CN110903539B - Ultraviolet irradiation low-smoke halogen-free material for optical cable - Google Patents

Ultraviolet irradiation low-smoke halogen-free material for optical cable Download PDF

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CN110903539B
CN110903539B CN201911231356.5A CN201911231356A CN110903539B CN 110903539 B CN110903539 B CN 110903539B CN 201911231356 A CN201911231356 A CN 201911231356A CN 110903539 B CN110903539 B CN 110903539B
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resin
parts
optical cable
flame retardant
ultraviolet light
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CN110903539A (en
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李同兵
刘悦
武涛
钟荣栋
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Guangdong Antop Polymer Technology Co ltd
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Guangdong Antopu Polymer Technology Co ltd
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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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which comprises the following preparation raw materials in parts by mass: 18-22 parts of EVA resin, 16-20 parts of PE resin, 4-6 parts of MAH modified resin, 44-70 parts of flame retardant and 0.5-2 parts of light curing agent. The ultraviolet light irradiation low-smoke halogen-free material for the optical cable prepared by the invention has excellent flame retardant property: the obtained material has excellent mechanical properties as shown by tensile strength tests; the optical cable prepared from the material is shown by the test of shaping capability to have stable outer diameter, good roundness, uniform and stable skin thickness, good temperature resistance and shaping capability in the online production process.

Description

Ultraviolet light irradiation low-smoke halogen-free material for optical cable
Technical Field
The invention relates to the field of optical cable materials, in particular to an ultraviolet light irradiation low-smoke halogen-free material for an optical cable.
Background
With the continuous development of communication technology, the optical cable is an important medium for transmitting data such as information and the like, belongs to an important supporting industry for national economic construction, and is widely applied to various fields of national economy. For optical fibers, high flame retardant performance is required to prevent the optical fibers from igniting and delaying combustion in case of fire, so that huge economic loss is caused, life and property safety of people is threatened, and environmental pollution is caused. Meanwhile, when the optical cable on the market is overhead outdoors or buried deeply underground, the mechanical property is insufficient, the quality problems of self-cracking, deformation and the like easily occur, the high temperature resistance of the existing optical cable is insufficient, the maximum service temperature is 70 ℃, and in the 5G communication era, the heat productivity of the optical module is remarkably increased and the optical cable is required to have higher temperature resistance; meanwhile, in large-scale data center construction, due to the fact that equipment in a machine room is dense and heat dissipation capacity is large, jumper cables are required to have higher temperature resistance. Crosslinking is one of the important means for improving the mechanical property and the temperature resistance of the polymer material.
The traditional crosslinking technology is divided into silane crosslinking agent crosslinking and electron beam irradiation crosslinking; however, silane crosslinking requires water molecules to participate in chemical reactions, and optical fibers in the optical cable are extremely sensitive to moisture, which can cause significant reduction in optical transmission performance; in the high-energy electron beam irradiation process, the electron beam damages the optical fiber, so that the traditional irradiation means cannot be used for the optical cable. The field of optical cables has no precedent for adopting irradiation sheath materials. The ultraviolet irradiation technique does not cause the above-mentioned problems, i.e., it does not require moisture to participate in the reaction, and the ultraviolet intensity is not sufficient to damage the optical fiber. However, because the outer sheath of the optical cable is of a hollow tubular structure and has a certain gap with the optical fibers distributed in the outer sheath, when ultraviolet irradiation processing is carried out, the irradiation equipment is arranged between the extruder head and the cooling water tank, when the outer sheath of the optical cable is extruded, the newly extruded sheath enters the ultraviolet irradiation equipment and passes through an irradiation space with the length of more than one meter, the material is always in a molten state, the melt strength of the traditional material is not high, and the problems of uneven thickness, poor roundness and the like of the outer sheath of the optical cable are caused because the sleeve is easy to collapse in the process. Therefore, it is highly desirable to develop a low-smoke halogen-free material for optical cable irradiated by ultraviolet light, which has good mechanical properties, temperature resistance and shaping capability.
Disclosure of Invention
In order to solve the technical problems, the invention provides an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which comprises the following preparation raw materials in parts by mass: 18-22 parts of EVA resin, 16-20 parts of PE resin, 4-6 parts of MAH modified resin, 44-70 parts of flame retardant and 0.5-2 parts of light curing agent.
As a preferable technical scheme, the content of VA in the EVA resin is 20-28 wt%.
As a preferable technical scheme, the melt flow rate of the EVA resin is 1-5 g/10 min.
As a preferable technical scheme, the density of the PE resin is 0.920-0.926 g/cm3。
As a preferable technical scheme, the melt flow rate of the PE resin is 1-2 g/10 min.
As a preferable technical solution, the MAH modified resin is selected from one or more of MAH modified POE resin, MAH modified EVA resin, MAH modified PP resin, MAH modified PVC resin, MAH modified PE resin, and MAH modified PET resin.
As a preferred technical scheme, the flame retardant is selected from one or more of borate flame retardant, siloxane flame retardant and metal oxide flame retardant.
As a preferable technical scheme, the mass ratio of the borate flame retardant to the siloxane flame retardant in the flame retardant is 1: (0.3-0.5).
As a preferable technical scheme, the preparation raw materials further comprise 0.01-0.1 part of ultraviolet absorbent and 1-2 parts of auxiliary agent.
The second aspect of the invention provides a preparation method of an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which comprises the following steps:
step a, adding the preparation raw materials into an internal mixer according to parts by weight, and heating and stirring uniformly to obtain a mixture;
and b, adding the mixture obtained in the step a into a screw extruder, and extruding and granulating to obtain the ultraviolet irradiation low-smoke halogen-free material for the optical cable.
Has the advantages that: the invention mainly uses EVA resin, PE resin, MAH modified resin, flame retardant and light curing agent to prepare the ultraviolet light irradiation low smoke halogen-free material with excellent flame retardant property for optical cable: the obtained material has excellent mechanical properties as shown by tensile strength tests; the optical cable prepared from the material is proved by the setting capability test to have stable outer diameter, good roundness, uniform and stable skin thickness, good temperature resistance and setting capability in the online production process after being irradiated for 4.5s at 120 ℃ by a 0.8kV ultraviolet irradiation instrument.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the technical problems, the invention provides an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which comprises the following preparation raw materials in parts by mass: 18-22 parts of EVA resin, 16-20 parts of PE resin, 4-6 parts of MAH modified resin, 44-70 parts of flame retardant and 0.5-2 parts of light curing agent.
In a preferred embodiment, the optical cable is irradiated by ultraviolet light, and the low-smoke halogen-free material comprises the following preparation raw materials in parts by mass: 20 parts of EVA resin, 18 parts of PE resin, 5 parts of MAH modified resin, 46 parts of flame retardant and 1 part of light curing agent.
< EVA resin >
EVA resin, an english name of Ethylene Vinyl Acetate Copolymer, is a resin material obtained by copolymerizing Ethylene and acetic acid.
In a preferred embodiment, the content of VA in the EVA resin is 20-28 wt%.
In a more preferred embodiment, the amount of VA in the EVA resin is 26 wt%.
The measurement method of the VA content (vinyl acetate content) is not particularly limited in the present invention, and any one of the measurement methods well known to those skilled in the art, such as nuclear magnetic spectroscopy, may be used.
In a preferred embodiment, the melt flow rate of the EVA resin is 1-5 g/10 min.
In a more preferred embodiment, the EVA resin has a melt flow rate of 4g/10 min.
The melt flow rate of the EVA resin refers to the melt flow rate at 190 ℃ and 2.16kg, abbreviated as MFR, and is the gram number of a molten material flowing out of a resin molten material through a standard capillary within a certain time (generally 10min) at a certain temperature and pressure in a standardized melt index instrument. The method for measuring the melt flow rate is not particularly limited, and any method known to those skilled in the art, such as ASTM D-1238, may be used.
The EVA resin is a Taiwan plastic 7470M, the content of VA is 26 wt%, and the melt flow rate at 190 ℃ and 2.16kg is 4g/10 min.
< PE resin >
PE resin, known by the english name polyethylene, is a thermoplastic resin obtained by polymerizing ethylene.
In a preferred embodiment, the PE resin has a density of 0.920 to 0.926g/cm3。
In a more preferred embodiment, the PE resin has a density of 0.924g/cm3。
The density is not particularly limited in the present invention, and any of the test methods known to those skilled in the art, such as ASTM D-792 test method, can be used.
In a preferred embodiment, the PE resin has a melt flow rate of 1 to 2g/10 min.
In a more preferred embodiment, the PE resin has a melt flow rate of 1.5g/10 min.
The melt flow rate of the PE resin refers to the Melt Flow Rate (MFR) of 2.16kg at 190 ℃, and is the gram number of molten material flowing out of a standard capillary within a certain time (generally 10min) at a certain temperature and pressure in a standardized melt index instrument. The method for measuring the melt flow rate is not particularly limited, and any method known to those skilled in the art, such as ASTM D-1238, may be used.
The PE resin is Exxon Mobil LD368, and the density is 0.924g/cm3The melt flow rate at 190 ℃ under 2.16kg was 1.5g/10 min.
< MAH-modified resin >
The MAH modified resin, i.e., maleic anhydride modified resin, refers to a modified material in which the resin has both a polar group aldehyde group and an olefin nonpolar segment through chemical blending modification.
In a preferred embodiment, the MAH-modified resin is selected from one or more of MAH-modified POE resin, MAH-modified EVA resin, MAH-modified PP resin, MAH-modified PVC resin, MAH-modified PE resin, and MAH-modified PET resin.
In a more preferred embodiment, the MAH-modified resin is a MAH-modified PE resin.
The MAH modified PE resin is HONEYWELL A-C575P.
< flame retardant >
The flame retardant is a substance capable of increasing the flame resistance of a high polymer material, and is mainly used for the high polymer materials such as plastics, rubber, fibers and the like.
In a preferred embodiment, the flame retardant is selected from one or more combinations of borate flame retardants, silicone flame retardants, metal oxide flame retardants.
In a more preferred embodiment, the borate flame retardant is selected from one or more combinations of zinc borate, calcium metaborate, ammonium pentaborate, sodium metaborate, ammonium fluoroborate, barium metaborate, zinc fluoroborate.
In a more preferred embodiment, the silicone flame retardant is selected from one or more combinations of polydimethylsiloxane, polymethylhydrosiloxane, polyborosiloxane, silicone copolymer, silicone composite.
In a more preferred embodiment, the metal oxide flame retardant is selected from one or more combinations of aluminum hydroxide, magnesium hydroxide, hydrotalcite, zinc oxide, tin oxide.
In a further preferred embodiment, the flame retardant is a mixture of borate flame retardant and silicone flame retardant.
In a preferred embodiment, the mass ratio of borate flame retardant to silicone flame retardant in the flame retardant is 1: (0.3-0.5).
In a more preferred embodiment, the mass ratio of borate flame retardant to silicone flame retardant in the flame retardant is 1: 0.4.
in a further preferred embodiment, the borate flame retardant is zinc borate.
The zinc borate is available from Guangdong Union chemical Co., Ltd, with a CAS number of 1332-07-6.
In a further preferred embodiment, the silicone flame retardant is polydimethylsiloxane.
The polydimethylsiloxane, CAS number 9006-65-9, was purchased from Tiaoh chemical Co., Ltd, Guangzhou.
< light curing agent >
The light curing agent is a reagent which can make the material quickly produce physical and chemical changes in a short time after being irradiated by light so as to be cross-linked and cured.
In a preferred embodiment, the light curing agent is selected from one or more combinations of benzophenone, thiopropoxythioanthrone, isopropylthioxanthone, anthraquinone, triallyl polychloride, triallyl trihydroxypropane ether, triallyl isocyanurate, 2, 4-dihydroxybenzophenone, 4 '-dihydroxybenzophenone, Michler's ketone.
In a more preferred embodiment, the photo-curing agent is benzophenone.
The benzophenone, CAS number 119-61-9, was purchased from Tiaoh chemical Co., Ltd, Guangzhou.
In the process of continuous research and development, the inventor finds that when the content of VA in the EVA resin is 20-28 wt%, the melt flow rate at 190 ℃ and 2.16kg is 1-5 g/10min, the density of the PE resin is 0.920-0.926 g/cm3, and the melt flow rate at 190 ℃ and 2.16kg is 1-2 g/10min, the mechanical property and the setting capacity of the obtained material after ultraviolet irradiation are obviously improved. The inventors believe, on the one hand, that lower melt flow rates of EVA resins and PE resins may increase melt strength, decrease melt viscosity, prevent collapse of the sleeve in the molten state; when the VA content of the EVA resin is different, the compatibility of the EVA and the PE is different. The inventor finds that when the EVA resin and the PE resin with specific VA content are compounded, the EVA and the PE have proper compatibility, the EVA and the PE are ensured to have maximum molecular chain entanglement, and an interpenetrating network structure is formed; under the condition, the chemical crosslinking is generated to the maximum extent between the EVA and the PE induced by the UV irradiation, so that the dimensional stability of the resin system in a molten state and the mechanical property of the final composite material are improved. The vinyl acetate chain segment part in the EVA resin molecular chain can generate maximum chain segment entanglement, and after ultraviolet irradiation, the free radicals generated by the light curing agent increase the number of crosslinkable sites of the system, so that the crosslinking network structure is further perfected, and the external force deformation resistance of the material is improved.
In a preferred embodiment, the preparation raw material further comprises 0.01-0.1 part of ultraviolet absorber and 1-2 parts of auxiliary agent.
In a more preferred embodiment, the preparation raw material further comprises 0.05 part of ultraviolet absorber and 1.5 parts of auxiliary agent.
< UV absorbers >
The ultraviolet absorbent is a light stabilizer which can ensure that the physical property and the chemical property of the material are kept stable after the material is irradiated by sunlight or a fluorescent light source.
In a preferred embodiment, the ultraviolet absorber is selected from the group consisting of UV-531, UV-9, UV-284, UV-326, UV-328, and UV-329.
In a preferred embodiment, the ultraviolet absorber is UV-284.
The UV-284, 2-hydroxy-4-methoxy-5-sulfobenzophenone, CAS No. 4065-45-6, was purchased from Tiaoao chemical Co., Ltd, Guangzhou.
< auxiliary agent >
An adjuvant, an agent that can further enhance the properties of the material. The auxiliary agent is not particularly limited in the present invention, and may be adjusted according to the actual circumstances, for example, the antioxidant 1010, CAS No. 6683-19-8, available from Tiaoao chemical Co., Ltd., Guangzhou city.
The second aspect of the invention provides a preparation method of an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which comprises the following steps:
step a, adding the preparation raw materials into an internal mixer according to parts by weight, and heating and stirring uniformly to obtain a mixture;
and b, adding the mixture obtained in the step a into a screw extruder, and extruding and granulating to obtain the ultraviolet irradiation low-smoke halogen-free material for the optical cable.
In a preferred embodiment, the preparation method of the optical cable low-smoke halogen-free material irradiated by ultraviolet light comprises the following steps:
step a, adding the preparation raw materials into an internal mixer according to parts by weight, and heating and uniformly stirring at 175 ℃ to obtain a mixture;
and step b, adding the mixture obtained in the step a into a screw extruder, and extruding and granulating to obtain the ultraviolet light irradiation low-smoke halogen-free material for the optical cable.
The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
The embodiment 1 of the invention provides an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which comprises the following preparation raw materials in parts by mass: 20 parts of EVA resin, 18 parts of PE resin, 5 parts of MAH modified resin, 46 parts of flame retardant, 1 part of light curing agent, 0.05 part of ultraviolet absorbent and 1.5 parts of auxiliary agent.
The EVA resin has VA content of 26 wt%, melt flow rate of 4g/10min at 190 deg.C and 2.16kg, and is brand No. of Taiwan plastic 7470M. The density of the PE resin is 0.924g/cm3The melt flow rate at 190 ℃ under 2.16kg was 1.5g/10min under the trade name Exxon Mobil LD 368. The MAH modified resin is HONEYWELL A-C575P. The flame retardant is zinc borate and polydimethyl siliconA mixture of siloxanes in a mass ratio of 1: 0.4; the light curing agent is benzophenone; the ultraviolet absorbent is UV-284; the auxiliary agent is an antioxidant 1010.
The preparation method of the ultraviolet light irradiation low-smoke halogen-free material for the optical cable comprises the following steps:
step a, adding the preparation raw materials into an internal mixer according to parts by weight, and heating and uniformly stirring at 175 ℃ to obtain a mixture;
and b, adding the mixture obtained in the step a into a screw extruder, and extruding and granulating to obtain the ultraviolet irradiation low-smoke halogen-free material for the optical cable.
Example 2
The embodiment 2 of the invention provides an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which comprises the following preparation raw materials in parts by mass: 18 parts of EVA resin, 16 parts of PE resin, 4 parts of MAH modified resin, 44 parts of flame retardant, 0.5 part of light curing agent, 0.01 part of ultraviolet absorbent and 1 part of auxiliary agent.
The content of VA in the EVA resin is 26 wt%, the melt flow rate at 190 ℃ and 2.16kg is 4g/10min, and the brand is Taiwan plastic 7470M. The density of the PE resin is 0.924g/cm3The melt flow rate at 190 ℃ under 2.16kg was 1.5g/10min under the trade name Exxon Mobil LD 368. The MAH modified resin is Honiville A-C575P. The flame retardant is a mixture of zinc borate and polydimethylsiloxane, and the mass ratio of the zinc borate to the polydimethylsiloxane is 1: 0.4; the light curing agent is benzophenone; the ultraviolet absorbent is UV-284; the auxiliary agent is an antioxidant 1010.
The preparation method of the ultraviolet light irradiation low-smoke halogen-free material for the optical cable comprises the same steps as the example 1.
Example 3
The embodiment 3 of the invention provides an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which comprises the following preparation raw materials in parts by mass: 22 parts of EVA resin, 20 parts of PE resin, 6 parts of MAH modified resin, 70 parts of flame retardant, 2 parts of light curing agent, 0.1 part of ultraviolet absorbent and 2 parts of auxiliary agent.
The VA content of the EVA resin is 26wt%, a melt flow rate of 4g/10min at 190 ℃ under 2.16kg, and a brand of Taiwan plastic 7470M. The density of the PE resin is 0.924g/cm3The melt flow rate at 190 ℃ under 2.16kg was 1.5g/10min under the trade name Exxon Mobil LD 368. The MAH modified resin is Honiville A-C575P. The flame retardant is a mixture of zinc borate and polydimethylsiloxane, and the mass ratio of the zinc borate to the polydimethylsiloxane is 1: 0.4; the light curing agent is benzophenone; the ultraviolet absorbent is UV-284; the auxiliary agent is an antioxidant 1010.
The preparation method of the ultraviolet light irradiation low-smoke halogen-free material for the optical cable comprises the same steps as the example 1.
Example 4
Embodiment 4 of the present invention provides an ultraviolet light irradiation low smoke and zero halogen material for an optical cable, which has a specific implementation manner similar to that in embodiment 1, except that the EVA resin with a VA content of 32 wt% and a melt flow rate of 43g/10min at 190 ℃ and 2.16kg is replaced with an EVA resin with a trademark of dupont 150W.
Example 5
An embodiment 5 of the invention provides an ultraviolet-irradiated low-smoke halogen-free material for an optical cable, which is similar to that in embodiment 1, except that the EVA resin is replaced by VA with a content of 28 wt%, a melt flow rate at 190 ℃ and 2.16kg is 25g/10min, and a trademark is tai-plast 7760S.
Example 6
Embodiment 6 of the present invention provides an ultraviolet light irradiation low smoke and zero halogen material for an optical cable, which has a specific implementation manner similar to that in embodiment 1, except that the EVA resin with a VA content of 28 wt% and a melt flow rate of 6g/10min at 190 ℃ and 2.16kg is replaced with an EVA resin having a trademark of dupont 260.
Example 7
Embodiment 7 of the present invention provides an ultraviolet light irradiation low smoke and zero halogen material for an optical cable, which has a specific implementation manner similar to that in embodiment 1, except that the EVA resin with a VA content of 28 wt% and a melt flow rate of 43g/10min at 190 ℃ and 2.16kg is replaced with an EVA resin with a trademark of dupont 240W.
Example 8
Embodiment 8 of the present invention provides an ultraviolet light irradiation low smoke and zero halogen material for optical cables, which has a specific implementation manner similar to that in embodiment 1, except that the PE resin is replaced with a resin having a density of 0.918g/cm3PE resin with a melt flow rate of 1g/10min at 190 ℃ and 2.16kg, trade name Exxon Mobil LL 1001.
Example 9
Embodiment 9 of the present invention provides an ultraviolet light irradiation low smoke and zero halogen material for optical cables, which has a specific implementation manner similar to that in embodiment 1, except that the PE resin is replaced with 0.9355g/cm density3PE resin having a melt flow rate of 5g/10min at 190 ℃ under 2.16kg, under the trade name Exxon Mobil LL6301 YM.
Example 10
Embodiment 10 of the invention provides an ultraviolet light irradiation low-smoke halogen-free material for an optical cable, which has a specific implementation mode similar to that of embodiment 1, except that the PE resin is replaced by a resin with a density of 0.92g/cm3PE resin with a melt flow rate of 0.8g/10min at 190 ℃ under 2.16kg, under the trademark Exxon Mobil LPX 56.
Example 11
Embodiment 11 of the present invention provides an ultraviolet light irradiation low smoke zero halogen material for optical cables, which has a specific implementation manner similar to that in embodiment 1, except that the PE resin is replaced with a resin having a density of 0.926g/cm3PE resin with a melt flow rate of 12g/10min at 190 ℃ under 2.16kg, under the trademark Exxon Mobil LPX 12.
Evaluation of Performance
1. And (3) testing the tensile strength: the ultraviolet light irradiation low-smoke halogen-free material for the optical cables obtained in the embodiments 1 to 5 and 8 to 9 is prepared according to GB/T1040.3-2006 part 3 of determination of tensile property of plastics: test conditions for thin plastics and sheets, samples (type 5) having a thickness of 1mm were prepared, and after irradiation with 0.8kV ultraviolet light at 120 ℃ for 5 seconds, the tensile strength was measured on a tensile tester at a speed of 25mm/min, and the average value thereof was calculated, and the results are shown in Table 1.
TABLE 1 tensile Strength test results
Tensile Strength (MPa)
Example 1 15.5
Example 2 15.5
Example 3 15.4
Example 4 8.7
Example 5 10.2
Example 8 9.8
Example 9 8.3
2. Testing the setting ability: the optical cable obtained in the embodiment 1-11 is irradiated by ultraviolet light to prepare an optical cable according to a method well known by the skilled person, and the optical cable with the length of 1m is selected as a sample for standby. And (3) testing the outer diameter of the sample before ultraviolet irradiation by using an outer diameter recorder, irradiating for 4.5s at 120 ℃ by using a 0.8kV ultraviolet irradiation instrument, randomly selecting 10 positions as test points, and recording the outer diameter of the sample after ultraviolet irradiation. And calculating the positive and negative tolerance of the outer diameter before and after ultraviolet irradiation, wherein the positive and negative tolerance of the outer diameter is the difference between the measured value of the outer diameter and the average value of the outer diameter. After three tests, the average value was calculated, and the results are shown in Table 2.
TABLE 2 test results of the setting ability
Tolerance of outer diameter after ultraviolet irradiation (+/-mm)
Example 1 0.005
Example 2 0.005
Example 3 0.004
Example 4 0.031
Example 5 0.028
Example 6 0.100
Example 7 0.073
Example 8 0.027
Example 9 0.029
Example 10 0.057
Example 11 0.063
The ultraviolet light irradiation low-smoke halogen-free material for the optical cable meets the performance requirements of YDT 1113-.
The combination of the above experimental results shows that: the invention mainly uses EVA resin, PE resin, MAH modified resin, flame retardant and light curing agent to prepare the ultraviolet light irradiation low smoke halogen-free material with excellent flame retardant property for optical cable: the tensile strength test shows that the tensile strength of the obtained material can reach 15.5MPa, which shows that the material has excellent mechanical property; the shaping capability test shows that the optical cable prepared from the material has stable outer diameter, good roundness, uniform and stable skin thickness and good temperature resistance and shaping capability in the online production process after being irradiated for 4.5s at 120 ℃ by a 0.8kV ultraviolet irradiation instrument.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. The invention is not limited to the embodiments described above, but rather, many modifications and variations may be made by one skilled in the art without departing from the scope of the invention.

Claims (6)

1. The ultraviolet light irradiation low-smoke halogen-free material for the optical cable is characterized by comprising the following preparation raw materials in parts by mass: 18-22 parts of EVA resin, 16-20 parts of PE resin, 4-6 parts of MAH modified resin, 44-70 parts of flame retardant and 0.5-2 parts of light curing agent;
the content of VA in the EVA resin is 20-28 wt%, and the melt flow rate of the EVA resin is 1-5 g/10 min;
the density of the PE resin is 0.920-0.926 g/cm3The melt flow rate of the PE resin is 1-2 g/10 min.
2. The ultraviolet light irradiation low smoke and zero halogen material for optical cable according to claim 1, wherein the MAH modified resin is selected from one or more of MAH modified POE resin, MAH modified EVA resin, MAH modified PP resin, MAH modified PVC resin, MAH modified PE resin, and MAH modified PET resin.
3. The ultraviolet light irradiation low-smoke halogen-free material for the optical cable as claimed in claim 1, wherein the flame retardant is selected from one or more of borate flame retardant, siloxane flame retardant and metal oxide flame retardant.
4. The ultraviolet light irradiation low-smoke halogen-free material for the optical cable as claimed in claim 3, wherein the mass ratio of the borate flame retardant to the siloxane flame retardant in the flame retardant is 1: (0.3-0.5).
5. The ultraviolet light irradiation low-smoke halogen-free material for the optical cable according to any one of claims 1 to 4, characterized in that the preparation raw materials further comprise 0.01 to 0.1 part of ultraviolet absorbent and 1 to 2 parts of auxiliary agent.
6. A method for preparing the ultraviolet light irradiation low smoke zero halogen material for the optical cable according to any one of claims 1 to 5 is characterized by comprising the following steps:
step a, adding the preparation raw materials into an internal mixer according to parts by weight, and heating and stirring uniformly to obtain a mixture;
and b, adding the mixture obtained in the step a into a screw extruder, and extruding and granulating to obtain the ultraviolet irradiation low-smoke halogen-free material for the optical cable.
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JP3884053B1 (en) * 2005-11-28 2007-02-21 株式会社フジクラ Radiation-resistant resin composition and radiation-resistant electric wire / cable
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CN104231396A (en) * 2014-09-17 2014-12-24 朱忠良 Halogen-free flame-retardant wire
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