CN112226070A - High-flame-retardant polyurethane material added with expanded graphite and preparation method thereof - Google Patents

High-flame-retardant polyurethane material added with expanded graphite and preparation method thereof Download PDF

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CN112226070A
CN112226070A CN202011116495.6A CN202011116495A CN112226070A CN 112226070 A CN112226070 A CN 112226070A CN 202011116495 A CN202011116495 A CN 202011116495A CN 112226070 A CN112226070 A CN 112226070A
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expanded graphite
parts
polyurethane material
material added
retardant polyurethane
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杨磊
王松奎
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Shandong Boshun New Material Co ltd
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Shandong Boshun New Material Co ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic

Abstract

The technical scheme of the invention discloses a high flame-retardant polyurethane material added with expanded graphite, which comprises polyether polyol, a polyisocyanate compound, expanded graphite, montmorillonite, an inorganic metal salt, a coupling agent, a foaming agent, a stabilizer and a catalyst; the flame retardant grade of the polyurethane material is improved by adding the expanded graphite, the montmorillonite, the inorganic metal salt and the coupling agent, the cost is low, and indexes such as mechanical property of the polyurethane material are not changed.

Description

High-flame-retardant polyurethane material added with expanded graphite and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of flame-retardant materials, in particular to a high-flame-retardant polyurethane material added with expanded graphite and a preparation method thereof.
Background
The polyurethane has the excellent performances of light weight, heat insulation, sound absorption, shock resistance, water resistance, corrosion resistance and the like, and is an ideal light structural material and energy absorption material. However, polyurethane is an organic polymer compound, and has poor fire resistance, and needs to be subjected to flame retardant modification. In order to improve the flame retardancy of polyurethane, a large amount of flame retardant is generally added to polyurethane. The traditional flame retardant is a halogen-containing flame retardant, releases a large amount of smoke and toxic gases during combustion, seriously endangers the life safety of people, and easily destroys the technical indexes such as mechanical strength and the like of the original plastic material.
With the progress of science and technology, the research and application of the expanded graphite as a novel and efficient environment-friendly flame retardant are more and more. The expanded graphite is a flame retardant with good plastic material, and has the characteristics of obvious flame retardant effect, good heat preservation effect, high expansion rate, good waterproofness and the like. The flame retardant can achieve ideal flame retardant effect when used alone or mixed with other flame retardants. Under the condition of high temperature, compounds in the layered structure of the expanded graphite are heated and decomposed and expanded into worm shapes with low density, when a fire disaster happens, the expanded graphite suffocates the flame through the instant increase of the volume, and simultaneously absorbs a large amount of environmental heat in the expansion process, so that the effect of reducing the temperature of the system is achieved, the purposes of flame retardance and fire prevention are achieved, the heat conduction between materials and a heat source is prevented, the contact between the generated combustible gas and oxygen is blocked, and the heat released by combustion is reduced. But the solubility of the expanded graphite with other components is poor, and the initial expansion temperature cannot be lower than the temperature in the preparation process of polyurethane, so that the problem that the expanded graphite begins to expand in the preparation process of the material and further the performance of the material is influenced is avoided. At present, expanded graphite is applied to preparation of polyurethane, and patent CN 105670039B discloses high-char-forming expandable graphite and application thereof in polyurethane rigid foam, wherein high-char-forming resin or cellulose is chemically modified and grafted to the surface of the expandable graphite, and the high-char-forming resin or cellulose is used together with polyether polyol, a polyisocyanate compound, a foaming agent, a foaming stabilizer and a foaming catalyst to prepare a material, so that the flame retardant property is improved, but the expanded graphite needs to be chemically modified, the steps are complex, and the cost is high. Patent CN 106496518B discloses a graphene modified polyurethane insulation board and a production method thereof, wherein the polyurethane insulation layer comprises polyether polyol, polymethine polyphenyl isocyanate, a flame retardant, expandable graphite and graphene, and has flame retardant and insulation properties, but the flame retardant is still added to improve the flame retardant grade, and other mechanical property indexes of the material are easily damaged.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a high flame-retardant polyurethane material added with expanded graphite and a preparation method thereof.
A high-flame-retardance polyurethane material added with expanded graphite comprises, by weight, 70-90 parts of polyether polyol, 150-180 parts of a polyisocyanate compound, 20-40 parts of expanded graphite, 4-10 parts of montmorillonite, 0.6-1 part of an inorganic metal salt, 1-3 parts of a coupling agent, 6-9 parts of a foaming agent, 2-4 parts of a stabilizer and 3-6 parts of a catalyst;
further, the polyether polyol is a polyether polyol having a hydroxyl value of 200-500mgKOH/g and a weight-average functionality of 2-4.
Further, the polyisocyanate compound is at least one selected from an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate.
Further, the particle size of the expanded graphite is 0.18 to 0.30 mm.
Further, the inorganic metal salt includes one of magnesium chloride hexahydrate, copper sulfate pentahydrate, and zinc nitrate.
Further, the coupling agent includes one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, isopropyltris (dioctylphosphato) titanate and isopropyltris (dioctylphosphato) titanate.
Further, the foaming agent comprises, by mass, 1-2 parts of monofluoro dichloroethane, 1-2 parts of pentane, 3-6 parts of N, N-dimethylbenzylamine and 1-2 parts of water.
Further, the stabilizer is polysiloxane.
Further, the catalyst is one or more of a metal salt catalyst and an organic amine catalyst.
Preferably, the catalyst is one or more of triethanolamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, diethylenetriamine, triethylenediamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, quaternary ammonium salts, potassium isooctanoate, stannous octoate and dibutyltin dilaurate.
A preparation method of a high flame-retardant polyurethane material added with expanded graphite comprises the following steps:
(1) performing low-temperature blast drying on the expanded graphite at the temperature of 60-80 ℃ for 4-6 h; carrying out high-temperature blast drying on the montmorillonite, wherein the temperature of the high-temperature blast drying is 100-110 ℃, and the drying time is 8-10 h;
(2) uniformly mixing and stirring monofluorodichloroethane, pentane, N-dimethylbenzylamine and water to prepare a foaming agent;
(3) sequentially adding a stabilizer, a catalyst, expanded graphite, montmorillonite, an inorganic metal salt, a coupling agent and a foaming agent into polyether polyol, and uniformly stirring at the rotating speed of 2500-;
(4) pouring a polyisocyanate compound into the polyether polyol mixture, uniformly stirring at the temperature of 23-25 ℃ by a high-speed stirrer at the rotating speed of 800-1200 r/min, pouring into a mold for foaming and molding, curing at the temperature of 65-80 ℃ for 1-3 min, and demolding to obtain the high-flame-retardant polyurethane material.
Montmorillonite reacts with inorganic salt metal ions, and exchangeable cations between inorganic metal cations and montmorillonite layers are exchanged, so that montmorillonite is peeled and dispersed into thinner single crystal sheets, and then the single crystal sheets are uniformly dispersed and filled in gaps of the expanded graphite, so that the structure of the expanded graphite is more compact, and the flame retardance is further improved. In addition, the montmorillonite expands after being added with water, and contracts after being heated, so that the montmorillonite is dried by high-temperature air blast and the expanded graphite is dried by low-temperature air blast in the step (1), so that the montmorillonite is more fully filled in gaps of the expanded graphite. The coupling agent modifies the surfaces of the montmorillonite and the expanded graphite, so that the compatibility of the montmorillonite, the expanded graphite and other components is better, and the expanded graphite is dispersed more uniformly and is not easy to migrate in the preparation process of the material. In addition, the montmorillonite has certain function of improving the mechanical property of the expanded graphite. Therefore, the defects of poor compatibility, easy migration, reduced mechanical property and the like of the expanded graphite and the polyurethane are overcome by adding the montmorillonite, the inorganic metal salt and the coupling agent.
The foaming agent is prepared by mixing monofluorodichloroethane, pentane, N-dimethylbenzylamine and water, and carbon dioxide gas is produced in the reaction process of the foaming agent and a polyisocyanate compound, so that the viscoelastic foam material is expanded, foamed and cured. The compatibility of the foaming agent is enhanced by mixing the four raw materials, and the N, N-dimethylbenzylamine can eliminate urea bonds generated by the reaction of water and isocyanate so as to generate allophanate, reduce the brittleness of the generated polyurethane material and improve the caking property of the polyurethane material. The application of water reduces the dosage of the organic foaming agent and accelerates the foaming process. Therefore, four kinds of foaming agent raw materials are mixed, the proportion of each raw material is reduced respectively, the adverse effect of each raw material in the foaming process is reduced, and 4 kinds of foaming agents are matched with each other, so that the foaming process is more efficient, the foaming effect is better and more stable, and the using amount of the foaming agent is reduced.
By adopting the technical scheme, the invention has the following beneficial effects:
(1) by adopting the technical scheme of the invention, the montmorillonite glass is dispersed into thinner single crystal chips under the action of the montmorillonite and the inorganic metal salt, the gaps of the expanded graphite are favorably filled, the structure is more compact, the flame retardance of the material is further improved, and the montmorillonite reacted with the inorganic metal salt forms a column support association structure under the high-temperature drying condition, forms larger space between layers and is matched with the expanded graphite, so that the flame retardance of the material is greatly improved. The coupling agent helps the montmorillonite and the expanded graphite to be uniformly distributed.
(2) The foaming agent ensures the stability of the foaming process, eliminates the urea bond formed by the reaction of water and polyisocyanate in the foaming process so as to generate allophanate, reduces the brittleness of polyurethane, improves the caking property of the polyurethane, and is beneficial to the stability and the improvement of the mechanical property of the material.
(3) According to the invention, solid expanded graphite, montmorillonite and the like are added into liquid polyether polyol and polyisocyanate compounds, and the stability and high efficiency of a reaction system are realized through a specific coupling agent, a foaming agent and a stabilizer, the addition amount is small, the cost is low when the flame retardant grade above B1 is reached, and the flame retardant grade is more stable; and no additional organic material is needed, the mechanical properties and the like of the original polyurethane material are not damaged, and the polyurethane material can be used for pipeline heat insulation, cold storage body, external wall heat insulation and the like, and meets the requirement of high flame retardance.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A high flame-retardant polyurethane material added with expanded graphite comprises 70g of polypropylene oxide glycol with a hydroxyl value of 450mgKOH/g, 150g of 4,4' -methylene diphenyl diisocyanate, 20g of expanded graphite with a particle size of 0.18-0.30mm, 4g of montmorillonite, 0.6g of magnesium chloride hexahydrate, 1g of gamma-aminopropyltriethoxysilane, 6g of a foaming agent, 2g of polysiloxane and 3g of triethanolamine;
further, the blowing agent comprises 1g of monofluorodichloroethane, 1g of pentane, 6g of N, N-dimethylbenzylamine and 1g of water.
A preparation method of a high flame-retardant polyurethane material added with expanded graphite comprises the following steps:
(1) carrying out low-temperature blast drying on the expanded graphite, wherein the temperature of the low-temperature blast drying is 60 ℃, and the drying time is 4 h; carrying out high-temperature forced air drying on the montmorillonite, wherein the temperature of the high-temperature forced air drying is 100 ℃, and the drying time is 8 h;
(2) uniformly mixing and stirring monofluorodichloroethane, pentane, N-dimethylbenzylamine and water to prepare a foaming agent;
(3) sequentially adding polysiloxane, triethanolamine, expanded graphite, montmorillonite, magnesium chloride hexahydrate, gamma-aminopropyltriethoxysilane and a foaming agent into polypropylene oxide glycol, and uniformly stirring at the rotating speed of 2500r/min by a high-speed stirrer at room temperature to obtain a polyether polyol mixture;
(4) pouring 4,4' -methylene diphenyl diisocyanate into the polyether polyol mixture, uniformly stirring at the temperature of 23 ℃ by a high-speed stirrer at the rotating speed of 800r/min, pouring into a mold for foaming and molding, curing at the temperature of 65 ℃ for 2min, and demolding to obtain the high-flame-retardant polyurethane material.
Example 2
A high-flame-retardant polyurethane material added with expanded graphite comprises 90g of 500mgKOH/g of polyethylene oxide glycol, 180g of diphenylmethane diisocyanate, 40g of expanded graphite, 10g of montmorillonite, 1g of copper sulfate pentahydrate, 3g of isopropyl tri (dioctyl phosphate acyloxy) titanate, 9g of foaming agent, 4g of polysiloxane and 6g of dibutyltin dilaurate;
further, the blowing agent comprised 2g of monofluorodichloroethane, 2g of pentane, 4g of N, N-dimethylbenzylamine, and 1g of water.
A preparation method of a high flame-retardant polyurethane material added with expanded graphite comprises the following steps:
(1) carrying out low-temperature blast drying on the expanded graphite, wherein the temperature of the low-temperature blast drying is 80 ℃, and the drying time is 6 h; carrying out high-temperature forced air drying on the montmorillonite, wherein the temperature of the high-temperature forced air drying is 110 ℃, and the drying time is 10 h;
(2) uniformly mixing and stirring monofluorodichloroethane, pentane, N-dimethylbenzylamine and water to prepare a foaming agent;
(3) sequentially adding polysiloxane, dibutyltin dilaurate, expanded graphite, montmorillonite, copper sulfate pentahydrate, isopropyl tri (dioctyl phosphate acyloxy) titanate and a foaming agent into polyethylene oxide glycol, and uniformly stirring at the rotating speed of 3000r/min by a high-speed stirrer at room temperature to obtain a polyether polyol mixture;
(4) pouring diphenylmethane diisocyanate into the polyether polyol mixture, uniformly stirring at 25 ℃ by a high-speed stirrer at the rotating speed of 1200r/min, pouring into a mold for foaming and molding, curing at 80 ℃ for 1-3 min, and demolding to obtain the high-flame-retardant polyurethane material.
Comparative example 1
The difference from example 1 is that the mass of montmorillonite and magnesium chloride hexahydrate in the raw material is reduced, namely a high flame retardant polyurethane material added with expanded graphite, comprising 70g of polypropylene oxide glycol with a hydroxyl value of 450mgKOH/g, 150g of 4,4' -methylene diphenyl diisocyanate, 20g of expanded graphite with a particle size of 0.18-0.30mm, 1g of montmorillonite, 0.15g of magnesium chloride hexahydrate, 1g of gamma-aminopropyltriethoxysilane, 6g of foaming agent, 2g of polysiloxane and 3g of triethanolamine;
further, the blowing agent comprises 1g of monofluorodichloroethane, 1g of pentane, 6g of N, N-dimethylbenzylamine and 1g of water.
Comparative example 2
The difference from example 1 is that montmorillonite and magnesium chloride hexahydrate are removed from the raw materials, namely a high flame retardant polyurethane material added with expanded graphite, comprising 70g of polypropylene oxide glycol with the hydroxyl value of 450mgKOH/g, 150g of 4,4' -methylene diphenyl diisocyanate, 20g of expanded graphite with the particle size of 0.18-0.30mm, 1g of gamma-aminopropyl triethoxysilane, 6g of foaming agent, 2g of polysiloxane and 3g of triethanolamine;
further, the blowing agent comprises 1g of monofluorodichloroethane, 1g of pentane, 6g of N, N-dimethylbenzylamine and 1g of water.
According to the fire performance grading of building materials and products (GB/8624-.
TABLE 1 Combustion Performance test results
Figure BDA0002730469270000061
From the results in table 1, it can be seen that the flame retardant rating of example 1 and example 2 is significantly improved compared to the flame retardant rating of comparative example 1 and comparative example 2, comparative example 1 and comparative example 2 are B2 rating, and example 1 and example 2 reach B1 rating. The content of montmorillonite in comparative example 1 is reduced, the flame retardant effect of the polyurethane material is obviously reduced, and when no montmorillonite is present in comparative example 2, the flame retardant effect of the polyurethane material is the worst, which shows that the flame retardant effect of the polyurethane material is effectively improved by the ratio of montmorillonite to expanded graphite. In addition, the raw material ratio of montmorillonite and expanded graphite in the embodiment 1 and the embodiment 2 remarkably improves the flame retardant property of the finally prepared polyurethane material compared with the comparative example 1, so that the stable and good flame retardant effect is realized under the condition of not adding a large amount of flame retardant.

Claims (8)

1. A high flame-retardant polyurethane material added with expanded graphite is characterized in that: the modified polyurethane foaming agent comprises, by weight, 70-90 parts of polyether polyol, 150-180 parts of a polyisocyanate compound, 20-40 parts of expanded graphite, 4-10 parts of montmorillonite, 0.6-1 part of an inorganic metal salt, 1-3 parts of a coupling agent, 6-9 parts of a foaming agent, 2-4 parts of a stabilizer and 3-6 parts of a catalyst.
2. The high flame retardant polyurethane material added with the expanded graphite according to claim 1, wherein: the polyether polyol is polyether polyol with a hydroxyl value of 200-500mgKOH/g and a weight-average functionality of 2-4; the polyisocyanate compound is at least one selected from an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate.
3. The high flame retardant polyurethane material added with the expanded graphite according to claim 1, wherein: the particle size of the expanded graphite is 0.18-0.30 mm.
4. The high flame retardant polyurethane material added with the expanded graphite according to claim 1, wherein: the inorganic metal salt comprises one of magnesium chloride hexahydrate, copper sulfate pentahydrate and zinc nitrate; the coupling agent comprises one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, isopropyltris (dioctylphosphonoxy) titanate and isopropyltris (dioctylphosphonoxy) titanate.
5. The high flame retardant polyurethane material added with the expanded graphite according to claim 1, wherein: the foaming agent comprises, by mass, 1-2 parts of monofluorodichloroethane, 1-2 parts of pentane, 3-6 parts of N, N-dimethylbenzylamine and 1-2 parts of water.
6. The high flame retardant polyurethane material added with the expanded graphite according to claim 1, wherein: the stabilizer is polysiloxane; the catalyst is one or more of a metal salt catalyst and an organic amine catalyst.
7. The high flame retardant polyurethane material added with expanded graphite according to claim 6, wherein: the catalyst is one or more of triethanolamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, diethylenetriamine, triethylene diamine, 2,4, 6-tri (dimethylaminomethyl) phenol, 1,3, 5-tri (dimethylaminopropyl) hexahydrotriazine, quaternary ammonium salts, potassium isooctanoate, stannous octoate and dibutyltin dilaurate.
8. The method for preparing the high flame-retardant polyurethane material added with the expanded graphite according to claim 1, which comprises the following steps:
(1) performing low-temperature blast drying on the expanded graphite at the temperature of 60-80 ℃ for 4-6 h; carrying out high-temperature blast drying on the montmorillonite, wherein the temperature of the high-temperature blast drying is 100-110 ℃, and the drying time is 8-10 h;
(2) uniformly mixing and stirring monofluorodichloroethane, pentane, N-dimethylbenzylamine and water to prepare a foaming agent;
(3) sequentially adding a stabilizer, a catalyst, expanded graphite, montmorillonite, an inorganic metal salt, a coupling agent and a foaming agent into polyether polyol, and uniformly stirring at the rotating speed of 2500-;
(4) pouring a polyisocyanate compound into the polyether polyol mixture, uniformly stirring at the temperature of 23-25 ℃ by a high-speed stirrer at the rotating speed of 800-1200 r/min, pouring into a mold for foaming and molding, curing at the temperature of 65-80 ℃ for 1-3 min, and demolding to obtain the high-flame-retardant polyurethane material.
CN202011116495.6A 2020-10-19 2020-10-19 High-flame-retardant polyurethane material added with expanded graphite and preparation method thereof Pending CN112226070A (en)

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