CN111040104A - Sound-absorbing flame-retardant vegetable oil-based polyurethane foam material and preparation method thereof - Google Patents
Sound-absorbing flame-retardant vegetable oil-based polyurethane foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sound-absorbing flame-retardant vegetable oil-based polyurethane foam material and a preparation method thereof, wherein the foam material comprises the following raw materials of vegetable oil polyalcohol, foam stabilizer, flame retardant, expandable graphite and Cu in parts by weight2O‑MoS2Hybrid particles, silica microcapsules, a cross-linking agent, water, a foaming catalyst, isocyanate and the like. The sound-absorbing flame-retardant vegetable oil-based polyurethane foaming material has good sound-absorbing flame-retardant property, and Cu2O‑MoS2The addition of the hybrid particles effectively improves the smoke suppression and toxicity suppression characteristics of the flame retardant material, the addition of the silicon dioxide microcapsules and the preheating treatment of the foam bare board can ensure that the molded part has a smooth appearance and no flaws.
Description
Technical Field
The invention relates to the technical field of polyurethane foaming production, in particular to a sound-absorbing flame-retardant vegetable oil-based polyurethane foaming material for parts such as a hood, a front wall, a side wall and the like of an automobile engine and a preparation method thereof.
Background
The semi-rigid polyurethane foam material has both the flexibility of the soft polyurethane foam and the rigidity of the hard polyurethane foam, and is widely applied to the fields of product packaging, automobile interior and exterior decoration and the like. With the development trend of the automobile industry, certain interior and exterior parts of automobiles need to meet the requirements of light weight, sound absorption, flawless appearance and the like, wherein semi-rigid polyurethane foam materials commonly used in automobile engine covers, front walls and side walls have the characteristics of low density, sound insulation and heat insulation. The automobile engine hood and side wall structure using polyurethane foam is 'fabric-polyurethane foam-fabric', and is formed by molding a polyurethane foam composite board through a special mold, wherein the fabric is generally bonded with a polyurethane foam sheet through an adhesive film or rubber powder with a melting point of 110-.
Patent CN103910854B discloses a low-density flame-retardant semi-rigid polyurethane foam and a preparation method thereof, the density of the prepared polyurethane foam is 8-25kg/m3, the prepared polyurethane foam is characterized by open pores, flame retardance and low density, and the surface appearance and the burning smoke suppression property of a formed part of a foam composite plate after mould pressing are not mentioned.
Patent CN102391456A discloses a polyurethane foam for heat and sound insulation of automobile engine, the foam density is 17 ± 3kg/m3, the foam is foamed by using a composition, the effect of raw material components on the foam performance is not mentioned, and the foam opening and flame retardant effect are not mentioned.
Patent CN106916438B discloses a halogen-free flame-retardant anti-dripping thermoplastic polyurethane elastomer material and a preparation method thereof, and a method of wrapping a halogen-free flame retardant by adopting a nano material plays an excellent flame-retardant effect. The patent belongs to the field of polyurethane elastomers, and does not relate to a foaming-gel balancing process of a polyurethane foaming material.
Patent CN106977684B discloses a high-flame-retardant halogen-free low-smoke low-toxicity single-component polyurethane foam gap filler with oxygen index not less than 32 and a preparation method thereof, wherein the gap filler needs good filling effect and mechanical property, and does not need to open pores of a foaming material.
Patent CN110283351A discloses a flame-retardant rigid polyurethane foam and a preparation method thereof, wherein a foaming agent uses n-pentane and is not foamed in full water.
Disclosure of Invention
The invention aims to provide a sound-absorbing flame-retardant vegetable oil-based polyurethane foam material and a preparation method thereof. In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
the invention discloses a sound-absorbing flame-retardant vegetable oil-based polyurethane foam material, which comprises the following raw materials in parts by weight:
Cu2O-MoS2the hybrid particles are made of Cu2O nanoparticle modified MoS2The hybrid particles with the laminated structure are added into the organic flame-retardant material, have good smoke suppression effect when a fire disaster occurs, and reduce the smoke toxicity of the material. The Cu2O-MoS2The hybrid particles have a special structure, MoS2Physical adsorption of Cu2The catalytic action of O has synergistic effect, so that the generation of harmful organic volatile matters such as carbon monoxide, nitrogen oxides and the like and toxic gases can be effectively reduced. The Cu2O-MoS2The hybrid particles have the function of foaming nucleation in the polyurethane foaming material, and the regularity of foam pores is promoted.
The silicon dioxide microcapsule is a phase change energy storage microcapsule with a wall material of silicon dioxide, the average grain diameter is 2-4 microns, and a core material of the phase change energy storage microcapsule is an aliphatic alkane organic phase change material, and the silicon dioxide microcapsule has the characteristics of high mechanical strength, high temperature resistance and high heat conduction speed, so that the silicon dioxide microcapsule can not be damaged under repeated heating and has a good energy storage effect. After the polyurethane foam board composite fabric is subjected to heating and molding, parts such as an automobile engine hood, a front wall, a side wall and the like are formed, in the heating and molding process of the composite board, the size change of polyurethane foam is reduced or slowed due to the action of a phase-change material, and the hot molding matching degree of the fabric and a foam core layer is improved, so that the problems of wrinkles, salient points, orange peel lines and the like caused by mismatching of the appearance of the parts due to size change are solved. Meanwhile, due to the energy storage and constant temperature characteristics of the phase-change material, the heat insulation performance of the foaming material is effectively improved.
As a further improvement, the combined vegetable oil polyol of the present invention is: a mixture of polyol a and polyol b in a weight ratio of 1: 0.11-0.33.
As a further improvement, the polyol a provided by the invention is a vegetable oil polyol with a hydroxyl value of 120-140mgKOH/g and an average functionality of 2; polyol b is a vegetable oil polyol having a hydroxyl value of 390-. The reaction degree of the polyol a and the isocyanate is high, and the excellent tensile strength and elongation of the foaming material are provided; and the polyurethane foam prepared by the polyol b has high crosslinking degree, forms a compact network structure and provides excellent compression strength for the foaming material.
As a further improvement, the polyol a is FH-2130 of Zhang Home aviation science and technology, and the polyol b is FH-8450 of Zhang Home aviation science and technology. The vegetable oil polyalcohol replaces the traditional petroleum-based polyalcohol, the utilization of renewable natural resources is realized, and the product quality is stable and environment-friendly.
As a further improvement, the foam stabilizer of the invention is: a mixture of foam stabilizer a and foam stabilizer b in a weight ratio of 1: 0.8-1.4. A stable foaming process for low density foams is provided.
As a further improvement, the foam stabilizer a is one or two of B123 and B110 of winning companies; foam stabilizer B is B8462 from winning company. The foam stabilizer a has a low proportion, which can cause the abnormalities of foam collapse, foam cracking and the like in the foaming process, the foam stabilizer b provides regular foam pores and high open-cell rate of the foam, and the foam has the problems of high closed pores, serious shrinkage and the like due to a low proportion.
As a further improvement, the foaming catalyst of the invention is: catalyst a and catalyst b with the weight ratio of 1:0.6-1.2, wherein the catalyst a is one or two of NE1070 and NE1091 of winning companies; catalyst b is NE300 from winning company. The foaming catalyst and the catalyst are compounded for use, so that stable foaming balance is provided, and a key effect is played on a foaming process. The use of only a single catalyst or too high or too low a proportion of one catalyst can result in an imbalance in the foaming process and failure to produce a normal foam. Wherein: the catalyst a is one or two of NE1070 and NE1091 of winning and creating companies, and is a master control gel; catalyst b was NE300 from winning company, the master control of foaming. Both catalysts belong to non-diffusion type catalysts, and cannot cause harm to process operators.
As a further improvement, the flame retardant is a phosphorus-nitrogen halogen-free flame retardant. When the material containing the phosphorus-nitrogen halogen-free flame retardant encounters fire, a large amount of smoke and toxic hydrogen halide gas are not generated in the flame retardant process.
As a further improvement, the expandable graphite is 150-200 meshes, the cross-linking agent is glycerol, and the isocyanate is modified diphenylmethane diisocyanate. The expandable graphite is in the mesh range, so that the dispersibility of the expandable graphite in the material liquid is good during foaming, particle accumulation cannot occur, and too large cells cannot be caused.
The invention also discloses a preparation method of the sound-absorbing flame-retardant vegetable oil-based polyurethane foam material, which comprises the following steps:
1) uniformly mixing the combined vegetable oil polyalcohol, the foam stabilizer and the flame retardant in proportion to form a material A, taking isocyanate as a material B, uniformly mixing the crosslinking agent, water and the foaming catalyst in proportion to form a material C, and weighing the expandable graphite and the Cu in proportion2O-MoS2The hybrid particles and the silicon dioxide microcapsules are placed in the same container; the material A and the material C are ensured to be uniform in system and have no bubbles; controlling the temperature of the material A and the material B at 22-25 ℃, and controlling the temperature of the material C at 18-20 ℃; the material temperature is controlled within the range, the foaming process is stable, the foam holes are uniform, the foam opening is high, and the difference between foams is small;
2) adding the material A and the material B into a foaming barrel according to the proportion, uniformly stirring, and then adding the weighed expandable graphite and Cu together2O-MoS2The hybrid particles and the silicon dioxide microcapsules are stirred uniformly again; the stirring rotating speeds of the two times are controlled to be 400-800r/min, and the stirring time is controlled to be 15-25 s; the raw materials of the components are fully mixed in the range, and air bubbles cannot be involved, so that the air bubbles can cause uneven foam cells;
3) immediately adding the weighed material C into the foaming barrel, fully stirring, quickly casting in a mold for reaction, controlling the stirring speed at 1000-1200r/min, and controlling the stirring time at 8-12 s; in the range, the raw materials are uniformly mixed and have good leveling property in the die;
4) and trimming after curing the foam, and cutting according to a set thickness to obtain a foam bare board, and heating the bare board in an oven at the temperature of 130-200 ℃ for not less than 2min to obtain the polyurethane foam material. The purpose of heating the bare board under these conditions is to release volatile substances from the foamed material and to break the remaining closed cells of the foam, while at the same time allowing unreacted groups in the material to react again and crosslink, thereby further increasing the strength of the material.
The invention has the following beneficial effects:
1) the sound-absorbing flame-retardant vegetable oil-based polyurethane foam material disclosed by the invention is a foam material used for parts such as a hood, a front wall and a side wall of an automobile engine, has good sound-absorbing flame-retardant property, and Cu2O-MoS2The addition of the hybrid particles effectively improves the smoke and toxicity inhibiting property of the flame retardant material.
2) According to the invention, vegetable oil polyol from renewable resources is adopted, and proper raw materials such as foam stabilizer and foaming catalyst are selected and proportioned, so that the prepared foaming material has low density, good opening property and regular cells.
3) The foaming material of the invention is added with the silicon dioxide microcapsule containing the organic phase change material, so that the constant temperature property of the foaming material is improved, and the heat insulation performance of parts such as a hood, a front wall, a side wall and the like of a molded automobile engine can be improved.
4) The foaming material of the invention is added with the silicon dioxide microcapsule, and simultaneously, the foam bare board is preheated, so that the molded part has smooth appearance and no flaw. After the foam bare board is subjected to preheating treatment, the foam opening rate is improved, so that the sound absorption performance of the foam is improved.
5) Inventive Cu2O-MoS2The hybrid particles are made of Cu2O nanoparticle modified MoS2The hybrid particles with the laminated structure are added into the organic flame-retardant material, have good smoke suppression effect when a fire disaster happens, reduce the smoke toxicity of the material, and are Cu2O-MoS2The hybrid particles have a special structure, MoS2Physical adsorption of Cu2The catalytic action of O has synergistic effect, so that the generation of harmful organic volatile matters and toxic gases such as carbon monoxide, nitrogen oxides and the like can be effectively reduced, and Cu2O-MoS2The hybrid particles are combined in the polyurethane foam materialThe foam nucleation promotes the regularity of the foam cells.
6) The silicon dioxide microcapsule is a phase change energy storage microcapsule with a wall material of silicon dioxide, the average particle size is 2-4 microns, and a core material of the phase change energy storage microcapsule is an aliphatic alkane organic phase change material, and the silicon dioxide microcapsule has the characteristics of high mechanical strength, high temperature resistance and quick heat conduction, so that the silicon dioxide microcapsule can not be damaged under repeated heating and has good energy storage effect Orange peel lines and the like, and the heat-insulating property of the foaming material is effectively improved due to the energy-storage constant-temperature characteristic of the phase-change material.
7) The combined vegetable oil polyol of the invention is: a mixture of polyol a and polyol b in a weight ratio of 1:0.11-0.33, polyol a being a vegetable oil polyol having a hydroxyl value of 120-140mgKOH/g and an average functionality of 2; polyol b is a vegetable oil polyol having a hydroxyl value of 390-. The reaction degree with isocyanate is high, and the excellent tensile strength and elongation of the foaming material are provided; the vegetable oil polyol with the average functionality of 8 is used for preparing the polyurethane foam, the crosslinking degree is high, a compact network structure is formed, and the excellent compression strength of the foaming material is provided; the vegetable oil polyhydric alcohol replaces the traditional petroleum-based polyhydric alcohol, the utilization of renewable natural resources is realized, and the product quality is stable and environment-friendly.
8) The foam stabilizer is a mixture of a foam stabilizer a and a foam stabilizer b, and the weight ratio of the foam stabilizer a to the foam stabilizer b is 1: 0.8-1.4. The foam stabilizer a is one or two of B123 and B110 of winning companies, provides a stable foaming process of low-density foam, and causes the foaming process to have abnormalities such as foam collapse and foam cracking due to too low proportion; the foam stabilizer B is B8462 of winning companies, provides regular cells and high open-cell rate of the foam, and the problems of high closed cells, severe shrinkage and the like of the foam can be caused by too low a proportion.
9) The polyurethane foaming of the invention must reach the equilibrium process of foaming and gel, and the ideal foam can be emitted. In a foaming system using full water as a foaming agent, the gel and foaming balance processes are realized through chemical reactions, namely a gel process of chemical reaction of isocyanate and polyalcohol and a foaming process of generating carbon dioxide through chemical reaction of isocyanate and water, wherein a foaming catalyst consists of a catalyst a and a catalyst b in a weight ratio of 1:0.6-1.2, and the stable foaming balance is provided by compounding the catalyst a and the catalyst b, so that the key effect on the foaming process is realized. The use of only a single catalyst or too high or too low a proportion of one catalyst can result in an imbalance in the foaming process and failure to produce a normal foam. Wherein: the catalyst a is one or two of NE1070 and NE1091 of winning and creating companies, and is a master control gel; catalyst b was NE300 from winning company, the master control of foaming. Both catalysts belong to non-diffusion type catalysts, and cannot cause harm to process operators.
10) The flame retardant is a phosphorus-nitrogen halogen-free flame retardant, and when a material containing the phosphorus-nitrogen halogen-free flame retardant encounters a fire, a large amount of smoke and toxic hydrogen halide gas are not generated in the flame retardant process. The expandable graphite of the invention has the particle size of 150-200 meshes, and the expandable graphite has good dispersibility in material liquid during foaming, does not generate particle accumulation and cause overlarge cells and Cu in the range of the mesh size2O-MoS2The hybrid particles have smoke suppression effect, and the smoke suppression performance is further improved.
Detailed Description
The invention discloses a sound-absorbing flame-retardant vegetable oil-based polyurethane foam material, which comprises the following raw materials in parts by weight:
the combined vegetable oil polyalcohol is as follows: a mixture of polyol a and polyol b in a weight ratio of 1:0.11-0.33, polyol a being a vegetable oil polyol having a hydroxyl value of 120-140mgKOH/g and an average functionality of 2; polyol b is vegetable oil polyol with the hydroxyl value of 390-; the foam stabilizer is: the weight ratio of the foam stabilizer a to the foam stabilizer B is 1:0.8-1.4, wherein the foam stabilizer a is one or two of B123 and B110 of winning companies; foam stabilizer B is B8462 from winning company. The foaming catalyst is: catalyst a and catalyst b with the weight ratio of 1:0.6-1.2, wherein the catalyst a is one or two of NE1070 and NE1091 of winning companies; the catalyst b is NE300 of winning companies, the flame retardant is a phosphorus-nitrogen halogen-free flame retardant, the expandable graphite is 150-mesh and 200-mesh, the crosslinking agent is glycerol, and the isocyanate is modified diphenylmethane diisocyanate. The preparation steps are as follows:
1) uniformly mixing the combined vegetable oil polyalcohol, the foam stabilizer and the flame retardant in proportion to form a material A, taking isocyanate as a material B, uniformly mixing the crosslinking agent, water and the foaming catalyst in proportion to form a material C, and weighing the expandable graphite and the Cu in proportion2O-MoS2The hybrid particles and the silicon dioxide microcapsules are placed in the same container; the material A and the material C are ensured to be uniform in system and have no bubbles; controlling the temperature of the material A and the material B at 22-25 ℃, and controlling the temperature of the material C at 18-20 ℃;
2) adding the material A and the material B into a foaming barrel according to the proportion, uniformly stirring, and then adding the weighed expandable graphite and Cu together2O-MoS2The hybrid particles and the silicon dioxide microcapsules are stirred uniformly again; the stirring rotating speeds of the two times are controlled to be 400-800r/min, and the stirring time is controlled to be 15-25 s;
3) immediately adding the weighed material C into the foaming barrel, fully stirring, quickly casting in a mold for reaction, controlling the stirring speed at 1000-1200r/min, and controlling the stirring time at 8-12 s;
4) and trimming after curing the foam, and cutting according to a set thickness to obtain a foam bare board, and heating the bare board in an oven at the temperature of 130-200 ℃ for not less than 2min to obtain the polyurethane foam material.
The technical solution of the present invention is further illustrated by the following specific examples:
the operation process is as follows:
examples 1-5 and comparative examples 1-3 materials A and C were mixed uniformly according to the formulation in Table 1, the powder was weighed and placed in the same container, the temperature of materials A and B was controlled at 22-25 deg.C, the temperature of materials C was controlled at 18-20 deg.C, materials A and B were added to the foaming barrel, stirred at 800r/min for 15s, then the powder was added together, stirred again at the same speed for 15s, then materials C were added to the foaming barrel, stirred at 1200r/min for 8s, then cast rapidly in the mold for reaction, after curing the foam, trimmed, cut to a set thickness to obtain a foam bare board, and the bare board was heated in a 200 deg.C oven for 2min to obtain a polyurethane foam.
Example 6 materials A and C were mixed uniformly according to the formulation of example 5 of Table 1, the powder was weighed and placed in the same container, the temperature of materials A and B was controlled at 22-25 deg.C, the temperature of materials C was controlled at 18-20 deg.C, materials A and B were added to the foaming tank, stirred at 400r/min for 25s, then the powder was added together, stirred again at the same speed for 25s, then materials C was added to the foaming tank, stirred at 1000r/min for 12s, then cast rapidly in a mold for reaction, after curing the foam, trimmed, cut to a set thickness to obtain a foam bare board, and the bare board was heated in a 200 deg.C oven for 2min to obtain a polyurethane foam.
Comparative example 4 is a polyurethane foam obtained without only the step of heating the foam bare board, compared with example 5.
TABLE 1 examples and comparative example formulations (amounts of components are in parts by weight)
TABLE 2 Properties of the foamed materials
Size of material after oven hold for 30s from 25 ℃ directly to 130 ℃, l ═ l0Original size of material at 25 ℃.
As can be seen from the comparison of the physical properties of the materials in the examples and comparative examples in Table 2, the foamed material prepared by the invention has good mechanical properties, flame retardant and smoke suppression properties, sound absorption properties and high temperature dimensional change resistance.
Comparative example 1 No Cu addition relative to example 52O-MoS2Hybrid particles, from the smoke level of the combustion test, illustrate Cu2O-MoS2The hybrid particles play a good smoke suppression role in the foamed material of the invention. Comparative example 2 no addition of silica microcapsules relative to example 5 illustrates that silica microcapsules exhibit good high temperature dimensional change resistance to the foamed material of the present invention from the results of high temperature dimensional change rate. Comparative example 3 shows that a suitable foam stabilizer formulation provides a high open cell content and good sound absorption performance from the viewpoint of open cell content and sound absorption results by changing the content of the foam stabilizer a to 1 and the content of the foam stabilizer b to 0, relative to example 5. Comparative example 4 lacks only the heating step for the foam bare board relative to example 5, and shows that heating the foam bare board improves the cell-breaking property of the foam from the viewpoint of the open cell content and the sound-absorbing result, thereby providing good sound-absorbing property of the foam.
Finally, it should also be noted that the above-mentioned list is only a specific embodiment of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
1. The sound-absorbing flame-retardant vegetable oil-based polyurethane foam material is characterized by comprising the following raw materials in parts by weight:
2. the sound-absorbing flame-retardant vegetable oil-based polyurethane foam material as claimed in claim 1, wherein the combined vegetable oil polyol is: a mixture of polyol a and polyol b in a weight ratio of 1: 0.11-0.33.
3. The sound-absorbing flame-retardant vegetable oil-based polyurethane foam material as claimed in claim 2, wherein the polyol a is a vegetable oil polyol having a hydroxyl value of 120-140mgKOH/g and an average functionality of 2; polyol b is a vegetable oil polyol having a hydroxyl value of 390-.
4. The sound-absorbing flame-retardant vegetable oil-based polyurethane foam material as claimed in claim 3, wherein the polyol a is FH-2130 and the polyol b is FH-8450, respectively.
5. The sound-absorbing flame-retardant vegetable oil-based polyurethane foam material according to claim 1, 2, 3 or 4, wherein the foam stabilizer is: a mixture of foam stabilizer a and foam stabilizer b in a weight ratio of 1: 0.8-1.4.
6. The sound-absorbing flame-retardant vegetable oil-based polyurethane foam material as claimed in claim 5, wherein the foam stabilizer a is one or two of B123 and B110 of Windpower company; the foam stabilizer B is B8462 of winning company.
7. The sound-absorbing flame-retardant vegetable oil-based polyurethane foam material as claimed in claim 5, wherein the foaming catalyst is: catalyst a and catalyst b with the weight ratio of 1:0.6-1.2, wherein the catalyst a is one or two of NE1070 and NE1091 of winning companies; catalyst b is NE300 from winning company.
8. The sound-absorbing flame-retardant vegetable oil-based polyurethane foam material as claimed in claim 5, wherein the flame retardant is a phosphorus-nitrogen halogen-free flame retardant.
9. The sound-absorbing flame-retardant vegetable oil-based polyurethane foam material as claimed in claim 5, wherein the expandable graphite is 150-200 mesh, the crosslinking agent is glycerol, and the isocyanate is modified diphenylmethane diisocyanate.
10. A method for preparing the sound-absorbing flame-retardant vegetable oil-based polyurethane foam material according to claim 1, 2, 3, 4, 6, 7, 8 or 9, wherein the method comprises the following steps:
1) uniformly mixing the combined vegetable oil polyalcohol, the foam stabilizer and the flame retardant in proportion to form a material A, taking isocyanate as a material B, uniformly mixing the crosslinking agent, water and the foaming catalyst in proportion to form a material C, and weighing the expandable graphite and the Cu in proportion2O-MoS2The hybrid particles and the silicon dioxide microcapsules are placed in the same container; the material A and the material C are ensured to be uniform in system and have no bubbles; controlling the temperature of the material A and the material B at 22-25 ℃, and controlling the temperature of the material C at 18-20 ℃;
2) adding the material A and the material B into a foaming barrel according to the proportion, uniformly stirring, and then adding the weighed expandable graphite and Cu together2O-MoS2The hybrid particles and the silicon dioxide microcapsules are stirred uniformly again; the stirring rotating speeds of the two times are controlled to be 400-800r/min, and the stirring time is controlled to be 15-25 s;
3) immediately adding the weighed material C into the foaming barrel, fully stirring, quickly casting in a mold for reaction, controlling the stirring speed at 1000-1200r/min, and controlling the stirring time at 8-12 s;
4) and trimming after curing the foam, and cutting according to a set thickness to obtain a foam bare board, and heating the bare board in an oven at the temperature of 130-200 ℃ for not less than 2min to obtain the polyurethane foam material.
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