CN109161203A - A kind of radiation hardness job that requires special skills graphene compounded rubber and preparation method - Google Patents
A kind of radiation hardness job that requires special skills graphene compounded rubber and preparation method Download PDFInfo
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- CN109161203A CN109161203A CN201810933692.3A CN201810933692A CN109161203A CN 109161203 A CN109161203 A CN 109161203A CN 201810933692 A CN201810933692 A CN 201810933692A CN 109161203 A CN109161203 A CN 109161203A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
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Abstract
The invention belongs to the technical field of compounded rubber, a kind of radiation hardness job that requires special skills graphene compounded rubber and preparation method are provided.Composite hydrogel is made by lead acetate and graphite oxide alkene reaction in this method, is freeze-dried and high temperature sintering is composite sponge, be kneaded after broken with rubber raw materials, filler, auxiliary agent, mixing, vulcanization, obtained graphene compounded rubber.It is compared with the traditional method, the compounded rubber of preparation of the invention, the leaded graphene with three-dimensional structure forms network structure in compounded rubber, good mechanical property, the radiation hardness ability of compounded rubber is significantly enhanced, excellent combination property, application prospect is good in radiation hardness job that requires special skills field.
Description
Technical field
The invention belongs to the technical fields of compounded rubber, provide a kind of radiation hardness job that requires special skills graphene compounded rubber
And preparation method.
Background technique
Ionising radiation has been widely used for the job that requires special skills field of contemporary science and technology, and the mankind obtain therefrom in enjoyment
Huge interests while, to avoid by the harm radiated, just should sufficiently pay attention to the protection to radiation.In hospital radiological department
Room, related nuclear power station operating room, in these application scenarios such as aerospace station, material often subjects ionising radiation, ion spoke
A variety of radiation environments such as penetrate, there are the photon of the high dose of a large amount of randomness, neutron, meson etc. in job that requires special skills field, this
A little high energy particles cause largely to endanger to working equipment, and shine the health of staff at seriously affecting, therefore resistance to
Ionizing Radiation is more and more important.
Since the mass fraction of the hydrogen of some rubber is very high and a kind of ideal neutron moderator, high energy can be used as
Radiation, the especially perforative ability of neutron irradiation, at this moment need rubber to have the perforative ability of good radiation protection.These are all said
Bright, it is very necessary for studying performance and measuring technology of the rubber under high-energy radiation.Rubber material is in the special type containing radiation
In operation, there is also irradiation effects, these effects such as cross-linking radiation, irradiation-induced degradation, gas release will lead to rubber power for rubber
Learn the variation of performance.
The approach for improving the radiation-resistant property of rubber at present, mainly has: introducing on rubber side chain containing conjugated structure
Bulky group mainly includes phenyl, condensed-nuclei aromatics etc.；Radiation resistance filler is blended in rubber, such as contains conjugated structure
Small organic molecule.Radiation energy on the one hand can be by being converted into the form of energy such as light, heat to radiation by the bulky group of conjugation
It can be carried out absorption and dissipate；On the other hand, the Active Radicals Produced that radiation is formed can be stablized, reduce free radical to cross-linked network
It destroys.
At present both at home and abroad in Radiation-resistant Polymers technology, especially achieved in terms of radiation resistant rubber centainly at
Effect.Wherein Li Puwang et al. has invented a kind of graphene-supported cerium oxide and rubber composite material and preparation method thereof (China
Application number of invention patent 201710730174.7), preparation method includes: that cerous nitrate solution is added drop-wise in graphene oxide solution together
When stir；It is added in hydrothermal synthesis reaction kettle and calcines, be cooled to room temperature；With water and ethanol washing, drying is obtained graphene-supported
Cerium oxide；Graphene-supported cerium oxide is filled into natural rubber-butadiene-styrene rubber, vulcanizing system is added and is kneaded to be kneaded
Glue vulcanizes on vulcanizing press, obtains graphene-supported cerium oxide and rubber composite material, can be used for preparing various shape
Anti-radiation windshield；The invention is compound by graphene and cerium oxide, and the speed of electronics transfer is improved using graphene as carrier,
It is filled into natural rubber and butadiene-styrene rubber, has not only played the role of electromagnetic shielding but also plays to natural rubber and butadiene-styrene rubber
Anti-aging effect, also have excellent mechanical property, antioxygenic property and submissive performance, can be used for preparing protection human health
Anti-radiation windshield.In addition, a kind of radiation resistant rubber and preparation method thereof (Chinese invention patent application number has bravely been invented in the village
201711094370.6), prepared using the following raw material: polybutadiene rubber, natural rubber, sulphur, silica, zinc oxide,
Lead oxide, calcium stearate, polyacrylic acid coated nano calcium carbonate particle, Eu2O3、Tb4O7, potassium titanate crystal whisker, aluminium hydroxide,
Toner, tetramethylthiuram disulfide, antioxidant 4020；The rubber of the invention improves under the synergistic effect of each component
The radiation resistance of the radiation resistant rubber of preparation.
As it can be seen that there are radiation hardness is poor for rubber material in job that requires special skills field in the prior art, and material mechanical performance exists
Rapid decrease in radiation to influence the safety of staff under job that requires special skills environment, therefore improves the radiation hardness of the material
Property, and take into account the mechanical property important in inhibiting of material.
Summary of the invention
In response to this, it is proposed that a kind of radiation hardness job that requires special skills graphene compounded rubber and preparation method, show
Work improves the radiation hardness ability of compounded rubber, and in radiation hardness job that requires special skills field, application prospect is good.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, passes through lead acetate and graphite oxide alkene reaction system
At composite hydrogel, be freeze-dried and high temperature sintering be composite sponge, after broken and rubber raw materials, filler, auxiliary agent be kneaded,
Graphene compounded rubber is made in mixing, vulcanization, and specific step is as follows for preparation:
(1) graphene oxide is configured to the high concentration solution of 2mg/mL, then lead acetate and reduction is added in ultrasonic disperse 1h
Agent is stirred well to uniformly, mixed liquor is heated to reaction in confined conditions, leaded graphene composite hydrogel is made；
(2) graphene composite hydrogel made from step (1) is freeze-dried, is subsequently placed in high temperature sintering under nitrogen protection, made
Obtain leaded three-dimensional grapheme composite sponge；
(3) graphene composite sponge made from step (2) is broken into fine powder, with silicon rubber, carbon black, hydroxy silicon oil, anti-scorch
Agent, anti-aging agent mixing, put into mixer and are kneaded, and rubber compound obtained carries out mixing after parking 6h, and vulcanization cream, benefit is then added
Vulcanized with vulcanizing press, discharged, graphene compounded rubber is made.
Preferably, step (1) reducing agent be ammonium sulfide, ferrous sulfate, sodium sulfite, sodium borohydride, stannous chloride,
At least one of potassium borohydride.
Preferably, the parts by weight of step (1) each raw material are 80 ~ 85 parts by weight of graphene oxide water solution, lead acetate
12 ~ 15 parts by weight, 3 ~ 5 parts by weight of reducing agent.
Preferably, the temperature of step (1) described reaction is 90 ~ 98 DEG C, and the time is 2 ~ 3h.
Preferably, the temperature of step (2) described high temperature sintering is 550 ~ 650 DEG C, and the time is 50 ~ 70min.
Preferably, step (3) antiscorching agent is oxalic acid, succinic acid, lactic acid, phthalic anhydride, salicylic acid, benzene first
At least one of acid, oleic acid.
Preferably, step (3) anti-aging agent is N- phenyl-β-naphthylamine salt, 2,2,4- trimethyl -1,2- dihyaroquinolines
Condensate, N, at least one of N'- bis- (betanaphthyl) p-phenylenediamine, 2-mercaptobenzimidazole.
Preferably, the parts by weight of step (3) each raw material are 4 ~ 8 parts by weight of graphene fine powder, silicon rubber 63 ~ 78
Parts by weight, 10 ~ 15 parts by weight of carbon black, 3 ~ 5 parts by weight of hydroxy silicon oil, 1.5 ~ 3 parts by weight of antiscorching agent, 0.5 ~ 1 parts by weight of anti-aging agent,
Vulcanize 3 ~ 5 parts by weight of cream.
Preferably, the vulcanization cream selects sulphur.
Preferably, the temperature of step (3) described vulcanization is 110 ~ 130 DEG C, and the time is 8 ~ 12min.
On the one hand, since the leaded graphene of three-dimensional structure can form network structure in compounded rubber after modification, increase
Big filler resists the surface area of radiation.On the other hand, the graphite containing conjugated structure in the leaded graphene-structured of three-dimensional structure
Alkene, metallic lead can realize absorption and dissipation to radiation energy by radiation energy being converted into the form of energy of light, heat,
The Active Radicals Produced that radiation is formed can be stablized simultaneously, destruction of the free radical to cross-linked network in compounded rubber is reduced, reduce spoke
Penetrate the harm of generation.Therefore, the present invention introduces lead element during preparing graphene hydrogel, and lead stabilization is made to be compound in stone
In the three-dimensional net structure of black alkene, and it is further used for modified rubber.
The present invention also provides a kind of compound rubbers of radiation hardness job that requires special skills graphene that above-mentioned preparation method is prepared
Glue.
The preparation method of the compounded rubber is that graphene oxide is configured to high concentration solution and ultrasound, and acetic acid is added
Lead, ammonium sulfide reducing agent, which is sufficiently stirred, is uniformly mixed it, which is reacted in confined conditions, obtains leaded graphite
The composite hydrogel of alkene, freeze-drying are placed under nitrogen protection gas after being sintered and obtain leaded three-dimensional grapheme composite sponge,
By the sponge Mechanical Crushing at fine powder, with silicon rubber, carbon black, hydroxy silicon oil and remaining auxiliary agent put into mixer and are kneaded,
Rubber compound is obtained, rubber compound is parked into a period of time, then vulcanization cream is added in mixing again, is vulcanized using vulcanizing press and is produced
Product.
The present invention provides a kind of radiation hardness job that requires special skills graphene compounded rubber and preparation methods, with prior art phase
Than the feature and excellent effect protruded is:
1. compounded rubber prepared by the present invention, has excellent performance, in radiation hardness job that requires special skills field, application prospect is good.
2. preparation method of the invention forms the leaded graphene with three-dimensional structure, can form net in compounded rubber
Network structure increases its surface area for resisting radiation, to improve the radiation resistance of compounded rubber.
3. compounded rubber produced by the present invention, can by the way that radiation energy is converted into light, thermal energy form can be carried out radiation
It absorbs and dissipates, while reducing destruction of the free radical to cross-linked network in compounded rubber, to enhance the resistance to spoke of compounded rubber
Penetrate ability.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
13kg lead acetate and 4 kg ammonium sulfides is added in the graphene oxide high concentration solution of 83kg 2mg/mL, is sufficiently stirred
To uniform, mixed liquor is heated to 95 DEG C of reaction 2.5h in confined conditions, leaded graphene composite hydrogel is made；Then
Graphene composite hydrogel is freeze-dried, is subsequently placed under nitrogen protection and is heated to 590 DEG C of high temperature sintering 58min, is made and contains
The three-dimensional grapheme composite sponge of lead；Then 6 kg graphene composite sponges are broken into fine powder, with 70kg silicon rubber, 13
Kg carbon black, 4kg hydroxy silicon oil, 2 kg oxalic acid, the mixing of 1 kgN- phenyl-β-naphthylamine salt, put into mixer and are kneaded, obtained mixed
Refining glue carries out mixing after parking 6h, and 4kg is then added and vulcanizes cream, vulcanizes 11min at 122 DEG C using vulcanizing press, discharges,
Graphene compounded rubber is made.
Test method:
Radiation hardness test (tensile strength): according to GB/T 528-2009 standard, 1 type is made in compounded rubber produced by the present invention
Dumb-bell shape standard sample is tested in 25 DEG C, relative humidity 55%, normal atmosphere pressure, is tried using instron
Speed 100mm/min is tested, initial tensile strength is measured；Then sample is put into irradiation field to be irradiated, emission types are penetrated for C-
Line, x- ray, electronics, B- ray；Radioactive isotope and pileradiation, dosage rate 108Gy/h takes out after radiating 36h,
Tensile strength is tested, 3 calculating average values are tested.
The data obtained is as shown in table 1.
Embodiment 2
12 kg lead acetates and 3kg ferrous sulfate are added in the graphene oxide high concentration solution of 85kg 2mg/mL, are sufficiently stirred
It mixes to uniform, mixed liquor is heated to 90 DEG C of reaction 3h in confined conditions, leaded graphene composite hydrogel is made；Then
Graphene composite hydrogel is freeze-dried, is subsequently placed under nitrogen protection and is heated to 550 DEG C of high temperature sintering 70min, is made and contains
The three-dimensional grapheme composite sponge of lead；Then 4 kg graphene composite sponges are broken into fine powder, with 78 kg silicon rubber,
10kg carbon black, 3 kg hydroxy silicon oils, 1.5 kg succinic acids, 0.5 kg 2,2,4- trimethyl -1,2- dihyaroquinoline condensate
Mixing puts into mixer and is kneaded, and rubber compound obtained carries out mixing after parking 6h, and 3kg is then added and vulcanizes cream, utilizes plate
Vulcanizer vulcanizes 12min at 110 DEG C, and graphene compounded rubber is made in discharging.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 3
15 kg lead acetates and 5 kg sodium sulfites are added in the graphene oxide high concentration solution of 80kg 2mg/mL, are sufficiently stirred
It mixes to uniform, mixed liquor is heated to 98 DEG C of reaction 2h in confined conditions, leaded graphene composite hydrogel is made；Then
Graphene composite hydrogel is freeze-dried, is subsequently placed under nitrogen protection and is heated to 650 DEG C of high temperature sintering 50min, is made and contains
The three-dimensional grapheme composite sponge of lead；Then 8 kg graphene composite sponges are broken into fine powder, with 63 kg silicon rubber, 15
Kg carbon black, 5 kg hydroxy silicon oils, 3 kg succinic acids, 1 kgN, N'- bis- (betanaphthyl) p-phenylenediamine, 2-mercaptobenzimidazole are mixed
It closes, puts into mixer and be kneaded, rubber compound obtained carries out mixing after parking 6h, and 5 kg vulcanization cream is then added, utilizes plate
Vulcanizer vulcanizes 8min at 130 DEG C, and graphene compounded rubber is made in discharging.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 4
13 kg lead acetates and 3 kg sodium borohydrides are added in the graphene oxide high concentration solution of 84kg 2mg/mL, are sufficiently stirred
It mixes to uniform, mixed liquor is heated to 92 DEG C of reaction 3h in confined conditions, leaded graphene composite hydrogel is made；Then
Graphene composite hydrogel is freeze-dried, is subsequently placed under nitrogen protection and is heated to 570 DEG C of high temperature sintering 65min, is made and contains
The three-dimensional grapheme composite sponge of lead；Then 5 kg graphene composite sponges are broken into fine powder, with 74 kg silicon rubber, 11
Kg carbon black, 4kg hydroxy silicon oil, 1.5 kg phthalic anhydrides, the mixing of 0.5kg2- mercaptobenzimidazole, put into mixer and mix
Refining, rubber compound obtained carry out mixing after parking 6h, and 4kg is then added and vulcanizes cream, is vulcanized at 115 DEG C using vulcanizing press
Graphene compounded rubber is made in 11min, discharging.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 5
14 kg lead acetates and 4 kg stannous chlorides are added in the graphene oxide high concentration solution of 82kg 2mg/mL, are sufficiently stirred
It mixes to uniform, mixed liquor is heated to 96 DEG C of reaction 2h in confined conditions, leaded graphene composite hydrogel is made；Then
Graphene composite hydrogel is freeze-dried, is subsequently placed under nitrogen protection and is heated to 620 DEG C of high temperature sintering 55min, is made and contains
The three-dimensional grapheme composite sponge of lead；Then 7 kg graphene composite sponges are broken into fine powder, with 68 kg silicon rubber,
14kg carbon black, 4 kg hydroxy silicon oils, 2 kg salicylic acids, the mixing of 1 kgN- phenyl-β-naphthylamine salt, put into mixer and are kneaded, make
The rubber compound obtained carries out mixing after parking 6h, and 4kg is then added and vulcanizes cream, vulcanizes 9min at 125 DEG C using vulcanizing press,
Graphene compounded rubber is made in discharging.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 6
14 kg lead acetates and 4 kg potassium borohydrides are added in the graphene oxide high concentration solution of 82kg 2mg/mL, are sufficiently stirred
It mixes to uniform, mixed liquor is heated to 94 DEG C of reaction 2.5h in confined conditions, leaded graphene composite hydrogel is made；So
Graphene composite hydrogel is freeze-dried afterwards, is subsequently placed under nitrogen protection and is heated to 600 DEG C of high temperature sintering 60min, is made
Leaded three-dimensional grapheme composite sponge；Then 6 kg graphene composite sponges are broken into fine powder, with 71kg silicon rubber, 12
Kg carbon black, 4 kg hydroxy silicon oils, 2 kg oleic acid, 1 kg2, the mixing of 2,4- trimethyl -1,2- dihyaroquinoline condensates, investment
It is kneaded in mixer, rubber compound obtained carries out mixing after parking 6h, and 4kg is then added and vulcanizes cream, is existed using vulcanizing press
Vulcanize 10min at 120 DEG C, discharge, graphene compounded rubber is made.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Comparative example 1
In graphene hydrogel preparation process, it is not added with lead acetate, other preparation conditions and embodiment 6 are consistent.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, which is characterized in that pass through lead acetate and oxygen
Graphite alkene reaction is made composite hydrogel, is freeze-dried and high temperature sintering is composite sponge, it is broken after with rubber raw materials, fill out
Material, auxiliary agent be kneaded, mixing, vulcanization, be made graphene compounded rubber, specific step is as follows for preparation:
(1) graphene oxide is configured to the high concentration solution of 2mg/mL, then lead acetate and reduction is added in ultrasonic disperse 1h
Agent is stirred well to uniformly, mixed liquor is heated to reaction in confined conditions, leaded graphene composite hydrogel is made；
(2) graphene composite hydrogel made from step (1) is freeze-dried, is subsequently placed in high temperature sintering under nitrogen protection, made
Obtain leaded three-dimensional grapheme composite sponge；
(3) graphene composite sponge made from step (2) is broken into fine powder, with silicon rubber, carbon black, hydroxy silicon oil, anti-scorch
Agent, anti-aging agent mixing, put into mixer and are kneaded, and rubber compound obtained carries out mixing after parking 6h, and vulcanization cream, benefit is then added
Vulcanized with vulcanizing press, discharged, graphene compounded rubber is made.
2. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, feature exist according to claim 1
In: step (1) reducing agent is ammonium sulfide, in ferrous sulfate, sodium sulfite, sodium borohydride, stannous chloride, potassium borohydride
It is at least one.
3. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, feature exist according to claim 1
Be in: parts by weight of step (1) each raw material, 80 ~ 85 parts by weight of graphene oxide water solution, 12 ~ 15 parts by weight of lead acetate,
3 ~ 5 parts by weight of reducing agent.
4. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, feature exist according to claim 1
In: the temperature of step (1) described reaction is 90 ~ 98 DEG C, and the time is 2 ~ 3h.
5. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, feature exist according to claim 1
In: the temperature of step (2) described high temperature sintering is 550 ~ 650 DEG C, and the time is 50 ~ 70min.
6. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, feature exist according to claim 1
In: step (3) antiscorching agent be oxalic acid, succinic acid, lactic acid, phthalic anhydride, salicylic acid, benzoic acid, in oleic acid extremely
Few one kind.
7. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, feature exist according to claim 1
In: step (3) anti-aging agent is N- phenyl-β-naphthylamine salt, 2,2,4- trimethyl -1,2- dihyaroquinoline condensate, N, N'-
At least one of two (betanaphthyl) p-phenylenediamine, 2-mercaptobenzimidazole.
8. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, feature exist according to claim 1
In: the parts by weight of step (3) each raw material are 4 ~ 8 parts by weight of graphene fine powder, 63 ~ 78 parts by weight of silicon rubber, carbon black 10
~ 15 parts by weight, 3 ~ 5 parts by weight of hydroxy silicon oil, 1.5 ~ 3 parts by weight of antiscorching agent, 0.5 ~ 1 parts by weight of anti-aging agent, vulcanization 3 ~ 5 weight of cream
Part.
9. a kind of preparation method of radiation hardness job that requires special skills graphene compounded rubber, feature exist according to claim 1
In: the temperature of step (3) described vulcanization is 110 ~ 130 DEG C, and the time is 8 ~ 12min.
10. the radiation hardness graphene compounded rubber that any one of claim 1 ~ 9 preparation method is prepared.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110289115A (en) * | 2019-02-22 | 2019-09-27 | 西南科技大学 | A kind of high-strength silicon rubber base flexibility neutron shielding material and preparation method thereof |
| CN111138726A (en) * | 2020-01-15 | 2020-05-12 | 福建五持恒科技发展有限公司 | Graphene natural rubber radiation-proof composite foam material and preparation method thereof |
| CN115772301A (en) * | 2022-12-29 | 2023-03-10 | 台州耘智科技有限公司 | Torsion-resistant cable material and preparation method thereof |
-
2018
- 2018-08-16 CN CN201810933692.3A patent/CN109161203A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110289115A (en) * | 2019-02-22 | 2019-09-27 | 西南科技大学 | A kind of high-strength silicon rubber base flexibility neutron shielding material and preparation method thereof |
| CN110289115B (en) * | 2019-02-22 | 2022-08-30 | 中国工程物理研究院核物理与化学研究所 | High-strength silicone rubber-based flexible neutron shielding material and preparation method thereof |
| CN111138726A (en) * | 2020-01-15 | 2020-05-12 | 福建五持恒科技发展有限公司 | Graphene natural rubber radiation-proof composite foam material and preparation method thereof |
| CN115772301A (en) * | 2022-12-29 | 2023-03-10 | 台州耘智科技有限公司 | Torsion-resistant cable material and preparation method thereof |
| CN115772301B (en) * | 2022-12-29 | 2023-12-29 | 浙江双士照明电器有限公司 | Torsion-resistant cable material and preparation method thereof |
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Application publication date: 20190108 |