巴西专利BR112013012211A2 reactive formulation to prepare a flame resistant polyurethane foam, process to prepare a flame resi

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专利摘要:
REACTIVE FORMULATION TO PREPARE A FLAME-RESISTANT FLEXIBLE POLYURETHANE FOAM, PROCESS TO PREPARE A FLAME-RESISTANT FLEXIBLE POLYURETHANE FOAM AND FLEXIBLE POLYURETHANE FOAM.The present invention relates to a reactive formulation used to prepare a flexible flame resistant polyurethane foam, which is particularly suitable for use in applications under the hood of vehicles that require noise attenuation and vibration control and a process for preparing said foam. In particular, the flexible flame resistant polyurethane foam is prepared with a reactive formulation comprising a side comprising (i) one or more organic isocyanates and a side B comprising (ii) one or more reactive components with isocyanate, (iii) a flame retardant component comprising a combination of red phosphorus, expandable graphite, and optionally sodium citrate, the flame retardant component not containing ammonium polyphosphate; and (iv) one or more additional components selected from a catalyst, a blowing agent, a cell opener, a surfactant, a crosslinker, a chain extender, a filler, a dye, a pigment, an antistatic agent, reinforcing fibers, an antioxidant, a preservative, or an acid scavenger, the resulting foam reaching the VO--0-, 5 steel rating according to the 94 under the Underwriters Làboratories' Flammability Test.
公开号:BR112013012211A2
申请号:R112013012211-0
申请日:2011-11-04
公开日:2020-10-13
发明作者:F. Michael Plaver；Jack E. Hetzner
申请人:Dow Global Technologies Inc；
IPC主号:

专利说明:

,; ::: 1 “REACTIVE FORMULATION TO PREPARE A FLAME-RESISTANT FLEXIBLE POLYURETHANE FOAM, PROCESS FOR PREPARING A FLEXIBLE POLYURETHANE FOAM RESISTANT TO
FLAME AND FLEXIBLE POLYURETHANE FOAM RESISTANT TO ”” 5 FLAME ”a Field of the invention oe The present invention relates to one. composition for: flexible flame resistant polyurethane foam, particularly suitable for use in under-o applications. hood of vehicles that require noise attenuation and vibration control. Background of the invention The control of noise and vibration It is a significant issue for vehicle manufacturers because noise in the cabin is an important factor in the comfort experience of car passengers. Measures for noise and vibration attenuation are therefore routinely incorporated into vehicles. Such mitigation measures often incorporate flexible polyurethane foams. However, typically, such foams are expected to perform one or more functions that cannot be compromised at the expense of noise and vibration absorption. Under-hood applications, for example, require a high degree of flame resistance, in some cases according to 225 the VO classification of the 94 “Underwriters” Laboratories (UL 94) standard. 'The use of flame retardants in polyurethane foams is = well known Methods for flame retardation that combine calcium carbonate, E 30 ammonium hydroxide or other inorganic compound, composed of halophosphoric acid, melamine, or other such compound with a polyol are well known. a large amount of such a compound is added to provide flame retardancy, which often results in considerable problems with regard to moldability, economy, and the like. Methods for making flexible polyurethane foam
| 1, 2: flame retardant may also include the addition of a | halogenated phosphoric acid ester as a retardant | calls for a composition for polyurethane foam based | polyester and the use of a reactive flame retardant that | r 5 add a phosphorus or halogen atom to the compound of | polyhydroxyl or organic polyisocyanate which is a raw material for polyurethane foam.
However, the urethane foam obtained by these methods fades over time, the foam itself deteriorates, and the adequate flame retardation is not maintained for a long time, since the flame retardant volatilizes. Due to the recent environmental and market trends, solutions with non-halogenated flame retardants have been sought.
USP 6,765,034 describes a | 15 flexible flame resistant polyurethane composition | for use in noise and vibration attenuation applications | which does not include flame retardants and which is based on the choice of a specific mixture of isocyanate and polyol.
Furthermore, the flammability of said foams is defined only in relation to the FMVSS302 flammability test, which is a less rigid flammability test compared to the UL 94 test. The FMVSS (Federal Motor Vehicle Safety Standard) 302 is a flame test horizontal which refers to the tendency of the material to melt (without flame propagation, therefore) unlike the UL 94 vertical flame test which describes à - Resistance of a material to combustion.
American patent publication No. 20030130365 Ô describes a process for preparing a flexible polyurethane foam from a "rigid polyurethane" foam, comprising an organic phosphate flame retardant in combination with expandable graphite.
This process, however, is carried out in multiple stages, which requires a crushing stage and a heating stage.
In addition, said polyurethane foams are evaluated using the EMVSS 302 less demanding flame propagation test, which does not mention the performance of
, »3 combustion resistance according to UL 94. USP patent 5,169.8 / 6 describes a flexible polyurethane foam comprising very high levels (20 to 50 weight percent) of expandable graphite” »5 incorporated into the cell walls that meet to the UL 94 VO standard. However, the process requires the addition of polyol in a separate + heated stream, one of which contains the expandable graphite. The high levels of graphite - expandable and the complex stages of the process contribute to generate a high cost product, which can negatively affect the properties of the resulting foam, such as tensile strength.
JP1998147623 describes a flexible polyurethane foam with a complex flame retardant mixture comprising ammonium polyphosphate, red phosphorus and expandable graphite. However, to meet the requirements of UL 94 V-2 or V-O0O, these foams need 4 to 9 times the amount of ammonium polyphosphate compared to the amount of red phosphorus.
There is a need, not yet met, for a flexible flame resistant polyurethane foam composition for noise attenuation and vibration control applications, which meets the requirements of UL 94 V-O0, and for a method for preparing said foam, that is cost effective, that does not require additional multiple process steps over conventional methods, and that does not require complex flame retardant mixtures and / or high levels of flame retardants. : - - - * Brief summary of the invention The present invention relates to a polyurethane foam: flexible flame resistant and process for its preparation. In one embodiment, the present invention is a reactive formulation for preparing a flexible flame resistant polyurethane foam, comprising a mixture of: (A) an A side comprising:
Í - | NES | i 4 Í t | ! (1) one or more organic isocyanates, and I (B) a B side comprising: (ii) one or more reactive components with isocyanate, (iii) a flame retardant component comprising a ”5 combination of: (iii.a) 0.1 to 6 parts by weight of red phosphorus, x S (iii.b) expandable graphite, preferably from 0.5 to 10 parts by weight, and -— (iii.o) - optionally sodium citrate, preferably when present, from 0.5 to 15 parts by weight, the flame retardant component does not contain ammonium polyphosphate and the parts by weight are based on the total weight of the B side, and (iv) one or more additional components, selected from a catalyst, a blowing agent, a cell opener, a surfactant, a crosslinker, a chain extender, a flame retardant, a filler / filler, a dye, a pigment, an antistatic agent, reinforcing fibers, an antioxidant, a preservative, or an acid scavenger Í 20, said to be flexible flame resistant polyurethane foam prepared with the formulation reactive action reaches a V-0 rating at 0.5 ", according to standard 94 for the flammability test (UL 94) according to standard 94 of Underwriters Laboratories.
In a preferred embodiment of the present invention, The organic isocyanate of the reactive formulation described above comprises monomeric MDI, polymeric MDI, its SS combinations and / or liquid variants thereof obtained by introducing uretonimine-forming and / or polyisocyanates. carbodiimide, said polyisocyanates: modified with carbodiimide and / or uretonimine containing an NCO index ranging from 29 to 33 percent and included in said polyisocyanate from 1 to 45 percent by weight of 2,4'-diphenylmethane diisocyanate as a monomer and / or a carbodiimidization product thereof.
In another preferred embodiment of the present invention, the isocyanate-reactive component of the reactive formulation described above comprises a polyether polyol capped with ethylene oxide.
Another embodiment of the present invention consists of a process for preparing a flame resistant flexible polyurethane foam, through the steps of: bi (1) forming: (A) an A side comprising: (i) one or more organic isocyanates, and (B) a B side comprising: (ii) one or more reactive components with isocyanate, (iii) a flame retardant component comprising a combination of: (iii.a) 0.1 to 6 parts by weight of red phosphorus, (iii.b) expandable graphite, preferably from 0.5 to 10 parts by weight, and (iii.c) optionally sodium citrate, preferably when present, from 0.5 to 15 parts by weight, the retardant component being flame does not contain ammonium polyphosphate and the parts by weight are based on the total weight of the B side, and (iv) one or more additional components, selected from a catalyst, a blowing agent, a cell opener, a surfactant, a crosslinker, a chain extender, a flame retardant, a filler / filler, a dye, a pigment, a antistatic agent, reinforcing fibers, an antioxidant, a preservative, or an acid scavenger; 7 (II) mix side A and side B together to form one | Reactive formulation; and '(1IT) subject the resulting reactive formulation to conditions sufficient to cure the reactive formulation and form a flexible polyurethane foam resistant to:' flame, the foam being preferably arranged around = -—- or in the vicinity of a vehicle's engine automotive like engine cover, engine noise isolator, fuel injector encapsulator, side cover,
crankcase cover, bottom cover, hood muffler, or a control panel muffler, and said foam meets the V-0 rating at 5 "according to - 94 Underwriters Flammability Test (UL 94) In a preferred embodiment of the reactive formulation and / or * process described above, the flame resistant flexible polyurethane foam has a density of 80 kg / m - at 140 o kg / m . - - -: In a preferred embodiment of the formulation reactive and / or process described above, the flame resistant flexible polyurethane foam has a tensile strength equal to or greater than 150 kPa. In a preferred embodiment of the reactive formulation and / or process described above, the flame resistant flexible polyurethane foam has an air flow resistivity of
40,000 raylis / m to 150,000 rayls / m. In yet another embodiment, the present invention is a flame resistant flexible polyurethane foam for use in a vehicle engine compartment, said foam being free of halogen and ammonium polyphosphate, with a UL 94 flammability rating from V-O0 to 0.5 ", a density between 80 kg / m And 140 kg / m And an air flow resistivity between 40,000 rayls / m
150,000 rayls / m. Detailed summary of the invention 'Flexible polyurethane foams, according to. . .gift. invention, are prepared with a reactive -.- formulation - 7 comprising a side A comprising one or more reactive isocyanates (1) and a side B comprising one or: more reactive components with isocyanate (ii), a flame retardant component ( iii) comprising a combination of red phosphorus (iii.a), expandable graphite (iii.b), and optionally, sodium citrate (iii.c), the flame retardant component not containing ammonium polyphosphate, and optionally a or more additives (iv).
= 7 Suitable organic isocyanates (i) for use in the composition and process of the present invention include any of the components known in the art, for the preparation of polyurethane foams, - 5 such as aliphatic, cycloaliphatic, araliphatic and preferably aromatic isocyanates, such as 1b toluene diisocyanate, in the form of its 2,4 and 2,6-isomers, and mixtures thereof, and diphenylmethane diisocyanate in the form of its .2,4'-, 2,21 and 4,4'- isomers and mixtures thereof, mixtures of diphenylmethane diisocyanates (MDI) and their oligomers having isocyanate functionality greater than 2, known in the art as "crude" or polymeric MDI (polyethylene polyphenylene polyisocyanates), the known MDI variants comprising urethane, allophanate, urea, biuret, carbodiimide, uretonimine and / or isocyanate groups.
Preferably, monomeric MDI, crude MDI, MDIT: polymeric, their combinations, and / or their liquid variants are obtained by introducing polyisocyanates. uretonimine and / or carbodiimide group builders, such | carbodiimide and / or modified polyisocyanates | uretonimine having an NCO index of 29 to 33 percent e! includes from 1 to 45 weight percent 2,4'-diphenylmethane diisocyanate in the form of a monomer and / or a | product of the carbodiimidization thereof.
For a good description of such polyisocyanates modified with carbodiimide and / or uretonimine. See USP 6.765.034, here .... - | 7 incorporated by reference in its entirety.
In the present invention, the organic isocyanate component may include one or more organic polyisocyanates, in addition | and / or in place of the monomeric MDI, as needed; as long as other polyisocyanate compounds do not adversely influence the noise attenuation, vibration control, and flame resistance properties of the flexible polyurethane foam.
Typical examples of these other polyisocyanate compounds include pre-
-— 8 isocyanate-terminated polymers formed through a reaction between at least one of the aforementioned monomeric MDI compounds, and appropriate active hydrogen compounds.
To improve the formability and other characteristics of the foam obtained, the other polyisocyanate compounds can be selected from isocyanates. organics such as tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI) and xylene diisocyanates (XDI) and their modifications.
These isocyanates can be used in combinations of two or more types.
Most preferably, polyisocyanates are used which have an average isocyanate functionality of 2.1 to 3.0 and preferably 2.2 to 2.8. The amount of polyisocyanate used in the preparation of a resilient flexible foam is typically sufficient to provide an isocyanate index of 0.6 to 1.5, preferably 0.6 to 1.2, although wider ranges may be used in special cases .
A preferred range is 0.7 to 1.05 and a more preferred range is 0.75 to 1.05. Side B of the present invention comprises an isocyanate-reactive component (ii) that includes any type of compound from those known in the art for that purpose, for example, polyamines, aminoalcohols and polyols.
Suitable polyols have been fully described in the state of the art and include reaction products for alkylene oxides, e.g. ethylene oxide and / or ce oxide. 7 propylene, with initiators containing from 2 to 8 active hydrogen atoms per molecule.
Suitable initiators: include polyols, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose; polyamines, for example, ethylene diamine, tolylene diamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines; and aminoalcohols, for example, ethanolamine and diethanolamine; and amincoalcohols, for example, ethanolamine and diethanolamine; and mixtures of such initiators. Other suitable polyols include polyesters obtained by condensing appropriate proportions of glycols and - 5 polyols with higher functionality with polycarboxylic acids. Other suitable polyols include - hydroxy-terminated polyethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes. Other suitable isocyanate-reactive components include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylolpropane, ethylene diamine, ethanolamine, diethanolamine, triethanolamine and the other initiators mentioned above. Mixtures of such isocyanate-reactive components can also be used. Most preferably, polyols are used which do not comprise primary, secondary or tertiary nitrogen atoms. Of particular importance for the preparation of the flexible polyurethane foams of the present invention are polyols and polyol mixtures containing hydroxyl equivalent weight equal to or greater than 1200, preferably equal to or greater than 1500, more preferably equal to or greater than 1700. Equivalent weight of polyol is the molecular weight of the polyol divided by the hydroxyl functionality of the molecule. Of particular importance for the preparation of the flexible polyurethane foams of the present invention are polyols and polyol mixtures containing an equivalent weight of: / hydroxyl equal to or less than 4000, preferably equal to or less than 3000 and more preferably equal to or less than 2500. The polyols used in the preparation of the flexible foams of the present invention have an average nominal hydroxyl functionality of 2 to 8, preferably 2 to |
4. Of particular importance for the preparation of flexible foams are the reaction products of alkylene oxides, for example, ethylene oxide and / or oxide
.. - mx mm to ul Cs -.- a. | |
Propylene, with initiators containing from 2 to 8 atoms | active hydrogen per molecule. Suitable initiators include polyols, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane - 5 diol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol and sorbitol; polyamines, for example, ethylene diamine, tolylene diamine, diaminodiphenylmethane and polymethylene polyphenylene diamines; and aminoalcohols, for example, ethanolamine and diethanolamine; and mixtures of such ”" 7 7 "10 primers. Other suitable polyols include polyesters obtained by condensing appropriate proportions of glycols and polyols of higher functionality with polycarboxylic acids. Others - “Suitable polyols include hydroxyl-terminated polyethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes. Preferred polyols are polyether polyols comprising ethylene oxide and / or propylene oxide units and most preferably polyoxyethylene polyoxypropylene polyols having an oxyethylene content of at least 10 percent and preferably 10 to 85 percent by weight. An isocyanate-reactive component comprises a polyether polyether capped with ethylene oxide.
Other polyols that can be used comprise dispersions or addition solutions or condensation polymers in polyols of the types described above. Such modified polyols, often referred to as "copolymer" polyols, have been fully described in the "state of the art" and include products obtained by in situ polymerization of one or more vinyl monomers, for example, styrene and acrylonitrile, in polymeric polyols, for example, polyether polyols, or by the in situ reaction between a polyisocyanate and a compound with amino or hydroxy functionality, such as triethanolamine, in a polymeric polyol.
Polymer modified polyols, which are particularly interesting according to the invention, are products
Mi eso :: p>,) -> 2 NnôB. | Í l 0 to “tt pb" MM o = 11 obtained by in situ polymerization of styrene and / or acrylonitrile in polyoxyethylene polyoxypropylene polyols and products obtained through the in situ reaction between a polyisocyanate and a compound with amino or - 5 hydroxy functionality (such as triethanolamine) in a polyoxyethylene polyoxypropylene glycol.
MM Polyoxyalkylene polyols containing 5 to 50 percent dispersed polymer are particularly useful. “Particle sizes of the dispersed polymer less than -—— 50 microns are preferred.
Mixtures of such isocyanate-reactive components can also be used.
Most preferably, polyols are used which do not comprise primary, secondary or tertiary nitrogen atoms.
Side B further comprises a flame retardant component (iii) which comprises a combination of red phosphorus (iiii.a) J, an expandable graphite (iii.b), and optionally sodium citrate (iii.c). In a preferred embodiment, the flame retardant component does not contain ammonium polyphosphate.
The red phosphorus that builds the composition for the flexible flame retardant polyurethane foam of the present invention is inorganic.
Inorganic red phosphorus may be untreated or the surface may be treated with an inorganic and / or organic substance (hereinafter referred to as coated red phosphorus), and the like.
It is especially preferable to use red phosphorus coated in terms of '---—- stability-and ease-of-handling.
Examples ... of 7 commercial red phosphorus products include NOVA RED "" and NOVA EXCEL "" by Rin Kagaku Kogyo Co., HISHIGUARDT "'by Nippon Chemicals Industries Co., and EXOLIT" "RP607 by Clariant.
Red phosphorus can be pure, concentrated or used as a mixture, solution or a thixotropic dispersion in a carrier medium, such as castor oil, diphenyloctyl phosphate, tris (chloropropyl) phosphate (TCPP), etc., for example, EXOLIT RP 6590 (TP ) and EXOLIT RP 6580
, NS mo '| . . 12 fr o amem: hip - - o = - by Clariant.
Red phosphorus (iii.a) is present in an amount | equal to or greater than 0.1 part based on the total weight of | side B, preferably equal to or greater than 0.5 part, and | -F 5 more preferably equal to or greater than 1 part based on the total weight of side B.
The red phosphorus (iii.a) is "present in an amount equal to or less than 10 parts, based on the total weight of side B, preferably equal to or less than 8 parts, and more preferably equal to or less than 6 parts, based on the total weight of side B.
The flame retardant component (iii) also consists of an expandable graphite (iii.b) well known in the art.
Examples include crystalline compounds that maintain the laminar structure of the carbon that generated a graphite interlayer compound through treatment of natural flocked graphite, pyrolytic graphite, Kish graphite, or other powder through concentrated sulfuric acid, 1 nitric acid, or other inorganic acid and nitric acid | concentrate, perchloric acid, permanganic acid, '20 nichromate, or other strong oxidizing agent.
Expandable graphite that has been neutralized with ammonia, with lower aliphatic amine, alkali metal compound, alkaline earth metal compound, or similar, is preferably | used.
Examples of aliphatic lower amines | 25 include monomethylamine, dimethylamine, trimethylamine, ethylamine, and the like.
Examples of alkali metal compounds and alkaline earth metal compounds as --— include hydroxides, oxides, -carbonates, sulphates, salts of '-' organic acid, and the like of potassium, sodium, calcium, barium, magnesium and the like.
Preferably, the expandable graphite flakes are 0.2 to 1.0 mm in size.
In one embodiment, the expandable graphite (iii.b) used is formed of graphite, with H; SO0, or SO., For example, having two free negative valences, which bond to two free positive valences of a hydrocarbon ring , incorporated between the graphite mesh planes.
When the flexible polyurethane foam is burned, the volume of this graphite expands 100 to 200 times, releasing SO; and / or SO, and water.
A loose and expanded mass is then formed that acts in isolation.
Examples of commercial expandable graphite products - 5 include NYAGRAPH "" by Naycol Nano Technologies, Inc., CA-608 "by Nippon Kasei Chemical Co., and CALLOTEK" "by 7 Graphitwerk Kropmuehlm AG. 'The expandable graphite (iii.b ) is present in an amount equal to or greater than 0.5 part based on the total weight of side B, preferably equal to or greater than 1 part, and more preferably equal to or greater than 2 parts based on the total weight of side B.
Expandable graphite (iii.b) is present in an amount equal to or less than parts, based on the total weight of the BB side, preferably equal to or less than 8 parts, and more | preferably less than or equal to 6 parts, based on the total weight of side B. the flame retardant component (iii) may optionally further consist of sodium citrate (ili.c) which is well known in the art.
If sodium citrate (iii.c) is present in the flame retardant component (iii) of the present invention, it is present in an amount equal to or greater than 0.5 part based on the total weight of side B, preferably | 25 equal to or greater than 1 part, and more preferably equal to or greater than 2 parts, based on the total weight of side B. | If sodium citrate (iii.oc) is present in | flame retardant component (iii) of the present invention, S it is present in an amount equal to or less than 15 parts, based on the total weight of the reactive component with isocyanate, preferably less than or equal to 12 parts, and more preferably less than or equal to 10 parts, based on the total weight of side B. na - In "one embodiment, -o-side A; the "B and / or other - reactive formulation of the present invention may comprise an additional compound other than ammonium polyphosphate, including the organic and / or inorganic, halogenated and / or non-halogenated type, in addition to red phosphorus (iii.a ), expandable graphite (iii.b) and optionally sodium citrate (iii.c) to improve the flame resistant performance of the flexible polyurethane foam produced with them.
In one embodiment, side A, side B, to the formulation. reactive, the flame retardant component (iii), and / or a: flexible polyurethane foam of the present invention, do not comprise or contain any flame retardant additives other than red phosphorus (iii.a), oO expandable graphite (iii. b) and optionally, sodium citrate (iii.c). In one embodiment, side A, side B, the reactive formulation and / or the flame retardant component (iii) and / or the flexible polyurethane foam of the present invention do not comprise “nor do they contain any other flame retardant additives other than red phosphorus (iii.a) and expandable graphite (iii.b). In another embodiment, side A, side B, the reactive formulation, the flame retardant component (iii) and / or the flexible polyurethane foam of the present invention do not contain a compound containing organic phosphorus.
In another embodiment, side A, side B, the reactive formulation, the flame retardant component (iii) and / or the flexible polyurethane foam of the present invention do not contain, well comprise casein.
In another embodiment, side A, side B, the "reactive formulation, the flame retardant component (iii) and / or the" flexible polyurethane foam of the present invention do not comprise or contain halogenated flame retardant.
In other words, side A, side B, and / or the reactive formulation of the present invention comprise only non-halogenated flame retardants.
The reaction of the reactive formulation of the present invention comprising one or more organic polyisocyanate (1), one or more reactive components with isocyanate (ii), and the flame retardant component (iii) comprising a combination of red phosphorus (iii.a), expandable graphite (iii.b) and optionally sodium citrate (iii.c), and the flame retardant component does not contain ammonium polyphosphate, to prepare a flexible polyurethane foam, it can be conducted in the presence of various types of other additional materials (iv), Li as may be useful in the specific manufacturing process used, or to impart the desired characteristics to the resulting foam.
These include, for example, catalysts, blowing agents, cell openers, surfactants, crosslinkers, chain extenders, flame retardants (other than red phosphorus, expandable ammonium polyphosphate, and sodium citrate), fillers, fillers, colorants , pigments, antistatic agents, reinforcing fibers, antioxidants,
preservatives, acid scavengers, and the like.
Side B may comprise one or more additional components (iv). For example, in order to prepare a flexible polyurethane foam of the present invention, a blowing agent, preferably water, is required.
However, if the amount of water is not sufficient to obtain the desired density of the foam, any other form of preparation of polyurethane foams can be additionally employed, such as the use of reduced or variable pressure, the use of a gas such as oxygen, N, and CO; z, O The use of more conventional blowing agents, such as chlorofluorocarbons, hydrofluorocarbons, hydrocarbons, and fluorocarbons, use other blowing agents, reactive, that is, agents that react with any of the ingredients in the reaction mixture and that, due to this' reaction, they release a gas that causes the mixture to foam, and The use of catalysts that improve the reaction that leads to the formation of gas such as the use of catalysts that increase the formation of carbodiimide, such as phospholene oxides.
Combinations of these forms of foam preparation can also be used.
The amount of blowing agent can vary widely and depends mainly on the desired density.
Water can be used as a liquid at room temperature, room temperature or at high temperature and as steam.
One embodiment of the present invention is a combination - blowing agent with water and CO ;, being CO; added to the ingredients for preparing the foam on top of. mixing a foam-making device to one of the isocyanate-reactive ingredients and - preferably to the polyisocyanate before the o-polyisocyanate is brought into contact with the isocyanate-reactive ingredients.
In one embodiment, the flexible polyurethane foam of the present invention is prepared with reactive formulations comprising (A) side A comprising an organic isocyanate (i) and (B) side B comprising an isocyanate reactive component (ii), and the flame retardant additive (iii) in the presence of water.
Preferably, such formulations contain from 1 to 7 weight percent, especially from 1 to 6 weight percent water, based on the total weight of the isocyanate-reactive component.
Desirable flexible polyurethane foam can be prepared in a block process or in a closed mold.
Closed mold molding processes are preferred for manufacturing molded products, such as under the hood applications, for example, engine encapsulation members.
As an additional component (iv), one or more catalysts ... may be present. on side B of. reactive formulation of. -.-- the present invention.
A preferred type of catalyst is a | 30 tertiary amine catalyst.
The tertiary amine catalyst can be any compound that has catalytic activity for the reaction between a polyol and an organic polyisocyanate and at least one tertiary amine group.
Representative tertiary amine catalysts include trimethylamine, triethylamine, dimethylethanolamine, N-methylmorpholine, N-ethyl-morpholine, N, N-dimethylbenzylamine, N, N-dimethylethanolamine,
'| | 17 'N, N, N', N'-tetramethyl-1, 4-butanediamine, N, N-dimethylpiperazine, 1,4-diazobicyclo-2,2,2-octane, bis (dimethylaminoethyl) ether, bis (2- dimethylaminoethyl) ether, morpholino, 4.4 '- (oxy-2,1-ethanediyl) bis, - 5 triethylenediamine, pentamethyl diethylene triamine, d dimethyl cyclohexyl amine, N-acetyl N, N-dimethyl amine, N-t coco- morpholine, N, N-dimethyl aminomethyl N-methyl ethanolamine, N, N, N-trimethyl-N'-hydroxyethyl bis (aminoethyl) ether, N, N-bis (3-dimethylaminopropyl) N-isopropanolamine, (N, N- dimethyl) amino-ethoxy ethanol, N, N, N ', N'-tetramethyl hexanediamine, 1,8-diazabicyclo-5.4, 0O-undecene-7, N, N-dimorpholinodiethyl ether, N-methyl imidazole, dimethyl aminopropyl dipropanolamine, bis (dimethylaminopropyl) amino-2-propanol, tetramethylamino bis (propylamino), (dimethyl (aminoethoxyethyl)) ((dimethylamine) (ethyl) ether, tris (dimethyl-amino propyl) amine, dicyclohexyl methylamine, bis (N, N -dimethyl-3-aminopropyl) amine, 1,2-ethylene piperidine and methylhydroxyethyl piperazine.
The B side of the reactive formulation may contain one or more other catalysts, in addition to or in place of the aforementioned tertiary amine catalyst. Among these, tin carboxylates and tetravalent tin compounds are of particular interest. Examples of these include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimercaptide, dialkyl tin acids, dibutyltin oxide, dimethyl tin dimercaptide, and similar dimethyl diisooctymercaptoacetate.
Catalysts are typically used in small amounts. For example, the total amount of catalyst used can be from 0.0015 to 5 weight percent, preferably from 0.01 to 1 weight percent, based on the total weight of the catalyst. reactive compound with isocyanate (ii). Organometallic catalysts are typically used in quantities at the minimum level of these ranges.
Side B can also comprise, as components
| DM MM MM MM 18 additional (iv) a crosslinker, which is preferably used, if applicable, in small quantities, up to 2 weight percent, up to 0.75 weight percent, or up to 0.5 percent in weight, based on the total weight of the oo 5 reactive compound with isocyanate (ii). The crosslinker contains at least three isocyanate-reactive groups per molecule and 'has an equivalent weight, per isocyanate-reactive group, from 30 to about 125 and preferably from 30 to 75. Amino alcohols, such as monoethanolamine, diethanolamine and triethanolamine are preferred types , although compounds such as glycerin, trimethylolpropane and pentaerythritol can also be used.
Side B may also comprise a surfactant as an additional component (iv). A surfactant is preferably included in the foam formulation to help stabilize it as it expands and cures.
Examples of surfactants include nonionic surfactants and wetting agents, such as those prepared by sequentially adding propylene oxide and then ethylene oxide to propylene glycol, solid or liquid organosilicones, and polyethylene glycol ethers of long chain alcohols.
Ionic surfactants, such as tertiary amine or alkanolamine salts of alkyl sulfate long chain esters, alkyl sulfonic acid esters and alkyl aryl sulfonic acids can also be used.
Surfactants prepared by the sequential addition of propylene oxide and then ethylene oxide to propylene glycol are. preferred, as are the 7 solid or liquid organosilicones.
Examples of useful organosilicone surfactants include Commercially available polysiloxane / polyether copolymers such as TEGOSTAB "" B-8729 and B-87191LF from Goldschmidt Chemical Corp., and NLAX "" L2171 surfactant from Momentive Performance Materials.
Liquid non-hydrolyzable organosilicones are more preferred.
When a surfactant is used, it is typically present in an amount of 0.0015 to 1 weight percent based on the total weight of the organic isocyanate (i). A cell opener may be present as an additional component (iv) on the B side of the reactive formulation.
The cell opener acts during the polymerization reaction to disrupt cell walls and therefore promote the formation of an open t cell structure.
A high open cell content (at least 25 percent in number, preferably at least 50 percent) - is generally beneficial for foams that are used in noise and vibration absorption applications.
A useful type of cell opener includes homopolymers of ethylene oxide or random copolymers of ethylene oxide and a small proportion of propylene oxide, which have a molecular weight of 5000 or more.
Such cell openers preferably have a hydroxyl functionality of at least 4, more preferably at least 6. Cell openers are preferably used in amounts of about 0.5 to about 5 weight percent based on the total weight of the reactive compound with isocyanate (ii). A chain extender can be employed in the form of an additional component (iv) on the B side of the reactive formulation of the present invention.
A chain extender is a compound that has exactly two isocyanate-reactive groups and an equivalent weight per isocyanate-reactive group of up to 499, preferably up to 250, and may also be present.
Chain extenders, if present, are and generally used..em. small amounts, such as IS up to 10, preferably up to 5 and more preferably up to 2 weight percent, based on the total weight of the isocyanate-reactive compound (ii). Examples of suitable chain extenders include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-dimethylolcyclohexane, 1,4-butane diol, 1,6-hexane diol, 1,3- propane diol, diethyl toluene diamine, polyethers with an amino termination, such as JEFFAMINE ”" "D-
400 from Huntsman Chemical Company, amino ethyl piperazine, 2-methyl piperazine, 1,5-diamino-3-methyl-pentane, isophorone diamine, ethylene diamine, hexane diamine, hydrazine, piperazine, mixtures thereof and the like. - 5 Side B can also comprise as an additional component (iv), a filler / filler that reduces the total cost 1, load capacity and other physical properties of the product.
The fill / fill constitutes up to about 50 percent of the total weight of the reactive polyurethane formulation (ie the combined weight of the organic isocyanate (i), the reactive compound with isocyanate (ii), and the flame retardant component (iii )). Appropriate fillers / fillers include talc, mica, montmorillonite, marble, barium sulfate (barites), granite, ground granite, ground glass, calcium carbonate, aluminum trihydrate, carbon, aramid, silica, silica-alumina, zirconia, talc, bentonite, antimony trioxide, kaolin, coal-based fly ash, and boron nitride.
The flexible foam can be manufactured according to the invention in a block process or in a closed molding process.
Block foam is formed as a large roll that is cut to the desired shape and size for use.
The closed molding processes can be the so-called hot molding process or the cold molding process, in which defoaming occurs in closed mold.
After the foam is cured, the mold is opened and the flexible foam removed. . ------ - <—--- An integral skin - can form - on the surface of the - foam in the mold.
A film, fabric, leather or other covering / coating material can be inserted into the mold before introducing the reactive formulation to produce a foam with a desirable-looking surface.
Polyurethane foam formulations containing a mixture of polypropylene oxides capped with ethylene oxide according to the invention have demonstrated good processing performance, especially in formulations
- 21 in which water is used as a blowing agent, especially when used as a single blowing agent, as described above.
Good processing in the present invention refers to the capacity of one. 5 Foam formulation consistently produce good quality foam in industrial environment.
Good processing * is indicated by a consistently uniform cell structure, complete mold filling, consistently »good surface appearance, consistent foam density», and consistency in the physical properties of the foam as the foam is produced over time. .
The foam formulation tolerates small changes in operating temperatures, catalyst levels and other process conditions that often cause significant product inconsistencies in other foam formulations with a high amount of water.
It is often preferred to compress the foam to open the cells.
A high open cell content (at least 25% in number, preferably at least 50%) is generally beneficial for foams that are used in noise and vibration absorption applications.
Flexible polyurethane foam is characterized by having a resilience, as determined according to the ASTM D-3574 ball drop resilience test, which measures the bounce height of a ball from the foam surface when the ball falls under specified conditions.
In the ASTM test, the foam displays e. an. resilience .de. at least 40%, especially at .... / 50% less. The flexible polyurethane foam of the present invention advantageously also has a density in. range from 4 to 10 pounds / cubic foot (pcf) (64-160 kg / ml), preferably from 5 to 8.8 pounds / cubic foot (80-140 kg / m ). The density is conveniently measured according to ASTM D 3574. The flexible polyurethane foam of the present invention advantageously has a tensile strength in the range of 150 to 800 kPa.
Preferably, the tensile strength q -. 22
U of the foam according to the present invention is equal to or greater than 150 kPa, more preferably equal to or greater than 200 kPa, more preferably equal to or greater than 250 kPa, and even more preferably equal to or greater than 300 - 5 kPa. Preferably, the tensile strength of the foam according to the present invention is equal to or greater than. 800 kPa, more preferably equal to or less than 500 kPa. The tensile strength is conveniently measured according to ASTM D 3574.
A means of measuring sound absorption performance in noise and vibration absorption applications, such as | | molded parts made of resilient and flexible polyurethane from | the present invention consists of using equipment, such as | as impedance tube, or what is generally called | 15 as reverb chambers, according to individual OEM specifications. Another test used to evaluate the acoustic absorption performance is air flow resistivity, according to ASTM C522-87. Preferably, for noise absorption and | 20 vibration, the air flow resistivity must be on! range of 30,000 and 200,000 rayls / m, more preferably | from 40,000 to 150,000 rayls / m. Rayls is the pressure divided by the volumetric flow rate, being equivalent to Pa / (mº / s) (or Pa-s / M). Air flow resistivity is given in rayls / m which is the pressure divided by the rate of; volumetric flow divided by the thickness of the foam specimen. | ce To manufacture flame resistant flexible polyurethane foam 1 - ”of the present invention, a reactive formulation is prepared, said reactive formulation comprising: one side | A comprising (i) one or more organic polyisocyanates | and a B side comprising (ii) one or more reactive components with isocyanate, (iii) a flame retardant component comprising a combination of: (iii.a) red Hd 35 phosphorus, (iii.b) expandable graphite, and ( iiií.o) L optionally sodium citrate and the flame retardant component does not contain ammonium polyphosphate; and | |
(iv) one or more additional components selected from a catalyst, a blowing agent, a cell opener, a surfactant, a crosslinker, a chain extender, a flame retardant (other than red phosphor, expandable graphite - 5, and sodium citrate), a filler, a dye, a powder, an antistatic agent, reinforcing fibers, an antioxidant, a preservative, or an acid scavenger. The "side B" is a premix comprising the appropriate amounts of polyol, flame retardant component, blowing agent, catalyst, foaming aid, and other adjuvants specific to the final polyol / foam component. Depending on the composition of the side. B, high temperatures, above 40ºC, may be necessary to mix the components. Preferably, side B is mixed at a temperature below 40 ° C, more preferably at room temperature (defined in the present invention as being 20 ° C to 30 ° C). The B side is then mixed with the specific organic (poly) isocyanate component, comprised on the "side A" in the desired relationship, forming the reactive formulation that, when mixed, allows the foaming reaction to occur. The polyol premix (side B) and the organic polyisocyanate component (side A) are mixed together using any known urethane foaming equipment. The resulting reactive formulation is subjected to sufficient conditions to cure the reactive formulation and form a flexible flame resistant polyurethane foam that obtains a VO UL 94 rating at 0.5 ". The" reactive formulation is introduced in an appropriate mold for it to occur a foaming / curing reaction within the mold to form the desired polyurethane foam is either left to foam / cure to form a block or is foamed in place.
-. ) u The flame resistant flexible polyurethane foam thus manufactured can be suitably used in flame resistant and noise and vibration absorption applications, in accordance with the present invention, for example foams
= 24 1 - = - - can be used and / or molded into an article for use in and / or molded / foamed on the spot in the form of an engine cover, an engine noise isolator, a fuel injector encapsulator, a side cover, a crankcase cover 5, a bottom cover, a hood muffler, and a control panel muffler, which are arranged “around or in the vicinity of a motor vehicle engine, to reduce the amount of sound or noise to be transmitted from the engine. In particular, the flame resistant flexible polyurethane foam can be properly used and / or molded into articles to be used for or molded / foamed on the spot as spacers or fillers to fill gaps or spaces between the engine and adjacent devices, or encapsulation engine parts to mitigate standing waves.
EXAMPLES Comparative Examples A to E and Examples 1 to 4 * comprise a reaction formulation used to provide a flexible polyurethane foam comprising a polyol component and other additives (side B) and an isocyanate component (side A). The polyol component comprises one or more polyol, catalyst, flame retardant component, reticulating agent (diethylene glycol), blowing agent (water), silicon surfactant, black dye, the components being pre-mixed. When mixing the polyol component, the phosphorus “The red is added first and finally the expandable graphite 7. All components are added to and mixed on side B at room temperature (in this case, around 23ºC). The isocyanate component comprises a carbodiimide-modified MDI with 72 weight percent of 4,4'-MDI and 2 weight percent 2,4'-MDI, an equivalent molecular weight of about 145, and a content of isocyanate of about 29, The polyol component and the isocyanate component are molded on a foam pad using an impact mixer under high
25 e and HiTech pressure equipped with a 40 "x 40" x 1 "frame with a 20" x 20 "x 1" mold insert. The top and bottom of the test mold are heated to 54ºC.
Side B is heated to 27ºC and side A to 27ºC.
A - 5 injection pressure for both side B and side A is 2000 pounds per square inch (psi). The * injection size is 680-750 grams (g) and the injection load time is 2.25 to 2.45 seconds (s). The curing time is 3 minutes (min). After the foam is cured, the mold is opened and the foam demoulded. : The composition of the polyol component (side B) for Comparative Examples A to E and each of Examples 1 to 4 are listed in Table 1, For Comparative Example A and E and Examples 1 to 4 a mixture is prepared of formulated polyol (comprising polyols and other additives) with the components described below.
The amounts are given by weight based on the total weight of the formulated polyol mixture.
The quantities for the components that make up the polyol component (B) are given in parts, based on the total weight of the polyol component (B). The ratio of the polyol component (B) and the isocyanate component (A) are given in; parties.
In Table 1: "Polyol-1" is a propylene oxide initiated with glycerin having a hydroxyl index of 56 and an equivalent weight of 1,000, supplied as a VORANOL "" polyol 2100 by The Dow Chemical Company; 'e =. - “7 Wpoliol-2" is a propylene oxide initiated with glycerin And 15% polyol capped with ethylene oxide having a hydroxyl index of 27.5 and an equivalent weight of 2040, supplied as VORANOL CP 6001 polyol by The Dow Chemical Company; "Isocyanate" is a carbodiimide modified MDI with 61 weight percent of 4,4'-MDI and 2 weight percent 2,4'-MDI, an equivalent molecular weight of about 145 and an isocyanate content of about 29 supplied as Isocyanate 143 by The Dow Chemical Company;
- - - - 26 ”” - - "DEG" is diethylene glycol; "TEGOSTAB" "B 4113" is a silicon surfactant of the type | low efficiency cell regulator supplied by | Goldschmidt Gmbh; “5" DABCO "" 33 LV "is 33% triethylene diamine in catalyst | Air Products' dipropylene glycol curing agent; | * "DABCO BL 11" is an bis (N, N-dimethylaminoethyl) ether at 70% | percent in dipropylene glycol blowing catalysts from - | Air Products; "Black" is a black dye supplied as POP 4654 Black by Day Glo; "EXOLIT AP 462" is a 30 percent by weight ammonium polyphosphate flame retardant, supplied by Clariant Pigment and Additive Division; | 15 "EXOLIT RP 607" is microencapsulated red phosphorus flame retardant supplied by Clariant Pigment and | Additive Division; | "NYAGRAPH FP" is an expandable graphite with an initial expansion temperature of 200ºC and an expansion volume of 180 milliliters per gram (ml / g) supplied by Naycol Nano Technologies, Inc .; "NYAGRAPH 351" is an expandable graphite with an initial expansion temperature of 150ºC and a volume of: expansion of 350 milliliters per gram (ml / g) supplied by Naycol Nano Technologies, Inc .; "Sodium citrate" is dehydrated sodium citrate provided by Fisher Scientific. - -: The properties for the foams resulting from polyol mixtures 7 resulting from Comparative Examples A and B and Example 1 are shown in Table 1. In Table 1: º "Processability" is determined visually, according to the appearance of the pad molded and evaluating the characteristics of "free" foam (eg if the foam mixture, foam growth rate, if the foam disintegrates).
"Isocyanate index" is the ratio of the actual amount of isocyanate to the theoretical amount of isocyanate
'. - 27
| necessary to react with the polyol component;
| "Density" is determined according to ASTM D3574 and is reported in kilograms per cubic meter (kg / m );
| "Resistance to airflow" is determined according to l bx 5 with ASTM C522-87 and reported in rayls / m;
| "Tensile strength" is determined according to ASTM
. D3574 and reported in kilopascals (kPa); "Elongation" is the tensile elongation at break and
-. determined according to ASTM D3574 and reported in
; 10 percentage (%); "Tear resistance" is determined according to ASTM D3574 and reported in Newtons per meter (N / m); and
"UL 94" is a vertical flammability test conducted
'according to Underwriters Laboratories standard 94 and
0.5 ", whereas 0.5" x 5 "foam samples, samples that do not meet / meet the requirements the ULK 94 requirements are not classified (NR). 2.
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权利要求:
Claims (1)
[1]
' 1
1. Reactive formulation to prepare a flexible flame-resistant polyurethane foam, characterized by the fact that it comprises a mixture of: o 5 (A) an A side comprising: (i) one or more organic isocyanates, and is (B) one side B comprising: (ii) one or more reactive components with isocyanate,. (iii) a flame retardant component comprising a combination of: (iii.a) 0.1 to 6 parts by weight of red phosphorus, (iii.b) expandable graphite, and (iii.c) optionally sodium citrate , the flame retardant component does not contain ammonium polyphosphate and the parts by weight are based on the total weight of the B side, and (iv) one or more additional components, selected from a catalyst, a blowing agent, an opener cells, a surfactant, a crosslinker, a chain extender, a flame retardant, a filler / filler, a dye, a pigment, an antistatic agent, reinforcing fibers, an antioxidant, a preservative, or an acid scavenger, the said flame resistant flexible polyurethane foam prepared with the reactive formulation reaches a rating V-0O at 0.5 ", according to the 94 standard for the flammability test (UL 94) of Underwriters Laboratories. eee -. 24 »Formulation, -of - according to“ “claim 1,” characterized by the fact that the is organic ocyanate comprise monomeric MDI, polymeric MDI, its. combinations and / or liquid variants thereof, obtained by introducing polyisocyanates forming groups uretonimine and / or carbodiimide, said polyisocyanates modified with carbodiimide and / or uretonimine containing an NCO index ranging from 29 to 33 percent and included in said polyisocyanate of 1 to 45 weight percent 2,4'-diphenylmethane diisocyanate in the form of a monomer and / or a carbodiimidization product thereof.
3. Formulation according to claim 1, characterized in that said isocyanate-reactive component comprises a polyol polyester capped with ethylene oxide.
+ 4. Formulation according to claim 1, characterized by the fact that the expandable graphite (iii.b) is present in an amount of 0.5 to 10 parts by weight, with parts by weight being based on the total weight on side B.
5. Formulation according to claim 4, characterized in that the flame retardant component also comprises: (iii.c) from 0.5 to 15 parts by weight of sodium citrate, with parts by weight being based on on the total weight of side B.
6. Process for preparing a flame resistant flexible polyurethane foam, characterized by the fact that it comprises the steps of: (1) forming: (A) an A side comprising: (i) one or more organic isocyanates, and (B) a side B comprising: (ii) one or more reactive components with isocyanate, (iii) a flame retardant component comprising a combination of: “O (iiji.va) 0.1 to 6 parts by weight of red phosphorus, a (iii .b) expandable graphite, and (iii.c) optionally sodium citrate, where the flame retardant component does not contain ammonium polyphosphate and the parts by weight are based on the total weight of side B, and (iv) a or more additional components, selected from a catalyst, a blowing agent, a cell opener, a surfactant, a crosslinker, a chain extender, a flame retardant, a filler / filler, a
'"3 dye, a pigment, an antistatic agent, reinforcing fibers, an antioxidant, a preservative, or an acid scavenger; (II) mix side A and side B together to form an a, 5 reactive formulation; and (III) subject the resulting reactive formulation to Conditions sufficient to cure the reactive formulation and form a flame resistant flexible polyurethane foam, said foam meeting the V-0 rating at 5 "according to standard 94 of the Flammability (UL 94) from Underwriters Laboratories.
7. Formulation according to claim 6 &, characterized by the fact that the flame resistant flexible foam has a density of 80 kg / m to 140 kg / m.
8. Formulation according to claim 6, characterized in that the flame resistant flexible polyurethane foam has a tensile strength equal to or greater than 150 kPa, 9 Formulation according to claim 6, characterized by the fact that a flame resistant flexible polyurethane foam having an air flow resistivity of 40,000 rayls / m to 150,000 rayls / m.
10. Formulation according to claim 6, characterized in that the flame resistant flexible polyurethane foam is arranged around or in the vicinity of the automotive vehicle engine such as engine cover, engine noise isolator, 'NS encapsulator. ...... in. injector .de. fuel, cap. side, lid. .
»Sump, bottom cover, hood muffler, or a control panel muffler.
11. Flame resistant flexible polyurethane foam for use in the engine compartment of a vehicle, characterized by the fact that it is free of halogen and ammonium polyphosphate and has a flammability rating of UL 94 from VO to 0.5 ", a density between 80 kg / m and 140 kg / m "and an air flow resistivity between 40,000 rayls / m and 150,000 rayls / m.

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EP3696206A1|2019-02-12|2020-08-19|Hilti Aktiengesellschaft|Foamable, multi-component composition which forms an insulating layer and its use|

KR102177328B1|2019-10-17|2020-11-11|한국화학연구원|Two liquid type polyurethane composition and semi-non-combustible polyurethane composite material manufactured from the same and method for manufacturing the same|

NL2024564B1|2019-12-23|2021-09-02|Stahl Int B V|Flame retardant mechanical foam|

KR102336423B1|2020-05-20|2021-12-07|병 국 박|Flame-retardant protective cover material for pipe and Manufacturing method thereof|

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法律状态:
2020-10-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2020-11-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2021-02-23| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

申请号 | 申请日 | 专利标题

US41496110P| true| 2010-11-18|2010-11-18|

US61/414,961|2010-11-18|

PCT/US2011/059253|WO2012067841A2|2010-11-18|2011-11-04|Flame resistant flexible polyurethane foam|

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