TWI425081B - Flame retardant foam material and method of forming the same - Google Patents

Description

Flame retardant foaming material and method of forming same

The present invention relates to a flame-retardant foaming material, and more particularly to a flame-retardant foaming material having a composite flame retardant system having a phosphorus-based flame retardant and a nitrogen-based flame retardant.

Foamed materials have a wide range of applications, and foamed materials may be used in various products, both domestically and industrially. For example, seat cushions, seat backs, canopies, various plaques, carpets, curtains, clothing linings, bedding, office supplies, sports equipment, music equipment, defense military supplies, or building materials.

Among various foaming materials, since the polyurethane foamed material has excellent chemical resistance, solvent resistance, abrasion resistance, and the like, it is widely used in industry. Polyurethane foams can be subdivided into soft, semi-rigid, or rigid foams. Generally, polyurethane flexible foam materials are mainly used for making furniture, mattresses, and cars for use as mats. Polyurethane rigid foam can be used as a thermal insulation foam for residential, automotive, aircraft, refrigerators, etc.

However, the above-mentioned foaming materials are mostly made of a polymer, which is easy to ignite and emit a large amount of smoke, which often causes the escape route to be shielded or the escaped person to be bruised, which has a great impact on public safety. With the increasing importance of environmental protection issues and the development of fire prevention regulations, in addition to trying to improve the problem of foaming materials that are prone to fire and smoke, it is also necessary to consider the maintenance of the environment to prevent the foam materials from emitting toxic gases to pollute the environment or injuring the escape. By.

Therefore, the industry urgently needs a non-flammable low-smoke foaming material, and the composition of the flame-retardant low-smoke foaming material and its manufacturing process also need to minimize the damage to the environment, and also maintain or enhance the physical properties of the foaming material.

The present invention provides a flame-retardant foaming material comprising a foaming material, a phosphorus-based flame retardant, a nitrogen-based flame retardant, and a layered inorganic powder.

The present invention further provides a method of forming a flame-retardant foaming material comprising mixing a polyol, a layered inorganic powder, a phosphorus-based flame retardant, and a nitrogen-based flame retardant, and foaming by mixing a diisocyanate to the above mixture.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

The invention provides a flame-retardant foaming material, comprising a composite flame retardant system composed of a phosphorus-based flame retardant and a nitrogen-based flame retardant, and is introduced into a foaming material together with the layered inorganic powder to form the flame-retardant foam of the present invention. material. When the flame-retardant foaming material of the invention encounters flame combustion, the composite flame-resistant agent system containing phosphorus and nitrogen can form an insulation layer together with the layered inorganic powder, and can isolate the flammable gas or the combustion-supporting gas to achieve low-smoke flame-proof. Effect. The flame-retardant foaming material of the invention does not need to add a halogen-containing additive, so that no toxic gas is generated and no harm to the human body or the environment is caused. Further, by the addition of the layered inorganic powder, the amount of the flame retardant can be reduced, and the flame retardant having a small molecule can be adsorbed without floating to the surface of the foamed material, and the physical properties of the foamed material can be increased.

The phosphorus/nitrogen composite flame retardant system and the layered inorganic powder of the present invention can be introduced into all compatible foam materials, and the materials thereof include, for example, polyurethane, polystyrene, polyethylene, polyvinyl chloride, or a combination thereof.

The phosphorus-based flame retardant in one embodiment of the present invention can increase the flame retardant property of the foamed material, and the weight percentage thereof can be, for example, about 5% to about 50%, preferably about 5% to the flame-retardant foaming material. About 25%. Suitable phosphorus-based flame retardants include, for example, phosphate, polyphosphoric acid, melamine phosphate, polyphosphoric acid, polyphosphate, red phosphorus encapsulated white phosphorus, red phosphorus, phosphate, or phosphite, diethyl N, N-bis ( 2-hydroxyethyl)aminoethyl phosphate, 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-benz enediol, 9,10-dihydro-9-oxo -10-itaconic acid-10-phospha-phenanthrene-10-oid, n-butyldihydroxypropylphosphine oxide, trihydroxypropylphosphine oxide, cyclooctylhydroxypropylphosphine oxide, phenylhydroxydihydroxyphenyl oxide Phosphorus, hydroxyl-containing phosphate, ammonium polyphosphate, melamine polyphosphate, 2,4,8,10-tetraoxy-3,9-diphosphorylcyclo[5.5]undecane-3.9 -Dioxo-3,9-dimelamine salt, bis(2,6,7-trioxo-1-phospho-bicyclo[2.2.2]octane-1-oxomethyl)phosphate melamine salt, 1-oxygen -4 hydroxymethyl-1-phospho-2,6,7-trioxabicyclo[2.2.2]octane, trimethylbenzene (phenol) phosphate (TCP), toluene diphenyl phosphate (CDP), phosphoric acid tri Xylene) ester (TXP), diphenyl phosphate Isooctyl ester, diphenyl phenyl phosphate, triphenyl phosphate (TPP), tris(isopropyl) phosphate, triethyl phosphate (TEP), xylylene diphenyl phosphate, diphenyl isodecyl phosphate , tris(butoxyethyl) phosphate, phenyl diisooctyl phosphate, phenyl diethyl phosphate, phenyl diisooctyl phosphite, triphenyl phosphite, trimethyl phosphite, phosphorus-containing polyhydric alcohol, Tris(2,4-di-tert-butylphenyl) phosphite, a cyclic phosphate, or a combination of the foregoing. Suitable commercial phosphorus-based flame retardants include, for example, PNX (AKOX NOBEL), Antiblaze 1045 (Hengqiao), DOPO (Hengqiao), TEP (Hengqiao), TOP (Hengqiao), TF-J12 (Daihachi) Chemical Industry), OP550 (Clariant Corporation), Frx-44-94S (nitex), or a combination of the foregoing. In an embodiment of the present invention, a liquid phosphorus-based flame retardant which is easy to process is used, and a phosphorus-based flame retardant which is liquid in nature or a phosphorus-based flame retardant which is liquid after reforming is used. In an embodiment of the invention, the phosphorus-based flame retardant is preferably less than 10,000 cps for subsequent processing and application. It should be noted that in addition to being generally more expensive, the phosphorus-based flame retardant is more likely to generate an acidic substance and adversely affect the flame-retardant foam material, such as yellowing or a decrease in physical properties. Therefore, the use of the phosphorus-based flame retardant needs to be reduced as much as possible to obtain a flame retardant foam material having a better physical property, and the production cost can be reduced.

The nitrogen-based flame retardant in one embodiment of the present invention can increase the flame retardant property of the foamed material, and the weight percentage thereof can be, for example, about 10% to about 50%, preferably about 20% to the nonflammable foaming material. About 40%. Suitable nitrogen-based flame retardants include, for example, melamine cyanurate, tris(2-Hydroxyethyl)-1,3,5-triazinetrione, melamine, melamine-formaldehyde, butoxymethyl melamine, hexamethoxymethylmelamine, methyl melamine ( Methyl melamine), methoxymethyl melamine, methoxymethyl methylol melamine, MC-25 (dough thick), or a combination of the foregoing. Suitable commercial nitrogen-based flame retardants include nitrogen-based flame retardants produced by Cytec industries INC., such as Cymel-1158, Cymel-303, Cymel-323, Cymel-325, Cymel-385, Cymel-300, Cymel-301, Cymel -350, Cymel-324, Cymel-202, Cymel-327, Cymel-370, Cymel-373, Cymel-380, Cymel-1130, Cymel-1131, Cymel-1133, Cymel-1135, Cymel-1116, Cymel-1156 , Cymel-1116, Cymel-1168, or a combination of the foregoing. In one embodiment of the present invention, a liquid nitrogen-based flame retardant which is easy to process is used, and a nitrogen-based flame retardant which is liquid in nature or a nitrogen-based flame retardant which is liquid after reforming is used. . In one embodiment of the present invention, a flame-resistant foamed material using a phosphorus/nitrogen composite flame retardant is less likely to generate smoke and toxic gases when burned than a foamed material containing no flame retardant or only a phosphorus-based flame retardant. At the beginning of the combustion, the phosphorus-based flame retardant generates phosphoric acid, and the nitrogen-based flame retardant generates ammonia and nitride. The mechanism that the foamed material is less prone to generate smoke is still unclear. It is not excluded because phosphoric acid may accelerate the dehydration and carbonization of the foamed material, and finally form a high-temperature shrinkage and phosphate ester, and a carbon layer foam layer is formed with the nitride to isolate the flammable gas. Or help gas and heat source to achieve the effect of flame retardant and smoke resistance. The addition of the nitrogen-based flame retardant can neutralize the acidic substance caused by the phosphorus-based flame retardant, and can protect the physical properties of the foamed material from the phosphorus-based flame retardant. In addition, since the foaming process of foaming material formation is very fast, in an embodiment of the invention, a liquid nitrogen-based flame retardant is preferably used, which can be uniformly mixed with other additive materials uniformly, so that the final formation is achieved. The overall properties of the flame retardant foam material are relatively uniform, increasing its reliability. In an embodiment of the invention, the viscosity of the nitrogen-based flame retardant is preferably less than 10,000 cps for subsequent processing and application.

The layered inorganic powder in one embodiment of the present invention can increase the flame retardant property of the foamed material, can also reduce the amount of the flame retardant used, and adsorb the less resistant flame retardant without floating to the foamed material. The surface is washed away by the flame retardant when the foamed material is washed, and the flame retardant property of the foamed material is lowered. The small-molecule flame-resistant agent may also be more uniformly dispersed in the foamed material by being adsorbed by the layered inorganic powder, and the flame-retardant and low-smoke properties of the foamed material as a whole are more uniform. Further, the addition of the layered inorganic powder can further increase the physical properties of the foamed material, such as strength, hardness, and abrasion resistance. The weight percentage of the layered inorganic powder may be, for example, from about 0.01% to about 50%, preferably from about 0.5% to about 5%, relative to the flame-retardant foaming material. Suitable layered inorganic powders include, for example, smectite clay, vermiculite, hallloysite, sericite, saponite, montmorillonite, Beidelite, nontronite, hectorite, layered double hydroxide (LDH), mica, talc, or a combination of the foregoing. Suitable commercial layered inorganic powders such as I28E (Donghou). Non-layered inorganic powders such as ATH (Showa Denko) can also be used. In one embodiment, a nano-sized layered inorganic powder is preferably employed to increase the reactive contact area with other reactants. In one embodiment, the foamed material blended with the layered inorganic powder has a lower amount of smoke during combustion, and the cause of the suppression of the amount of smoke is not clear, and it is not excluded because the layered inorganic powder can be Together with the flame retardant, a multi-layered barrier layer is formed, thereby suppressing the entry of flammable or combustion-supporting gas into the foamed material, and insulating the heat source to suppress the effect of smoking. In one embodiment, the surface of the layered inorganic powder used has a functional group (for example, an OH group) capable of releasing moisture or a temperature-reducing substance, and can release a cooling-lowering substance (for example, water) during combustion to suppress the foaming material. Burning and smoking.

Hereinafter, a method of forming a flame-retardant foamed material of the present invention will be described by taking a polyurethane flame-retardant foamed material according to an embodiment of the present invention as an example. The skilled person can form a flame retardant foam of other materials by the method of forming the embodiment of the present invention without departing from the spirit of the present invention.

A method for forming a polyurethane flame retardant foam according to an embodiment of the present invention includes uniformly mixing a polyol, a layered inorganic powder, a phosphorus-based flame retardant, and a nitrogen-based flame retardant, and then adding the above mixture to a diisocyanate ( Isocyanate) and quickly and evenly mixed to foam it into a polyurethane flame retardant foam. In one embodiment, the polyurethane flame retardant foam material is formed by first uniformly mixing the layered inorganic powder with the phosphorus-based flame retardant and the nitrogen-based flame retardant, and first adsorbing the flame retardant on the layered inorganic powder, and then first adsorbing the flame retardant on the layered inorganic powder. Add the polyol and mix well. Thereafter, the mixture was added to the diisocyanate to be mixed and foamed. It should be noted that the foaming of the polyurethane is completed in a short period of time. Therefore, it is preferred to use a liquid flame retardant to form a mixture with the polyol and the layered inorganic powder, so that the flame retardant is preferably dispersed in the foaming. In the material. The layered inorganic powder may be added in an amount of from about 0.01 phr to about 50 phr, preferably from about 0.5 phr to about 5 phr, relative to the amount of the polyol added. The phosphorus-based flame retardant may be added in an amount of from about 5 phr to about 50 phr, preferably from about 5 phr to about 35 phr, relative to the amount of polyol added. The nitrogen-based flame retardant may be added in an amount of from about 10 phr to about 50 phr, preferably from about 20 phr to about 40 phr, relative to the amount of the polyol added.

In one embodiment of the invention, the polyol used to form the polyurethane flame retardant foam comprises polypropylene glycol (PPG), polytetramethyl ether glycol (PTMEG), polyether polyol, polyester polyol. (polyester polyol), or a combination of the foregoing.

In an embodiment of the invention, the diisocyanate used to form the polyurethane flame retardant foam comprises toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), HDI, IPDI (aliphatic isoester) H ₁₂ MDI (hydrogenated MDI) and oligomeric diisocyanate, or a combination of the foregoing.

Further, in an embodiment of the present invention, other additives may be introduced into the system of the polyurethane flame retardant foam to assist in foaming or to improve the properties of the foam. The additive includes, for example, a chain extender, a foamed structural stabilizer, an ammonia-based catalyst, a metal catalyst, a foaming agent, a reinforcing additive, a colorant, or a combination thereof. Suitable chain extenders include short chain polyols such as ethylene glycol (EG), butylene glycol (BG), diethylene glycol, triethylene glycol, 1,2-propanediol ( 1,2-propanediol), 1,3-propanediol, 1,6-hexanediol, or a combination thereof. Suitable foaming structure stabilizers include polysiloxanes. A suitable ammonia-based catalyst accelerates the reaction between the polyol and the diisocyanate, such as TEA. Suitable metal catalysts accelerate the reaction between water and the diisocyanate, for example, T9, T12, or a combination of the foregoing. Suitable blowing agents include hydrofluorocarbons (HFC), water, dichloromethane, acetone, or combinations of the foregoing. Suitable reinforcing additives can increase strength and hardness, such as calcium carbonate, barium oxide, or combinations of the foregoing. In addition, different colors of color can be added depending on the actual application.

Hereinafter, some specific examples and comparative examples of the polyurethane flame retardant foam of the present invention will be described.

[Examples]

Each of the examples or comparative examples listed below will form each urethane foamed material in a similar formulation method. First, the layered inorganic powder, the phosphorus-based flame retardant, and the nitrogen-based flame retardant are subjected to polishing and stirring to form a uniformly mixed organic/inorganic flame resistant agent system (partial comparative examples are not added with all the materials). The flame retardant system was then added to the polyol and pre-stirred for 5 minutes at a stirring speed of 500 rpm. Then, the diisocyanate was added, and the mixture was emulsified and stirred at a stirring speed of 3000 rpm for 5 seconds, and the mixture was introduced into a mold to be foamed to complete the polyurethane foaming materials of the respective examples and comparative examples, wherein the polyols used were all members. And the company's PAPI-27, and the diisohydrogenate is the XRP-3212 (Index=1.0) of the adopter and company. Table 1 lists the materials and suppliers of the flame retardant or layered inorganic powder used in each of the examples.

Table 2 below lists the flame and smoke resistance characteristics of the polyurethane foamed material obtained by the above-described polyurethane foam forming method with different flame retardant systems added. The numerical value of the column of the flame retardant (phr) refers to the amount of the flame retardant added (partially a single flame retardant and partly a phosphorus/nitrogen composite flame retardant) required for passing the foamed material through the CAL117A flame retardant test. The column of powder (phr) means the amount of the layered inorganic powder added. The self-extinguishing (s) column refers to the self-extinguishing time required for the CAL117A flame retardant test. Blank refers to a polyurethane foam material to which no flame retardant or layered inorganic powder is added, and the Blank foam material cannot pass the CAL117A flame retardant test. The amount of the layered inorganic powder and the flame retardant added is relative to the amount of the polyol added.

Among them, the CAL117A flame retardant test method (CA117 for short) is as follows, and the obtained polyurethane flame retardant foam material is made into 10 test pieces having a width and a height of 304.88 mm, 76.2 mm, and 12.7 mm, respectively. Before the test, the test piece was stored at a temperature of 21 ° C and a relative humidity of 55% or less for 24 hours. Five of the test pieces were aged in an oven at a temperature of 100 ° C for 24 hours. During the measurement, the test piece was placed vertically in the test cabinet, and the test piece was ignited for 12 seconds at a distance of 19.05 mm from the bottom surface of the test piece with a Bunsen burner (flame height of 38.1 mm). If the measurement result satisfies the following conditions, the material to be tested passes the CAL117A test. The conditions include (1) the average length of 10 test pieces charred to carbon is less than 152.44 mm, (2) the maximum length of single test piece carbonized to less than 203.2 mm, and (3) the average time of 10 test pieces with flame burning Less than 5 seconds, (4) the maximum time for a single test piece to have a flame burn is less than 10 seconds, and (5) the average time for the absence of flame combustion of 10 test pieces is less than 15 seconds.

As shown in Table 2, it can be found that after the introduction of the phosphorus-based flame retardant or the nitrogen-based flame retardant into the polyurethane foam, the polyurethane foam can pass the CAL117A flame retardant test. Further, the use of a phosphorus/nitrogen composite flame retardant system (for example, Comparative Examples 2 and 4) can achieve a better low smoke effect than the use of a single phosphorus-based flame retardant (for example, Comparative Examples 1 and 3), and can also reduce the phosphorus-based flame retardant. The amount of (such as CG1045 or TEP) reduces the influence of the acidic substance of the phosphorus-based flame retardant on the physical properties of the polyurethane foam, and because the price of the phosphorus-based flame retardant is relatively high, the use of the phosphorus/nitrogen composite flame retardant system can further save costs. . Further, in Examples 1 and 2, in the phosphorus/nitrogen composite flame retardant system, a layered inorganic powder (for example, I28E) is further introduced, which can further reduce the smoke density, and can prevent the small molecules of the flame retardant from floating on the surface of the foamed material. , causing the flame retardant to be easily washed away or causing problems in use. Among them, the first embodiment requires less additive than the second embodiment to pass the CAL117A flame retardant test, however, the self-extinguishing time is longer. The reason for this is not clear at present, and it is not excluded because the nitrogen-based flame retardant CY303 in the second embodiment is a modified liquid nitrogen-based flame retardant, so that it is more easily mixed with other materials than the solid nitrogen-based flame retardant mela. The polyurethane foam material formed thereof has relatively uniform flame retardant properties and is relatively easy to self-extinguish.

The embodiments of the present invention have many advantages, such as the use of a phosphorus/nitrogen composite flame retardant system, which enables the foamed material to have significantly inflammable low-smoke properties and better physical properties, and can greatly reduce the amount of phosphorus-based flame retardant required. Can save

Claims (11)

A flame-retardant foaming material comprises: a foaming material; a phosphorus-based flame retardant, the phosphorus-based flame retardant is 5 to 50% by weight, wherein the phosphorus-based flame retardant is a liquid flame retardant, and the phosphorus is flame resistant The material of the agent includes phosphoric acid, polyphosphoric acid, polyphosphoric acid, polyphosphate, phosphite, diethyl N, N-bis (2-hydroxyethyl) aminoethyl phosphate, hydroxy phosphate, and trimethyl phosphate (phenol) ester (TCP). ), toluene diphenyl phosphate (CDP), tris(xyl) phosphate (TXP), diphenyl isooctyl phosphate, diphenyl phenyl phosphate, triphenyl phosphate (TPP), tris(isopropyl phosphate) Benzene ester, triethyl phosphate (TEP), diphenyl diphenyl phosphate, diphenylisodecyl phosphate, tris(butoxyethyl) phosphate, phenyl diisooctyl phosphate, phenyl phosphate, sub Benzyl isooctyl phosphate, triphenyl phosphite, trimethyl phosphite, phosphorus-containing polyhydric alcohol, cyclic phosphate, or a combination thereof; a nitrogen-based flame retardant, the content of the nitrogen-based flame retardant is 10 ~50wt%, wherein the nitrogen-based flame retardant is a liquid flame retardant, and the material of the nitrogen-based flame retardant comprises butoxymethyl melamine, hexamethoxymethylmelam Ine, methoxymethyl melamine, methoxymethyl methylol melamine, or a combination thereof; and a layered inorganic powder, the layered inorganic powder is contained in an amount of 0.01 to 50% by weight, wherein the flame retardant foaming material does not include a halogen additive, and the The material of the layered inorganic powder includes smectite clay, vermiculite, tubular kaolin, sericite, saponite, montmorillonite, rich Beidelite, nontronite, hectorite, layered double hydroxide (LDH), mica, talc, or a combination thereof. The flame retardant foaming material according to claim 1, wherein the material of the foaming material comprises polyurethane, polystyrene, polyethylene, polyvinyl chloride, or a combination thereof. The flame retardant foaming material according to claim 1, wherein the phosphorus-based flame retardant has a viscosity of less than 10,000 cps. The flame retardant foaming material according to claim 1, wherein the nitrogen-based flame retardant has a viscosity of less than 10,000 cps. A method for forming a flame-retardant foaming material, comprising: mixing a polyol, a layer of inorganic powder, a phosphorus-based flame retardant, and a nitrogen-based flame retardant, wherein the layered inorganic powder is added in an amount of 0.01 ~50wt%, the phosphorus-based flame retardant is added in an amount of 5 to 50% by weight, and the nitrogen-based flame retardant is added in an amount of 10 to 50% by weight, and the phosphorus-based flame retardant is a liquid flame retardant, and the phosphorus is flame resistant. The material of the agent includes phosphoric acid, polyphosphoric acid, polyphosphoric acid, polyphosphate, phosphite, diethyl N, N-bis (2-hydroxyethyl) aminoethyl phosphate, hydroxy phosphate, and trimethyl phosphate (phenol) ester (TCP). ), toluene diphenyl phosphate (CDP), tris(xyl) phosphate (TXP), diphenyl isooctyl phosphate, diphenyl phenyl phosphate, triphenyl phosphate (TPP), tris(isopropyl phosphate) Benzene ester, triethyl phosphate (TEP), diphenyl diphenyl phosphate, diphenylisodecyl phosphate, tris(butoxyethyl) phosphate, phenyl diisooctyl phosphate, phenyl phosphate, sub Benzyl isooctyl phosphate, triphenyl phosphite, trimethyl phosphite, phosphorus-containing polyhydric alcohol, cyclic phosphate, or a combination thereof, the nitrogen-based flame retardant is a liquid flame retardant, and the material of the nitrogen-based flame retardant comprises butoxymethyl melamine, hexamethoxymethylmelamine, methoxymethyl melamine, methoxymethyl methylol melamine, Or a combination of the foregoing, the material of the layered inorganic powder comprises smectite clay, vermiculite, halloysite, sericite, saponite, montmorillonite Montmorillonite, beidellite, nontronite, hectorite, layered double hydroxide (LDH), mica, talc, or the foregoing Combining; and mixing the monoisocyanate to the above mixture to foam, and not adding the halogen additive to the above mixture. A method of forming a flame-retardant foamed material according to claim 5, wherein the phosphorus-based flame retardant has a viscosity of less than 10,000 cps. A method of forming a flame-retardant foamed material according to claim 5, wherein the nitrogen-based flame retardant has a viscosity of less than 10,000 cps. The method for forming a flame-retardant foaming material according to claim 5, wherein the polyol, the layered inorganic powder, the phosphorus-based flame retardant, and the nitrogen-based flame retardant are mixed first. The inorganic powder is uniformly mixed with the phosphorus-based flame retardant and the nitrogen-based flame retardant, and then uniformly mixed with the polyol. The method for forming a flame-retardant foaming material according to claim 5, wherein the polyol comprises polypropylene glycol (PPG), polytetramethyl ether glycol (PTMEG), polyether polyol, Polyester polyol, or a combination of the foregoing. The method for forming a flame-retardant foaming material according to claim 5, wherein the diisocyanate comprises toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), HDI, IPDI (fat) Group Isoesters), H ₁₂ MDI (hydrogenated MDI) and oligomeric diisocyanates, or combinations of the foregoing. The method for forming a flame-retardant foaming material according to claim 5, further comprising adding a chain extender, a foaming structure stabilizer, an ammonia-based catalyst, a metal catalyst, a foaming agent, A reinforcing additive, a colorant, or a combination thereof, is used in the mixture of the polyol, the phosphorus-based flame retardant, and the nitrogen-based flame retardant.