CN111635592A - Cable composite material for engineering equipment and preparation method and application thereof - Google Patents
Cable composite material for engineering equipment and preparation method and application thereof Download PDFInfo
- Publication number
- CN111635592A CN111635592A CN202010384614.XA CN202010384614A CN111635592A CN 111635592 A CN111635592 A CN 111635592A CN 202010384614 A CN202010384614 A CN 202010384614A CN 111635592 A CN111635592 A CN 111635592A
- Authority
- CN
- China
- Prior art keywords
- parts
- composite material
- halogen
- flame retardant
- ionic liquid
- 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.)
- Pending
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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a cable composite material for engineering equipment, a preparation method and application thereof, and is characterized in that the cable composite material comprises the following raw materials in parts by mass: ethylene propylene diene monomer 100-300 weight portions; phenolic resin pre-crosslinking functional master batch: 10-100 parts; ethylene-vinyl acetate copolymer: 50-150 parts; 10-100 parts of an elastomer coupling agent; mineral filler: 30-100 parts; ionic liquid modifier: 20-50 parts; halogen-free flame retardant: 200 portions and 600 portions; vulcanizing agent: 5-20 parts of a solvent; auxiliary vulcanizing agent: 5-15 parts; high gloss retroreflective elements: 10-55 parts; high-transparency engineering plastic powder: 10-55 parts; other additives: 2-10 parts. The material disclosed by the invention has the advantages of meeting the performance requirements of high dimensional stability, high and low temperature resistance, oil resistance, impact resistance, compression resistance, acid and alkali resistance, wear resistance, stress cracking resistance, low smoke, zero halogen, flame retardance and the like, and can be used as a material for sheathing and insulating electric wires and cables in engineering equipment such as large intelligent agricultural machinery, an intelligent coal mining machine for opencast coal mines, an intelligent coal mining machine for underground coal mines, an engineering construction shield machine and the like.
Description
Technical Field
The invention belongs to the technical and scientific fields of high polymer materials, particularly relates to a high polymer composite material, and particularly relates to a cable composite material for engineering equipment, and a preparation method and application thereof.
Background
The intelligent equipment industry in China initially forms an industrial system represented by a novel sensor, an intelligent control system, an industrial robot and an automatic complete set production line, but in the aspects of core technologies such as insulation and sheath of cables for intelligent equipment, production, design and processing technology of the cables for intelligent equipment and the like, the simulation or introduction of foreign technologies is mainly taken as a main point, and particularly in the aspects of cables for intelligent agricultural machinery, intelligent coal mining machines for open mines, intelligent coal mining machines for underground mines and shield machines for engineering construction, the cables for power, signal and sensing transmission and the like need to meet basic functions, and have the performances such as high dimensional stability, high and low temperature resistance, oil resistance, impact resistance, compression resistance, wear resistance, stress cracking resistance, low smoke, zero halogen and flame retardance, low toxicity, rapid deformation recovery and the like. At present, related patents related to the research and development of the materials exist in China, for example, the invention patent CN109273159A uses a modified thermoplastic elastomer as an insulating layer of a robot cable, so that the flexibility and the bending resistance of the cable can be realized, but other important properties such as low-smoke halogen-free flame retardant and the like are not investigated and evaluated; the invention patent CN105694238A discloses an insulating rubber material prepared by using ethylene propylene diene monomer as a matrix and specially used for a coal cutter cable, which has excellent electrical insulating property and high mechanical strength, but the formula system of the material does not relate to flame retardant property, oil resistance and the like, and the material does not relate to the retroreflective function of the engineering cable. Therefore, the research and the preparation of the low-smoke halogen-free flame-retardant halogen-free cable composite material for the engineering equipment have important significance for breaking through the foreign technical barriers, further improving the manufacturing level of the engineering equipment in China and promoting the industrial development.
Disclosure of Invention
The invention aims to provide a cable composite material for engineering equipment and a preparation method and application thereof. In order to realize the purpose, the invention firstly introduces the phenolic resin pre-crosslinking functional master batch as a tackifying and reinforcing component, constructs a multiple interpenetrating crosslinking network in a system, and improves the mechanical and electrical properties from the perspective of a material body; and the flame-retardant ionic liquid containing rich N, P flame-retardant elements, rigid ring structures and high-reactivity vinyl is used as the surface modifier of the inorganic flame retardant, and the interaction between the flame retardant and the polyolefin matrix is improved and the flame retardant performance of the material is improved through the surface activity of the ionic liquid and the synergistic crosslinking effect of the ionic liquid in the vulcanization process. Meanwhile, the flame retardant property of the material is further ensured by the action of an acid source and an air source of the ionic liquid in the combustion process of the composite material and the graphitization of the high-activity vinyl in the combustion process. In addition to the synergistic flame-retardant effect, high-activity vinyl in the ionic liquid can be enriched on the surface of the filler, and the high-activity vinyl and the matrix can generate chemical crosslinking reaction in the vulcanization process of the material, so that the interaction between the filler and the matrix is further improved, and the thickness of an interface layer between the filler and the matrix is increased. Meanwhile, cross-linking reaction can also occur between the filler and the filler in the vulcanization process, the physical adsorption part between the catalytic fillers is converted into stable chemical covalent bond action, and a layer of soft interface layer is formed between the fillers, so that the filler finally forms a multi-level, multi-scale, high-elastic and loose-structure solid network structure in a polymer matrix. Due to the existence of the network structure, the static induction effect of anions and cations in ILs is combined, so that the material is endowed with high elasticity and strong deformation recovery capability, and the strength, flexibility and controllable deformation recovery of the material are realized.
The technical scheme is as follows:
the cable composite material for the engineering equipment comprises the following raw materials in percentage by mass:
ethylene propylene diene monomer: 100-300 parts;
phenolic resin pre-crosslinking functional master batch: 10-100 parts;
ethylene-vinyl acetate copolymer: 50-150 parts;
10-100 parts of an elastomer coupling agent;
mineral filler: 30-100 parts;
ionic liquid modifier: 20-50 parts of
Halogen-free flame retardant: 200 portions and 600 portions;
vulcanizing agent: 5-20 parts of a solvent;
auxiliary vulcanizing agent: 5-15 parts;
high gloss retroreflective elements: 10-55 parts;
high-transparency engineering plastic powder: 10-55 parts;
2-10 parts of other additives.
The phenolic resin pre-crosslinking functional master batch is a melt blend of low molecular weight polyethylene or polypropylene-coated hexamethylenetetramine and 1-alkyl (hydroxyl) -3-methylimidazole p-sulfonic polystyrene salt, wherein the phenolic resin pre-crosslinking functional master batch is one or a mixture of cashew nut shell oil modified phenolic resin, tall oil modified phenolic resin and novolac epoxy resin; the ionic liquid modifier is one or a mixture of more of 1-vinyl-3-hydroxyethyl imidazole phosphate, 1, 3-dimethyl imidazole dimethyl phosphate, 1-butyl-3-methyl imidazole dibutyl phosphate, 1-butyl-3-methyl imidazole p-toluenesulfonate and 1-benzyl-3-methyl imidazole bis (trifluoromethanesulfonyl) imide.
Further, the halogen-free flame retardant is one or a mixture of more of magnesium hydroxide, aluminum hydroxide, zinc borate, ammonium polyphosphate, aluminum hypophosphite, triisopropylphenyl phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Further, the ethylene propylene diene monomer is a mixture of one or more of series EPDM with ethylidene-norbornene content of 0.5-10%, vinyl content of 25-65%, melt mass flow rate of 0.1-40g/10min under the test conditions of temperature of 190 ℃ and load weight of 2.16Kg, and weight average molecular weight of 150000-.
Further, the ethylene-vinyl acetate copolymer has a vinyl acetate group content of 20 to 60% and a melt mass flow rate of 0.1 to 40g/10min under a test condition of a temperature of 190 ℃ and a load weight of 2.16 Kg.
Further, the elastomer coupling agent is one or a mixture of ethylene-vinyl acetate copolymer grafted glycidyl methacrylate and ethylene-vinyl acetate copolymer grafted maleic anhydride.
Further, the mineral filler is one or a mixture of more of high-silicon-content talcum powder, phlogopite powder, wollastonite and nano-silica with surface grafted with mercaptosilane, wherein the particle size of the high-silicon-content talcum powder is 0.1-2 mu m, the content of the silica is more than or equal to 70 percent, and the loss on ignition at 800 ℃ is less than or equal to 2 percent; the mesh number of the phlogopite powder is 100-2000 meshes, the content of silicon dioxide is 30-50%, the content of aluminum oxide is 10-20%, and the content of magnesium oxide is 20-35%; the particle diameter of the nano silicon dioxide with the surface grafted with the mercaptosilane is 15-150nm, and the relative grafting rate is 0.1-10%.
Further, the vulcanizing agents are dicumyl peroxide, dibenzoyl peroxide and one or more of 1, 3-bis (tert-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
Further, the auxiliary vulcanizing agent is one or a mixture of more of hexamethylene tetramine, triallyl cyanurate, triallyl isocyanurate and trimethylolpropane trimethacrylate.
Further, the high-gloss retroreflective unit is a mixture of one or more of glass microspheres, microprisms, barium sulfate, titanium dioxide and aluminum oxide; wherein the particle size of the glass beads is 1-650 μm, the content of silicon dioxide is 60-90%, the rounding rate is 95-98%, and the refractive index is 1.6-1.9; the particle size of the barium sulfate is 0.1-5 μm, the whiteness is more than or equal to 95, and the ignition loss is less than or equal to 2% at 800 ℃; oxidation of hydrogen dioxideThe titanium has a particle diameter of 10-20nm and a specific surface area of 60-90m2(ii)/g; the particle diameter of the alumina is 10-30nm, and the specific surface area is 50-200m2/g。
Further, the high-transparency engineering plastic is a mixture of one or more of polyphenylene oxide powder, polyarylsulfone and polyethersulfone powder.
Further, the other additives are an anti-aging agent, a lubricant, an antioxidant, a nucleating agent, silicone master batches and a pigment. The anti-aging agent is one or a mixture of more of styrenated phenol, 4-methyl-6-tert-butylphenol, 4-bis (2, 2-dimethylbenzyl) diphenylamine, 4 '-bis (dimethylbenzyl) diphenylamine, N-phenyl-alpha-aniline, 4' -dioctyl diphenyl, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline and 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer.
A method for preparing the cable composite material for the engineering equipment comprises the following steps: firstly, dissolving an ionic liquid modifier in an alcohol solvent, adding a halogen-free flame retardant, performing ultrasonic oscillation for 15-20min to obtain a suspension, freezing the suspension in a low-temperature refrigerator for 2-4h, and performing freeze drying by a freeze dryer for 1.5-2h to remove the alcohol solvent to obtain the halogen-free flame retardant modified by the ionic liquid; the alcohol solvent is methanol or anhydrous methanol; then adding the ethylene propylene diene monomer, the phenolic resin pre-crosslinking functional master batch, the ethylene-vinyl acetate copolymer, the elastomer coupling agent, the mineral filler, the ionic liquid modified halogen-free flame retardant and other additives into a high-speed mixer with the rotation speed of 2000 revolutions per minute for mixing for 15 minutes, adding the blend into an internal mixer after uniform mixing, controlling the temperature to be 95-105 ℃ and internally mixing for 10-15 minutes, then extruding and granulating the materials by a single-screw extruder with the temperature of 80-105 ℃, blending the particles with a high-gloss unit, extruding and granulating by an extruder with the temperature of 80-105 ℃, the length-diameter ratio of 44 and the rotation speed of an extrusion screw of 150 revolutions per minute, finally internally mixing the obtained materials with high-transparency engineering plastic powder, a vulcanizing agent and an auxiliary vulcanizing agent for 5-10 minutes, and obtaining the cable composite material for engineering equipment.
The application of the cable composite material for engineering equipment is characterized in that the composite material can be used for manufacturing sheaths, insulating layers and retro-reflecting layers of wires and cables in modern engineering equipment such as intelligent agricultural machinery, intelligent coal mining machines for open mines, intelligent coal mining machines under wells, shield machines for engineering construction and the like.
The beneficial effects of the invention are as follows:
1. according to the invention, the ethylene propylene diene monomer, the ethylene-vinyl acetate copolymer and the elastomer coupling agent are blended, so that the good dispersion compatibility of the matrix and other components is ensured, meanwhile, the phenolic resin pre-crosslinking functional master batch is introduced as a tackifying and reinforcing component, a multiple interpenetrating cross-linked network is constructed in the system, and the mechanical and electrical properties are improved from the perspective of the material body; the elastomer coupling agent can modify the surface of the high-transparency engineering plastic powder to obtain the oil-resistant, alkali-resistant, wear-resistant and high-gloss organic functional master batch, and the oil resistance and wear resistance of the cable material can be improved while the excellent electrical performance of the cable material is ensured.
2. In the aspect of flame retardant performance, the invention adopts the halogen-free flame retardant modified by the ionic liquid, selects the nano magnesium hydroxide, the nano aluminum hydroxide and the nano zinc borate as the main components of the smoke-eliminating flame retardant, and introduces the high-silicon talcum powder and the mica sheet with large specific surface area as the carriers and the auxiliary dispersing agents of the flame retardant. Meanwhile, the flame-retardant ionic liquid containing rich N, P flame-retardant elements, rigid ring structures and high-reactivity vinyl is used as the surface modifier of the inorganic flame retardant, and the interaction between the flame retardant and a polyolefin matrix is improved and the flame retardant performance of the material is improved through the surface activity of the ionic liquid and the synergistic crosslinking effect of the ionic liquid in the vulcanization process. Meanwhile, the flame retardant property of the material is further ensured by the action of an acid source and an air source of the ionic liquid in the combustion process of the composite material and the graphitization of the high-activity vinyl in the combustion process.
3. In addition to the synergistic flame-retardant effect, high-activity vinyl in the ionic liquid can be enriched on the surface of the filler, and the high-activity vinyl and the matrix can generate chemical crosslinking reaction in the vulcanization process of the material, so that the interaction between the filler and the matrix is further improved, and the thickness of an interface layer between the filler and the matrix is increased. Meanwhile, cross-linking reaction can also occur between the filler and the filler in the vulcanization process, the physical adsorption part between the catalytic fillers is converted into stable chemical covalent bond action, and a layer of soft interface layer is formed between the fillers, so that the filler finally forms a multi-level, multi-scale, high-elastic and loose-structure solid network structure in a polymer matrix. Due to the existence of the network structure, the static induction effect of anions and cations in ILs is combined, so that the material is endowed with high elasticity and strong deformation recovery capability, and the strength, flexibility and controllable deformation recovery of the material are realized.
4. In the aspect of a retroreflection technology, a high-gloss filler with an intrinsic retroreflection function and a retroreflection unit are selected to be matched with high-transparency engineering plastic powder to improve retroreflection efficiency, meanwhile, high-molecular-weight silicone master batches are introduced to serve as a dispersion carrier of the retroreflection unit, material blending and processing sequences in a processing process and a combination of a double-screw conveying element, a reverse-thread element, a kneading element and a mixing element are adjusted according to a solid conveying mechanism, the retroreflection unit is induced to be selectively and continuously dispersed in a matrix, and the glossiness and the reflection efficiency of the material are further improved while the wear resistance of the material is improved. The composite material prepared by the technical means can realize the regulation and the synergy among multiple performances.
Detailed Description
The examples used various raw materials specifically were:
the density of the ethylene propylene diene monomer 1 is 0.970g/cm3Mooney viscosity [ ML1+4125 deg.C]For 140, the ethylene-norbornene content was 2.8%, the vinyl content was 58%, and the weight average molecular weight was 325000 preferably EPDM36140P from DuPont Dow.
The density of the ethylene propylene diene monomer 2 is 0.880g/cm3Mooney viscosity [ ML1+4125 deg.C]For 45, the ethylene-norbornene content is 0.5%, the vinyl content is 70%, the weight average molecular weight is 150000, preferably EPDM3745P from Dupont Dow.
The phenolic resin pre-crosslinking functional master batch 1 is
T6000 and low molecular weight polyethylene or polypropylene coated hexamethylenetetramineAnd 1-alkyl (hydroxy) -3-methylimidazole p-sulfo polystyrene salt melt blend
The phenolic resin pre-crosslinking functional master batch 2 is a melt blend of phenolic epoxy resin DEN438 and hexamethylenetetramine and 1-alkyl (hydroxyl) -3-methylimidazole p-sulfonic polystyrene salt coated by low molecular weight polyethylene or polypropylene
The ethylene-vinyl acetate copolymer had a vinyl acetate content of 28% and a density of 0.951g/cm3The melt index is 3g/10min at 190 ℃/2.16kg test conditions, preferably EVA265 from DuPont Dow.
The elastomer coupling agent is glycidyl methacrylate grafted ethylene-vinyl acetate copolymer, preferably easy-to-select SOG-02, and the grafting rate is 0.8-1.2%.
The high-transparency engineering plastic is a 1:1 mixture of Sabic polyphenylene oxide powder PX9406-701 and German Bassfer polyether sulfone powder E7020P according to a mass ratio.
The ionic liquid modifier is a blend of 1-vinyl-3-hydroxyethyl imidazole phosphate, 1, 3-dimethyl imidazole dimethyl phosphate and 1-benzyl-3-methylimidazole bistrifluoromethylsulfonyl imide according to the mass ratio of 3:2:1
The halogen-free flame retardant is a mixture of magnesium hydroxide from Zenghui chemical industry Co., Ltd, aluminum hydroxide HT-205 from Jinan Thai chemical industry Co., Ltd and zinc borate HT-207 from Jinan Thai chemical industry Co., Ltd in a mass ratio of 8:8: 1.
The mineral filler is a mixture of talc powder with high silicon content of Asfeng powder raw material Limited company in Quanzhou city and mica powder of Limited liability company in Chuzhou Gerui mining industry in a mass ratio of 1: 1.
The high gloss retroreflective elements 1 are glass microspheres HN38 from shanxi hero science & ltd.
High gloss retroreflective element 2 is reflexive ink8011 from 3M usa.
The vulcanizing agent is Chinese petrochemical dicumyl peroxide and Ackso-Nobel DCP odorless bridging agent BIPB.
The co-curing agent is triallyl cyanurate of Guangzhou Gannan New Material Co.
The anti-aging agent is a mixture of Chinese petrochemical 2-thiol benzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline and N, N' -di (beta-naphthyl) p-phenylenediamine according to the mass ratio of 3:2: 2.
The coupling agent is a silane coupling agent gamma-methacryloxypropyltrimethoxysilane for Dow Corning.
The antioxidant is a mixture of tris (2, 4-di-tert-butyl) phenyl phosphite and pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in a mass ratio of 1:1, preferably 168 and 1010 from BASF corporation.
Other auxiliary agents including macromolecular compatilizers, lubricants, nucleating agents, antistatic agents, color master batches and the like are common commercial industrial products in the manufacture of cable insulation and sheath materials.
The following examples are composed of the raw materials of the cable composite material for engineering equipment in parts by weight, as shown in table 1:
TABLE 1 raw materials and amounts used in the examples
The manufacturing method of the cable composite material for the engineering equipment comprises the following steps:
firstly, dissolving an ionic liquid modifier in an alcohol solvent, then adding a halogen-free flame retardant, obtaining a suspension after ultrasonic oscillation for 20min, freezing the suspension in a low-temperature refrigerator for 3h, and freeze-drying the suspension for 2.0h by a freeze dryer to remove the alcohol solvent, thus obtaining the halogen-free flame retardant modified by the ionic liquid. After the modification of the ionic liquid is finished, adding the ethylene propylene diene monomer, the phenolic resin pre-crosslinking functional master batch, the ethylene-vinyl acetate copolymer, the elastomer coupling agent, the mineral filler, the ionic liquid modified halogen-free flame retardant and other additives into a high-speed mixer at the rotating speed of 2000 rpm for mixing for 15 minutes, after uniform mixing, adding the blend into an internal mixer, controlling the temperature at 100 ℃ for internal mixing for 15 minutes, then extruding and granulating the materials by a single-screw extruder at the temperature of 90 ℃, blending the particles with a high-gloss unit, extruding and granulating by a double-screw extruder at the temperature of 90 ℃ and the length-diameter ratio of 44, and finally internally mixing the obtained materials with high-transparency engineering plastic powder, a vulcanizing agent and an auxiliary vulcanizing agent for 10 minutes to obtain the cable composite material for engineering equipment.
To demonstrate the effect of the present invention, a formulation of a comparative example is provided as shown in table 2:
TABLE 2 raw materials and amounts used in respective proportions
The preparation methods and the steps of comparative examples 1,2 and 3 were exactly the same as those of the above 7 examples.
The main performance indexes of the composites prepared in examples 1-7 are shown in Table 3:
TABLE 3 examples material properties
The main performance indicators of the composites prepared in comparative examples 1-3 are shown in table 4: table 4 comparative material properties
The comparison between the embodiment and the comparative example shows that the material prepared by the technical scheme disclosed by the invention can simultaneously meet the performance requirements of high dimensional stability, high and low temperature resistance, oil resistance, impact resistance, pressure resistance, wear resistance, stress cracking resistance, acid and alkali resistance, low smoke, zero halogen, flame retardance and the like.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications can be made to the embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (8)
1. The cable composite material for the engineering equipment is characterized by comprising the following raw materials in percentage by mass:
ethylene propylene diene monomer: 100-300 parts;
phenolic resin pre-crosslinking functional master batch: 10-100 parts;
ethylene-vinyl acetate copolymer: 50-150 parts;
10-100 parts of an elastomer coupling agent;
mineral filler: 30-100 parts;
ionic liquid modifier: 20-50 parts of
Halogen-free flame retardant: 200 portions and 600 portions;
vulcanizing agent: 5-20 parts of a solvent;
auxiliary vulcanizing agent: 5-15 parts;
high gloss retroreflective elements: 10-55 parts;
high-transparency engineering plastic powder: 10-55 parts;
2-10 parts of other additives.
2. The composite material for the wire and cable for engineering equipment as claimed in the preceding claim, wherein the phenolic resin pre-crosslinked functional masterbatch is a melt blend of one or a mixture of cashew nut shell oil modified phenolic resin, tall oil modified phenolic resin and novolac epoxy resin, and low molecular weight polyethylene or polypropylene coated hexamethylenetetramine and 1-alkyl (hydroxy) -3-methylimidazole p-sulfo polystyrene salt.
3. The cable composite for engineering equipment according to the preceding claim, wherein the ionic liquid modifier is one or a mixture of more of 1-vinyl-3-hydroxyethylimidazole phosphate, 1, 3-dimethylimidazole dimethyl phosphate, 1-butyl-3-methylimidazole dibutyl phosphate, 1-butyl-3-methylimidazole p-toluenesulfonate, 1-benzyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt.
4. The cable composite material for engineering equipment as claimed in the preceding claim, wherein the halogen-free flame retardant is a mixture of one or more of magnesium hydroxide, aluminum hydroxide, zinc borate, ammonium polyphosphate, aluminum hypophosphite, triisopropylphenyl phosphate, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
5. The cable composite material for engineering equipment as claimed in the above claim, wherein the material is prepared by a method comprising the steps of dissolving an ionic liquid modifier in an alcohol solvent, adding a halogen-free flame retardant, ultrasonically shaking for 15-20min to obtain a suspension, freezing the suspension in a low-temperature refrigerator for 2-4h, and freeze-drying the suspension for 1.5-2h by a freeze dryer to remove the alcohol solvent to obtain the halogen-free flame retardant modified by the ionic liquid; the alcohol solvent is methanol or anhydrous methanol; then adding the ethylene propylene diene monomer, the phenolic resin pre-crosslinking functional master batch, the ethylene-vinyl acetate copolymer, the elastomer coupling agent, the mineral filler, the ionic liquid modified halogen-free flame retardant and other additives into a high-speed mixer with the rotating speed of 2000 r/min for mixing for 15min, adding the blend into an internal mixer after uniform mixing, controlling the temperature to be 95-105 ℃, internally mixing for 10-15min, then the materials are extruded and granulated by a single screw extruder with the temperature of 80-105 ℃, and the particles and the high-gloss retroreflective units are blended and then extruded and granulated by a double-screw extruder with the temperature of 80-105 ℃, the length-diameter ratio of 44 and the rotating speed of an extrusion screw of 150 revolutions per minute, and finally the obtained material is banburied with high-transparency engineering plastic powder, a vulcanizing agent and an auxiliary vulcanizing agent for 5-10 min.
6. The cable composite material for engineering equipment as claimed in claim 4, wherein the ethylene propylene diene monomer is ethyleneA mixture of one or more of EPDM series having a norbornene content of 0.5-10%, a vinyl content of 25-65%, a melt mass flow rate of 0.1-40g/10min at 190 ℃ under the test conditions of a load weight of 2.16Kg, and a weight average molecular weight of 150000-350000; further preferably, the ethylene-vinyl acetate copolymer has a vinyl acetate group content of 20 to 60% and a melt mass flow rate of 0.1 to 40g/10min under a test condition of a temperature of 190 ℃ and a load weight of 2.16 Kg; further preferably, the elastomer coupling agent is one or a mixture of ethylene-vinyl acetate copolymer grafted glycidyl methacrylate and ethylene-vinyl acetate copolymer grafted maleic anhydride; preferably, the mineral filler is one or a mixture of more of high-silicon-content talcum powder, phlogopite powder, wollastonite and nano-silica with the surface grafted with mercaptosilane, wherein the particle size of the high-silicon-content talcum powder is 0.1-2 mu m, the content of the silica is more than or equal to 70 percent, and the loss on ignition at 800 ℃ is less than or equal to 2 percent; the mesh number of the phlogopite powder is 100-2000 meshes, the content of silicon dioxide is 30-50%, the content of aluminum oxide is 10-20%, and the content of magnesium oxide is 20-35%; the particle diameter of the nano silicon dioxide with the surface grafted with mercaptosilane is 15-150nm, and the relative grafting rate is 0.1-10%; further preferably, the vulcanizing agents are dicumyl peroxide, dibenzoyl peroxide and one or more of 1, 3-bis (tert-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; further preferably, the co-vulcanizing agent is one or more of hexamethylene tetramine, triallyl cyanurate, triallyl isocyanurate and trimethylolpropane trimethacrylate; further preferably, the high gloss retroreflective elements are a mixture of one or more of glass microspheres, microprisms, barium sulfate, titanium dioxide and alumina; wherein the particle size of the glass beads is 1-650 μm, the content of silicon dioxide is 60-90%, the rounding rate is 95-98%, and the refractive index is 1.6-1.9; the particle size of the barium sulfate is 0.1-5 μm, the whiteness is more than or equal to 95, and the ignition loss is less than or equal to 2% at 800 ℃; the titanium dioxide has a particle size of 10-20nm and a specific surface area of 60-90m2(ii)/g; the particle diameter of the alumina is 10-30nm, and the specific surface area is 50-200m2(ii)/g; further, the method can be used for preparing a novel materialPreferably, the high-transparency engineering plastic is a mixture of one or more of polyphenylene oxide powder, polyarylsulfone and polyethersulfone powder, further preferably, the other additives are an anti-aging agent, a lubricant, an antioxidant, a nucleating agent, a silicone master batch and a pigment, and further preferably, the anti-aging agent is a mixture of one or more of styrenated phenol, 4-methyl-6-tert-butylphenol, 4-bis (2, 2-dimethylbenzyl) diphenylamine, 4 '-bis (dimethylbenzyl) diphenylamine, N-phenyl- α -aniline, 4' -dioctylbenzene, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline and 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer.
7. A method for preparing the cable composite material for engineering equipment as claimed in any one of claims 1 to 6, characterized in that the preparation method of the composite material comprises the following steps: firstly, dissolving an ionic liquid modifier in an alcohol solvent, adding a halogen-free flame retardant, performing ultrasonic oscillation for 15-20min to obtain a suspension, freezing the suspension in a low-temperature refrigerator for 2-4h, and performing freeze drying by a freeze dryer for 1.5-2h to remove the alcohol solvent to obtain the halogen-free flame retardant modified by the ionic liquid; the alcohol solvent is methanol or anhydrous methanol; then adding the ethylene propylene diene monomer, the phenolic resin pre-crosslinking functional master batch, the ethylene-vinyl acetate copolymer, the elastomer coupling agent, the mineral filler, the ionic liquid modified halogen-free flame retardant and other additives into a high-speed mixer with the rotation speed of 2000 revolutions per minute for mixing for 15 minutes, adding the blend into an internal mixer after uniform mixing, controlling the temperature to be 95-105 ℃ and internally mixing for 10-15 minutes, then extruding and granulating the materials by a single-screw extruder with the temperature of 80-105 ℃, blending the particles with a high-gloss unit, extruding and granulating by an extruder with the temperature of 80-105 ℃, the length-diameter ratio of 44 and the rotation speed of an extrusion screw of 150 revolutions per minute, finally internally mixing the obtained materials with high-transparency engineering plastic powder, a vulcanizing agent and an auxiliary vulcanizing agent for 5-10 minutes, and obtaining the cable composite material for engineering equipment.
8. Use of a composite material according to any one of claims 1 to 6 or a composite material prepared by the method according to claim 7, wherein the composite material is used for the manufacture of sheaths, insulation and retroreflective layers of wires and cables in modern engineering equipment such as intelligent agricultural machinery, intelligent coal mining machines for open coal mines, intelligent coal mining machines for underground wells and shield machines for engineering construction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010384614.XA CN111635592A (en) | 2020-05-08 | 2020-05-08 | Cable composite material for engineering equipment and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010384614.XA CN111635592A (en) | 2020-05-08 | 2020-05-08 | Cable composite material for engineering equipment and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111635592A true CN111635592A (en) | 2020-09-08 |
Family
ID=72328341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010384614.XA Pending CN111635592A (en) | 2020-05-08 | 2020-05-08 | Cable composite material for engineering equipment and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111635592A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625331A (en) * | 2020-12-08 | 2021-04-09 | 江苏达胜高聚物股份有限公司 | Flame-retardant PE cable material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597395A (en) * | 2009-06-24 | 2009-12-09 | 上海至正道化高分子材料有限公司 | A kind of fireproofing cable material without halide and preparation method thereof |
| CN103724820A (en) * | 2013-12-06 | 2014-04-16 | 成都闿阳科技有限公司 | Automobile trunk sealing strip based on ethylene-propylene-diene rubber |
| CN105622872A (en) * | 2014-12-15 | 2016-06-01 | 彤程化学（中国）有限公司 | Cashew nut shell oil modified novolac resin and preparation method and application of cashew nut shell oil modified novolac resin |
| CN107163336A (en) * | 2017-06-05 | 2017-09-15 | 薛念念 | A kind of fire-retardant high-damping thermoplastic elastomer (s) and preparation method thereof |
| CN110041607A (en) * | 2019-04-30 | 2019-07-23 | 合肥工业大学 | A kind of metal hydroxides-boron nitride hydridization filler/blend rubber nuclear power cable Insulation Material and preparation method |
-
2020
- 2020-05-08 CN CN202010384614.XA patent/CN111635592A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597395A (en) * | 2009-06-24 | 2009-12-09 | 上海至正道化高分子材料有限公司 | A kind of fireproofing cable material without halide and preparation method thereof |
| CN103724820A (en) * | 2013-12-06 | 2014-04-16 | 成都闿阳科技有限公司 | Automobile trunk sealing strip based on ethylene-propylene-diene rubber |
| CN105622872A (en) * | 2014-12-15 | 2016-06-01 | 彤程化学（中国）有限公司 | Cashew nut shell oil modified novolac resin and preparation method and application of cashew nut shell oil modified novolac resin |
| CN107163336A (en) * | 2017-06-05 | 2017-09-15 | 薛念念 | A kind of fire-retardant high-damping thermoplastic elastomer (s) and preparation method thereof |
| CN110041607A (en) * | 2019-04-30 | 2019-07-23 | 合肥工业大学 | A kind of metal hydroxides-boron nitride hydridization filler/blend rubber nuclear power cable Insulation Material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 张殿荣 等: "《现代橡胶配方设计》", 31 October 2001, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625331A (en) * | 2020-12-08 | 2021-04-09 | 江苏达胜高聚物股份有限公司 | Flame-retardant PE cable material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108102207B (en) | Halogen-free flame-retardant thin-wall oil-resistant cable insulation and sheath manufactured through multiple crosslinking process and manufacturing method and application thereof | |
| CN102040841B (en) | Dynamic vulcanization halogen-free flame retardant silicon rubber/polyolefin thermoplastic elastomer | |
| CN102977605B (en) | A kind of silicone rubber crosslinking fire-resistant cable material and preparation method thereof | |
| CN109971110B (en) | Silane cross-linked halogen-free flame-retardant TPE cable material and preparation method and application thereof | |
| CN106349685A (en) | High-oil-resistance charging-pile halogen-free flame-retardant TPU (thermal receiver unit) cable 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 | |
| CN110283415B (en) | Thermoplastic elastomer with both conductivity and flame retardance and preparation method thereof | |
| CN105367883A (en) | Micro cross-linked low-smoke zero-halogen flame-retardant polyolefin cable material and preparation method thereof | |
| CN112442227B (en) | Low-smoke halogen-free cable material and preparation method and application thereof | |
| CN1241983C (en) | Halogen-free flame-retardant dynamic vulcanized ternary ethylene-propylene rubber/ polypropylene thermoplastic elastomer | |
| CN114058111A (en) | High-flexibility oil-resistant low-smoke halogen-free flame-retardant cable material and preparation method thereof | |
| CN111961274A (en) | Insulating material for photovoltaic cable and preparation method thereof | |
| CN112226058A (en) | Antistatic heat conduction material and preparation method and application thereof | |
| CN114822947A (en) | Thermoplastic elastomer energy new energy cable | |
| CN111635592A (en) | Cable composite material for engineering equipment and preparation method and application thereof | |
| CN104893085A (en) | Soft halogen-free flame-retardant insulation material for home appliances and preparation method thereof | |
| CN103756268A (en) | Polyimide fiber enhanced PBT (Polybutylece Terephthalate) composite material and preparation method thereof | |
| CN103044796B (en) | A kind of epoxy resin strengthens polystyrene bittern-free flame-proof material and preparation method thereof | |
| CN103102692B (en) | Halogen-free flame retardant silicone rubber/modified polyamide thermoplastic elastomer and preparation method thereof | |
| CN111647271A (en) | High-temperature-resistant flame-retardant organic silicon elastomer cable material and preparation method thereof | |
| CN111635578A (en) | Preparation method of halogen-free low-smoke flame-retardant cross-linked polyolefin sheath material for electric vehicle cable | |
| CN113736183B (en) | Anti-seismic low-smoke halogen-free flame-retardant cable sheath material and preparation method and application thereof | |
| CN114864163B (en) | High-temperature-resistant flame-retardant cable | |
| CN105602081B (en) | Composite material of illite powder and thermoplastic elastomer POE, and preparation method and application thereof | |
| CN112430388A (en) | High-performance halogen-free flame-retardant PC/GF composite material and product thereof |
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 |