KR101340061B1 - Spray type flame retardant polyurethane foam and method for producing the same - Google Patents

Abstract

The present invention relates to an on-site flame retardant polyurethane foam which produces a resin premix using aromatic polyester polyol and mannich polyol and makes the resin premix react with polyisocyanate in order to have enhanced flame retardant, and to a method for producing the same. The present invention provides a method for producing an on-site flame retardant polyurethane foam insulator and an on-site flame retardant polyurethane foam insulator which is obtained by polymerizing terephthalic acid, diethylene glycol, and the likes, and uses polyester polyol having 250 mgKOH/g or less of hydroxyl value, the mannich polyol in which phenol or p-nonylphenol with enhanced carbonization film formation, formalin, alkanolamine, ethylene oxide, propylene oxide, and the likes are used as main ingredients, and resin premixes the same using foaming agents, catalysts, organic phosphorus flame retardants, surfactants, and the likes, and mixes with polyisocyanate in a volume ratio of 1:1, and constructs using a high pressure foaming machine.

Description

Field-type flame retardant polyurethane foam and its manufacturing method {Spray type flame retardant polyurethane foam and method for producing the same}

The present invention is to prepare a resin premix using an aromatic polyester polyol and a Mannich polyol, and then react the resin premix with a polyisocyanate, thereby making a field-formable polyurethane foam having improved flame retardancy and its preparation. It is about a method.

More specifically, the present invention is a polyester polyol obtained by polymerizing terephthalic acid and diethylene glycol (DEG) and having a hydroxyl value (OH-Value) of 250 mgKOH / g or less, and forming a carbide film. The excellent phenol or p-nonylphenol, formalin, alkanol amine, ethylene oxide, propylene oxide, and the like are used as the raw material of Manniche polyol, and a blowing agent Pre-mixed resin using a catalyst, organophosphorus flame retardant, foam stabilizer, etc., and then mixed with polyisocyanate in a volume ratio of 1: 1 and constructed using a high pressure foaming machine, excellent flame retardant field construction type polyurethane foam insulation and its preparation It is about a method.

On-site construction type polyurethane foam is used in many places such as refrigerated warehouses, logistics warehouses, and general buildings because of its excellent thermal insulation performance, but it is limited because it is vulnerable to fires such as fire accidents in Sealand, Icheon logistics warehouse, etc.

Existing field spray polyurethane foams are generally pre-prepared resin premixes and polyisocyanates with a mixture of two or three polyether polyols, blowing agents (such as HCFC 141b), catalysts, flame retardants, foam stabilizers, and 1% by weight of water Was mixed at a volume ratio of 1: 1 and sprayed onto the skin's surface (ceiling, wall, etc.) through a mixing gun using a high pressure foaming machine.

Specifically, the raw material of the conventional polyurethane foam is composed of a resin premix (Resin Premix) and polyisocyanate, and their mixing ratio is about 1: 1 by volume ratio. The raw material of the resin premix includes a plurality of polyols such as polyol A, polyol B, polyol C, a blowing agent, two to three catalysts, a flame retardant, a foam stabilizer, and the like.

Polyol A is a polyol having 5 to 6 functional groups made by polymerizing alkylene oxides such as ethylene oxide (EO) and propylene oxide (PO) on sucrose, which is mainly used. The hydroxyl value is 400 to 450 mgKOH / g. Use a lot of phosphorus to increase the strength of the spray polyurethane foam insulation.

Polyol B is a polyol made by polymerizing an alkylene oxide such as ethylene oxide and propylene oxide in an amine base such as toluene diamine and ethylenediamine. The hydroxyl value is about 550 to 650 mgKOH / g in a resin premix of about 30 to 50% by weight. Can be used to produce low thermal conductivity, the thermal performance of polyurethane foams.

Polyol C is a polyester polyol used to reduce the price of the resin premix and is used in the resin premix at about 10-30%. If used a lot, the dimensional stability of the foam made by the field spray has a disadvantage, and the compression or bending strength is lowered.

The blowing agent serves to foam while the foaming agent vaporizes due to the heat of reaction during the polyurethane reaction that occurs when the resin premix and the polyisocyanate are mixed. As the blowing agent, 1.1-dichloro-1-1-fluoro-ethane (trade name 141b) of hydrochlorofluorocarbons (HCFC) having a low boiling point is used as the physical blowing agent, and about 25 to 35% by weight of the resin premix is used. do. In recent years, alternative blowing agents have been studied because 141b type blowing agents have been found to adversely affect global warming and will be banned in the next few years.

Resin catalysts are widely used as the catalyst, for example, N, N, N ', N'-tetramethyl-1,6-hexanediamine (TMHDA), N, N-dimethylcyclohexylamine (DMCHA), N One or more of, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA) is used in combination, and the amount used is 0.3 to 2.0 wt% in the total resin premix.

A foam stabilizer is used to uniformly foam cell size and distribution of foam during foaming. The foam stabilizer is a siloxane-based surfactant as a polyether polydimethylsiloxane copolymer, a polydimethyl copolymer, B-8404, B-8462, Union Carbide's L-5420 and L-5340 are mainly used.

As flame retardant, tris (chloroisopropyl) phosphate and Dai-Hichi CR-530 are mainly used, but there is no significant improvement in flame retardancy.

As described above, 60 to 70 wt% of polyols (A, B, C total), 10 to 25 wt% of blowing agent (HCFC 141b), 1.0 to 3.0 wt% of catalyst, 0.5 to 2.0 wt% of foam stabilizer, flame retardant 10 After preparing a resin premix containing ˜20 wt%, the polyisocyanate (Crude-MDI) containing 31.3 wt% of isocyanate groups was reacted with the resin premix in an equivalent to equivalent ratio, but adjusting the isocyanate index to 1.2 to 1.35. Manufacture polyurethane foam insulation for field spraying. At this time, the isocyanate index is calculated by the following equation, and as the value of the isocyanate index increases, the flame retardancy is excellent.

[Equation 1]

Isocyanate Index = (amount of isocyanate actually used) / (amount of isocyanate theoretically required)

In order to improve the flame retardancy of the polyurethane foam, a lot of efforts have been continued at home and abroad.

According to Japanese Patent Application Laid-Open No. Hei 5-176817 and Japanese Patent Laid-Open Publication No. Hei 5-253402, in order to compensate that the hydroxyl group of the resol-type phenol resin is oxidized and inferior in heat resistance, a method of using a noblock resin and a polyvinylphenol in parallel is devised. However, it is difficult to find the proper concentration of mixed resin and the curing speed of foam is not suitable for the field construction type.

In addition, Japanese Patent Application Laid-open No. Hei 10-204141 attempts to increase the flame retardancy by reducing the halogen flame retardant and adding the methol melamine compound to the phenol resin, but there is a problem with the smell of formaldehyde and environmental wastewater treatment.

An object of the present invention is to contribute to the prevention of a lot of property damage and casualty damage by providing a field construction type polyurethane foam and a method for producing the flame retardant performance is improved.

In order to achieve the above object, the present invention comprises a polyol mixture consisting of aromatic polyester polyols, Mannich polyols and polyester polyols, trimerization catalysts and polyisocyanates, wherein the aromatic polyester polyols are terephthalic acid and dialkylene. Polyols obtained by polymerizing glycols, which have a hydroxyl value of 100 to 160 mgKOH / g, comprising 60 to 75% by weight relative to the polyol mixture, wherein the Mannich polyol is a phenolic compound, formaldehyde, alkanol amine and alkylene A polyol obtained by polymerizing an oxide, having a hydroxyl value of 400 to 500 mgKOH / g, contained in an amount of 15 to 25% by weight based on the polyol mixture, and a polyester polyol in an amount of 5 to 15% by weight, based on the polyol mixture. Wherein the trimerization catalyst is N-hydroxy-alkylquaternery ammonium carbocyre Bit, and the on-site construction-type flame-retardant, characterized in that the isocyanate index is from 1.5 to 2.0, the polyurethane is a foam.

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The field construction type flame retardant polyurethane foam according to the present invention is a field spray type rigid urethane foam having excellent flame retardancy, and can minimize many life and property damages caused by fire occurring in the field by electric leakage, oxygen welding, and the like. .

Hereinafter, the present invention will be described in detail.

Field construction type flame retardant polyurethane foam insulation according to the present invention can be largely described in three ways.

The first feature of the present invention is the use of aromatic polyester polyols using certain raw materials and having certain physical properties. As an aromatic polyester polyol, the polyol obtained by superposing | polymerizing a terephthalic acid and a dialkylene glycol like the following Reaction Formula 1 is preferable. Diethylene glycol, dipropylene glycol, and the like may be used as the dialkylene glycol, and a metal catalyst may be used in the reaction. Unlike the conventional polyol A using sucrose and alkylene oxide, in the present invention, terephthalic acid and By using the aromatic polyester polyol using dialkylene glycol in the resin premix, the flame retardance of a polyurethane foam can be improved.

[Reaction Scheme 1]

It is preferable that the hydroxyl value of the said aromatic polyester polyol is 100-160 mgKOH / g. Unlike conventional polyol A having a relatively high hydroxyl value, in the present invention, by using an aromatic polyester polyol having a relatively low hydroxyl value, physical properties such as flame retardancy of polyurethane foam can be further improved.

The amount of the aromatic polyester polyol is preferably 60 to 80% by weight, more preferably 65 to 75% by weight based on the total weight.

A second feature of the invention is the use of Mannich polyols using certain raw materials and having specific properties. The Mannich polyol is preferably a polyol obtained by polymerizing a phenol compound, formaldehyde, alkanol amine, and alkylene oxide having excellent flame retardancy. Phenol, nonylphenol, etc. can be used as a phenol compound, Ethylene oxide, a propylene oxide, etc. can be used as an alkylene oxide. The polymerization reaction can proceed under basic catalyst and at 50 to 70 ° C.

Unlike conventional polyol B, in the present invention, by using a mannium polyol using a phenolic compound, formaldehyde, alkanol amine excellent in flame retardancy, by forming a carbon film (Char Coal), flame retardancy, in particular flame propagation rate and smoke The density can be significantly improved.

The hydroxyl value of the Mannich polyol is preferably 400 to 500 mgKOH / g. Unlike conventional polyol B, which has a relatively high hydroxyl value, in the present invention, by using a Mannich polyol having a relatively low hydroxyl value, physical properties such as flame retardancy of polyurethane foam can be further improved.

The amount of the Mannich polyol used is preferably 15 to 25% by weight based on the total weight of the polyol component. In addition, the molecular weight of the Mannich polyol is preferably 500 to 600, the number of functional groups (OH groups) is 5 to 6 / mol, the viscosity is about 10,000 mPa · s, and the water content (Water Content) is preferably 0.1% or less.

In the present invention, in addition to the aromatic polyester polyol and Mannich polyol, other polyols corresponding to the conventional polyol C may be included. The content of other polyols may be from 5 to 15% by weight, based on the total weight of the polyol component.

A third feature of the present invention is to raise the isocyanate index (NCO INDEX = NCO / OH) from 1.5 to 2.0 using a specific catalyst. The higher the value of the isocyanate index, the better the flame retardancy. The present invention is characterized in that the isocyanate index is higher than the conventional (about 1.3).

In the present invention, it is possible to increase the flame retardancy by preparing a polyisocyanate foam using a trimerization catalyst. Specifically, by forming an isocyanate functional group using a trimerization catalyst, as in Scheme 2, the in-situ polyurethane resin premix may be formed into a PIR (polyisocyanate) foam to improve flame retardancy.

[Reaction Scheme 2]

As the trimerization catalyst, one or more of N-hydroxy-alkyl quaternary ammonium carbocylate and tris (dimethylaminomethyl) phenol can be selected and used. The amount of the trimerization catalyst is preferably 0.5 to 3.0 parts by weight based on 100 parts by weight of the total polyol components.

In addition to the polyols and catalysts described above, blowing agents, foam stabilizers, flame retardants and the like can be used as raw materials for the resin premixes.

As the blowing agent, 1.1-dichloro-1-1-fluoro-ethane (trade name 141b) of hydrochlorofluorocarbons (HCFCs) having a low boiling point can be used as the physical blowing agent. The content of the blowing agent is suitably 25 to 35 parts by weight based on 100 parts by weight of the polyol.

As the foam stabilizer, polyether polydimethylsiloxane copolymer, polydimethyl copolymer, B-8404, B-8462, Union Carbide's L-5420, L-5340, etc. may be used as the siloxane surfactant. The content of the foam stabilizer is appropriately 0.5 to 5 parts by weight based on 100 parts by weight of the polyol.

Examples of the flame retardant include tris (chloroisopropyl) phosphate (TCPP), tris (chloroethyl) phosphate (TCEP), and Daichichi C12-530. The content of the flame retardant is suitably 10 to 30 parts by weight based on 100 parts by weight of the polyol.

After preparing the resin premix by mixing the polyol, catalyst, foaming agent, foam stabilizer, and flame retardant, the resin premix and isocyanate are mixed at a volume ratio of about 1: 1, and using a high pressure foaming machine, the surface of the skin adhered to the site It can be sprayed on (ceiling, wall, etc.). As foaming equipment Graco. Gusmer, Gras-craft, etc. equipment can be used, and it is transported to high pressure by using a foaming machine, and it can be used in the field through the spray gun as a mechanism by collision at a pressure of about 50 kg / ㎠ and a temperature of 50 to 60 ℃. It can be foamed.

Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples are only for illustrating the present invention, and the scope of the present invention is not limited by the following Examples.

[Example]

After preparing a resin premix with the ingredients and contents of Table 1, the resin premix and isocyanate were mixed at a volume ratio of 1: 1, and a field-type flame-retardant polyurethane foam was constructed by using a foaming machine.

ingredient Content (g) Aromatic Polyester Polyols
Raw materials: terephthalic acid and diethylene glycol
-Hydroxyl value: 150 mgKOH / g 70 Mannich Polyols
Raw materials: phenol, formaldehyde, alkanol amine, ethylene oxide
Hydroxyl value: 450 mgKOH / g 20 Polyester polyol
Raw materials: adipic acid and diethylene glycol 10 Flame Retardant (TCPP) 20 Foaming Agent (HCFC 141b) 25 Defoamer (B-8462) 1.5 Catalyst ① Amine Catalyst (DABCO33LV)
② trimerization catalyst (PC-410, TMR-2) 2
2.5

[Comparative Example]

As a conventional polyurethane foam for on-site spray, the resin premix in the raw material used the ingredients and contents shown in Table 2 below.

ingredient Content (g) Polyol A
Raw materials: ortho toluene diamine and propylene oxide
-OH value: 450 mgKOH / g 60 Polyol B
Raw materials: sugar and propylene oxide
-OH value: 600 mgKOH / g 30 Polyol C (Polyester Polyol)
Raw materials: adipic acid and diethylene glycol 10 Foaming Agent (HCFC 141b) 25 Flame Retardant (TCPP) 17 Catalyst 1 (triethylenetetraamine) 1.5 Catalyst 2 (bis (2-dimethylaminoethyl) ether) 2.0 Defoamer (silicone oil) 1.2 Water (distilled water) 0.5

[Test Example]

Flame retardant performance was evaluated for Examples and Comparative Examples. Flame retardant performance was evaluated by heat release rate test and gas hazard test by request from Korea Fire Insurance Association's Disaster Prevention Testing Institute. The results are shown in Table 3.

The heat resistance test was performed according to KS F ISO 5660-1: 2008. Specifically, the radiant heat of the cone heater was set to about 50 kW / m 2 and the discharge flow rate was set to about 0.024 m 3 / s, and then maintained. The holder was placed on the mass measuring device, the radiant heat shield was removed and heated for 5 minutes, the maximum heat release rate and the total amount of heat released were measured, and after completion of heating, the specimen holder was removed from the mass measuring device and the test body was observed. .

The gas hazard test was carried out according to KS F 2271: 2006. Specifically, after maintaining the temperature in the test box at 30 ° C, eight rotating baskets containing one rat were placed in the test box, and the test body was heated. After the mixture was heated in a furnace for 6 minutes, the behavior stop time of each experimental white rat was measured for 15 minutes after the start of heating.

Test Items Details standard Example Comparative Example Heat release rate Total emitted heat (MJ / ㎡) 8 MJ / ㎡ or less 1.9 6.1 200 kW / ㎡
Timeout in seconds For more than 10 seconds
Not exceed 200 kW / ㎡
Would not 0 7 sec Harmful cracks,
Hole and melting etc Not to be none none gas
Hazard Average Behavioral Downtime of Rats
(Minutes: seconds) More than 9 minutes 14:23 9:02

As can be seen in Table 3, the flame retardant performance of the field spray type rigid polyurethane foam according to the present invention was significantly superior to the conventional products.

Claims (12)

Raw materials include polyol mixtures consisting of aromatic polyester polyols, Mannich polyols and polyester polyols, trimerization catalysts and polyisocyanates,
The aromatic polyester polyol is a polyol obtained by polymerizing terephthalic acid and dialkylene glycol, having a hydroxyl value of 100 to 160 mgKOH / g, contained in an amount of 60 to 75 wt% based on the polyol mixture,
The Mannich polyol is a polyol obtained by polymerizing a phenol compound, formaldehyde, alkanol amine, and alkylene oxide, having a hydroxyl value of 400 to 500 mgKOH / g, contained in an amount of 15 to 25 wt% based on the polyol mixture,
The polyester polyol is included in an amount of 5 to 15% by weight based on the polyol mixture,
The trimerization catalyst is N-hydroxy-alkyl quaternary ammonium carbocylate, it is included in the range of 0.5 to 3.0 parts by weight based on 100 parts by weight of the polyol mixture,
Field construction type flame-retardant polyurethane foam, characterized in that the isocyanate index is 1.5 to 2.0.
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