CN111647265B - Oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material and preparation method thereof - Google Patents
Oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material and preparation method thereof Download PDFInfo
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- CN111647265B CN111647265B CN202010522684.7A CN202010522684A CN111647265B CN 111647265 B CN111647265 B CN 111647265B CN 202010522684 A CN202010522684 A CN 202010522684A CN 111647265 B CN111647265 B CN 111647265B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/40—High-molecular-weight compounds
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/003—Apparatus or processes specially adapted for manufacturing conductors or cables using irradiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
- H01B13/24—Sheathing; Armouring; Screening; Applying other protective layers by extrusion
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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Abstract
The invention discloses an oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material and a preparation method thereof, wherein a polyurethane prepolymer which has a certain molecular weight and isocyanate groups at two ends is synthesized by applying the reaction of polyol and polyisocyanate and controlling the R value to be 2.05-2.45. The isocyanate-terminated polyurethane prepolymer is mixed with white carbon black, a flame retardant and a mineral filler, and functional inorganic particles with polyurethane as a soft shell and the filler as a hard core are formed through physical dispersion and mechanochemical reaction. The hardness of the polyurethane cable material can be reduced, and the flexibility and the oil resistance of the polyurethane cable material can be improved. The cable material forms a multi-layer network structure through irradiation crosslinking and secondary vulcanization processes, so that the mechanical property of the material is improved, and the dimensional shrinkage rate of the material in the molding process is reduced. The oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material can be used for manufacturing low-smoke halogen-free flame-retardant cables, flexible special cables, insulation and sheaths of wires for new energy automobiles and Chinese standard motor train units.
Description
Technical Field
The invention belongs to the field of polymer functionalized modification science and high polymer materials for cables, relates to an oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material and a preparation method thereof, and particularly relates to a cable insulation and sheath material for manufacturing low-smoke halogen-free flame-retardant cables, flexible special cables, new energy automobiles and Chinese standard motor train units and a preparation method thereof.
Background
With the continuous improvement of the quality requirements of the cable products in the market, the domestic cable industry is accelerating the updating and upgrading of the products. The low-smoke halogen-free flame-retardant cable, the flexible special cable, the cable for illuminating new energy automobiles and Chinese standard motor train units have more strict requirements on the performance of the cable products due to the special use environment of the cable, on one hand, the cable materials are used as power transmission carriers and signal transmission paths and need to meet basic performance requirements of halogen-free flame retardance, high strength, bending resistance, wear resistance, tear resistance, high dimensional stability, thin wall, low toxicity and the like, on the other hand, the cable materials are harsh in use environment, such as power energy cables applied to wind power generation engineering, mining mechanical engineering, desert, ice snow and other extreme environments, and have good performances of high and low temperature resistance, environmental stress cracking resistance, light aging resistance, oil resistance, hydrolysis resistance, wind erosion resistance, oxidation resistance and the like while meeting various basic performance requirements. In addition, for some industrial TPU cables, such as industrial robot and manipulator cables, a high degree of torsion resistance and repeated bending properties are often required depending on the use characteristics of the equipment. However, the development of the cable is still in the beginning stage in China, and some core production technologies are monopolized abroad, so that the insulating and sheathing materials which can completely meet the requirements cannot be developed at the present stage.
With regard to the development of the special cable, some related inventions have been disclosed so far, but the materials reported in these patents still cannot fully satisfy the requirements. The patent with application publication number CN 103214749A adopts modified sulfonated polyethylene, maleic anhydride grafted polyolefin elastomer, thermoplastic polyurethane elastomer, flame retardant and other additives to prepare the thermoplastic polyurethane elastomer cable material, and the cable material can work at high temperature and has good flame retardant property and mechanical property, but the oil resistance is not good enough. The patent with application publication number CN 102977585A combines polar rubber such as chloroprene rubber, nitrile rubber and the like with a polyurethane thermoplastic elastomer, and simultaneously introduces reinforcing filler and other auxiliary agents into a system to prepare the polyurethane flame-retardant environment-friendly cable material. The patent with application publication number CN 103467971A discloses a high-flame-retardant and high-weather-resistance modified polyurethane cable material and a preparation method thereof, chlorinated polyethylene is selected as a synergistic flame retardant to endow the material with excellent flame retardant performance, but the material contains halogen, so that the material can cause harm to the environment. In addition, some of the materials reported in the related patents and documents which are already disclosed do not carry out surface treatment on the filler in the preparation process, so that the mechanical properties of the material cannot meet the index requirements, and the material has high hardness and is limited in use.
Aiming at the defects of the prior art, the invention prepares the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material, and the isocyanate-terminated polyurethane prepolymer is used for coating the surfaces of the flame retardant, the white carbon black and the mineral filler, so that the rigidity and toughness balance of the material is improved, the hardness of the material is reduced, the material has good flexibility, wear resistance, thermal oxygen resistance, light aging resistance and flame retardance, the Limiting Oxygen Index (LOI)% of the material is 39, and the performances of oil resistance, aging resistance, environmental stress cracking resistance and the like can meet the requirements of industrial indexes.
Disclosure of Invention
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly discloses a preparation method of an isocyanate-terminated polyurethane prepolymer, which comprises the following steps:
the method comprises the following steps: taking a proper amount of polyhydric alcohol for vacuum drying, adding the polyhydric alcohol into a flask with a stirrer, a condenser pipe and a nitrogen protection device after dehydration treatment, and then placing the flask into a constant-temperature oil bath pan;
step two: adding a certain amount of polyisocyanate into a flask according to a set R value, wherein the R value is the ratio of the number of isocyanate groups in the polyisocyanate to the number of terminal hydroxyl groups in the polyol, and is expressed by a formula of R ═ n (-NCO)/n (-OH), the preferable interval of the R value is 2.05-2.45, and then adding a catalyst into the system in an amount of five thousandths of the content of the polyisocyanate;
step three: after the material addition is finished, the reaction system is placed at 30 ℃ for heat preservation for 30min, then the temperature is raised to 80 ℃ for reaction for 4 hours, and then the product is collected, so as to obtain the isocyanate-terminated polyurethane prepolymer.
Preferably, the polyol is one or a mixture of polyester polyol or polyether polyol, wherein the polyester polyol is one or a mixture of polycarbonate diol or polycaprolactone diol, the relative molecular mass is 2000-5000, and the water content is less than 0.1%; the polyether polyol is one or a mixture of polypropylene glycol, polyethylene glycol or polytetrahydrofuran ether glycol, the relative molecular mass is 3000-6000, and the water content is less than 0.5%.
Preferably, the polyisocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and toluene diisocyanate.
Preferably, the catalyst is one of dibutyltin dilaurate, triethylene diamine, N' -dimethylcyclohexylamine and stannous octoate.
More preferably, the polyol raw material of the isocyanate-terminated polyurethane prepolymer is polypropylene glycol (PPG) with a relative molecular mass of 3000, 4000 or 5000, the hydroxyl value of the prepolymer is 34-42(KOH mg/g) when polypropylene glycol with a relative molecular mass of 3000 is selected, the hydroxyl value of the prepolymer is 26-30(KOH mg/g) when polypropylene glycol with a relative molecular mass of 4000 is selected, and the hydroxyl value of the prepolymer is 20-24(KOH mg/g) when polypropylene glycol with a relative molecular mass of 5000 is selected; the raw material of the polyisocyanate is isophorone diisocyanate (IPDI) with the purity of 99.0-99.9%; the catalyst raw material is dibutyltin dilaurate.
The invention also discloses an oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material and a preparation method thereof, and the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material is characterized by comprising the following raw materials in parts by weight:
preferably, the thermoplastic polyurethane elastomer is polyether thermoplastic polyurethane elastomer, the Shore A hardness is 50-85, and the density is 1.05-1.45g/cm3。
Preferably, the polar rubber is one or more of ethylene-vinyl acetate rubber, acrylate rubber, nitrile rubber, hydrogenated nitrile rubber and ethylene-acrylate rubber. Wherein the ethylene-vinyl acetate rubber has a vinyl acetate content of 15-50% and a melt index of 0.5-35 g/ml under the test condition of 190 ℃/2.16kg10min, melting point of 50-90 deg.C, Shore A hardness of 45-90, and density of 0.90-1.15g/cm3(ii) a The acrylate rubber is epoxy type, the epoxy group content is 0.1-10%, and the Mooney viscosity [ ML1+ 4100 DEG C]25-55, the glass transition temperature is-40 to-10 ℃, and the density is 1.05-1.20g/cm3(ii) a The acrylonitrile monomer accounts for 15-50% of the nitrile rubber, and the Mooney viscosity [ ML1+ 4100 DEG C]50-90, and the density is 0.95-1.10g/cm3(ii) a The content of bound acrylonitrile in the hydrogenated nitrile rubber is 15-50%, and the Mooney viscosity [ ML1+ 4100 DEG C]50-90, iodine value center value 8-30mg/100 mg; the content of acrylic ester in the ethylene-acrylic ester rubber is 10-42%, and the Mooney viscosity [ ML1+ 4100 DEG C]15-75, and density of 1.00-1.10g/cm3。
Preferably, the mass fraction of the third monomer ENB in the ethylene propylene diene monomer is 4.9-9%, and the Mooney viscosity [ ML1+ 4125 ℃ C ] is 20-90;
more preferably, the ethylene propylene diene monomer contains ENB as the third monomer in 4.9 wt% and has a Mooney viscosity [ ML1+ 4125 ℃ ] of 25.
Preferably, the high molecular compatilizer is one of ethylene-octene copolymer grafted glycidyl methacrylate, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate terpolymer, wherein the grafting ratio of the ethylene-octene copolymer grafted glycidyl methacrylate is 2.5-3.5%, the melt index is 2.0-6.0g/10min under the test condition of 190 ℃/2.16kg, the Shore A hardness is 65-90, and the density is 0.80-1.10g/cm3(ii) a The content of methyl acrylate in the ethylene-methyl acrylate copolymer is 15-25%, the melt index is 0.5-4.5g/10min under the test condition of 190 ℃/2.16kg, and the density is 0.95-1.15g/cm3The Vicat softening point is 45-65 ℃; the content of ethyl acrylate in the ethylene-ethyl acrylate copolymer is 10-30%, the melt index is 3.5-10g/10min under the test condition of 190 ℃/2.16kg, and the density is 0.85-1.10g/cm3The Vicat softening point is 55-80 ℃; the ethylene-methyl acrylate-glycidyl methacrylateThe density of the glyceride terpolymer is 0.90-1.45g/cm3The melt index is 5-15g/10min under the test condition of 190 ℃/2.16 kg.
More preferably, the macromolecular compatilizer is an ethylene-methyl acrylate-glycidyl methacrylate terpolymer with the density of 1.05-1.45g/cm3The melt index was 12g/10min at 190 ℃/2.16kg test conditions.
Preferably, the inorganic flame retardant is one or a mixture of magnesium hydroxide, aluminum hydroxide, zinc borate, zinc stannate, antimony trioxide and hydrated magnesium silicate.
More preferably, the halogen-free flame retardant is a mixture of magnesium hydroxide, aluminum hydroxide and zinc borate, the mass ratio is 5:5:1, and the particle size is 0.1-5 μm.
Preferably, the phosphorus flame retardant is one or a mixture of melamine polyphosphate, ammonium polyphosphate, zinc hypophosphite, calcium hypophosphite, trioctyl phosphate, triisopropylphenyl phosphate, pentaerythritol phosphate, dimethyl methyl phosphate and diethyl ethyl phosphate.
More preferably, the phosphorus flame retardant is pentaerythritol phosphate, which is more likely to form a char layer during combustion and has high flame retardant efficiency, compared to commonly used ammonium polyphosphate.
Preferably, the white carbon black is fumed silica, the fineness is 4000-6000 meshes, and the content of silicon dioxide is higher than 99.8%.
Preferably, the mineral filler is one or more of calcined kaolin, wollastonite powder, porous quartz powder, diatomite and bentonite.
More preferably, the mineral filler wollastonite powder has a silica content of 70%, a fineness of 3000 meshes and a whiteness of 90.
Preferably, the vulcanization accelerator is one or more of zinc oxide, tetramethylthiuram disulfide (TMTD), N-oxydiethylene-2-benzothiazolesulfenamide (NOBS) in a mixture.
Preferably, the radiation sensitizer is one or more of triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diallyl phthalate, and N, N' -m-phenylene bismaleimide.
Preferably, the antioxidant comprises two of a hindered phenol type thermal oxidation resistant aging agent and a light stabilizer, wherein the hindered phenol type thermal oxidation resistant aging agent is one or a mixture of N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl), and the light stabilizer is one or a mixture of a compound hindered amine light stabilizer, a hindered benzoate light stabilizer, a triazine ultraviolet light absorber and a benzotriazole ultraviolet light absorber.
More preferably, the anti-aging agent is a mixture of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) and a complex hindered amine light stabilizer cyanogen V703 in a mass ratio of 1:1: 1.
Preferably, the coupling agent is one or a mixture of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane or gamma-methacryloxypropyltrimethoxysilane.
Preferably, the antistatic agent is one or a mixture of trihydroxyethyl methyl quaternary ammonium methyl sulfate or ethoxylated alkylamine.
The invention also discloses the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) firstly, weighing thermoplastic polyurethane elastomer, polar rubber, ethylene propylene diene monomer, high molecular compatilizer, isocyanate-terminated polyurethane prepolymer, inorganic flame retardant, phosphorus flame retardant, white carbon black, mineral filler, anti-aging agent, coupling agent, antistatic agent and calcium stearate according to a formula proportion, premixing the weighed white carbon black, inorganic flame retardant and mineral filler to obtain primary mixed filler, uniformly dropwise adding the prepared isocyanate-terminated polyurethane prepolymer into the primary mixed filler, performing dispersion mixing treatment on the primary mixed filler containing the isocyanate-terminated polyurethane prepolymer at the rotating speed of 1600 plus 2300r/min by using a high-speed mixer for 5-8min, and coating the surface of the primary mixed filler by the isocyanate-terminated polyurethane prepolymer through mechanical force induction, constructing functional particles with a mixed filler as a hard core and polyurethane as a soft shell to obtain a modified mixed filler, then mixing the modified mixed filler and the rest of all raw materials at a high speed of 1600-2300r/min for 8-15min to obtain a mixture, and then carrying out melt extrusion, granulation and drying on the mixture by a double-screw extruder to obtain filling master batches, wherein the temperature of the double-screw extruder is set as follows: the feeding section is 180-190 ℃, the conveying section is 185-195 ℃, the mixing section is 190-200 ℃, the exhaust section is 190-200 ℃ and the homogenizing section is 195-205 ℃; (2) mixing the filling master batch prepared in the step (1) with the vulcanization accelerator and the radiation sensitizer at a high speed of 1600-2300r/min for 5-12min, and then performing melt extrusion on a cable metal conductor by using a cable extruder to obtain an extruded cable, wherein the process temperature of the extruder is set as follows: the first section is 190 ℃ in 180 DEG, the second section is 195 ℃ in 185 DEG, the third section is 205 ℃ in 195 DEG, the fourth section is 210 ℃ in 200 DEG, the fifth section is 220 ℃ in 210 DEG, and the head is 215 ℃.
(3) Irradiating and crosslinking the extruded cable prepared in the step (2) by an electron accelerator, wherein the irradiation parameters are set as follows: the beam voltage is 1.8-2.2MeV, the beam intensity is 10mA, the paying-off speed is 4-6m/min, the irradiation dose is 160-260kGy, and the irradiation time is 6-20 min; and after the irradiation is finished, conveying the cable to a high-pressure steam pipeline for secondary vulcanization, controlling the steam pressure to be 0.5-1.5MPa, the temperature to be 180-200 ℃, and vulcanizing for 20-30min to obtain the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable.
The invention has the following beneficial effects:
compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a synthesis method of an isocyanate-terminated polyurethane prepolymer, namely the polyurethane prepolymer with two ends being blocked by isocyanate groups is prepared by a one-time feeding method for regulating and controlling an R value, and the synthesis method has the advantages of simple synthesis process, short production period and high yield.
2) The invention uses the synthesized isocyanate-terminated polyurethane prepolymer to carry out coating modification on the white carbon black, the flame retardant and the mineral filler to form a soft-package hard core-shell structure, and the integral hardness of the material can be reduced.
3) The polarity of the isocyanate-terminated polyurethane prepolymer synthesized by the method is similar to that of the thermoplastic polyurethane elastomer, and meanwhile, the prepolymer molecules have higher molecular weight and can be tightly entangled with macromolecular chains of the thermoplastic polyurethane elastomer, so that the compatibility between the prepolymer and the polyurethane elastomer is improved. Meanwhile, the isocyanate group of the isocyanate-terminated polyurethane prepolymer can react with the hydroxyl on the surface of the filler, and the isocyanate-terminated polyurethane prepolymer can be used as a reactive coupling agent to improve the dispersion of the white carbon black, the flame retardant and the mineral filler in the polymer and improve the interfacial binding force between the filler and the matrix, thereby effectively playing the role of blocking the filler particles and improving the oil resistance and the mechanical property of the material.
4) The base material is a mixture consisting of a thermoplastic polyurethane elastomer, polar rubber and a high-molecular compatilizer, and after the isocyanate-terminated polyurethane prepolymer, the flame retardant, the reinforcing filler, other raw materials and the auxiliary agent are introduced, the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material can be prepared by the processing technology and can be applied to preparing sheaths and insulating layers of cables for lighting of low-smoke halogen-free flame-retardant cables, flexible special cables, new energy automobiles and Chinese standard motor train units.
5) The anti-aging system is a thermal-oxidative aging resistant and light stabilizer compound system, bisphenol hindered phenol organic matters are selected as a thermal-oxidant, each molecule of the antioxidant has two phenolic hydroxyl groups, so that the anti-aging efficiency is high, the volatilization and extraction loss of the antioxidant is low, and the antioxidant has high thermal stability, so that the anti-aging effect is good.
6) The invention provides a preparation method of an oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material, namely, the mixed rubber material is irradiated at room temperature, the molecular chain segments in the amorphous area in the material are promoted to be crosslinked under the action of an irradiation sensitizer in the process to form a local chemical micro-crosslinking network, so that the material is endowed with certain strength, secondly vulcanizing the irradiated material under the conditions of high temperature and high pressure, further perfecting the cross-linked network structure of the rubber material through the synergistic effect of the vulcanization accelerator and the excessive radiation sensitizer, constructing a large-range and uniform chemical cross-linked network, after the secondary vulcanization process, the crystal perfection degree and the crystallinity of the non-crosslinked part of the material are higher, and perfect physical entanglement and chemical crosslinking network structures exist in the material at the same time, so that the mechanical property of the material is greatly improved, and the material also has higher flexibility.
Detailed Description
The present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to these examples.
The following examples used the following raw materials:
isocyanate-terminated polyurethane prepolymer: the preparation method of the polyether type isocyanate-terminated polyurethane prepolymer comprises the following steps:
the method comprises the following steps: taking 15g of polypropylene glycol with the relative molecular mass of 3000 and the hydroxyl value of 40(KOH mg/g), 19g of polypropylene glycol with the relative molecular weight of 4000 and the hydroxyl value of 30(KOH mg/g), drying in vacuum, adding the dehydrated polypropylene glycol into a 500ml flask with a stirrer, a condenser pipe and a nitrogen protection device, and then placing a reaction system in a constant-temperature oil bath kettle;
step two: adding 9.5g of isophorone diisocyanate into a three-neck flask according to the set R value of 2.2, and then dropwise adding 0.0475g of dibutyltin dilaurate into the system;
step three: after the material feeding is finished, firstly, the reaction system is placed at 30 ℃ for heat preservation for 30min, then the temperature is raised to 80 ℃ for reaction for 4 hours, and then a product is collected to obtain an isocyanate-terminated polyurethane prepolymer;
the thermoplastic polyurethane elastomer is polyether type thermoplastic polyurethane elastomer, the Shore A hardness is 50-85, and the density is 1.10g/cm3Preferably of Wanhua chemistry
WHT-C885；
The ethylene-vinyl acetate rubber has a vinyl acetate content of 28% and a density of 0.951g/cm3A melt index of 3g/10min at 190 ℃/2.16kg test conditions, preferably EVA-265 from DuPont, USA;
the mass fraction of the third monomer ENB in the ethylene propylene diene monomer is 4.9 percent, the Mooney viscosity [ ML1+ 4125 ℃ C ] is 25, and the EPDM-IP 4725P of Dow in America is preferred;
the density of the ethylene-methyl acrylate-glycidyl methacrylate terpolymer is 1.05-1.45g/cm3A melt index of 12g/10min at 190 ℃/2.16kg test conditions, preferably Elvaloy PTW from DuPont, USA;
the magnesium hydroxide, the aluminum hydroxide and the zinc borate are three inorganic flame retardants, are mixed according to the mass ratio of 5:5:1, have the particle size of 0.1-5 mu m, and are provided by the Jinan Taxing Fine chemical Co., Ltd;
pentaerythritol phosphate as a phosphorus flame retardant, preferably a golden mallow chemical product;
the white carbon black is fumed silica with fineness of 5000 meshes and specific surface area of 200m2(ii)/g, preferably T-200 of hundred million parts of Industrial science, Inc., State;
the mineral filler is wollastonite powder, the content of silicon dioxide is 70%, the fineness is 3000 meshes, the whiteness is 96, and the mineral filler is provided by mineral products Limited of Beijing navigation of the river;
the vulcanization accelerator is zinc oxide, tetramethylthiuram disulfide (TMTD), N-oxydiethylene-2-benzothiazole sulfonamide (NOBS) according to the mass ratio of 1: 2: 1;
the radiation sensitizer is trimethylolpropane triacrylate and triallyl isocyanurate according to the mass ratio of 1: 1.5;
the anti-aging agent is a mixture of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) and a complex hindered amine light stabilizer cyanogen V703 in a mass ratio of 1:1: 1;
the coupling agent is gamma-aminopropyl triethoxysilane;
the antistatic agent is trihydroxyethyl methyl quaternary ammonium methyl sulfate.
Other production raw materials and processing aids are common commercial industrial products in the field of cable material processing.
The formula of the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material is shown in the table I.
TABLE 1 oil-resistant, low-smoke, halogen-free, flame-retardant, flexible polyurethane cable material example
The preparation method of the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material comprises the following steps:
(1) firstly weighing thermoplastic polyurethane elastomer, ethylene-vinyl acetate rubber, ethylene propylene diene monomer rubber, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polyether type isocyanate-terminated polyurethane prepolymer, magnesium hydroxide, aluminum hydroxide, zinc borate, pentaerythritol phosphate, white carbon black, mineral filler, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl), cyanoter V703, gamma-aminopropyltriethoxysilane, trihydroxyethylmethyl quaternary ammonium methyl sulfate and calcium stearate according to the formula proportion, premixing the weighed white carbon black, inorganic flame retardant and mineral filler, obtaining a primary mixed filler, uniformly dropwise adding the prepared isocyanate-terminated polyurethane prepolymer into the primary mixed filler, dispersing and mixing the primary mixed filler containing the isocyanate-terminated polyurethane prepolymer by using a high-speed mixer at a rotating speed of 2000r/min for 8min, coating the surface of the primary mixed filler by using the isocyanate-terminated polyurethane prepolymer through a mechanical force induction effect, constructing functional particles with the mixed filler as a hard core and polyurethane as a soft shell to obtain a modified mixed filler, then placing the modified mixed filler and the rest of all raw materials at the rotating speed of 2000r/min for high-speed mixing for 12min to obtain a mixture, and performing melt extrusion, granulation and drying on the mixture by using a double-screw extruder to obtain filled master batches, wherein the temperature of the double-screw extruder is set as follows: the feeding section is 185 ℃, the conveying section is 190 ℃, the mixing section is 195 ℃, the exhaust section is 195 ℃ and the homogenizing section is 200 ℃;
(2) mixing the filling master batch prepared in the step (1) with a vulcanization accelerator and a radiation sensitizer at a high speed of 2000r/min for 8min, and then performing melt extrusion on a cable metal conductor by using a cable extruder to obtain an extruded cable, wherein the process temperature of the extruder is set as follows: the first zone was 185 deg.C, the second zone was 190 deg.C, the third zone was 200 deg.C, the fourth zone was 205 deg.C, the fifth zone was 215 deg.C, and the head was 215 deg.C.
(3) Irradiating and crosslinking the extruded cable prepared in the step (2) by an electron accelerator, wherein the irradiation parameters are set as follows: the beam voltage is 2.0MeV, the beam intensity is 10mA, the paying-off speed is 5m/min, the irradiation dose is 210kGy, and the irradiation time is 13 min; and after the irradiation is finished, conveying the cable to a high-pressure steam pipeline for secondary vulcanization, controlling the steam pressure to be 1.0MPa, the temperature to be 190 ℃ and the secondary vulcanization time to be 25min, and finishing the manufacture.
To prove the effect of the invention, 3 groups of proportions are provided, and the formula is shown in the following table:
table 2 comparative example of cable material
The preparation methods and the steps of the comparative examples 1 and 2 are completely the same as those of the above five examples.
The preparation method of comparative example 3 includes the following steps:
(1) firstly, weighing thermoplastic polyurethane elastomer, ethylene-vinyl acetate rubber, ethylene propylene diene monomer rubber, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, magnesium hydroxide, aluminum hydroxide, zinc borate, pentaerythritol phosphate, white carbon black, mineral filler, cyanote V703, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl), gamma-aminopropyltriethoxysilane, trihydroxyethylmethyl quaternary ammonium methyl sulfate and calcium stearate according to the formula proportion, mixing the weighed raw materials at a high speed of 2000r/min for 12min to obtain a mixture, and then carrying out melt extrusion, granulation and drying on the mixture by using a double-screw extruder to obtain the filling master batch, wherein the temperature of the double-screw extruder is set as follows: the feeding section is 185 ℃, the conveying section is 190 ℃, the mixing section is 195 ℃, the exhaust section is 195 ℃ and the homogenizing section is 200 ℃;
(2) mixing the filling master batch prepared in the step (1) with zinc oxide and trimethylolpropane trimethacrylate at a high speed for 8min at a rotating speed of 2000r/min, and then performing melt extrusion on a cable metal conductor by using a cable extruder to obtain an extruded cable, wherein the process temperature of the extruder is set as follows: the first zone was 185 deg.C, the second zone was 190 deg.C, the third zone was 200 deg.C, the fourth zone was 205 deg.C, the fifth zone was 215 deg.C, and the head was 215 deg.C.
(3) Irradiating and crosslinking the extruded cable prepared in the step (2) by an electron accelerator, wherein the irradiation parameters are set as follows: the beam voltage is 2.0MeV, the beam intensity is 10mA, the paying-off speed is 5m/min, the irradiation dose is 210kGy, and the irradiation time is 13min, thus finishing the manufacturing.
Test and results
The main properties of the cable materials of examples 1 to 5 are shown in the following table:
TABLE 3 oil-resistant, low-smoke, halogen-free, flame-retardant, flexible polyurethane cable materials ExampleSamplex Properties
The main performance indexes of the cable materials prepared in comparative examples 1 to 3 are shown in the following table:
table 4 comparative example of cable material
By comparing the examples with the comparative examples, it can be found that: introducing polyether type isocyanate-terminated polyurethane prepolymer into the material, improving the compatibility between the reinforcing filler and the polyurethane thermoplastic elastomer, improving the oil resistance of the material and simultaneously reducing the hardness of the material; because the inorganic mineral filler has the characteristics of high heat resistance, gas barrier, electric insulation and the like, after the inorganic mineral filler is introduced into the material, the flame retardant property is more excellent, and the volume resistivity is further improved; the material prepared by the process of irradiation crosslinking and secondary vulcanization treatment is higher in crosslinking degree and crystallinity than the material prepared by a single irradiation crosslinking process, so that the cable material produced by the irradiation crosslinking and secondary vulcanization processes has higher mechanical property and oil resistance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. An oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material is prepared from the following raw materials in parts by weight:
30-40 parts of thermoplastic polyurethane elastomer
7-10 parts of polar rubber
10-15 parts of ethylene propylene diene monomer
5-8 parts of macromolecular compatilizer
6-8 parts of isocyanate-terminated polyurethane prepolymer
80-100 parts of inorganic flame retardant
5-8 parts of phosphorus flame retardant
14-20 parts of white carbon black
5-15 parts of mineral filler
3-7 parts of vulcanization accelerator
0.5 to 3 portions of radiation sensitizer
3-5 parts of anti-aging agent
0.2 to 1.5 portions of coupling agent
1-2 parts of antistatic agent
1-2 parts of calcium stearate
The isocyanate-terminated polyurethane prepolymer is prepared by the following preparation method:
the method comprises the following steps: taking a proper amount of polyhydric alcohol for vacuum drying, adding the polyhydric alcohol into a flask with a stirrer, a condenser pipe and a nitrogen protection device after dehydration treatment, and then placing the flask into a constant-temperature oil bath pan;
step two: adding a certain amount of polyisocyanate into a flask according to a set R value, wherein the R value is the ratio of the number of isocyanate groups in the polyisocyanate to the number of terminal hydroxyl groups in the polyol, and is expressed by a formula of R = n (-NCO)/n (-OH), the interval of the R value is 2.05-2.45, and then adding a catalyst into the system in an amount of five thousandths of the content of the polyisocyanate;
step three: after the material addition is finished, the reaction system is placed at 30 ℃ for heat preservation for 30min, then the temperature is raised to 80 ℃ for reaction for 4 hours, and then the product is collected, so as to obtain the isocyanate-terminated polyurethane prepolymer.
2. The cable material according to claim 1, wherein the polyol is one or a mixture of polyester polyol or polyether polyol; wherein the polyester polyol is one or a mixture of polycarbonate diol or polycaprolactone diol, the number average molecular weight is 2000-5000, and the water content is less than 0.1 percent; the polyether polyol is one or a mixture of polypropylene glycol, polyethylene glycol or polytetrahydrofuran ether glycol, the number average molecular weight is 3000-6000, and the water content is less than 0.5 percent; the polyisocyanate is one or a mixture of isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and toluene diisocyanate; the catalyst is one or a mixture of dibutyltin dilaurate, triethylene diamine, N' -dimethyl cyclohexylamine and stannous octoate.
3. The cable material of claim 2, wherein: the thermoplastic polyurethane elastomer is a polyether thermoplastic polyurethane elastomer, the Shore A hardness is 50-85, and the density is 1.05-1.45g/cm3；
The polar rubber is one or a mixture of ethylene-vinyl acetate rubber, acrylate rubber, nitrile rubber, hydrogenated nitrile rubber and ethylene-acrylate rubber; wherein the ethylene-vinyl acetate rubber contains 15-50% of vinyl acetate, has a melt index of 0.5-35 g/10min under the test condition of 190 ℃/2.16kg, a melting point of 50-90 ℃, a Shore A hardness of 45-90 and a density of 0.90-1.15g/cm3(ii) a The acrylate rubber is epoxy type, the epoxy group content is 0.1-10%, and the Mooney viscosity [ ML (1 + 4) 100 DEG C]25 to 55 percent, the glass transition temperature is between-40 ℃ and-10 ℃, and the density is between 1.05 and 1.20g/cm3(ii) a The acrylonitrile-butadiene rubber contains 15-50% of acrylonitrile monomer and has Mooney viscosity [ ML (1 + 4) 100 DEG C]50-90, and the density is 0.95-1.10g/cm3(ii) a The content of bound acrylonitrile in the hydrogenated nitrile rubber is 15-50%, and the Mooney viscosity [ ML (1 + 4) 100 DEG C]Is 50-90, iodine value center value of 8-30mg/100 mg; the ethylene-acrylate rubber has an acrylate content of 10-42% and a Mooney viscosity [ ML (1 + 4) 100 DEG C]15-75, and density of 1.00-1.10g/cm3；
The ethylene propylene diene monomer comprises 4.9-9% of a third monomer ENB by mass and 20-90% of Mooney viscosity [ ML (1 + 4) 125 ℃;
the high molecular compatilizer is one of ethylene-octene copolymer grafted glycidyl methacrylate, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate terpolymer, wherein the grafting ratio of the ethylene-octene copolymer grafted glycidyl methacrylate is 2.5-3.5%, the melt index is 2.0-6.0g/10min under the test condition of 190 ℃/2.16kg, the Shore A hardness is 65-90, and the density is 0.80-1.10g/cm3(ii) a The content of methyl acrylate in the ethylene-methyl acrylate copolymer is 15-25%, the melt index is 0.5-4.5g/10min under the test condition of 190 ℃/2.16kg, and the density is 0.95-1.15g/cm3The Vicat softening point is 45-65 ℃; the content of ethyl acrylate in the ethylene-ethyl acrylate copolymer is 10-30%, the melt index is 3.5-10g/10min under the test condition of 190 ℃/2.16kg, and the density is 0.85-1.10g/cm3The Vicat softening point is 55-80 ℃; the density of the ethylene-methyl acrylate-glycidyl methacrylate terpolymer is 0.90-1.45g/cm3The melt index is 5-15g/10min under the test condition of 190 ℃/2.16 kg;
the inorganic flame retardant is one or a mixture of more of magnesium hydroxide, aluminum hydroxide, zinc borate, zinc stannate, antimony trioxide and hydrated magnesium silicate;
the phosphorus flame retardant is one or a mixture of more of melamine polyphosphate, ammonium polyphosphate, zinc hypophosphite, calcium hypophosphite, trioctyl phosphate, triisopropylphenyl phosphate, pentaerythritol phosphate, dimethyl methyl phosphate and diethyl ethyl phosphate;
the white carbon black is gas-phase white carbon black with the fineness of 4000-6000 meshes and the silicon dioxide content higher than 99.8%:
the mineral filler is one of calcined kaolin, wollastonite powder, porous powder quartz, diatomite and bentonite;
the vulcanization accelerator is one or a mixture of more of zinc oxide, tetramethyl thiuram disulfide and N-oxydiethylene-2-benzothiazole sulfonamide; the radiation sensitizer is one or a mixture of more of triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diallyl phthalate and N, N' -m-phenylene bismaleimide; the anti-aging agent is a hindered phenol type anti-thermal-oxidative aging agent and a light stabilizer, wherein the hindered phenol type anti-thermal-oxidative aging agent is one or a mixture of N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl), and the light stabilizer is one or a mixture of a compound hindered amine light stabilizer, a hindered benzoate light stabilizer, a triazine ultraviolet absorber and a benzotriazole ultraviolet absorber;
the coupling agent is one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane or gamma-methacryloxypropyltrimethoxysilane;
the antistatic agent is one or a mixture of trihydroxyethyl methyl quaternary ammonium methyl sulfate and ethoxylated alkylamine.
4. The preparation method of the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable material according to any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) preparing an isocyanate-terminated polyurethane prepolymer:
the method comprises the following steps: taking a proper amount of polyhydric alcohol for vacuum drying, adding the polyhydric alcohol into a flask with a stirrer, a condenser pipe and a nitrogen protection device after dehydration treatment, and then placing the flask into a constant-temperature oil bath pan;
step two: adding a certain amount of polyisocyanate into a flask according to a set R value, wherein the R value is the ratio of the number of isocyanate groups in the polyisocyanate to the number of terminal hydroxyl groups in the polyol, and is expressed by a formula of R = n (-NCO)/n (-OH), the interval of the R value is 2.05-2.45, and then adding a catalyst into the system in an amount of five thousandths of the content of the polyisocyanate;
step three: after the material feeding is finished, firstly, the reaction system is placed at 30 ℃ for heat preservation for 30min, then the temperature is raised to 80 ℃ for reaction for 4 hours, and then a product is collected to obtain an isocyanate-terminated polyurethane prepolymer;
(2) firstly, weighing thermoplastic polyurethane elastomer, polar rubber, ethylene propylene diene monomer, high molecular compatilizer, isocyanate-terminated polyurethane prepolymer, inorganic flame retardant, phosphorus flame retardant, white carbon black, mineral filler, anti-aging agent, coupling agent, antistatic agent and calcium stearate according to a formula proportion, premixing the weighed white carbon black, inorganic flame retardant and mineral filler to obtain primary mixed filler, uniformly dropwise adding the prepared isocyanate-terminated polyurethane prepolymer into the primary mixed filler, performing dispersion mixing treatment on the primary mixed filler containing the isocyanate-terminated polyurethane prepolymer at the rotating speed of 1600 plus 2300r/min by using a high-speed mixer for 5-8min, and coating the surface of the primary mixed filler by the isocyanate-terminated polyurethane prepolymer through mechanical force induction, constructing functional particles with a mixed filler as a hard core and polyurethane as a soft shell to obtain a modified mixed filler, then placing the modified mixed filler and the rest of all raw materials at a high speed of 1600-2300r/min for mixing for 8-15min to obtain a mixture, and then performing melt extrusion, granulation and drying on the mixture by a double-screw extruder to obtain filling master batches, wherein the temperature of the double-screw extruder is set as follows: the feeding section is 180-190 ℃, the conveying section is 185-195 ℃, the mixing section is 190-200 ℃, the exhaust section is 190-200 ℃ and the homogenizing section is 195-205 ℃;
(3) mixing the filling master batch prepared in the step (2) with the vulcanization accelerator and the radiation sensitizer at a high speed of 1600-2300r/min for 5-12min, and then performing melt extrusion on a cable metal conductor by using a cable extruder to obtain an extruded cable, wherein the process temperature of the extruder is set as follows: the first section is 180-190 ℃, the second section is 185-195 ℃, the third section is 195-205 ℃, the fourth section is 200-210 ℃, the fifth section is 210-220 ℃, and the head is 215 ℃;
(4) irradiating and crosslinking the extruded cable prepared in the step (3) by an electron accelerator, wherein the irradiation parameters are set as follows: the beam voltage is 1.8-2.2MeV, the beam intensity is 10mA, the paying-off speed is 4-6m/min, the irradiation dose is 160-260kGy, and the irradiation time is 6-20 min; and after the irradiation is finished, conveying the cable to a high-pressure steam pipeline for secondary vulcanization, controlling the steam pressure to be 0.5-1.5MPa, the temperature to be 180-200 ℃, and vulcanizing for 20-30min to obtain the oil-resistant low-smoke halogen-free flame-retardant flexible polyurethane cable.
5. The use of the cable material according to any one of claims 1 to 3 or the cable obtained by the preparation method according to claim 4, wherein the cable material is used for manufacturing low-smoke halogen-free flame-retardant cables, flexible special cables, and insulating sheaths of wires for new energy automobiles and national standard motor train units.
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