CN103030874B - Irradiation crosslinking slurry-resistant, low-smoke, halogen-free and high-flame-retardant sheath material and fabrication method thereof - Google Patents
Irradiation crosslinking slurry-resistant, low-smoke, halogen-free and high-flame-retardant sheath material and fabrication method thereof Download PDFInfo
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Abstract
The invention provides an irradiation crosslinking slurry-resistant, low-smoke, halogen-free and high-flame-retardant sheath material which comprises the following components in parts by weight: 100 parts of base resin, 130-160 parts of flame retardant, 1.0-2.5 parts of coupling agent, 10-20 parts of compatilizer, 0.5-1 part of antioxidant, 1-2 parts of crosslinking sensitizer, 0.2-0.6 part of anti-ultraviolet agent, and 0.5-3 parts of lubricant, wherein the base resin comprises the following components: an ethylene-butyl acrylate (EEA) copolymer and high-density polyethylene (HDPE) at a weight ratio of (85-70):(15-30); and the flame retardant is magnesium hydroxide. The irradiation crosslinking slurry-resistant, low-smoke, halogen-free and high-flame-retardant sheath material is excellent in mechanical property.
Description
Technical field
Low-smoke bittern-free highly fire-proof sheath material that the present invention relates to a kind of cross-linking radiation and preparation method thereof, particularly relates to a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material and preparation method thereof.
Background technology
In the construction and use procedure of offshore platform, can cable select the whether suitable operation being related to whole plateform system safe.Therefore cable is called as the blood vessel of platform.Selected cable not only demand fulfillment International Electrotechnical Commission (IEC) relevant criterion, also to meet other technologies specification (as NEK606) etc.
At present, the domestic cable producer that independently can produce offshore platform is little, most of cable all dependence on import.Major cause meets the jacket material producer that on oil platform, environment for use requires almost not have.China all needs Imported oil platform cable or CABLE MATERIALS every year.Seriously constrain the development of China's marine economy.
In sum, provides the art a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material being applicable to offshore platform and preparation method thereof.
Summary of the invention
The first object of the present invention is that obtaining one overcomes the deficiencies in the prior art, provides a kind of cross-linking radiation, resistance to mud, high flame retardant, the low-smoke halogen-free flame-retardant sheath material that mechanical property is superior.
The second object of the present invention is that obtaining one overcomes the deficiencies in the prior art, provides a kind of cross-linking radiation, resistance to mud, high flame retardant, the preparation method of the low-smoke halogen-free flame-retardant sheath material that mechanical property is superior.
A first aspect of the present invention provides a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material, wherein, each component of described sheath material and parts by weight as follows:
Described base resin comprises following component: ethylene-butyl acrylate copolymer, and high density polyethylene(HDPE) (HDPE) and both weight ratios are followed successively by (85 ~ 70): (15 ~ 30);
And described fire retardant is magnesium hydroxide.
In a specific embodiment of the present invention,
The melting index of described ethylene-butyl acrylate copolymer is: 2 ~ 6g/10min, measure, and test condition is: temperature is 190 DEG C, and load is 2.16KG with GB/T3682-2000 method;
Wherein the mass percentage of butyl acrylate is: 10 ~ 30%, with the total weight of ethylene-butyl acrylate copolymer ().
In a specific embodiment of the present invention, the median particle diameter of described magnesium hydroxide is 1.25 ~ 1.65 μm, and specific surface area is 4-6m
2/ g.
In a specific embodiment of the present invention, described coupling agent is vinyltriethoxysilane.
In a specific embodiment of the present invention, described compatilizer is the multipolymer of Ethylene-butyl acrylate grafted maleic anhydride.
In a specific embodiment of the present invention, described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).
In a specific embodiment of the present invention, described crosslinking sensitizer is the one in triallyl isocyanurate (TAIC), trihydroxy methyl propane trimethyl acrylate.
In a specific embodiment of the present invention, described anti ultraviolet agent is one or both mixing in UV944, UV531.
In a specific embodiment of the present invention, described lubricant is silicone master batch, and in silicone master batch, the number-average molecular weight of siloxanes is 600,000 ~ 850,000.
A second aspect of the present invention provides a kind of preparation method of a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as described in the present invention, and described preparation method comprises the following steps:
Fire retardant, coupling agent, crosslinking sensitizer, anti ultraviolet agent are proportionally mixed to temperature to 70 DEG C ± 5 DEG C, discharging is placed, and with other components by proportioning extruding pelletization, obtains the described a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material.
Embodiment
The present inventor, through extensive and deep research, by improving preparation technology, overcoming the deficiencies in the prior art, obtaining a kind of cross-linking radiation, resistance to mud, high flame retardant, the low-smoke halogen-free flame-retardant sheath material that mechanical property is superior.Complete the present invention on this basis.
Herein, term " contains " or " comprising " represents that various composition can be applied in mixture of the present invention or composition together.Therefore, term " primarily of ... composition " and " by ... form " be included in term and " contain " or in " comprising ".
Herein, the universal standard of mensuration reference this area of described " resistance to mud " performance.Usually, determined by three tests such as the test of the Sea of resistance to Carbo (oil base) drilling fluid, oil resistant test IRM903, the bittern of resistance to Calcium Bromide (water base) tests.
Herein, the universal standard of mensuration reference this area of the flame retardant properties of described sheath material.Usually, vertical combustion (FV-0 level) is adopted to measure.
Herein, the flame retardant cable of resistance to mud can be obtained after described sheath material makes sample through cross-linking radiation.Described cross-linking radiation is the ordinary skill in the art, is known for those skilled in the art.Specifically such as, adopt electron accelerator irradiation to be cross-linked, irradiation dose is 12Mrad ~ 15Mrad.
Technical conceive of the present invention is as follows:
The invention provides a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material and preparation method thereof, each component of described sheath material and parts by weight as follows: base resin 100 parts; Fire retardant: 130 ~ 160 parts; Coupling agent 1.0 ~ 2.5 parts; Compatilizer: 10 ~ 20 parts; 0.5 ~ 1 part, oxidation inhibitor; Crosslinking sensitizer: 1 ~ 2 part; Anti ultraviolet agent: 0.2 ~ 0.6 part; Lubricant 0.5 ~ 3 part; Described base resin comprises following component: ethylene-butyl acrylate copolymer, and high density polyethylene(HDPE) (HDPE) and both weight ratios are followed successively by (85 ~ 70): (15 ~ 30).Described fire retardant is magnesium hydroxide, and coupling agent is vinyltriethoxysilane, and compatilizer is the multipolymer of Ethylene-butyl acrylate grafted maleic anhydride, and lubricant is silicone master batch.The invention provides a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material and preparation method thereof, cable is after cross-linking radiation, and performance meets the requirement of anti-SHF mud in offshore platform cable and Norway NEK606 standard.
Below describe in detail to various aspects of the present invention:
A first aspect of the present invention provides a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material, wherein, each component of described sheath material and parts by weight as follows:
Described base resin comprises following component: ethylene-butyl acrylate copolymer, and high density polyethylene(HDPE) (HDPE) and both weight ratios are followed successively by (85 ~ 70): (15 ~ 30);
And described fire retardant is magnesium hydroxide.
Described base resin can by blended acquisition.Described blend method is not specifically limited, and can adopt conventional blend method, this is known for those skilled in the art.
Molecular weight and the model of described ethylene-butyl acrylate copolymer are not specifically limited, as long as melting index meets necessary requirement.
In a specific embodiment of the present invention, the melting index of described ethylene-butyl acrylate copolymer is: 2 ~ 6g/10min, measure, and test condition is: temperature is 190 DEG C, and load is 2.16KG with GB/T3682-2000 method.Preferably, wherein the mass percentage of butyl acrylate is: 10 ~ 30%, with the total weight of ethylene-butyl acrylate copolymer.
Described high density polyethylene(HDPE) (HDPE) is known for those skilled in the art.
Contriver finds, adopts the cooperation of specific base resin and specific fire retardant, can reach good resistance to mud property and flame retardant properties simultaneously.
In a specific embodiment of the present invention, the median particle diameter of described magnesium hydroxide is 1.25 ~ 1.65 μm, and specific surface area is 4-6m
2/ g.
In a specific embodiment of the present invention, described coupling agent is vinyltriethoxysilane.
In a specific embodiment of the present invention, described compatilizer is the multipolymer of Ethylene-butyl acrylate grafted maleic anhydride.Can also contain the compatilizer of other types in described compatilizer, the weight content of the compatilizer of described other types is no more than 5% of compatilizer gross weight, can not produce limit goal of the invention of the present invention.
In a specific embodiment of the present invention, described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).
In a specific embodiment of the present invention, described crosslinking sensitizer is the one in triallyl isocyanurate (TAIC), trihydroxy methyl propane trimethyl acrylate.
In a specific embodiment of the present invention, described anti ultraviolet agent is one or both mixing in UV944, UV531.
In a specific embodiment of the present invention, described lubricant is silicone master batch, and in silicone master batch, the number-average molecular weight of siloxanes is 600,000 ~ 850,000.
Sheath material of the present invention can also contain other acceptable auxiliary agents, such as this area acceptable releasing agent, antiaging agent etc., only otherwise to goal of the invention of the present invention produces and limits.
A second aspect of the present invention provides a kind of preparation method of a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as described in the present invention, and described preparation method comprises the following steps:
Fire retardant, coupling agent, crosslinking sensitizer, anti ultraviolet agent are proportionally mixed to temperature to 70 DEG C ± 5 DEG C, discharging is placed, and with other components by proportioning extruding pelletization, obtains the described a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material.
Advantage
A kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material of the present invention and preparation method thereof tool has the following advantages:
1. the present invention adopts ethylene-butyl acrylate copolymer as a part for matrix resin, and compared with ethylene-vinyl acetate (EVA), be all ethylene copolymer, EBA has higher thermostability, resistance to deterioration.Better erosion resistance, oil-proofness, resistance to mud.
2. the present invention adopts high density polyethylene(HDPE) as a part for matrix resin, and high density polyethylene(HDPE) compares linear low density polyethylene, has better thermotolerance.High density polyethylene(HDPE) compares the high degree of crystallinity of linear low density polyethylene tool, makes material have better oil-proofness, solvent resistance.
3. the present invention adopts magnesium hydroxide as main fire retardant, meets the processing conditions of selected resin system, and fire retardant material is in combustion testing process, and become charcoal superior, material flame retardant rating meets the requirement of FV-0 level.
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight part, and all per-cent is weight percentage.
Embodiment 1
Each ingredient names and each composition weight number as follows:
The preparation method of foregoing invention, it comprises following processing step:
Fire retardant, coupling agent, crosslinking sensitizer, anti ultraviolet agent are proportionally mixed to temperature to 70 DEG C ± 5 DEG C, discharging is placed, with other components by proportioning extruding pelletization.
Carry out performance detection experiment to the product in embodiment 1, each performance value is as shown in PERFORMANCE EXAMPLES.
Embodiment 2
Each ingredient names and each composition weight number as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1
Carry out performance detection experiment to the product in embodiment 2, each performance value is as shown in PERFORMANCE EXAMPLES.
Embodiment 3.
Each ingredient names and each composition weight number as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 3, each performance value is as shown in PERFORMANCE EXAMPLES
Embodiment 4.
Each ingredient names and each composition weight number as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 4, each performance value is as shown in PERFORMANCE EXAMPLES
Embodiment 5.
Each ingredient names and each composition weight number as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 5, each performance value is as shown in PERFORMANCE EXAMPLES
PERFORMANCE EXAMPLES
Table 1 embodiment product performance test result
Conclusion:
As can be seen from above-mentioned PERFORMANCE EXAMPLES, sheath material of the present invention not only reaches the standard of three tests such as the test of the Sea of resistance to Carbo (oil base) drilling fluid, oil resistant test IRM903, the bittern of resistance to Calcium Bromide (water base) test, all has excellent performance in flame retardant resistance, mechanical property simultaneously.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. the cross-linking radiation low-smoke bittern-free highly fire-proof of a resistance to mud sheath material, wherein, each component of described sheath material and parts by weight as follows:
Described base resin comprises following component: ethylene-butyl acrylate copolymer, and high density polyethylene(HDPE) (HDPE) and both weight ratios are followed successively by (85 ~ 70): (15 ~ 30);
And described fire retardant is magnesium hydroxide.
2. a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as claimed in claim 1, is characterized in that,
The melting index of described ethylene-butyl acrylate copolymer is: 2 ~ 6g/10min, measure, and test condition is: temperature is 190 DEG C, and load is 2.16KG with GB/T3682-2000 method;
Wherein the mass percentage of butyl acrylate is: 10 ~ 30%, with the total weight of ethylene-butyl acrylate copolymer.
3. a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as claimed in claim 1, is characterized in that: the median particle diameter of described magnesium hydroxide is 1.25 ~ 1.65 μm, and specific surface area is 4-6m
2/ g.
4. a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as claimed in claim 1, is characterized in that: described coupling agent is vinyltriethoxysilane.
5. a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as claimed in claim 1, is characterized in that: described compatilizer is the multipolymer of Ethylene-butyl acrylate grafted maleic anhydride.
6. a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as claimed in claim 1, it is characterized in that: described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).
7. a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as claimed in claim 1, is characterized in that: described crosslinking sensitizer is the one in triallyl isocyanurate (TAIC), trihydroxy methyl propane trimethyl acrylate.
8. a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as claimed in claim 1, is characterized in that: described anti ultraviolet agent is one or both mixing in UV944, UV531.
9. a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material as claimed in claim 1, it is characterized in that: described lubricant is silicone master batch, in silicone master batch, the number-average molecular weight of siloxanes is 600,000 ~ 850,000.
10. a preparation method for a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of the resistance to mud sheath material as described in claim arbitrary in claim 1 ~ 9, is characterized in that: described preparation method comprises the following steps:
Fire retardant, coupling agent, crosslinking sensitizer, anti ultraviolet agent are proportionally mixed to temperature to 70 DEG C ± 5 DEG C, discharging is placed, and with other components by proportioning extruding pelletization, obtains the described a kind of cross-linking radiation low-smoke bittern-free highly fire-proof of resistance to mud sheath material.
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| CN201210593460.0A CN103030874B (en) | 2012-12-31 | 2012-12-31 | Irradiation crosslinking slurry-resistant, low-smoke, halogen-free and high-flame-retardant sheath material and fabrication method thereof |
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| CN201210593460.0A CN103030874B (en) | 2012-12-31 | 2012-12-31 | Irradiation crosslinking slurry-resistant, low-smoke, halogen-free and high-flame-retardant sheath material and fabrication method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108034121A (en) * | 2017-12-20 | 2018-05-15 | 苏州希普拉斯新材料有限公司 | Flame resistance irradiation is crosslinked low-smoke low-halogen polyolefine material |
| CN111117048A (en) * | 2019-12-24 | 2020-05-08 | 上海至正道化高分子材料股份有限公司 | Thermoplastic low-smoke halogen-free sheath material for third-generation nuclear power station cable and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105462052A (en) * | 2015-12-24 | 2016-04-06 | 上海至正道化高分子材料股份有限公司 | 125 DEG C irradiation crosslinking low-smoke halogen-free cable material for automotive wires and preparation method thereof |
| CN106928532A (en) * | 2015-12-29 | 2017-07-07 | 天津市普立泰高分子科技有限公司 | Thermoplastic low-smoke halide-free high fire-retardance polyolefin jacket material and preparation method thereof |
| CN112143088A (en) * | 2020-09-22 | 2020-12-29 | 重庆会通科技有限公司 | Permanent antistatic PE (polyethylene) breathable film composite material and preparation method thereof |
| CN113773596A (en) * | 2021-09-03 | 2021-12-10 | 会通新材料(上海)有限公司 | High-mechanical-property high-flame-retardant mud-resistant cable sheath material and preparation method thereof |
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| CN101914236A (en) * | 2010-08-19 | 2010-12-15 | 王进 | Irradiation crosslinking halogen-free high flame-retardant cable material and preparation method thereof |
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