TWI398455B - Polyurethane flame-proof foam material and manufacturing method thereof - Google Patents

Description

Polyurethane fire resistant foaming material and preparation method thereof

The present invention relates to a flame-proof material, and in particular, to a polyurethane fire-resistant foaming material and a process for producing the same.

In recent years, with the rapid development of industry and commerce, although it has brought many material enjoyment and convenience to life, it has brought many new social problems, including hazardous substances and waste electronic products. Since these discarded electronic products and substances are likely to cause serious harm to the human body and the environment, countries around the world have also established new regulations based on environmental protection reasons to impose stricter regulations on hazardous substances and discarded electronic products.

In the case of the European Union, the European Union has launched the Restriction of Hazardous Substances (RoHS) and Waste Electric and Electronic Equipment (WEEE) on July 1, 2006. The main restrictions are Covers ten categories of products such as information and home appliances, including six chemicals including lead, cadmium, mercury, hexavalent chromium, poly-brominated biphenyls (PBB) and poly-brominated diphenyl Ethers (PBDE). , the highest content should not exceed 1000ppm. Similar bans have been issued in other major countries or regions of the world.

Therefore, in order to comply with the ban of the EU and other countries, how to cooperate with the ban to make electronic products using other alternative materials that will not harm the environment and the human body has become the focus of research and development in the world. In particular, most of the general fire-resistant foaming materials contain banned halogen components, and it is urgent to switch to other environmentally friendly alternative materials to comply with the current national laws and regulations.

Accordingly, it is an object of the present invention to provide a polyurethane flame resistant foaming material and method of making the same to solve the problems encountered in the prior art.

According to a specific embodiment, the method for preparing a polyurethane fire resistant foaming material according to the present invention comprises the steps of: (a) mixing a polyol, a catalyst and an auxiliary agent with each other; (b) adding an isocyanate Adding to the mixed solution formed in the step (a) and stirring at a high speed; (c) injecting the mixed solution after the step (b) into a mold for foam molding, thereby forming the polyurethane flame resistant foaming material. .

In a practical application, the step (c) is to form the polyurethane fire-resistant foaming material by a free foam molding method or a compression foam molding method; and the step (b) is to cause the polyol and the isocyanate to be The monofunctional polymerization is carried out with the aid of the catalyst and the auxiliary agent, and the flame resistance of the flame is blocked by a symbiotic synergistic mechanism.

According to another embodiment, the polyurethane fire-retardant foaming material of the present invention comprises a polymer which is formed by a polyfunctional reaction of a polyhydric alcohol and an isocyanate through a functional group, and is formed by a symbiosis. The mechanism of action renders the polymer a flame resistant material with a flame blocking.

In practical applications, the polyol is a monofunctional organophosphorus polymer polyol, and the functional organophosphorus polymer polyol and the isocyanate are supported by a catalyst and an auxiliary agent to carry out the functional group polymerization reaction. The functional organic phosphating polymer polyol has zero chlorine content and bromine content. The symbiotic synergistic mechanism is produced by an inorganic compound and/or a nitrogen-based compound derivative in combination with a monofunctional organic phosphating polymer. Wherein the inorganic compound is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate and calcium carbonate; the nitrogen compound derivative is selected from the group consisting of ammonium polyphosphate, strontium and trimer One of the groups consisting of ammonium cyanide.

Compared with the prior art, the polyurethane anti-combustion foaming material and the manufacturing method thereof according to the present invention are combined with a symbiotic agent such as an inorganic compound, a nitrogen-based compound derivative and a functional organic phosphating polymer, through chemical polymerization. The reaction produces a non-halogen polyurethane foam material, which causes an increase in the oxygen index, a decrease in the system temperature, a decrease in the cleavage radicals, a formation of a non-combustible coke layer and a glassy melt upon burning of the material. It prevents the flame from spreading and can shield the heat source, so it can simultaneously protect the substrate and block the flame.

Therefore, the polyurethane fire-resistant foaming material of the invention not only has high safety and fire resistance, but also is a halogen-free and low-pollution material, so it can be applied to various buildings, vehicles or office equipment. It is highly competitive in the market for cushions, compartments, shock absorption and fire resistance.

The advantages and spirit of the present invention will be further understood from the following detailed description of the invention.

In general, the following mechanisms are commonly used to suppress combustion and cause the flame to extinguish:

(1) Physical dilution: increasing the amount of heat of the material and reducing the amount of combustibles in the material by filling in an inert endothermic filler. For example, glass fibers, hollow glass spheres, and talc are examples of this type.

(2) Chemical interaction: Free radicals are generated by thermal decomposition to capture highly active gas phase hydroxyl groups and hydrogen radicals, resulting in a slower rate of thermal cracking chain reaction. For example, brominated flame retardants fall into this category.

(3) inert gas dilution: due to the release of a large amount of water vapor and non-flammable gas when decomposed by heat, thereby diluting the content of combustible gas and oxygen near the flame, and lowering the temperature of the place, causing the combustion to become More difficult. For example, metal hydroxides, nitrogen compounds, and carbonates fall into this category.

(4) Thermal quenching: The heat released during combustion is reduced by means of endothermic decomposition, thereby lowering the temperature of the combustion products. For example, metal hydroxides and carbonates fall into this category.

(5) Protective coating: a non-combustible glassy molten layer or coke layer is formed on the surface to isolate oxygen and heat transfer and reduce the release of flammable gas, thereby reducing the degree of thermal cracking of the material. For example, the phosphide is thermally decomposed to form a polyphosphoric acid and coke layer, and an intumescent flame retardant belongs to this category.

Based on the above-described combustion inhibition mechanism, the present invention provides a polyurethane flame-retardant foaming material and a method for preparing the same, which are synergistically completed by combining a symbiotic agent such as an inorganic compound, a nitrogen-based compound derivative, and a functional organic phosphating polymer. The utility model has the advantages of high-energy, low-pollution, halogen-free and symbiotic self-extinguishing, and the safety of the polyurethane foaming material of the invention can be greatly improved. Operational and fire resistance.

Compared with the highly toxic aromatic bromides (such as polybrominated biphenyls (PBB), polybrominated diphenyl ethers (PBDE), organic chlorides and antimony oxides) that are widely used today, the environmental pollution and the harm to human and animal health, The polyurethane anti-combustion foaming material and the method for producing the same according to the present invention are combined with a symbiotic agent such as an inorganic compound, a nitrogen-based compound derivative and a functional organic phosphating polymer to form a non-halogen-containing polyurethane via chemical polymerization. Acid ester foaming material.

It is worth noting that the material will release water and carbon dioxide when burned, thereby reducing the temperature of the surrounding environment and diluting the concentration of combustible gas; releasing phosphoric acid at high temperatures to promote carbonization of the polymer material and further dehydrating the ester. It is formed into a glassy polyphosphoric acid to cover the surface of the combustion product to achieve the effect of isolating oxygen and inhibiting the release of volatile lysate.

Next, the polyurethane anti-combustion foaming material proposed by the present invention and a method for producing the same will be further described in detail.

A method of making a polyurethane fire resistant foaming material in accordance with an embodiment of the present invention. First, the ratio of the various components required for preparing the polyurethane foam test piece is: 100 parts of the polymer polyol; 1 part of the surfactant; 5-30 parts of the additive; 0.3 part of the ammonium promoter; tin promoter 0.2 Parts; water 3.2 parts; diisocyanate 30 parts, but not limited to this.

Next, please refer to FIG. 1 , which is a flow chart showing a method for manufacturing the polyurethane fire resistant foaming material. As shown in FIG. 1, first, the method performs step S10, and an appropriate amount of the polymerized polyol, the accelerator, the additive, and the surfactant are added to a container and uniformly stirred.

Next, the method proceeds to step S12, and the isocyanate is added to the mixed solution formed in the step S10, and stirred at a high speed. In practical applications, the method is stirred at a high speed of 3000 rpm for about 8 to 10 seconds, but is not limited thereto.

Thereafter, the method performs step S14, and the stirred mixed solution is immediately injected into a mold for foam molding to form the polyurethane flame resistant foaming material. Actually, the step S14 may be carried out by a free foam molding method or a compression foam molding method to form the polyurethane flame resistant foaming material without any limitation.

It should be noted that, in this embodiment, the polyol may be a monofunctional organic phosphating polymer polyol, and the functional organic phosphating polymer polyol has zero chlorine content and bromine content, thereby realizing the present invention. The non-halogen polyurethane fire resistant foaming material to be realized by the invention. Further, the functional organic phosphating polymer polyol has a phosphorus content of about 9% to 22%, but is not limited thereto.

In one embodiment, the functional organophosphorus polymer polyol and the isocyanate are subjected to functional group polymerization with the aid of a promoter and an auxiliary agent, and the flame-retardant function of the flame is blocked by a symbiotic synergistic mechanism. .

In fact, the symbiotic synergistic mechanism can be synergistically produced by an inorganic compound, a nitrogen compound derivative, and a functional organic phosphating polymer. The inorganic compound may be aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate or calcium carbonate; the nitrogen compound derivative may be ammonium polyphosphate, hydrazine or melamine, but not limited thereto.

After the preparation of the polyurethane foam material test piece is completed through the above steps S10 to S14, in order to test the flame resistance of the polyurethane foam material, the polyurethane foam material test piece can be further used. Conduct a flame resistance test. In general, the horizontal burning test for foaming materials generally has UL94HBF horizontal burning test, UL94HF-1 horizontal burning test and UL94HF-2 horizontal burning test. Among them, the UL94HBF horizontal burning test requires that the burning rate be less than 40mm / min and the length of the loss must not exceed 100mm. The requirements for UL94HF-1 horizontal burning test and UL94HF-2 horizontal burning test are shown in Table 1 below.

Among them, the 4/5 of Table 1 represents four of the five test pieces, and 1/5 represents one of the five test pieces, and the size of the test piece is: length 150 mm * width 50 mm * height 10 mm.

As for the present embodiment, the UL94 HF-1 horizontal burning test was used to test the polyurethane foam test piece, and the experimental data is shown in Table 2 below.

Obviously, it can be seen from Table 2 that the polyurethane foam material test piece prepared by the preparation method of the present invention can successfully pass the UL94 HF-1 horizontal burning test, and is representative of the preparation method according to the present invention. The polyurethane foaming material does have quite excellent flame resistance. Further, the density of the polyurethane foamed material produced by the preparation method of the present invention is about 20 to 75 kg/m 3 , but not limited thereto.

According to another embodiment, the polyurethane fire-retardant foaming material of the present invention comprises a polymer which is formed by a polyfunctional reaction of a polyhydric alcohol and an isocyanate through a functional group, and is formed by a symbiosis. The mechanism of action renders the polymer a flame resistant material with a flame blocking.

In practical applications, the polyol may be a monofunctional organophosphorus polymer polyol, and the functional organophosphorus polymer polyol and the isocyanate are supported by a catalyst and an auxiliary agent to carry out the functional group polymerization. In the reaction, the functional organic phosphating polymer polyol has zero chlorine content and bromine content.

Further, the symbiotic synergistic mechanism is produced by synergistic synthesis of an inorganic compound and/or a nitrogen-based compound derivative with a monofunctional organic phosphating polymer. Wherein, the inorganic compound may be aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate or calcium carbonate; the nitrogen compound derivative may be ammonium polyphosphate, cerium or melamine, but not limit.

It is worth noting that since the conventional polyurethane resin has polymer flammability, after adding a flame retardant, the viscosity of the polyurethane resin is greatly increased, which makes subsequent processing difficult. In view of this, the preparation method of the polyurethane anti-combustion foaming material proposed by the invention can effectively overcome the problem, thereby greatly improving the flame resistance and operability of the polyurethane anti-combustion foaming material. . In summary, the polyurethane foamed material prepared according to the preparation method of the present invention has low addition amount, low viscosity increase, no halogen, no heavy metal, easy subsequent injection molding, and maintains the original physical properties of the material. Mechanical properties and other advantages.

Compared with the prior art, the polyurethane anti-combustion foaming material and the manufacturing method thereof according to the present invention are combined with a symbiotic agent such as an inorganic compound, a nitrogen-based compound derivative and a functional organic phosphating polymer, through chemical polymerization. The reaction produces a non-halogen polyurethane foaming material, which causes an increase in the oxygen index, a decrease in the system temperature, a decrease in cracking radicals, a formation of a non-combustible coke layer and a glassy melt on the surface, thereby preventing flame diffusion and The heat source can be shielded, so that it can simultaneously protect the substrate and block the flame. Therefore, the polyurethane anti-combustion foaming material of the invention not only has high safety and fire resistance, but also is a halogen-free low-pollution material, so its application range is quite wide, including automobiles, synthetic leather, furniture. The use of high-performance materials and related structures such as construction, office equipment and transportation tools to enhance the safety of polyurethane foam products while achieving multiple objectives such as technological innovation, safety improvement and productization. Very competitive in the market.

The features and spirit of the present invention will be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed.

S10~S14. . . Process step

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing a method of manufacturing a polyurethane fire resistant foaming material in accordance with an embodiment of the present invention.

S10~S14. . . Process step

Claims (4)

A polyurethane flame resistant foaming material comprising: a polymer formed by a polyfunctional reaction of a polyhydric alcohol and an isocyanate through a functional group, and having a symbiotic synergistic mechanism to cause the polymer to have a flame retardant material for blocking flame; a monofunctional organophosphorus polymer polyol having a phosphorus content of 9% to 22%; an isocyanate; an inorganic compound, which is aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate and One of the group consisting of calcium carbonate; and a nitrogen-based compound derivative selected from the group consisting of ammonium polyphosphate, strontium and melamine ammonium; wherein the functional organic phosphorus The functional polymer polyol is reacted with the isocyanate under the aid of a promoter and a surfactant, and the inorganic compound and the nitrogen compound derivative and the functional organic phosphating polymer polyol Synergistically generating a symbiotic synergistic mechanism to form a flame resistant polymer material having a blocking flame; and the accelerator comprises a ammonium promoter and a tin promoter having a density of 20 to 75 Kg / m ³ The polyurethane anti-combustion foaming material according to claim 1, wherein the functional organic phosphating polymer polyol has a chlorine content And the bromine content is zero. A method for producing a polyurethane flame resistant foaming material, comprising the steps of: (a) mixing a monofunctional organic phosphating polymer polyol, a surfactant, a promoter, and an additive with each other, Wherein, the accelerator comprises a mono-ammonium promoter and a tin promoter, and the functional organophosphorus polymer polyol has a phosphorus content of 9% to 22%; (b) adding the isocyanate to the step (a) The mixed solution is stirred at a high speed of 3000 rpm for 8 to 10 seconds, wherein the ratio of the polyol, the surfactant, the ammonium promoter, the tin promoter, the additive, water, and the isocyanate is 100. :1:0.3:0.2:5:3.2:30; and (c) injecting the mixed solution of the step (b) into a mold for foam molding, and adding an inorganic compound and a nitrogen-based compound derivative to the mold The functional organophosphorus polymer polyol and the isocyanate are subjected to the functional group polymerization reaction with the aid of a promoter and a surfactant, and the inorganic compound and the nitrogen compound derivative are functionalized with the functional group. Sexual organic phosphating high score A polyol to produce a synergistic symbiotic synergistic mechanism, thereby forming a density of 20 ~ 75Kg / m ³ one fire resistant polyurethane foam. The method of claim 3, wherein the step (c) is performed by a free foam molding method or a compression foam molding method to form the polyurethane flame resistant foaming material.