CN113308038B - Silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material capable of resisting temperature of 125 ℃, and preparation method and application thereof - Google Patents
Silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material capable of resisting temperature of 125 ℃, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113308038B CN113308038B CN202110574822.0A CN202110574822A CN113308038B CN 113308038 B CN113308038 B CN 113308038B CN 202110574822 A CN202110574822 A CN 202110574822A CN 113308038 B CN113308038 B CN 113308038B
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- retardant
- flame
- density polyethylene
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08L23/06—Polyethene
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- 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
- C08L2205/02—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
Landscapes
- 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 a silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material capable of resisting 125 ℃, and a preparation method and application thereof, wherein the silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material comprises a material A: high density polyethylene, first linear low density polyethylene, maleic anhydride grafted polyethylene, first maleic anhydride grafted polyolefin elastomer, first flame retardant, silane, initiator, first antioxidant, first lubricant, material B: the second linear low-density polyethylene, the second maleic anhydride grafted polyolefin elastomer, the second flame retardant, the second antioxidant, the catalyst and the second lubricant; the flame retardant consists of decabromodiphenylethane, antimony trioxide, magnesium hydroxide and a flame retardant synergist; the material A, B is prepared respectively, and the material is mixed and crosslinked to prepare the thin-wall automobile wire insulating layer at a high paying-off speed, and excellent mechanical and mechanical properties, flame retardant property, 125 ℃ high temperature resistance and scraping and abrasion resistance are obtained.
Description
Technical Field
The invention belongs to the technical field of automobile original wire materials, particularly relates to a flame-retardant polyolefin material for thin-wall and even ultrathin-wall automobile original wire materials, and particularly relates to a 125-DEG C-resistant silane self-crosslinking low-halogen flame-retardant polyolefin automobile original wire material as well as a preparation method and application thereof.
Background
In recent years, economy is rapidly developed, the total domestic production value is higher and higher, the living standard of people is continuously improved, automobiles also gradually become a household necessity, therefore, the sales volume of automobiles is increased year by year, and simultaneously, higher and higher requirements are also put forward on new performances of automobiles, for example, lightweight and thinner (some require conductor area to be less than 0.5 square millimeter) are required on automobile wires, the requirements on insulating layers of the electric wires on the automobiles are higher and higher, the requirements on high and low temperature resistance, scratch and abrasion resistance and good flame retardance are required, meanwhile, the wire discharging speed is required to be high based on the influence of production capacity, but the original automobile wires on the market at present basically cannot be paid off at high speed when thin-wall or even ultra-thin-wall automobile wire insulating layers are prepared, so that the production capacity is seriously reduced, and the glue breaking phenomenon is easy to occur when the wire is paid off at high speed.
For example, the invention patent CN112409671a discloses a silane self-crosslinking halogen-free low-smoke flame-retardant polyolefin automotive raw material, a preparation method and an application thereof, which comprises a material a and a material B, wherein the raw materials of the material a comprise a first base resin, a compatilizer, a first flame retardant, silane, an initiator and a first antioxidant, the raw materials of the material B comprise a second base resin, a second flame retardant, a second antioxidant and a catalyst, the first base resin and the second base resin are independently composed of low-melt-index high-density polyethylene and high-melt-index high-density polyethylene, the melt index of the low-melt-index high-density polyethylene is 0.5-2.0g/10min, and the melt index of the high-melt-index high-density polyethylene is 8.0-30.0g/10min; wherein, in the first base resin or the second base resin, the low-melting-index high-density polyethylene accounts for 30-70% and the high-melting-index high-density polyethylene accounts for 30-70% by mass percentage; the compatilizer is composed of maleic anhydride grafted ethylene butyl acrylate copolymer and maleic anhydride grafted polyethylene, and the feeding mass ratio of the maleic anhydride grafted ethylene butyl acrylate copolymer to the maleic anhydride grafted polyethylene is 1: 1.8-2.2; the absolute value of the difference between the specific gravity of the material A and the specific gravity of the material B is less than 0.05; although the polyolefin automobile raw wire material can be quickly crosslinked under natural conditions and still has excellent physical and mechanical properties on the premise of higher paying-off speed, in fact, the premise is to produce an insulating layer with conventional wall thickness, and for thin-wall or even ultrathin-wall automobile wire insulating layers, the high paying-off speed cannot be realized, otherwise, the glue breaking phenomenon is easy to occur during quick paying-off.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art and provide an improved silane self-crosslinking low-halogen flame-retardant polyolefin automobile raw wire material which can be used for preparing thin-wall and even ultra-thin-wall automobile wire insulating layers at a higher paying-off speed and obtains excellent mechanical and mechanical properties and flame retardant properties.
The invention also provides a preparation method of the silane self-crosslinking low-halogen flame-retardant polyolefin automobile raw material.
The invention also provides application of the silane self-crosslinking low-halogen flame-retardant polyolefin automobile raw wire material in preparation of a thin-wall automobile cable, wherein the thickness of the thin-wall automobile cable is less than or equal to 1mm.
In order to achieve the purpose, the invention adopts a technical scheme that:
the silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material comprises a material A and a material B, wherein the raw material of the material A comprises a first base resin, a first compatilizer, a first flame retardant, silane, an initiator, a first antioxidant and a first lubricant, and the raw material of the material B comprises a second base resin, a second flame retardant, a second antioxidant, a catalyst and a second lubricant; wherein the first base resin is composed of a high density polyethylene and a first linear low density polyethylene, and the second base resin is a second linear low density polyethylene;
the first flame retardant and the second flame retardant are independently composed of decabromodiphenylethane, antimony trioxide, magnesium hydroxide and a flame-retardant synergist;
the first compatilizer is composed of maleic anhydride grafted polyethylene and a first maleic anhydride grafted polyolefin elastomer, the raw material of the material B also comprises a second compatilizer, and the second compatilizer is a second maleic anhydride grafted polyolefin elastomer.
According to some preferred aspects of the present invention, the first base resin has a charge mass ratio of the high density polyethylene to the first linear low density polyethylene of 1: 0.3-3;
the melt index of the high density polyethylene is 0.5-2.0g/10min, and the melt index of the first linear low density polyethylene and the melt index of the second linear low density polyethylene are both 15.0-30.0g/10min.
According to some preferred aspects of the invention, in the first flame retardant, the mass ratio of the decabromodiphenylethane to the antimony trioxide to the magnesium hydroxide to the flame retardant synergist is 1: 0.4-1.0: 0.2-2.0: 0.2-4.0;
in the second flame retardant, the mass ratio of decabromodiphenylethane, antimony trioxide, magnesium hydroxide and the flame retardant synergist is 1: 0.4-1.0: 0.2-2.0: 0.2-3.0;
the flame-retardant synergist is one or more of calcium carbonate, talcum powder, hydrotalcite, silicon dioxide, zinc borate, zinc oxide, montmorillonite, clay, pottery Clay, magnesium oxide, aluminum oxide and glass powder.
According to some preferred aspects of the present invention, in the first compatibilizer, the mass ratio of the maleic anhydride grafted polyethylene to the first maleic anhydride grafted polyolefin elastomer is 1: 0.25 to 3.5;
the grafting rate of the maleic anhydride grafted polyethylene is 0.5-0.8%, and the melt index is 1.0-1.8g/10min;
the grafting rate of the first maleic anhydride grafted polyolefin elastomer and the grafting rate of the second maleic anhydride grafted polyolefin elastomer are both 0.5-0.8%, and the melt indexes are both 0.6-1.5g/10min.
According to some preferred aspects of the invention, in the automobile raw line material, the content of the material A is 93-97% and the content of the material B is 3-7% by mass percentage;
the material A comprises, by mass, 20-60% of first base resin, 2-14% of first compatilizer, 16-60% of first flame retardant, 1-5% of silane, 0.1-0.8% of initiator, 0.2-2% of first antioxidant, 0.4-4% of first lubricant, and optionally 0.2-0.8% of first water scavenger;
the material B comprises, by mass, 20% -60% of second base resin, 4% -14% of second compatilizer, 16% -55% of second flame retardant, 10% -40% of second antioxidant, 0.6% -1.8% of catalyst, 3% -15% of second lubricant, and optionally 1% -4% of second water scavenger.
According to some preferred aspects of the present invention, the first antioxidant is composed of a hindered phenol antioxidant and a phosphite antioxidant, the feeding mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 0.1-10, the hindered phenol antioxidant comprises antioxidant 1010, and the phosphite antioxidant comprises antioxidant HP-10;
the second antioxidant is composed of a thiobisphenol antioxidant and a thioether antioxidant, the feeding mass ratio of the thiobisphenol antioxidant to the thioether antioxidant is 1: 0.25-4.0, the thiobisphenol antioxidant comprises an antioxidant TBM-6, and the thioether antioxidant comprises an antioxidant AO-412S.
According to some preferred aspects of the present invention, the first lubricant consists of methyl silicone rubber, magnesium stearate, pentaerythritol stearate and erucamide in a feed mass ratio of 1: 0.1-10;
the second lubricant is composed of methyl silicone rubber, magnesium stearate and pentaerythritol stearate which are fed in a mass ratio of 1: 0.2-5.
According to some specific and preferred aspects of the present invention, the silane is a silane coupling agent 172.
According to some specific and preferred aspects of the invention, the initiator is dicumyl peroxide.
According to some specific and preferred aspects of the present invention, the catalyst is dibutyltin dilaurate.
According to some specific and preferred aspects of the present invention, the first water scavenger and the second water scavenger are both silane coupling agents 171.
According to some preferred aspects of the present invention, the absolute value of the difference between the specific gravity of the material a and the specific gravity of the material B is 0.05 or less.
The invention provides another technical scheme that: the preparation method of the silane self-crosslinking low-halogen flame-retardant polyolefin automobile raw material comprises the following steps:
preparation of material A:
granulating part of the first base resin in the material A, and all of the first antioxidant, the first flame retardant and the first lubricant into flame-retardant master batches in banburying equipment;
then extruding the flame-retardant master batch and the rest of the first base resin, the first compatilizer, the silane and the initiator in a double-screw extruder, forming, and then selectively adding a first water removing agent to prepare a material A;
preparation of material B:
mixing and banburying the raw materials in the material B, then adopting a single-screw extruder to carry out die face granulation, and then selectively adding a second water removing agent to prepare the material B;
and (3) respectively carrying out aluminum-plastic vacuum packaging on the prepared material A and the material B according to a proportion, and filling the materials into an outer bag to obtain the silane self-crosslinking low-halogen flame-retardant polyolefin automobile original wire material.
When the automobile cable is applied at the later stage, the A material and the B material which are prepared in proportion in the outer bag are mixed, extruded and naturally crosslinked to prepare the thin-wall automobile cable.
The silane self-crosslinking low-halogen flame-retardant polyolefin automobile raw material can realize rapid crosslinking under natural conditions, and avoids the problem of high energy consumption caused by water bath or steam crosslinking.
In the invention, the problem of nonuniform dispersion of the flame retardant is better solved by adopting the form of the prefabricated master batch in the preparation process of the material A.
In some preferred embodiments of the present invention, the twin-screw extruder is a high-torque twin-screw strand extruder (phi 75), the twin-screw length-diameter ratio is 64, 2 low-speed mixers are connected with 2 automatic solid particle weighing scales, 2 liquid scales are respectively connected with the heating zones in sections 4 and 6, and a vacuum extractor is connected with section 13.
In some preferred embodiments of the present invention, during the preparation of material a, the remaining first base resin and the first compatibilizer are mixed and fed into the twin-screw extruder, and the flame-retardant masterbatch is also fed into the twin-screw extruder, and under the protection of nitrogen, the silane and the initiator are mixed according to 1:1 and fed from the liquid scale to section 6, and the other silane is fed from the liquid scale to section 4. The control error of the metering scale is +/-0.005 percent.
In some preferred embodiments of the invention, during the preparation of the material a, the twin-screw extruder temperature zone is set to a temperature: the fuselage: a first area: 110-130 ℃, two areas: 130-150 ℃, three zones: 150-170 ℃ and four zones: 150-170 ℃ and five regions: 170-190 ℃ and six regions: 170-190 ℃ and seven regions: 180-200 ℃, eight regions: 190-210 ℃, nine zones: 190-210 ℃, ten zones: 190-210 ℃, eleven region: 190-210 ℃, twelve regions: 190-210 ℃, thirteen regions: 190-210 ℃ and fourteen regions: 190-210 ℃, fifteen areas: 200-220 ℃, head: 210-230 ℃, die: 220-240 ℃ and the temperature fluctuation of each zone is controlled to be +/-0.5 ℃.
In some preferred embodiments of the invention, during the preparation of the material A, the main machine rotation speed of the twin-screw extruder is 200-300rpm, the vacuumizing device is started, the negative pressure is set to be-0.50-0.70 MPa, and the material A is qualified after the current fluctuation is +/-3%.
The invention provides another technical scheme that: the silane self-crosslinking low-halogen flame-retardant polyolefin automobile raw wire material is applied to preparation of thin-wall automobile cables, and the thickness of each thin-wall automobile cable is less than or equal to 1mm.
According to the invention, the melt indices mentioned in the present invention are all determined according to the ASTM D1238 standard at 190 ℃ under a test load of 2.16 kg.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention provides an improved polyolefin automobile original wire material based on the problem of low productivity caused by insufficient wire releasing speed when the thin-wall or even ultra-thin-wall automobile wire insulating layer is prepared from the polyolefin automobile original wire material in the prior art, the automobile original wire material is two-component, each component adopts specific base resin and compatilizer, and is matched with compounded flame retardant, so that the automobile original wire material can have higher wire releasing speed and better productivity on the premise of endowing the thin-wall or even ultra-thin-wall automobile wire insulating layer with excellent mechanical and mechanical properties and flame retardant performance when the thin-wall or even ultra-thin-wall automobile wire insulating layer is prepared, and the automobile original wire material also has better temperature-resistant grade (more than 125 ℃) and scratch and abrasion resistance.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not noted are generally those in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art. In the following, unless otherwise specified, "%" means mass percent. In the following, high density polyethylene is abbreviated as HDPE and is purchased from TAISOX 8010 of Tai plastic alkene, and the melt index is 1.0g/10min; linear low density polyethylene LLDPE (linear low density polyethylene), tai Mo alkene 3470, and melt index 23.0g/10min;
maleic anhydride grafted polyethylene (MAH-g-PE), available from energetic MC-216A; maleic anhydride grafted polyolefin elastomer (MAH-g-EPM), available from EP70, brassica oleracea;
decabromodiphenylethane is Yabao 8010; magnesium hydroxide is Yabao H5; the talcum powder is a new Shanghai Qian material JQ-5; di-tert-butylperoxyisopropyl benzene (BIPB); antioxidant 1010 from Ciba; antioxidant HP-10 was purchased from Ai Dike ADK, japan; antioxidant TBM-6 was purchased from Santa lecott; antioxidant AO-412S was purchased from Japanese Ai Dike ADK; methyl silicone rubber was purchased from jiahua.
Examples 1 to 4
The embodiments provide a silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material, which comprises a material A and a material B, wherein the feeding mass ratio of the material A to the material B is 95: 5, and the raw material formula of the material A and the material B is shown in the following table 1.
TABLE 1
The preparation method of the silane self-crosslinking low-halogen flame-retardant polyolefin automobile raw wire material comprises the following steps:
preparation of material A:
granulating 2/5 of the first base resin in the material A, all the first antioxidant, the first flame retardant and the first lubricant into flame-retardant master batches in banburying equipment, wherein the banburying temperature is 155 ℃;
then mixing the rest of the first base resin and the first compatilizer, adding the mixture into a double-screw extruder, adding the flame-retardant master batch into the double-screw extruder, under the protection of nitrogen, adding silane and an initiator into the mixture according to 3:1 from a liquid scale to section 6, adding other silanes into the mixture from the liquid scale to section 4, controlling the error of the weighing to be +/-0.005%, mixing, extruding, granulating, cooling, and adding a first water removing agent to prepare a material A; wherein, the twin-screw extruder adopts high-torque twin-screw brace extruder (phi 75), twin-screw draw ratio 64 to 2 low-speed mixers connect 2 automatic weighers of solid particle, 2 liquid weighers to connect respectively in 4 th section and 6 th section heating area, evacuating device connects in 13 sections, and the twin-screw extruder warm area sets up the temperature: the fuselage: a first region: 120 ℃ and a second zone: 140 ℃ and three zones: 160 ℃ and four zones: 160 ℃ and five regions: 180 ℃ and six zones: 180 ℃ and seven regions: 190 ℃ and eight zones: 200 ℃ and nine zones: 200 ℃ and ten regions: 200 ℃ and eleven regions: 200 ℃ and twelve regions: 200 ℃ and thirteen regions: 200 ℃ and fourteen regions: 200 ℃ and fifteen regions: 210 ℃, head: 220 ℃, mold: the temperature fluctuation of each area is controlled to be +/-0.5 ℃; the main machine rotating speed of the double-screw extruder is 250rpm, a vacuumizing device is started, the negative pressure is set to be-0.60 MPa, and the yield is set to be 500kg/h; after the current fluctuation is +/-3%, the normal output is realized.
Preparation of material B:
mixing the raw materials in the material B, mixing the raw materials by an internal mixer (the mixing temperature is 150 ℃), feeding the mixed material blocks into a single-screw extruder by a double-cone feeding die surface to be cut into granules (the extrusion temperature is 120 ℃,130 ℃,140 ℃,140 ℃, 145 ℃ and 145 ℃ in the machine body), and adding a second water removing agent into the finished product granules to prepare the material B;
and respectively carrying out aluminum-plastic vacuum packaging on the prepared material A and the material B according to a proportion, and filling the materials into an outer bag to obtain the silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material.
And when the material is applied at the later stage, mixing the material A and the material B, extruding and crosslinking.
Comparative example 1
Basically, the method is the same as the embodiment 1, and the differences are that: no LLDPE was added to the first base resin and the HDPE content was adjusted accordingly.
Comparative example 2
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the first base resin and the second base resin were both adjusted to: the polyethylene is composed of low-melt-index high-density polyethylene (purchased from Daqing petrochemical, the mark is 5000S, and the melt index is 0.9g/10 min) and high-melt-index high-density polyethylene (purchased from fushun petrochemical, the mark is 2911, and the melt index is 20g/10 min) which are fed in a mass ratio of 4:6.
Comparative example 3
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the MAH-g-EPM in the material A or the material B is replaced by maleic anhydride grafted ethylene butyl acrylate copolymer.
Performance testing
1. The materials prepared in the above examples 1 to 4 and comparative examples 1 to 3 were mixed according to their respective formulations with the material A and the material B, extruded (extrusion temperature: body 140 ℃, 180 ℃, 200 ℃, head 210 ℃), then crosslinked in a water bath at 90 + -2 ℃ for 12h, dried in an oven at 100 ℃ for 3h, adjusted at room temperature for 6h, and then subjected to the following performance tests, as shown in Table 2.
TABLE 2
2. The materials prepared in the above examples 1 to 4 and comparative examples 1 to 3 were mixed according to their respective formulations with the material A and the material B, extruded (extrusion temperature: body 140 ℃, 160 ℃, 180 ℃, 190 ℃, 200 ℃, neck 200 ℃, head 210 ℃), and then naturally crosslinked at a temperature of 23 + -2 ℃ and a humidity of 50 + -10% to prepare a thin-walled automobile cable, and the prepared thin-walled automobile cable was subjected to the following performance tests, and the measured properties were as shown in the following Table 3.
TABLE 3
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Claims (7)
1. The silane self-crosslinking low-halogen flame-retardant polyolefin automobile raw material is characterized by comprising the following components in percentage by mass: 93-97% of material A and 3-7% of material B;
the material A comprises the following raw materials in percentage by mass: 20-60% of first base resin, 4-14% of first compatilizer, 16-60% of first flame retardant, 172-5% of silane coupling agent, 0.1-0.8% of initiator, 0.2-2% of first antioxidant, 0.4-4% of first lubricant and optionally 0.2-0.8% of first water removing agent;
the material B comprises the following raw materials in percentage by mass: 20-60% of second base resin, 2-14% of second compatilizer, 16-55% of second flame retardant, 10-40% of second antioxidant, 0.6-1.8% of catalyst, 3-15% of second lubricant and optionally 1-4% of second water removing agent;
the first base resin is composed of high-density polyethylene and first linear low-density polyethylene, the second base resin is second linear low-density polyethylene, the feeding mass ratio of the high-density polyethylene to the first linear low-density polyethylene is 1: 0.3-3, the melt index of the high-density polyethylene is 0.5-2.0g/10min, and the melt index of the first linear low-density polyethylene and the melt index of the second linear low-density polyethylene are both 15.0-30.0g/10 min;
the first flame retardant and the second flame retardant are independently composed of decabromodiphenylethane, antimony trioxide, magnesium hydroxide and a flame retardant synergist; in the first flame retardant, the mass ratio of decabromodiphenylethane, antimony trioxide, magnesium hydroxide and the flame retardant synergist is 1: 0.4-1.0: 0.2-2.0: 0.2-4.0; in the second flame retardant, the mass ratio of decabromodiphenylethane, antimony trioxide, magnesium hydroxide and the flame retardant synergist is 1: 0.4-1.0: 0.2-2.0: 0.2-3.0;
the first compatilizer is composed of maleic anhydride grafted polyethylene and a first maleic anhydride grafted polyolefin elastomer, and the second compatilizer is a second maleic anhydride grafted polyolefin elastomer; in the first compatilizer, the feeding mass ratio of the maleic anhydride grafted polyethylene to the first maleic anhydride grafted polyolefin elastomer is 1: 0.25-3.5; the grafting rate of the maleic anhydride grafted polyethylene is 0.5-0.8%, and the melt index is 1.0-1.8g/10min; the grafting rate of the first maleic anhydride grafted polyolefin elastomer and the grafting rate of the second maleic anhydride grafted polyolefin elastomer are both 0.5-0.8%, and the melt indexes are both 0.6-1.5g/10min.
2. The silane self-crosslinking low-halogen flame-retardant polyolefin automotive baseline material of claim 1, wherein the flame-retardant synergist is one or more of calcium carbonate, talcum powder, hydrotalcite, silica, zinc borate, zinc oxide, montmorillonite, clay, pottery Clay, magnesium oxide, aluminum oxide and glass powder.
3. The silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material as claimed in claim 1, wherein the first antioxidant is composed of a hindered phenol antioxidant and a phosphite antioxidant, the feeding mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 0.1-10, the hindered phenol antioxidant comprises antioxidant 1010, and the phosphite antioxidant comprises antioxidant HP-10;
the second antioxidant is composed of a thiobisphenol antioxidant and a thioether antioxidant, the feeding mass ratio of the thiobisphenol antioxidant to the thioether antioxidant is 1: 0.25-4.0, the thiobisphenol antioxidant comprises an antioxidant TBM-6, and the thioether antioxidant comprises an antioxidant AO-412S.
4. The silane self-crosslinking low-halogen flame-retardant polyolefin automotive base stock according to claim 1, wherein the first lubricant is composed of methyl silicone rubber, magnesium stearate, pentaerythritol stearate and erucamide in a charge mass ratio of 1: 0.1-10;
the second lubricant is composed of methyl silicone rubber, magnesium stearate and pentaerythritol stearate which are fed in a mass ratio of 1: 0.2-5.
5. The silane self-crosslinking low-halogen flame-retardant polyolefin automotive baseline material of claim 1, wherein the initiator is dicumyl peroxide, the catalyst is dibutyltin dilaurate, and the first and second water scavengers are both silane coupling agents 171; and/or the absolute value of the difference between the specific gravity of the material A and the specific gravity of the material B is less than or equal to 0.05.
6. A method for preparing the silane self-crosslinking low-halogen flame-retardant polyolefin automotive wire stock according to any one of claims 1 to 5, wherein the preparation method comprises the following steps:
preparation of material A:
granulating part of the first base resin in the material A, and all of the first antioxidant, the first flame retardant and the first lubricant into flame-retardant master batches in banburying equipment;
then extruding the flame-retardant master batch, the rest first base resin, the first compatilizer, the silane coupling agent 172 and the initiator in a double-screw extruder, forming, and then selectively adding a first water removing agent to prepare a material A;
preparation of material B:
and mixing and banburying the raw materials in the material B, then adopting a single-screw extruder to carry out die face granulation, and then selectively adding a second water removing agent to prepare the material B.
7. Use of the silane self-crosslinking low-halogen flame-retardant polyolefin automotive raw wire material as defined in any one of claims 1 to 5 in the preparation of thin-walled automotive cables having an insulation thickness of 1mm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110574822.0A CN113308038B (en) | 2021-05-26 | 2021-05-26 | Silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material capable of resisting temperature of 125 ℃, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110574822.0A CN113308038B (en) | 2021-05-26 | 2021-05-26 | Silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material capable of resisting temperature of 125 ℃, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113308038A CN113308038A (en) | 2021-08-27 |
| CN113308038B true CN113308038B (en) | 2023-02-28 |
Family
ID=77374749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110574822.0A Active CN113308038B (en) | 2021-05-26 | 2021-05-26 | Silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material capable of resisting temperature of 125 ℃, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113308038B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059374A (en) * | 2012-12-07 | 2013-04-24 | 江苏德威新材料股份有限公司 | High-temperature-resistant silane-crosslinked flame-retardation insulating material for automobile wires and preparation method thereof |
| CN107663330A (en) * | 2016-07-28 | 2018-02-06 | 中广核拓普（四川）新材料有限公司 | A kind of 125 DEG C of silane self-crosslinking low-smoke halogen-free flame-proof cable materials of heatproof and preparation method thereof |
| CN108623894A (en) * | 2018-04-28 | 2018-10-09 | 江苏德威新材料股份有限公司 | A kind of silane self-crosslinking bittern-free flame-proof material and its preparation method and application |
| CN110272607A (en) * | 2019-07-10 | 2019-09-24 | 江苏上上电缆集团有限公司 | 150 DEG C of crosslinked with silicane low smoke halogen-free flame-retardant polyolefin Insulation Materials of one kind and preparation method thereof |
| CN112409671A (en) * | 2020-11-20 | 2021-02-26 | 杭州以田科技有限公司 | Silane self-crosslinking halogen-free low-smoke flame-retardant polyolefin automobile original line material and preparation method and application thereof |
-
2021
- 2021-05-26 CN CN202110574822.0A patent/CN113308038B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059374A (en) * | 2012-12-07 | 2013-04-24 | 江苏德威新材料股份有限公司 | High-temperature-resistant silane-crosslinked flame-retardation insulating material for automobile wires and preparation method thereof |
| CN107663330A (en) * | 2016-07-28 | 2018-02-06 | 中广核拓普（四川）新材料有限公司 | A kind of 125 DEG C of silane self-crosslinking low-smoke halogen-free flame-proof cable materials of heatproof and preparation method thereof |
| CN108623894A (en) * | 2018-04-28 | 2018-10-09 | 江苏德威新材料股份有限公司 | A kind of silane self-crosslinking bittern-free flame-proof material and its preparation method and application |
| CN110272607A (en) * | 2019-07-10 | 2019-09-24 | 江苏上上电缆集团有限公司 | 150 DEG C of crosslinked with silicane low smoke halogen-free flame-retardant polyolefin Insulation Materials of one kind and preparation method thereof |
| CN112409671A (en) * | 2020-11-20 | 2021-02-26 | 杭州以田科技有限公司 | Silane self-crosslinking halogen-free low-smoke flame-retardant polyolefin automobile original line material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113308038A (en) | 2021-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107857932B (en) | Chemical crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof | |
| CN108239330B (en) | Irradiation crosslinking low-smoke halogen-free flame retardant for automobile wire and preparation method thereof | |
| CN103059404A (en) | Radiation cross-linking low-smoke halogen-free flame-retardant polyolefin insulating material and preparation method thereof | |
| CN109251399B (en) | Soft low-smoke halogen-free high-flame-retardant oil-resistant cable material for high-voltage line in vehicle and preparation method thereof | |
| CN1315932C (en) | Polyropylene resin composite and thermal contraction film made by it | |
| MX2013003607A (en) | Recyclable thermoplastic insulation with improved breakdown strength. | |
| CN112053808A (en) | Manufacturing process of ultraviolet crosslinked cable | |
| CN108239331B (en) | Thermoplastic halogen-free flame-retardant material and preparation method thereof | |
| CN105001503A (en) | High-extrusion-rate heat-shrinkable tube and production method thereof | |
| CN111051398A (en) | Reactive compounding of ethylene-vinyl acetate | |
| JP6770796B2 (en) | Fiber reinforced polypropylene resin composition | |
| CN105315532B (en) | A kind of thermoplasticity soft low-smoke halogen-free CABLE MATERIALS and preparation method thereof | |
| CN105802023A (en) | Irradiation type EPDM and PP blended electric wire and cable insulative material and preparing method thereof | |
| KR101992598B1 (en) | Polymer compound composition for thermoplastic resin and method of manufacturing polymer compound using the same | |
| CN113308038B (en) | Silane self-crosslinking low-halogen flame-retardant polyolefin automobile original line material capable of resisting temperature of 125 ℃, and preparation method and application thereof | |
| CN102295797B (en) | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof | |
| CN114292461B (en) | Irradiation crosslinking halogen-free flame-retardant polyolefin material for new energy automobile wires and preparation method and application thereof | |
| CN113121907A (en) | Preparation of silane self-crosslinking polyolefin automobile cable material | |
| KR20180129985A (en) | Flame retardant polypropylene composition | |
| CN114773719A (en) | Polyolefin material and preparation method and application thereof | |
| CN112409671B (en) | Silane self-crosslinking halogen-free low-smoke flame-retardant polyolefin automobile raw material, and preparation method and application thereof | |
| CN113956577A (en) | Silane self-crosslinking low-smoke halogen-free flame-retardant polyolefin oil-resistant elastomer material and preparation method and application thereof | |
| CN112430367A (en) | Irradiation crosslinking silicone rubber substrate energy storage cable material and preparation method thereof | |
| CN116135921B (en) | Silane crosslinked polyolefin flame-retardant cable material for energy storage cable, and preparation method and application thereof | |
| EP3503122A1 (en) | Polymer composition for insulation layer of power cable, insulation layer including the same and power cable including the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |