Nuclear ship cable high flame resistance, low smoke Halogen protective cover material and preparation method thereofTechnical field
The present invention relates to fireproofing cable material without halide fields, and in particular to it is high to meet nuclear ship cable to one kindFlame-retardant low-smoke halogen-free protective cover material and preparation method thereof.
Background technique
As the safe operation of the rapid development that the naval weapon in China is equipped, ship cable is improved due to being directly related toThe fighting capacity on naval vessel and personnel safety problem and it is more aobvious important.
The advantage that nuclear power is big with its power, cruising ability is strong has big in the military boats and ships such as nuclear submarine, nuclear aircraft carrierThe application of amount.As the cable of nuclear ship inner main component, compared with naval vessel powered by conventional energy, use environment is more dislikedIt is bad, partial cables be laid in high temperature and humidity, laying environment in, and in nuclear power unit equipment regular starting, become functionRate or vibration can make junction poor contact good, and the cable of junction is caused to be easy aging.Such installation environment, it is desirable that electricityCable can high-temp resisting high-humidity resisting, radiation hardness, oil resistant, service life that is fire-retardant and can at least reaching 40 years, the performance of cable is wantedAsk higher.Also to material, more stringent requirements are proposed for this, and common cable for ship material is difficult to meet these requirements.
Ship cable material currently on the market, on hypotoxicity, radiation hardness, high temperature high voltage resistant performance and used life orIt is more or it is few have the defects that certain, therefore, there is an urgent need in the art to provide a kind of nuclear ship cable met the requirementsSheath material.
Therefore, there is an urgent need in the art to provide with excellent high temperature and humidity resistance, hypotoxicity, radiation hardness, Yi JimanThe nuclear ship cable sheath material and preparation method thereof that 90 degree of 40 years service life of foot requires.
Summary of the invention
The present invention is intended to provide one kind meets nuclear ship cable high flame resistance, low smoke Halogen protective cover material.
The second object of the present invention is that providing one kind meets nuclear ship cable high flame resistance, low smoke Halogen protective cover materialPreparation method.
In the first aspect of the present invention, a kind of nuclear ship cable high flame resistance, low smoke Halogen protective cover material combination is providedObject comprising each component it is as follows in parts by weight:
In another preferred example, the vinyl-acrylate copolymer is selected from following one or more: ethylene-Methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) and ethylene butyl acrylate copolymer (EBA)；
The polyester elastomer is the block copolymer of polybutylene terephthalate (PBT) hard section and polyester soft segment, described poly-The fusing point of ester elastomer is not higher than 190 DEG C；
The nylon elastomer is polyamide and polyether block copolymer, and the fusing point of the nylon elastomer is not higher than 190℃；
The polyethylene is selected from hp-ldpe, linear low density polyethylene or high density polyethylene (HDPE)；
The weight ratio of the polyester elastomer and nylon elastomer is (1-2): (1-2).
In another preferred example, the compatilizer is following one or more: vinyl-acrylate copolymer connectsBranch maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride and PE grafted maleic anhydride.
In another preferred example, the fire retardant is the combination of magnesium hydroxide, zinc borate and antimony oxide；The combinationWeight ratio be
120-150 parts of magnesium hydroxide；
15-25 parts of zinc borate；
15-25 parts of antimony oxide.
In another preferred example, the fire retarding synergist be selected from ammonium octamolybdate, zinc stannate, hexaphenoxycyclotriphosphazene,Melamine polyphosphate (MPP) or triazines carbon forming agent.
In another preferred example, the radiation hardness auxiliary agent is the combination of inorganic radiation hardness auxiliary agent and UV stabilizer；It is described resistance toThe weight ratio for radiating the inorganic radiation hardness auxiliary agent of auxiliary agent and UV stabilizer is (3-5): 1.
In another preferred example, antioxidant is Hinered phenols antioxidant, sulfur type antioxidant and phosphite ester antioxidantCombination；The combined weight ratio is
2-4 parts of Hinered phenols antioxidant；
2-4 parts of sulfur type antioxidant；
1 part of phosphite ester antioxidant.
In another preferred example, the processing aid be selected from following one or more: polyethylene wax, microcrystalline wax,Zinc stearate and silicone master batch；
The assistant crosslinking agent is selected from following one or more: triallyl hydroxyurea acid esters (TAC), triallyl isocyanideUrea acid esters (TAIC), trihydroxy methyl propane trimethyl acrylate (TMPTMA) and more vinyl polysiloxanes.
In the second aspect of the present invention, it is high to provide a kind of nuclear ship cable provided present invention as described aboveProtective cover material obtained by flame-retardant low-smoke halogen-free sheath feed composition.
In the third aspect of the present invention, it is high to provide a kind of nuclear ship cable provided present invention as described aboveThe preparation method of flame-retardant low-smoke halogen-free protective cover material, described method includes following steps:
By vinyl-acrylate copolymer, polyester elastomer, nylon elastomer, polyethylene, compatilizer, fire retardant, fire-retardantThe nuclear ship provided by the invention of synergist, radiation hardness auxiliary agent, antioxidant, processing aid and assistant crosslinking agent as described aboveAfter cable is mixed with high flame resistance, low smoke Halogen protective cover material composition ratio, using double-screw extruding pelletizing machine extruding pelletization, obtainThe nuclear ship cable high flame resistance, low smoke Halogen protective cover material provided present invention as described above.
Accordingly, nuclear ship provided by the invention has excellent high temperature and humidity resistance, low with cable sheath materialToxicity, radiation hardness, and meet the requirement of 90 degree 40 years service lifes, solve those skilled in the art's serious hope for a long time butThe technical problem for the nuclear ship cable sheath material that do not capture always.
Specific embodiment
The present inventor after extensive and in-depth study, uses vinyl-acrylate copolymer, polyester elastomer, nylonElastomer and polyethylene are as resin formula, while the radiation hardness auxiliary agent formed using inorganic radiation hardness auxiliary agent and UV stabilizer,It obtains one kind and meets nuclear ship cable high flame resistance, low smoke Halogen protective cover material and preparation method thereof, can satisfy 90 degree 40The service life requirement in year.The present invention is completed on this basis.
In the present invention, term " containing " or " comprising " indicate that various composition can be applied to mixture or group of the invention togetherIt closes in object.Therefore, term " mainly by ... form " and " consist of " are included in term " containing " or " comprising ".
It is described in detail to various aspects of the present invention below:
Nuclear ship cable high flame resistance, low smoke Halogen sheath feed composition
In the first aspect of the present invention, a kind of nuclear ship cable high flame resistance, low smoke Halogen protective cover material combination is providedObject, each component are as follows in parts by weight:
In one embodiment of the invention, the vinyl-acrylate copolymer is ethylene-methyl acrylate copolymerizationObject (EMA), ethylene-ethyl acrylate copolymer (EEA), one of ethylene butyl acrylate copolymer (EBA) or any twoKind or more mixing；With the total weight of copolymer, the content of corresponding acrylate is 25-40%.
In one embodiment of the invention, the polyester elastomer be polybutylene terephthalate (PBT) hard section andThe fusing point of the block copolymer of polyester soft segment, the polyester elastomer is not higher than 190 DEG C.
In one embodiment of the invention, the nylon elastomer be polyamide and polyether block copolymer, it is describedThe fusing point of nylon elastomer is not higher than 190 DEG C.
In a kind of specific embodiment of the invention, the weight ratio of the polyester elastomer and nylon elastomer is (1-2): (1-2).
In one embodiment of the invention, the polyethylene is hp-ldpe, linear low density polyethyleneThe finger that melts of any one in alkene, high density polyethylene (HDPE), the polyethylene is 0.5-4g/10min, with GB/T 3682-2000 methodMeasurement.
In one embodiment of the invention, selected fire retardant be magnesium hydroxide, antimony oxide, zinc borate orA combination thereof；
Preferably, selected fire retardant is the combination of magnesium hydroxide, zinc borate, antimony oxide；And the combinationWeight ratio is
120-150 parts of magnesium hydroxide
15-25 parts of zinc borate
15-25 parts of antimony oxide.
In one embodiment of the invention, the retardant synergist is ammonium octamolybdate, zinc stannate, six phenoxy group rings threePhosphonitrile, melamine polyphosphate (MPP), any one in triazines carbon forming agent.
In one embodiment of the invention, the radiation hardness auxiliary agent is the group of inorganic radiation hardness auxiliary agent and UV stabilizerIt closes.
In a kind of specific embodiment of the invention, the weight ratio of the inorganic radiation hardness auxiliary agent and UV stabilizer is(3-5): 1.
In a preferred example, the inorganic radiation hardness auxiliary agent is at least one of barium sulfate, boron carbide, boron nitride；InstituteStating UV stabilizer is 2'- (2'- hydroxyl -3'- tert-butyl -5'- methyl) chloro- benzotriazole of -5- (UV326), N, N '-is bis--(2,2,6,6- tetramethyl -4- piperidyl) -1,6- hexamethylene diamine and the chloro- 1,3,5- triazine of 2,4,6- tri- polymer and 1,1,3,3- tetramethylThe reaction product (UV944) of base butylamine, dimethyl succinate polymerize with 4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine ethanolAny one in the double -2,2,6,6- tetramethyl piperidine alcohol esters (UV770) of object (UV622), decanedioic acid.
In one embodiment of the invention, the antioxidant is by Hinered phenols antioxidant, sulfur type antioxidant and AsiaPhosphoric acid ester antioxidant composition；
It is furthermore preferred that the weight ratio of above-mentioned Hinered phenols antioxidant, sulfur type antioxidant and phosphite ester antioxidant combinationExample be
2-4 parts of Hinered phenols antioxidant；
2-4 parts of sulfur type antioxidant；
1 part of phosphite ester antioxidant.
In a kind of specific embodiment of the invention, the Hinered phenols antioxidant is selected from β-(3,5- di-t-butyl -4-Hydroxy phenyl) propionic acid n-octadecane base alcohol ester (antioxidant 1076), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasonsDoutrate (antioxidant 1010), N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidantOr isocyanuric acid three (4- tert-butyl -3- hydroxyl -2,6- xylyl) ester (antioxidant 1790) 1098).
In a kind of specific embodiment of the invention, the sulfur type antioxidant is selected from the double lauryls of thio-2 acid(DLTP), distearyl thiodipropionate (DSTP), β-dodecyl propane thioic acid pentaerythritol ester (412S) or 2- mercaptanBase benzimidazole zinc (antioxidant MB Z).
In a kind of specific embodiment of the invention, the phosphite antioxidant is three [2.4- DI-tert-butylphenol compounds]Phosphite ester (irgasfos 168).
In one embodiment of the invention, the compatilizer be vinyl-acrylate copolymer grafted maleic anhydride,At least one of ethylene-vinyl acetate copolymer grafted maleic anhydride and PE grafted maleic anhydride；Wherein maleic anhydride connectsBranch rate is 0.5-5%.
In one embodiment of the invention, selected processing aid is polyethylene wax, microcrystalline wax, stearic acidZinc, one kind of silicone master batch or any two or more mixture；And/or
The assistant crosslinking agent is triallyl hydroxyurea acid esters (TAC), Triallyl isocyanurate (TAIC), trimethyl thirdOne of olefin(e) acid trihydroxymethylpropanyl ester (TMPTMA), more vinyl polysiloxanes or any two or more mixing.
Preparation method
It is of the invention that a kind of nuclear ship cable high flame resistance, low smoke Halogen protective cover material of the present invention is also providedPreparation method includes the following steps:
By vinyl-acrylate copolymer, polyester elastomer, nylon elastomer, polyethylene, compatilizer, fire retardant, fire-retardantSynergist, radiation hardness auxiliary agent, antioxidant, processing aid and assistant crosslinking agent etc. are mixed according to formula, then carry out mixing, closeBulk material after refining uses double-screw extruding pelletizing machine extruding pelletization, obtains masterbatch.
It in a specific embodiment, will be by vinyl-acrylate copolymer, polyester elastomer, nylon elastomer, poly-Ethylene, compatilizer, fire retardant, retardant synergist, radiation hardness auxiliary agent, antioxidant, processing aid and assistant crosslinking agent etc. in proportion intoIt after row ingredient, is put into high-speed mixer, is stirred at room temperature 3-5 minutes, is mixed evenly, it is close that mixer progress is then addedDouble-screw extruding pelletizing is added by bipyramid forced feed machine in bulk material after mixing by refining.
In the specific embodiment of the present invention, screw zones temperature are as follows: 200-190 DEG C of feeding section, conveying section190-180 DEG C, 180-170 DEG C of melt zone, 180-170 DEG C of head.
Purposes
The present invention provides a kind of nuclear ship cable high flame resistance, low smoke Halogen sheath feed composition of the present inventionObtained protective cover material；The nuclear ship cable high flame resistance, low smoke Halogen sheath being prepared by the protective cover material is also provided.
The method that this field routine can be used obtains sheath, such as, but not limited to, squeezes to protective cover material provided by the inventionSheath and cross-linking radiation out.
Advantage
1, the present invention is using preparations such as vinyl-acrylate copolymer, polyester elastomer, nylon elastomer, polyethyleneProtective cover material processing technology is simple, and crowded linear velocity is very fast, and equipment investment is lower, and comprehensive cost performance is superior.
2, protective cover material of the invention has excellent high temperature high voltage resistant performance, radiation resistance, oil resistance, anti-flammabilityEnergy and comprehensive mechanical performance.
3, for sheath made of protective cover material of the invention after cross-linking radiation, properties are superior, can satisfy IEEE383With the correlated performance requirement in GJB 1916-94 to nuclear ship.
Unless specific instructions, various raw materials of the invention can be by being commercially available；Or the routine side according to this fieldMethod is prepared.Unless otherwise defined or described herein, all professional and scientific terms and art technology used herein are ripeIt is identical to practice meaning known to personnel.Furthermore any method similar to or equal to what is recorded and material all can be applied to thisIn inventive method.
Other aspects of the present invention are apparent to those skilled in the art due to this disclosure's.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present inventionRather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually marks according to countryQuasi- measurement.If being built without corresponding national standard according to general international standard, normal condition or according to manufacturerThe condition of view carries out.Unless otherwise stated, otherwise all number is parts by weight, and all percentage is weight percentage, instituteThe polymer molecular weight stated is number-average molecular weight.
Unless otherwise defined or described herein, all professional and scientific terms used herein and the skilled people of art technologyMeaning known to member is identical.Furthermore any method similar to or equal to what is recorded and material all can be applied to the present inventionIn method.
Below in conjunction with specific embodiment, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate the present inventionRather than it limits the scope of the invention.
Following related products performance test methods are as follows:
(1) tensile property is tested:
According to GB/T 1040-2008 standard testing tensile property；
(2) oxygen index (OI) is tested:
According to GB/T 2406.1-2008 standard testing flame retardant property；
(3) smoke density is tested
According to GB/T 17651.2-1998 standard testing smoke density performance；
(4) Thermal life evaluation is tested
The long-term thermal life of material is evaluated according to GB/T 11026-2016；
(5) hot elongation test
According to the heat extensibility energy of GB/T 2951.21-2008 Standards for Testing Materials.
(6) oil resistance
According to GB/T 2951.21-2008 standard testing oil resistance.
(7) radiation resistance
According to the chronic exposure ageing properties of IEC 61244:2014 standard material；
(8) high temperature high voltage resistant performance
According to the high temperature high voltage resistant performance of GB/T 22577-2008 standard material.
Embodiment 1
The each component title and each component parts by weight of formula are as shown in table 1:
Table 1
| Title | Weight/kg | Title | Weight/kg |
| EBA | 30 | Barium sulfate | 8 |
| Polyester elastomer | 20 | UV770 | 2 |
| Nylon elastomer | 20 | Antioxidant 1010 | 1 |
| LDPE | 15 | Anti-oxidant DLTP | 1 |
| EBA grafted maleic anhydride | 15 | Irgasfos 168 | 0.4 |
| Magnesium hydroxide | 120 | PE wax | 0.5 |
| Antimony oxide | 25 | Silicone master batch | 1.5 |
| Zinc borate | 25 | TAIC | 2 |
| Zinc stannate | 15 | | |
Preparation method: by vinyl-acrylate copolymer, polyester elastomer, nylon elastomer, polyethylene, compatilizer, resistanceAfter combustion agent, retardant synergist, radiation hardness auxiliary agent, antioxidant, processing aid and assistant crosslinking agent etc. carry out ingredient in proportion, it is put into heightIt in fast mixing machine, is stirred at room temperature 3-5 minutes, is mixed evenly, mixer is then added and carries out mixing, by the bulk after mixingDouble-screw extruding pelletizing, screw zones temperature is added by bipyramid forced feed machine in material are as follows: and 200-190 DEG C of feeding section, conveying section190-180 DEG C, 180-170 DEG C of melt zone, 180-170 DEG C of head.
After squeezing out sheath and cross-linking radiation to the protective cover material in embodiment 1, performance detection test is carried out, each performance value is such asShown in table 10.
Embodiment 2
The each component title and each component parts by weight of formula are as shown in table 2:
Table 2
Preparation method is same as Example 1.
By obtaining the product in embodiment 2 with method identical in embodiment, and performance detection test is carried out, each performanceNumerical value is as shown in table 10.
Embodiment 3
The each component title and each component parts by weight of formula are as shown in table 3:
Table 3
| Title | Weight/kg | Title | Weight/kg |
| EEA | 30 | Boron nitride | 7 |
| Polyester elastomer | 30 | UV944 | 1.5 |
| Nylon elastomer | 15 | Antioxidant 1098 | 0.9 |
| LLDPE | 15 | Antioxidant DSTP | 0.9 |
| EVA grafted maleic anhydride | 10 | Irgasfos 168 | 0.3 |
| Magnesium hydroxide | 130 | PE wax | 0.5 |
| Antimony oxide | 15 | Silicone master batch | 1.5 |
| Zinc borate | 25 | TAIC | 2 |
| Ammonium octamolybdate | 10 | | |
Preparation method is same as Example 1.
By obtaining the product in embodiment 3 with method identical in embodiment, and performance detection test is carried out, each performanceNumerical value is as shown in table 10.
Embodiment 4
The each component title and each component parts by weight of formula are as shown in table 4:
Table 4
| Title | Weight/kg | Title | Weight/kg |
| EEA | 35 | Boron nitride | 7 |
| Polyester elastomer | 15 | UV944 | 1.5 |
| Nylon elastomer | 30 | Antioxidant 1098 | 0.9 |
| LLDPE | 10 | Antioxidant DSTP | 0.9 |
| EVA grafted maleic anhydride | 10 | Irgasfos 168 | 0.3 |
| Magnesium hydroxide | 140 | PE wax | 0.5 |
| Antimony oxide | 25 | Silicone master batch | 1.5 |
| Zinc borate | 15 | TMPTMA | 2 |
| Ammonium octamolybdate | 10 | | |
Preparation method is same as Example 1.
By obtaining the product in embodiment 4 with method identical in embodiment, and performance detection test is carried out, each performanceNumerical value is as shown in table 10.
Embodiment 5
The each component title and each component parts by weight of formula are as shown in table 5:
Table 5
| Title | Weight/kg | Title | Weight/kg |
| EMA | 45 | Boron nitride | 8 |
| Polyester elastomer | 20 | UV622 | 2 |
| Nylon elastomer | 15 | Antioxidant 1790 | 1 |
| HDPE | 15 | Antioxidant 412S | 1 |
| PE grafted maleic anhydride | 5 | Irgasfos 168 | 0.3 |
| Magnesium hydroxide | 130 | PE wax | 0.5 |
| Antimony oxide | 15 | Silicone master batch | 1.5 |
| Zinc borate | 15 | TMPTMA | 2 |
| Triazines carbon forming agent | 20 | | |
Preparation method is same as Example 1.
By obtaining the product in embodiment 5 with method identical in embodiment, and performance detection test is carried out, each performanceNumerical value is as shown in table 10.
Embodiment 6
The each component title and each component parts by weight of formula are as shown in table 6:
Table 6
| Title | Weight/kg | Title | Weight/kg |
| EMA | 40 | Boron nitride | 6 |
| Polyester elastomer | 30 | UV622 | 1.6 |
| Nylon elastomer | 10 | Antioxidant 1790 | 1 |
| HDPE | 10 | Antioxidant 412S | 1 |
| PE grafted maleic anhydride | 10 | Irgasfos 168 | 0.3 |
| Magnesium hydroxide | 150 | PE wax | 0.5 |
| Antimony oxide | 25 | Silicone master batch | 1.5 |
| Zinc borate | 15 | TMPTMA | 2 |
| Triazines carbon forming agent | 15 | | |
Preparation method is same as Example 1.
By obtaining the product in embodiment 6 with method identical in embodiment, and performance detection test is carried out, each performanceNumerical value is as shown in table 10.
Comparative example 1
The each component title and each component parts by weight of formula are as shown in table 7:
Table 7
Preparation method is same as Example 1.
By obtaining the product in comparative example 1 with method identical in embodiment, and performance detection test is carried out, each performanceNumerical value is as shown in table 11.
Comparative example 2
The each component title and each component parts by weight of formula are as shown in table 8:
Table 8
| Title | Weight/kg | Title | Weight/kg |
| EVA | 70 | UV622 | 2 |
| HDPE | 15 | Antioxidant 1790 | 1 |
| PE grafted maleic anhydride | 15 | Antioxidant 412S | 1 |
| Magnesium hydroxide | 150 | Irgasfos 168 | 0.3 |
| Antimony oxide | 20 | PE wax | 0.5 |
| Zinc borate | 20 | Silicone master batch | 1.5 |
| Triazines carbon forming agent | 15 | TMPTMA | 2 |
| Boron nitride | 8 | | |
Preparation method is same as Example 1.
By obtaining the product in comparative example 2 with method identical in embodiment, and performance detection test is carried out, each performanceNumerical value is as shown in table 11.
Comparative example 3
The each component title and each component parts by weight of formula are as shown in table 9:
Table 9
Preparation method is same as Example 1.
By obtaining the product in comparative example 3 with method identical in embodiment, and performance detection test is carried out, each performanceNumerical value is as shown in table 11.
The performance test results of embodiment 1-6 are as shown in table 10:
Table 10
The performance test results of comparative example 1-3 are as shown in table 11:
Table 11
The result shows that nuclear ship cable provided by the invention is excellent with the properties of high flame resistance, low smoke Halogen protective cover materialIt is different, it can satisfy high temperature high voltage resistant, radiation hardness, oil resistant, flame-retardancy requirements in nuclear ship index；Heat aging property is good,It can satisfy the life requirements of at least 40 years (90 degree)；Low-smoke non-halogen flame-retardant, good mechanical property.The processing performance of resulting materials is excellentIt is different, it is processed into the surface-brightening of cable, can quickly be squeezed out, high production efficiency, can be used for nuclear power military boats and ships cable cover(ing),It has broad application prospects.
The foregoing is merely illustrative of the preferred embodiments of the present invention, the substantial technological content model being not intended to limit the inventionIt encloses, substantial technological content of the invention is broadly defined in the scope of the claims of application, any technology that other people completeEntity or method also or a kind of equivalent change, will if identical with defined in the scope of the claims of applicationIt is considered as being covered by among the scope of the claims.
All references mentioned in the present invention is incorporated herein by reference, independent just as each documentIt is incorporated as with reference to such.In addition, it should also be understood that, those skilled in the art can be right after having read above content of the inventionThe present invention makes various changes or modifications, and these equivalent forms also fall within the scope of the appended claims of the present application.