CN113174105A - Temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material and preparation method thereof - Google Patents
Temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material and preparation method thereof Download PDFInfo
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- CN113174105A CN113174105A CN202110516644.6A CN202110516644A CN113174105A CN 113174105 A CN113174105 A CN 113174105A CN 202110516644 A CN202110516644 A CN 202110516644A CN 113174105 A CN113174105 A CN 113174105A
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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
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- 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
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- 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
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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
- 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
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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
- 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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Abstract
The invention discloses a temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material and a preparation method thereof, belonging to the field of ultraviolet crosslinking polyolefin materials, and the cable material comprises matrix resin polyolefin A, matrix resin polyolefin B, a compatilizer, an inorganic flame retardant A, an inorganic flame retardant B, a synergistic flame retardant, a lubricant, a coupling agent, a compound flame-retardant synergistic agent, a compound antioxidant and a compound photosensitizer; the flame retardant synergist is added to improve the flame retardance of the material, and the high-melting-point polyolefin is added, and the heat resistance of the material is enhanced by the synergistic effect of the high-molecular-weight antioxidant and various antioxidants, so that the cable material achieves the purposes of good flame retardance and high heat resistance.
Description
Technical Field
The invention relates to the field of ultraviolet light crosslinked polyolefin materials, in particular to a temperature-resistant ultraviolet light crosslinked low-smoke halogen-free flame-retardant cable material and a preparation method thereof.
Background
The flame-retardant cable material is divided into a halogen-containing flame-retardant cable material and a halogen-free flame-retardant cable material, and the halogen-containing flame-retardant cable material is limited to be used along with scientific progress and environmental protection requirements; the application of the halogen-free flame-retardant cable material is widely developed and is mainly used for manufacturing connecting wires inside electrical equipment in the electronic industry, and the UL electronic wire is the most common electronic wire in the electronic industry.
The low-smoke halogen-free flame-retardant cable material mostly achieves the purpose of flame retardance by adding a large amount of inorganic flame retardant into polyolefin, the mechanical property reduction of the cable material can be influenced by adding a large amount of inorganic flame retardant, and the UL electronic wire is generally smaller in wire diameter and higher in mechanical property of the flame-retardant material. As the UL electronic wire needs to be ensured to be ventilated for 200 times/hour under the use environment and test, the retention rate of the mechanical property of the wire after the aging of the UL aging box is not lower than 80 percent, the method puts a very high requirement on the thermo-oxidative aging capability of the material.
Disclosure of Invention
The invention aims to provide a temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material and a preparation method thereof.
The technical scheme of the invention is as follows: a temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material comprises the following components in percentage by weight:
wherein the matrix resin polyolefin A is any one or a mixture of ethylene-vinyl acetate (EVA), ethylene-octene copolymer (POE) and ethylene-ethyl acrylate copolymer (EAA);
the matrix resin polyolefin B is any one or a mixture of more of Linear Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE) and polypropylene (PP);
the compatilizer is any one or a mixture of more of ethylene-vinyl acetate grafted maleic anhydride copolymer (EVA-g-MAH), ethylene-octene copolymer grafted maleic anhydride copolymer (POE-g-MAH) and polypropylene grafted maleic anhydride copolymer (PP-g-MAH);
the inorganic flame retardant A is aluminum hydroxide, and the inorganic flame retardant B is magnesium hydroxide;
the synergistic flame retardant is any one or a mixture of melamine, melamine cyanurate and piperazine pyrophosphate;
the lubricant is any one of polyethylene wax and polypropylene wax or a mixture of the polyethylene wax and the polypropylene wax;
the coupling agent is any one or a mixture of more of silane coupling agent, aluminate coupling agent and titanate coupling agent;
the compound flame-retardant synergist is any one or a mixture of zinc borate, montmorillonite, kaolin and silicone;
the compound antioxidant is any one or a mixture of more of benzophenone, hindered phenol, phosphite and hindered amine;
the compound photosensitizer is any one or a mixture of a plurality of triallyl cyanurate (TAC), triallyl trihydroxypropane (TMPTME), triallyl isocyanurate (TAIC) and Benzophenone (BP).
According to a further technical scheme, the matrix resin polyolefin A is ethylene-vinyl acetate (EVA), the weight percentage content of vinyl acetate in the ethylene-vinyl acetate (EVA) is 25% -33%, and the melt index is 4-9.
According to the further technical scheme, the matrix resin polyolefin B is polypropylene (PP), the polypropylene (PP) is homopolymerized, and the melt index is 3-16.
According to a further technical scheme, the grafting rate of the polypropylene grafted maleic anhydride copolymer (PP-g-MAH) is 0.7-1.3%.
Further technical scheme, the particle size of the aluminum hydroxide D50: 3-9 um, particle size D50 of magnesium hydroxide: 3-9 um.
According to a further technical scheme, the piperazine pyrophosphate is hyperbranched piperazine, the polypropylene wax is metallocene synthetic polypropylene wax, and the coupling agent is any one or a mixture of more of silane coupling agent, aluminate coupling agent and titanate coupling agent.
According to a further technical scheme, the compound flame-retardant synergist is prepared from kaolin: silicone: 0.5-2% of zinc borate: 0.5-1: 0.1-1, and carrying out compounding preparation.
According to a further technical scheme, the compound antioxidant is prepared by the following steps of 1010: 168: DSTP: 412S is 0.5-1.5: 0.2-1: 0.1-0.5: 0.1-0.8, and compounding to obtain the product.
According to a further technical scheme, the compound photosensitizer is prepared by the following steps of: TMPTME: TAIC is 0.5-1.5: 0.5-2: 0.1-1, and carrying out compounding preparation.
The invention discloses a preparation method of a temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material, which specifically comprises the following steps:
(1) premixing an inorganic flame retardant A, an inorganic flame retardant B and a coupling agent in proportion, wherein the premixing temperature is 80-100 ℃, and the mixing time is 40-50 minutes;
(2) and sequentially adding the matrix resin polyolefin A, the matrix resin polyolefin B and the compatilizer into an internal mixer according to a ratio, internally mixing for 5-15 minutes, then adding other component auxiliaries, mixing, discharging, and granulating by using a double-screw extrusion granulator to obtain the composite material.
The invention has the beneficial effects that:
according to the invention, the flame retardance of the material can be better improved by adding the flame-retardant synergist, and the heat resistance of the material is enhanced by adopting the synergistic effect of the high-molecular-weight antioxidant and multiple antioxidants, so that the cable material achieves the purposes of good flame retardance and high heat resistance.
Detailed Description
The invention will be further illustrated and understood by the following non-limiting examples.
The invention provides a temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material, which comprises the following components in percentage by weight:
wherein the matrix resin polyolefin A is any one or a mixture of ethylene-vinyl acetate (EVA), ethylene-octene copolymer (POE) and ethylene-ethyl acrylate copolymer (EAA);
the matrix resin polyolefin B is any one or a mixture of more of Linear Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE) and polypropylene (PP);
the compatilizer is any one or a mixture of more of ethylene-vinyl acetate grafted maleic anhydride copolymer (EVA-g-MAH), ethylene-octene copolymer grafted maleic anhydride copolymer (POE-g-MAH) and polypropylene grafted maleic anhydride copolymer (PP-g-MAH);
the inorganic flame retardant A is aluminum hydroxide; the inorganic flame retardant B is magnesium hydroxide;
the synergistic flame retardant is any one or a mixture of melamine, melamine cyanurate and piperazine pyrophosphate;
the lubricant is any one or a mixture of polyethylene wax and polypropylene wax;
the coupling agent is any one or a mixture of more of silane coupling agent, aluminate coupling agent and titanate coupling agent;
the compound flame-retardant synergist is any one or a mixture of zinc borate, montmorillonite, kaolin and silicone;
the compound antioxidant is any one or a mixture of more of benzophenone, hindered phenol, phosphite and hindered amine;
the compound photosensitizer is any one or a mixture of a plurality of triallyl cyanurate (TAC), triallyl trihydroxypropane (TMPTME), triallyl isocyanurate (TAIC) and Benzophenone (BP).
Example 1:
the temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material comprises the following raw material components in percentage by weight:
since the carrier used in this example is ethylene-vinyl acetate (EVA), in order to avoid the unstable state caused by the reaction of magnesium hydroxide with acetic acid, which is a decomposition substance of ethylene-vinyl acetate (EVA), the inorganic flame retardant in the present invention is mainly aluminum hydroxide, and the resin filled with aluminum hydroxide under the same conditions has better toughness and ductility, and is suitable for preparing electronic wires.
Wherein: the compound flame-retardant synergist is prepared from kaolin: silicone: 1-zinc borate: 0.7: 0.1 is compounded to obtain;
the compound antioxidant is prepared by the following raw materials: antioxidant 168: antioxidant DSTP: antioxidant 412S ═ 1: 0.5: 0.1:
0.1 is compounded to obtain;
the compound photosensitizer is prepared by using BP: TMPTME: TAIC 1: 0.7: 0.2 is compounded to obtain;
the components are prepared by the following steps:
(1) preparing an inorganic fuel barrier: weighing aluminum hydroxide, magnesium hydroxide and a coupling agent, and then putting the weighed materials into a kneader for mixing, wherein the premixing temperature is 80-100 ℃, and the mixing time is 40-50 minutes; the rotating speed of the kneader is 30-45 rpm;
(2) sequentially adding 27 wt% of ethylene-vinyl acetate (EVA) with vinyl acetate, 7 wt% of polypropylene (PP) with melt index and 0.9 wt% of polypropylene grafted maleic anhydride copolymer (PP-g-MAH) into an internal mixer according to a proportion, internally mixing for 5-15 minutes, then adding other raw material components according to a proportion, mixing for 2 minutes, and discharging the materials from the internal mixer into a double-screw extrusion granulator;
(3) and after the double-screw extrusion homogenization, the preparation of the granules is finished, wherein the temperature of each section of the double-screw extrusion granulator is as follows: the first zone is 125 + -3 deg.C, the second zone is 135 + -3 deg.C, the third zone is 145 + -3 deg.C, the fourth zone is 155 + -3 deg.C, the fifth zone is 165 + -3 deg.C, and the head zone is 155 + -3 deg.C.
Example 2:
the temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material comprises the following raw material components in percentage by weight, and the compounding proportion and the operation steps of the rest raw materials are consistent with those of the embodiment 1:
the products prepared in the examples 1 and 2 and the market irradiation products are subjected to national standard tests, and the test results are as follows:
in conclusion, the flame retardance of the material can be better improved by adding the flame-retardant synergist, and the heat resistance of the material is enhanced by adding the synergistic effect of multiple antioxidants, so that the cable material achieves the purposes of good flame retardance and high heat resistance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way and substantially, and all technical solutions falling within the spirit of the present invention are considered to be within the scope of the present invention.
Claims (10)
1. The temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material is characterized by comprising the following components in percentage by weight:
wherein the matrix resin polyolefin A is any one or a mixture of ethylene-vinyl acetate (EVA), ethylene-octene copolymer (POE) and ethylene-ethyl acrylate copolymer (EAA);
the matrix resin polyolefin B is any one or a mixture of more of Linear Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE) and polypropylene (PP);
the compatilizer is any one or a mixture of more of ethylene-vinyl acetate grafted maleic anhydride copolymer (EVA-g-MAH), ethylene-octene copolymer grafted maleic anhydride copolymer (POE-g-MAH) and polypropylene grafted maleic anhydride copolymer (PP-g-MAH);
the inorganic flame retardant A is aluminum hydroxide;
the inorganic flame retardant B is magnesium hydroxide;
the synergistic flame retardant is any one or a mixture of melamine, melamine cyanurate and piperazine pyrophosphate;
the lubricant is polyethylene wax,Polypropylene waxEither one or a mixture of both;
the coupling agent is any one or a mixture of more of silane coupling agent, aluminate coupling agent and titanate coupling agent;
the compound flame-retardant synergist is any one or a mixture of zinc borate, montmorillonite, kaolin and silicone;
the compound antioxidant is any one or a mixture of more of benzophenone, hindered phenol, phosphite and hindered amine;
the compound photosensitizer is any one or a mixture of a plurality of triallyl cyanurate (TAC), triallyl trihydroxypropane (TMPTME), triallyl isocyanurate (TAIC) and Benzophenone (BP).
2. The temperature-resistant ultraviolet-crosslinked low-smoke halogen-free flame-retardant cable material according to claim 1, wherein the matrix resin polyolefin A is ethylene-vinyl acetate (EVA), the weight percentage of vinyl acetate in the ethylene-vinyl acetate (EVA) is 25-33%, and the melt index is 4-9.
3. The temperature-resistant ultraviolet-crosslinked low-smoke halogen-free flame-retardant cable material as claimed in claim 1, wherein the matrix resin polyolefin B is polypropylene (PP), the polypropylene (PP) is of a homopolymerization type, and the melt index is 3-16.
4. The temperature-resistant ultraviolet-crosslinked low-smoke halogen-free flame-retardant cable material as claimed in claim 1, wherein the grafting ratio of the polypropylene-grafted maleic anhydride copolymer (PP-g-MAH) is 0.7-1.3%.
5. The temperature-resistant ultraviolet-crosslinked low-smoke halogen-free flame-retardant cable material according to claim 1, wherein the particle size of the aluminum hydroxide D50: 3-9 um, particle size D50 of magnesium hydroxide: 3-9 um.
6. The temperature-resistant ultraviolet-crosslinked low-smoke halogen-free flame-retardant cable material according to claim 1, wherein the piperazine pyrophosphate is hyperbranched piperazine, the polypropylene wax is metallocene synthetic polypropylene wax, and the coupling agent is any one or a mixture of silane coupling agent, aluminate coupling agent and titanate coupling agent.
7. The temperature-resistant ultraviolet-crosslinked low-smoke halogen-free flame-retardant cable material as claimed in claim 1, wherein the compounded flame-retardant synergist is prepared from kaolin: silicone: 0.5-2% of zinc borate: 0.5-1: 0.1-1, and carrying out compounding preparation.
8. The temperature-resistant ultraviolet-crosslinked low-smoke halogen-free flame-retardant cable material according to claim 1, characterized in that the compound antioxidant is a compound antioxidant prepared from 1010: 168: DSTP: 412S is 0.5-1.5: 0.2-1: 0.1-05: 0.1-0.8, and compounding to obtain the product.
9. The temperature-resistant ultraviolet-crosslinked low-smoke halogen-free flame-retardant cable material as claimed in claim 1, wherein the compounded photosensitizer is a photosensitizer prepared from BP: TMPTME: TAIC is 0.5-1.5: 0.5-2: 0.1-1, and carrying out compounding preparation.
10. The preparation method of the temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material as claimed in claim 1, which is characterized by comprising the following steps:
(1) premixing an inorganic flame retardant A, an inorganic flame retardant B and a coupling agent in proportion, wherein the premixing temperature is 80-100 ℃, and the mixing time is 40-50 minutes;
(2) and sequentially adding the matrix resin polyolefin A, the matrix resin polyolefin B and the compatilizer into an internal mixer according to a ratio, internally mixing for 5-15 minutes, then adding other component auxiliaries, mixing, discharging, and granulating by using a double-screw extrusion granulator to obtain the composite material.
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| CN202110516644.6A CN113174105A (en) | 2021-05-12 | 2021-05-12 | Temperature-resistant ultraviolet crosslinking low-smoke halogen-free flame-retardant cable material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480795A (en) * | 2021-08-03 | 2021-10-08 | 山东华凌电缆有限公司 | Low-smoke halogen-free flame-retardant polyethylene sheath material and preparation method thereof |
| CN114736450A (en) * | 2022-03-10 | 2022-07-12 | 金发科技股份有限公司 | High-thermal-shrinkage-resistance and high-toughness thermo-oxidative-aging-resistance polyolefin material and preparation method and application thereof |
| CN114891293A (en) * | 2022-04-29 | 2022-08-12 | 四川大学 | Halogen-free low-smoke flame-retardant cable material and preparation method thereof |
| CN115232404A (en) * | 2022-09-06 | 2022-10-25 | 金旸（厦门）新材料科技有限公司 | Precipitation-resistant high-appearance phosphorus-nitrogen flame-retardant polypropylene composite material and preparation method thereof |
| CN115612199A (en) * | 2022-10-28 | 2023-01-17 | 江苏北化新橡新材料科技有限公司 | Ultraviolet crosslinking wear-resistant short-circuit-resistant halogen-free flame-retardant polyolefin material capable of resisting temperature of 125 ℃ and preparation method thereof |
| CN116462902A (en) * | 2023-04-03 | 2023-07-21 | 江苏益帆高分子材料有限公司 | LLDPE/POE/BR-based micro-crosslinking modified low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
| CN117447788A (en) * | 2023-12-23 | 2024-01-26 | 河北尚华新材料股份有限公司 | Low-smoke halogen-free flame-retardant cable material for photovoltaic cable and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480795A (en) * | 2021-08-03 | 2021-10-08 | 山东华凌电缆有限公司 | Low-smoke halogen-free flame-retardant polyethylene sheath material and preparation method thereof |
| CN114736450A (en) * | 2022-03-10 | 2022-07-12 | 金发科技股份有限公司 | High-thermal-shrinkage-resistance and high-toughness thermo-oxidative-aging-resistance polyolefin material and preparation method and application thereof |
| CN114891293A (en) * | 2022-04-29 | 2022-08-12 | 四川大学 | Halogen-free low-smoke flame-retardant cable material and preparation method thereof |
| CN115232404A (en) * | 2022-09-06 | 2022-10-25 | 金旸（厦门）新材料科技有限公司 | Precipitation-resistant high-appearance phosphorus-nitrogen flame-retardant polypropylene composite material and preparation method thereof |
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| CN115612199A (en) * | 2022-10-28 | 2023-01-17 | 江苏北化新橡新材料科技有限公司 | Ultraviolet crosslinking wear-resistant short-circuit-resistant halogen-free flame-retardant polyolefin material capable of resisting temperature of 125 ℃ and preparation method thereof |
| CN116462902A (en) * | 2023-04-03 | 2023-07-21 | 江苏益帆高分子材料有限公司 | LLDPE/POE/BR-based micro-crosslinking modified low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
| CN117447788A (en) * | 2023-12-23 | 2024-01-26 | 河北尚华新材料股份有限公司 | Low-smoke halogen-free flame-retardant cable material for photovoltaic cable and preparation method thereof |
| CN117447788B (en) * | 2023-12-23 | 2024-04-12 | 河北尚华新材料股份有限公司 | Low-smoke halogen-free flame-retardant cable material for photovoltaic cable and preparation method thereof |
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