KR100613887B1 - Manufacturing method for the composites of phenol resin foam - Google Patents

Abstract

The present invention relates to a method for producing a flame-retardant phenolic resin foam, and more particularly, to a resol-type phenolic resin in which a formaldehyde is removed from a phenol molecule with an aqueous ammonia solution, to which a weakly acidic curing agent is added, and to which water is generated by adding an isocyanate compound. And foaming by using CO ₂ as a blowing agent, the ozone layer destruction caused by the use of a blowing agent such as CFC (chlorofluorocarbon) or hydrocarbons, and flame retardants such as phosphorus and halogens used in the production of conventional phenol resin foams, toxicity during combustion The present invention provides a method for producing a high quality flame retardant phenolic resin foam which improves environmental problems such as gas generation, forms a uniform closed cell, and improves flame retardancy, heat insulation, low smoke resistance, water resistance, and mechanical properties.

Formaldehyde, Phenolic Resin, Resol Type Phenolic Resin, Flame Retardant

Description

Manufacturing method for the composites of phenol resin foam

1 is a graph comparing the thermal characteristics of various insulating materials.

The present invention relates to a method for producing a flame-retardant phenolic resin foam, and more particularly, to a resol-type phenolic resin in which a formaldehyde is removed from a phenol molecule with an aqueous ammonia solution, to which a weakly acidic curing agent is added, and to which water is generated by adding an isocyanate compound. And foaming by using CO ₂ as a blowing agent, the ozone layer destruction caused by the use of a blowing agent such as CFC (chlorofluorocarbon) or hydrocarbons, and flame retardants such as phosphorus and halogens used in the production of conventional phenol resin foams, toxicity during combustion The present invention provides a method for producing a high quality flame retardant phenolic resin foam which improves environmental problems such as gas generation, forms a uniform closed cell, and improves flame retardancy, heat insulation, low smoke resistance, water resistance, and mechanical properties.

Styrofoam, urethane foam, glass fiber and epoxy resin insulators are mostly used as the heat insulator using foams, and the base material of the above heat insulator is made of thermoplastic resin, which is weak against heat, and thus is vulnerable to fire. As styrofoam and urethane foam insulation used as building materials and molding materials of various structures are made of combustible materials, fires are frequently generated both domestically and internationally. In order to solve the problem, it is necessary to use special materials that are flame retardant. However, there is almost no production of thermal insulation materials that are environmentally friendly and flame retardant. In addition, although glass fiber and asbestos insulation materials have been developed, they are not widely used because they are not only carcinogens but also have high production prices.

The phenolic resin foam among the insulation materials is particularly applied in various industrial applications, such as building materials of various interior and exterior materials for building construction or industrial insulation materials because it has flame retardancy, heat resistance, low smoke resistance, dimensional stability, excellent workability and high insulation properties among various organic resin foams .

Such a conventional phenol resin foam is obtained by adding a foaming agent, a plasticizer, a foaming agent, a surfactant, a curing agent, a flame retardant, and the like to a phenol resin of a predetermined ratio.

As the blowing agent, relatively high boiling point CFC-based or HCFC-based halogenated hydrocarbon-based blowing agents such as 1,1,2-trichloro-1,2,2-trifluoroethane and dichlorodifluoromethane were used. There are serious environmental problems that destroy the ozone layer, and their use is regulated. On the other hand, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, 1,1,1,2, of HCs or HFCs having almost zero global warming destruction coefficient and almost no destruction of ozone layer. Although 2-pentafluoro ethane and the like have been attracting attention, they have a disadvantage in that the pressure at the time of foaming increases due to the low boiling point, and the bubble wall of the foam is broken or the bubble diameter is increased, which lowers the thermal insulation effect, and also the thermal conductivity of the foaming agent itself. There is a problem that it is difficult to obtain a phenol foam having a good thermal insulation performance because of a high.

Flame retardants such as halogen-based, phosphorus-based and antimony trioxide are added alone or in combination to impart flame retardancy to the foam. Toxic gases such as hydrogen halide and antimony halide are known to be generated during combustion. For this reason, the use of blowing agents for halogen-based refrigerants and flame retardants such as halogen-based, phosphorus-based and antimony trioxide have been strengthened, and efforts to develop alternative materials have been spreading. That is, since the materials added to give a function to the foam generates a variety of problems, efforts have been made to solve the problem through the study of alternative materials or various experiments, especially the flame retardancy to the foam without the addition of a flame retardant Grant research needs to be carried out.

Known techniques according to the above conducting research include the following.

Japanese Patent Application Laid-Open No. 53-13669 proposes a technique for minimizing the amount of water in a resol-type phenolic resin or foaming using a high molecular weight phenolic resin to improve the strength of the bubble wall upon foaming and obtaining an independent foamed foam. However, the high-viscosity phenolic resin has a disadvantage in that it is difficult to handle and the foaming is weak at the time of foaming, so it is expensive in terms of economy.

According to Japanese Patent Application Laid-Open No. 3-106947, liquefied carbon dioxide is used as a hydrocarbon blowing agent known to have almost no global ozone depletion coefficient in place of the blowing agent of halogens or derivatives thereof, and Japanese Patent Laid-Open No. 4-239040 decomposes barium carbonate. It is proposed to use carbon dioxide gas generated as a blowing agent, and Japanese Patent Laid-Open No. 3-169621 proposes a technique of using CFC-113, liquefied carbon dioxide, and carbonate in combination.

However, the above blowing agents of hydrocarbons have a high thermal conductivity of the gas itself, but have a very low boiling point, and have a good thermal insulation performance because the independent foam ratio is lowered and the diameter of the bubbles is larger than that of the foams obtained from the halogen hydrocarbon blowing agents. It is difficult to obtain, and also has a weak mechanical strength such as brittleness, there is a problem that it is difficult to produce a foam that satisfies various physical properties.

Japanese Patent Application Laid-Open No. 4-503829 proposes a method for producing a phenolic foam having good thermal insulation by adding perfluorocarbon to a hydrocarbon blowing agent, pentane. There is a problem in that a fine hole is formed in the base wall, and the thermal conductivity decreases as the blowing agent is gradually replaced with air through the minute hole. In addition, the perfluorocarbon used as the blowing agent is very expensive, and thus there is a problem in that the manufacturing cost is high. .

Japanese Patent Laid-Open No. 3-179401 uses a very strong acid as a curing agent when foaming a phenolic resin. In other words, inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, and organic acids such as phenolsulfonic acid and benzenesulfonic acid are used as essential components. Such strong acids remain in the foam and have a strong corrosive problem when used in building and industrial insulation materials or materials. The disadvantage is that the field of application is limited.

According to US Pat. No. 443,3120, there is proposed a method of performing foam curing at a high temperature of 50 ° C. or higher when preparing a phenolic foam. In this case, when foaming is performed at room temperature, curing is slow and strength is lowered. In addition, it is difficult to maintain the high temperature curing temperature conditions in the field when providing the foam thus prepared for construction or industrial use.

As described above, in the production of foams of phenolic resins, environmental problems occur in the conventional methods, and foaming methods using CFCs, HCFCs, HFCs, etc., which are regulated materials for use, and curing methods by adding strong acid when the foaming agent is cured. Various problems such as the maintenance of the mechanical strength of the foam have emerged.

Accordingly, the necessity of a study for preparing a foam of phenol resin which can improve the above problems is highlighted.

Accordingly, the inventors of the present invention have made efforts to meet the above necessity. As a result, by adding a weakly acidic curing agent to a resol-type phenolic resin and stirring it at high speed, by applying an isocyanate compound to water and CO ₂ as a blowing agent, In addition, the use of a separate blowing agent or flame retardant can be excluded, and also by making the entire process of foam production at room temperature, it was found that the state of curing at a high temperature can be maintained to complete the present invention.

Therefore, the present invention applies water and CO ₂ generated during foam production due to the addition of isocyanate compounds as a blowing agent, instead of using a blowing agent that causes the problem of destruction of the earth ozone layer in the production of phenolic resin foam, resol type phenolic resin The purpose of the present invention is to provide a phenolic resin foam and a method for producing the same, which are environmentally friendly and clean without adding a flame retardant.

In addition, the present invention is a phenolic resin foam having excellent thermal stability, economical and does not generate harmful substances when pyrolysis of waste when using the phenolic resin foam prepared at high temperature due to the entire process of manufacturing the phenolic resin foam at room temperature and Its purpose is to provide a method for its manufacture.

The present invention is 100 parts by weight of the resol-type phenol resin; 10 to 80 parts by weight of isocyanate compound; 5-15 weight part of weakly acidic hardening | curing agents; And 40 to 80 parts by weight of a siloxane foam stabilizer, a nonionic surfactant, or a mixture thereof.

In another aspect, the present invention (a) adding 2 to 10 parts by weight of an aqueous ammonia solution to 100 parts by weight of the resol-type phenolic resin; (b) adding 40 to 80 parts by weight of a siloxane foam stabilizer, a nonionic surfactant or a mixture thereof and stirring the step (a); (c) adding 5 to 15 parts by weight of a weakly acidic curing agent to step (b) to cure at room temperature; And (d) adding a 40 to 80 parts by weight of isocyanate compound to step (c), followed by stirring, followed by foaming.

Hereinafter, the present invention will be described in detail.

In the present invention, a weakly acidic curing agent is added to a resol-type phenolic resin from which formaldehyde has been removed from the phenol molecule with an aqueous ammonia solution, and then cured by adding an isocyanate compound to foam using water and CO ₂ as a blowing agent. The invention excludes the use of flame retardants. According to the present invention, ozone layer destruction caused by the use of flame retardants such as phosphorus and halogen-based flame retardants such as CFC (chlorofluorocarbon) or hydrocarbons used in the production of conventional phenol resin foams, and toxicity upon combustion It is possible to produce high-quality flame-retardant phenolic resin foams that improve environmental problems such as gas generation, form uniform closed cells, and improve flame retardancy, heat insulation, low smoke, water resistance, and mechanical properties.

In general, phenolic resin foam is added to the phenolic resin by pouring a hard acid, hardening agent, surfactant, foaming agent, foaming agent, flame retardant, etc. into the phenolic resin, or by pouring the foam obtained by the high-speed stirring mixing method, high pressure impact mixing method directly into the mold or under pressure It prepares by making it flow-in-curing, foaming on conditions of 90-120 degreeC high temperature, and making it flow.

The use of a foaming agent and a flame retardant separate from the conventional manufacturing method of the above-described phenol resin foam foam, and consists of a composition for curing and foaming at room temperature using a weakly acidic curing agent.

The flame-retardant phenolic resin foam foam composition of the present invention and its manufacturing method will be described in detail for each manufacturing step.

First, step (a) is performed by adding an aqueous ammonia solution to the resol-type phenolic resin.

Even if a small amount of unreacted formaldehyde is contained, the resol type phenol resin used in the present invention can be used by introducing a pretreatment step. Prior to preparing the phenol resin foam, an aqueous ammonia solution is added and stirred to neutralize the unreacted formaldehyde remaining in the resol type phenol resin. The aqueous solution of ammonia (1 to 10% concentration) is used in an amount of 2 to 10 parts by weight, preferably 4 to 6 parts by weight, based on 100 parts by weight of the resol-type phenolic resin. Since there is no smell, it is easy to handle the foam and advantageous to improve working conditions.

Secondly, in step (a), a siloxane foam stabilizer, a nonionic surfactant, or a mixture thereof is added and stirred to the ammonia-treated resol type phenol resin.

A nonionic interface is used for the purpose of adjusting the bubble size and the flexibility of the foam by using a siloxane foam stabilizer for the purpose of uniformly controlling the bubble size, excellent thermal insulation, foam stabilization and uniform distribution of the foam when foaming a phenolic resin. Activators are used. The siloxane foam stabilizer and the nonionic surfactant can be used alone or in combination. The siloxane foam stabilizer can be used that contains a large amount of silicon groups or hydroxyl groups in the form of a silicon-based polymer, and specifically, for example, siloxane, silicone oil, silicone resin, or the like can be used. Alternatively, as the nonionic surfactant, ethylene adipate, ethylene glycol, adipic acid and phthalic acid may be used as main components, and commercially available products include MX-8651 (Gangnam Chemical), B-8469, B-8462, L-5420 (manufactured by Witco, Goldschmidt, etc.) may be used.

Such siloxane foam stabilizers, nonionic surfactants or mixtures thereof are 40 to 80 parts by weight with respect to 100 parts by weight of the phenolic resin, and when the amount is less than the above range, the physical properties of the foam are removed. Affects. In particular, when the siloxane foam stabilizer and a nonionic surfactant are used in combination, it is preferable to use the mixing ratio in a weight ratio of 1: 1 to 10.

Third, (c) step of curing at room temperature by adding a weakly acidic curing agent to the step (b).

In the present invention, unlike the strong acid curing agent used in the manufacture of foam in general, the curing reaction occurs by high-speed stirring using a weak acid curing agent.

As the weakly acidic curing agent, it may be used to dissociate in water and have a weak acidity of about pH 3 to 6, and specifically, for example, one selected from paratoluenesulfonic acid, phenolsulfonic acid and benzoic acid may be used. It is more preferable if it is added in a solid state and stirred at high speed. These acid hardeners help the phenolic resin foam to maintain the desired foaming rate and to cure, improve the appearance of the product and maintain the mechanical strength, wherein the weakly acidic curing agent is 5 to 100 parts by weight of phenolic resin. If the amount is less than 5 parts by weight, the curing and foaming of the foam is not sufficient, if the amount is more than 15 parts by weight, the foaming rate is too fast, it is difficult to control the foam and obtain a good foam in appearance none.

The curing is carried out at room temperature, the room temperature may vary depending on the season and place where the reaction is carried out, it is carried out in the range of about 15 ~ 30 ℃.

Fourth, (d) step of adding a isocyanate compound to the step (c), stirring and foaming.

In general, a foaming agent is used to facilitate foaming of the phenol resin, but the present invention is characterized by not using a separate blowing agent. In the present invention, an isocyanate compound is added so that sufficient foaming effect can be obtained without using a blowing agent.

That is, when the foam is prepared when the isocyanate compound is added to the step (c) and then stirred, heat is generated, which is to be foamed by the generated water and CO ₂ . All reactions of the present invention are carried out in a range of room temperature, and each step is stirred for 2 to 80 minutes, preferably 30 to 50 minutes at a high speed of at least 1500 rpm, preferably 500 to 3000 rpm. Once all mixing is complete, the foam mixture is poured into the mold and foamed.

As the isocyanate compound, aliphatic isocyanate, aromatic isocyanate, etc. may be used, and specifically, diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate, MDI), toluene diisocyanate (2,4-toluene diisocyanate, TDI) and hexa Methylene diisocyanate (HDI) and the like can be selected or used alone or in combination. The amount of the isocyanate compound is 40 to 80 parts by weight based on 100 parts by weight of the phenolic resin. If the amount is less than 40 parts by weight, bubbles do not easily occur during foaming and do not cure uniformly. If the amount exceeds 80 parts by weight, bubbles are suddenly generated, making it difficult to balance the foaming pressure in the bubble with a uniform distribution of the bubbles and breaking the walls of the bubble. Thus, the thermal conductivity of the foam is increased, which lowers the thermal insulation effect.

On the other hand, the foam has been used by adding a flame retardant in order to have the function of heat insulation and low smoke, but the amount of addition of the flame retardant is increasing since the improvement of the fire protection performance is required by the revision of the fire prevention standard. The flame retardant is not limited to the use of organic flame retardants or inorganic flame retardants, but the use of inorganic flame retardants rather than organic, because there is a problem that toxic gases are generated when burning. Such inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, gypsum, talc, clay and the like, which are solid and used in powder form. After the inorganic flame retardant is added to the phenol resin, sedimentation and aggregation may occur as time passes.

However, in the present invention, since the foamed by using a resol-type phenolic resin having a flame retardant already, since the flame retardancy of the foam is expressed even without adding a flame retardant, it can be said to be excellent in terms of environment, production process, and production cost.

As described above, the phenol resin foam prepared in the present invention has a density of 0.030 to 0.035 g / cm 3 and a thermal conductivity of 0.020 to 0.025 Kcal / m.h. The appearance of the foam is dark yellow and each cell is foamed without a hole in the wall in a closed cell state.

When foam is foamed, the bubble size and distribution are constant, which means that it is excellent in heat insulation and low smokeability, and it is a good foam when the ratio of each bubble in the foam is independently present without pores (independent bubble ratio) is 70% or more. .

The size of the foam of the foam is usually suitable 50.0 ~ 160.0 ㎛, the foam of the phenol resin foam prepared in the present invention falls in the size range of 50.0 ~ 100.0 ㎛.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

Example 1

 50 g of flame-retardant resol type phenol resin was added 1.0-3.0 g of aqueous ammonia solution at a concentration of 1%, and neutralized formaldehyde completely.10 g of foam stabilizer MX-8651 and 20 g of surfactant B-8462 were added to the neutralized phenol resin. Stirred at rpm for 10 minutes at high speed.

Here, 3.0 g of paratoluenesulfonic acid was added in a solid state, mixed, 30.0 g of MDI was added thereto, and high speed stirring was performed at 2500 rpm for 10 minutes to slowly start foaming. The foam was prepared at room temperature (25 ° C.). The entire reaction was performed at room temperature.

Examples 2-6

Next, foams were prepared by mixing the components shown in Table 1 and the same order as in Example 1 above.

division Ingredient (unit: g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Phenolic Resin ¹⁾ 50 50 50 50 50 20 Foam stabilizer ²⁾ 10 10 10 10 10 10 Surfactants B-8462 ³⁾ 20 - 20 - 20 - B-8469 ⁴⁾ - 20 - 20 - 20 Curing agent ⁵⁾ 3 3 3 3 3 3 Isocyanate MDI ⁶⁾ 30 30 15 15 - - TDI ⁷⁾ - - 15 15 30 30 1) Obtained by treatment with ammonia water in resol type phenolic resin. 2) MX-8651, main component polyol, manufacturer Gangnam Hwaseong. 3), 4) Principal ingredient-silicon, manufacturer Goldschmidt. 5) Solid paratoluenesulfonic acid 6) 4,4'-diphenylmethane diisocyanate 7) 2,4-toluene diisocyanate

Experimental Example 1: Comparison of thermal properties (volatility, combustion temperature)

The phenol resin composition before foaming of Examples 1 and 2, the phenol resin foams prepared in Examples 1 and 2, styrofoam and urethane foams, which are conventionally commercialized foams, were used for one hour at a temperature ranging from 100 ° C to 700 ° C. After firing, the results of analyzing the volatilities are shown in Table 2 below.

Temperature (1 hour, ℃) Volatility of the Foam (% by weight) Styrofoam Urethane Foam Pre-foaming resin composition Examples 1-2 100 1.8 1.4 14.8 13.6 150 2.6 7.9 29.6 22.5 200 7.9 16.4 32.0 25.4 250 55.2 29.6 35.8 33.2 300 97.4 71.8 38.6 34.9 400 100.0 96.6 46.9 59.6 500 - 100.0 62.6 71.7 600 - - 66.6 78.1 700 - - 69.8 80.6 700 (3 hours) - - 70.9 88.9

As shown in Table 2, the styrofoam and urethane foam were 100% volatilized at 400 ℃ and 500 ℃. However, the phenol resin foams prepared in Examples 1 to 2 of the present invention showed 80% volatilization even at 700 ° C.

According to the volatilization tendency according to temperature (100-700 ° C.), styrofoam rapidly increased at 250 ° C. and urethane foam rapidly increased at 300 ° C., whereas the phenol resin foams prepared in Examples 1 to 2 of the present invention As the temperature rose to 100 to 700 ° C, the volatilization gradually increased. This demonstrates that the phenolic resin foam prepared in the present invention is heat stable and excellent in heat resistance.

The volatilities after calcining the resol type phenolic resin and the phenolic resin foam of Example 1 for 3 hours at 700 ° C. respectively before foaming were 70.9% and 88.95%, respectively. The amount of the resol type phenol resin in the phenol resin foam is less than 50% by weight in the total composition, even if all of the highly volatile additives in the foam volatilized, the heat resistance of the prepared phenol foam is very excellent.

On the other hand, the existing foamed styrofoam is a shrinkage of the foam is generated at 100 ℃ or less, the urethane foam is a shrinkage (foam) foam (form) at 140 ~ 200 ℃ occurs. Thus, when the foam shrinks and hardens, heat insulation, which is a characteristic of the foam, is lost. Therefore, when the foam is used as a heat insulating material, the effect is lowered.

On the other hand, the phenolic resin foam of the present invention starts discoloration at 200 ℃ or more, and since the curing of the foam starts at a higher temperature, it can be seen that the form is not cured by heat to the highest temperature as compared to other foams to maintain the form have.

Therefore, the phenolic resin foam of the present invention has high heat resistance and is suitable for use as a heat insulating material because the temperature of its use range is very wide from high temperature to cryogenic temperature.

As shown in Table 2, as a result of analyzing the heat resistance and thermal properties of the resol-type phenolic resin foam prepared in the present invention, both show the physical properties satisfying suitable conditions.

Experimental Example 2 Analysis of Foaming Degree and Physical Properties

As in Examples 1 to 6, when the foaming additives for the phenolic resin were changed, the foaming degree and the physical properties of the foams were analyzed in the following manner.

1) Foaming degree: volume measurement (cm 3 / g)

2) Reduced thermogravimetric weight: using TGA analyzer held in our laboratory

3) Thermal Conductivity: Analyzed by the thermal conductivity measuring instrument held in our laboratory

division Example Styrofoam Urethane Foam Glass wool Rock wool One 2 3 4 5 6 Foaming degree (cm 3 / g) 32 32 29 28 26 24 32 25 0.2 0.3 Thermogravimetric reduction (600 ℃, wt.%) 35 35 40 40 45 45 100 100 35 30 Thermal Conductivity (Kcal / m.h. ℃) 0.028 0.027 0.025 0.025 0.023 0.021 0.032 0.020 0.033 0.053

First, CO ₂ and water, which act as a blowing agent, were formed among the foaming additives, and compared with varying amounts and compositions of MDI and TDI serving as crosslinking agents.

Examples 1 and 2 were mixed with 30 g of MDI alone, Examples 3 and 4 were mixed with 15 g of MDI and 15 g of TDI, and Examples 5 and 6 were foamed with only 30 g of TDI.

TGA analysis from 0 to 600 ° C for the measurement of the thermal weight loss of the foam showed that the foam with MDI as the foaming additive had the lowest thermal weight reduction, and the higher the MDI mixing ratio than the foam with only TDI, the lower the thermal weight. Was less. In the heat resistance of the foam, it can be said that the foam of the foamed mixture containing MDI is the most excellent in heat resistance.

In addition, in order to determine the effect of the surfactant in the foaming additive of the foam in Examples 1 and 2 and added to the foam and the same MDI 30g while changing the surfactants B-8462 and B-8469, respectively. In Examples 3 and 4, 15 g of MDI and 15 g of TDI were mixed and the effects of B-8462 and B-8469 were compared. In Examples 5 and 6, 30 g of TDI was added to B-8462 and B-8469. Foamed.

TGA thermal analysis of the foam showed that the foam with surfactant B-8462 had less thermal weight loss than the foam with B-8469. This is more thermally stable than foams with B-8462 foamed with B-8469.

 Thermal insulation, which is one of the thermal properties, can be known by thermal conductivity (K-factor) according to the density of the foam. In order to know the thermal properties of the phenol resin foam prepared in the present invention, it is shown in FIG.

 The lower the thermal conductivity, the better the thermal insulation, as shown in Figure 1, the thermal conductivity of the phenolic resin foam prepared according to Examples 5 to 6 of the present invention is represented by 0.021 ~ 0.026Kcal / mh ℃, Styrofoam ( Compared with 0.032 Kcal / mh ° C), rock wool (0.053 Kcal / mh ° C), and glass wool (0.033 Kcal / mh ° C), they show similar or lower thermal conductivity. The urethane foam (0.015 ~ 0.020 Kcal / m.h. ℃) appears to have a lower thermal conductivity than the phenol resin foam, but as shown in Figure 1 shows an unstable thermal conductivity distribution with respect to temperature. On the other hand, the thermal conductivity of the phenol resin foam has a stable distribution, and the thermal conductivity is almost constant.

Therefore, phenolic resin foam having a stable and low thermal conductivity can be said to be easy to use as a heat insulating material or a heat insulating material due to its excellent heat insulating properties.

As described above, the phenol resin foam prepared according to the present invention is foamed by using water and CO ₂ generated during the reaction without using a separate blowing agent, thereby using a blowing agent such as conventional halogen hydrocarbons. There is an environmentally friendly and clean process that can eliminate the environmental problems such as ozone layer destruction caused by.

In addition, it has excellent properties as a molding material such as strength, adhesiveness, heat resistance, and water resistance, and therefore, a resol type phenolic resin having excellent flame retardancy is used among phenol resins used for electronic parts, aircraft parts, building materials, and structural materials. It is possible to exclude the use of additional flame retardants, so that the flame retardant added to impart flame retardancy in the manufacture of existing foams is an eco-friendly production process that solves the problems caused during the manufacturing process or as a product due to the generation of toxic gas during combustion. It is possible to produce a phenolic resin foam having excellent properties such as heat insulation, heat resistance, and heat insulation.

According to the present invention, it is expected to be utilized as an alternative material that can solve problems such as styrofoam and urethane foam insulation which are widely used as existing insulation, and various applications of high-functional phenolic resin foams to industrial and construction materials are expected. .

Claims (5)

delete delete delete (a) adding 2-10 parts by weight of an aqueous ammonia solution to 100 parts by weight of the resol-type phenolic resin, followed by occlusion; (b) adding 40 to 80 parts by weight of a siloxane foam stabilizer, a nonionic surfactant or a mixture thereof and stirring the step (a); (c) adding 5 to 15 parts by weight of a weakly acidic curing agent to step (b) to cure at room temperature; And, (d) adding 40 to 80 parts by weight of an isocyanate compound to step (c), followed by stirring and foaming Flame-retardant phenolic resin foam manufacturing method comprising a. The method of claim 4, wherein the weakly acidic curing agent is added in a solid state.

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