CN107236182A - The oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material - Google Patents

Abstract

An oil-resistant, mud-resistant, radiation-resistant cross-linked flame-retardant cable material of the present invention is composed of the following materials in parts by weight: ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide terpolymer, high-density polyethylene, polyethylene graft Copolymer of maleic anhydride, carbon black, aluminum hydroxide flame retardant, magnesium hydroxide flame retardant, coupling agent, crosslinking sensitizer, antioxidant, silicone, lubricant; wherein, the ethylene acetic acid The vinyl acetate VA content in the ethylene copolymer is 33%, and the melt index of this ethylene vinyl acetate copolymer is 0.2g/10min; Described crosslinking sensitizer is trimethallyl isocyanate TMAIC prepolymer, polymerization degree n is 2-10, its monomer is trimethallyl isocyanate TMAIC, and its molecular weight is 291.35. The invention is low-smoke and non-toxic, easy to entrust irradiation processing, and improves the compatibility of the filler and the base material in the blended material and the mechanical properties of the material.

Description

Oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material

technical field

The invention relates to the field of low-smoke, halogen-free, flame-retardant cable materials, in particular to an oil-resistant, mud-resistant, radiation-resistant cross-linked flame-retardant cable material.

Background technique

With the official drilling of Offshore Oil 981, China's first self-designed and built "sixth-generation deepwater semi-submersible drilling platform" in 2012, it marks a substantial step forward in the deepwater strategy of China's offshore oil industry. The technology of deep-water platforms has matured, and at the same time, higher technical requirements have been put forward for the cables used for oil platforms. Special cables for oil platforms are required to have properties such as oil resistance, mud resistance, high temperature resistance, low temperature resistance, abrasion resistance, high mechanical strength, halogen-free, and low smoke due to the particularity of the environment in which they are used. For cables used on oil platforms, more stringent requirements for oil resistance and oil sludge resistance have always been the main problems in the research of the cable industry.

At present, domestic manufacturers not only produce special cables for oil platforms, but also have the ability to produce mud-resistant sheath materials, and the mud-resistant performance is very unstable, so cables and materials mainly rely on imports.

Most of the patents published in China on mud-resistant cables for oil platforms only propose that the sheath is made of low-smoke, halogen-free mud-resistant materials, and do not point out the preparation technology of the materials. How to solve the technical problems of high cost, large amount of smoke during combustion, large investment in equipment, and complicated process has become the direction of efforts of ordinary skilled in the art.

Contents of the invention

The object of the present invention is to provide an oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material. The oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material is low-smoke and non-toxic. Halogen-free, flame-retardant and mud-resistant sheathing material that meets the Norwegian NEK606 standard for halogen-free/mud-proof cables for offshore platforms.

In order to achieve the purpose of the above invention, the technical solution adopted in the present invention is: an oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material, the raw material formula is composed of the following materials in parts by weight: 25-45 parts of ethylene vinyl acetate copolymer, Vinyl acetate-carbon monoxide terpolymer 12-18 parts, high-density polyethylene 30-45 parts, polyethylene grafted maleic anhydride copolymer 5-15 parts, carbon black 8-10 parts, aluminum hydroxide flame retardant 115 parts, magnesium hydroxide flame retardant 35 parts, coupling agent 0.7~1.8 parts, crosslinking sensitizer 1.5~3 parts, antioxidant 1.4~2.4 parts, silicone 3~4 parts, lubricant 0.5~1 share;

The radiation-crosslinked flame-retardant cable material is obtained through the following steps:

The first step: Mix the ethylene vinyl acetate copolymer EVA, ethylene-vinyl acetate-carbon monoxide terpolymer, polyethylene and polyethylene grafted maleic anhydride copolymer in a high-speed mixer for 30 seconds at high speed according to the formula weight Then, it is mixed and plasticized by a twin-screw granulator. The processing temperature is: 120-130°C in the conveying section, 140-155°C in the melting section, 160-170°C in the mixing section, and 155-165°C in the exhaust section. Chemical section 155～165℃, head 160～170℃;

The second step: Add the above materials into carbon black, aluminum hydroxide flame retardant, magnesium hydroxide flame retardant, silane coupling agent, cross-linking sensitizer trimethallyl isocyanate TMAIC prepolymerized by formula weight compound, antioxidant 1010, antioxidant DLTP, silicone masterbatch and lubricant, mixed in a high-speed mixer for 30 seconds, and then kneaded and plasticized in a two-stage machine for granulation. The two-stage machine includes twin-screw processing The temperature is: conveying section 100-115°C, melting section 120-135°C, mixing section 140-150°C, exhaust section 145-155°C, homogenizing section 145-155°C, head 150-160°C, including single The temperature of the screw is: 120-135°C in the first zone, 120-135°C in the second zone, 120-135°C in the third zone, 130-145°C in the head, and packaged after pelletizing and air-cooling;

The third step: put the material obtained in the second step on the wire and cable extruder production line, in the first zone 110-120 ℃, in the second zone 120-140 ℃, in the third zone 135-155 ℃, in the fourth zone 135-155 ℃, the machine head Extruded at a temperature of 130-150°C, coated on the conductor core, and then irradiated, the thermal extension is 15%-25% after irradiation;

Wherein, the vinyl acetate VA content in the ethylene vinyl acetate copolymer is 33%, and the melt index of this ethylene vinyl acetate copolymer is 0.2g/10min;

The carbon monoxide content in the ethylene-vinyl acetate-carbon monoxide terpolymer is 8-12%, the vinyl acetate VA content in the ethylene-vinyl acetate copolymer EVA is 24-30%, and the ethylene-vinyl acetate-carbon monoxide terpolymer The melt index of the product is 35g/10min;

Described polyethylene is high-density polyethylene, and melt index is 0.08g/10min;

The graft ratio of the copolymer of polyethylene grafted maleic anhydride is 0.6%～1.2%;

The carbon black is carbon black produced by a furnace method, the particle size is 12-30nm, and the oil absorption value is 50-80cc/100g;

The halogen-free flame retardant is a mixture of aluminum hydroxide and magnesium hydroxide in a mass ratio of 2 to 3:1, and the average particle size is 0.8 to 1.5 μm;

The coupling agent is a silane coupling agent A-172 or Z-6173;

The cross-linking sensitizer is trimethallyl isocyanate TMAIC prepolymer, the molecular structure is shown in the following formula, the degree of polymerization n is 2-10, and its monomer is trimethallyl isocyanate TMAIC, the molecular weight is 291.35;

The antioxidant is a mixture of 1010 and DLTP in a mass ratio of 0.8-1:1-1.2.

The technical scheme of further improvement of above-mentioned technical scheme is as follows:

1. In the above scheme, the mass content of the active ingredient silicone in the silicone masterbatch is 50%.

2. In the foregoing scheme, the lubricant is at least one of PE wax, EVA wax, calcium stearate or zinc stearate.

3. In the above scheme, the average particle size of the aluminum hydroxide flame retardant is 0.8-1.5 μm.

4. In the above scheme, the average particle size of the magnesium hydroxide flame retardant is 0.8-1.5 μm.

Due to the application of the above-mentioned technical solution, the present invention has the following advantages compared with the prior art:

1. The oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material of the present invention uses ethylene-vinyl acetate copolymer EVA, ethylene-vinyl acetate-carbon monoxide terpolymer, polyethylene and polyethylene-grafted maleic anhydride copolymer as the base material resin, adding aluminum hydroxide and magnesium hydroxide flame retardants, and furnace carbon black, and adopting a two-stage machine under the action of silane coupling agent, crosslinking sensitizer TMAIC prepolymer and antioxidant and other additives , that is, equipment consisting of twin-screw and single-screw, through two-step technology, can improve the compatibility of fillers and base materials in blended materials, and improve the mechanical properties of materials; finally, the Halogen-free /Mud-proof cable The standard halogen-free flame-retardant sheath material for mud-resistant cables, after irradiation processing, becomes an irradiation cross-linked mud-resistant low-smoke halogen-free flame-retardant cable for oil platforms.

2. The oil-resistant, mud-resistant and radiation-resistant cross-linked flame-retardant cable material of the present invention is one of the characteristics of the present invention, and the base material is ethylene-vinyl acetate-carbon monoxide terpolymer. , the oil resistance is equivalent to EVM with high VA content; reasonable compounding with EVA copolymer, high-density polyethylene and PE grafted maleic anhydride copolymer not only eliminates stickiness and knots in the production process of high VA content EVM However, it maintains satisfactory heat resistance and low temperature performance; more importantly, under the reinforcing effect of furnace carbon black (3.3% to 3.5%), it achieves superior high oil resistance and Mud performance, after irradiation, it has passed the requirements of Norwegian standard NEK606 for oil and mud resistance.

3. The oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material of the present invention uses trimethylallyl isocyanate TMAIC prepolymer as a cross-linking sensitizer, which is another major feature of the present invention. The TMAIC prepolymer is used to After formulating, the radiation cross-linking effect of the product is greatly improved. Under the same thermal elongation (10%) requirements, the radiation dose is reduced from the original 25Mrad to the current 15Mrad, which greatly reduces the processing difficulty and The processing cost ensures that it is easy to meet the radiation crosslinking requirements of low thermal elongation required for high oil resistance and mud resistance, which further promotes the realization of the high oil resistance and mud resistance scheme.

4. The oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material of the present invention uses aluminum hydroxide and magnesium hydroxide to endow the product with halogen-free flame-retardant properties, and is used in conjunction with lubricant silicone masterbatch to have obvious synergistic effects. It can improve the flame retardant effect of the composite flame retardant system, such as encrustation and drip resistance. At the same time, adding silane coupling agent to modify the inorganic filler can improve the compatibility between the inorganic flame retardant and the base material, so that it is beneficial to improve the aging performance, oil resistance and mud resistance of the material. The antioxidant system adopts the combination of antioxidant 1010 and DLTP, which has an obvious synergistic effect, so that the product can still meet certain aging performance requirements while significantly reducing the amount of antioxidant, that is, after a certain high temperature aging, the material The structure and performance have a certain degree of retention, and at the same time, the oil resistance and mud resistance of the product are guaranteed; the formula of conventional low-smoke halogen-free flame-retardant cable materials is technically improved by adding ethylene-vinyl acetate-carbon monoxide terpolymer Reinforcing with carbon black, as well as the promotion of the cross-linking effect by the efficient cross-linking sensitizer TMAIC prepolymer, effectively improve the oil resistance and mud resistance of the halogen-free flame-retardant sheathing material, and finally can be well It meets the requirements of Norwegian NEK606 standard for halogen-free/mud-proof cables for offshore platforms.

detailed description

The present invention will be further described below in conjunction with embodiment:

Example: an oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material, the material formula:

Preparation Process

The first step: Mix the ethylene vinyl acetate copolymer EVA, ethylene-vinyl acetate-carbon monoxide terpolymer, polyethylene and polyethylene grafted maleic anhydride copolymer in a high-speed mixer for 30 seconds at high speed according to the formula weight Then, it is mixed and plasticized by a twin-screw granulator. The processing temperature is: 120-130°C in the conveying section, 140-155°C in the melting section, 160-170°C in the mixing section, and 155-165°C in the exhaust section. The heating section is 155-165°C, and the head is 160-170°C.

The second step: Add the above materials into carbon black, aluminum hydroxide flame retardant, magnesium hydroxide flame retardant, silane coupling agent, cross-linking sensitizer trimethallyl isocyanate TMAIC prepolymerized by formula weight compound, antioxidant 1010, antioxidant DLTP, silicone masterbatch and lubricant, mixed in a high-speed mixer for 30 seconds, and then kneaded and plasticized in a two-stage machine for granulation. The two-stage machine includes twin-screw processing The temperature is: conveying section 100-115°C, melting section 120-135°C, mixing section 140-150°C, exhaust section 145-155°C, homogenizing section 145-155°C, head 150-160°C, including single The temperature of the screw is: 120-135°C in the first zone, 120-135°C in the second zone, 120-135°C in the third zone, 130-145°C in the machine head, and package after pelletizing and air-cooling.

The third step: put the material obtained in the second step on the wire and cable extruder production line, in the first zone 110-120 ℃, in the second zone 120-140 ℃, in the third zone 135-155 ℃, in the fourth zone 135-155 ℃, the machine head It is extruded at a temperature of 130-150°C, coated on the conductor core, and then processed by irradiation. After irradiation, the thermal extension is 15%-25%, which meets the Norwegian NEK606 standard for halogen-free/mud-proof cables for offshore platforms. The cables are tested according to the cable standards.

2. Technical indicators

As can be seen from the above examples, the present invention enables more sufficient, uniform and effective cross-linking reactions to occur in the material by adding ethylene-vinyl acetate-carbon monoxide terpolymer and high-efficiency cross-linking sensitizer TMAIC prepolymer , so it has higher oil resistance and mud resistance; the products made of this cable sheathing material can meet the requirements of the Norwegian NEK606 standard for halogen-free/mud-proof cables for offshore platforms.

The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (5)

1. a kind of oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material, it is characterised in that：Composition of raw materials by following parts by weight material Material composition：25~45 parts of ethylene-vinyl acetate copolymer, 12~18 parts of ethene-vinyl acetate-carbon monoxide terpolymer, height 8 ~ 10 parts of 5~15 parts of copolymer, carbon black, the aluminium hydroxide flame-retardant of 30~45 parts of density polyethylene, Research of Grafting Malaic Anhydride Onto Polyethylene 115 parts of agent, 35 parts of flame retardant of magnesium hydroxide, 0.7 ~ 1.8 part of coupling agent, 1.5 ~ 3 parts of crosslinking sensitizer, antioxidant 1.4 ~ 2.4 Part, 3~4 parts of silicone, 0.5~1 part of lubricant；

The resistance to flame-proof cable material of cross-linking radiation is obtained by following steps：

The first step：By the ethylene-vinyl acetate copolymer EVA measured by formulation weight, ethene-vinyl acetate-carbon monoxide ternary The copolymer of copolymer, polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene is mixed 30 seconds in high-speed mixer high speed, Ran Houjing Dual-screw pelletizer mixing plasticizing is granulated, and processing temperature is：120~130 DEG C of transportation section, 140~155 DEG C of melt zone, mixing section 160~170 DEG C, 155~165 DEG C of exhaust section, 155~165 DEG C of homogenizing zone, 160~170 DEG C of head；

Second step：Above-mentioned material is added into the carbon black measured by formulation weight, aluminium hydroxide fire retardant, magnesium hydroxide flame retardant Agent, silane coupler, crosslinking sensitizer front three are for allyl iso cyanurate TMAIC prepolymers, antioxidant 1010, antioxidant DLTP, silicone master batch and lubricant, are mixed 30 seconds in high-speed mixer, then kneading plasticizing granulation, double ranks in double rank machines The processing temperature of machine including twin-screw is：100~115 DEG C of transportation section, 120~135 DEG C of melt zone, 140~150 DEG C of mixing section, 145~155 DEG C of exhaust section, 145~155 DEG C of homogenizing zone, 150~160 DEG C of head, including single screw rod temperature are：First area 120~ 135 DEG C, the second 120~135 DEG C of area, the 3rd 120~135 DEG C of area, 130~145 DEG C of head is packed after pelletizing is air-cooled；

3rd step：Second step resulting materials are squeezed on line machine production line in electric wire, in 110~120 DEG C of an area, two areas 120 ~140 DEG C, three 135~155 DEG C of areas, four 135~155 DEG C of areas extrude at a temperature of 130~150 DEG C of head, are coated on conductor lines On core, then irradiation processing is carried out, heat extension 15%~25% after irradiation；

Wherein, the vinyl acetate VA contents in the ethylene-vinyl acetate copolymer are 33%, this ethylene-vinyl acetate copolymer Melt index (MI) is 0.2g/10min；

Carbon monoxide content is 8~12% in the ethene-vinyl acetate-carbon monoxide terpolymer, and ethylene-vinyl acetate is common Vinyl acetate VA contents in polymers EVA are 24~30%, the melt of the ethene-vinyl acetate-carbon monoxide terpolymer Index is 35g/10min；

The polyethylene is high density polyethylene (HDPE), and melt index (MI) is 0.08g/10min；

The grafting rate of the copolymer of the Research of Grafting Malaic Anhydride Onto Polyethylene is 0.6%~1.2%；

The carbon black is the carbon black that oven process is generated, and particle diameter is 12~30nm, and oil factor is 50~80cc/100g；

The halogen-free flame retardants is aluminium hydroxide and magnesium hydroxide according to 2 ~ 3：1 mass ratio compounds the mixture to be formed；

The coupling agent is silane coupling A -172 or Z-6173；

The crosslinking sensitizer be front three for allyl iso cyanurate TMAIC prepolymers, molecular structure is shown below, the degree of polymerization N be 2~10, monomer be front three for allyl iso cyanurate TMAIC, molecular weight is 291.35；

The antioxidant is 1010 and DLTP according to 0.8 ~ 1：The mixture of 1 ~ 1.2 mass ratio compounding.

2. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material according to claim 1, it is characterised in that：The silicone is female The mass content of active ingredient silicone is 50% in grain.

3. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material according to claim 1, it is characterised in that：The lubricant For at least one of PE waxes, EVA waxes, calcium stearate or zinc stearate.

4. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material according to claim 1, it is characterised in that：The hydroxide Aluminium fire retardant average grain diameter is 0.8 ~ 1.5 μm.

5. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material according to claim 1, it is characterised in that：The hydroxide Magnesium fire retardant average grain diameter is 0.8 ~ 1.5 μm.