WO2021129216A1

WO2021129216A1 - Pvc cable material and preparation method therefor

Info

Publication number: WO2021129216A1
Application number: PCT/CN2020/128362
Authority: WO
Inventors: 潘卫东; 范魏魏; 周方方
Original assignee: 江苏达胜高聚物股份有限公司
Priority date: 2019-12-28
Filing date: 2020-11-12
Publication date: 2021-07-01
Also published as: CN111019269B; CN111019269A

Abstract

Disclosed are a PVC cable material and a preparation method therefor. The PVC cable material comprises the following components in parts by weight: 90-110 parts of a PVC resin, 30-50 parts of dioctyl terephthalate, 5-20 parts of soybean oil epoxide, 10-20 parts of a filler, 1-10 parts of an organic flame retardant, 1-10 parts of an inorganic flame retardant, 3-6 parts of a main antioxidant, 3-6 parts of an auxiliary antioxidant, 1-5 parts of a lubricant, and 1-5 parts of a stabilizer. All the components in the PVC cable material are matched with one another and have a synergistic effect, so not only are the smoke suppression and flame retardance of the cable material effectively improved, but also the mechanical strength of the cable material can be improved, mechanical damage is effectively reduced, and the service life of a cable is prolonged.

Description

PVC cable material and preparation method thereof

Technical field

The application belongs to the technical field of cable materials, and relates to a PVC cable material and a preparation method thereof.

Background technique

Wire and cable products have brought great convenience and improvement to human life and work. Among them, PVC cables have long been an important place in wire and cable insulation protection materials because of their low price and excellent performance. But the flame-retardant properties of PVC wires and cables have always plagued everyone. At present, the flame-retardant materials of wires and cables contain halogens. When the wires and cables catch fire, there will be problems such as prolonged combustion, dripping and a large amount of toxic smoke. How to reduce the smoke from plastic burning The secondary damage caused by poison and dripping is extremely important. At present, the flame retardant performance of domestic wire and cable sheathing materials is mainly concentrated on organic phosphorus nitrogen and inorganic hydrates. However, the current research results still have flame retardant effects and thermal insulation. Poor temperature effect and other issues.

CN107619560A discloses a high-temperature-resistant flame-retardant PVC cable material. The high-temperature flame-retardant PVC cable material is composed of the following components by weight: 120-150 parts of polyvinyl chloride, 5-10 parts of magnesium-aluminum alloy, and flame retardant 50-100 parts, 20-50 parts of dispersant and 5.2-10 parts of composite flame retardant synergist. The flame retardant is as high as 50-100 parts, and the percentage of the raw material is 25-31%. The flame retardant performance of the material is improved by increasing the amount of flame retardant, but increasing the amount of flame retardant will cause the mechanical properties of the material and the low temperature resistance And other issues such as performance degradation.

CN102911460A discloses a halogen-free flame-retardant polyvinyl chloride pipe and a preparation process thereof, which are made of the following parts by weight of raw materials: 100 parts of polyvinyl chloride resin, 0.1-10.0 parts of heat stabilizer, and 1-20 parts of toughening agent , 10-80 parts of metal hydroxide flame retardant, 1-20 parts of metal compound flame retardant synergist, 0.5-3.0 parts of processing aids, 1.1-5 parts of lubricants, 0.01-5 parts of antioxidants, colorants 0.03-5 parts, 0.1-5 parts of ultraviolet absorber. This kind of PVC pipe also improves the flame retardant performance of the material by increasing the amount of flame retardant. Although the flame retardant performance is good, the corrosion resistance is poor, and the impact resistance of the PVC pipe is poor and the brittleness is greater.

CN105482296A discloses a light-weight, heat-resistant and flame-retardant modified PVC resin compound cable material. The cable material is made of the following parts by weight of raw materials: 55-65 parts of PVC resin, 30-40 parts of ethylene-vinyl acetate copolymer , Tomaline 0.01-0.02, 10-15 parts of expandable graphite, 5-8 parts of polytetramethylene glycol ether, 15-22 parts of aluminum silicate, 3-4 parts of tungoleic acid, hexamethyl diazide Silane 3-4 parts, etc.; although the cable material has good flame retardant properties, more expandable graphite is added to it. Because expandable graphite is a conductor, adding it as a filler to the cable material will greatly reduce its insulation performance , Resulting in dangers such as electric leakage and electric shock, which poses a great safety hazard.

Therefore, the development of a PVC cable material with a small amount of flame retardant and good flame retardant effect is the focus of current research in this field.

Summary of the invention

The purpose of this application is to provide a PVC cable material and a preparation method thereof. The various components in the PVC cable material cooperate with each other and synergistically increase the effect, which not only effectively improves the smoke suppression and flame retardancy of the cable material, but also can improve the cable The mechanical strength of the material effectively reduces mechanical damage and helps to extend the service life of the cable.

To achieve this goal, this application adopts the following technical solutions:

In the first aspect, the present application discloses a PVC cable material. The PVC cable material includes 90-110 parts by weight of PVC resin, 30-50 parts of dioctyl terephthalate, and epoxy soybean oil. -20 parts, filler 10-20 parts, organic flame retardant 1-10 parts, inorganic flame retardant 1-10 parts, main antioxidant 5-10 parts, auxiliary antioxidant 5-10 parts, lubricant 1- 5 parts and 1-5 parts of stabilizer.

In this application, the weight parts of the PVC resin is 90-110 parts, for example, it can be 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 99 parts, 100 parts, 112 parts, 114 parts, 116 parts. , 118 copies, 120 copies.

In this application, the weight parts of the dioctyl terephthalate is 30-50 parts, for example, it can be 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts , 46, 48, 50.

In this application, the parts by weight of the epoxy soybean oil is 5-20 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts , 14 shares, 15 shares, 16 shares, 17 shares, 18 shares, 19 shares, 20 shares.

In this application, the weight parts of the composite filler is 10-20 parts, for example, it can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts. , 20 copies.

In this application, the weight parts of the organic flame retardant is 1-10 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 servings.

In this application, the weight parts of the inorganic flame retardant is 1-10 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 servings.

In this application, the weight parts of the primary antioxidant is 3-6 parts, for example, 3 parts, 4 parts, 5 parts, and 6 parts.

In this application, the weight parts of the auxiliary antioxidant is 3-6 parts, for example, 3 parts, 4 parts, 5 parts, and 6 parts.

In this application, the weight parts of the lubricant is 1-5 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts.

In this application, the weight parts of the stabilizer is 1-5 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts.

In this application, dioctyl terephthalate (DOTP) and epoxidized soybean oil work together to act as a plasticizer for PVC resins. They are combined with PVC molecules by hydrogen bonds or van der Waals forces, and they are added during processing and molding. Plasticity, flow properties, and further increase the flexibility of the finished product. After plasticization of DOTP and epoxy soybean oil, the PVC resin layered structure is separated. There are more free DOTP and epoxy soybean oil regions between the PVC resin layers, and there is a relatively complete network in the PVC resin. Structure, it is precisely because of the existence of these network structures that the PVC resin plasticized by DOTP has higher hardness, and the PVC resin plasticized by DOTP has greater elongation at break, tensile resistance and softness. degree.

In this application, after the PVC cable material is heated, the composite filler, composite flame retardant, main antioxidant, and auxiliary antioxidant cooperate with each other to have a synergistic effect, and melt to form a covering layer on the surface of the PVC resin to become a cohesive phase. A barrier between the flame and the flame, which can not only isolate oxygen, prevent the diffusion of combustible gases, but also block heat conduction and heat radiation, reduce the heat feedback to the PVC resin, thereby inhibiting thermal cracking and combustion reactions, and reducing the PVC resin material The temperature of the surface and flame zone slows down the speed of the thermal cracking reaction and inhibits the generation of combustible gases and smoke. In this application, antioxidants are divided into primary antioxidants and auxiliary antioxidants. The primary antioxidants can react with free radicals to interrupt the growth of active chains, and the auxiliary antioxidants can inhibit and delay free radicals during the initiation process. The formation of radicals decomposes hydroperoxides and passivates the metal ions remaining in the resin.

Optionally, the degree of polymerization of the PVC resin is 1700-1800, for example, it may be 1700, 1710, 1720, 1730, 1740, 1750, 1760, 1780, 1790, 1800.

In this application, the degree of polymerization of PVC resin is 1700-1800. In this range, the molecular chain of PVC resin is long and has high curling properties, the entanglement points between molecular chains are increased, the crystallinity is high, the force between molecular chains is enhanced, and the molecular chain It is difficult to slip between them; at the same time, because it can absorb more plasticizers, the effect of plasticizers can be maximized. If the polymerization of the PVC resin is too small, the force between the molecular chains is small, resulting in a decrease in the strength, heat resistance, resilience, wear resistance, and cold resistance of the product. If the polymerization of the PVC resin is too large, If the spacing between PVC macromolecules is too large, the rheological properties of the process will decrease.

Optionally, the filler includes any one or a combination of at least two of organically modified montmorillonite, mesoporous silica, nano-activated calcium carbonate, halloysite nanotubes, bentonite, or diatomite.

In this application, organically modified montmorillonite and mesoporous silica can be used as composite fillers to be blended with PVC resin and evenly distributed in the PVC resin master batch, which can not only effectively improve the thermal stability of PVC resin, but also delay The degradation of PVC resin achieves the purpose of synergistic flame retardancy, and can also significantly improve the strength, stiffness and toughness of PVC resin. Organically modified montmorillonite is structurally used for extremely high surface area and high aspect ratio, which can give PVC resin good barrier properties, and because PVC resin molecules enter between the mesoporous silica particles, it is organically modified. The combined action of montmorillonite and mesoporous silica restricts the movement of PVC resin molecular chains, thereby significantly improving the heat resistance and dimensional stability of the PVC cable material described in the present application.

Optionally, the organically modified montmorillonite includes glycidyl methacrylate modified montmorillonite, betaine modified montmorillonite, stearyl dimethyl benzyl ammonium chloride modified montmorillonite Modified montmorillonite with octadecyltrimethylammonium bromide;

Optionally, the particle size of the mesoporous silica is 80-100 μm, for example, 80 μm, 82 μm, 84 μm, 86 μm, 88 μm, 90 μm, 92 μm, 94 μm, 96 μm, 98 μm, 100 μm.

Optionally, the specific surface area of the mesoporous silica is 500-600m ² /g, for example, it can be 500m ² /g, 510m ² /g, 520m ² /g, 530m ² /g, 540m ² /g, 550m ² /g, 560m ² /g, 570m ² /g, 580m ² /g, 590m ² /g, 600m ² /g.

Optionally, the mass ratio of the organic flame retardant and the inorganic flame retardant is (2-4):1, for example, it can be 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1.

In this application, the organic flame retardant and the inorganic flame retardant are coordinated with each other in a specific ratio to achieve synergy, which can not only ensure the dispersion of the flame retardant in the PVC resin, but also ensure that the composite flame retardant can be fast at high temperatures. A stable covering layer is formed, which insulates oxygen and prevents combustible gas from escaping outward, and produces a cross-linked solid substance or carbonized layer with a more stable structure. At the same time, it also dilutes the oxygen concentration in the combustion zone and prevents combustion. Continued to achieve high-efficiency flame-retardant effect.

Optionally, the organic flame retardant includes diphenyl isooctyl phosphite, tris(nonylphenyl) phosphite, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate Or any one or a combination of at least two of the tris(dichloropropyl) phosphates.

Optionally, the inorganic flame retardant is a phosphate flame retardant.

Optionally, the phosphate includes any one or a combination of at least two of diammonium hydrogen phosphate, ammonium pyrophosphate, aluminum hypophosphite, or ammonium polyphosphate.

Optionally, the primary antioxidant is a hindered phenolic antioxidant.

Optionally, the hindered phenolic antioxidant includes 2,6-tributyl-4-methylphenol, bis(3,5-tributyl-4-hydroxyphenyl)sulfide or tetra[β- (3,5-Tributyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester of one kind or a mixture of at least two kinds.

Optionally, the auxiliary antioxidant is a combination of thioester antioxidants.

Optionally, the thioester antioxidant includes dilauryl thiodipropionate, lauryl octadecyl thiodipropionate, di(tridecyl thiodipropionate), or dilauryl thiodipropionate. (Tetradecyl ester) any one or a combination of at least two.

Optionally, the lubricant includes any one or a combination of at least two of magnesium stearate, calcium stearate, zinc stearate, polyethylene wax, montan wax, or paraffin wax;

Optionally, the stabilizer includes dibutyl tin dilaurate, isooctyl dimercaptoacetate di-n-octyl tin, methyl tin mercaptan, butyl tin mercaptan, dibutyl tin dichloride or octyl tin mercaptan Any one or a combination of at least two of them.

Optionally, the PVC cable material further includes an ultraviolet absorber.

Optionally, the weight parts of the ultraviolet absorber in the PVC cable material are 0.5-2 parts, for example, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts.

Optionally, the ultraviolet absorber includes 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone or 2-(2'-hydroxy-3', Any one or a combination of at least two of 5'-di-tert-butylphenyl)-5-chlorobenzotriazole.

Optionally, the PVC cable material further includes a colorant.

Optionally, the weight part of the colorant in the PVC cable material is 0.5-1 part, for example, it can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part.

Optionally, the colorant includes any one or a combination of at least two of titanium dioxide, carbon black, or toner.

In the second aspect, the present application provides a method for preparing the PVC cable material as described in the first aspect, and the preparation method includes the following steps:

(1) Mix and stir PVC resin, dioctyl terephthalate and epoxy soybean oil according to the formula amount to obtain a mixed slurry;

(2) Add composite filler, composite flame retardant, main antioxidant, auxiliary antioxidant, lubricant and stabilizer to the mixed slurry obtained in step (1), mix and stir to obtain a mixture;

(3) Extruding and pelletizing the mixture material obtained in step (2) to obtain the PVC cable material.

Optionally, the mixing and stirring in step (1) is performed in a high-speed mixer.

Optionally, the mixing and stirring in step (1) is performed under a vapor pressure of 0.15-0.25 MPa, for example, the vapor pressure can be 0.15 MPa, 0.16 MPa, 0.17 MPa, 0.18 MPa, 0.19 MPa, 0.2 MPa, 0.21 MPa, 0.22MPa, 0.23MPa, 0.24MPa, 0.25MPa.

Optionally, the mixing and stirring temperature in step (1) is 70-80°C, for example, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C.

Optionally, the mixing and stirring time in step (1) is 3-5 min, for example, 3 min, 3.2 min, 3.4 min, 3.6 min, 3.8 min, 4 min, 4.2 min, 4.4 min, 4.6 min, 4.8 min, 5min.

Optionally, the rotation speed of the mixing and stirring in step (1) is 600-800r/min, for example, it can be 600r/min, 620r/min, 640r/min, 680r/min, 700r/min, 720r/min, 740r/min. min, 760r/min, 780r/min, 800r/min.

Optionally, the mixing and stirring in step (2) is: first performing high-speed stirring and then performing low-speed stirring.

Optionally, the temperature of the high-speed stirring is 110-120°C, for example 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, 120°C ℃.

Optionally, the high-speed stirring time is 5-10 min, for example, it may be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min.

Optionally, the rotation speed of the high-speed stirring is 1500-2000 r/min, for example, it can be 1500 r/min, 1600 r/min, 1700 r/min, 1800 r/min, 1900 r/min, 2000 r/min.

Optionally, the low-speed stirring temperature is 40-50° C., for example, 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47° C., 48° C., 49° C., 50° C. ℃.

Optionally, the low-speed stirring time is 10-20 min, for example, it may be 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min, 20 min.

Optionally, the rotation speed of the low-speed stirring is 100-200r/min, for example, it can be 100r/min, 110r/min, 120r/min, 130r/min, 140r/min, 150r/min, 160r/min, 170r/min. min, 180r/min, 190r/min, 200r/min.

Optionally, the extrusion in step (3) is performed in a first-stage twin-screw extruder.

Optionally, the upper-stage twin-screw processing temperature of the first-stage twin-screw extruder is 140-175°C, for example, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C. ℃.

Optionally, the lower-stage single-screw temperature of the first-stage twin-screw extruder is 130-165°C, for example, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C .

Optionally, the one-stage twin-screw extruder includes a first zone, a second zone, a third zone, a fourth zone and a die head which are sequentially connected.

Optionally, the working temperature of the first zone is 175-185°C (for example, it can be 175°C, 176°C, 177°C, 178°C, 179°C, 180°C, 181°C, 182°C, 183°C, 184°C , 185℃), the working temperature of the second zone is 180-190℃ (for example, it can be 180℃, 181℃, 182℃, 183℃, 184℃, 185℃, 186℃, 187℃, 188℃, 189℃, 190℃), the working temperature of the third zone is 185-195℃ (for example, it can be 185℃, 186℃, 187℃, 188℃, 189℃, 190℃, 191℃, 192℃, 193℃, 194℃, 195℃ ℃), the working temperature of the fourth zone is 185-195℃ (for example, it can be 185℃, 186℃, 187℃, 188℃, 189℃, 190℃, 191℃, 192℃, 193℃, 194℃, 195℃ ), the working temperature of the die head is 185-195℃ (for example, it can be 185℃, 186℃, 187℃, 188℃, 189℃, 190℃, 191℃, 192℃, 193℃, 194℃, 195℃) .

Optionally, the pelletizing in step (3) adopts an air-cooled grinding surface hot pelletizing method

Compared with the prior art, this application has the following beneficial effects:

(1) The various components of the PVC cable material described in this application cooperate with each other and synergistically increase the effect, which not only effectively improves the smoke suppression and flame retardancy of the cable material, but also enables the cable material to have good mechanical strength, thermal aging performance, Wear resistance and traction resistance improve the service life of the cable in harsh environments.

(2) The tensile strength of the building wire cable material provided by this application is above 16MPa, the elongation at break is above 200%, the oxygen index is above 32%, the electrolyte strength is above 20MV/m, and a single vertical burning is passed.

Detailed ways

The technical solutions of the present application will be further explained through specific implementations below. It should be understood by those skilled in the art that the described embodiments are merely to help understand the application and should not be regarded as specific limitations to the application.

Example 1

This embodiment provides a PVC cable material, which in parts by weight includes: 100 parts of PVC resin (degree of polymerization of 1700), 40 parts of dioctyl terephthalate, 10 parts of epoxy soybean oil, 10 parts of montmorillonite modified with octadecyldimethylbenzylammonium chloride, 5 parts of mesoporous silica (particle size of 80μm, specific surface area of 600m ² /g), diphenyl isooctyl phosphite 6 parts, 2 parts of diammonium hydrogen phosphate, 6 parts of 2,6-tributyl-4-methylphenol, 5 parts of dilauryl thiodipropionate, 2 parts of calcium stearate, 1 part of dibutyl tin dilaurate Parts, 0.5 parts of 2-hydroxy-4-methoxybenzophenone, 0.5 parts of carbon black.

The preparation method of the PVC cable material in this embodiment includes the following steps:

(1) Add PVC resin, dioctyl terephthalate and epoxidized soybean oil into a high-speed mixer according to the formula, and heat to 70℃ with a steam pressure of 0.15MPa, and mix and stir for 3min at a speed of 800r/min. , Get the mixed slurry;

(2) Add octadecyl dimethyl benzyl ammonium chloride modified montmorillonite, mesoporous silica, diphenyl isooctyl phosphite, and dihydrogen phosphate to the mixed slurry obtained in step (1). Ammonium, 2,6-tributyl-4-methylphenol, dilauryl thiodipropionate, calcium stearate, dibutyltin dilaurate, 2-hydroxy-4-methoxybenzophenone, For carbon black, first stir at a high speed of 1500r/min at 120℃ for 5min, and then stir at a speed of 100r/min at 50℃ for 10min at a low speed to obtain a mixture;

(3) The mixture material obtained in step (2) is added to a first-stage twin-screw extruder for extrusion. The upper-stage twin-screw processing temperature of the first-stage twin-screw extruder is 140°C, and the first-stage twin-screw extruder has a processing temperature of 140°C. The temperature of the lower-stage single screw exiting the machine is 130°C, the working temperature in the first zone is 175°C, the working temperature in the second zone is 180°C, the working temperature in the third zone is 185°C, and the working temperature in the fourth zone is 185°C, the working temperature of the die head is 185°C; the air-cooled grinding surface hot pelletizing method is adopted, and the pellets enter the silo through a cyclone separator and a vibrating screen to obtain the PVC cable material.

Example 2

This embodiment provides a PVC cable material. The PVC cable material includes, in parts by weight: 110 parts of PVC resin (with a degree of polymerization of 1800), 50 parts of dioctyl terephthalate, and 20 parts of epoxidized soybean oil. 7.5 parts of octadecyltrimethylammonium bromide modified montmorillonite, mesoporous silica (particle size of 100μm, specific surface area of 500m ^{2 /} g) 2.5 parts, tris(nonylphenyl) phosphite 8 Parts, 2 parts of ammonium polyphosphate, 5 parts of 2,6-tributyl-4-methylphenol, 6 parts of lauryl octadecyl thiodipropionate, 4 parts of zinc stearate, 2 parts of dibutyl tin dilaurate , 1 part of 2-hydroxy-4-n-octyloxy benzophenone and 1 part of titanium dioxide.

(1) Add PVC resin, dioctyl terephthalate and epoxidized soybean oil into a high-speed mixer according to the formula, and heat to 80°C with a steam pressure of 0.2MPa, and mix and stir for 5 minutes at a speed of 600r/min. , Get the mixed slurry;

(2) Add octadecyltrimethylammonium bromide modified montmorillonite, mesoporous silica, tris(nonylphenyl) phosphite, and diammonium hydrogen phosphate to the mixed slurry obtained in step (1) , 2,6-tributyl-4-methylphenol, lauryl octadecyl thiodipropionate, zinc stearate, dibutyltin dilaurate, 2-hydroxy-4-n-octyloxybenzophenone And titanium dioxide, first stir at a high speed of 2000r/min at 110°C for 10min, and then stir at a speed of 200r/min at 40°C for 20min to obtain a mixture;

(3) The mixture material obtained in step (2) is added to a first-stage twin-screw extruder for extrusion. The upper-stage twin-screw processing temperature of the first-stage twin-screw extruder is 175°C, and the first-stage twin-screw extruder The temperature of the lower-stage single screw exiting the machine is 165°C, the working temperature in the first zone is 185°C, the working temperature in the second zone is 190°C, the working temperature in the third zone is 195°C, and the working temperature in the fourth zone is 195°C, the working temperature of the die head is 195°C; the air-cooled grinding surface hot pelletizing method is adopted, and the pellets enter the silo through a cyclone separator and a vibrating screen to obtain the PVC cable material.

Example 3

This embodiment provides a PVC cable material, which in parts by weight includes: 80 parts of PVC resin (polymerization degree of 1750), 30 parts of dioctyl terephthalate, 10 parts of epoxy soybean oil, 5 parts of glycidyl methacrylate modified montmorillonite, 5 parts of mesoporous silica (particle size of 100 μm, specific surface area of 500 m ² /g), 6 parts of tris(nonylphenyl) phosphite, 6 parts of pyrophosphoric acid 3 parts of ammonium, 5 parts of bis(3,5-tributyl-4-hydroxyphenyl) sulfide, 5 parts of lauryl stearyl thiodipropionate, 2 parts of paraffin wax, 2 parts of methyl tin mercaptan.

(1) Add PVC resin, dioctyl terephthalate and epoxidized soybean oil into a high-speed mixer according to the formula amount, heat it to 80℃ with a steam pressure of 0.25MPa, and mix and stir for 3min at a speed of 600r/min , Get the mixed slurry;

(2) Add glycidyl methacrylate modified montmorillonite, mesoporous silica, tris(nonylphenyl phosphite, diammonium hydrogen phosphate, bis(3, 5-Tributyl-4-hydroxyphenyl) sulfide, lauryl octadecyl thiodipropionate, paraffin wax, tin methyl mercaptan, first stir at a high speed of 2000r/min at 110℃ for 10min, and then Stir at a speed of 200r/min for 20min at a low speed at 40°C to obtain a mixture;

Example 4

This embodiment provides a PVC cable material. Compared with embodiment 1, the only difference is that 4 parts of diphenyl isooctyl phosphite and 4 parts of diammonium hydrogen phosphate. The content of other components and the preparation method are the same as those of the embodiment. 1.

Example 5

This embodiment provides a PVC cable material. Compared with embodiment 1, the only difference is that the diphenyl isooctyl phosphite is 7 parts and the diammonium hydrogen phosphate is 1 part. The content of other components and the preparation method are the same as those in the embodiment. 1.

Example 6

This embodiment provides a PVC cable material. Compared with embodiment 1, the difference is only: the filler does not contain octadecyl dimethyl benzyl ammonium chloride modified montmorillonite, but only contains mesoporous silica 15 parts, the content of other components and the preparation method are the same as in Example 1.

Example 7

This embodiment provides a PVC cable material. Compared with embodiment 1, the difference is only that: the filler does not contain mesoporous silica, and only contains montmorillonite modified by octadecyl dimethyl benzyl ammonium chloride 15 parts, the content of other components and the preparation method are the same as in Example 1.

Example 8

This embodiment provides a PVC cable material. Compared with Embodiment 1, the only difference is: the degree of polymerization of the PVC resin is 1500, and the content of other components and the preparation method are the same as in Embodiment 1.

Example 9

This embodiment provides a PVC cable material. Compared with Embodiment 1, the only difference is: the degree of polymerization of the PVC resin is 2000, and the content of other components and the preparation method are the same as in Embodiment 1.

Comparative example 1

This comparative example provides a PVC cable material. Compared with Example 1, the only difference is: the PVC cable material does not contain dioctyl terephthalate, the epoxy soybean oil is added to 50 parts, and the content of other components is The preparation method is the same as in Example 1.

Comparative example 2

This comparative example provides a PVC cable material. Compared with Example 1, the only difference is: the PVC cable material does not contain epoxy soybean oil, dioctyl terephthalate is added to 50 parts, and the content of other components is The preparation method is the same as in Example 1.

Comparative example 3

This comparative example provides a PVC cable material. Compared with Example 1, the only difference is: the dioctyl terephthalate is 10 parts, the epoxy soybean oil is 30 parts, and the content of other components and the preparation method are the same. Example 1.

Comparative example 4

This comparative example provides a PVC cable material. Compared with Example 1, the only difference is: the PVC cable material does not contain dilauryl thiodipropionate (auxiliary antioxidant), 2,6-tributyl -4-methylphenol (main antioxidant) was added to 11 parts, and the content of other components and the preparation method were the same as in Example 1.

Comparative example 5

This comparative example provides a PVC cable material. Compared with Example 1, the only difference is: the PVC cable material does not contain 2,6-tributyl-4-methylphenol (the main antioxidant), thio Dilauryl dipropionate (auxiliary antioxidant) was added to 11 parts, and the content of other components and the preparation method were the same as in Example 1.

Comparative example 6

This comparative example provides a PVC cable material. Compared with Example 1, the difference is that the flame retardant does not contain the organic flame retardant diphenyl isooctyl phosphite, and only contains 8 parts of diammonium hydrogen phosphate, and the content of other components And the preparation method is the same as in Example 1.

Comparative example 7

This comparative example provides a PVC cable material. Compared with Example 1, the difference is that the flame retardant does not contain the inorganic flame retardant diammonium hydrogen phosphate, and only contains 8 parts of diphenyl isooctyl phosphite, and the content of other components And the preparation method is the same as in Example 1.

Test example 1

The performance of the cable materials provided in the above examples 1-9 and comparative examples 1-7 was tested. The test standards include: tensile strength, elongation at break: GB/T2951; oxygen index (oxygen index refers to the specified conditions Below, the minimum oxygen concentration required for flaming combustion of the material in the oxygen-nitrogen mixed gas stream is expressed as the value of the volume percentage occupied by oxygen. A high oxygen index indicates that the material is not easy to burn, and a low oxygen index indicates that the material is easy to burn): ISO 4586, single vertical burning: GB/T18380-2008, electrolyte strength, measured by electrolyte analyzer (PL1000A), the specific test results are shown in Table 1:

Table 1

It can be seen from the above test results that the tensile strength of the PVC cable material prepared in Examples 1-9 is above 16MPa, the elongation at break is above 200%, the oxygen index is above 32%, and the electrolyte strength is above 20MV/m. It fully illustrates that the various components in the PVC cable material described in the present application cooperate with each other and synergistically increase the effect, which not only effectively improves the smoke suppression and flame retardancy of the cable material, but also enables the cable material to have good mechanical strength and electrical properties.

Test example 2

According to the JB/T10436 standard, the temperature resistance performance of the cable materials provided in the above Examples 1-9 and Comparative Examples 1-7 was tested. The thermal aging test method is to heat to (135±2) ℃ and maintain 240h, respectively Test the tensile strength, elongation at break, and the quality of the insulation and sheath after aging, and calculate the tensile change rate of the insulation and sheath, the change rate of the insulation and sheath breaking elongation; the mass loss after aging: low temperature bending test method ：Cooling temperature (-40±2)℃, time 16h, the diameter of the test rod is 4 to 5 times the outer diameter of the cable, winding 3 to 4 times, after the test, there should be no visible cracks on the surface. The specific test results are shown in Table 2.

Table 2

It can be seen from the above test results that the tensile change rate of the PVC cable materials prepared in Examples 1-9 after the heat aging test is below 20%, the elongation change rate at break is below 20%, and the mass loss rate after aging is 18%. Below, this fully illustrates that the various components in the PVC cable material described in this application cooperate with each other and synergistically increase the effect, which not only effectively improves the smoke suppression and flame retardancy of the cable material, but also improves the strength of the cable and effectively reduces mechanical damage. Extend the service life of the cable. The cable material of the application also has excellent wear resistance, corrosion resistance, heat aging resistance and low temperature performance.

The applicant declares that this application uses the above-mentioned embodiments to illustrate the PVC cable material and its preparation method described in this application, but this application is not limited to the above-mentioned embodiments, which does not mean that this application must rely on the above-mentioned embodiments to be implemented.

Claims

A PVC cable material, which in parts by weight includes: 90-110 parts of PVC resin, 30-50 parts of dioctyl terephthalate, 5-20 parts of epoxy soybean oil, 10-20 parts of filler, organic resistance 1-10 parts of burning agent, 1-10 parts of inorganic flame retardant, 3-6 parts of main antioxidant, 3-6 parts of auxiliary antioxidant, 1-5 parts of lubricant and 1-5 parts of stabilizer.
The PVC cable material according to claim 1, wherein the degree of polymerization of the PVC resin is 1700-1800.
The PVC cable material according to claim 1 or 2, wherein the filler comprises any of organically modified montmorillonite, mesoporous silica, nano-activated calcium carbonate, halloysite nanotubes, bentonite or diatomite One or a combination of at least two.
The PVC cable material according to claim 3, wherein the filler is organically modified montmorillonite and/or mesoporous silica;

Optionally, the organically modified montmorillonite includes glycidyl methacrylate modified montmorillonite, betaine modified montmorillonite, stearyl dimethyl benzyl ammonium chloride modified montmorillonite Modified montmorillonite with octadecyltrimethylammonium bromide;

Optionally, the particle size of the mesoporous silica is 80-100 μm;

Optionally, the specific surface area of the mesoporous silica is 500-600 m 2 /g.
The PVC cable material according to any one of claims 1 to 4, wherein the mass ratio of the organic flame retardant to the inorganic flame retardant is (2-4):1;

Optionally, the organic flame retardant includes diphenyl isooctyl phosphite, tris(nonylphenyl) phosphite, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate Or any one or a combination of at least two of the tris(dichloropropyl) phosphate;

Optionally, the inorganic flame retardant is a phosphate flame retardant;

Optionally, the phosphate includes any one or a combination of at least two of diammonium hydrogen phosphate, ammonium pyrophosphate, aluminum hypophosphite, or ammonium polyphosphate.
The PVC cable material according to any one of claims 1-5, wherein the primary antioxidant is a hindered phenolic antioxidant;

Optionally, the hindered phenolic antioxidant includes 2,6-tributyl-4-methylphenol, bis(3,5-tributyl-4-hydroxyphenyl)sulfide or tetra[β- (3,5-Tributyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester of one kind or a mixture of at least two kinds;

Optionally, the auxiliary antioxidant is a combination of thioester antioxidants;

Optionally, the thioester antioxidant includes dilauryl thiodipropionate, lauryl octadecyl thiodipropionate, di(tridecyl thiodipropionate), or dilauryl thiodipropionate. (Tetradecyl ester) any one or a combination of at least two.
The PVC cable material according to any one of claims 1-6, wherein the lubricant comprises magnesium stearate, calcium stearate, zinc stearate, polyethylene wax, montan wax or paraffin wax Any one or a combination of at least two;

Optionally, the stabilizer includes dibutyl tin dilaurate, isooctyl dimercaptoacetate di-n-octyl tin, methyl tin mercaptan, butyl tin mercaptan, dibutyl tin dichloride or octyl tin mercaptan Any one or a combination of at least two of them;

Optionally, the PVC cable material further includes an ultraviolet absorber;

Optionally, the weight part of the ultraviolet absorber in the PVC cable material is 0.5-2 parts;

Optionally, the ultraviolet absorber includes 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone or 2-(2'-hydroxy-3', Any one or a combination of at least two of 5'-di-tert-butylphenyl)-5-chlorobenzotriazole;

Optionally, the PVC cable material further includes a colorant;

Optionally, the weight part of the colorant in the PVC cable material is 0.5-1 part;

Optionally, the colorant includes any one or a combination of at least two of titanium dioxide, carbon black, or toner.
The method for preparing the PVC cable material according to any one of claims 1-7, which comprises the following steps:

(1) Mix and stir PVC resin, dioctyl terephthalate and epoxy soybean oil according to the formula amount to obtain a mixed slurry;

(2) Add filler, organic flame retardant, inorganic flame retardant, main antioxidant, auxiliary antioxidant, lubricant and stabilizer to the mixed slurry obtained in step (1), and mix and stir to obtain a mixed material;

(3) Extruding and pelletizing the mixture material obtained in step (2) to obtain the PVC cable material.
The preparation method according to claim 8, wherein the mixing and stirring in step (1) is carried out in a high-speed mixer;

Optionally, the mixing and stirring in step (1) is carried out under a vapor pressure of 0.15-0.25 MPa;

Optionally, the temperature of the mixing and stirring in step (1) is 70-80°C;

Optionally, the mixing and stirring time in step (1) is 3-5 min;

Optionally, the rotation speed of the mixing and stirring in step (1) is 600-800 r/min.
The preparation method according to claim 8 or 9, wherein the mixing and stirring in step (2) is: first performing high-speed stirring and then performing low-speed stirring;

Optionally, the temperature of the high-speed stirring is 110-120°C;

Optionally, the high-speed stirring time is 5-10 min;

Optionally, the rotational speed of the high-speed stirring is 1500-2000 r/min;

Optionally, the temperature of the low-speed stirring is 40-50°C;

Optionally, the low-speed stirring time is 10-20 min;

Optionally, the rotation speed of the low-speed stirring is 100-200 r/min.
The preparation method according to any one of claims 8-10, wherein the extrusion in step (3) is carried out in a first-stage twin-screw extruder;

Optionally, the upper-stage twin-screw processing temperature of the first-stage twin-screw extruder is 140-175°C;

Optionally, the lower-stage single-screw temperature of the first-stage twin-screw extruder is 130-165°C;

Optionally, the first-stage twin-screw extruder includes a first zone, a second zone, a third zone, a fourth zone, and a die head which are sequentially connected;

Optionally, the working temperature of the first zone is 175-185°C, the working temperature of the second zone is 180-190°C, the working temperature of the third zone is 185-195°C, and the working temperature of the fourth zone is 185 -195℃, the working temperature of the die head is 185-195℃;

Optionally, the pelletizing in step (3) adopts an air-cooled grinding surface hot pelletizing method.