CN111892799A - Low-density flame-retardant polymer product, preparation method and application thereof - Google Patents
Low-density flame-retardant polymer product, preparation method and application thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides a low-density flame-retardant polymer product, a preparation method and application thereof. The low density flame retardant polymer article of the present invention comprises the following composition: 1-99 parts by weight of a polymer matrix; 1-99 parts by weight of an aerogel composite; wherein the low-density polymer product has an apparent density of 0.05 to 0.95g/cm3UL94 flame retardant ratingNot less than V1, and an oxygen index > 27. The invention adopts the specific aerogel composite porous material, the final product achieves the UL94 flame retardant not lower than the V1 level, and has good mechanical property, so the invention can be widely applied to the fields such as automobile parts and interior materials, packaging materials, building heat preservation, living goods or aerospace, national defense equipment and the like which need to meet the industrial flame retardant standard.
Description
Technical Field
The present invention relates to a low density flame retardant polymer article, a method of making and use thereof, and more particularly to a low density flame retardant polymer article comprising an aerogel composite, a method of making and use thereof.
Background
The polymer product has wide application, and the density of the material is further reduced by adding the filling material with low density and high performance, so that the energy consumption can be reduced, and the advantages of the polymer product on automobile parts, interior materials and packaging materials are more obvious. The substrate of the polymer product can be solid polymer or polymer foam.
The polymer foam material is a porous material having innumerable micropores inside, which is made of polymer resin as a main raw material, and has characteristics of light weight, heat insulation, sound absorption, shock resistance, corrosion resistance and the like, so that the polymer foam material is widely applied to the fields of daily necessities, shoe materials, sports goods, packaging, buildings, automobiles and the like. Generally, fillers for weight reduction, improvement of physical properties (such as mechanical properties or sound absorption), flame retardancy, or improvement of economy are added during foaming of polymer foams. The fillers that are currently common include organic fillers such as melamine, rosin, cyclopentadienyl resins or polymer-modified polyoxyethylene polyols and the like, and inorganic fillers such as carbon black, siliceous minerals, metal oxides or metal salts and the like.
The conventional aerogel is a novel material containing silica as a main component, has various characteristics such as heat insulation, heat preservation, flame retardancy, etc. due to its specific nanoporous structure, and can achieve better material dispersion with a smaller amount, and thus has begun to be applied as a novel filler in polymer foam materials. However, most of the conventional aerogels exist in a powder state, which often brings adverse effects to the foaming process of the polymer substrate, for example, the foaming system is unbalanced and cannot be foamed, or experimental conditions such as reaction temperature or pressure need to be strictly controlled, so that the process is complicated, the cost is high, and the application in an industrial scale is not suitable.
The invention patent CN106810761A discloses a flame-retardant polypropylene foam board modified by hybrid polytetrafluoroethylene silicon aerogel. The hybrid polytetrafluoroethylene silicon aerogel colloidal compound is prepared by adding polytetrafluoroethylene ultrafine powder into the traditional silicon aerogel, then putting the hybrid polytetrafluoroethylene silicon aerogel colloidal compound and a coupling agent into a high-speed mixer and feeding the mixture into an extruder for molding, so that the hybrid polytetrafluoroethylene silicon aerogel is grafted onto a polypropylene resin base material. However, the modified aerogel is still mainly in powder form and is bonded to the polypropylene resin substrate through chemical bonds, and the preparation process is complicated.
Patent CN102471520B discloses an insulating polymer foam and aerogel composite article formed by defining at least one cavity in an extruded thermoplastic polymer foam and embedding an aerogel material such as silica, alumina, or the like, into the cavity defined by the extruded thermoplastic polymer foam. However, it is required to define the cavity in the polymer foam in advance by a cold forming method, particularly, to press a mold projection into the polymer foam at a temperature lower than the softening temperature of the polymer foam, to compress a portion of the polymer foam by the projection to create the cavity, the manufacturing process is complicated and there is a limit to the improvement of the properties of the foamed product.
Therefore, it is an urgent need in the art to find a new aerogel material that is beneficial to the foaming system, based on the original foaming process of the polymer foam matrix, to be mixed into the polymer resin matrix as a filler and better combined with the polymer resin matrix, so as to prepare a polymer foamed product with excellent performance.
Disclosure of Invention
In view of the problems of the prior art, the present invention provides a low density flame retardant polymer article. The low-density flame-retardant polymer product comprises an aerogel composite material different from the traditional aerogel powder as a filler, so that the production process of the low-density flame-retardant polymer is simpler and more optimized, and the obtained final product has better performance.
The technical scheme of the invention is as follows:
a low density flame retardant polymeric article comprising the following composition:
1-99 parts by weight of a polymer matrix;
1-99 parts by weight of an aerogel composite;
wherein the low-density polymer product has an apparent density of 0.05 to 0.95g/cm3The UL94 flame retardant rating is at least V1 and the oxygen index is > 27.
Specifically, the total heat release amount of the flame-retardant polymer foamed product in 600s is less than 10MJ/m2The smoke density grade sdr is less than 20, the heat conductivity coefficient is less than 0.035W/m.K, and the compressive strength is 0.05-50 MPa.
In particular, the aerogel composite can be incorporated as a filler into the polymer matrix to form the final article of the present invention. In the flame retardant polymer article, the aerogel composite can be uniformly dispersed in the polymer matrix in the form of a filler, or the aerogel composite and the polymer matrix can be wrapped outside the polymer matrix in a layered form, and the bulk volume of the aerogel composite accounts for at least 50% of the flame retardant polymer foamed article.
Specifically, the aerogel composite can have an average particle size of 0.1mm to 10mm and a density of 0.05 to 0.5g/cm3The organic-inorganic composite material of (1), which may comprise an organic material and an inorganic material in a mass ratio of 9:1 to 1: 9. Preferably, the aerogel composite can have a porosity greater than 90%.
Specifically, the polymer matrix comprises at least one of epoxy resin, polyurethane, polyolefin, polystyrene, polyvinyl chloride, polyimide, polyacrylate, phenolic resin, polyurea-aldehyde, epoxy resin, ethylene-vinyl acetate copolymer, melamine formaldehyde, polyurethane, and silicone.
Specifically, the polymer matrix is a polymer foam matrix comprising at least one of polyurethane foam, polyolefin foam, polystyrene foam, polyvinyl chloride foam, polyimide foam, polyacrylate foam, phenolic resin foam, polyurea foam, epoxy resin foam, ethylene-vinyl acetate copolymer foam, melamine formaldehyde foam, polyurethane foam, silicone foam.
Specifically, in the aerogel composite material, the organic material includes at least one of polyurethane resin, polyolefin resin, aqueous acrylic resin, aqueous epoxy resin, aqueous silicone resin, aqueous fluorocarbon resin, vinyl acetate-vinyl polymer gum, polyvinyl acetal, water-soluble protein, cellulose, chitosan, pectin, guar gum, and alginate, and the inorganic material includes at least one of silica, sodium oxide, alumina, titania, zirconia, magnesia, and natural and synthetic inorganic materials containing these compositions. Preferably, the inorganic material is montmorillonite.
Specifically, the aerogel composite can have a thermal conductivity of less than 0.040W/K-m, and a UL94 flame retardant rating of V0.
In particular, for different types of polymer foam matrices, specific aerogel composites can be added to achieve better compatibility of both the matrix and the filler, such as polyurethane foam matrices, optionally aerogel composites comprising polyurethane resins; such as a polypropylene foam matrix, optionally with an aerogel composite comprising a polypropylene resin.
The invention also provides a preparation method of the flame-retardant polyurethane foaming product, which comprises the following steps:
(1) preparing the aerogel composite material:
weighing the raw materials according to the mass ratio, and uniformly mixing and stirring the organic material, the inorganic material and the solvent at the rotating speed of 100-10000rpm, wherein an additive is optionally added to obtain a homogeneous mixed solution;
and (3) carrying out freeze-drying treatment on the homogenized mixture.
(2) Blending the polymer matrix and the aerogel composite to combine the aerogel composite as a filler with the polymer matrix to produce the low density flame retardant polymer article.
In the step (1), the homogeneous mixed solution is frozen into a solid state at a temperature of 0-195 ℃, and then is subjected to freeze-drying treatment at a temperature of 0-50 ℃ and a pressure of 1-100Pa, so as to obtain the aerogel composite material.
Specifically, the homogeneous mixed solution is poured into a mold, and is subjected to freezing molding for 1-12 hours, demolding, crushing and freeze-drying treatment to obtain the product with the particle size of 0.1-10mm and the density of 0.05-0.5g/cm3The aerogel composite. In particular, the mould may be plasticRubber or metal articles.
Specifically, the solvent may be at least one of water or tert-butyl alcohol, propanol, isopropanol, acetone, dimethyl sulfoxide, the additive may be at least one of a flame retardant and a surfactant, the additive may be at least one of a phosphorus flame retardant such as polyphosphate and derivatives thereof, expanded graphite, and the like, and the surfactant may be at least one of an organosilicon compound containing a reactive group such as hexamethylsilazane, trimethylchlorosilane, trimethylethylsilane, and the like.
In the step (2), specifically, when the polymer foam substrate is a polymer foam substrate, foaming or molding each material for preparing the polymer foam substrate, and before or during the foaming or molding process, adding the aerogel composite material into a reaction system, and combining the aerogel composite material as a filler with the polymer foam substrate to prepare the low-density flame-retardant polymer foam product, wherein the polymer foam substrate can be obtained by physical foaming or chemical foaming, the physical foaming is performed by compression molding, and the chemical foaming is a one-step foaming method.
Specifically, some additives or other fillers, such as at least one of flame retardant, catalyst, foam stabilizer, may be added to the reaction system before or during the foaming process.
Specifically, the flame retardant comprises at least one of phosphorus flame retardants such as ammonium polyphosphate, melamine polyphosphate, tetrakis (hydroxymethyl) phosphonium chloride and derivatives thereof, N-hydroxymethyl (dimethyl) phosphonic acid acrylamide and derivatives thereof, aliphatic phosphate, cyclotriphosphazene and derivatives thereof, pentaerythritol phosphate and derivatives thereof, expanded graphite and the like.
Specifically, the catalyst includes at least one of an organotin catalyst, a tertiary amine catalyst, organobismuth, a polyurethane catalyst A-1, a polyurethane catalyst A-2, and the like. Wherein, the organic tin catalyst can be selected from stannous octoate, and the tertiary amine catalyst can be selected from diethanolamine or triethylene diamine.
Specifically, the foam stabilizer comprises at least one of organosilicon compounds containing active groups, such as hexamethylsilazane, trimethylchlorosilane, trimethylethylsilane and the like.
Specifically, the other filler is at least one of alkali-resistant glass fiber mesh cloth, polyvinyl alcohol fiber mesh cloth, polypropylene fiber mesh cloth, polyvinyl chloride fiber mesh cloth, asbestos mesh cloth, aramid fiber mesh cloth and the like which play a toughening role on the polymer foamed product, or is at least one of foamed clay, kaolin and the like.
The sum of the additives and fillers does not exceed 30% by mass based on the flame retardant polymer foamed article.
For the polyurethane foam matrix, it is preferably obtained using a chemical foaming process, for example using a one-shot foaming process. The low density polyurethane foam article can be obtained by adding the aerogel composite while preparing the polyurethane foam matrix. The specific process is as follows: mixing and stirring the material A and the material B for preparing the polyurethane foam matrix at normal temperature and normal pressure, adding the aerogel composite material before or in the foaming process of the material A and the material B, and uniformly dispersing the aerogel composite material in the polyurethane foam matrix in the form of a filler after the reaction time of 100-1000s to obtain the polyurethane foam product.
Specifically, the mass ratio of the material A to the material B is 100:40 to 40: 100.
Specifically, the a-side includes an isocyanate component, such as at least one of diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI), a modified isocyanate.
The material B comprises components which are reactive to isocyanate, such as polyester polyol, polyether polyol and the like.
Specifically, the weight average molecular weight of the polyester polyol or polyether polyol is 1000-100000 g/mol.
Wherein the polyester polyol is formed by the polycondensation of an acid (anhydride) and a polyol, the acid (anhydride) comprising: at least one of phthalic acid (anhydride), isophthalic acid (anhydride), terephthalic acid (anhydride), succinic acid (anhydride), adipic acid (anhydride), glutaric acid (anhydride), and the like, and the polyhydric alcohol is at least one of ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, dipropylene glycol, and the like.
Wherein the polyether polyol is obtained by polymerizing propylene oxide and ethylene oxide or butylene oxide serving as polymerization monomers, and generally, the polyether polyol has a hydroxyl value of 10-1000mg KOH/g and a viscosity of 300-500mPa & s at 25 ℃.
Specifically, for the polyurethane foam matrix, the aerogel composite used is preferably one containing a polyurethane resin as an organic material and clay as an inorganic material.
The foam material is mainly prepared by compression molding of polymer foam matrixes such as polyolefin, polystyrene, polyvinyl chloride, polyimide, polyacrylate, phenolic resin, polyurea-aldehyde, epoxy resin, ethylene-vinyl acetate copolymer, melamine formaldehyde or polyurethane. Specifically, the expanded beads used for preparing such expanded products and the aerogel composite are put into a mold of a specific shape, mixed and stirred at a high temperature, and the expanded beads are expanded by heating and pressurizing with steam, and the expanded beads are welded together between the expanded beads to form the product, in which the aerogel composite moves with the expanded beads to form a porous binder between the expanded beads, while the structure of the aerogel composite is substantially maintained. The polymer foamed product prepared by the method not only improves the flame retardant property, but also enhances the air permeability of the material.
In particular, the appropriate temperature and pressure conditions during the foaming process may be adjusted for different types of polymer foam substrates.
In particular, the expanded beads are commercially available or can be prepared according to the prior art. Generally, the process for preparing the expanded beads is a physical expansion process, such as a continuous extrusion expansion process. Firstly, adding a polymer resin and additives thereof into a screw extruder, injecting a physical foaming agent into a cylinder from an injection port, then changing the high pressure to the normal pressure when a polymer resin melt containing the physical foaming agent is extruded from a head port die, expanding gas dissolved in the resin melt to complete foaming, and completing the extrusion and foaming at one time.
The technical scheme provided by the invention can have the following beneficial effects:
(1) the present invention provides a low density flame retardant polymer article comprising a polymer matrix and an aerogel composite. The aerogel composite material is an organic-inorganic composite material, the average particle size of the aerogel composite material can reach 0.1-10mm, and the density of the aerogel composite material is 0.05-0.5g/cm3Organic material and inorganic material with the mass ratio of 9:1-1: 9. The density of the final polymer article is reduced by adding a low density porous aerogel composite as a second component.
Compared with the powder aerogel materials commonly used in the polymer products in the prior art, the aerogel composite material has better compatibility with the polymer matrix due to the composite material containing the organic material and the inorganic material, is uniformly dispersed in the polymer matrix in the form of filler in the final flame-retardant polymer product or is wrapped outside the polymer matrix in the form of layering with the polymer matrix, and the volume of the bulk can be as high as more than 50%.
(2) In the field of foam materials, inorganic additives are added to achieve a flame retardant effect, but the content of the inorganic additives cannot be too high, and usually accounts for about 15% of the final foamed product. Too high a proportion of inorganic substances increases the viscosity of the reaction system accordingly, resulting in failure to foam. The present inventors have unexpectedly discovered that aerogel composites can be present in the final low density flame retardant polymer foamed article in a proportion of up to 90% by weight, without degrading the foamed system while imparting flame retardant properties to the final foamed article.
(3) The flame-retardant polymer foaming product is prepared by directly adding a specific aerogel composite material into a reaction system on the basis of the original foaming system of the polymer foam matrix. Particularly, for the one-step foaming process at normal temperature and normal pressure, due to the good compatibility of the aerogel composite material and the polymer foam matrix, the problem that the conventional powdery aerogel material is directly doped into a polymer resin base material to cause unbalance of a foaming system or incapability of foaming is solved. And for the mixture with the foaming beads under a high-temperature system and the realization of a flame-retardant polymer foaming material system through compression molding, the preparation method can organically combine the characteristics of the materials and improve the flame-retardant performance, and the preparation method is optimized in preparation process, simple and controllable in reaction conditions and more suitable for industrial application.
(4) In the prior art, aerogel particles need to be modified correspondingly aiming at different types of foaming products, and the processing technology also needs to be individualized aiming at different polymer foam matrixes and aerogel particles. The specific aerogel composite material adopted by the invention does not need chemical modification treatment, is suitable for various polymer foam matrixes and foaming processes, and can be selected from aerogel composite materials with better compatibility according to different polymer foam matrixes, so that the final flame-retardant polymer foamed product has better performance.
(5) The invention adopts the specific aerogel composite porous material, and the aerogel composite material has excellent flame retardant property, can help a polymer matrix system to improve the flame retardant property, reaches at least the grade of UL 94V 1, and has good mechanical property, so the aerogel composite porous material can be widely applied to the fields such as automobile parts and interior materials, packaging materials, building heat preservation, living goods or aerospace, national defense equipment and the like which all need to meet the industrial flame retardant standard.
The foregoing summary is provided for the purpose of illustration only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, the present invention is further illustrated by the following detailed description.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
Example 1
(1) Preparing an aerogel composite material:
mixing 10 parts by weight of alginate, 5 parts by weight of inorganic clay and 85 parts by weight of water at normal temperature, and stirring for 5 minutes at the speed of 1000 revolutions per minute by a high-speed stirrer to form a homogeneous mixed solution with certain viscosity;
pouring the above homogenized mixture into a mold, freezing at-20 deg.C for 12 hr for molding, demolding, pulverizing in a pulverizer, and lyophilizing at 25 deg.C and 40Pa for 24 hr to obtain a product with particle diameter of 0.1-0.5mm and density of 0.12g/cm3I.e. alginate-clay composites.
(2) Preparation of Low Density epoxy resin samples
Under normal temperature and pressure, 100 parts by weight of low molecular weight bisphenol A epoxy resin and 15 parts by weight of aerogel composite material are uniformly stirred, and then normal temperature curing is carried out for 24 hours.
The polymer samples prepared were subjected to the following performance tests:
article density according to GB4472-74 and GB/T6343-2009 test standards: 0.75g/cm3The density of the polymer article without the aerogel composite added is: 1.15g/cm3；
The UL94 flame retardant rating tested according to GB/T2408-2008 standard is V1;
the oxygen index tested according to GB/T2406.2-2009 reaches 28, reaches the standard of a flame-retardant material, and the oxygen index of a polymer product without the aerogel composite material is 18, so that the polymer product belongs to a combustible material.
Example 2
(1) Preparing an aerogel composite material:
mixing 10 parts by weight of alginate, 5 parts by weight of inorganic clay and 85 parts by weight of water at normal temperature, and stirring for 5 minutes at the speed of 1000 revolutions per minute by a high-speed stirrer to form a homogeneous mixed solution with certain viscosity;
pouring the above homogenized mixture into a mold, freezing at-20 deg.C for 12 hr for molding, demolding, and pulverizing in a pulverizerPulverizing, and freeze-drying at 25 deg.C and 40Pa for 24 hr to obtain powder with particle diameter of 1-2mm and density of 0.1g/cm3I.e. alginate-clay composites.
(2) Preparation of flame retardant polyurethane foamed samples
At normal temperature and normal pressure, the following raw materials are uniformly stirred and poured into a mould to complete foaming after 240 seconds:
a material: TDI 80/20, 40 parts by weight;
b, material B: 100 parts by weight of polyether polyol, the weight average molecular weight is 5000 g/mol;
auxiliary agent: 1 part of diethanolamine and 0.2 part of stannous octoate; 0.5 part by weight of polyphosphate; 0.5 part by weight of trimethylchlorosilane; 3 parts of water;
aerogel composite material: 15 parts by weight;
the prepared polymer foamed samples were subjected to the following performance tests:
the apparent density of the tested material according to the GB/T6343-2009 standard is as follows: 0.20g/cm3
The UL94 flame retardant rating tested according to GB/T2408-2008 standard is V0;
according to the oxygen index tested by the GB/T2406.2-2009 standard, the oxygen index reaches 33, reaches the standard of a flame-retardant material, and the oxygen index of a polyurethane foaming product without the aerogel composite material is 23, so that the polyurethane foaming product belongs to a combustible material;
the thermal conductivity coefficient tested according to the GB/T3399-1982 standard is 0.030W/m.K;
a smoke density rating of 19 as tested according to GB/T8627-2007 standard;
the total heat release amount in 600S tested according to the GB20284-2006 standard is 9MJ/m2。
Example 3
(1) Preparing an aerogel composite material:
mixing 12.5 parts by weight of polyurethane emulsion (with a solid content of 40%), 5 parts by weight of alginate, 5 parts by weight of inorganic clay and 77.5 parts by weight of water at normal temperature, and stirring for 5 minutes at a speed of 1000 rpm by a high-speed stirrer to form a homogeneous mixed solution with a certain viscosity;
pouring the above homogenized mixture into a mold, freezing at-20 deg.C for 20 hr for molding, demolding, pulverizing in a pulverizer, and lyophilizing at 25 deg.C and 40Pa for 24 hr to obtain a product with particle diameter of 0.2-0.3mm and density of 0.1g/cm3The particles of (a), namely polyurethane-alginate-clay composites.
(2) Preparation of flame retardant polyurethane foamed samples
At normal temperature and normal pressure, the following raw materials are uniformly stirred and poured into a mould to be foamed after 600 seconds to finish:
the material A is MDI, 35 weight portions;
b, material B: 100 parts by weight of polyester polyol, the weight average molecular weight being 15000 g/mol;
auxiliary agent: 1 part by weight of organic bismuth, 2 parts by weight of triethylene diamine and 0.5 part by weight of polyphosphate; 0.8 part by weight of trimethylethylsilane; water: 2.5 parts by weight;
aerogel composite material: 10 parts by weight
The prepared polymer foamed samples were subjected to the following performance tests:
the apparent density of the tested material according to the GB/T6343-2009 standard is as follows: 0.27g/cm3
The UL94 flame retardant rating tested according to GB/T2408-2008 standard is V0;
an oxygen index of 35 as tested according to GB/T2406.2-2009;
the heat conductivity coefficient tested according to the GB/T3399-1982 standard is 0.033W/m.K;
the smoke density tested according to GB/T8627-2007 standard is 15;
the total heat release amount in 600S tested according to the GB20284-2006 standard is 7MJ/m2。
Example 4
(1) Preparing an aerogel composite material:
mixing 5 parts by weight of inorganic clay, 5 parts by weight of aqueous polyurethane emulsion and 90 parts by weight of water at normal temperature, and stirring for 5 minutes at 10000rpm by a high-speed stirrer to form a homogeneous mixed solution with certain viscosity;
pouring the homogenized mixture into small holesThe mold is frozen and molded at-196 deg.C for 20 hr, demolded, and then lyophilized at 25 deg.C under 40Pa for 24 hr to obtain a powder with a particle size of 5mm and a density of 0.1g/cm3I.e., a polyurethane-clay composite.
(2) Preparation of flame retardant polyurethane foamed samples
Mixing the prepared polyurethane-clay composite material with polyurethane foaming beads according to the mass ratio of 1:10, pouring the mixture into a mold for mold pressing and thermal forming, controlling the processing temperature to be 120-130 ℃, forming and demolding after 10 minutes, and finishing the forming after 20 minutes.
The prepared polymer foamed samples were subjected to the following performance tests:
the apparent density of the tested material according to the GB/T6343-2009 standard is as follows: 0.21g/cm3
The UL94 flame retardant rating tested according to GB/T2408-2008 standard is V0;
an oxygen index of 33 as tested according to GB/T2406.2-2009;
the heat conductivity coefficient tested according to the GB/T3399-1982 standard is 0.037W/m.K;
a smoke density rating of 18 as tested according to GB/T8627-2007 standard;
the total heat release amount in 600S tested according to the GB20284-2006 standard is 8MJ/m2。
Example 5
(1) Preparing an aerogel composite material:
dissolving 10 parts by weight of polypropylene (molecular weight 10000-; adding 10 parts by weight of Cloisite series montmorillonite, and stirring for 5 minutes at the speed of 1000 revolutions per minute by a high-speed stirrer to form a homogeneous mixed solution with certain viscosity;
pouring the above homogenized mixture into spherical metal mold, freezing at-72 deg.C for 0.5 hr for molding, demolding, and lyophilizing at 5 deg.C and 25Pa for 24 hr to obtain product with particle size of 5mm and density of 0.1g/cm3The microsphere of (1), namely the polypropylene montmorillonite composite material.
(2) Preparation of flame-retardant Polypropylene foamed sample
And putting 90 parts by weight of polypropylene foaming beads and 10 parts by weight of the polypropylene montmorillonite composite material into a metal mold for mold pressing and thermoforming, wherein the polypropylene montmorillonite composite material and the polypropylene foaming beads are put into the metal mold in the sequence that the bottom layer is the polypropylene montmorillonite composite material, the middle layer is the polypropylene foaming beads, and the outermost layer is the polypropylene montmorillonite composite material, controlling the processing temperature to be 130-150 ℃, and forming and demolding after 10 minutes.
The prepared polymer foamed samples were subjected to the following performance tests:
the apparent density of the tested material according to the GB/T6343-2009 standard is as follows: 0.08g/cm3
The UL94 flame retardant rating tested according to GB/T2408-2008 standard is V0;
an oxygen index of 30 as tested according to GB/T2406.2-2009;
the thermal conductivity coefficient tested according to the GB/T3399-1982 standard is 0.035W/m.K;
the smoke density tested according to GB/T8627-2007 standard is grade 19;
total heat release amount within 600S tested according to GB20284-2006 Standard 9MJ/m2。
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, but any modifications or equivalent variations made according to the technical spirit of the present invention are within the scope of the present invention as claimed.
Claims (10)
1. A low density flame retardant polymer article comprising the following composition:
1-99 parts by weight of a polymer matrix;
1-99 parts by weight of an aerogel composite;
wherein the low-density flame-retardant polymer product has an apparent density of 0.05 to 0.95g/cm3The UL94 flame retardant rating is not less than V1 and the oxygen index is > 27.
2. The low density flame retardant polymer of claim 1Article, characterized in that said low density flame retardant polymer foamed article has a total heat release of < 10MJ/m within 600s2The smoke density grade sdr is less than 20, the heat conductivity coefficient is less than 0.035 w/m.K, and the compressive strength is 0.05-50 MPa.
3. The low density flame retardant polymer product of claim 1, wherein the aerogel composite is uniformly dispersed in the polymer matrix in the form of filler, or the aerogel composite and the polymer matrix are wrapped outside the polymer matrix in the form of layered structure in the low density flame retardant polymer product.
4. The low density flame retardant polymer article of claim 1, wherein the aerogel composite is 0.1mm to 10mm in average particle size and 0.05 to 0.5g/cm in density3The organic-inorganic composite material comprises an organic material and an inorganic material in a mass ratio of 9:1 to 1: 9.
5. The low density flame retardant polymeric article of claim 1 wherein the polymeric matrix comprises at least one of epoxy, polyurethane, polyolefin, polystyrene, polyvinyl chloride, polyimide, polyacrylate, phenolic resin, polyurea-aldehyde, epoxy, ethylene vinyl acetate, melamine formaldehyde, polyurethane, silicone.
6. The low density flame retardant polymer article of claim 1 wherein the polymer matrix is a polymer foam matrix comprising at least one of polyurethane foam, polyolefin foam, polystyrene foam, polyvinyl chloride foam, polyimide foam, polyacrylate foam, phenolic foam, polyurea foam, epoxy foam, ethylene vinyl acetate foam, melamine formaldehyde foam, polyurethane foam, silicone foam.
7. The low density flame retardant polymer article of claim 1 wherein in the aerogel composite the organic material comprises at least one of polyurethane resin, polyolefin resin, aqueous acrylic resin, aqueous epoxy resin, aqueous silicone resin, aqueous fluorocarbon resin, vinyl acetate-vinyl polymer gum, polyvinyl acetal, water soluble protein, cellulose, chitosan, pectin, guar gum, alginate and the inorganic material comprises at least one of silica, sodium oxide, alumina, titania, zirconia, magnesia and natural and synthetic inorganics containing these compositions.
8. A method of making a low density flame retardant polymer article according to any of claims 1 to 7, comprising the steps of:
(1) preparing the aerogel composite material:
weighing the raw materials according to the mass ratio, and uniformly mixing and stirring the organic material, the inorganic material and the solvent at the rotating speed of 1000-10000rpm, wherein an additive is optionally added to obtain a homogeneous mixed solution;
freeze-drying the homogeneous mixed solution to obtain the aerogel composite material;
(2) blending the polymer matrix and the aerogel composite to combine the aerogel composite as a filler with the polymer matrix to produce the low density flame retardant polymer article.
9. The method of claim 8, wherein in the step (2), when the polymer matrix is a polymer foam matrix, the low-density flame-retardant polymer foamed article is prepared by foaming or compression molding of respective materials of the polymer foam matrix, and comprises the steps of: adding the aerogel composite to the polymer matrix prior to, or during, the foaming or molding process to bond the aerogel composite to the polymer foam matrix.
10. Use of a low density flame retardant polymer article according to any of claims 1 to 7 in the field of automotive parts and interior materials, packaging materials, building insulation, living goods or aerospace, defense equipment.
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| CN114106411A (en) * | 2021-12-06 | 2022-03-01 | 太原理工大学 | Preparation method of flame-retardant self-extinguishing type biomass aerogel phase-change composite heat storage material |
| CN116120620A (en) * | 2023-03-07 | 2023-05-16 | 北京清冠科技有限公司 | Preparation method of low-density aerogel/polyvinyl chloride foam composite material |
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