CN101358004B - IXPE electron radiation on crosslinking polyethylene conductive foam and preparation method thereof - Google Patents
IXPE electron radiation on crosslinking polyethylene conductive foam and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an IXPE electronic radiation crosslinked polyethylene conductive foam and a preparation method thereof. The IXPE electronic radiation crosslinked polyethylene conductive foam mainly contains the mother batch: low density polyethylene; accessories: ethylene-vinyl acetate copolymer, azodicarbonamide blowing agent, polyethylene wax lubrication additive, titanate ester coupling agent and conductive carbon black which are mixed for processing, extruded for molding, radiated for crosslinking, heated for foaming, and treated by secondary processing, etc, to produce the IXPE electronic radiation crosslinked polyethylene conductive foam. The crosslinking of the product of the invention can be easily controlled, the foaming process is stable, the foam pores are fine and even, the quality of the surface is high without unpleasant odor, the foam pores are obstructed, the production can be carried out continually, the electrical conductivity is stable, the product is lightweight, non-toxic, extremely less absorbent; the thermal conductivity is slow, aging resistant, chemical corrosion resistant, pulverization resistant, and a plurality of porous foam materials can be easily achieved; in addition, the product has good properties to be treated by the secondary processing procedures, such as bonding, machining, hot forming, etc.
Description
Technical field
The present invention relates to a kind of IXPE electron radiation crosslinking polyethylene conductive foam and preparation method thereof, high-tech industries such as this conducting foam can be used on a large scale, super large-scale integration, photoelectron, microelectronic industry and communication, space flight, IT, when turnover, transportation work in-process surface-mounted integrated circuit and fearness some products of electrostatic or work in-process, also can find application, play bumper and absorbing shock and prevent the electrostatic effect again.
Background technology
The conducting foam of Ying Yonging mainly contains anti-electrostatic PE Foam and block polyethylene of mold pressing or EVA conducting foam in the market.
The anti-electrostatic PE Foam is because be uncrosslinked polythene material, and not crosslinked polyethylene anti-electrostatic foaming is a physical blowing, and foam bubble sky is very big, compressive strength is low, and rebound resilience is poor, the feel extreme difference, the expansion ratio of adding it is single, and the thickness single error is bigger, and heatproof is lower, its Application Areas is narrower, the application scenario class is lower, and its surface resistivity and volume specific resistance instability can not be regulated according to customer requirement, resistivity is bigger, 10
8-10
11Ω can't regulate, and it makes the PE Foam of anti-electrostatic by add static inhibitor in PE Foam, and this anti-electrostatic PE Foam anti-electrostatic timeliness is short, and the anti-electrostatic timeliness is 3-6 month, and it is bigger that antistatic performance is influenced by the environment humidity.
For the polyethylene of moulded from foam or the block conducting foam of EVA, though bubble is empty fine and smooth, mechanical property is relatively poor, and tear strength, compressive strength, compression set are poor than the product of radiation crosslinking; Product can not continuous production, and the different thickness product only obtains by slicing, and product does not have the skinning epidermis, in post-treatment, can not carry out heat bonding, use the processing limitation bigger, the bad control of product soft or hard density has linking agent remaining, smell is bigger, not environmental protection has certain toxicity, and product does not have epidermis, the product of no continuous length, power consumption, production efficiency is low.
Summary of the invention
In order to solve existing this technical problem of over-all properties difference of conducting foam in the prior art, the invention provides a kind of electron radiation crosslinking polyethylene conductive foam.
Based on this electron radiation crosslinking polyethylene conductive foam, the present invention also provides a kind of preparation method of electron radiation crosslinking polyethylene conductive foam.
The present invention solves the technical scheme that first technical problem adopts: a kind of IXPE electron radiation crosslinking polyethylene conductive foam is provided, described IXPE electron radiation crosslinking polyethylene conductive foam comprises major ingredient new LDPE (film grade) and auxiliary material ethylene-vinyl acetate copolymer, the weight ratio of described new LDPE (film grade) and described ethylene-vinyl acetate copolymer is 65-75:25-35, and described IXPE electron radiation crosslinking polyethylene conductive foam also comprises and accounts for described new LDPE (film grade) and described ethylene-vinyl acetate copolymer gross weight 4%-6%, the azodicarbonamide foaming agent of 9%-11% or 14%-16%, 1% polyethylene wax lubricating auxiliary agent, the conductive carbon black of 0.5% titanate coupling agent and 4.5%-5.5% or 6.5%-7.5%.
According to a preferred embodiment of the invention: the weight ratio of described major ingredient new LDPE (film grade) and described auxiliary material ethylene-vinyl acetate copolymer is 70:30.
According to a preferred embodiment of the invention: the solution index of described major ingredient new LDPE (film grade) is MI=1.5-2.0.
According to a preferred embodiment of the invention: described azodicarbonamide foaming agent is a particulate state, particle diameter 4 μ-6 μ.
According to a preferred embodiment of the invention: described conductive carbon black is formed with the high chain-like structure of ghost, through the nearly nanometer of special processing product primary structure particle diameter, specific surface area is big, dispersed high, because the reticulated structure that the wadding aggregate constitutes makes the conductivity that itself has extra-high-speed, than resistance less than 0.20 Ω .cm.
According to a preferred embodiment of the invention: described IXPE electron radiation crosslinking polyethylene conductive foam was an antistatic foam when adding proportion of described high electric conductivity carbon black accounted for described major ingredient new LDPE (film grade) and described auxiliary material ethylene-vinyl acetate copolymer gross weight ratio and is 4.5%-5.5%; Described IXPE electron radiation crosslinking polyethylene conductive foam is a conducting foam when accounting for described major ingredient new LDPE (film grade) and described auxiliary material ethylene-vinyl acetate copolymer gross weight ratio and being 6.5%-7.5%.
In order to solve second technical problem of the prior art, the invention provides a kind of preparation method of IXPE electron radiation crosslinking polyethylene conductive foam, described preparation method comprises step: the first, described major ingredient new LDPE (film grade), described auxiliary material ethylene-vinyl acetate copolymer, described azodicarbonamide foaming agent, described polyethylene wax lubricating auxiliary agent, described titanate coupling agent and described high electric conductivity carbon black are carried out mixing mixing, carry out mixing granulator processing at 120 ℃-125 ℃; The second, making master batch being carried out extrusion moulding is master slice, and master slice is at the uniform velocity extruded; Three, to the described master slice of at the uniform velocity extruding carry out continuously, irradiation processing uniformly; Four, the described master slice after the described irradiation processing is carried out continuously 140 ℃-155 ℃ thermal pretreatment in the foaming furnace preheating section, the master slice foaming section that enters foaming furnace is continuously carried out 220 ℃-230 ℃ foaming and is handled then.
According to a preferred embodiment of the invention: former membrana oralis gap is greater than the thickness of described master slice but be no more than 10% of master slice thickness when in described second step described foaming coiled material master slice being carried out extrusion moulding.
According to a preferred embodiment of the invention: irradiation processing is undertaken by rumbatron described in described the 3rd step, and the energy of described rumbatron is 2.5Mev, and sweep length is 800-1000mm.
According to a preferred embodiment of the invention: master slice at the uniform velocity evenly moved in foaming furnace continuously during described the 4th step thermal pretreatment and foaming were handled, and thickness is that to be about 2 meters/minute, thickness be that the described master slice translational speed of 3mm is about 1 meter/minute to the continuous translational speed of described master slice of 1mm.
The invention has the beneficial effects as follows: radiant crosslinked polyethylene conducting foam of the present invention (IXPE), crosslinked relatively easy to control, foaming is stable, abscess is fine and closely woven evenly, surface quality is good, free from extraneous odour, foam structure is a closed pore, the product light weight, nontoxic,, water-absorbent is extremely low, thermal conductivity is little, ageing-resistant, resistance to chemical attack, not efflorescence, obtain easily the cellular material of different multiples band epidermis, simultaneously the product continuous length, electroconductibility is steady in a long-term but also have the superperformance of secondary processing such as can carrying out bonding, machining, thermoforming.
Description of drawings
Fig. 1. foam preparation method schema in IXPE electron radiation crosslinking polyethylene conductive foam of the present invention and preparation method thereof;
Fig. 2. foam foam expansion, product thickness, master slice thickness and additive capacity concern contrast table.
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
Radiation crosslinking is that ionizing rays makes that linear polyethylene is crosslinked to contain certain cancellated polymkeric substance, and the polyethylene linear macromolecular material that is crystal type, after the crystalline structure fusing, melt viscosity can sharply descend, and is unfavorable for protecting gas and is difficult to make foam material.Radiation crosslinking then can make it crosslinked by special radiation processing, improves poly temperature-viscosity changing conditions, helps protecting gas with after this radiation modification technology in foaming process, forms more fine and smooth foam structure.In the system raw material of polyethylene foam, various by a certain percentage auxiliary agents also can improve the quality that improves foaming, by adding extraordinary conductive carbon black, make special IXPE radiant crosslinked polyethylene conducting foam.
Specifically, IXPE electron radiation crosslinking polyethylene conductive foam, described IXPE electron radiation crosslinking polyethylene conductive foam comprises major ingredient new LDPE (film grade) and auxiliary material ethylene-vinyl acetate copolymer, the weight ratio of described new LDPE (film grade) and described ethylene-vinyl acetate copolymer is 65-75:25-35, described IXPE electron radiation crosslinking polyethylene conductive foam also comprises and accounts for described new LDPE (film grade) and described ethylene-vinyl acetate copolymer gross weight 4%-6%, the azodicarbonamide foaming agent of 9%-11% or 14%-16%, 1% polyethylene wax lubricating auxiliary agent, the electroconductibility of 0.5% titanate coupling agent and 4.5%-5.5% or 6.5%-7.5% is formed with the high chain-like structure of ghost than the good special carbon black of common carbon black-high electric conductivity carbon black, through the nearly nanometer of special processing product primary structure particle diameter, specific surface area is big, dispersed high, because the reticulated structure that the wadding aggregate constitutes makes the conductivity that itself has extra-high-speed, than resistance less than 0.20 Ω .cm.
Optimum ratio as top IXPE electron radiation crosslinking polyethylene conductive foam prescription, the mass ratio of described new LDPE (film grade) and described ethylene-vinyl acetate copolymer is 70:30, the whipping agent Cellmic C 121 of choosing in the prescription is Powdered, and the powder diameter is about 5 μ; The total mass ratio that the whipping agent Cellmic C 121 accounts for described new LDPE (film grade) and described ethylene-vinyl acetate copolymer is preferably 5%, 10%, 15%, adds the described whipping agent Cellmic C 121 of different ratios and can make the different described IXPE electron radiation crosslinking polyethylene conductive foam material of corresponding 10,20 or 25 times of soft or hards; Whipping agent Cellmic C 121 owing to interpolation in the course of processing is a powder, will in the course of processing, there be problems such as shearing and internal friction like this, in order to solve the problem of these existence, need to add the lubricating auxiliary agent polyethylene wax in the mixing granulator course of processing of product, adding proportion is 1% of described major ingredient and a described auxiliary material gross weight; The ratio of adding the high electric conductivity carbon black is the 4.5%-5.5% or the 6.5%-7.5% of described major ingredient and described auxiliary material gross weight; Because the adding of high electric conductivity carbon black can reduce the specific resistance of described major ingredient new LDPE (film grade) significantly, and catastrophe point of existence in the change procedure of specific resistance, when the add-on of extraordinary conductive carbon black during in 4.5% left and right sides, the add-on subtle change all can cause the wide variation of the specific resistance of major ingredient new LDPE (film grade), after add-on acquires a certain degree and forms whole connected network, stable and lower resistivity are arranged.The key that can the high electric conductivity carbon black form whole connected network is the selection of high electric conductivity carbon black, the high electric conductivity carbon black of selecting among the present invention is that electroconductibility is than the good special carbon black of common carbon black, it is a kind of high conductive novel carbon black, it is formed with the high chain-like structure of ghost, through the nearly nanometer of special processing product primary structure particle diameter, specific surface area is big, and is dispersed high, because the reticulated structure that the wadding aggregate constitutes makes the conductivity that itself has extra-high-speed, than resistance less than 0.20 Ω .cm.Can obtain fine electron radiation crosslinking polyethylene conductive foam by adding this novel high electric conductivity carbon black.Because, the carbon black of market previous step just can be effective because of its poorly conductive need add several times of high electric conductivity amount of carbon blacks, but a large amount of powdered carbon blacks add the mechanical property that affiliation destroys the foam material, make in the course of processing of material and form the bubble sky because of not protecting gas, can not do foam.But the quality of the foam material that adding high electric conductivity carbon black is produced is just very good.Find that according to a large amount of experiments the ratio when interpolation high electric conductivity carbon black is the 4.5%-5.5% of described major ingredient and described auxiliary material gross weight, preferred 5% o'clock, the resistance of foam is 107 ' Ω-109 ' Ω, the IXPE electron radiation crosslinking polyethylene conductive foam of this moment is an antistatic foam, when the ratio of adding the high electric conductivity carbon black is the 6.5%-7.5% of described major ingredient and described auxiliary material gross weight, preferred 7% o'clock, the resistance of foam is 105 ' Ω, and the IXPE electron radiation crosslinking polyethylene conductive foam of this moment is a conducting foam.In order to increase the consistency of powdery high electric conductivity carbon black and density polyethylene, the mechanical property of foam material is provided, add the titanate coupling agent that accounts for described major ingredient and described auxiliary material gross weight 0.5%.
Below the preparation method of IXPE electron radiation crosslinking polyethylene conductive foam is elaborated: described preparation method comprises step: the first, described major ingredient new LDPE (film grade), described auxiliary material ethylene-vinyl acetate copolymer, described azodicarbonamide foaming agent, described polyethylene wax lubricating auxiliary agent, described titanate coupling agent and described high electric conductivity carbon black are carried out mixing mixing, carry out mixing granulator processing at 120 ℃-125 ℃; The second, making master batch being carried out extrusion moulding is master slice, and master slice is at the uniform velocity extruded; Three, to the described master slice of at the uniform velocity extruding carry out continuously, irradiation processing uniformly; Four, the described master slice after the described irradiation processing is carried out continuously 140 ℃-155 ℃ thermal pretreatment in the foaming furnace preheating section, the master slice foaming section that enters foaming furnace is continuously carried out 220 ℃-230 ℃ foaming and is handled then.
Mixing granulator technology is to the influence of foam product performance:
Azodicarbonamide foaming agent (AC whipping agent) is a powdery, and the dispersion state in polyethylene directly influences all even fine and closely woven degree of foam product abscess.In order better to make azodicarbonamide foaming agent and other material reach mixed uniformly purpose, need carry out each material mixing, mixing temperature will be carried out strict control, generally will be a little more than the fusing point of new LDPE (film grade) for well, the too high meeting of temperature causes the decomposition of azodicarbonamide foaming agent, temperature is crossed the low dispersion effect that can influence azodicarbonamide foaming agent again, find that through a large amount of experiments temperature is best 120 ℃ of effects, the time of batch mixing is unsuitable long, batch mixing can cause the internal friction of each material and decompose for a long time, with shortest time of reaching dispersion effect for well, be generally about 10 minutes.
The master slice extruding-out process:
The geometrical dimension of foaming coiled material (master slice), width, thickness, the apparent mass that superficial appearance has determined final foamed products basically, the main technique condition is temperature, rotating speed, head pressure, mouthful die clearance, the selection of parameter under the Undec prerequisite of material, guarantee the master slice plasticizing evenly, even, the smooth surface of thickness, internal cause power be even.Temperature is the highest to be no more than 125 ℃; Rotating speed can not be too fast, and too fast meeting causes the decomposition of each material, finds that through a large amount of experiments rotating speed is best less than 800 rev/mins; Head pressure is less than 8mpa, and the membrana oralis gap of head is larger than the thickness of master slice, but can not be excessive, does not surpass 10% of master slice thickness; Theoretically, master slice thickness d
0And corresponding relation is between product thickness d1
d
0(n is a foam expansion), the relation of master slice width and product width is also similar.But because there is internal stress in master slice, be heated thickness under the internal stress effect, width of master slice increases in foaming process in actual production, and contraction in length is so the existence of internal stress is very big to product size Changing Pattern influence in the foaming process.The existence of internal stress in addition can cause that the product in the foaming process curls, adhesion, so must eliminate the internal stress in the master slice as far as possible.The internal stress of eliminating in the master slice will realize that by the method for selecting suitable head membrana oralis gap the membrana oralis gap of choosing described head above the institute in head membrana oralis gap is larger than the thickness of master slice, but can not be excessive, gets final product above 10% of master slice thickness.Clout between three rollers is even, tiny, and the distance between head and three rollers is as far as possible little, and general distance is not more than about 20CM.
Irradiation processing technology:
In the production of radiation crosslinking foaming coiled material, necessarily require to master slice carry out continuously, irradiation processing uniformly, this has only the rumbatron irradiation could satisfy processing requirement.Select for use the energy of accelerator must be able to satisfy the processing of thick master slice, the accelerator energy that we select for use is 2.5Mev, can satisfy the processing request that thickness is 3mm master slice product, the sweep length of accelerator also will satisfy the irradiation requirement of maximum width master slice, selecting sweep length in the production is that 800-1000mm gets final product, and transmits the speed of master slice in the irradiation process and wants evenly, if it is inhomogeneous to transmit the speed of master slice, the homogeneity of material acceptable dose can be influenced, the instability of product performance can be caused.So it laterally is to want on the width evenly that the master slice irradiation dose is not only required in, requiring simultaneously vertically is also to want continuously evenly on the length direction.To play bulla when foam in the position that dosage is too big, even can not foam, and the little position meeting adhesion of dosage, or trickling.Be difficult to be launched into planarizing material during the horizontal inhomogeneous foaming of dosage, vertical inhomogeneous continuous rolling that then is difficult to, vertically, transverse dosage evenly requires electronics that the irradiated electrons bundle sent vertically, transversely to reach uniform degree, by our a large amount of experiments aborning, the multiple of determining the soft or hard degree is 10 times, the dosage of 20 times and 25 times conducting foams is respectively 75-85kgy, 60-70kgy, 55-65kgy is the optimal dose scope, the radiation dose of the master slice of different thickness also can be different simultaneously, same multiplying power product its dosage when master slice thickness is 1mm will be 3mm a little more than master slice thickness, and exceeding amplitude is about 10%.Detailed numerical value can be consulted Fig. 2.
Foam process:
In the present embodiment, horizontal foaming furnace is adopted in the foaming of master slice, foaming furnace is divided into preheating section and foaming section, wherein the described master slice after described irradiation processing is carried out 140 ℃-155 ℃ thermal pretreatment in earlier by foaming furnace, then become conducting foam by 220 ℃-230 ℃ foaming in the foaming furnace continuously; The guipure speed of transporting master slice in foaming furnace is different to its transfer rate of master slice of different thickness, and thickness is that the described master slice translational speed of 1mm is that 2 meters/minute, thickness are that the described master slice translational speed of 3mm is 1 meter/minute.
IXPE electron radiation crosslinking polyethylene conductive foam of the present invention is compared than foam, the moulded from foam EVA foam of PE Foam, chemically crosslinked, foam smooth surface exquisiteness, and the bubble sky is very little, compressive strength is big, and rebound resilience is good, good hand touch, expansion ratio is easy to control, and thickness thickness error easy to control is little, great thermotolerance; Radiation crosslinking conducting foam antistatic performance is good, and its surface resistivity and volume specific resistance are highly stable, generally 10
3-10
6Between the Ω, can carry out flexible according to customer requirement simultaneously, the anti-electrostatic timeliness is long, and permanent antistatic, antistatic performance are not influenced by the environment humidity.Product environment-protecting asepsis odorlessness, product have good mechanical intensity, production efficiency higher, energy-conservation, and moulded from foam conducting foam product does not have epidermis, the product of no continuous length, and power consumption, production efficiency are low.
IXPE electron radiation crosslinking polyethylene conductive foam of the present invention, only control degree of crosslinking by irradiation dose, product is more easy to control, steady quality, in production is crosslinked, need not to add linking agent, whipping agent gets final product with common whipping agent, the whipping agent low price, raw materials cost is low, and cross-linking agent-free exists, product is tasteless, environmental protection can be produced slim product, simultaneously because radiation crosslinking is advanced crosslinked, steep empty fine and smooth smooth surface, mechanical property, tear strength, compressive strength, compression set are better like this.
IXPE electron radiation crosslinking polyethylene conductive foam of the present invention can continuous production, can obtain easily the different thickness product according to customer requirement, and product has the skinning epidermis, can carry out heat bonding in post-treatment, and product soft or hard density is easy to control.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (5)
1. the preparation method of an IXPE electron radiation crosslinking polyethylene conductive foam, it is characterized in that: the raw material that described preparation method adopts comprises major ingredient new LDPE (film grade) and auxiliary material ethylene-vinyl acetate copolymer, the weight ratio of described new LDPE (film grade) and described ethylene-vinyl acetate copolymer is 65-75: 25-35, also comprise and account for described new LDPE (film grade) and described ethylene-vinyl acetate copolymer gross weight 4%-6%, the azodicarbonamide foaming agent of 9%-11% or 14%-16%, 1% polyethylene wax lubricating auxiliary agent, the high electric conductivity carbon black of 0.5% titanate coupling agent and 4.5%-5.5% or 6.5%-7.5%, and comprise the following steps:
A1. described major ingredient new LDPE (film grade), described auxiliary material ethylene-vinyl acetate copolymer, described azodicarbonamide foaming agent, described polyethylene wax lubricating auxiliary agent, described titanate coupling agent and described high electric conductivity carbon black are carried out mixing mixing, carry out mixing granulator processing at 120 ℃-125 ℃;
A2. making master batch being carried out extrusion moulding is master slice, and master slice is at the uniform velocity extruded;
A3. to the described master slice of at the uniform velocity extruding carry out continuously, irradiation processing uniformly;
A4. the described master slice after the described irradiation processing is carried out continuously 140 ℃-155 ℃ thermal pretreatment in the foaming furnace preheating section, the master slice foaming section that enters foaming furnace is continuously carried out 220 ℃-230 ℃ foaming and is handled then.
2. the preparation method of IXPE electron radiation crosslinking polyethylene conductive foam according to claim 1 is characterized in that: the weight ratio of described major ingredient new LDPE (film grade) and described auxiliary material ethylene-vinyl acetate copolymer is 70: 30.
3. the preparation method of IXPE electron radiation crosslinking polyethylene conductive foam according to claim 1 and 2 is characterized in that: described azodicarbonamide foaming agent is a particulate state, particle diameter 4 μ m-6 μ m.
4. the preparation method of IXPE electron radiation crosslinking polyethylene conductive foam according to claim 1 and 2 is characterized in that: former membrana oralis gap was greater than the thickness of described master slice but be no more than 10% of master slice thickness when described A2 carried out extrusion moulding to described foaming coiled material master slice in the step.
5. the preparation method of IXPE electron radiation crosslinking polyethylene conductive foam according to claim 1 and 2, it is characterized in that: irradiation processing is undertaken by rumbatron described in the described A3 step, the energy of described rumbatron is 2.5Mev, and sweep length is 800-1000mm.
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| CN101358004A (en) | 2009-02-04 |
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