CN105175905A - Preparation method of tear-resistant halogen-free flame retardant polymer cover insulating material for cables - Google Patents
Preparation method of tear-resistant halogen-free flame retardant polymer cover insulating material for cables Download PDFInfo
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- CN105175905A CN105175905A CN201510569496.9A CN201510569496A CN105175905A CN 105175905 A CN105175905 A CN 105175905A CN 201510569496 A CN201510569496 A CN 201510569496A CN 105175905 A CN105175905 A CN 105175905A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08L2203/00—Applications
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- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
The invention discloses a preparation method of a tear-resistant halogen-free flame retardant polymer cover insulating material for cables. The material is mainly prepared from the following raw materials according to the weight: 100 to 200g of ethylene-propylene-diene monomer rubber, 5 to 50g of thermoplastic elastomer, 100 to 250g of medium density polyethylene (PE), 100 to 150g of ethylene-vinyl acetate copolymer (EVA), 10 to 50g of compatilizer, 145 to 265g of aluminium hydroxide, 145 to 265g of magnesium hydrate, 1 to 3g of complex antioxidant, 10 to 20g of fumed silica, and 1 to 3g of polysiloxane master batch. The tear-resistant halogen-free flame retardant polymer cover insulating material has a tear-resistant performance and excellent mechanical property and weatherability. The preparation method comprises the following steps of weighing ingredients according to the formula to obtain a mixture; melt blending through an internal mixer at the temperature of 160 to 175 DEG C for 15 to 25min, and then pelleting through an extruder; extruding particles through an extruder to extrude wires; irradiating through an electron accelcrator to enable a polymer to be subjected to crosslinking modification, and obtaining the tear-resistant halogen-free flame retardant polymer cover insulating material for the cables, wherein the tearing strength of the tear-resistant halogen-free flame retardant polymer cover insulating material achieves more than 15.2KN/m.
Description
Technical field
The present invention, by a kind of new processing method of cable anti tear Halogenless fire retarded polymer sheath insulation material, belongs to Technology field prepared by functionalized macromolecular flame-proof composite material.
Background technology
Low smoke no-halogen wire cable is not only a large amount of for space flight war products, and commercial boats, important ground job facilities and covil construction, electronic apparatus, computer etc. are also widely applying low smoke and zero halogen wire product.The popularization of safety product and electronic peripheral product runs into very large resistance, and its major cause is that composite flame-proof material technology is immature, and when extruding cable, Drawing abillity can affect product performance, mainly embodies a concentrated reflection of the following aspects:
1. fire-retardant problem
Macromolecular material fire-retardant not only relevant with itself flame-retarding characteristic, and relevant with its shape and structure.The flame resistivity of thin electric wire usually can not reach the requirement of relevant criterion, as electric wire, the supply lead of the standards such as U.S.'s rule, Europe rule, sundial, the external diameter of these wire rods is less, usually at below 10mm, but flame-retardancy requirements is very high, VW-1 or single vertical combustion testing be passed through; And it is poor to there is mechanical and physical performance problem; Halide-free smokeless CABLE MATERIALS has very high filling usually, environmental stress crack resistance ability is poor, and the softening temperature of adding material is not high, when being used in open air, under the acting in conjunction of the various unfavorable factors such as uviolizing, hot environment, internal stress, moving and be more easily torn in use procedure.
2. contour machining procedure problem
The contour machining procedure of halide-free smokeless CABLE MATERIALS, although effectively solve in production unit and production technique; But very high for flame-retardancy requirements, as U.S. rule electric wire, supply lead, charger for mobile phone line, earphone cord, computer peripheral line etc., the forming process of these thin electric wires is more difficult than cable, optical cable etc. a lot; Will produce these products smoothly, not only Halogen production technique needs to improve, and also needs to add the auxiliary agent improving flow processability energy in the material.
3. Cost Problems
Due to the impact by factors such as starting material prior art and the monopolizations of external large producer, the material cost of high-quality halide-free smokeless anti tear CABLE MATERIALS exceeds much than existing market common product.
And medium-density polyethylene (MDPE) is a kind of polyethylene just found broad application in recent years, its performance between high density polyethylene(HDPE) (HDPE) and Low Density Polyethylene (LDPE) between the two, both the rigidity of HDPE had been maintained, there are again the flexibility of LDPE, creep resistant, integrate both advantages, have overwhelming superiority in manufacture gas-distribution pipe, water distributing pipe, communication and cable sheath, thus more and more pay close attention to by market.Special performance establishes market position: MDPE because of its good environmental stress crack resistance, weldability and long service life etc., application development is rapid in recent years, consumption increase is very fast, and MDPE is considered at present the most suitable sheath material of communication cable in the world, optical fiber cable.In order to obtain special property material, the material that usually also will add resistance to tearing good carrys out modification. and white carbon black, as the strengthening agent of a kind of environmental protection, excellent performance and flame retardant, is mainly used in the fields such as rubber item, weaving, coating, plastics.Thermal silica is one of ultra tiny New Inorganic Materials of extremely important high-tech, because its particle diameter is very little, specific surface area is large, superficial attractive forces is strong, surface energy is large, and the aspects such as chemical purity is high, dispersing property good, thermal resistance, resistance have special performance, with its superior stability, reinforcing, thickening property and thixotropy, show unique characteristics in numerous subject and field, have the effect do not replaced.Thermal silica is the main resistance to tearing filler of MDPE, MDPE is filled after adopting different types of white carbon black modified by silane coupling agent, add the additive with a fixed structure and participate in cross-linking radiation process as Concentrative crosslinking agent, wherein additive is mainly polysiloxane, this can be avoided silicone oil, the spilling of paraffin wet goods small molecules lubricant and cause material property bad.The anti tear enhanced mechanism of MDPE can be explained by appropriate Concentrative crosslinking theory.Add elasticator and MDPE is blended, again by the process of electron beam irradiation MDPE, thus form stronger cross-linked network structure, and chemical action can be produced with the active site of inorganic nano-particle sub-surface, stronger supplementary function is had to network, tear stress in process can be evenly spread on the molecule of surrounding rapidly by cross-linking set, thus avoid stress concentration, make tear strength obtain larger raising.
The radiation modification of polymer composite is that radiation chemistry is applied to field of new, and obtains an aspect of very fast development.At present, the industry of polymer radiation processing is flourish in countries in the world, becomes an emerging high-tech industry, the preparation of radiation cross-link wire cable, heat-shrinkage material, organic PTC (positive temperature coefficient) material, foam materials etc.; The technology such as the radiation vulanization of radio polymerization, radiation degradation, radiation grafting, rubber and radiation coating solidification have developed into large-scale industry all.And many new engineering plastics, the preparation of matrix material etc. all realizes by the method for radiation crosslinking.Polymer materials is after radiation crosslinking, certain cross-linking set is formed between polymer macromolecule, thus the molecular weight of polymkeric substance is improved, and form a kind of molecule of tridimensional network, the physical properties of polymkeric substance is had an impact, this can improve the interface compatibility of fire retardant in polyolefine, the interaction of both raisings, in combustion, more easily forms layer of charcoal simultaneously, the oxygen in combustion processes and heat exchange can be completely cut off, well play solid phase fire retardation.Obtain the polymer composite of flame retardant properties and mechanical property excellence, there is very excellent processing characteristics simultaneously.Can be used for manufacturing various irradiation electric wire, thermal contraction cable sheath etc.Solve in halide-free low-smoke fireproof cable material technical barriers such as causing cable easily to be torn because adding a large amount of inorganic combustion inhibitor, thermal contraction is large, the insulation resistance that makes moist significantly reduces.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cable anti tear Halogenless fire retarded polymer sheath insulation material, and improved the performances such as fire-retardant, the physical mechanical of material by electron beam irradiation.The preparation method of a kind of cable anti tear of the present invention Halogenless fire retarded polymer sheath insulation material, is characterized in that having following process and step:
A. material component formula is determined;
Terpolymer EP rubber (EPDM) 100-200 gram; Thermoplastic elastomer 5-50 gram; Medium-density polyethylene (MDPE) 100-250 gram; Ethylene-vinyl acetate copolymer (EVA) 100-150 gram; Compatilizer-acrylic ester grafted polyethylene 10-50 gram; Aluminium hydroxide 145-265 gram; Magnesium hydroxide 145-265 gram, composite antioxidant 1-3 gram; Polysiloxane master batch 1-3 gram; Thermal silica 10-20 gram;
B. admixtion is obtained by above-mentioned formula weigh batching;
C. by Banbury mixer melt blending, temperature is 160 ~ 175 ° of C, and the time is 15 ~ 25 minutes, then by forcing machine granulation;
D. particle is extruded wire rod by forcing machine;
E. carry out cross-linking radiation through rumbatron, beam energy is 1.5MeV to 3MeV, obtains cable anti tear Halogenless fire retarded polymer sheath insulation material, and irradiation dose is 200-250 kilogray (kGy) (kGy).
The advantage of the inventive method is that technique is simple, easy to operate, reaction efficiency is high, required time is shorter; And have excellent tear resistance, electric property, heat aging property are excellent, oil resistance, wet-hot aging performance are excellent, halide-free smokeless low toxicity and flame retardant properties is good, the plurality of advantages of long service life.Tearing toughness reaches more than 15.2KN/m.Now by specific embodiments of the invention describe as after.
Example one
Process and the step of this example are as follows:
A. in the present embodiment, first prepare burden by the weight demands of desired substance, each material allocation amount is as follows: terpolymer EP rubber (EPDM) 100 grams; Thermoplastic elastomer (TPE): 50 grams; Medium-density polyethylene: 100 grams; Ethylene-vinyl acetate copolymer: 100 grams; Compatilizer (acrylic ester grafted polyethylene): 10 grams; Magnesium hydroxide 200 grams; 200 grams, aluminium hydroxide; Thermal silica 15 grams; Polysiloxane master batch: 2 grams, composite antioxidant: 2 grams.
Described terpolymer EP rubber (EPDM) ethylene, propylene segment mol ratio is 60:40, Third monomer is ethylidene bornylene, and the mass percent that Third monomer accounts for the total mass of three kinds of monomers is 3%, and number-average molecular weight is 150,000,100 ° of C mooney viscosities are 50Pas, and Shore A hardness is 40.Described thermoplastic elastomer (TPE) is ethylene-propylene copolymer, number-average molecular weight 150,000, and 100 ° of C mooney viscosities are 50Pas, and Shore A hardness is 60,190.。Be 5g/10min with the melting index under 2.16kg;
Melting index under described medium-density polyethylene alkene number-average molecular weight 80,000,190 ° of C and 2.16kg is 2-5g/10min;
The vinyl acetate content of described ethylene-vinyl acetate copolymer is 50wt%, and the melting index under 190 ° of C and 2.16kg is 5g/10min;
Described compatilizer is acrylic ester grafted polycthylene grafted polyethylene, and percentage of grafting is that under 2%, 190 ° of C and 2.16kg, melting index is 2g/10min;
Described aluminium hydroxide adopts aminosilane to carry out modification, and its particle diameter D50 is 2 microns, order number 5000 order;
Described polysiloxane master batch is made up of by weight following component: medium-density polyethylene: 10 grams, polysiloxane: 45 grams, thermal silica: 15 grams;
Described siloxanes is methyl vinyl silicone, number-average molecular weight 600,000.Described thermal silica, order number 5000 order.
Described composite antioxidant is made up of by weight following component: antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester): 50 grams, oxidation inhibitor 1024(N, N '-bis-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine): 50 grams
B. admixtion is obtained by above-mentioned formula weigh batching;
C. by Banbury mixer melt blending, temperature is 160 ~ 175 ° of C, and the time is 15 ~ 25 minutes, then by forcing machine granulation;
D. particle is extruded wire rod by forcing machine;
E. carry out cross-linking radiation through rumbatron, beam energy is 1.5MeV to 3MeV, obtains cable anti tear Halogenless fire retarded polymer sheath insulation material; Irradiation dose is 200-250 kilogray (kGy) (kGy).Its performance is as shown in table 1.
Claims (1)
1. a cable preparation method for anti tear Halogenless fire retarded polymer sheath insulation material, is characterized in that having following process and step:
A. material component formula is determined;
Terpolymer EP rubber (EPDM) 100-200 gram; Thermoplastic elastomer 5-50 gram; Medium-density polyethylene (MDPE) 100-250 gram; Ethylene-vinyl acetate copolymer (EVA) 100-150 gram; Compatilizer-acrylic ester grafted polyethylene 10-50 gram; Aluminium hydroxide 145-265 gram; Magnesium hydroxide 145-265 gram; Composite antioxidant 1-3 gram; Silicone master batch 1-3 gram; Thermal silica 10-20 gram;
B. admixtion is obtained by above-mentioned formula weigh batching;
C. by Banbury mixer melt blending, temperature is 160 ~ 175 ° of C, and the time is 15 ~ 25 minutes, then by forcing machine granulation;
D. particle is extruded wire rod by forcing machine;
E. carry out cross-linking radiation through rumbatron, obtain cable anti tear Halogenless fire retarded polymer sheath insulation material, irradiation dose is 200-250 kilogray (kGy) (kGy).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105513715A (en) * | 2015-12-31 | 2016-04-20 | 天长市富信电子有限公司 | Production process of low-smoke flame-retardant power line |
| CN105632595A (en) * | 2015-12-31 | 2016-06-01 | 天长市富信电子有限公司 | Production technology of fire-resistant power cable |
| CN107556602A (en) * | 2017-09-20 | 2018-01-09 | 无锡市永兴金属软管有限公司 | A kind of compound materials of halogen free flame retardant cable sheath and preparation method thereof |
| CN109825093A (en) * | 2019-03-12 | 2019-05-31 | 湖南七纬科技有限公司 | A kind of fire retardant insulating cable material and preparation method thereof |
-
2015
- 2015-09-10 CN CN201510569496.9A patent/CN105175905A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105513715A (en) * | 2015-12-31 | 2016-04-20 | 天长市富信电子有限公司 | Production process of low-smoke flame-retardant power line |
| CN105632595A (en) * | 2015-12-31 | 2016-06-01 | 天长市富信电子有限公司 | Production technology of fire-resistant power cable |
| CN107556602A (en) * | 2017-09-20 | 2018-01-09 | 无锡市永兴金属软管有限公司 | A kind of compound materials of halogen free flame retardant cable sheath and preparation method thereof |
| CN109825093A (en) * | 2019-03-12 | 2019-05-31 | 湖南七纬科技有限公司 | A kind of fire retardant insulating cable material and preparation method thereof |
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Application publication date: 20151223 |