CN115433400A - Process for producing halogen-free flame-retardant cable - Google Patents
Process for producing halogen-free flame-retardant cable Download PDFInfo
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- CN115433400A CN115433400A CN202210877087.5A CN202210877087A CN115433400A CN 115433400 A CN115433400 A CN 115433400A CN 202210877087 A CN202210877087 A CN 202210877087A CN 115433400 A CN115433400 A CN 115433400A
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- flame retardant
- cable
- parts
- retardant
- free flame
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- B29B9/02—Making granules by dividing preformed material
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a process for producing a halogen-free flame-retardant cable, which belongs to the technical field of electric wires and cables, firstly discloses a detailed processing method of LDPE and TPE and corresponding performances thereof, improves the flame-retardant performance of a cable material by compounding a flame retardant, and can improve the mechanical performance of the material; and finally, crosslinking the cable material by an electron beam radiation crosslinking process, thereby further improving the performance of the material and finally obtaining the cable with the halogen-free flame retardant characteristic. Therefore, the process for producing the halogen-free flame-retardant cable solves the technical problem that the flame-retardant cable in the prior art is poor in flame-retardant effect.
Description
Technical Field
The invention relates to the technical field of wires and cables, in particular to a process for producing a halogen-free flame-retardant cable.
Background
With the continuous progress of the technology level, the productivity in the world is greatly improved. The improvement of productivity is inseparable from the appearance of high-power electrical appliances, and certain potential safety hazards are caused when the high-power electrical appliances are used. Therefore, in the manufacturing process of the electric wire and cable, the safety protection measures need to be increased so as to reduce the probability of fire. When the fire-proof function is added in the manufacturing process of the electric wire and the electric cable, the flame-retardant material is mainly considered to be added in the manufacturing material. The development of 23428for flame retardant materials has begun since the last century. In the flame retardant materials of the last century, a certain amount of halogen-containing flame retardant is added, and the materials have a certain flame retardant effect, but once the materials are combusted, a large amount of harmful gas is generated, so that the materials have serious harm to human bodies. The smoke generated by the burning of the halogen-containing material not only has the harmful effects of heat damage, poison, suffocation and the like, but also has the harm of reducing brightness in a fire scene, thereby seriously influencing the escape time and causing secondary damage. Therefore, the flame retardant material with environmental protection and excellent performance has become a relatively important research and development direction in the cable industry today. In view of this, chinese patent CN102136317B discloses a halogen-free flame-retardant cable which can generate high flame retardancy, and can suppress generation of a gap between an insulated wire and a coating layer even if being irradiated with an electron beam, thereby preventing a decrease in adhesion strength. The halogen-free flame-retardant cable is provided with an inner layer on the outer side of a multi-core twisted wire formed by twisting a plurality of insulated wires having an insulating layer on the outer periphery of a conductor, and an outer layer on the inner layer, wherein the outer layer is composed of a resin composition containing a flame retardant in an amount of 30 parts by mass or more per 100 parts by mass of Thermoplastic Polyurethane (TPU), the inner layer is composed of a resin composition containing an ethylene vinyl acetate copolymer having an acetic acid component (VA) content of 33% or more, and the outer layer is formed by crosslinking treatment. The disclosed halogen-free flame-retardant cable can suppress a decrease in adhesion strength between an insulated wire and an inner layer and can achieve high flame retardancy.
However, the halogen-free flame retardant cable disclosed above has a technical problem of poor flame retardant effect. Specifically, in the above-disclosed halogen-free flame-retardant cable, a resin composition in which Melamine Cyanurate (MC) and a phosphorus compound are mixed into Thermoplastic Polyurethane (TPU) is used as the outermost layer of the coating layer, thereby achieving high flame retardancy; further, even when the electric wire is irradiated with an electron beam, a gap generated between the insulated wire and the coating layer can be suppressed, and the decrease in adhesion strength can be prevented. More specifically, the cable is heated due to the energy of the electron beam irradiation, and the EVA crystals are melted and expanded. Therefore, in the expanded state, a crosslinking reaction occurs in the Thermoplastic Polyurethane (TPU) and EVA, and the structures of both are fixed. When the irradiation is complete, it is cooled to ambient temperature, causing the EVA to shrink. Therefore, it is considered that since EVA is not bonded to the insulated wire, EVA is shrunk on the side of Thermoplastic Polyurethane (TPU), and a gap is generated between EVA and the insulated wire. Therefore, the halogen-free flame-retardant cable disclosed above can prevent expansion and inhibit the formation of the gap by using EVA with a small amount of crystalline component, thereby improving the flame-retardant effect of the product. TPU is a common and flammable polymer, however, the essential components required for combustion are oxygen, heat, and fuel; therefore, it is necessary to improve the flame retardant effect of the polymer by blending modification based on the material characteristics of the polymer itself.
Disclosure of Invention
Therefore, it is necessary to provide a process for producing a halogen-free flame retardant cable, aiming at the technical problem of poor flame retardant effect of the flame retardant cable in the prior art.
A process for producing a halogen-free flame-retardant cable, comprising the steps of:
s1: preparing base materials according to the mass portion: 100 parts of a blend of a thermoplastic elastomer and low-density polyethylene, 3 parts of dioctyl phthalate and 5 parts of paraffin;
s2: putting all the base materials into an electric heating constant-temperature air blast drying oven, and keeping the base materials in a constant-temperature air blast environment at 100 ℃ for drying for 2-3 hours;
s3: preparing a compound flame retardant according to the mass portion: 50-100 parts of organic modified aluminum hydroxide, 0-8 parts of microencapsulated red phosphorus, 0-10 parts of intumescent flame retardant and 0-10 parts of organic modified montmorillonite;
s4: premixing the base material and the compound flame retardant, and then banburying all the materials for 10 minutes at 140 ℃ by using an internal mixer;
s5: transferring the internally mixed materials to a two-roll plastic mixing mill, setting the plastic mixing temperature at 110-120 ℃ to uniformly mix the materials, discharging and cutting the materials for later use;
s6: after the material is kept stand for 24 hours, adding the material into a continuous extruder, and coating the material outside a cable core wire;
s7: and (3) cooling the coated cable through a continuous cooling water tank, and winding by using a winding machine to obtain a cable product.
Further, in step S1, the thermoplastic elastomer is added to the blend of the thermoplastic elastomer and the low density polyethylene in an amount of 30% to 70%.
Specifically, in step S1, the ratio of the thermoplastic elastomer to the low density polyethylene in the blend of the thermoplastic elastomer and the low density polyethylene is 3 to 7.
Further, in the step S3, the mass parts of the compound flame retardant are as follows: 60 parts of organic modified aluminum hydroxide, 6 parts of microencapsulated red phosphorus, 5 parts of intumescent flame retardant and 10 parts of organic modified montmorillonite.
Further, in step S5, the internally mixed material is added with dibenzoyl peroxide or triallyl isocyanurate and mixed uniformly, and then transferred to a two-roll mill.
Further, in step S7, the coated cable is placed on the plane of the turnover trolley, and after the electron beam accelerator is raised to 4Mev and the high voltage is stabilized, the trolley with the cable passes through the electron beam according to preset process parameters.
Specifically, the radiation dose is 60 to 90kGy.
Specifically, the irradiation process is 3 to 5m/min.
In conclusion, the process for producing the halogen-free flame-retardant cable firstly discloses a detailed processing method and corresponding properties of LDPE and TPE, improves the flame-retardant property of the cable material through compounding of the flame retardant, and can improve the mechanical properties of the material; and finally, crosslinking the cable material by an electron beam radiation crosslinking process, thereby further improving the performance of the material and finally obtaining the cable with the halogen-free flame retardant characteristic. In particular, the tensile strength of the LDPE/TPE binary blends tends to decrease with increasing TPE component, while the elongation at break tends to increase. Also, when the ratio of LDPE to TPE is 7 to 3, the tensile strength and elongation at break of the material is relatively suitable. Furthermore, by utilizing the synergistic flame retardant effect among ATH, MRP, IFR and OMMT, the addition amount of the inorganic flame retardant can be effectively controlled, so that the flame retardant property of the material is ensured, and the problem of reduction of the mechanical property of the material caused by addition of a large amount of inorganic matters is solved, thereby reducing the influence on the mechanical property of the composite material. Furthermore, compared with the traditional chemical crosslinking, the electron beam radiation crosslinking has the advantages of high efficiency and no pollution, and the gel content of the halogen-free flame-retardant LDPE/TPE composite material reaches 67%. The crosslinking sensitizer TAIC accelerates the crosslinking reaction in the application of radiation crosslinking and improves the crosslinking density of the material. From the viewpoint of efficiency, cost and resource saving, the optimum radiation dose is 60-90kGy. Finally, according to the research on the processing technology and performance and the consideration of the cost when an internal mixer and an open mill are used for processing, the raw materials are premixed in proportion and poured into a high-speed mixer, and the materials are uniformly mixed and then processed and granulated by a double-screw extruder; then, when the composite material is used for producing a cable by continuous extrusion, finally, the flame retardance and the mechanical property of the cable are tested to reach excellent levels. Therefore, the process for producing the halogen-free flame-retardant cable solves the technical problem that the flame-retardant cable in the prior art is poor in flame-retardant effect.
Drawings
Fig. 1 is a process flow diagram of a process for producing a halogen-free flame-retardant cable according to the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, as those skilled in the art will recognize without departing from the spirit and scope of the present invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, but are not intended to indicate or imply that the device or element so referred to must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "above," and "over" a second feature may be directly on or obliquely above the second feature, or simply mean that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "upper," "lower," "left," "right," and the like as used herein are for illustrative purposes only and do not denote a unique embodiment.
Referring to fig. 1, fig. 1 is a process flow diagram of a process for producing a halogen-free flame retardant cable according to the present invention. As shown in fig. 1, the process for producing a halogen-free flame-retardant cable of the present invention comprises the following steps:
s1: preparing base materials according to the mass portion: 100 parts of a blend of a thermoplastic elastomer and low-density polyethylene, 3 parts of dioctyl phthalate and 5 parts of paraffin;
s2: putting all the base materials into an electric heating constant-temperature air blast drying oven, and keeping the base materials in a constant-temperature air blast environment at 100 ℃ for drying for 2-3 hours;
s3: preparing a compound flame retardant according to the mass portion: 50-100 parts of organic modified aluminum hydroxide, 0-8 parts of microencapsulated red phosphorus, 0-10 parts of intumescent flame retardant and 0-10 parts of organic modified montmorillonite;
s4: premixing the base material and the compound flame retardant, and then banburying all the materials for 10 minutes at 140 ℃ by using an internal mixer;
s5: transferring the internally mixed materials to a two-roll plastic mixing mill, setting the plastic mixing temperature at 110-120 ℃ to uniformly mix the materials, discharging and cutting the materials for later use;
s6: after the material is kept stand for 24 hours, adding the material into a continuous extruder, and coating the material outside a cable core wire;
s7: and (3) cooling the coated cable through a continuous cooling water tank, and winding by using a winding machine to obtain a cable product.
In particular, thermoplastic elastomers, referred to as TPEs for short, are referred to as third generation rubbers because they have both the physicomechanical properties of vulcanized rubbers and the technical processability of thermoplastics. TPE has the advantages of easy formability and various processing modes of general plastics, and does not need vulcanization, and compared with the traditional vulcanized rubber, the industrial production efficiency of TPE is improved by 10-20 times. Moreover, the TPE has good thermoplasticity, flexibility, weather resistance, electrical property and physical and mechanical property, and can be processed according to the common methods of injection molding, extrusion, calendering and the like; moreover, the thermoplastic properties of TPE allow it to be used for multiple processing and recycling, not only reducing processing costs, but also having little environmental impact. Based on the above advantages, the present invention is used for a base material for making a cable jacket. In addition, blending is a common, efficient and effective method in the preparation of polymer-based high-performance composites. The blended material can have the properties of the base material, and other properties not possessed by each component can also be obtained. Further, low density polyethylene, abbreviated LDPE; it has excellent cold and low temperature resistance, electrical insulation, chemical stability, etc., but lacks flexibility and aging resistance, thereby limiting its application in cable materials. As mentioned above, TPE has better ductility, bending resistance, thermal-oxidative aging resistance, good processability and the like, and TPE and LDPE have good compatibility. Therefore, the TPE and the LDPE are blended to realize the advantage complementation of the two materials, so that the flexibility, the initial property and the ageing resistance of the materials are improved, the rubber-plastic blended composite material with excellent comprehensive performance is prepared, and the rubber-plastic blended composite material is applied to the outer sheath material of the cable.
Further, dioctyl phthalate, abbreviated as DOP in English, is an organic lipid compound, can be used as a plasticizer in the invention, is mainly used for blending processing between the TPE and the LDPE, but the addition amount of the DOP is controlled to be less than 10% of the total mass of the TPE and the LDPE, and the invention further discloses that the addition amount of the DOP is 3% of the total mass of the TPE and the LDPE. Further, paraffin, also called crystal form wax, is a non-polar solvent soluble in gasoline, carbon disulfide, xylene, ether, benzene, chloroform, carbon tetrachloride, naphtha, and the like, and insoluble in polar solvents such as water and methanol. The polymer is used as a compatilizer in the invention, and the blending system between the polymer materials is mostly incompatible or partially compatible. Phase separation often occurs because incompatible blended systems are processed with too high a build-up of molecular internal energy and in excess of the dispersed intermolecular forces of attraction between the two polymers. Although TPE and LDPE have good compatibility, the paraffin is introduced as a compatilizer of the TPE and the LDPE, so that the performance of a two-phase interface of the TPE and the LDPE can be effectively improved, the adhesion between the TPE and the LDPE is improved, and the phase separation phenomenon is avoided. This is because the polar groups in the compatibilizer molecule can physically and chemically react with the polymer to change the phase interface between incompatible polymers, which is a key factor in making incompatible systems compatible. The paraffin wax in the blending system of TPE and LDPE reasonably improves the interface state between polymers to ensure that the polymers have better adhesive property.
Furthermore, different mixing ratios of the TPE and the LDPE have different material mechanical properties, so that the TPE and the LDPE can be formed into blends according to different ratios shown in the following table 1, the total mass part of the blends is 100 parts, and DOP and paraffin are added into each blend in the same ratio; for example, 3 parts DOP and 5 parts paraffin wax were added to each blend. Then, taking out the materials by an internal mixer under the same processing conditions, and cutting the materials for standby. And then, adding the blended raw materials into a die, fixing and molding the materials on a hydraulic machine through the die, setting the temperature of an upper plate and the temperature of a lower plate of the hydraulic machine to be 160 ℃, setting the pressure of the upper plate and the lower plate of the hydraulic machine to be 10MPa, setting the hydraulic molding time to be 6min, and then cold-pressing the die for 5-10min under the pressure of 10MPa to prepare the binary blend sheet with the length, width and thickness of 100X100X1mm for later use.
Table 1: LDPE/TPE binary blend mass ratio
Further, based on 7 binary blend sheets prepared respectively according to the blending ratios of the LDPE/TPE binary blends in the table 1, the mechanical property test is continuously carried out according to the relevant standard of the standard GB/T3682-2000. The specific test conditions were: test speed 200mm/min, test temperature: 25 +/-2 ℃ and L O 25mm, 6mm in width and a thickness according to the binary blend sheet described aboveDepending on the material. Each mechanical property data is determined by averaging five samples. In addition, the performance of the LDPE/TPE binary blend after aging is also determined together, and the specific conditions of the aging test are as follows: heating from-80 deg.C to 70 deg.C at a rate of 5 deg.C/min, maintaining for 1h, cooling from 70 deg.C to-80 deg.C at a rate of 5 deg.C/min, maintaining for 1h, repeating the heating operation, and repeating the heating and cooling cycles for 72 times. The mechanical properties of the samples after aging testing were tested again under the mechanical property testing conditions, and the summary results are shown in table 2:
table 2: mechanical properties of binary blends with different proportions before and after aging
As can be seen from Table 2 above, the tensile strength of the binary blend gradually decreases and the elongation at break gradually increases with increasing TPE component from 0% to 100%. This is because TPE and LDPE act as the soft and hard phases, respectively, in the blend. Thus, as the content of the soft phase, i.e. TPE, in the system increases, and as the content of the hard phase, i.e. LDPE, decreases, the strength of the blend decreases, but the ductility increases. Meanwhile, as can be seen from table 2, the mechanical properties of the blends after thermo-oxidative aging are all reduced. Wherein the tensile strength loss after thermo-oxidative aging of pure LDPE is 58.97%, the elongation at break is 51.91%, and the corresponding retention rates are 41.03% and 48.09%, respectively. However, when TPE is added to the LDPE system, the tensile strength retention of the blend can be improved by 56.26% to 73.55% and the elongation at break retention can be improved by between 60.11% to 71.13%, so that it can be seen that the loss of the mechanical properties of the material is greatly reduced. Therefore, the TPE has obvious improvement effect on the mechanical property retention rate of the LDPE/TPE binary blend. This is because TPE itself has excellent resistance to thermal oxidative aging, which when dispersed in a blend, improves the resistance of the blend to thermal oxidative aging. Meanwhile, the resin section in the TPE molecular chain and the LDPE can form a resonance structure, and the blend has a resonance effect, so that the stability of the material is improved, and the thermo-oxidative aging resistance of the material is improved. Furthermore, when the addition amount of the TPE is between 30% and 70%, the effect of improving the mechanical properties of the blend is better, and particularly when the addition amount of the TPE is 30% and the addition amount of the LDPE is 70%, the overall performance improving effect is the best.
Furthermore, the polymer material undergoes aggregation state transition in the processing process, and conditions such as different processing time or processing temperature and the like often have great influence on the transition, so that the mechanical property of the material is influenced. Respectively changing the processing conditions of the binary blend materials, and performing supplementary tests according to the mechanical property test conditions to know that when the processing time is respectively 5min, 10min or 15min, the maximum value of the tensile strength of the blend is respectively 11.12MPa, 11.40MPa or 10.85 MPa, and the corresponding processing temperature is respectively 160 ℃, 140 ℃ or 120 ℃. Therefore, under the condition that the processing temperature and the processing time respectively reach 140 ℃ and 10min, the material shows better tensile strength. This is because the internal crosslinking of the blend is significant and the strength is improved with increasing processing time and temperature. However, when the processing time and temperature are further increased, degradation starts to occur inside the blend, and the degradation rate is greater than the crosslinking rate, so that the strength of the material begins to be reduced.
Furthermore, the blend of LDPE and TPE has good mechanical properties, and based on the material characteristics, the blend of LDPE and TPE has excellent electrical insulation properties, so that it is suitable for the application in the products of wires and cables. However, the polymeric materials are generally flammable, as are LDPE and TPE. Therefore, the blending system of LDPE and TPE needs to be further improved in flame retardant property by flame retardant. Specifically, the aluminum hydroxide flame retardant, abbreviated as ATH in english, in the development and application processes of the halogen-free flame retardant belongs to a flame retardant with low smoke, no halogen and excellent flame retardant effect. Moreover, the smoke generating amount can be effectively controlled, the dripping is well inhibited, and the filling and reinforcing effects can be realized. The factor hindering the filling effect of ATH is that when the filling amount is too large, the physical properties of the material are greatly reduced. According to the existing research, when different flame retardants are compounded for use, a synergistic flame retardant effect exists among the components, and the flame retardant efficiency can be improved to the maximum extent while the addition amount of the flame retardants is reduced. The invention discloses microencapsulated red phosphorus with a synergistic flame retardant effect, wherein the red phosphorus is abbreviated as MRP in English, an intumescent flame retardant is abbreviated as IFR in English, and organic montmorillonite is abbreviated as OMMT in English.
Further, in the steps, after the base material and the compound flame retardant are mixed and stand for 24 hours, the raw materials after blending can be added into a preset die, the raw materials are fixedly molded on a hydraulic press through the die, the temperature of an upper plate and the temperature of a lower plate of the hydraulic press are both set to be 160 ℃, the pressure is set to be 10MPa, the hydraulic molding time is set to be 6min, and then the die is subjected to cold pressing for 5-10min under the pressure of 10MPa, so that the flame-retardant sheet with the length, the width and the thickness of 100mm, 100mm and 1mm respectively is prepared for standby. Flame-retardant sheet samples with different flame retardant addition amounts were prepared in sequence according to the formulation of the compounded flame retardant shown in Table 3 below, respectively, in combination with the above steps. Then, according to the oxygen index test method: the test is carried out according to the relevant standard of GB/T1040-2004, and the requirements of the spline are as follows: 70-150mm, 6.5 +/-1.5 mm in width and 3.0 +/-0.5 mm in thickness and a mechanical property test method: the mechanical property test is carried out according to the relevant standard of the standard GB/T3682-2000. The specific test conditions were: test speed 200mm/min, test temperature: 25 +/-2 ℃ and L O 25mm in width and 6mm in thickness, depending on the flame-retardant sheet material described above. The results of the oxygen index measurement and the structure of the mechanical properties are summarized in Table 4.
Table 3: sample formula with different flame retardant addition amounts
Further, the flame retardant samples prepared according to the formulas in table 3 above are subjected to an oxygen index test and a mechanical property test in sequence according to the steps, and the experimental results are summarized as shown in table 4 below. In particular, the method comprises the following steps of,the oxygen index method can perform visual evaluation on the flame retardant property of the high polymer material, and the experiment mainly reveals the relative combustibility of the corresponding high polymer material. As shown in Table 4, 0%, 50% and 100% of ATH is added to the flame retardant samples No. 1 to No. 3, respectively, and it can be seen from the results of the experiments that as the addition amount of ATH increases from 0 to 100%, the tensile strength and oxygen index of the LDPE/TPE composite respectively show a decreasing trend and an increasing trend. This is because Al is a product of the thermal decomposition of ATH 2 O 3 The chemical property is stable, and the composite can be covered on the surface of the composite, so that the heat exchange between the outside and the inside of the compound matrix is prevented, and the oxygen concentration on the surface of the material is reduced. However, when the addition amount is too large, ATH can agglomerate, which can destroy the continuity of the internal structure of the material and lead to the reduction of the mechanical properties of the material. When the amount of dpath was 100% by weight, the tensile strength of the polymer decreased from 11.41MPa to 7.49, which was 34.13%. Therefore, when single ATH is added as a flame retardant, although a large amount of ATH can be added to effectively improve the oxygen index of the LDPE/TPE composite material, the method can greatly reduce the tensile strength of the material and seriously affect the mechanical properties of the material. Therefore, in order to reduce the addition amount of the flame retardant, improve the oxygen index of the LDPE/TPE composite material and ensure the mechanical property of the material, the synergistic flame retardant effect needs to be fully utilized. As can be seen from Table 4, after the MRP, IFR and OMMT are added into the system in sequence, the tensile strength of the LDPE/TPE composite material is obviously improved. Compared with the method of adding single ATH as a flame retardant material, the tensile strength of the LDPE/TPE composite material under the same condition is improved by about 12.19%, and the oxygen index of the LDPE/TPE composite material is obviously improved by 6.18%, 13.17% and 21.01% respectively along with the addition of a small amount of synergistic flame retardant. In conclusion, MRP, IFR, OMMT and ATH have a synergistic flame-retardant effect on the LDPE/TPE composite material, so that the flame-retardant property of the material is improved, and the strength of the material can be ensured.
Table 4: tensile strength and oxygen index of composite material under different formula flame retardants
Further, the processing conditions of the binary blend and the flame retardant material are respectively changed, and supplementary tests are carried out according to the mechanical property test conditions, so that when the processing time is respectively 5min, 10min or 15min, the maximum value of the tensile strength of the blend is respectively 8.18MPa, 9.35MPa or 8.85 MPa, and the corresponding processing temperatures are respectively 160 ℃, 140 ℃ or 120 ℃. Therefore, under the condition that the processing temperature and the processing time respectively reach 140 ℃ and 10min, the material shows better tensile strength. This is because the internal crosslinking of the blend is significant and the strength is improved with increasing processing time and temperature. However, when the processing time and temperature are further increased, degradation starts to occur inside the blend, and the degradation rate is greater than the crosslinking rate, so that the strength of the material begins to be reduced. The influence of the processing conditions on the material is similar to that of the binary blend, namely, the high polymer material has uniformity in the processing conditions.
Furthermore, the electron beam radiation process is an environment-friendly processing process widely applied to polymer modification, and the heat resistance, flame retardance and mechanical properties of the high polymer material after radiation crosslinking treatment are all obviously improved. Among them, peroxide crosslinking has excellent adaptability, but the crosslinking reaction usually causes whitening of the polymer surface and blooming, and the odor of the product generated in the process is relatively large and harmful to human health. Meanwhile, due to the residue of the crosslinking agent inside the polymer, the degradation reaction of the polymer during use is accelerated, resulting in a decrease in the aging resistance of the polymer. In addition, radiation crosslinking mainly induces crosslinking, grafting, polymerization and degradation physicochemical change through ionizing radiation, and a processed product does not have radioactivity. Moreover, no chemical cross-linking agent is needed in the radiation cross-linking, and the energy consumption is low, the energy is saved, and the production efficiency is relatively high. Thus, compared to chemical crosslinking, radiation crosslinking has many advantages, such as controllable crosslinking, no pollution, no chemical residue, and capability of completing crosslinking at normal temperature and pressure. Therefore, the electron beam radiation crosslinking method can be applied to the modification of polymers, particularly polyolefins. The invention further discloses that LDPE/TPE is used as a matrix, on the basis of adding the compound flame retardant, radiation crosslinking and chemical crosslinking are respectively adopted, the materials are subjected to radiation crosslinking with different radiation doses and chemical crosslinking under different peroxide crosslinking agent addition amounts, and the differences of the radiation crosslinking and the chemical crosslinking are compared through a gel content test. At the same time, the use of triallyl isocyanurate as a crosslinking sensitizer revealed a positive role of the crosslinking agent in the radiation crosslinking reaction.
Specifically, in the chemical crosslinking modification method, materials are premixed according to the formula of the base material and the formula of the compound flame retardant, then the materials are mixed for 10min at 140 ℃ by using an internal mixer, after the materials are taken out, dibenzoyl peroxide is continuously added and is uniformly mixed in a double-roll plastic mixer, and the materials are taken out and cut for standby. After standing for 24 hours, weighing a proper amount of materials, putting the materials into a preset die, carrying out compression molding on the materials in a hydraulic molding machine, wherein the temperature of an upper die and the temperature of a lower die are respectively 160 ℃, the pressure is set to be 10MPa, the pressure maintaining time is 6min, and then, keeping the die at the cold pressure of 10MPa for 5-10min to obtain the material for later use. In the radiation crosslinking modification method, the method for preparing the radiation base material is similar to the chemical crosslinking modification method, and only dibenzoyl peroxide needs to be changed into triallyl isocyanurate. Specifically, the English name of dibenzoyl peroxide is abbreviated as BPO; and the triallyl isocyanurate is abbreviated as TAIC in english.
Further, the chemical crosslinking modified base material and the radiation crosslinking modified base material are respectively placed on a storage table board of the turnover trolley, and after the electron beam accelerator is raised to 4Mev and the high voltage is stabilized, the trolley passes through the electron beam according to preset process parameters. Thereby achieving irradiation of the sample. The radiation doses were irradiated at 0kGy, 30kGy, 60 kGy, 90kGy, 120 kGy and 150kGy, respectively. Where 0kGy is the control group, i.e.the sample is not irradiated. The radiation dose and process conversion are shown in table 5 below, and the difference in the radiation dose of the samples is controlled by the irradiation process.
Table 5: corresponding control of radiation dose and process parameters
Further, continuously testing the gel content and the mechanical property of the product, wherein the gel content specifically comprises the following steps: the test was carried out according to GB/T18474-2001. The extract was heated under reflux in a Soxhlet extractor for 24 hours using 80% pure xylene as the extraction liquid. After the reflux was stopped, the sample was immediately taken out and washed with absolute ethanol. Drying in an oven at 100-120 deg.C for 3 hr, taking out, weighing, calculating gel content according to a preset formula, and taking the average value of five samples. The calculation formula is as follows: gel content = mass of sample after test/mass of sample before test X100%. The mechanical property test comprises the following steps: the mechanical property test is carried out according to the relevant standard of the standard GB/T3682-2000. The testing speed is 200mm/min, and the testing temperature is as follows: 25 +/-2 ℃ and L O 25mm in width and 6mm in thickness, according to the binary blend sheet described above. Each mechanical property data is determined by averaging five samples. Table 6 below shows the effect of different cross-linking agents on the gel content of the composite; the following table 7 shows the effect of different radiation doses on the gel content of the composite.
Table 6: effect of different crosslinkers on gel content of composites
Table 7: effect of different radiation doses on gel content of composite materials
Specifically, the size of the crosslinking density of the polymer can be indirectly reflected by measuring the gel content. As shown in Table 6, when the crosslinking processing mode adopts chemical crosslinking, that is, BPO is used as a crosslinking agent, the gel content of the halogen-free flame-retardant LDPE/TPE composite material can only reach 58% at most, and at this time, the addition amount of the chemical crosslinking agent BPO is 5%. When electron beam radiation crosslinking is adopted, the gel content of the halogen-free flame-retardant LDPE/TPE composite material can reach 67% when the addition amount of a crosslinking sensitizer TAIC is only 3%. Meanwhile, chemical crosslinking needs to be carried out at high temperature, a large amount of waste gas is generated to pollute the environment, and radiation crosslinking only needs to be carried out at normal temperature and does not generate emission. Therefore, electron beam radiation crosslinking has the advantages of high efficiency and no pollution compared with traditional chemical crosslinking. Furthermore, table 7 further reveals that the LEPE/TPE/TAIC composite system has a higher gel content compared to a material system without TAIC, because TAIC is easily subjected to a cyclic hydrogenation reaction under the action of radiation, a polyfunctional allyl radical and a polyethylene radical generated by radiation generate a termination reaction, and a radical reaction between larger molecular chains is easy, so that the introduction of TAIC accelerates a crosslinking reaction, thereby increasing the crosslinking density. The radiation process is most suitable when the radiation dose is 60-90kGy, considering the production efficiency and the cost synchronously.
Further, the mechanical property of the halogen-free flame-retardant LDPE/TPE composite material under different radiation doses is further disclosed according to the mechanical property test method. As can be seen from the experimental data in table 8, the tensile strength of the composite increased first and then decreased as the radiation dose increased. The tensile strength of the composite material which is not subjected to radiation processing is 10.39MPa, and the maximum value of the tensile strength of the composite material which is subjected to radiation processing is 12.28 MPa, which is improved by 18.24%. However, in the radiation process of the polymer, crosslinking and degradation are possible to occur simultaneously, but only one aspect is dominant, when the radiation dose is too large, molecular chains are cracked, degradation reaction is dominant, and the tensile strength is reduced. At the same time, the elongation at break of the composite material decreases with increasing radiation dose and shows a linearly decreasing relationship. This phenomenon is expected because the polymer is subjected to radiation crosslinking during the process of electron irradiation, and as the irradiation dose is increased, more crosslinking points are generated in the molecular chain, so that the slippage between the molecular chains is difficult, and the elongation at break of the material is reduced. In combination with the gel test experiment, it can be further determined that electron beam radiation treatment is beneficial to improving the mechanical properties of the material, and the radiation process is most suitable when the radiation dose is 60-90kGy.
Table 8: influence of different radiation doses on mechanical properties of composite materials
Furthermore, according to relevant standards of GB/T2406-1993, the oxygen index of the halogen-free flame-retardant LDPE/TPE composite material under different radiation doses is experimentally tested, and the data are summarized in Table 9. As can be seen from the data in table 9, the oxygen index of the composite system changes from rising to falling with increasing radiation dose. When the radiation dose reaches 90kGy, the oxygen index reaches 30.11 percent, and the integral rising amplitude reaches 3.25 percent. When the radiation dose is in the range of 0-90kGy, a three-dimensional network structure is generated inside the composite material, so that the dispersion degree of the matrix is small. Meanwhile, the flame retardant particles are easier to embed due to the generation of the structure, and the dispersion uniformity of the flame retardant in the base material is improved, so that the flame retardant property of the whole system is obviously improved. In the case of a radiation dose in the range of 90-150 kGy, the oxygen index of the composite material itself is significantly reduced. This is because the degradation effect inside the polymer is greater than the crosslinking effect after the radiation dose is too large, the crosslinked structure is reduced, and the structure of the flame retardant may be destroyed, so that the flame retardant property of the material itself is affected. That is, the composite material after proper electron beam radiation crosslinking treatment is favorable for improving the flame retardant property, and the optimal radiation dose is 60-90kGy.
Table 9: effect of different radiation doses on oxygen index of composite materials
In conclusion, the process for producing the halogen-free flame-retardant cable firstly discloses a detailed processing method of LDPE and TPE and corresponding performances thereof, improves the flame-retardant performance of the cable material through compounding of the flame retardant, and can improve the mechanical performance of the material; and finally, crosslinking the cable material by an electron beam radiation crosslinking process, thereby further improving the performance of the material and finally obtaining the cable with the halogen-free flame retardant characteristic. In particular, the tensile strength of the LDPE/TPE binary blend tends to decrease with increasing TPE component, while the elongation at break tends to increase. Also, when the ratio of LDPE to TPE is 7 to 3, the tensile strength and elongation at break of the material is relatively suitable. Furthermore, the additive amount of the inorganic flame retardant can be effectively controlled by utilizing the synergistic flame retardant effect among ATH, MRP, IFR and OMMT, so that the flame retardant property of the material is ensured, and the problem of reduction of the mechanical property of the material caused by the addition of a large amount of inorganic matters is solved, thereby reducing the influence on the mechanical property of the composite material. Furthermore, compared with the traditional chemical crosslinking, the electron beam radiation crosslinking has the advantages of high efficiency and no pollution, and the gel content of the halogen-free flame-retardant LDPE/TPE composite material reaches 67%. The crosslinking sensitizer TAIC accelerates the crosslinking reaction in the application of radiation crosslinking, and improves the crosslinking density of the material. From the viewpoint of efficiency, cost and resource saving, the optimum radiation dose is 60-90kGy. Finally, according to the study on the processing technology and performance when an internal mixer and an open mill are used for processing and the consideration on the cost, the raw materials are premixed in proportion and poured into a high-speed mixer, and the materials are uniformly mixed and then processed and granulated by a double-screw extruder; then, when the composite material is used for producing a cable by continuous extrusion, finally, the flame retardance and the mechanical property of the cable are tested to reach excellent levels. Therefore, the process for producing the halogen-free flame-retardant cable solves the technical problem that the flame-retardant cable in the prior art is poor in flame-retardant effect.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A process for producing a halogen-free flame-retardant cable is characterized by comprising the following steps:
s1: preparing a base material according to the mass portion: 100 parts of a blend of a thermoplastic elastomer and low-density polyethylene, 3 parts of dioctyl phthalate and 5 parts of paraffin;
s2: putting all the base materials into an electric heating constant-temperature air blast drying oven, and keeping the base materials in a constant-temperature air blast environment at 100 ℃ for drying for 2-3 hours;
s3: preparing a compound flame retardant according to the mass portion: 50-100 parts of organic modified aluminum hydroxide, 0-8 parts of microencapsulated red phosphorus, 0-10 parts of intumescent flame retardant and 0-10 parts of organic modified montmorillonite;
s4: premixing the base material and the compound flame retardant, and then banburying all the materials for 10 minutes at 140 ℃ by using an internal mixer;
s5: transferring the internally mixed materials to a two-roll plastic mixing mill, setting the plastic mixing temperature at 110-120 ℃ to uniformly mix the materials, discharging and cutting the materials for later use;
s6: after the material is kept stand for 24 hours, adding the material into a continuous extruder, and coating the material outside a cable core wire;
s7: and (4) after the coated cable is cooled by the continuous cooling water tank, winding by using a winding machine to obtain a cable product.
2. The process for producing halogen-free flame retardant cable according to claim 1, wherein: in step S1, the thermoplastic elastomer is added to the blend of thermoplastic elastomer and low density polyethylene in an amount of 30% to 70%.
3. The process for producing halogen-free flame retardant cable according to claim 2, wherein: in step S1, the ratio of thermoplastic elastomer to low density polyethylene in the blend of thermoplastic elastomer and low density polyethylene is 3 to 7.
4. The process for producing halogen-free flame retardant cable according to claim 1, wherein: in the step S3, the mass part ratio of the compound flame retardant is as follows: 60 parts of organic modified aluminum hydroxide, 6 parts of microencapsulated red phosphorus, 5 parts of intumescent flame retardant and 10 parts of organic modified montmorillonite.
5. The process for producing halogen-free flame-retardant cable according to claim 1, wherein: in step S5, the internally mixed material is added with dibenzoyl peroxide or triallyl isocyanurate and is transferred to a two-roll mill after being uniformly mixed.
6. The process for producing halogen-free flame retardant cable according to claim 5, wherein: in step S7, the coated cable is first placed on the plane of the turnaround cart, and after the electron beam accelerator is raised to 4Mev and the high voltage is stabilized, the cart is made to pass the cable under the electron beam according to preset process parameters.
7. The process for producing halogen-free flame-retardant cable according to claim 6, wherein: the radiation dose is 60 to 90kGy.
8. The process for producing halogen-free flame retardant cable according to claim 7, wherein: the irradiation process is 3 to 5m/min.
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