CN113524822A - Low-smoke halogen-free rubber-plastic heat-insulating material and manufacturing method thereof - Google Patents
Low-smoke halogen-free rubber-plastic heat-insulating material and manufacturing method thereof Download PDFInfo
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- CN113524822A CN113524822A CN202110632806.2A CN202110632806A CN113524822A CN 113524822 A CN113524822 A CN 113524822A CN 202110632806 A CN202110632806 A CN 202110632806A CN 113524822 A CN113524822 A CN 113524822A
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Abstract
The invention provides a low-smoke halogen-free rubber-plastic heat-insulating material and a manufacturing method thereof, wherein the low-smoke halogen-free rubber-plastic heat-insulating material comprises a first rubber-plastic layer, a first heat-insulating layer, a nano metal layer, a second heat-insulating layer and a second rubber-plastic layer which are sequentially stacked; the first rubber-plastic layer and the second rubber-plastic layer are made of the same material and respectively comprise 70-90 wt% of a rubber main body, 7-20 wt% of a flame retardant and 5-13 wt% of a filler; the first heat-insulating layer and the second heat-insulating layer are made of the same material. The rubber-plastic layer is added with the flame retardant and the filler, so that the rubber-plastic layer has certain flame retardant performance while the rubber-plastic performance is improved; the heat insulation performance of the material can be improved through the heat insulation layer; the support property and rigidity of the material can be improved through the nano metal layer, the low-smoke halogen-free rubber-plastic heat-insulating material provided by the invention has better physical and chemical stability and flame retardance, and the problem of how to improve the physical and chemical properties of rubber and plastic on the basis of ensuring the flame retardance of rubber and plastic is solved.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a low-smoke halogen-free rubber-plastic heat-insulating material and a manufacturing method thereof.
Background
Rubber and plastic are the general names of rubber and plastic products. Plastics and rubber are both high-molecular materials, mainly composed of carbon and hydrogen atoms, and some of them contain a small amount of oxygen, nitrogen, chlorine, silicon, fluorine, sulfur and other atoms, and their properties and uses are special. At normal temperature, the plastic is solid and hard and cannot be stretched and deformed; the rubber has low hardness, elasticity and can be stretched and lengthened, and the rubber can recover to the original shape after being stretched.
The rubber plastic material belongs to a flammable product due to the uniqueness of the chemical structure, and generates molten drops in the combustion process. In order to meet the requirements of flame retardance in use, methods of increasing the oxygen index and adding flame retardant additives are internationally and generally adopted. The flame retardant is mainly divided into a halogen-based additive and a metal hydroxide flame retardant. The halogen additive refers to a flame retardant containing halogen, such as chlorine flame retardants, bromine flame retardants and the like, which release inert gas to isolate oxygen under the action of flame, so as to achieve the purpose of flame retardance; on the other hand, under the action of high temperature, the halogen flame retardant cannot be fully combusted due to condensed phase thermal decomposition products, a large amount of toxic corrosive gas is generated, secondary pollution is formed, although combustion is prevented, the generated smoke has high concentration and high smoke density, and the generated toxic gas again damages the health of people. The metal hydroxide flame retardant is a flame retardant containing hydroxides such as aluminum hydroxide, magnesium hydroxide and the like, the additive absorbs heat and dehydrates at the temperature of more than 200 ℃ to take away generated combustion heat, and oxide produced by dehydration forms a firm and compact flame retardant barrier on the surface of a material to play a role in heat insulation protection, so that the combustion speed is reduced, flame spread is prevented, the purpose of inhibiting combustion is achieved, no molten drop is generated, and the concentration of smoke generated by combustion is small, thus the flame retardant is an ideal flame retardant additive.
At present, in the field of rubber and plastic, in addition to the requirement of flame retardant property of rubber and plastic, rubber and plastic are expected to have other properties, such as heat preservation. Patent application No. 201810608564.1, entitled "preparation process of low-smoke halogen-free rubber-plastic heat-insulating material" discloses a preparation process of low-smoke halogen-free rubber-plastic heat-insulating material, which comprises a rubber-plastic base material, a filling system, a vulcanization system, a foaming system, a flame-retardant system and a composite pasting system, wherein a thermoplastic elastomer and low-smoke components are added in a formula, and the formula comprises the following components in parts by weight: 30-50 parts of nitrile rubber, 10-20 parts of EVA (ethylene vinyl acetate), 5-8 parts of nano silicon dioxide, 5-10 parts of PVC (polyvinyl chloride), 2-10 parts of basalt, 5-10 parts of zirconia, 25-35 parts of expanded perlite, 11-15 parts of plasticizer, 5-10 parts of halogen-free flame retardant, 2-5 parts of filler, 5-10 parts of thermoplastic elastomer, 10-11 parts of filling and reinforcing system, 11-15 parts of low-temperature resistant plasticizer, 1.2-1.5 parts of vulcanization system, 10-12 parts of foaming system and 12-15 parts of low-smoke flame retardant system, and 1-5 parts of antibacterial and fireproof system. Also, for example, patent application No. 201710773952.0 entitled "low-smoke halogen-free rubber-plastic thermal insulation material" discloses a low-smoke halogen-free rubber-plastic thermal insulation material, which comprises a body, wherein the surface of the body is symmetrically provided with a moisture-blocking layer; the body comprises the following components in parts by weight: 35-47 parts of nitrile rubber, 37-44 parts of epoxy silane cross-linking agent, 4-13 parts of aluminum hydroxide, 3-9 parts of magnesium oxide, 18-25 parts of triethanolamine, 19-29 parts of low-floating-fiber alkali-free long-cut glass fiber, 16-30 parts of calcium oxide, 3-8 parts of talcum powder, 26-38 parts of mannitol, 11-24 parts of carbon black, 11-15 parts of accelerator TMTD9-15 and 10-20 parts of hollow microspheres, wherein the length of the low-floating-fiber alkali-free long-cut glass fiber is 3-6mm, and the diameter of the low-floating-fiber alkali-free long-cut glass fiber is 11-14 mu m.
Although the low-smoke halogen-free rubber-plastic heat-insulating material disclosed by the prior patent technology can effectively resist flame and realize low smoke, the low-smoke halogen-free rubber-plastic heat-insulating material is complex in components, easy to age and poor in physical and chemical properties, so that the application range is limited.
Disclosure of Invention
The invention aims to provide a low-smoke halogen-free rubber-plastic heat-insulating material and a manufacturing method thereof, and aims to solve the problem of improving the physical and chemical properties of rubber and plastic on the basis of ensuring the flame retardant property of rubber and plastic.
In order to solve the technical problem, the invention provides a low-smoke halogen-free rubber-plastic heat-insulating material which comprises a first rubber-plastic layer, a first heat-insulating layer, a nano metal layer, a second heat-insulating layer and a second rubber-plastic layer which are sequentially stacked; the first rubber-plastic layer and the second rubber-plastic layer are made of the same material and respectively comprise 70-90 wt% of a rubber main body, 7-20 wt% of a flame retardant and 5-13 wt% of a filler; the first heat-insulating layer and the second heat-insulating layer are made of the same material.
Optionally, in the low-smoke halogen-free rubber-plastic heat-insulating material, the rubber main body is ethylene propylene diene monomer, the ratio of ethylene to propylene in the ethylene propylene diene monomer is 55: 45-78: 22, and a third monomer in the ethylene propylene diene monomer comprises 32-47 wt% of ethylidene norbornene and 53-68 wt% of dicyclopentadiene.
Optionally, in the low-smoke halogen-free rubber-plastic heat-insulating material, the rubber main body is organosilicon modified ethylene propylene rubber, nylon modified ethylene propylene rubber, maleic anhydride modified ethylene propylene rubber or acrylonitrile grafted ethylene propylene rubber.
Optionally, in the low-smoke halogen-free rubber-plastic heat-insulating material, the flame retardant comprises 20-32 wt% of aluminum hydroxide, 18-42 wt% of magnesium hydroxide, 10-28 wt% of zinc borate, 8-22 wt% of polyether-ether-ketone, 6-10 wt% of melamine and 5-8 wt% of zinc oxide.
Optionally, in the low-smoke halogen-free rubber-plastic heat-insulating material, the filler comprises 30-48 wt% of white carbon black, 20-36 wt% of azodicarbonamide, 15-24 wt% of nano organic montmorillonite and 8-12 wt% of zirconia.
Optionally, in the low-smoke halogen-free rubber-plastic heat-insulating material, the first heat-insulating layer and the second heat-insulating layer are made of graphene.
Optionally, in the low-smoke halogen-free rubber-plastic heat-insulating material, the thickness of the first rubber layer is 3-8 mm; the thickness of the first heat-preservation layer is 0.2-1 mm; the thickness of the nano metal layer is 3-9 nm, the nano metal layer is in a grid shape, and the mesh number is 500-2000 meshes; the thickness of the second heat-insulating layer is consistent with that of the first heat-insulating layer, and the difference value is not more than +/-15%; the thickness of the second rubber layer is consistent with that of the first rubber layer, and the difference is not more than +/-20%.
In order to solve the above technical problem, the present invention further provides a method for manufacturing a low-smoke halogen-free rubber-plastic thermal insulation material, for manufacturing the low-smoke halogen-free rubber-plastic thermal insulation material, wherein the method comprises:
extruding a sheet-like first rubber-plastic layer;
forming a first heat preservation layer on one side surface of the first rubber-plastic layer at the temperature of 80 +/-10 ℃, and pressing for 3-5 s under the pressure of 0.3-0.8 MPa;
cooling to 26-40 ℃, and paving a nano metal layer on the surface of the first heat preservation layer, wherein the width of the nano metal layer is 3-9 nm, and the mesh number is 500-2000 meshes;
heating to 40-60 ℃, forming a second heat-insulating layer on the surface of the nano metal layer, and pressing for 5-8 s under 0.5-1 MPa;
and extruding a second flaky rubber-plastic layer on the surface of the second heat-insulating layer, and pressing for 8-12 s under 1.2-2.6 MPa.
Optionally, in the manufacturing method of the low-smoke halogen-free rubber-plastic thermal insulation material, the first rubber-plastic layer and the second rubber-plastic layer have the same extrusion process, including:
pouring the rubber main body, the flame retardant and the filler into an internal mixer in sequence, and mixing for 150-280 s at 135-178 ℃ to obtain mixed rubber;
pouring the mixed rubber into an extruder, and performing calendering molding at 65-125 ℃ to obtain sheet rubber and plastic;
and vulcanizing the flaky rubber and plastic by adopting a peroxide vulcanization system to obtain a rubber and plastic layer.
Optionally, in the manufacturing method of the low-smoke halogen-free rubber-plastic heat insulating material, the forming method of the first heat insulating layer and the second heat insulating layer includes:
and forming a graphene layer on the surface of one side of the first rubber-plastic layer by using chemical vapor deposition to serve as the first heat-insulating layer, and forming a graphene layer on the surface of the nano metal layer to serve as the second heat-insulating layer.
The invention provides a low-smoke halogen-free rubber-plastic heat-insulating material and a manufacturing method thereof, wherein the low-smoke halogen-free rubber-plastic heat-insulating material comprises a first rubber-plastic layer, a first heat-insulating layer, a nano metal layer, a second heat-insulating layer and a second rubber-plastic layer which are sequentially stacked; the first rubber-plastic layer and the second rubber-plastic layer are made of the same material and respectively comprise 70-90 wt% of a rubber main body, 7-20 wt% of a flame retardant and 5-13 wt% of a filler; the first heat-insulating layer and the second heat-insulating layer are made of the same material. The rubber-plastic layer is added with the flame retardant and the filler, so that the rubber-plastic layer has certain flame retardant performance while the rubber-plastic performance is improved; the heat insulation performance of the material can be improved through the heat insulation layer; the support property and rigidity of the material can be improved through the nano metal layer, the low-smoke halogen-free rubber-plastic heat-insulating material provided by the invention has better physical and chemical stability and flame retardance, and the problem of how to improve the physical and chemical properties of rubber and plastic on the basis of ensuring the flame retardance of rubber and plastic is solved.
Drawings
FIG. 1 is a schematic structural diagram of a low-smoke halogen-free rubber-plastic thermal insulation material provided in this embodiment;
FIG. 2 is a flow chart of a manufacturing method of the low-smoke halogen-free rubber-plastic thermal insulation material provided in this embodiment;
wherein the reference numerals are as follows:
110-a first rubber-plastic layer; 120-a first insulating layer; 130-nano metal layer; 140-a second insulating layer; 150-a second rubber-plastic layer.
Detailed Description
The low-smoke halogen-free rubber-plastic thermal insulation material and the manufacturing method thereof provided by the invention are further described in detail with reference to the accompanying drawings and specific examples. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention. Further, the structures illustrated in the drawings are often part of actual structures. In particular, the drawings may have different emphasis points and may sometimes be scaled differently.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the accompanying drawings are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order, and it is to be understood that such structures as are used are interchangeable where appropriate. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The embodiment provides a low-smoke halogen-free rubber-plastic thermal insulation material, as shown in fig. 1, which includes a first rubber-plastic layer 110, a first thermal insulation layer 120, a nano metal layer 130, a second thermal insulation layer 140, and a second rubber-plastic layer 150 stacked in sequence; the first rubber-plastic layer 110 and the second rubber-plastic layer 150 are made of the same material and respectively comprise 70-90 wt% of a rubber main body, 7-20 wt% of a flame retardant and 5-13 wt% of a filler; the first insulating layer 120 and the second insulating layer 140 are made of the same material.
According to the low-smoke halogen-free rubber-plastic heat-insulating material provided by the embodiment, the flame retardant and the filler are added into the materials of the first rubber-plastic layer and the second rubber-plastic layer, so that the rubber-plastic has certain flame retardant property and the physical and chemical properties are improved; the heat insulation performance of the material can be improved through the first heat insulation layer and the second heat insulation layer; the support and rigidity of the material can be improved through the nano metal layer. The low-smoke halogen-free rubber-plastic heat-insulating material provided by the invention has better physical and chemical stability and flame retardance, and solves the problem of how to improve the physical and chemical properties of rubber and plastic on the basis of ensuring the flame retardance of rubber and plastic.
In addition, the first rubber and plastic layer and the second rubber and plastic layer are made of the same materials, and the first heat-insulating layer and the second heat-insulating layer are made of the same materials, so that the manufacturing complexity is reduced, the front side and the back side of the manufactured product do not need to be distinguished, and the properties of any one of the two sides as a functional surface are consistent.
Specifically, in the embodiment, the rubber main body can be ethylene propylene diene monomer, the ethylene/propylene ratio in the ethylene propylene diene monomer is 55: 45-78: 22, and the third monomer in the ethylene propylene diene monomer comprises 32-47 wt% of ethylidene norbornene and 53-68 wt% of dicyclopentadiene.
ethylene-Propylene-Diene monomer (EPDM), which is a copolymer of ethylene, Propylene and a small amount of nonconjugated Diene, is a kind of ethylene-Propylene rubber, and has excellent aging resistance such as ozone resistance, heat resistance, weather resistance and the like because the main chain is composed of chemically stable saturated hydrocarbons and only contains unsaturated double bonds in the side chains, and can be widely used in the fields of automobile parts, waterproof materials for buildings, wire and cable sheaths, heat-resistant rubber tubes, adhesive tapes, automobile sealing parts and the like.
The inventors found that when the ratio of ethylene to propylene was changed from 50:50 to 80:20, the produced ethylene-propylene-diene rubber had higher green strength, higher tensile strength, higher crystallization and higher glass transition temperature, and could convert the raw material polymer into pellets, thereby obtaining better extrusion characteristics; but at the same time, poor calendering compatibility, poor low temperature characteristics, and poor compression set. Further, the inventors have found that, by appropriately increasing the propylene content ratio, better processability, better low-temperature characteristics, better compression set, and the like can be obtained. Through a large number of scientific reasoning and experimental verification, the inventor finds that when the proportion of ethylene to propylene in the ethylene propylene diene rubber is 55: 45-78: 22, the ethylene propylene diene rubber has good mixing property and strain resistance while obtaining good pressure strength, temperature resistance and basic characteristics.
In ethylene-propylene-diene monomer, the third monomers commonly used are Ethylidene Norbornene (ENB), dicyclopentadiene (DCPD) and 1, 4-Hexadiene (HD). Ethylidene Norbornene (ENB) has the characteristics of rapid vulcanization, high tensile strength and low permanent deformation; dicyclopentadiene (DCPD) is scorch resistant, low permanent set and low cost.
In this example, the production of ethylene-propylene-diene monomer was carried out using a mixture of Ethylidene Norbornene (ENB) and dicyclopentadiene (DCPD) as the third monomer. At the mixing ratio of Ethylidene Norbornene (ENB) and dicyclopentadiene (DCPD) that this embodiment provided, when manufacturing ethylene propylene diene monomer, not only can comparatively quick realization vulcanize, and can not take place the scorch because of high temperature, can also guarantee that ethylene propylene diene monomer has lower permanent deformation and higher tensile strength, further improved production efficiency on material cost's basis.
In addition, in this embodiment, the rubber main body may also be silicone-modified ethylene-propylene rubber, nylon-modified ethylene-propylene rubber, maleic anhydride-modified ethylene-propylene rubber, or acrylonitrile-grafted ethylene-propylene rubber.
The modified ethylene-propylene rubber is mainly prepared by the steps of brominating, chloridizing, sulfonating, anhydrizing, maleic anhydrizing, modifying organic silicon, modifying nylon and the like. The modification mode of the ethylene propylene rubber also comprises the grafting of acrylonitrile or acrylic ester and the like. Specifically, the acrylonitrile grafted ethylene propylene rubber takes toluene as a solvent and perchlorinated benzyl alcohol as an initiator, and acrylonitrile is grafted to the ethylene propylene rubber at the temperature of 65-90 ℃. The acrylonitrile modified ethylene propylene rubber not only keeps the corrosion resistance of the ethylene propylene rubber, but also obtains the oil resistance equivalent to butyronitrile-26, and has better physical and mechanical properties and processability.
The manufacturing method of the modified ethylene propylene rubber described in this embodiment is well known to those skilled in the art, and will not be described herein.
In the embodiment, the flame retardant comprises 20-32 wt% of aluminum hydroxide, 18-42 wt% of magnesium hydroxide, 10-28 wt% of zinc borate, 8-22 wt% of polyether ether ketone, 6-10 wt% of melamine and 5-8 wt% of zinc oxide.
Aluminum hydroxide and magnesium hydroxide are commonly used non-halogen flame retardants at present.
The zinc borate is also an environment-friendly non-halogen flame retardant, has the characteristics of no toxicity, low water solubility, high thermal stability, small granularity, small specific gravity, good dispersibility and the like, and is widely applied to the fields of plastics, rubber, coatings and the like as an efficient flame retardant. The zinc borate can be used as a multifunctional synergistic additive to be added into a flame retardant, so that the flame retardant property is effectively improved, and the generation of smoke during combustion is reduced; in addition, the rubber and plastic product can be adjusted in chemical, mechanical, electrical and other properties. The flame retardant effect of borates includes: forming a glassy inorganic intumescent coating; promoting the carbon formation; hindering the escape of volatile combustibles; and dehydration at high temperature, and has the effects of absorbing heat, foaming and diluting combustible materials. The flame retardant mechanism of zinc borate is: when the temperature is higher than 300 ℃, the zinc borate is thermally decomposed to release crystal water, and the effects of absorbing heat and cooling and diluting oxygen in air are achieved. On the other hand, zinc borate decomposes at high temperatures to form boron oxide, which adheres to the surface of the polymer to form a coating layer that inhibits the generation of combustible gases and also inhibits oxidation reactions and thermal decomposition.
Polyether-ether-ketone (PEEK) is a high polymer consisting of repeating units containing one ketone bond and two ether bonds in a main chain structure, and belongs to a special high polymer material. The polyetheretherketone has high glass transition temperature (Tg =143 ℃) and melting point (Tm =343 ℃), the load heat distortion temperature is as high as 316 ℃, and the instantaneous service temperature can reach 300 ℃. Polyetheretherketone also has rigidity and flexibility, is excellent in fatigue resistance particularly under alternating stress, is comparable to alloy materials, and has wear resistance, corrosion resistance, easy workability, insulation, excellent sliding properties, and the like.
The self-extinguishing property of the polyether-ether-ketone ensures that the polyether-ether-ketone can reach 94V-0 grade of UL standard even if no flame retardant is added, and the polyether-ether-ketone has the lowest fuming property and non-toxic characteristic.
The inventor finds that melamine has non-flammable property and can be used as a flame retardant synergist, so that the flame retardant performance of the flame retardant is improved.
In this example, zinc borate, polyetheretherketone and zinc oxide were used for smoke suppression, and melamine was used as a flame retardant synergist, with aluminium hydroxide and magnesium hydroxide acting as the main flame retardant. Through the component configuration of the substances, the rubber-plastic layer can obtain higher flame retardant performance and generate less smoke during combustion.
Of course, in other embodiments, wollastonite, sepiolite and other components can also be added as the flame retardant synergist; adding calcium phosphomolybdate, calcium molybdate and the like as smoke suppressants. The specific proportion of the flame-retardant synergist and the smoke suppressant is adjusted according to different components so as to obtain the optimal low-smoke flame-retardant effect. The flame retardant component provided by the embodiment can obtain a better low-smoke flame retardant effect in the range of each component.
Further, in the embodiment, the filler comprises 30-48 wt% of white carbon black, 20-36 wt% of azodicarbonamide, 15-24 wt% of nano organic montmorillonite and 8-12 wt% of zirconia.
The white carbon black is a general term for white powdery X-ray amorphous silicic acid and silicate products, mainly refers to precipitated silica, fumed silica and ultrafine silica gel, and also includes powdery synthetic aluminum silicate, calcium silicate and the like, and has the advantages of high temperature resistance, incombustibility, tastelessness, no odor and good electrical insulation. The white carbon black is largely classified into precipitated white carbon black and fumed white carbon black according to the production method. The fumed silica is white amorphous flocculent semitransparent solid colloidal nano particles (the particle size is less than 100 nm) in a normal state, is nontoxic and has a huge specific surface area. The precipitated white carbon black is mainly used as a reinforcing agent, a friction agent and the like of natural rubber and synthetic rubber. The fumed silica is mainly used as a reinforcing agent, a coating and an unsaturated resin thickener of silicone rubber. The white carbon black has super strong adhesive force, tear resistance, heat resistance and ageing resistance, so that part of carbon black can be replaced in black rubber products to obtain high-quality rubber products, such as off-road tires, engineering tires, radial tires and the like.
Specifically, in this embodiment, the fumed silica having an average particle diameter of less than 80nm is used as a reinforcing agent for the rubber layer, so as to improve the adhesion and tear resistance of the rubber layer and the insulating layer, and improve the heat resistance and aging resistance of the rubber layer.
Azodicarbonamide (also known by the english name azodicarbonamide) and azodicarbonamide, diazenedicarboxylic acid amide (diazinenedicarboxamide), which are commercially available as blowing agents AC or blowing agents adc (foamer adc), is a white or pale yellow powder, is non-toxic, odorless, nonflammable, and has self-extinguishing properties. The product adopting azodicarbonamide has good elasticity, uniform cell diameter and good strength.
Montmorillonite (montmorillonite), montmorillonite and microcrystalline kaolinite are natural minerals of silicate, are main mineral components of bentonite ore, have an average wafer thickness of less than 25nm, and can be used as bleaching agent and adsorbent filler. The modified montmorillonite has strong adsorption capacity and good dispersion performance, can be widely applied to the polymer material industry as an additive of a nano polymer material, and improves the impact resistance, the fatigue resistance, the dimensional stability, the gas barrier performance and the like, thereby playing a role in enhancing the comprehensive physical properties of the polymer and improving the material processing performance.
Specifically, in this embodiment, modified nano organic montmorillonite is used, the average wafer thickness is not more than 20nm, and the rubber-plastic layer has good fatigue resistance and waterproof and heat-insulating properties after the modified nano organic montmorillonite is added. Of course, in other embodiments, rectorite can be added to improve the heat insulation performance and elasticity of the rubber-plastic layer.
The zirconia has the characteristics of high temperature resistance, corrosion resistance, oxidation resistance, thermal shock resistance, non-volatility, no pollution and stable high-temperature chemical property, and is the most top refractory fiber material in the world at present. After the zirconium oxide is added, the rubber-plastic layer has better high-temperature resistance, so that the material is prevented from burning at a lower temperature, and the flame retardant property of the material is improved.
Still further, in this embodiment, the first insulating layer and the second insulating layer are both made of graphene. The graphene layer can sensitively detect the change of the environment, and can form a sensor for measurement. The graphene is light in weight and stable in chemical property, and can increase the strength and the heat-insulating property of the material.
In this embodiment, the metal selected for the nano-metal layer may be copper, silver, aluminum, iron, or even an alloy, and is preferably copper. Copper is low in price and has higher hardness and processability, so that the stress of the material is improved; in addition, when the material has thermal conductivity, the local high temperature of the material can be quickly conducted to the periphery, so that the problems of deformation, cracking and the like caused by local heating of the material are effectively reduced; and when the material has conductivity, the material can be combined with a graphene thermal insulation layer to form a sensor to sense the stress change of the material.
In the embodiment, the thickness of the first rubber layer is 3-8 mm; the thickness of the first heat-preservation layer is 0.2-1 mm; the thickness of the nano metal layer is 3-9 nm, the nano metal layer is in a grid shape, and the mesh number is 500-2000 meshes; the thickness of the second heat-insulating layer is consistent with that of the first heat-insulating layer, and the difference value is not more than +/-15%; the thickness of the second rubber layer is consistent with that of the first rubber layer, and the difference is not more than +/-20%.
It should be noted that the terms "consistent" and "consistent" are not intended to be exactly equal, but all conform to the same dimensions and tolerances; the term "difference" is understood here to mean a tolerance range, the tolerance value being a percentage multiplied by the thickness. Due to the limitations of the manufacturing process, the stacked structure cannot ensure the thickness of the stacked structure to be completely consistent on the basis of ensuring the bonding between the layers, and therefore, a certain tolerance is set to be suitable.
In this embodiment, since the thicknesses of the first rubber layer and the second rubber layer are the same, and the thicknesses of the first heat-insulating layer and the second heat-insulating layer are the same, the manufactured material does not need to be divided into the front side and the back side, and has the same performance.
The embodiment also provides a manufacturing method of the low-smoke halogen-free rubber-plastic thermal insulation material, as shown in fig. 2, the manufacturing method includes:
s1, extruding a flaky first rubber and plastic layer;
s2, forming a first heat preservation layer on one side surface of the first rubber-plastic layer at the temperature of 80 +/-10 ℃, and pressing for 3-5S under the pressure of 0.3-0.8 MPa;
s3, cooling to 26-40 ℃, laying a nano metal layer on the surface of the first heat preservation layer, wherein the width of the nano metal layer is 3-9 nm, and the mesh number is 500-2000 meshes;
s4, heating to 40-60 ℃, forming a second heat preservation layer on the surface of the nano metal layer, and pressing for 5-8S under 0.5-1 MPa;
and S5, extruding a second flaky rubber-plastic layer on the surface of the second heat-insulating layer, and pressing for 8-12S under 1.2-2.6 MPa.
In the embodiment, the first heat-preservation layer and the first rubber-plastic layer are pressed under pressure at a higher temperature, so that the first heat-preservation layer and the first rubber-plastic layer can be preliminarily bonded; then laying a nano metal layer at normal temperature to prevent the nano metal particles from being oxidized and being actively moved by molecules due to the influence of high temperature; the second heat-insulating layer is formed after the temperature is raised, and the lamination is carried out under a certain pressure, wherein the pressure is greater than the pressure of the first heat-insulating layer and the first rubber-plastic layer, because the four-layer structure needs to be laminated at the moment, the adhesion degree among multiple layers needs to be ensured, and the proper improvement of the lamination time is beneficial to ensuring the adhesion degree among the layers; after the extrusion of the second rubber-plastic layer, it takes a longer time to apply a greater pressure and press, thus ensuring the adhesion between each layer of material.
Meanwhile, it can be expected that since the first rubber-plastic layer and the first heat-insulating layer are laminated for three times, the second rubber-plastic layer is laminated for only one time, and the second heat-insulating layer is laminated for only two times, the thickness of the first rubber-plastic layer is larger than that of the second rubber-plastic layer when the first rubber-plastic layer is formed, so that the thicknesses of the first rubber-plastic layer and the second heat-insulating layer are consistent after lamination; and, because in this embodiment, first heat preservation and second heat preservation are graphite alkene, are inelastic material, therefore the thickness of first heat preservation slightly is greater than the thickness of second heat preservation and can guarantee that both thickness are unanimous after the pressfitting.
Specifically, in this embodiment, the extrusion process of the first rubber-plastic layer is the same as that of the second rubber-plastic layer, and includes:
pouring the rubber main body, the flame retardant and the filler into an internal mixer in sequence, and mixing for 150-280 s at 135-178 ℃ to obtain mixed rubber;
pouring the mixed rubber into an extruder, and performing calendering molding at 65-125 ℃ to obtain sheet rubber and plastic; wherein the temperature of the extruder body can be 60-70 ℃, the temperature of the extruder head can be 80-130 ℃, and the temperature of the die can be 90-140 ℃;
vulcanizing the flaky rubber and plastic by adopting a peroxide vulcanization system to obtain a rubber and plastic layer; in this embodiment, the peroxide used for vulcanization may be one or more of DCP (dicumyl peroxide), BPO or DCBP, and the co-crosslinking agent may be one or more of TAIC, TAC or HVA-2.
The specific manufacturing process of the rubber-plastic layer is well known to those skilled in the art, and the differences from the prior art are emphasized here, and the details of the similarities are not repeated.
And, in this embodiment, the method of forming the first insulating layer and the second insulating layer includes:
and forming a graphene layer on the surface of one side of the first rubber-plastic layer by using chemical vapor deposition to serve as the first heat-insulating layer, and forming a graphene layer on the surface of the nano metal layer to serve as the second heat-insulating layer.
The low-smoke halogen-free rubber-plastic thermal insulation material provided by the invention is described in the following specific examples, wherein the first to fourth examples mainly illustrate the characteristics of different formulations of the rubber main body in the rubber-plastic layer (the first rubber-plastic layer and the second rubber-plastic layer) provided by the invention, and the fifth to eighth examples mainly illustrate the overall performance of different formulations of the rubber-plastic layer (the first rubber-plastic layer and the second rubber-plastic layer) provided by the invention.
[ EXAMPLES one ]
The rubber main body selected in this example is ethylene propylene diene monomer, wherein the ratio of ethylene to propylene is 55:45, the ratio of Ethylidene Norbornene (ENB) in the third monomer is 32%, and the ratio of dicyclopentadiene (DCPD) is 68%.
The ethylene propylene diene monomer has general tensile strength, but has scorch resistance, good extrusion performance and processing performance, good low temperature resistance and low permanent strain.
When the rubber-plastic layer is formed by taking the rubber-plastic composite material as a rubber main body, 75% of the rubber main body, 15% of the flame retardant and 10% of the filler are selected for processing, so that the formed rubber-plastic layer is good in elasticity, ageing-resistant, corrosion-resistant, insulating, capable of effectively retarding flame during combustion and little in generated smoke.
[ example two ]
The rubber main body selected in this example is ethylene propylene diene monomer, wherein the ratio of ethylene to propylene is 78:22, the ratio of Ethylidene Norbornene (ENB) in the third monomer is 47%, and the ratio of dicyclopentadiene (DCPD) is 53%.
Compared with the first embodiment, the ethylene propylene diene monomer has higher tensile strength and glass body transition temperature, and has better basic performance and strain resistance; meanwhile, compared with the first embodiment, the vulcanization speed is higher, and the characteristics of low permanent deformation are achieved.
When the ethylene propylene diene monomer rubber is used as a rubber main body to form a rubber-plastic layer, 75% of the rubber main body, 15% of a flame retardant and 10% of a filler are selected for processing, so that the formed rubber-plastic layer is good in tensile strength, good in strain force, ageing-resistant, corrosion-resistant, capable of effectively resisting flame during combustion and almost free of smoke.
[ EXAMPLE III ]
The rubber main body selected in the embodiment is ethylene propylene rubber modified by maleic anhydride. The modified ethylene propylene rubber has high toughness and mechanical property and is low temperature resistant.
When the ethylene propylene rubber modified by maleic anhydride is used as a rubber main body to form a rubber-plastic layer, 75% of the rubber main body, 15% of a flame retardant and 10% of a filler are selected for processing, and the formed rubber-plastic layer is low-temperature resistant, has high stress characteristic, wear resistance and excellent flame retardant property, and almost generates no smoke during combustion.
[ EXAMPLE IV ]
The rubber body selected in the embodiment is acrylonitrile grafted ethylene propylene rubber. The modified ethylene propylene rubber not only keeps the corrosion resistance of the ethylene propylene rubber, but also obtains the oil resistance equivalent to butyronitrile-26, and has better physical and mechanical properties and processability.
When the acrylonitrile grafted ethylene propylene rubber is used as a rubber main body to form a rubber-plastic layer, 75% of the rubber main body, 15% of the flame retardant and 10% of the filler are selected for processing, and the formed rubber-plastic layer is resistant to oil and corrosion and has better mechanical toughness and stress strength. Can effectively resist flame during combustion and generate little smoke.
It should be noted that the flame retardant and the filler used in the first to fourth examples are consistent in component, so that the difference between the physicochemical properties and the flame retardant properties of the rubber-plastic layer after the rubber-plastic layer is manufactured by using different rubber bodies can be seen.
[ EXAMPLE V ]
The rubber main body selected in this embodiment is ethylene propylene diene monomer, wherein the ratio of ethylene to propylene is 65:35, and the ratio of ethylidene norbornene and dicyclopentadiene in the third monomer is 40: 60.
In this example, the flame retardant comprises 25% aluminum hydroxide, 30% magnesium hydroxide, 15% zinc borate, 12% polyetheretherketone, 10% melamine, and 8% zinc oxide. The filler comprises 40% of white carbon black, 30% of azodicarbonamide, 20% of nano organic montmorillonite and 10% of zirconia.
The rubber main body, the flame retardant and the filler are mixed, rolled and vulcanized according to the ratio of 75:15:10, and the obtained rubber-plastic layer has high tensile strength and vulcanization rate, and is good in temperature resistance and strain resistance. When burning, it has better flame-retardant performance and low smoke characteristic.
[ EXAMPLE six ]
The rubber body selected in this embodiment is the same as that in the fifth embodiment.
Wherein the flame retardant comprises 20% of aluminum hydroxide, 40% of magnesium hydroxide, 10% of zinc borate, 19% of polyetheretherketone, 6% of melamine and 5% of zinc oxide. The filler comprises 30% of white carbon black, 34% of azodicarbonamide, 24% of nano organic montmorillonite and 12% of zirconia.
The rubber main body, the flame retardant and the filler are mixed, rolled and vulcanized according to the ratio of 75:15:10, and the obtained rubber-plastic layer has high elasticity, aging resistance and high temperature resistance, has good flame retardant performance during combustion and almost does not generate smoke.
[ EXAMPLE VII ]
The rubber body and filler selected for this example are the same as those of example five.
Wherein the flame retardant comprises 30% of aluminum hydroxide, 20% of magnesium hydroxide, 25% of zinc borate, 9% of polyetheretherketone, 8% of melamine and 8% of zinc oxide.
The rubber main body, the flame retardant and the filler are mixed, rolled and vulcanized according to the ratio of 75:15:10, and the obtained rubber-plastic layer has high tensile strength and vulcanization rate, and is good in temperature resistance and strain resistance. Has better flame retardant property and almost no smoke generation when burning.
[ example eight ]
The rubber body, flame retardant and filler selected in this example are the same as those in the fifth example. When the rubber-plastic layer is formed, the rubber main body accounts for 80%, the flame retardant accounts for 15% and the filler accounts for 5%, mixing, calendering and vulcanizing are carried out according to the proportion, and the obtained rubber-plastic layer has high tensile strength and vulcanization rate, and is good in temperature resistance and strain resistance. When burning, it has better flame-retardant and low-smoke properties.
Through the fifth embodiment to the eighth embodiment, it can be seen that under the condition that the rubber main body is the same, different flame retardants and fillers can enable the generated rubber-plastic layer to have different physicochemical properties; and even if the components of the pixel main body, the flame retardant and the filler are consistent, the proportion is different when the rubber-plastic layer is manufactured, and the generated rubber-plastic layer also has different physical and chemical properties.
In addition, from the first to eighth embodiments, it can be confirmed that the rubber-plastic layer produced within the range of the components provided by the present invention has good flame retardant property and low smoke property. The heat preservation effect of the material is improved through the heat preservation layer, and the stress strength of the material is improved through the nano metal layer, so that the overall performance of the material is improved.
In summary, the low-smoke halogen-free rubber-plastic thermal insulation material and the manufacturing method thereof provided by the embodiment include a first rubber-plastic layer, a first thermal insulation layer, a nano metal layer, a second thermal insulation layer and a second rubber-plastic layer which are stacked in sequence; the first rubber-plastic layer and the second rubber-plastic layer are made of the same material and respectively comprise 70-90 wt% of a rubber main body, 7-20 wt% of a flame retardant and 5-13 wt% of a filler; the first heat-insulating layer and the second heat-insulating layer are made of the same material. The rubber-plastic layer is added with the flame retardant and the filler, so that the rubber-plastic layer has certain flame retardant performance while the rubber-plastic performance is improved; the heat insulation performance of the material can be improved through the heat insulation layer; the support property and rigidity of the material can be improved through the nano metal layer, the low-smoke halogen-free rubber-plastic heat-insulating material provided by the invention has better physical and chemical stability and flame retardance, and the problem of how to improve the physical and chemical properties of rubber and plastic on the basis of ensuring the flame retardance of rubber and plastic is solved.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.
Claims (10)
1. A low-smoke halogen-free rubber-plastic heat-insulating material is characterized by comprising a first rubber-plastic layer, a first heat-insulating layer, a nano metal layer, a second heat-insulating layer and a second rubber-plastic layer which are sequentially stacked; the first rubber-plastic layer and the second rubber-plastic layer are made of the same material and respectively comprise 70-90 wt% of a rubber main body, 7-20 wt% of a flame retardant and 5-13 wt% of a filler; the first heat-insulating layer and the second heat-insulating layer are made of the same material.
2. The low-smoke halogen-free rubber-plastic heat-insulating material as claimed in claim 1, wherein the rubber body is ethylene propylene diene monomer, the ethylene/propylene ratio in the ethylene propylene diene monomer is 55: 45-78: 22, and the third monomer in the ethylene propylene diene monomer comprises 32-47 wt% of ethylidene norbornene and 53-68 wt% of dicyclopentadiene.
3. The low-smoke halogen-free rubber-plastic heat-insulating material as claimed in claim 1, wherein the rubber main body is silicone modified ethylene propylene rubber, nylon modified ethylene propylene rubber, maleic anhydride modified ethylene propylene rubber or acrylonitrile grafted ethylene propylene rubber.
4. The low-smoke halogen-free rubber-plastic heat-insulating material as claimed in claim 1, wherein the flame retardant comprises 20-32% by weight of aluminum hydroxide, 18-42% by weight of magnesium hydroxide, 10-28% by weight of zinc borate, 8-22% by weight of polyether ether ketone, 6-10% by weight of melamine and 5-8% by weight of zinc oxide.
5. The low-smoke halogen-free rubber-plastic thermal insulation material as claimed in claim 1, wherein the filler comprises 30-48 wt% of white carbon black, 20-36 wt% of azodicarbonamide, 15-24 wt% of nano organic montmorillonite and 8-12 wt% of zirconia.
6. The low-smoke halogen-free rubber-plastic thermal insulation material as claimed in claim 1, wherein the first thermal insulation layer and the second thermal insulation layer are made of graphene.
7. The low-smoke halogen-free rubber-plastic heat-insulating material as claimed in claim 1, wherein the thickness of the first rubber layer is 3-8 mm; the thickness of the first heat-preservation layer is 0.2-1 mm; the thickness of the nano metal layer is 3-9 nm, the nano metal layer is in a grid shape, and the mesh number is 500-2000 meshes; the thickness of the second heat-insulating layer is consistent with that of the first heat-insulating layer, and the difference value is not more than +/-15%; the thickness of the second rubber layer is consistent with that of the first rubber layer, and the difference is not more than +/-20%.
8. A manufacturing method of a low-smoke halogen-free rubber-plastic heat-insulating material is used for manufacturing the low-smoke halogen-free rubber-plastic heat-insulating material as claimed in any one of claims 1 to 7, and is characterized by comprising the following steps:
extruding a sheet-like first rubber-plastic layer;
forming a first heat preservation layer on one side surface of the first rubber-plastic layer at the temperature of 80 +/-10 ℃, and pressing for 3-5 s under the pressure of 0.3-0.8 MPa;
cooling to 26-40 ℃, and paving a nano metal layer on the surface of the first heat preservation layer, wherein the width of the nano metal layer is 3-9 nm, and the mesh number is 500-2000 meshes;
heating to 40-60 ℃, forming a second heat-insulating layer on the surface of the nano metal layer, and pressing for 5-8 s under 0.5-1 MPa;
and extruding a second flaky rubber-plastic layer on the surface of the second heat-insulating layer, and pressing for 8-12 s under 1.2-2.6 MPa.
9. The manufacturing method of the low-smoke halogen-free rubber-plastic thermal insulation material according to claim 8, wherein the first rubber-plastic layer and the second rubber-plastic layer have the same extrusion process, and the method comprises the following steps:
pouring the rubber main body, the flame retardant and the filler into an internal mixer in sequence, and mixing for 150-280 s at 135-178 ℃ to obtain mixed rubber;
pouring the mixed rubber into an extruder, and performing calendering molding at 65-125 ℃ to obtain sheet rubber and plastic;
and vulcanizing the flaky rubber and plastic by adopting a peroxide vulcanization system to obtain a rubber and plastic layer.
10. The manufacturing method of the low-smoke halogen-free rubber-plastic thermal insulation material according to claim 8, wherein the forming method of the first thermal insulation layer and the second thermal insulation layer comprises the following steps:
and forming a graphene layer on the surface of one side of the first rubber-plastic layer by using chemical vapor deposition to serve as the first heat-insulating layer, and forming a graphene layer on the surface of the nano metal layer to serve as the second heat-insulating layer.
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| CN108440848A (en) * | 2018-03-30 | 2018-08-24 | 解飞 | Enhancing composite butyl self-adhesion EP rubbers waterproof roll and its production method in a kind of |
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| CN101704976A (en) * | 2009-11-27 | 2010-05-12 | 北京化工大学 | Low smoke halogen-free flame retardant ethylene-propylene-diene rubber and preparation method by extrusion molding thereof |
| CN107893485A (en) * | 2017-11-22 | 2018-04-10 | 邹城市邹旺食用菌有限公司 | A kind of efficient energy-saving heat-preservation plate |
| CN207527164U (en) * | 2017-11-30 | 2018-06-22 | 长春师范大学 | A kind of freeze protected rubber pipe equipped with graphene insulating layer |
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Application publication date: 20211022 |