CN106674579A - Method for preparing irradiation crosslinking accelerator for engineering plastics - Google Patents
Method for preparing irradiation crosslinking accelerator for engineering plastics Download PDFInfo
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- CN106674579A CN106674579A CN201611070677.8A CN201611070677A CN106674579A CN 106674579 A CN106674579 A CN 106674579A CN 201611070677 A CN201611070677 A CN 201611070677A CN 106674579 A CN106674579 A CN 106674579A
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by 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
- C08J2323/06—Polyethene
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- General Chemical & Material Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
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Abstract
The invention discloses a method for preparing an irradiation crosslinking accelerator for engineering plastics. The method comprises the following steps: 1, uniformly mixing double bond-containing organic amine and benzene-containing acid anhydride, and adding 300 milliliters of dimethylbenzene to obtain a premixed solution, wherein the molar ratio of the added double bond-containing organic amine and the benzene-containing acid anhydride is 1:(1 to 2.5); 2, adding an SO4<2->/ZrO2-HMS solid acid catalyst into the solution in step 1 for stirring and dispersing, wherein the mass of the added solid acid is 0.3 to 1.2 grams; 3, performing stirring for 3h at low temperature -5 DEG C, and filtering, washing and drying a product to obtain the irradiation crosslinking accelerator. According to the method for preparing the irradiation crosslinking accelerator for the engineering plastics, the synthesis efficiency is improved, the synthesis time is shortened, and separation of the synthesis product is also facilitated.
Description
Technical field
The present invention relates to cross-linked accelerating agent for irradiation technical field, more particularly to a kind of engineering plastics cross-linked accelerating agent for irradiation
Preparation method.
Background technology
Radiation Chemistry of Polymer be study ionising radiation and polymer and monomer interact the chemical change that produces and its
Effect, it includes various polymerizations, crosslinking, grafting and cracking that ionising radiation triggers etc..With nuclear reactor and accelerator art
Develop rapidly, for radiation provide various radiation sources, Radiation Chemistry of Polymer is gradually applied to the life of macromolecule product material
Produce and modified, be referred to as macromolecule RADIATION PROCESSING, the main crosslinking with radiation including electric wire and cable（Such as IXPE
Product）, the radiosterilization of health care product is plastic foamed, curing of coatings and the vulcanization of rubber etc..
Wherein, macromolecule crosslinking with radiation technology be exactly using high energy or ionising radiation trigger electrostrictive polymer from excite, from
And some secondary reactions are produced, and further cause chemical reaction, the formation of cross-linked network between macromolecule is realized, it is polymer modification
Prepare one of effective means of new material.After macromolecule crosslinking with radiation, not only make its structure that respective change occur with performance, and
And widened its range of application（Such as improve intensity, hardness and heat resistance）.High energy or ionization used in crosslinking with radiation
Radiation includes High energy electromagnetic ripple（Such as X-ray and gamma-rays）, the charged ion of high energy（As β particles or electronics, proton, α particles and
Neutron etc. and nuclear fission fragment）.Gamma-rays application technology is more ripe, and Co-60 radiographic sources are more universal, and penetration power is strong, and radiation is handed over
Connection effect is good；Next to that penetration power is less than gamma-ray electron-beam radiation source, their action principle is substantially similar.With it is traditional
Chemical crosslinking（Peroxide triggers crosslinking）Compare, crosslinking with radiation has that to be not required to catalyst, initiator, post processing simple, can be
Reacted under normal temperature and pressure, it is pollution-free etc..Peroxide trigger crosslinking need high-temperature service and crosslinking with radiation in addition to radiation source,
It is not required to special installation.Therefore, it is better than peroxide crosslinking technology in many aspects, has obtained extensive in crosslinked polymer
Using.Crosslinking with radiation is not only suitable for the production of small-scale low-voltage cable, and cannot be crosslinked with chemical method suitable for some
Material, such as ETFE（Ethylene-tetrafluoroethylene copolymer）、PVDF（Kynoar）、PVC（Polyvinyl chloride）, rubber, PP（Poly- third
Alkene）, HDPE（High density polyethylene (HDPE)）Deng.If ETFE and PVC is under its processing temperature, most of peroxide have all been decomposed, because
And be difficult to be carried out with chemical crosslink technique.If with cross-linking radiation, using suitable with preferable cross-linking effect can be obtained, making crosslinking
PVC had both had original flexible, fire retardant, inexpensive advantage, there is very high-wearing feature, heat resistance again, resistance to flatiron weldability and resistance to cut through
Property, can mutually be equal to fluoroplastics wire, and low cost.And thermally sensitive peroxide be not both suitable for high-rate of shear or
High temperature needed for high linear speed, is also unsuitable for thin-wall product or complex-shaped product, and electronic beam irradiation technology can be fitted
For these occasions.
During the crosslinking with radiation of polymeric articles, irradiation dose is a very important factor.Work as irradiation dose
Preferable crosslinking degree is not reached when too low, and when irradiation dose is too high, not only irradiation processing high cost but also irradiation also can
Base polymer is caused to damage.In order to improve the degree of cross linking and improve crosslinking rate, irradiation dose, cross-linking radiation sensitizer are reduced
It is to have to use for important additives.Addition Cucumber often accelerates reaction speed in the polymer, and this phenomenon is referred to as quick
Change is acted on, and the additive is referred to as cross-linked accelerating agent for irradiation or sensitizer.The sensitization of crosslinking with radiation is for improving materials'use performance
There is important value with range of application.Cross-linked accelerating agent for irradiation is structurally characterized in that it has the unsaturated knot of polyfunctional monomer
Structure, is radical reaction in irradiation processing, then carries out the graft crosslinking of monomer radical and base resin.The master of sensitizer
Wanting function has, and 1>Promote polymer crosslinking, including easy crosslinking with radiation polymer such as polyethylene（PE）, crosslinking, drop can be promoted
Low radiation dose；The polymer such as ETFE of crosslinking is difficult, after adding crosslinking sensitizer it can be promoted to crosslink；2>Irradiated
Destruction of the radiation to base polymer is reduced in journey.Additionally, some sensitizers can also play plasticising in polymer processing
Effect.
Conventional cross-linking radiation sensitizer mainly has three classes at present：Simple function group, two functional groups and trifunctional.Simple function
Group's sensitizer, such as ethylene acrylic esters；Two functional group's sensitizers such as diallyl fumarate, glycol diacrylate and
Glycol methacrylate etc.；Trifunctional sensitizer, such as TAC (TAC), (triallyl is different for TAIC
Cyanurate), TMPTA (three acrylic acid trihydroxy methyl propyl ester) etc..Its cross-linking efficiency is trifunctional>Two functional groups>Single official
Can group.For example, many experiments are proved, TAC, TAIC, TMPTA etc. can significantly improve the degree of cross linking of PE, improve mechanical strength, drop
The cross-linked dosage of low PE.But, the processing temperature of engineering plastics will typically promote higher than common plasticses, therefore these cross-linking radiations
Enter agent and the upper limitation of application is there is in the irradiation processing of engineering plastics, such as in process, TAIC, TMPTA etc.,
Vapored away more than 140 DEG C, the effect that irradiation promotes is not had completely.So synthesizing dystectic cross-linked accelerating agent for irradiation
It is necessary vital task in engineering plastics irradiation processing field.Additionally, process of the existing cross-linked accelerating agent for irradiation in irradiation
In easily decompose, the cross-linked accelerating agent for irradiation of decomposition has had a strong impact on electrical insulation capability of polymer etc..Phenyl ring has the big π of ring-type
Bond structure, has shielding action to high-energy radiation ray, therefore benzene ring structure is introduced in cross-linked accelerating agent for irradiation, can improve point
The radiation resistance of son.
The content of the invention
It is an object of the invention to provide a kind of preparation method of engineering plastics cross-linked accelerating agent for irradiation, the engineering plastics are used
The preparation method of cross-linked accelerating agent for irradiation improves combined coefficient, shortens generated time, also helps the separation of synthetic product.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of engineering plastics are promoted with cross-linking radiation
The preparation method of agent, comprises the following steps：
Step one, double bond organic amine will be contained and be well mixed containing benzoic anhydride after, add 300ml dimethylbenzene, obtain premixed solution,
The organic amine containing double bond for adding is 1 with the mol ratio containing benzoic anhydride：（1~2.5）；
Step 2, to（1）SO is added in solution4 2-/ZrO2- HMS solid acid catalysts and dispersed with stirring, add solid acid
Quality is 0.3 ~ 1.2g；
Step 3, -5 DEG C of stirring 3h of low temperature, product filtering, washing, the dry acquisition cross-linked accelerating agent for irradiation.
The further improved technical scheme of above-mentioned technical proposal is as follows：
1. in such scheme, the organic amine containing double bond be N- ethyl-methyls allylamine, bisacrylamide in one or two
Mixing.
2. in such scheme, it is described containing benzoic anhydride be 4- methyl tetrahydro phthalic anhydrides, phthalate anhydride in one or two mix
Close.
3. in such scheme, the whipping temp in the step one is 15 ~ 35 DEG C.
4. in such scheme, the whipping temp in the step 2 is 15 ~ 35 DEG C, and mixing time is 0.2 ~ 2h.
5. in such scheme, drying temperature is 45 ~ 105 DEG C in the step 3, and drying time is 10 ~ 36h.
6. in such scheme, the solution molar concentration containing double bond organic amine is 0.3 ~ 1mol/L.
7. in such scheme, the mass concentration of the solid acid solution is 1-4g/L.
Due to the utilization of above-mentioned technical proposal, the present invention has following advantages compared with prior art：
The preparation method of engineering plastics cross-linked accelerating agent for irradiation of the present invention, it uses SO4 2-/ZrO2- HMS solid acids are used as conjunction
Into catalyst, combined coefficient is not only increased, shorten generated time, also help the separation of synthetic product；Secondly, it is containing
Benzoic anhydride is synthesis material, introduces benzene ring structure, not only increases the fusing point of crosslinking accelerator, further improves crosslinking
The radioresistance stability of accelerator, the engineering plastics cross-linked accelerating agent for irradiation prepared increases and with phenyl ring due to molecular weight
Structure, thus it is low with high-temperature volatile, there is good compatibility with engineering plastics.
Specific embodiment
With reference to embodiment, the invention will be further described：
Embodiment：A kind of preparation method of engineering plastics cross-linked accelerating agent for irradiation, comprises the following steps：
Step one, double bond organic amine will be contained and be well mixed containing benzoic anhydride after, add 300ml dimethylbenzene, obtain premixed solution,
The organic amine containing double bond for adding is 1 with the mol ratio containing benzoic anhydride：（1~2.5）；
Step 2, to（1）SO is added in solution4 2-/ZrO2- HMS solid acid catalysts and dispersed with stirring, add solid acid
Quality is 0.3 ~ 1.2g；
Step 3, -5 DEG C of stirring 3h of low temperature, product filtering, washing, the dry acquisition cross-linked accelerating agent for irradiation.
Above-mentioned organic amine containing double bond is one or two mixing in N- ethyl-methyls allylamine, bisacrylamide.
Above-mentioned is one or two mixing in 4- methyl tetrahydro phthalic anhydrides, phthalate anhydride containing benzoic anhydride.
Whipping temp in above-mentioned steps one is 15 ~ 35 DEG C.
Whipping temp in above-mentioned steps two is 15 ~ 35 DEG C, and mixing time is 0.2 ~ 2h.
Drying temperature is 45 ~ 105 DEG C in above-mentioned steps three, and drying time is 10 ~ 36h.
The above-mentioned solution molar concentration containing double bond organic amine is 0.3 ~ 1mol/L.
The mass concentration of above-mentioned solid acid solution is 1-4g/L.
Step one, the zirconyl chloride solution of 0.1-0.2mol/L and molecular sieve HMS are sufficiently mixed（50ml:1g）, stirring
4-6h, then it is 7-9 that precipitating reagent ammoniacal liquor to p H values are slowly added dropwise, gained dries 0.5h, is stirred at being deposited in 70 DEG C
0.5h, then stands 12h.Mixed sediment is washed with deionized, is examined with silver nitrate solution into filtrate and does not measure Cl-Untill
（Checked with the silver nitrate solution of 0.1mol/L）.Resulting filter cake is dried overnight at 110 DEG C, then uses finite concentration
(10 mL/ g) sulfuric acid solution impregnates 4h, and roasting 4h is that SO is obtained at a certain temperature after drying4 2-/ ZrO2-HMS solids
Acid.
Step 2, double bond organic amine will be contained and be well mixed containing benzoic anhydride after, add 300ml dimethylbenzene, premixed
Solution, the organic amine containing double bond for being added is 1 with the mol ratio containing benzoic anhydride：（1-2.5）；
Step 3, to solid acid catalyst and dispersed with stirring is added in step 2 solution, add the quality of solid acid for 0.3-
1.2g；
Step 4, -5 DEG C of stirring 3h of low temperature, product filtering, washing are dried.
Mixing or whipping temp are 15-35 DEG C.
Mixing time is 0.2-2h.
Drying temperature is 45-105 DEG C, and drying time is 10-36h.
The molar concentration containing double bond Amine Solutions is 0.3-1mol/L.
The molar concentration containing benzoic acid anhydride solution is 0.3-1.2mol/L.
The mass concentration of the solid acid solution is 1-4g/L.
The organic amine containing double bond is one or two the mixing in N- ethyl-methyls allylamine and bisacrylamide；Institute
It is one or two the mixing in 4- methyl tetrahydro phthalic anhydrides and phthalate anhydride to state containing benzoic anhydride；The solid acid is self-control
SO4 2-/ ZrO2-HMS catalyst.
Wash time is not more than 0.5h.
Embodiment 1：
Step one, will contain after bisacrylamide is well mixed with 4- methyl tetrahydro phthalic anhydrides, add 300ml dimethylbenzene, obtain pre-
Miscible fluid, the bisacrylamide for being added is 1 with the mol ratio of 4- methyl tetrahydro phthalic anhydrides：1；
Step 2, to solid acid catalyst and dispersed with stirring is added in step one solution, add the quality of solid acid for 0.3g；
10min is washed in step 3, -5 DEG C of stirring 3h of low temperature, product filtering, and 80 DEG C dry 12h and obtain cross-linked accelerating agent for irradiation 1.
Embodiment 2：
Step one, will contain after N- ethyl-methyl allylamines are well mixed with phthalate anhydride, add 300ml dimethylbenzene, obtain
Premixed solution, the N- ethyl-methyls allylamine for being added is 2 with the mol ratio of phthalate anhydride：1；
Step 2, to solid acid catalyst and dispersed with stirring is added in step one solution, add the quality of solid acid for 0.5g；
20min is washed in step 3, -5 DEG C of stirring 3h of low temperature, product filtering, and 80 DEG C dry 24h and obtain cross-linked accelerating agent for irradiation 2.
Embodiment 3：
Step one, will contain after bisacrylamide is well mixed with phthalate anhydride, add 300ml dimethylbenzene, obtain pre- miscible
Liquid, the organic amine containing double bond for being added is 1 with the mol ratio containing benzoic anhydride：1；
Step 2, to solid acid catalyst and dispersed with stirring is added in step one solution, add the quality of solid acid for 0.4g；
30min is washed in step 3, -5 DEG C of stirring 3h of low temperature, product filtering, and 80 DEG C dry 20h and obtain cross-linked accelerating agent for irradiation 3.
Test case：
1st, knowable to the DSC spectrograms of comparing embodiment 1, embodiment 2 and the gained engineering plastics cross-linked accelerating agent for irradiation of embodiment 3,
The engineering plastics cross-linked accelerating agent for irradiation that preparation method of the present invention is obtained, between 200-300 DEG C, this is moulded its fusing point with journey
The processing temperature of material matches.
2nd, the irradiation facilitation of testing example gained engineering plastics cross-linked accelerating agent for irradiation
Electron Beam Irradiation and cobalt source irradiation method is respectively adopted carries out cross-linking radiation promotion assessment to conventional engineering plastics.It is right
UHMWPE is irradiated using cobalt source, and 3 parts of embodiment 1 and the gained engineering plastics of embodiment 2 cross-linked accelerating agent for irradiation, spoke are added respectively
According to dosage 10MGy, gained sample creep is according to the measure of GB/T 11546.1-2008 creep of plastics performances, part 1：Draw
Stretch creep to be tested, heat resistance is tested with TGA, acquired results such as table 1；Electron beam irradiation is used to nylon PA6, point
Tian Jia not embodiment 1 and 1 part of the gained engineering plastics cross-linked accelerating agent for irradiation of embodiment 2, irradiation dose 10MGy, gained sample
Mechanical performance is tested according to GB/T 1040-2006, and heat resistance is tested with TGA, acquired results such as table 2.
Table 1
As shown in Table 1, the cross-linked accelerating agent for irradiation of embodiment of the present invention 1-3 improves compared to for more no added with creep properties,
Temperature capability is improved.
Table 2
As shown in Table 2, because the introducing of organic amine increased the compatibility of crosslinking accelerator and PA6, while double bond functional group
Introducing increased the probability of PA6 crosslinkings with radiation, thus the embodiment of the present invention 1 ~ 3 cross-linked accelerating agent for irradiation compared to more no added
Speech, with fracture strength enhancing, temperature capability is improved.
The above embodiments merely illustrate the technical concept and features of the present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of engineering plastics cross-linked accelerating agent for irradiation, it is characterised in that：Comprise the following steps：
Step one, double bond organic amine will be contained and be well mixed containing benzoic anhydride after, add 300ml dimethylbenzene, obtain premixed solution,
The organic amine containing double bond for adding is 1 with the mol ratio containing benzoic anhydride：（1~2.5）；
Step 2, to（1）SO is added in solution4 2-/ZrO2- HMS solid acid catalysts and dispersed with stirring, add the matter of solid acid
It is 0.3 ~ 1.2g to measure；
Step 3, -5 DEG C of stirring 3h of low temperature, product filtering, washing, the dry acquisition cross-linked accelerating agent for irradiation.
2. the preparation method of engineering plastics cross-linked accelerating agent for irradiation according to claim 1, it is characterised in that：It is described to contain
Double bond organic amine is one or two mixing in N- ethyl-methyls allylamine, bisacrylamide.
3. the preparation method of engineering plastics cross-linked accelerating agent for irradiation according to claim 1, it is characterised in that：It is described to contain
Benzoic anhydride is one or two mixing in 4- methyl tetrahydro phthalic anhydrides, phthalate anhydride.
4. the preparation method of engineering plastics cross-linked accelerating agent for irradiation according to claim 1, it is characterised in that：The step
Whipping temp in rapid one is 15 ~ 35 DEG C.
5. the preparation method of engineering plastics cross-linked accelerating agent for irradiation according to claim 1, it is characterised in that：The step
Whipping temp in rapid two is 15 ~ 35 DEG C, and mixing time is 0.2 ~ 2h.
6. the preparation method of engineering plastics cross-linked accelerating agent for irradiation according to claim 1, it is characterised in that：The step
Drying temperature is 45 ~ 105 DEG C in rapid three, and drying time is 10 ~ 36h.
7. the preparation method of engineering plastics cross-linked accelerating agent for irradiation according to claim 1, it is characterised in that：It is described to contain
The solution molar concentration of double bond organic amine is 0.3 ~ 1mol/L.
8. the preparation method of engineering plastics cross-linked accelerating agent for irradiation according to claim 1, it is characterised in that：It is described solid
The mass concentration of body acid solution is 1-4g/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810835A (en) * | 2017-02-13 | 2017-06-09 | 肇庆汇展塑料科技有限公司 | A kind of heat-and corrosion-resistant engineering plastics preparation method |
| CN110483878A (en) * | 2019-09-03 | 2019-11-22 | 中广核高新核材科技（苏州）有限公司 | Radiation resistance crosslinked ethene-tetrafluoroethylene copolymer insulation material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037797A (en) * | 2015-08-06 | 2015-11-11 | 中广核三角洲（江苏）塑化有限公司 | Crosslinking sensitizer for fluorine-containing polymer |
-
2016
- 2016-11-29 CN CN201611070677.8A patent/CN106674579B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037797A (en) * | 2015-08-06 | 2015-11-11 | 中广核三角洲（江苏）塑化有限公司 | Crosslinking sensitizer for fluorine-containing polymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810835A (en) * | 2017-02-13 | 2017-06-09 | 肇庆汇展塑料科技有限公司 | A kind of heat-and corrosion-resistant engineering plastics preparation method |
| CN110483878A (en) * | 2019-09-03 | 2019-11-22 | 中广核高新核材科技（苏州）有限公司 | Radiation resistance crosslinked ethene-tetrafluoroethylene copolymer insulation material |
| CN110483878B (en) * | 2019-09-03 | 2022-04-05 | 中广核高新核材科技（苏州）有限公司 | Radiation-resistant crosslinked ethylene-tetrafluoroethylene copolymer insulating material |
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