CN117624701A - Synchronous radiation crosslinking preparation method of poly ETFE material, product and application thereof - Google Patents
Synchronous radiation crosslinking preparation method of poly ETFE material, product and application thereof Download PDFInfo
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- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 title claims abstract description 118
- 238000004132 cross linking Methods 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 48
- 230000005855 radiation Effects 0.000 title claims abstract description 45
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000003708 ampul Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 17
- 229910052786 argon Inorganic materials 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 230000005251 gamma ray Effects 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 230000005469 synchrotron radiation Effects 0.000 claims description 14
- JJLUWYULIBMDGF-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluorododeca-1,11-diene Chemical compound C=CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C JJLUWYULIBMDGF-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- KGJWCQOEERZJMB-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-1,3-bis(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)OC(F)=C(F)F KGJWCQOEERZJMB-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000009849 vacuum degassing Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000005587 bubbling Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002411 thermogravimetry Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003431 cross linking reagent Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
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- 229920005601 base polymer Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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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
- 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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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a synchronous radiation crosslinking preparation method of a poly ETFE material, which comprises the following steps: cleaning with a first solvent to remove impurities on the surface of the ETFE film; and then adding the ETFE film, the perfluoro-divinyl monomer and the second solvent into a vacuum degassing glass ampoule, bubbling with argon, and then radiating with gamma-rays at a dosage rate of 14-16 kGy/h, washing with hexafluorobenzene for 23-24h after reaching the radiation dosage, and then drying in vacuum until the weight is constant, thus obtaining the poly ETFE material. The invention also discloses a poly ETFE material prepared from the perfluoro-divinyl monomer and the ETFE matrix, which has good compatibility, high crosslinking rate and good chemical stability and thermal stability. The invention also discloses an application of the synchronous radiation crosslinking preparation method of the ETFE material.
Description
Technical Field
The invention relates to the field of high molecular fluorine polymer materials, in particular to a synchronous radiation crosslinking preparation method of a polymer ETFE material, a product and application thereof.
Background
Ethylene-tetrafluoroethylene copolymers (ETFE) are widely used in the fields of construction, electronics, automotive, aerospace, energy and chemical industry. The molecular chain of the poly (ethylene-tetrafluoroethylene copolymer) resin is in a zigzag structure phase, and the-CF 2-interacts with the-CH 2-on the adjacent molecular chain, so that the poly (ethylene-tetrafluoroethylene copolymer) resin has excellent mechanical strength and toughness, good electrical property, weather resistance and the like. However, articles processed from unmodified ETFE are susceptible to cracking, wherein the lack of functional moieties renders the ETFE chemically inert, and most studies have been to functionalize ETFE by radiation graft copolymerizing monomers with different side functional groups, imparting desired properties thereto. Currently, radiation grafting involves two different methods, pre-irradiation and synchrotron radiation. In the pre-irradiation process, the polymer is irradiated without air or with air, generating free radicals on the polymer backbone, prior to reaction with the grafting monomer. In the synchrotron radiation process, when a mixture of base polymer and grafting monomer is subjected to radiation, the radical formation on the polymer backbone and the grafting process occur simultaneously. However, although irradiation grafting can significantly improve the tensile strength, modulus and cut resistance of ETFE, the rate and extent of irradiation grafting significantly depend on the effect of grafting conditions such as grafting degree, monomer concentration and film thickness, and also reduces the aging resistance and thermal stability of ETFE while improving mechanical properties. At present, grafting is performed by crosslinking, but the chemical crosslinking method also has the problems of residual crosslinking agent, uneven crosslinking, change of physical properties after crosslinking and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the first aim of the invention is to provide a synchronous radiation crosslinking preparation method of a polymer ETFE material, which can solve the problems that ETFE is non-uniform in crosslinking and the material performance is influenced after radiation in a crosslinking and radiation graft copolymerization method.
The second object of the present invention is to provide a poly ETFE material, which can solve the problems of easy cracking, poor toughness and poor electrical properties of the current unmodified ETFE.
The third object of the invention is to provide an application of the ETFE material, which can solve the application problems of ETFE in the fields of construction, electronics, automobiles, aerospace, energy sources, chemical industry and the like.
The invention adopts the following technical scheme:
a synchronous radiation crosslinking preparation method of a polymer ETFE material comprises the following steps:
step (1), cleaning an ETFE film by using a first solvent, taking the cleaned ETFE film, a perfluorinated divinyl monomer and a second solvent as a reaction system, irradiating with gamma rays under the protection of inert gas, and carrying out synchronous radiation crosslinking on the reaction system;
and (2) transferring the ETFE film subjected to radiation crosslinking in the reaction system, washing and vacuum drying to constant weight, and thus preparing the ETFE polymer material.
Further, the step (1) is to add the ETFE film, the perfluoro-divinyl monomer and the second solvent, which are washed by the first solvent, into the vacuum deaerated glass ampoule as a reaction system, then to bubble and fill the glass ampoule with inert gas, and to perform gamma-ray irradiation on the glass ampoule; the inert gas is argon; the size of the glass ampoule is 25 ml-30 ml.
Further, the first solvent is one of acetone, ethanol or methanol; the second solvent is one of N, N-dimethylformamide, N-dimethylacetamide or acetone.
Further, in the step (1), the perfluoro-divinyl monomer is one of 1, 8-divinyl perfluorooctane and perfluoro 1, 3-bis (vinyloxy) propane.
Further, in the step (1), the dosage rate of the gamma-ray irradiation is 14-16 kGy/h, and the total dosage of the gamma-ray irradiation is 500-1000 kGy.
Further, in the step (1), the thickness of the ETFE film is 20 μm to 30 μm; the ETFE film had a size of (2 cm-3 cm) X (4 cm-5 cm).
Further, in the step (1), the addition amount of the perfluoro-divinyl monomer is 5ml to 15ml; the volume ratio of the perfluoro-divinyl monomer to the second solvent is 1: (1-2).
Further, in the step (2), transferring the ETFE film after radiation crosslinking in the reaction system to a Soxhlet apparatus, washing with hexafluorobenzene for 23-24h, and then vacuum drying at 40-41 ℃ to constant weight to complete the preparation of the ETFE material.
The second object of the invention is achieved by the following technical scheme:
a poly ETFE material is prepared by a synchronous radiation crosslinking preparation method of the poly ETFE material.
The third object of the invention is achieved by the following technical scheme:
the synchronous radiation crosslinking preparation method of the polymer ETFE material is applied to the preparation of cables, wires, pipelines and films.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the synchronous radiation crosslinking preparation method of the poly ETFE material, provided by the invention, the perfluoro-divinyl monomer is used as a crosslinking agent, and the ETFE molecular chain is crosslinked through synchronous radiation, so that the poly ETFE material with a compact and flat surface is integrally formed; the degree of crosslinking and the formation of a crosslinked network can be controlled by controlling the radiation dose and the radiation time; the cross-linking agent perfluoro-divinyl monomer and the ETFE matrix have good compatibility, high cross-linking rate and excellent physical properties of the cross-linked product;
2. the preparation method of the synchronous radiation crosslinking of the poly ETFE material can reduce the residue of the crosslinking agent, has uniform radiation crosslinking, is simple to operate, has short crosslinking time, saves production time and cost, and can be widely applied to the fields of preparing high-performance materials, cables, wires, pipelines, films and the like;
3. the polymer ETFE material is a polymer with a three-dimensional network structure, the heat resistance, chemical resistance, mechanical property and other comprehensive properties of the material are improved, the tensile strength, modulus and cutting resistance of ETFE are obviously improved, and the material is not easy to crack and is not chemically inert.
Drawings
FIG. 1 is a TGA graph of a poly (ethylene-tetrafluoroethylene copolymer) film prepared in example 1.
FIG. 2 is a TGA graph of the poly (ethylene-tetrafluoroethylene copolymer) film prepared in example 2.
FIG. 3 is a TGA graph of the poly (ethylene-tetrafluoroethylene copolymer) film prepared in example 3.
FIG. 4 is a TGA graph of the poly (ethylene-tetrafluoroethylene copolymer) film prepared in example 4.
FIG. 5 is a TGA graph of comparative example 2 compared to a poly (ethylene-tetrafluoroethylene copolymer) film prepared in example 1.
FIG. 6 is a TGA graph of the product of comparative example 1 compared to a poly (ethylene-tetrafluoroethylene copolymer) film prepared in example 1.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with specific embodiments. It will be apparent that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Radiation grafting is an effective method of modifying important properties of natural and synthetic polymers, and radiation grafting is one of the most effective methods of introducing reactive functional groups into grafted polymer chains in polymer films due to its many unique advantages, such as high reactivity, deep penetration capability, and rapid processing time, as compared to other grafting methods. Radiation grafting can be carried out by two different methods, pre-irradiation and simultaneous irradiation. In the pre-irradiation process, the polymer is irradiated without air or with air, generating free radicals on the polymer backbone, prior to reaction with the grafting monomer. Researchers have conducted extensive research on radiation grafted fluoropolymers and found that the rate and extent of grafting is significantly dependent on the effect of grafting conditions such as grafting degree, monomer concentration and film thickness. Therefore, the preparation method of the synchronous radiation crosslinking of the ETFE material comprises the following steps:
step (1), cleaning an ETFE film by using a first solvent, taking the cleaned ETFE film, a perfluorinated divinyl monomer and a second solvent as a reaction system, irradiating with gamma rays under the protection of inert gas, and carrying out synchronous radiation crosslinking on the reaction system;
and (2) transferring the ETFE film subjected to radiation crosslinking in the reaction system, washing and vacuum drying to constant weight, and thus preparing the ETFE polymer material.
In the synchrotron radiation process, when a mixture of base polymer and grafting monomer is subjected to radiation, the radical formation on the polymer backbone and the grafting process occur simultaneously. The traditional chemical crosslinking method mainly comprises the methods of organic peroxide crosslinking, mercaptan crosslinking, thermal crosslinking and the like. These methods have a good crosslinking effect, but have problems such as residual crosslinking agent, non-uniformity of crosslinking, and change in physical properties after crosslinking. In contrast, radiation crosslinking can reduce the residual problem of crosslinking agent, and at the same time, radiation crosslinking can realize uniformity of crosslinking, thereby obtaining more uniform material
Further, the step (1) is to carry out synchrotron radiation crosslinking on a vacuum degassed glass ampoule; the inert gas is argon; the size of the glass ampoule is 25 ml-30 ml.
Preferably, the glass ampoule is 25ml or 30ml in size.
Further, the step (1) is carried out with synchrotron radiation crosslinking at 20-25 ℃.
Further, the first solvent is one of acetone, ethanol or methanol; the second solvent is one of N, N-dimethylformamide, N-dimethylacetamide or acetone.
Further, in the step (1), the perfluoro-divinyl monomer is one of 1, 8-divinyl perfluorooctane and perfluoro 1, 3-bis (vinyloxy) propane.
Further, in the step (1), the dosage rate of the gamma-ray irradiation is 14-16 kGy/h, and the total dosage of the gamma-ray irradiation is 500-1000 kGy.
Preferably, the dosage rate of the gamma-ray irradiation can be 14kGy/h, 15kGy/h and 16kGy/h. More preferably, the dose rate of the gamma-ray irradiation is 15kGy/h.
Preferably, the total dose of the gamma-ray irradiation may be 500kGy, 800kGy, 1000kGy.
Further, in the step (1), the thickness of the ETFE film is 20 μm to 30 μm; the ETFE film had a size of (2 cm-3 cm) X (4 cm-5 cm).
Preferably, the perfluorodivinyl monomer may be added in an amount of 5ml to 7ml, 7ml to 10ml, 10ml to 12ml, 12ml to 15ml. More preferably, the perfluorodivinyl monomer is added in an amount of 5ml.
Preferably, the size of the ETFE film may be 2cm×4cm, 2cm×4.5cm, 2cm×5cm, 2.5cm×4cm, 2.5cm×4.5cm, 2.5cm×5cm, 3cm×4cm, 3cm×4.5cm, 3cm×5cm. More preferably, the ETFE film has dimensions of 2cm by 4cm.
Further, in the step (1), the addition amount of the perfluoro-divinyl monomer is 5ml to 15ml; the volume ratio of the perfluoro-divinyl monomer to the second solvent is 1: (1-2).
Preferably, the volume ratio of the perfluoro-divinyl monomer to the second solvent is 1:1 or 1:2.
further, in the step (2), transferring the ETFE film after radiation crosslinking in the reaction system to a Soxhlet apparatus, washing with hexafluorobenzene for 23-24h, and then vacuum drying at 40-41 ℃ to constant weight to complete the preparation of the ETFE material.
The invention will be further described with reference to the accompanying drawings and detailed description below:
example 1
A synchronous radiation crosslinking preparation method of a polymer ETFE material comprises the following steps:
(1) Cleaning an ETFE film: cleaning by using an acetone solvent to remove impurities on the surface of the ETFE film;
(2) Synchrotron radiation crosslinking in ETFE films: to a vacuum degassed 25ml glass ampoule, an ETFE film having an area of 2cm by 4cm and a thickness of 25 μm, 5ml of 1, 8-divinyl perfluorooctane and 10ml of acetone were added, and then the ampoule was bubbled with argon and filled. Gamma-ray irradiation was performed on an argon-filled ampoule at a dose rate of 16kGy/h using a Co-60 source device of Japan Atomic Energy Agency (JAEA) at room temperature, and after reaching an irradiation dose of 1000kGy, the ETFE film was transferred from the ampoule to a soxhlet apparatus, and washed with hexafluorobenzene for 23 hours to remove ungrafted homopolymer and residual 1, 8-divinyl perfluorooctane monomer, and vacuum-dried at 40 ℃ to constant weight, to obtain a polyethetfe film excellent in heat resistance, chemical resistance and mechanical properties. The amount of the obtained ETFE material can be obtained by weighing it.
Example 2
A synchronous radiation crosslinking preparation method of a polymer ETFE material comprises the following steps:
(1) Cleaning an ETFE film: cleaning by using an ethanol solvent to remove impurities on the surface of the ETFE film;
(2) Synchrotron radiation crosslinking in ETFE films: to 30ml of glass ampoule subjected to vacuum degassing, ETFE film having an area of 3cm by 4cm and a thickness of 20 μm, 5ml of 1, 8-divinyl perfluorooctane and 10ml of acetone were added, then the ampoule was bubbled and filled with argon, gamma-ray irradiation was performed at room temperature on the argon-filled ampoule at a dose rate of 15kGy/h using Co-60 source equipment of Japanese atomic energy mechanism (JAEA), after reaching an irradiation dose of 800kGy, the ETFE film was transferred from the ampoule to a Soxhlet apparatus, and washed with hexafluorobenzene for 24 hours to remove ungrafted homopolymer and residual 1, 8-divinyl perfluorooctane monomer, and vacuum-dried at 41℃to constant weight, to obtain a polyethylene terephthalate film excellent in heat resistance, chemical resistance and mechanical properties. The amount of the obtained ETFE material can be obtained by weighing it.
Example 3
A synchronous radiation crosslinking preparation method of a polymer ETFE material comprises the following steps:
(1) Cleaning an ETFE film: using methanol solvent to clean to remove impurities on the surface of the ETFE film;
(2) Synchrotron radiation crosslinking in ETFE films: to 30ml glass ampoule for vacuum degassing, ETFE film having an area of 2cm by 4cm and a thickness of 30 μm, 5ml of perfluoro 1, 3-bis (vinyloxy) propane and 5ml of N, N-dimethylformamide solvent were added, then the ampoule was bubbled and filled with argon, gamma-ray irradiation was performed on the argon-filled ampoule at a dose rate of 15kGy/h using Co-60 source equipment of Japanese atomic energy organization (JAEA) at room temperature, after reaching an irradiation dose of 500kGy, the ETFE film was transferred from the ampoule to Soxhlet apparatus and washed with hexafluorobenzene for 24 hours to remove ungrafted homopolymer and residual perfluoro 1, 3-bis (vinyloxy) propane monomer, and after vacuum drying to constant weight at 40℃, a poly ETFE film excellent in heat resistance, chemical resistance and mechanical properties was obtained. The amount of the obtained ETFE material can be obtained by weighing it.
Example 4
A synchronous radiation crosslinking preparation method of a polymer ETFE material comprises the following steps:
(1) Cleaning an ETFE film: using methanol solvent to clean to remove impurities on the surface of the ETFE film;
(2) Synchrotron radiation crosslinking in ETFE films: to 30ml glass ampoule for vacuum degassing, ETFE film having an area of 2cm by 4cm and a thickness of 30 μm, 5ml of perfluoro 1, 3-bis (vinyloxy) propane and 5ml of N, N-dimethylformamide solvent were added, then the ampoule was bubbled and filled with argon, gamma-ray irradiation was performed on the argon-filled ampoule at a dose rate of 15kGy/h using Co-60 source equipment of Japanese atomic energy organization (JAEA) at room temperature, after reaching an irradiation dose of 500kGy, the ETFE film was transferred from the ampoule to Soxhlet apparatus and washed with hexafluorobenzene for 24 hours to remove ungrafted homopolymer and residual perfluoro 1, 3-bis (vinyloxy) propane monomer, and after vacuum drying to constant weight at 40℃, a poly ETFE film excellent in heat resistance, chemical resistance and mechanical properties was obtained. The amount of the obtained ETFE material can be obtained by weighing it.
Comparative example 1
Only gamma-ray irradiation treatment was performed on the ETFE film raw material, and the irradiation conditions were the same as those of example 1. No perfluoro divinyl monomer is used as a cross-linking agent. The method comprises the following steps:
(1) Cleaning by using an acetone solvent to remove impurities on the surface of the ETFE film;
(2) To a vacuum degassed 25ml glass ampoule, an ETFE film having an area of 2cm by 4cm and a thickness of 25 μm was added, and then the ampoule was bubbled with argon gas and filled. Gamma-ray irradiation was performed on an argon-filled ampoule at a dose rate of 16kGy/h using a Co-60 source device of Japan Atomic Energy Agency (JAEA) at room temperature, and after reaching an irradiation dose of 1000kGy, the ETFE film was transferred from the ampoule to a soxhlet apparatus, and washed with hexafluorobenzene for 23 hours to remove ungrafted homopolymer and residual 1, 8-divinyl perfluorooctane monomer, and vacuum-dried at 40 ℃ to constant weight, to obtain a polyethetfe film excellent in heat resistance, chemical resistance and mechanical properties. The amount of the obtained ETFE material can be obtained by weighing it.
Comparative example 2
ETFE film raw material not crosslinked by synchronous radiation
Performance detection
Thermogravimetric analysis (TGA) was performed on examples 1-4 and comparative examples 1-2 and the results are shown in fig. 1-6.
The TGA test result of example 1 is shown in fig. 1, and the initial degradation temperature (T5) of the polyethylene terephthalate film prepared in this example is 532 ℃. The TGA test result of the ETFE material of comparative example 2, which was not crosslinked by synchrotron radiation, is shown in fig. 5, and the initial degradation temperature (T5) thereof is only 400 ℃. Example 1 has significantly improved thermal stability compared to the ETFE film stock of comparative example 1, which has not been cross-linked by synchrotron radiation.
The TGA test result of example 2 is shown in fig. 2, and the initial degradation temperature (T5) of the polyethylene terephthalate film prepared in this example is 530 ℃. The TGA test result of example 2 is shown in fig. 3, and the initial degradation temperature (T5) of the polyethylene terephthalate film prepared in this example is 528 ℃. The TGA test result of example 4 is shown in fig. 4, and the initial degradation temperature (T5) of the polyethylene terephthalate film prepared in this example is 526 ℃. Examples 1-4 all showed good thermal stability.
Comparative example 1 the irradiation treatment alone was the current conventional method without using a perfluoro divinyl monomer as a crosslinking agent, and the TGA profile of the product obtained by irradiation crosslinking of ETFE film using the conventional method as in comparative example 1 was shown in fig. 6, the initial degradation temperature (T5) of the product was 450.6 ℃, and the thermal stability of the product obtained in comparative example 1 was significantly lower than that of the TGA profile of example 1. It is demonstrated that the thermal stability of the poly ETFE material can be improved by using perfluoro-divinyl monomer as a cross-linking agent. And the synchronous action of the perfluoro-divinyl monomer and the irradiation treatment has obvious performance advantage compared with the conventional method.
Furthermore, it should be understood that although the present disclosure describes embodiments in terms of various embodiments, not every embodiment is described in terms of a single embodiment, but rather that the descriptions of embodiments are merely provided for clarity, and that the descriptions of embodiments in terms of various embodiments are provided for persons skilled in the art on the basis of the description. It will be apparent to those skilled in the art from this disclosure that various other changes and modifications can be made which are within the scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the synchronous radiation crosslinking of the ETFE material is characterized by comprising the following steps of:
step (1), cleaning an ETFE film by using a first solvent, taking the cleaned ETFE film, a perfluorinated divinyl monomer and a second solvent as a reaction system, irradiating with gamma rays under the protection of inert gas, and carrying out synchronous radiation crosslinking on the reaction system;
and (2) transferring the ETFE film subjected to radiation crosslinking in the reaction system, washing and vacuum drying to constant weight, and thus preparing the ETFE polymer material.
2. The method for preparing a poly ETFE material according to claim 1, wherein step (1) is to add the ETFE film, the perfluoro-divinyl monomer and the second solvent after the first solvent cleaning as a reaction system into a vacuum deaerated glass ampoule, then to bubble and fill the glass ampoule with an inert gas, and to perform γ -ray irradiation on the glass ampoule; the inert gas is argon; the size of the glass ampoule is 25 ml-30 ml.
3. The method for preparing a polyethylene terephthalate (ETFE) material by synchrotron radiation crosslinking according to claim 1, wherein the first solvent is one of acetone, ethanol or methanol; the second solvent is one of N, N-dimethylformamide, N-dimethylacetamide or acetone.
4. The method for preparing a polyethetfe material according to claim 1, wherein in step (1), the perfluoro-divinyl monomer is one of 1, 8-divinyl perfluorooctane and perfluoro-1, 3-bis (vinyloxy) propane.
5. The method for preparing a polymer ETFE material according to claim 1, wherein in step (1), the dose rate of the gamma-ray irradiation is 14kGy/h to 16kGy/h, and the total dose of the gamma-ray irradiation is 500kGy to 1000kGy.
6. The method for preparing a poly ETFE material according to claim 2, wherein in step (1), the ETFE film has a thickness of 20 μm to 30 μm; the ETFE film had a size of (2 cm-3 cm) X (4 cm-5 cm).
7. The method for preparing a poly ETFE material by synchrotron radiation crosslinking according to claim 6, wherein in the step (1), the addition amount of the perfluoro-divinyl monomer is 5ml-15ml; the volume ratio of the perfluoro-divinyl monomer to the second solvent is 1: (1-2).
8. The method for preparing the poly ETFE material by synchronous radiation crosslinking according to claim 1, wherein in the step (2), the ETFE film after radiation crosslinking in the reaction system is transferred to a rope type device, washed for 23-24 hours by hexafluorobenzene, and then dried to constant weight in vacuum at 40-41 ℃ to complete the preparation of the poly ETFE material.
9. A polyettfe material, characterized in that it is prepared by a process for preparing a polyettfe material according to any one of claims 1 to 8 by synchrotron radiation crosslinking.
10. Use of a process for the preparation of a polyethylen fe material according to any one of claims 1 to 8 for the preparation of cables, wires, pipes and films.
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