CN111892763A - Radiation crosslinking ethylene-tetrafluoroethylene copolymer foam material and preparation method thereof - Google Patents
Radiation crosslinking ethylene-tetrafluoroethylene copolymer foam material and preparation method thereof Download PDFInfo
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- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 title claims abstract description 60
- 230000005855 radiation Effects 0.000 title claims abstract description 55
- 238000004132 cross linking Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000006261 foam material Substances 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000005187 foaming Methods 0.000 claims abstract description 48
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- -1 allylic imides Chemical class 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 125000000746 allylic group Chemical group 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a radiation crosslinking ethylene-tetrafluoroethylene copolymer foam material and a preparation method thereof, wherein the preparation material of the radiation crosslinking ethylene-tetrafluoroethylene copolymer foam material comprises the following components in parts by weight: 78.5-96.4 parts of ethylene-tetrafluoroethylene copolymer, 3-20 parts of sensitizer, 0.5-1 part of antioxidant and 0.1-0.5 part of coupling agent. The cross-linked ethylene-tetrafluoroethylene copolymer has high temperature resistance, the long-term use temperature exceeds 200 ℃, the use in most temperature-resistant places can be met, and meanwhile, the cross-linked ethylene-tetrafluoroethylene copolymer has low dielectric constant, and the dielectric constant is further reduced after foaming, so that the prepared foaming material has excellent dielectric property and is an excellent high-frequency base material.
Description
Technical Field
The invention relates to a radiation crosslinking ethylene-tetrafluoroethylene copolymer foam material and a preparation method thereof.
Background
At present, most of foaming materials in the market are prepared by taking low-density polyethylene (LDPE) as a main raw material, adding a foaming agent Azodicarbonamide (AC) and other chemical raw materials, and performing mixing granulation, extrusion processing, radiation crosslinking, foaming molding and other steps.
The ethylene-tetrafluoroethylene copolymer (ETFE for short), a transparent crystalline material, has a melting point of 255-280 ℃, and is the toughest and lightest fluoroplastic. ETFE has excellent dielectric property, insulating property and mechanical property, and is resistant to irradiation, cracking and aging, various chemical solvents and high and low temperatures, the long-term working temperature is between-65 ℃ and 150 ℃, and the long-term working temperature is increased to 200 ℃ after ETFE irradiation crosslinking, so that the dielectric property is further improved.
Disclosure of Invention
The invention aims to solve the problems and provide a radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material which has excellent dielectric property, high temperature resistance level and low cost.
In order to achieve the purpose, the invention provides a radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material, which comprises the following components: 78.5-96.4 parts of ethylene-tetrafluoroethylene copolymer, 3-20 parts of sensitizer, 0.5-1 part of antioxidant and 0.1-0.5 part of coupling agent.
Preferably, the melting point of the ethylene-tetrafluoroethylene copolymer is 290-320 ℃, and the melt index is 5.0-10.0 g/10 min.
Preferably, the sensitizer is one or more of allyl non-esters such as allyl imides, allyl triazines, or isocyanates.
Preferably, the antioxidant is one or two of antioxidant 1010 or DSTP.
Preferably, the coupling agent is a silane-based coupling agent.
According to another aspect of the present invention, there is provided a method for preparing the above radiation crosslinked ethylene-tetrafluoroethylene copolymer foamed material, comprising the steps of:
and (3) processing the master batch: firstly, uniformly mixing the preparation materials of the radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material by a high-speed mixer to form a mixture, then extruding the mixture by a double-screw extruder to obtain master batch particles, and drying the master batch particles for later use;
an extrusion step: extruding the dried master batch particles through a single-screw extruder to form an extruded sheet;
an irradiation step: the extruded sheet is subjected to radiation crosslinking in a high-speed electronic field to prepare a radiation sheet;
a foaming step: and placing the radiation sheet into a high-pressure reaction kettle for gas foaming to obtain the foaming material.
Preferably, in the masterbatch processing step, the temperature ranges are: 290-320 ℃, and the screw rotation frequency of the double-screw extruder is more than 800 Hz.
Preferably, in the extruding step, the temperatures of the sections of the single-screw extruder are respectively set as follows: the temperature of the first zone is 270-275 ℃, the temperature of the second zone is 280-285 ℃, the temperature of the third zone is 280-285 ℃, the temperature of the fourth zone is 280-285 ℃, the temperature of the fifth zone is 290-295 ℃, the temperature of the sixth zone is 290-300 ℃, the temperature of the seventh zone is 290-300 ℃, the temperature of the connecting body is 280-290 ℃, the temperature of the three zones of the die is 290-300 ℃, and the rotation frequency of the screw of the single screw extruder is 800 Hz.
Preferably, the electron energy of the radiation crosslinking is 1-2MeV and the radiation dose is 10-12 mrads.
Preferably, in the foaming step, the pressure of the high-pressure reaction kettle is 30-60 MPa, the temperature is 50-250 ℃, and the foaming time is 1-3 h.
Compared with the prior art, the invention has the following beneficial technical effects:
the radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material adopts a crosslinking ethylene-tetrafluoroethylene copolymer as a base material, the crosslinking ethylene-tetrafluoroethylene copolymer has higher temperature resistance level, so that the prepared foaming material can be used for a long time at the temperature of more than 200 ℃ and can meet the use requirements of most temperature resistant places, meanwhile, the crosslinking ethylene-tetrafluoroethylene copolymer has lower dielectric constant, the dielectric constant is further reduced after foaming, and the prepared foaming material has excellent dielectric property and is an excellent high-frequency base material.
Detailed Description
In order to explain the technical contents, formulation ratios, and objects and effects of the present invention in detail, the following description will be given in conjunction with the embodiments.
The invention provides a radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material, which comprises the following components in parts by weight: 78.5-96.4 parts of ethylene-tetrafluoroethylene copolymer, 3-20 parts of sensitizer, 0.5-1 part of antioxidant and 0.1-0.5 part of coupling agent.
The radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material takes ethylene-tetrafluoroethylene copolymer as a main material, and the ethylene-tetrafluoroethylene copolymer is 78.5 to 96.4 parts by weight, and typical but non-limiting parts by weight are 78.5 parts, 80 parts, 85 parts, 90 parts, 95 parts or 96.4 parts.
In the embodiment of the invention, the melting point of the ethylene-tetrafluoroethylene copolymer is 290-320 ℃, the melt index is 5.0-10.0 g/10min, and the melt index of the low-density polyethylene is detected under the conditions of 190 ℃ of temperature and 2.16kg of load.
According to the radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material, the sensitizer is 3-20 parts by weight, typically but not limitingly 3 parts, 5 parts, 10 parts, 15 parts or 20 parts by weight, and the addition amount of the sensitizer is less than 3 parts, so that the ethylene-tetrafluoroethylene copolymer cannot be crosslinked during subsequent radiation crosslinking, and further cannot be foamed; the addition amount of the sensitizer is more than 20 parts, which can cause the crosslinking degree to be too large during radiation crosslinking and influence normal foaming.
In the embodiment of the present invention, the sensitizer is preferably one or more of allyl non-esters such as allyl acyl, allyl imide, allyl triazine, or isocyanate, and the sensitizer has excellent thermal stability at 200 ℃ or higher due to its aromatic ring or heterocyclic structure.
The radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material comprises 0.5-1 part of antioxidant by weight, typically but not limited to 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part by weight, and the addition amount of the antioxidant is less than 0.5 part, so that the product is yellow; the addition amount of the antioxidant is more than 1 part, which is not beneficial to subsequent radiation crosslinking.
In the embodiment of the invention, the antioxidant is preferably one or two of antioxidant 1010 and DSTP.
The radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material has the coupling agent of 0.1-0.5 part by weight, and the typical but non-limiting parts by weight are 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part.
In the embodiment of the present invention, the coupling agent is preferably a silane coupling agent.
According to another aspect of the present invention, there is provided a method for preparing the above radiation crosslinked ethylene-tetrafluoroethylene copolymer foamed material, comprising the steps of:
and (3) processing the master batch: firstly, uniformly mixing the preparation materials of the radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material by a high-speed mixer to form a mixture, then extruding the mixture by a double-screw extruder to obtain master batch particles, and drying the master batch particles for later use;
an extrusion step: extruding the dried master batch particles through a single-screw extruder to form an extruded sheet;
an irradiation step: the extruded sheet is subjected to radiation crosslinking in a high-speed electronic field to prepare a radiation sheet;
a foaming step: and placing the radiation sheet into a high-pressure reaction kettle for gas foaming to obtain the foaming material.
In the embodiment of the invention, in the masterbatch processing step, the temperature range is as follows: 290-320 ℃, and the screw rotation frequency of the double-screw extruder is more than 800 Hz.
The preparation of the master batch particles and the performance of each aspect are directly influenced by technological parameters such as temperature, screw rotation frequency and the like, and the following influences can be generated when the temperature and the screw rotation frequency are not in the range: (1) the extrusion temperature is higher, the rotation frequency of the screw is too high, and the sensitizer is easy to decompose; (2) the temperature is low, the screw rotation frequency is too low, the raw materials are not melted, and the plasticization is not good.
In the embodiment of the invention, in the extrusion step, the temperatures of all sections of the single-screw extruder are respectively set as follows: the temperature of the first zone is 270-275 ℃, the temperature of the second zone is 280-285 ℃, the temperature of the third zone is 280-285 ℃, the temperature of the fourth zone is 280-285 ℃, the temperature of the fifth zone is 290-295 ℃, the temperature of the sixth zone is 290-300 ℃, the temperature of the seventh zone is 290-300 ℃, the temperature of the connecting body is 280-290 ℃, the temperature of the three zones of the die is 290-300 ℃, and the rotation frequency of the screw of the single screw extruder is 800 Hz.
In the embodiment of the invention, the electron energy of the radiation crosslinking is 1-2MeV, and the radiation dose is 10-12 megarads.
The radiation energy and radiation dose directly affect the normal foaming of the material, and outside of this range the following effects occur: (1) too large irradiation dose, hard foaming sheet, and failure to foam normally (2) too low irradiation dose, sticky foaming system, failure to expand normally.
In the embodiment of the invention, in the foaming step, the pressure of the high-pressure reaction kettle is 30-60 MPa, the temperature is 50-250 ℃, and the foaming time is 1-3 h.
The process parameters such as autoclave pressure, reaction temperature, reaction time and the like directly influence the cells, multiplying power, functionality and the like of the foaming material, and the following influences can be generated within the range no longer: (1) the product efficiency is affected due to too low temperature and too low gas dissolving speed, and energy consumption waste is caused due to too high temperature; (2) the reaction time is too short, the gas solubility is not enough, the product multiplying power is influenced, the reaction time is too long, and the production efficiency is low.
The radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material provided by the invention has high temperature resistance grade, the long-term use temperature exceeds 200 ℃, the use in most temperature-resistant places can be met, and the radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material has excellent dielectric property and is an excellent high-frequency base material.
In order to better understand the technical scheme, the technical scheme is described in detail by combining specific examples, the examples are only preferred embodiments of the invention and are not limiting, and unless otherwise stated, all parts are by weight:
example 1
The preparation material of example 1 comprises the following components:
86 parts of ethylene-tetrafluoroethylene copolymer, 13 parts of sensitizer, 0.7 part of antioxidant and 0.3 part of coupling agent.
The melting point of the ethylene-tetrafluoroethylene copolymer is 290-320 ℃, and the melt index is 5.0-10.0 g/10 min.
The sensitizer is triallyl isocyanate, the antioxidant is antioxidant 1010, and the coupling agent is coupling agent A171.
The preparation method of the radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material comprises the following steps:
and (3) processing the master batch: firstly, uniformly mixing the preparation materials of the radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material by a high-speed mixer to form a mixture, then extruding the mixture by a double-screw extruder to obtain master batch particles, and drying the master batch particles for later use, wherein in the master batch processing process, the temperature ranges are as follows: 290-320 ℃, and the screw rotation frequency of the double-screw extruder is 800 Hz;
an extrusion step: extruding the dried master batch particles through a single-screw extruder to form an extruded sheet, wherein in the extruding step, the temperature of each section of the single-screw extruder is respectively set as follows: the first zone is 270-275 ℃, the second zone is 280-285 ℃, the third zone is 280-285 ℃, the fourth zone is 280-285 ℃, the fifth zone is 290-295 ℃, the sixth zone is 290-300 ℃, the seventh zone is 290-300 ℃, the connector temperature is 280-290 ℃, the temperature of the three zones of the die is 290-300 ℃, and the rotation frequency of the screw of the single screw extruder is 800 Hz;
an irradiation step: the extruded sheet is subjected to radiation crosslinking in a high-speed electronic field to prepare a radiation sheet; the electron energy of the radiation crosslinking is 1-2MeV, and the radiation dose is 10-12 megarads;
a foaming step: the radiation sheet is placed in a high-pressure reaction kettle for gas foaming to prepare the foaming material, in the foaming step, the pressure of the high-pressure reaction kettle is 30-60 MPa, the temperature is 50-250 ℃, and the foaming time is 1-3 hours.
Example 2
Based on example 1, the difference is only that: in example 2, it was prepared from the following materials: 78.5 parts of ethylene-tetrafluoroethylene copolymer, 20 parts of sensitizer, 1 part of antioxidant and 0.5 part of coupling agent. The sensitizer is triallyl cyanate, the antioxidant is antioxidant 1010, and the coupling agent is coupling agent A151.
Example 3
Based on example 1, the difference is only that: in example 3, it was prepared from the following materials: 96.4 parts of ethylene-tetrafluoroethylene copolymer, 3 parts of sensitizer, 0.5 part of antioxidant and 0.1 part of coupling agent. The sensitizer is triallyl isocyanate, the antioxidant is antioxidant DSTP, and the coupling agent is coupling agent A172.
Example 4
Based on example 1, the difference is only that: in example 4, it was prepared from the following materials: 80 parts of ethylene-tetrafluoroethylene copolymer, 19 parts of sensitizer, 0.8 part of antioxidant and 0.2 part of coupling agent. The sensitizer is triallyl cyanate, the antioxidant is antioxidant DSTP, and the coupling agent is coupling agent A172.
Example 5
Based on example 1, the difference is only that: in example 5, it was prepared from the following materials: 90 parts of ethylene-tetrafluoroethylene copolymer, 9 parts of sensitizer, 0.7 part of antioxidant and 0.3 part of coupling agent. The sensitizer is triallyl isocyanate, the antioxidant is antioxidant 1010, and the coupling agent is coupling agent A171.
Example 6
Based on example 1, the difference is only that: in example 6, it was prepared from the following materials: 95 parts of ethylene-tetrafluoroethylene copolymer, 4 parts of sensitizer, 0.6 part of antioxidant and 0.4 part of coupling agent. The sensitizer is triallyl cyanate, the antioxidant is antioxidant DSTP, and the coupling agent is coupling agent A151.
Comparative example 1
Based on example 1, the difference is only that: in comparative example 1, it was prepared from the following materials: 75 parts of ethylene-tetrafluoroethylene copolymer, 23.5 parts of sensitizer, 1 part of antioxidant and 0.5 part of coupling agent.
Comparative example 2
Based on example 1, the difference is only that: in comparative example 1, it was prepared from the following materials: 97 parts of ethylene-tetrafluoroethylene copolymer, 2 parts of sensitizer, 0.5 part of antioxidant and 0.5 part of coupling agent.
The prepared materials of the above examples 1 to 6 and comparative examples 1 to 2 were used to produce radiation-crosslinked ethylene-tetrafluoroethylene copolymer foams, respectively, according to the above-described preparation methods.
The results of the tests on the samples produced according to the above methods of examples 1 to 6 and comparative examples 1 to 2 are as follows:
the foamed materials of examples 1 to 6 were able to be foam-molded normally, while those of comparative examples 1 to 2 were unable to be molded or foam without keeping air.
As shown in the test results in the table, the radiation crosslinked ethylene-tetrafluoroethylene copolymer foamed material of the invention adopts the crosslinked ethylene-tetrafluoroethylene copolymer as the base material, the prepared foamed material still has excellent mechanical properties under the condition that the temperature exceeds 200 ℃, the use in most temperature-resistant places can be met, and the dielectric constant of the foamed material after the crosslinked ethylene-tetrafluoroethylene copolymer is foamed is further reduced, so that the prepared foamed material has excellent dielectric properties and is an excellent high-frequency base material.
The present invention is not limited to the above-described embodiments, and various changes may be made by those skilled in the art, which changes are equivalent or similar to the present invention and are intended to be included within the scope of the appended claims.
Claims (10)
1. The radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material is characterized in that the preparation material comprises the following components in parts by weight: 78.5-96.4 parts of ethylene-tetrafluoroethylene copolymer, 3-20 parts of sensitizer, 0.5-1 part of antioxidant and 0.1-0.5 part of coupling agent.
2. The radiation crosslinked ethylene-tetrafluoroethylene copolymer foamed material according to claim 1, wherein the ethylene-tetrafluoroethylene copolymer has a melting point of 290 to 320 ℃ and a melt index of 5.0 to 10.0g/10 min.
3. The radiation crosslinked ethylene-tetrafluoroethylene copolymer foamed material according to claim 1, wherein the sensitizer is one or more of allylic non-esters such as allylic imides, allyltriazine, or isocyanates.
4. The radiation crosslinked ethylene-tetrafluoroethylene copolymer foamed material according to claim 1, wherein the antioxidant is one or both of antioxidant 1010 and DSTP.
5. The radiation crosslinked ethylene-tetrafluoroethylene copolymer foamed material according to claim 1, wherein the coupling agent is a silane-based coupling agent.
6. A method for preparing a radiation crosslinked ethylene-tetrafluoroethylene copolymer foamed material according to any one of claims 1 to 5, comprising the steps of:
and (3) processing the master batch: firstly, uniformly mixing the preparation materials of the radiation crosslinking ethylene-tetrafluoroethylene copolymer foaming material as defined in any one of claims 1 to 5 by a high-speed mixer to form a mixture, then extruding the mixture by a double-screw extruder to obtain master batch particles, and drying the master batch particles for later use;
an extrusion step: extruding the dried master batch particles through a single-screw extruder to form an extruded sheet;
an irradiation step: the extruded sheet is subjected to radiation crosslinking in a high-speed electronic field to prepare a radiation sheet;
a foaming step: and placing the radiation sheet into a high-pressure reaction kettle for gas foaming to prepare the foaming material.
7. The method of claim 6, wherein in the masterbatch processing step, the temperature ranges are: 290-320 ℃, and the screw rotation frequency of the double-screw extruder is more than 800 Hz.
8. The method for preparing the rubber composition according to claim 6, wherein in the extruding step, the temperatures of all sections of the single-screw extruder are respectively set as follows: the temperature of the first zone is 270-275 ℃, the temperature of the second zone is 280-285 ℃, the temperature of the third zone is 280-285 ℃, the temperature of the fourth zone is 280-285 ℃, the temperature of the fifth zone is 290-295 ℃, the temperature of the sixth zone is 290-300 ℃, the temperature of the seventh zone is 290-300 ℃, the temperature of the connecting body is 280-290 ℃, the temperature of the three zones of the die is 290-300 ℃, and the rotation frequency of the screw of the single screw extruder is 800 Hz.
9. The method of claim 6, wherein the radiation crosslinking has an electron energy of 1 to 2MeV and a radiation dose of 10 to 12 mrads.
10. The preparation method of claim 6, wherein in the foaming step, the pressure of the high-pressure reaction kettle is 30-60 MPa, the temperature is 50-250 ℃, and the foaming time is 1-3 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232391A (en) * | 2022-08-04 | 2022-10-25 | 广州敬信高聚物科技有限公司 | Foaming ethylene-tetrafluoroethylene copolymer cable material and preparation method thereof |
Citations (2)
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| CN115232391A (en) * | 2022-08-04 | 2022-10-25 | 广州敬信高聚物科技有限公司 | Foaming ethylene-tetrafluoroethylene copolymer cable material and preparation method thereof |
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