KR20130012489A - Heat insulating board - Google Patents

Abstract

The present invention relates to a thermal insulation insulating material for ships.

Description

Method of manufacturing thermal insulation materials for ships {HEAT INSULATING BOARD}

The present invention relates to a method for producing a thermal insulation insulating material for ships.

Thermal insulation in ships plays an important role in various parts such as protection of life from fire and maintenance of comfort, and other thermal heat dissipation and heat shielding, and its use ranges from pipe cover to cabin panel, Various performances are required depending on the location of use.

Insulation materials used in ships are mostly glass wool such as glass wool, rock wool, etc., and some polyurethane foam insulation materials are used, but most of them are halogen or phosphorus-based flame retardants.

Glass fiber such as glass wool or rock wool is used as a ship insulation material because it is very incombustible to fire, and some used polyurethane foams also have good moldability, good thermal insulation, light weight, and low price. I use it a lot.

Therefore, the present invention is to overcome the shortcomings of the existing material and to develop a new thermal insulation material having a non-combustibility required by the international standard, an insulation construction module using the same, a panel and a fire door that satisfies the high temperature fireproof performance and lightweight sound insulation performance required in shipyards do.

A phenolic resin is reacted with a silane compound to prepare a compound having organic and inorganic properties, and a curing solvent, a foaming solvent, a flame retardant additive, and the like are mixed at a predetermined ratio, and the mixture is coated on a porous inorganic composite through a stirring device to perform heat compression molding. Marine thermal insulation comprising a phenol pearlite material prepared by performing.

According to the present invention, the properties and compounding technology of new non-combustible materials can be utilized as basic data for the development of thermal insulation materials, which are the main materials of the expandable thermal insulation structures applied to fireproof structural walls and penetrations of marine plants, which are currently urgently developed. .

In addition, it is possible to reduce the weight per unit area and maintain high sound insulation compared to the same application thickness, and to secure expression ability to satisfy the design requirements of foreign ship owners such as Europe by various types of modularity.

In domestic and foreign countries, a method of manufacturing non-combustible fireproof panels using inorganic materials (cement, lightweight aggregate, etc.) has been proposed, but there are disadvantages of increasing the load of the structure, reducing the moving performance and reducing the construction effect, and also the inorganic fiber. A technique of combining a flame retardant and a coating material has been proposed, but a product that satisfies the standards of ship design and international standards has not yet appeared.

Preparation of compounds having organic-inorganic properties by phenol resins reacting with silane compounds The next step is to mix a curing solvent, a foaming solvent, a flame retardant additive, etc. in a proportion, and to coat the porous inorganic composite with a stirring device to heat compression molding. Do this.

Molding conditions are 5 ~ 30 minutes by adding a temperature between 150 ~ 180 ℃ molding time and temperature can be adjusted according to the size of the material. At this time, the phenol resin is firmly adhered to the surface of the inorganic material by the blowing agent and forms a foaming cell in the form of a foam.

The finely foamed cell structure on the surface of the particles acts as a factor of maintaining high stability and bonding force by increasing the specific surface area of the adhesive surface while reducing the density of the material.

Synthetic reaction using conventional phenolic resin is limited to quasi-non-combustible, not non-combustible, because non-combustible is difficult to exhibit when the content of the organic material with low heat resistance (non-flammability) occupies more than 20% of the total. The test conditions for ship's materials must withstand more than 30 in an electric furnace at 750 ° C, so it is difficult to satisfy the above conditions with general organic materials.

In addition, halogen-based compounds having excellent flame retardancy act as a cause of defects in smoke density and toxicity test due to toxic gases emitted during combustion.

The silane compounds used in the phenol resins exhibited comparable performance and accounted for less than 1% of the total.

The change of curing catalyst had no significant effect on the incombustibility but only the reaction rate.

In general, the amount of foaming solvents is small and the effect on the nonflammability is very small.

Silane coupling treatment on the surface of the inorganic material to enhance the interfacial adhesion between composite materials such as GFRP and the porous inorganic material where the surface of the inorganic material and the surface of the organic material should be in contact, or the coating of mica pearl or colorant-containing acrylic resin on the surface of the glass bottle A silane coupling agent is used for primers, binders, and the like for strengthening the interfacial adhesion in the case of the above. It is still recognized that the alkoxy silane coupling agent is hydrolyzed to produce silanol, which silanol is dehydrated and condensed with silanol on the glass surface to form and modify the organic layer of the monomolecular layer on the glass surface.

In this study, it was confirmed that ring-opening reaction and reactivity were accelerated when epoxy silane compound was added to phenol monomer, and amino silane compound was introduced to solve the problem of rapid reaction. As a result, the relative reaction rate was stably maintained, and even in the final cured product, a compound having increased binding strength without significant difference with the silane-treated resin cured product was obtained.

One class of silicon hydride: SinH2n + 2. It corresponds to the paraffinic hydrocarbon CnHn + 1. Typical examples include monosilane, disilane, trisilane, tetrasilane, and the like. In 1857 F. Mueller dissolved aluminum containing silicon in hydrochloric acid and proved its production. All spontaneously ignite in the air, but are stable at room temperature if the air is blocked and preserved.

Compared with the corresponding paraffinic hydrocarbons, it is clearly unstable and reacts with water, alkali hydroxide solution, etc., or is susceptible to thermal decomposition. Normally, magnesium silicide (Mg2Si), which is produced by ignition of a mixture of magnesium powder and fine powder of silica, is decomposed into acid to form a mixture with hydrogen. Derivatives are obtained by substituting hydrogen with alkyl groups, halogens, hydroxyl groups and the like, and are very important as a matrix of organosilicon compounds. Extremely toxic.

Monosilane: Formula SiH4. Colorless gas with an unusual odor, melting point -184.7 ° C, boiling point -112 ° C. It spontaneously ignites in air. It reacts with alkaline hydroxide solution to generate hydrogen and alkali alkali. When heated, it decomposes into hydrogen and silicon. It is stable at room temperature.

In this study, the ring-opening reaction occurred and the reactivity was increased when the epoxy-based silane compound was added to the phenol monomer, and in order to solve the problem of rapid reaction, a moderately reactive compound including the amino-based silane compound was tested. Used. As a result, the relative reaction rate was stably maintained, and even in the final cured product, a compound having increased binding strength without significant difference with the silane-treated resin cured product was obtained.

A closer examination of the function of the silane used in this experiment is a part that should be continued in the future. In this experiment, foaming and molding characteristics were measured with a simple test, and thus, a more accurate reaction mechanism is not known.

In the curing process, it can be estimated that the resin proceeds to c-stage when the curing proceeds by heating through a B-stage resin which is not soluble in various solvents. Bonds between aromatic rings are mostly made of -CH2- bonds, although there are some -CH2-0-CH2- bonds. The B-stage stage resin produced from resol is sometimes called resitol and the C-stage stage resin is called resit. Thus, the crosslinking agent is added in the second part of the second step part and the reaction proceeds further.

Formaldehyde may be added, but hexamethylenetetramine or paraformaldehyde is often used in novolak reactions. In these phenolic resins, branches of nitrogen are partially present in the final product.

The reaction mechanism of the resin used in the present development process is that a small amount of formaldehyde

As it continues to exist, most addition reactions are presumed to be driven by condensation reactions.

It is assumed that the siloxane reaction caused by the silane compound acting as an additive occurs incidentally, but a clearer reaction mechanism will be identified through subsequent experiments and IR analysis.

As the use of non-combustible materials has been widely extended to construction, aircraft, ships, etc., the necessity of safety consideration in case of fire continues to increase. In addition, in recent years, development of materials suitable for the environment as well as high flame retardancy is strongly desired, and development of a product having high flame retardancy, low harmfulness and low smoke resistance has emerged as an important task.

  In Europe, where the problem of recycling, together with the dehalogenation of non-combustibles, is increasing, regulations on imported products are being tightened. Such demands in Europe, the major export market of the domestic shipbuilding industry, have a great impact on ship importers and the domestic shipbuilding material industry, a major source of non-combustible materials.

  On the other hand, given that most of the flame retardants consumed in Korea are being imported, it is necessary to induce the technology development of SMEs and to promote the growth of the flame retardant industry by avoiding the dependency on imports of flame retardants through the creation of potential demand. have.

Recently, plastics have been used for construction. As it is widely expanded to automobiles, electrical appliances, aircraft, ships, etc., the necessity of flame retardancy considering safety in the event of a fire continues to increase. Plastics are mostly organic materials composed of carbon, hydrogen, and oxygen, and are easily burned. Therefore, materials added to prevent physical burns by improving physical and chemical properties are called flame retardants. These flame retardants should be well mixed with raw materials and additives, not affect the mechanical properties of the final product, and produce less fumes and toxic gases during combustion.

Halogen flame retardants can be divided into bromine and chlorine, but bromine-based flame retardants are overwhelmingly high. Bromine-based flame retardants have excellent flame retardant effect and are excellent in cost / performance ratio, and are used as main flame retardants such as housing materials for electric and OA devices, ABS resins, PS, PBT, PET, and epoxy resins.

Currently, due to the environmental pressure, the flame retardant properties are very excellent, and bromine flame retardants have not been developed yet, so the demand for brominated flame retardants is in addition to the ongoing research into alternatives at home and abroad. Is increasing year by year. This is because the scope of application is gradually increasing and diversified to furniture, textiles, electronics exterior materials such as TVs, VTRs, computers, etc. in order to secure export markets to the US, Japan, and Europe where the flame retardancy is established.

The flame retardant mechanism of the halogen flame retardant is as follows. The main mechanism is the stabilization of active OH radicals by the radical trapping effect in the gas phase.

There are many types of inorganic flame retardants, but mainly aluminum hydroxide, antimony oxide (trioxide, pentoxide), magnesium hydroxide, zinc stannate, phosphate, guanidine-based, molybdate, and zirconium are mainly included in the inorganic flame retardant. These flame retardants vary in their properties and vary from as much as 50 times the amount of resin to the addition of small amounts, depending on the amount added.

The main products of the inorganic type are aluminum hydroxide and antimony. Aluminum hydroxide is inexpensive and has a high amount of additives.

Aluminum hydroxide is an inorganic flame retardant, accounting for 30% of the total flame retardant. Aluminum hydroxide is a non-toxic (halogen-free), low smoke, corrosion resistance of the processing machine, excellent electrical insulation and low price, it is currently used as a flame retardant filler in the fields of home appliances, automobiles, building materials, wires, cables. Aluminum hydroxide is basically a high endothermic amount of 470 kcal / kg, and suppresses combustion so that the temperature of the polymer is low. On the other hand, the degree of decomposition is 200 ℃ or more, and can be used because it is stable in the molding processing temperature range of the polymer. Flame retardant resins include thermosetting resins such as UPE, phenol, epoxy, melamine and acrylic, as well as PVC, PE, PP, EVA and synthetic rubber, latex, papermaking, and synthetic fibers.

As a flame retardant, antimony trioxide has a large synergistic effect, and therefore is commonly used with halogen flame retardants such as chlorine and bromine. Flame retardants are widely used in various general-purpose synthetic resins such as UPE, phenol, epoxy, polyurethane, PVC, PE, PP, PS, and ABS, and various engineering plastics requiring high flame retardant effect. Not yet applied.

Magnesium hydroxide is used as a raw material and intermediate of various magnesium oxides, and the flame retardant effect per compounding amount is known to be superior to that of aluminum hydroxide. In particular, when used in combination with carbon black and the like, it is known that the flame retardant effect is significantly improved. Magnesium hydroxide is also used in polyolefin, nylon, PVC, and some synthetic rubbers. Since the price is low and it has characteristics such as suppressing toxic gas and smoke generation, stable demand is expected in the future.

Phosphorus-based flame retardants can be roughly divided into inorganic and organic.

As an inorganic type, ammonium phosphate, ammonium polyphosphate, etc. which are largely used are used. Red is a flame retardant effect that prevents decomposition in the condensed phase and increases the carbonization rate. It is mainly used for nylon epoxy resin. Ammonium phosphate is used in cellulose, textiles, paper, wood, and the like, and ammonium polyphosphate is used in addition to polyene, ethylene-vinyl acetate, and urethane elastomers by flame retardation through carbonization.

In the organic type, as shown in Table 2-4, fat, organic additives, and haloalkyl phosphates are used. In this case, the chloroalkyl functional group prevents the flame retardant from evaporating or dissolving in water. Triaryl phosphate among aromatic phosphates was first synthesized 80 years ago and used as a flame retardant of cellulose nitrate or acetate which is combustible, and has been used as a vinyl plastic flame retardant since the mass production of PVC. Its main uses are automotive interiors, wire insulators, conveyor belts, and vinyl foams. Recently, it is used in flexible polyurethane foams with polybromide additives.

The types and characteristics of representative aromatic phosphates are shown in Table 2-5.

The organic phosphorus compound having a hydroxyl group (Table 2-6) has a lot of efforts to develop a flame retardant as the flammability of reinforced urethane foams used in buildings and transportation vehicles has emerged as a great risk, and one of them is a phosphorus having a hydroxyl group. It was developed in the context of introducing a compound, but not many commercialized.

Phosphorus-containing methylol compounds are mainly used in fabrics such as cotton and blends, and are used in industrial clothing, military uniforms, and hospital supplies. It is already commercialized in curtains, bedding, and children's pajamas.

Efforts have been made to make unsaturated phosphorus compounds, ie vinyl or allyl phosphorus compound flame retardants, but not many are commercially available.

As the demand for the development of new flame retardants as halogen-based alternative flame retardants increases, the usage is increasing in Western Europe, along with phosphorus and inorganic compounds. It is less toxic than halogen type and has the characteristics of easy handling. In particular, there is no generation of toxic gases during pyrolysis of melamine-containing soft polyurethane foam products, and less smoke than other flame retardants. EPA reports that melamine has a low risk of toxicity to the environment and no evidence of adverse effects on human health and the environment. Melamine is therefore not included in Title III.313 of SARA, a classification of toxic chemicals.

Representative applications of melamine-based flame retardants include nylon, polyurethane, and the like, and epoxy, polyester, PBT, polypropylene, and the like have been suggested.

In Korea, melamine cyanurate (MC) is used as a flame retardant for some uses of nylon, and in other fields, application experiments have recently been attempted due to lack of information on melamine-based flame retardants.

When 0.76% of carbon steel is gradually cooled at a temperature of about 750 ° C. or higher, a transformation occurs at 650 ° C. to 600 ° C. (this transformation is called A1 transformation), and a pearlite structure appears. When examined under a microscope using a ray of light, pearly luster appears and is called pearlite.

  This alternates layers of α iron (called ferrite) and iron carbide Fe 3 C (called cementite).

As the cooling rate from high temperature increases, the Ar1 point (A1 at the time of cooling) decreases and the pearlite layer becomes fine. In steels with less than 0.76% of carbon, the structure at room temperature becomes perlite and ferrite, and in steels with more than 0.76% of carbon or pearlite and cementite.

Perlite The material, mainly called perlite, is an inorganic material and has a low density, light weight, and therefore, it is resistant to fire and does not generate toxic gas.

Therefore, as an additive to building materials, it also plays a role in making inorganic materials lighter.

It is sprayed on building steel structure to protect steel structure in case of fire and used as fireproof material.

In this experiment, various materials such as vermiculite and foam glass in addition to perlite were reviewed as non-combustible fillers. As a result, perlite was found to be the most favorable perlite material in terms of processability, price, and raw material acquisition process.

The commercial use of foam glass dates back to the 1930s. In the early days, it was specially formulated with pure glass raw materials. Today, more than 98% of the glass is recycled. The basic principle of foam glass is to heat the glass to temperatures between 700 and 900 ° C to generate gas. The gas expands to form a cell structure, thereby forming a porous body. Foam glass is made from molten glass or sintered glass particles. In the latter case, a foaming agent is required and when heated, gas is generated to expand the molten glass.

Since the 1930s, a number of patents have been filed for manufacturing, but only a few have been commercialized.

Accurately describing patents for commercial use is ambiguous and the reality is that you have to rely on information provided by the manufacturer for different recipes.

In the TGA test results, it was confirmed that the loss of 3.2wt% occurred when the temperature was raised to 1000 ° C. The combustion of primary volatile organics occurred near 200 ℃ and the secondary combustion of phenolic compounds developed by our company occurred near around 600 ℃. Thereafter, the combustion of carbides and the oxidative decomposition of aluminum hydroxide contained in the porous foaming agent are estimated to have occurred.

No further reaction or change of organic polymer was observed in the DSC graph. This is believed to be due to the fact that sufficient crosslinking has already occurred during the molding process, and a peak estimated to be heatflow was observed in the graph around 175 ° C, which may take into account that our material is molded in the temperature range of about 150 ~ 180 ° C. When the glass transition temperature of the phenolic compound.

In the case of phenolic foam, when only 5 minutes of the test was performed with a material without a metal surface material, the material penetrated into the flame and was impossible to measure.

In glass wool, the flame did not penetrate longer than phenol foam, but after 15 minutes, the flame penetrated and no further measurement was possible.

The material of the pearlite system was not penetrated even if the material was exposed to the flame for more than 30 minutes, and the temperature on the opposite side of the 50mm material was also maintained at a relatively low temperature due to the thermal insulation performance.

As a result of the above experiment, it was confirmed that the thermal insulation performance at high temperature showed the best result in the pearlite-based product developed by us, and it was also confirmed that the nonflammable performance also passed the A60 standard.

The phenomena seen in the above experiments also showed that the non-combustibility and insulation properties of the materials are affected by the properties of the materials that are not carbonized in the air. It did not appear to be.

Claims (1)

Preparing a compound having organic-inorganic properties by pre-reacting a phenol resin with a silane compound, mixing a curing solvent, a foaming solvent, a flame retardant additive, and the like at a predetermined ratio; Coating the porous inorganic composite material through a stirring device to perform a heat compression molding, marine thermal insulation material manufacturing method.