80% hydrazine hydrate (238.8 gr, 3.82 mol) was added to the ethyl carbazate (211.5 gr, 1.85 mol) obtained in a 2 L four-necked glass flask and reacted at 70 ° C. for 3 hours. Powder is generated. This was filtered and purified with 200 ml of ethanol to obtain carbohydrazide (95.5 g, yield 50%).

[Example 16] Production of carbodicarbazide

(Carbohydrazide, 60 g, 0.67 mol), 400 ml of distilled water and acetic acid (200 ml, 3.35 mol) were placed in a four-necked reactor and stirred at room temperature. Sodium isocyanate (65.33 g, 1 mol) was slowly added to the mixture. When all the mixture was added, the mixture was heated at 55 ° C for 16 hours while stirring to obtain a white powder. The mixture was filtered and purified by distillation in 100 ml of distilled water and dried to obtain carbodisemicarbazide (79 g, yield 90%) as a white solid.

[Example 17] Preparation of foaming agent represented by compound 2a

(Carbodisemicarbazide, 50 gr, 0.284 mol), sodium bromide (NaBr, 102.9 g) and distilled water (25 ml) were placed in a four-necked reactor and chlorine gas was introduced into the reaction solution for about 5 hours Stirring is performed while the temperature does not exceed 20 占 폚. The reaction is performed by filtering about 2 ml of the reaction solution, diluting with methanol until the white solid is not left. The reaction solution is filtered and flowed with ethanol until the reaction solution has a pH of 7, followed by drying. (14.82 g, yield 30%, DT 160 캜, GV 200 ml / g) in the form of powder of an orange color was obtained.

[Experimental Example 1] Evaluation of characteristics of foaming agent

500 mg of each of the foaming agent and the comparative example (azodicarbonamide) prepared in Examples 5 to 8, 11 to 13 and 16 were placed in a test tube together with 10 ml of paraffin oil and decomposed using a pyrolysis apparatus The decomposition temperature and the gas volume generated during the decomposition were measured, and the results are shown in Table 1 and FIG.

Example constitutional formula Decomposition temperature DT (캜) Gas volume GV (ml / g) Comparative Example (ADCA)

204 220 Example 5

136 124 Example 6

138 124 Example 7

156 92 Example 8

156 128 Example 11

178 84 Example 12

182 80 Example 13

212 110 Example 14

125 220 Example 17

160 200

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing decomposition temperatures and gas volume decomposition curves of conventional azodicarbonamide (a) and Example 16 (b). FIG. As shown in FIG. 1 and Table 1, the foaming agent according to the present invention has good foaming performance in comparison with conventional azodicarbonamide, and does not generate harmful gas such as ammonia and formamide, Amide.

[Experimental Example 2] Evaluation of foaming performance

4 phr of the foaming agent prepared in Example 16 and 100 mg of the azodicarbonamide (ADCA) blowing agent as a comparative example were added to 100 g of the PVC sol, which is the foaming resin, and the mixture was stirred at a speed of 3,000 rpm on a mechanical stirrer And mixed for 2 minutes. 100 g of the mixed sol was poured into a coating paper, applied with a 1.1 mm bar-coater, and put into a hot-air circulating oven to prepare a PVC foam. At this time, the temperature of the hot air circulating oven was 210 ° C. and the foaming time was 1 minute and 14 seconds. The results are shown in Table 2 and FIG.

subject Expansion ratio Formamide concentration Comparative Example (ADCA, D300L) 4.8 T 307 ppm Example 16 3.23 T (67.3%) N.D.

2 is a photograph showing a polyvinyl chloride foamed state using Example 16. Fig. As shown in FIG. 2 and Table 2, it can be seen that the foaming agent according to the present invention has a foaming magnification of about 33% lower than that of the conventional azodicarbonamide but does not generate a reproductive toxic substance, formamide.

Claims (8)

A blowing agent represented by the following formula (1) or (2).
[Chemical Formula 1]

(2)

Wherein R ₁ , R ₂ , R ₄ and R ₅ each independently represent hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, which contains or does not contain a hetero atom, an amine group or a combination thereof, R ₃ is hydrogen or a C 1-10 alkyl group, X ₁ and X ₂ are oxygen, sulfur or imine, provided that when X ₁ is oxygen (O), at least one of R ₁ to R ₃ is not hydrogen , R is a single bond or a double bond. The method of claim 1, wherein each of R ₁ , R ₂ , R _4, and R ₅ is independently a branched or linear alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, A cycloalkyl group or cycloalkenyl group having 3 to 10 carbon atoms, a hydroxy group, an aryl group having 4 to 15 carbon atoms, a heterocyclic group having 2 to 15 carbon atoms and containing 1 to 5 hetero atoms, an amine group (-NH ₂ ) An alkylamine or an arylamine group of 1 to 20 carbon atoms. The compound according to claim 1, wherein each of R ₁ and R ₂ is independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkenyl group having 5 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, Group, R ₃ is hydrogen or an alkyl group having 1 to 6 carbon atoms, and X ₁ is an oxygen or sulfur atom. The method of claim 1, wherein R ₄ and R ₅ are selected from the group consisting of an amine group (-NH ₂ ), an alkylamine group having 1 to 20 carbon atoms, a cycloalkylamine group having 5 to 15 carbon atoms, a cycloalkenylamine group having 5 to 10 carbon atoms And an arylamine group having 5 to 15 carbon atoms, X ₂ is oxygen, and R is a single bond or a double bond. The blowing agent of claim 1, wherein the foaming agent represented by the formula (1)

(Compound 1a),

(Compound 1b),

(Compound 1c),

(Compound 1d),

(Compound 1e),

(Compound 1f),

(Compound 1g),

(Compound 1h),

(Compound 1i),

(Compound 1j),

(Compound 1k),

(Compound 11),

(Compound 1m),

(Compound 1n),

(Compound 1o),

(Compound 1p),

(Compound 1q),

(Compound 1r),

(Compound 1s),

(Compound 1t),

(Compound 1u),

(Compound 1v) and

(Compound 1w), < / RTI >
The foaming agent represented by the general formula (2)

(Compound 2a),

(Compound 2b)

(Compound 2c),

(Compound 2d),

(Compound 2e),

(Compound 2f),

(Compound 2g) and

(Compound 2h). ≪ / RTI > 100 parts by weight of a resin; And
A master batch comprising 10 to 80 parts by weight of a blowing agent represented by the following formula (1) or (2).
[Chemical Formula 1]

(2)

Wherein R ₁ , R ₂ , R ₄ and R ₅ each independently represent hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, which contains or does not contain a hetero atom, an amine group or a combination thereof, R ₃ is hydrogen or a C 1-10 alkyl group, X ₁ and X ₂ are oxygen, sulfur or imine, provided that when X ₁ is oxygen (O), at least one of R ₁ to R ₃ is not hydrogen , R is a single bond or a double bond. The method of claim 6, wherein the resin is selected from the group consisting of polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), polyamide, acetal, styrene butadiene rubber From the group consisting of ethylene-vinyl acetate copolymer (EVA), ethylene propylene rubber (EPDM), thermoplastic elastomer (TPE), thermoplastic polyurethane (TPU), thermoplastic rubber (TPR), ABS resin, rubber, epoxy resin and acrylic resin The master batch, which is selected. A foamed foamed article using the foaming agent represented by the following formula (1) or (2).
[Chemical Formula 1]

(2)

Wherein R ₁ , R ₂ , R ₄ and R ₅ each independently represent hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, which contains or does not contain a hetero atom, an amine group or a combination thereof, R ₃ is hydrogen or a C 1-10 alkyl group, X ₁ and X ₂ are oxygen, sulfur or imine, provided that when X ₁ is oxygen (O), at least one of R ₁ to R ₃ is not hydrogen , R is a single bond or a double bond.

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