KR20220149377A - A semi-nonflammable foam containing modified red phosphorus used as insulation - Google Patents

Abstract

The present invention relates to a semi-nonflammable foam used as an insulation material and, more specifically, to a semi-nonflammable foam manufactured by foaming a foam composition comprising: (a) a high-content aromatic base polyester polyol; (b) surface-modified red phosphorus; and (c) polyisocyanate. According to the present invention, it is possible to provide a semi-nonflammable foam and a foam composition used therein, wherein the semi-nonflammable foam has semi-nonflammable performance with only a single material without a surface agent, can maintain a shape of the insulation material by forming a hard char layer on a surface thereof despite being heated at high temperatures like a fire, can prevent fire spreading by blocking oxygen, and can be used as an insulation material suitable for manufacturing a foam through a continuous process due to excellent storage stability of mixed polyol even when a powdery flame retardant is mixed.

Description

{A semi-nonflammable foam containing modified red phosphorus used as insulation}

The present invention relates to a semi-incombustible foam containing modified red phosphorus used as a heat insulator. In particular, it has semi-non-combustible performance with only a single material without a surface agent, and forms a hard char layer on the surface even when heated to a high temperature such as a fire to form a heat insulating material In addition to preventing the spread of fire by blocking oxygen, the mixed polyol has excellent storage stability even when powdered flame retardants are mixed. It relates to non-combustible foams and foam compositions used therein.

The content described below merely provides background information related to the present invention and does not constitute the prior art.

The indoor space is heated in winter, and cooling in the summer using an air conditioner is performed. Since the increase in heating and cooling efficiency of the indoor space can be obtained through heat insulation, insulation construction using various heat insulating materials is being performed.

In particular, a large-scale fire accident recently caused a lot of casualties and property damage. In this case, the so-called 'dry-bit method' was used to construct the exterior walls of the building with insulation, adhesive mortar, and finishing materials without flame retardant or non-flammable performance. This is attributed to the rapid spread of the fire, which in turn caused more damage.

Accordingly, the government has significantly strengthened fire safety standards for building finishing materials by amending the 'Rules on Standards for Evacuation/Fire Protection Structures of Buildings, etc.', and has been in effect since April 2016.

Typical examples of thermal insulation materials used in conventional insulation construction include styrofoam, polyurethane foam, and polyethylene foam. Among them, polyurethane is widely used because it has the best thermal conductivity. However, polyurethane foam, which is widely used as a heat insulator, has many problems in use due to its high flammability in case of fire and the generation of a large amount of toxic gas in the early stage of a fire.

In addition, the government is encouraging the use of single materials that satisfy the requirements of Table 1 by amending the Building Act (revision of March 23, 2021).

Test Methods Test Items before revision after revision cone calorimetric method
(KS F ISO 5660-1) total heat release 8MJ/㎡ or less 8MJ/㎡ or less heat dissipation continuously
Time exceeding 200kw/m3 10sec or less 10sec or less Fire-harmful cracks and holes penetrating the specimen there won't be there won't be thickness shrinkage - 20% or less gas fluency test
(KS F 2271) more than 9 minutes more than 9 minutes Specimen composition Composite material testing possible single material only

However, in the case of conventionally used organic insulation materials, there are problems in that they do not meet the requirements of the revised building law.

Specifically, Korea Patent Registration No. 10-0628669 (September 20, 2006) discloses conventional polyisocyanates, halogenated reactive compounds in conventional polyol compositions, expanded graphite, and phosphate ester compounds in order to make a rigid foam with enhanced flame retardancy. By using a flame retardant, a foam that can withstand the high-temperature heat generated in case of fire to some extent was realized, but the rigid foam made in this way does not satisfy the domestic building law in the harmfulness of the gas generated in the case of a fire due to the use of a halogenated reactive compound. .

In addition, Korea Patent No. 10-1850997 (April 16, 2018) discloses an organic flame retardant (melamine phosphate, etc.), an inorganic phosphorus flame retardant ( Ammonium polyphosphate, etc.) and melamine-based flame retardants (melamine, etc.) were used in 100 to 130 parts by weight in 100 parts by weight of the mixed polyol to achieve semi-incombustible performance, but the viscosity of the mixed polyol was low due to too much flame retardant of the powder. It is difficult to use with the existing equipment, or even if the equipment is replaced, it causes a problem that powder and liquid are separated, making it very difficult to make an actual product.

In addition, Korea Patent No. 10-1967821 (2019. 04. 04) discloses a method for manufacturing a rigid polyurethane foam that is easy to handle, has excellent flame retardancy, and maintains a constant shape when heated. is added as an essential flame retardant, and any one or more of phosphate esters, phosphates, bromine-containing flame retardants, boron-containing flame retardants, antimony flame retardants, and metal hydroxides are added, and a conventional polyisocyanate is mixed thereto to form a rigid polyurethane foam excellent in flame retardancy. How to make is presented. However, this technology also has a problem in that the solid powder and the liquid are separated, so it is not suitable for a system that produces an insulating material in a continuous process.

In addition, Korean Patent No. 10-2156004 (2020.09.09.) discloses a method for manufacturing a rigid polyurethane foam that maintains a constant shape when heated such as in a fire, adding red phosphorus to a conventional mixed polyol as an essential flame retardant, A method of making a rigid polyurethane foam excellent in flame retardancy performance by adding a needle-like inorganic filler having an aspect ratio of about 5 to 50 and mixing a conventional polyisocyanate therein is proposed. However, this technology also has a problem in that the solid powder and the liquid are separated, so it is not suitable for a system that produces an insulating material in a continuous process.

Korean Patent No. 10-0628669 (2006. 09. 20) Republic of Korea Patent Publication No. 10-2008-003968 (2008.01.09.) Korean Patent No. 10-1850997 (April 16, 2018)

The present invention has semi-non-combustible performance with only a single material without a surface agent, forms a hard char layer on the surface even when heated to a high temperature, such as a fire, to maintain the shape of the insulating material, and prevents the spread of fire by blocking oxygen An object of the present invention is to provide a semi-incombustible foam used as an insulator suitable for the production of foam through a continuous process, and a foam composition used therefor, as well as preventing it, and the storage stability of the mixed polyol is excellent even when the powdery flame retardant is mixed.

In order to solve this problem, the present invention

(a) a high content aromatic base polyester polyol;

(b) red phosphorus surface-modified with a flame retardant; and

(c) polyisocyanates

It provides a semi-incombustible foam prepared by foaming a foam composition comprising a.

Specifically, the foam composition

(a) 100 parts by weight of a high content aromatic base polyester polyol;

(b) 5 to 40 parts by weight of red phosphorus surface-modified with a flame retardant; and

(c) a polyisocyanate such that the polyisocyanate index is INDEX 150 to 500;

The foam composition may further include (d) surface-modified expanded graphite.

Preferably, the (a) high content aromatic base polyester polyol contains 15 to 30% by weight of the aromatic structure relative to the molecular weight in the molecular structure.

Preferably, the surface-modified red phosphorus (b) is surface-modified with at least one material selected from the group consisting of melamine, melamine cyanurate, and melamine polyphosphate.

Preferably, the foam has a total heat release of 8MJ/m2 or less according to the cone calorimeter method (KS F ISO 5660-1), and the time for which the heat release continuously exceeds 200kw/m3 is 10sec or less, and a room that penetrates the test body There are no cracks or holes harmful to burns, and the thickness shrinkage is less than 20%.

Also, the present invention

(a) high content aromatic base polyester;

(b) red phosphorus surface-modified with a flame retardant; and

(c) polyisocyanates

It provides a foam composition comprising a.

The foaming agent composition may further include (d) surface-modified expanded graphite.

Preferably, the surface-modified red phosphorus (b) is surface-modified with at least one material selected from the group consisting of melamine, melamine cyanurate, and melamine polyphosphate.

According to the present invention, it has semi-incombustible performance with only a single material without a surface agent, and can maintain the shape of the insulating material by forming a hard char layer on the surface even when heated to a high temperature such as a fire. It is possible to provide a semi-incombustible foam used as a heat insulator suitable for the production of foam through a continuous process and a foam composition used therein because the storage stability of the mixed polyol is excellent even when a powdery flame retardant is mixed.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In the present invention, the isocyanate index means the actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required for reaction of the polyol in the reaction mixture with active hydrogen, multiplied by 100. It can also be written as (Eq of NCO/Eq of active hydrogen) x 100.

Red phosphorus forms a char layer that blocks oxygen on the surface layer and is used as a flame retardant because it has an excellent effect in preventing flame propagation. Production is not easy by causing problems in fields.

The present invention improves the flame retardancy of the foaming agent by modifying the surface of red phosphorus, and at the same time enables a continuous process by avoiding increase in the viscosity of the foam composition, and overcomes the problem of storage stability.

The semi-incombustible foam of the present invention is

(a) a high content aromatic base polyester polyol;

(b) red phosphorus surface-modified with a flame retardant; and

(c) polyisocyanates

It is characterized in that it is prepared by foaming a foam composition comprising a.

Specifically, the foam composition

(a) 100 parts by weight of a high content aromatic base polyester polyol;

(b) 5 to 40 parts by weight of red phosphorus surface-modified with a flame retardant; and

(c) a polyisocyanate such that the polyisocyanate index is INDEX 150 to 500;

Specifically, the step (a) the high content of the aromatic base polyester polyol is S1) preparing an acid containing an aromatic residue; S2) a) 1.1 to 1.8 moles of monoethylene glycol (MEG) or diethylene glycol (DEG) in 1 mole of the acid containing the aromatic acid group; and b) mixing 0.1 to 0.4 moles of PEG (polyethylene glycol) having a molecular weight of 150 to 600; S3) raising the temperature of the mixture of step S2) using an ester reaction catalyst and condensing the mixture until the acid value is 1.5 mgKOH/g or less; can be prepared including. The acid containing (a) the aromatic moiety is not particularly limited, and preferably terephthalic acid (TPA), phthalic anhydride (PA), isophthalic acid (IPA), and tri At least one selected from the group consisting of melittic acid (trimellitic acid: TMA). Preferably, the (a) high content aromatic base polyester polyol contains 15 to 30% by weight of the aromatic structure relative to the molecular weight in the molecular structure. In this case, it has semi-incombustible performance with only a single material without a surface agent, can suppress the amount of toxic gas generated, and has excellent storage stability of the mixed polyol even when powdered flame retardants are mixed, so it is suitable for the production of foam through a continuous process do.

In the present invention, (b) modified red phosphorus is preferably red phosphorus having a particle size of 20 to 250 μm, surface-modified with at least one material selected from the group consisting of melamine, melamine cyanurate, and melamine polyphosphate. it's good In this case, it has semi-incombustible performance with only a single material without a surface agent, forms a hard char layer on the surface even when heated to a high temperature, such as a fire, to maintain the shape of the insulating material, and prevents the spread of fire by blocking oxygen It is suitable for the production of foam through a continuous process because of the excellent storage stability of the mixed polyol even when the powdery flame retardant is mixed as well as string.

In the present invention, the foam composition may further include (d) modified expanded graphite. Preferably, for the surface-modified expanded graphite, expanded graphite having a particle size of 20 to 400 μm is impregnated with a liquid organophosphorus flame retardant and filtered through a sieve may be used. The impregnation time may be arbitrarily adjusted, and specifically may be 1 to 24 hours.

Preferably, the liquid organophosphorus flame retardant TPP (Triphenyl phosphate), TXP (Trixylenyl phosphate), TCP (Tricresyl phosphate), REOFOS (Triisophenyl phosphate), TCEP (TrisChloroethypho sphate), TCPP (TrisChloroprophyl phosphate), TEP (Triethyl phosphate), DMMP (Dimethyl methyl phosphate), TMCPP (Tris (monochloropropyl) Phosphate), and TMP (Trimethyl phosphate) is one selected from the group consisting of. In this case, it has semi-incombustible performance with only a single material without a surface agent, forms a hard char layer on the surface even when heated to a high temperature, such as a fire, to maintain the shape of the insulating material, and prevents the spread of fire by blocking oxygen It is suitable for the production of foam through a continuous process because of the excellent storage stability of the mixed polyol even when the powdery flame retardant is mixed as well as string.

In the present invention, the (c) polyisocyanate is preferably included so that the isocyanate index is 150 to 500. In this case, it has excellent flame retardancy, can significantly reduce the generation of harmful gases in case of fire, has excellent thermal insulation properties, is lightweight and easy to install insulators, is advantageous for thinning, has excellent durability, has excellent strength, and is waterproof at the same time. This excellent flame-retardant foam can be produced.

In addition, the foam composition in the present invention is a trimerization catalyst; urethane catalyst; and blowing agents. As the trimerization catalyst, a known trimerization catalyst may be used, and of course, a commercially available trimerization catalyst may be used. As a specific example, potassium octoate may be used, but is not limited thereto. As the urethane catalyst, a known urethane catalyst may be used, and of course, a commercially available urethane catalyst may be used. As a specific example, tributylamine or pentamethyldiethylenetriamine may be used, but is not limited thereto. It goes without saying that a known foaming agent may be used as the foaming agent, and a commercially available foaming agent may be used. Specific examples may include HCFC-141b, HFC-365mfc/227, HFC-245fa, HFO-1234ze(E), HFO-1234ze(F), HFO-1336mzz(Z), Cyclo-pentane, n-pentane , iso-pentane may also be used, but is not limited thereto.

In addition, in the present invention, the foam composition may further include known additives such as cell stabilizers, flame retardants, chain extenders, epoxy resins, acrylic resins, fillers or pigments, which may be conventionally included in the foaming composition. The additives may each independently be used in an amount known in the art within the range of 0.01 to 40 parts by weight based on 100 parts by weight of the polyester polyol.

In addition, the foam composition is one or more materials selected from the group consisting of graphite, graphene, carbon nanotubes, fullerene, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate, and calcium sulfate, each independently polyester polyol 100 It may be further included in an amount of 0.1 to 20 parts by weight based on parts by weight.

In the present invention, the remaining components other than the (e) polyisocyanate in the foam composition may be premixed first, and then (e) polyisocyanate may be mixed and foamed.

The semi-incombustible foam of the present invention may be prepared by foaming the foam composition, and a conventional foaming method may be applied as the foaming method.

In the semi-incombustible foam according to the present invention, the total heat emission of the foam according to the cone calorimeter method (KS F ISO 5660-1) is 8MJ/m2 or less, and the time that the heat emission continuously exceeds 200kw/m3 is 10sec or less, and the test specimen There are no cracks and holes that are harmful to fire protection, and excellent flame retardant performance with a thickness shrinkage of 20% or less can be satisfied.

Foams of Examples 1 to 5 of the present invention were prepared as shown in Table 2 below, and foams were prepared as in Comparative Examples 1 to 4 as shown in Table 3. The physical properties of the prepared foams were measured and shown in Tables 2 and 3.

- Assessment Methods

- Storage stability of the liquid: After stirring the flame retardant and additives to the mixed poly (polyol, catalyst, foam stabilizer, foaming agent) for about 1 hour using a high-speed stirrer of 2000 RPM or higher, transfer the stirred liquid to a transparent flask, and then put it in a transparent flask for 3 days. It was observed whether the separation of the solid and liquid phases occurred.

- Cone calorimeter method: It was observed using a KS F ISO 5660-1 test device.

Example 1 Example 2 Example 3 Example 4 Example 5 polyol JKC-200 100 100 100 100 100 catalyst
3 3 3 3 3 antifoaming agent DC-193 2 2 2 2 2 blowing agent water 1.5 1.5 1.5 1.5 1.5 physical foaming agent 30 35 40 35 35 flame retardant modified red phosphorus 20 20 20 10 20 Modified Expanded Graphite 20 20 20 20 10 isocyanate P-MDI 141 247 353 247 247 Index 200 350 500 350 350 Liquid storage stability O O O O O Density (kg/m3) 40 42 45 38 39 cone calorimetric method Total heat released (MJ/㎡) 6.9 5.7 6.2 6.7 5.7 Cracks or holes that are harmful to fire O O O O O thickness shrinkage O O O O O Gas toxicity (min) 9'05“ 9'55“ 9'45“ 9'07“ 9'16“

JKC-200: High content TPA-based polyester polyol developed by Daehan Polytech, OHV=200 mgKOH/g

Catalyst: Air product, PC-5, K-15, PC-8 = 1.0/2.0/0.5 weight ratio

Modified red phosphorus: Red phosphorus obtained by surface-modifying red phosphorus having a particle size of 20 to 250 μm with melamine cyanurate.

Expanded graphite: expanded graphite obtained by surface-modifying 20 to 400 μm of expanded graphite with a liquid organophosphorus flame retardant

Physical blowing agent: HFC-245fa

P-MDI: Wanhua's PM-200, NCO%=31.1%

Explanation of symbols: O (no problem), × there is a problem)

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 polyol JKS-200 100 100 JKC-200 100 Ether pool 100 catalyst
3 3 3 3 antifoaming agent DC-193 2 2 2 2 blowing agent water 1.5 1.5 1.5 1.5 physical foaming agent 35 35 35 35 flame retardant modified red phosphorus 20 unmodified red phosphorus 20 20 Modified Expanded Graphite 20 Unmodified expanded graphite 20 isocyanate P-MDI 247 247 247 247 Index 350 350 350 350 Liquid storage stability O × O × Density (kg/m3) 34 40 cone calorimetric method Total heat released (MJ/㎡) 14.2 13.2 Cracks or holes that are harmful to fire × × thickness shrinkage × × Gas toxicity (min) 8'30“ 6'10“

JKC-200: Daehan Polytech Co., Ltd. high content TPA-based polyester polyol, OHV=200 mgKOH/g

JKS-200: Daehan Polytech Co., Ltd. high content PA-based polyester polyol, OHV-200 mgKOH/g

Ether Polyol: Initiator Sugar, polyether polyol reacted with glycerol with propylene oxide, OHV=350mgKOH/g

Catalyst: Air product, PC-5, K-15, PC-8 = 1.0/2.0/0.5 weight ratio

Physical blowing agent: HFC-245fa

P-MDI: PM-200 from Wanhua, NCO%=31.1%

Explanation of symbols: O (no problem), × there is a problem)

As shown in Tables 2 and 3 above, in the case of the semi-nonflammable foam of Example 1 according to the present invention, all of the semi-nonflammable flame retardant properties could be satisfied only with a single foam material, but in the case of the foams of Comparative Examples 1 to 5, a single foam The material alone did not satisfy all of the semi-nonflammable flame retardant properties.

Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improved forms of the present invention are also provided by those skilled in the art using the basic concept of the present invention as defined in the following claims. is within the scope of the right.

Claims (9)

(a) a high content aromatic base polyester polyol;
(b) red phosphorus surface-modified with a flame retardant; and
(c) polyisocyanates
A semi-incombustible foam prepared by foaming a foam composition comprising a. According to claim 1,
(a) 100 parts by weight of a high content aromatic base polyester polyol;
(b) 5 to 40 parts by weight of red phosphorus surface-modified with a flame retardant; and
(c) a semi-incombustible foam comprising a polyisocyanate such that the polyisocyanate index is INDEX 150 to 500. According to claim 1,
(d) Semi-incombustible foam, characterized in that it further comprises a surface-modified expanded graphite. According to claim 1,
The (b) surface-modified red phosphorus is a semi-incombustible foam, characterized in that the surface is modified with at least one material selected from the group consisting of melamine, melamine cyanurate, and melamine polyphosphate. According to claim 1,
The foam has a total heat release of 8MJ/m2 or less according to the cone calorimeter method (KS F ISO 5660-1), and the time when the heat release rate continuously exceeds 200kw/m3 is 10sec or less, and harmful cracks from fire that penetrate the specimen and semi-incombustible foam, characterized in that there is no hole, and the thickness shrinkage is 20% or less. (a) a high content aromatic base polyester polyol;
(b) red phosphorus surface-modified with a flame retardant;
(c) polyisocyanates
A foam composition comprising a. 7. The method of claim 6,
The (a) high content aromatic base polyester polyol has an aromatic structure in the molecular structure of the foam composition, characterized in that it contains 15 to 30% by weight relative to the molecular weight. 7. The method of claim 6,
(d) Semi-incombustible foam, characterized in that it further comprises a surface-modified expanded graphite. 7. The method of claim 6,
The (b) surface-modified red phosphorus is a semi-incombustible foam, characterized in that the surface is modified with at least one material selected from the group consisting of melamine, melamine cyanurate, and melamine polyphosphate.