Environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating and preparation method thereof

Abstract

The present invention relates to the field of cable technology, and more specifically, to an environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating and a preparation method thereof. The environmentally friendly water supply and drainage wire comprises: a core wire; a flame retardant insulation foaming layer coated on the outside of the core wire; and a flame retardant insulation extrusion layer coated on the flame retardant insulation foaming layer; the material of the flame retardant insulation foaming layer comprises: cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, composite flame retardant foaming agent and catalyst A; the mass ratio of cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, composite flame retardant foaming agent and catalyst A is (20-40): (60-80): (40-50): (70-90): (0.5-1); the present invention solves the problem that the water supply and drainage wire in the prior art cannot meet the good flame retardancy and resistance to corrosion of various organic solvents required by the chemical industry.

Description

Technical Field

[0001] The present invention relates to the technical field of cables, and more specifically to an environmentally friendly water supply and drainage electric wire based on polyurethane modified flame retardant insulation coating and a preparation method thereof. Background Art

[0002] Water supply and drainage cables refer to cables that provide power to related equipment in water supply and drainage systems. Since the environment and working conditions faced by water supply and drainage cables are usually more complicated, they have higher requirements in terms of waterproofness, acid and alkali resistance, flexibility and temperature resistance compared to ordinary cables.

[0003] The application scenarios of water supply and drainage cables are very wide, covering many fields such as industry, commerce and residential buildings. In the chemical industry, since the chemical production process will discharge sewage containing various organic pollutants, such as oil, sulfur, cyanide, phenol, ammonia, acidic sewage, etc., and the high temperature process in the chemical production process discharges sewage containing various pollutants at high temperatures, and organic pollutants are flammable and explosive, the water supply and drainage cables used in the chemical industry need to be waterproof, acid and alkali resistant, flexible, and temperature resistant, as well as have good flame retardancy and resistance to corrosion by various organic solvents.

[0004] The Chinese patent with publication number CN104867603A discloses an environmentally friendly acid- and alkali-resistant electric wire, which includes seven outer protective layers and a conductor. The seven outer protective layers are, from the inside to the outside, a nickel tape shielding layer, a nitrile insulation layer, a silver-plated copper tape armor layer, an ethylene-propylene rubber insulation layer, an aluminum tape shielding layer, a chlorosulfonated ethylene-propylene sheath layer, and a chlorosulfonated polyethylene sheath layer. The conductor is a silver-plated annealed nickel conductor, 24 of which are extruded inside the nickel tape shielding layer, a nitrile insulation layer is wrapped outside the nickel tape shielding layer, a silver-plated copper tape armor layer is wrapped outside the nitrile insulation layer, and an ethylene-propylene rubber insulation layer is wrapped outside the silver-plated copper tape armor layer. This kind of electric wire is acid- and alkali-resistant, environmentally friendly, flame-retardant, and high-temperature resistant, and is particularly suitable for use in chemical sites. However, the technical solution consists of seven protective layers, and the process is relatively complicated.

[0005] The Chinese patent with publication number CN102300348A discloses a waterproof, acid mist proof, corrosion-resistant, chemical-resistant self-limiting temperature tracing cable, comprising an insulated conductor, an aluminum-plastic composite tape longitudinal sheath and a polyethylene sheath layer are sequentially arranged outside the insulated conductor; the insulated conductor comprises a tinned copper wire conductor, a PTC heating layer and a polytetrafluoroethylene insulation layer are sequentially arranged outside the tinned copper wire conductor; at least one drainage wire is arranged between the polytetrafluoroethylene insulation layer and the aluminum-plastic composite tape longitudinal sheath. This technical solution solves the defect that the actual life of traditional cables is far lower than the designed life due to corrosion and long-term immersion in acidic and alkaline liquids and gases, and is suitable for heating pipelines and tanks that are often exposed to aromatic solvents in refineries, petrochemical plants and general chemical plants. However, this technical solution also does not have flame retardant properties, and the polyethylene sheath is easy to deform and difficult to degrade under high temperature conditions, which is not environmentally friendly. Summary of the invention

[0006] The present invention aims to solve the problem that the water supply and drainage wires in the prior art cannot meet the requirements of the chemical industry, that is, they have good high temperature water resistance, acid and alkali resistance, flexibility, temperature resistance, and also need to have good flame retardancy and resistance to corrosion by various organic solvents.

[0007] The first aspect of the present invention provides an environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating, comprising: a core wire; a flame retardant insulation foam layer coated on the outside of the core wire; and a flame retardant insulation extrusion layer coated on the flame retardant insulation foam layer;

[0008] The raw materials of the flame retardant insulating foam layer include: cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, composite flame retardant foaming agent and catalyst A; the mass ratio of cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, composite flame retardant foaming agent and catalyst A is (20-40): (60-80): (40-50): (70-90): (0.5-1);

[0009] The raw materials of the flame retardant insulation extrusion layer include, by weight: 60-80 parts of thermoplastic polyurethane, 30-50 parts of composite flame retardant foaming agent, and 1-2 parts of antioxidant;

[0010] The preparation method of the composite flame retardant foaming agent comprises the following steps:

[0011] S1, dispersing ammonium polyphosphate and boron nitride in ethanol, adding a silane coupling agent and stirring to react, washing and drying after the reaction to obtain a mixture;

[0012] S2. After the mixture is evenly mixed with water, fluorinated silicone is added, and the mixture is stirred at a speed of 10000-15000 r / min to obtain a composite flame retardant foaming agent;

[0013] The mass ratio of the ammonium polyphosphate, boron nitride, silane coupling agent, fluorinated silicone and water is (10-15): (1-3): (5-8): (20-40): (60-80).

[0014] In the process of preparing the flame-retardant insulating foam layer, due to the poor compatibility of the flame retardant in the polyurethane system, the obtained flame-retardant insulating foam layer has the problems of uneven foaming and poor flame retardant performance. To further solve the above problems, the inventors found through a large number of experiments that when the preparation method of the composite flame retardant foaming agent of the present invention is adopted and the mass ratio of ammonium polyphosphate, boron nitride, silane coupling agent, fluorinated siloxane and water is strictly controlled to be (10-15): (1-3): (5-8): (20-40): (60-80), the obtained environmentally friendly water supply and drainage wire not only has good flame retardancy, but also has good high temperature water resistance. The inventors speculate that it is because ammonium polyphosphate and boron nitride can be effectively wrapped on the surface of fluorinated silicone to form an emulsion with a core-shell structure at this mass ratio, which can not only make ammonium polyphosphate and boron nitride stably exist in the polyurethane system, but also the water in the emulsion acts as a foaming agent, which improves the foaming stability, and then gives full play to the synergistic effect between ammonium polyphosphate and boron nitride, thereby improving the flame retardancy of the environmentally friendly water supply and drainage wire. At the same time, the composite flame retardant foaming agent of the present invention has super hydrophobicity, which improves the hydrophobicity of the flame retardant insulation foaming layer, thereby improving the high temperature water resistance of the environmentally friendly water supply and drainage wire. In addition, the inventors found that the composite flame retardant foaming agent can also be directly used in the flame retardant insulation extrusion layer, so that the environmentally friendly water supply and drainage wire has very excellent flame retardancy.

[0015] Preferably, the silane coupling agent is selected from at least one of γ-glycidyl ether propyl trimethoxy silane, γ-glycidyl ether propyl triethoxy silane and 3-glycidyl ether propyl methyl diethoxy silane.

[0016] Preferably, the fluorine-containing siloxane is selected from at least one of heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane and tridecafluorooctyltriethoxysilane.

[0017] Preferably, the fluorinated siloxane is a mixture of heptadecafluorodecyltriethoxysilane and tridecafluorooctyltrimethoxysilane, and the mass ratio of the two is (1-2): (1-2).

[0018] Preferably, the cashew nut shell oil polyester diol has a hydroxyl value of 80-100 mgKOH / g and a viscosity of 2500-2800 cps / 25°C.

[0019] Preferably, the bio-based polyether polyol is a bio-based polyether-polytrimethylene ether glycol, and the molecular weight of the bio-based polyether-polytrimethylene ether glycol is 900-1100 g / mol and the hydroxyl value is 102-124.6 mgKOH / g.

[0020] In addition, during the preparation of the flame-retardant insulating foam layer, the inventors found that when a specific cashew nut shell oil polyester diol is used in combination with a specific bio-based polyether-polytrimethylene ether glycol, the flexibility, insulation, and high-temperature water resistance of the environmentally friendly water supply and drainage wires are further improved. It was unexpectedly found that the acid and alkali resistance of the environmentally friendly water supply and drainage wires is significantly improved.

[0021] Preferably, the catalyst A is selected from at least one of triethylenediamine and tetramethylethylenediamine.

[0022] Preferably, the added amount of ethanol is 20-40 times the total mass of ammonium polyphosphate and boron nitride.

[0023] Preferably, the stirring speed of the stirring reaction in S1 is 300-500 r / min, the temperature of the stirring reaction is 25-30° C., and the reaction time is 20-30 min.

[0024] Preferably, the stirring time in S2 is 4-8 min.

[0025] Preferably, the method for preparing the thermoplastic polyurethane comprises the following steps:

[0026] (1) Mix the bio-based polyol and diisocyanate B, raise the temperature to 60-80°C, add catalyst B, and react for 0.5-2h to obtain prepolymer A;

[0027] (2) Dissolve the biomass material in dimethyl sulfoxide, add diisocyanate C and mix, heat to 60-80°C, add catalyst C, and react for 0.5-2h to obtain prepolymer B;

[0028] (3) Prepolymer A and prepolymer B are mixed, trimethylolpropane is added and mixed, the temperature is raised to 60-80°C, and the reaction is carried out for 0.5-2h to obtain thermoplastic polyurethane.

[0029] Preferably, the mass ratio of the bio-based polyol, diisocyanate B and catalyst B is (40-60): (20-40): (0.02-0.08).

[0030] Preferably, the ratio of the biomass material, dimethyl sulfoxide, diisocyanate C and catalyst C is (5-15) g: (50-150) mL: (5-10) g: (0.001-0.01) g.

[0031] Preferably, the mass ratio of the prepolymer A, prepolymer B and trimethylolpropane is (2-4): (1-3): (0.1-0.3).

[0032] Preferably, the bio-based polyol comprises cashew nut shell liquid Mannich polyol, castor oil polyol and cashew nut shell liquid polyether diol; the mass ratio of the three is 1:(3-5):(1-3).

[0033] Preferably, the cashew nut shell liquid Mannich polyol has a functionality of 3-4, a hydroxyl value of 200-400 mgKOH / g, and a viscosity of 4000-6000 cps / 25°C;

[0034] Preferably, the castor oil polyol has a functionality of 2, a hydroxyl value of 200-300 mgKOH / g, and a viscosity of 200-400 cps / 25°C;

[0035] Preferably, the cashew nut shell liquid polyether diol has a hydroxyl value of 50-60 mgKOH / g and a viscosity of 400-500 cps / 25°C.

[0036] The inventors have found that only when specific cashew nut shell liquid Mannich polyols, specific castor oil polyols and specific cashew nut shell liquid polyether diols are used as bio-based polyols, the prepared thermoplastic polyurethane used to prepare the flame-retardant insulating extruded layer has excellent high temperature water resistance and acid and alkali resistance.

[0037] Preferably, the diisocyanate A, diisocyanate B and diisocyanate C are all selected from at least one of aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate.

[0038] Preferably, the diisocyanate A is an aliphatic diisocyanate.

[0039] Preferably, the diisocyanate B and the diisocyanate C are both a mixture of an aromatic diisocyanate and an aliphatic diisocyanate; the mass ratio of the aromatic diisocyanate to the aliphatic diisocyanate is (3-4):(1-2).

[0040] Preferably, the aliphatic diisocyanate is at least one selected from isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and 1,4-cyclohexane diisocyanate.

[0041] Preferably, the aromatic diisocyanate is selected from at least one of toluene diisocyanate, p-phenylene diisocyanate and 4,4-diphenylmethane diisocyanate.

[0042] Preferably, the catalyst B and the catalyst C are both selected from at least one of dibutyltin dilaurate and stannous octoate.

[0043] Preferably, the biomass material comprises chitosan oligosaccharide and sodium alginate; the mass ratio of the two is (10-20): (5-8).

[0044] The inventors found that when introducing chitosan oligosaccharide and sodium alginate into the side chains of thermoplastic polyurethane, the obtained thermoplastic polyurethane, when applied to the insulating extrusion layer, not only improves the high temperature water resistance of the environmentally friendly water supply and drainage wire, but also significantly improves the resistance to various organic solvents. The inventors speculate that the introduction of biomass materials into the side chains of polyurethane changes the chain structure of polyurethane and improves the thermal stability of thermoplastic polyurethane; at the same time, the insulating extrusion layer obtained by the polyurethane grafted with biomass materials can form a stable anti-solvent barrier on its surface, and this barrier effect can effectively reduce the erosion of solvents. In addition, the flame-retardant insulating extrusion layer formed by the thermoplastic polyurethane grafted with biomass materials can improve the comprehensive performance of the water supply and drainage wire through polar interaction with the flame-retardant insulating foaming layer.

[0045] Preferably, the antioxidant is selected from at least one of antioxidant 1010 , antioxidant 168 , antioxidant 1076 and antioxidant 164 .

[0046] Preferably, the core wire is formed by 5-8 conductor monofilaments twisted in the same direction.

[0047] Preferably, the conductor is a copper conductor or a tin-copper conductor.

[0048] Preferably, the thickness of the flame retardant insulating foam layer is 0.3-0.5 mm.

[0049] Preferably, the thickness of the flame retardant insulating extruded layer is 0.8-1 mm.

[0050] During the experiment, the inventors found that when the flame-retardant insulating extruded layer is directly coated on the outside of the core wire, the obtained environmentally friendly water supply and drainage wire has good acid and alkali resistance. However, when placed at high temperature, especially under high temperature water, the flame-retardant insulating extruded layer and the core wire are not only separated, but also have poor insulation performance. To solve this technical problem, the inventors tried various solutions and found that firstly coating the outside of the core wire with a flame-retardant insulating foam layer and then coating the flame-retardant insulating extruded layer on the flame-retardant insulating foam layer can avoid the separation of the flame-retardant insulating extruded layer and the core wire. At the same time, it was unexpectedly found that the insulation and flexibility of the environmentally friendly water supply and drainage wire are also improved. The inventor speculates that this is because the technical solution of the present invention first forms a sponge layer on the surface of the core wire through the foaming effect of polyurethane. The sponge layer serves as an intermediate carrier between the core wire and the flame-retardant insulating extruded layer, which can absorb the stress caused by thermal expansion while preventing moisture penetration, thereby avoiding separation of the flame-retardant insulating extruded layer and the core wire; at the same time, the porous structure of the sponge layer effectively prevents heat transfer and has good air tightness, thereby improving the insulation of the environmentally friendly water supply and drainage wires in high-temperature water; there are a large number of bubbles inside the sponge layer, which can effectively disperse stress and can compress and rebound when subjected to external force, thereby absorbing and releasing energy, thereby increasing the flexibility of the environmentally friendly water supply and drainage wires.

[0051] The second aspect of the present invention provides a method for preparing an environmentally friendly water supply and drainage wire based on a polyurethane modified flame retardant insulation coating, comprising the following steps:

[0052] Step 1, mixing cashew nut shell oil polyester diol, bio-based polyether polyol, composite flame retardant foaming agent and catalyst uniformly to obtain component A; placing the core wire in diisocyanate A to obtain component B; adding component A to component B for foaming to obtain a flame retardant insulating foaming layer coated on the outside of the core wire;

[0053] Step 2: Mix thermoplastic polyurethane, composite flame retardant foaming agent, lubricant and antioxidant, and extrude them on the outside of the flame retardant insulation foaming layer (flame retardant insulation extrusion layer) to obtain environmentally friendly water supply and drainage wires based on polyurethane modified flame retardant insulation coating.

[0054] Beneficial effects:

[0055] 1. When the preparation method of the composite flame retardant foaming agent of the present invention is adopted and the mass ratio of ammonium polyphosphate, boron nitride, silane coupling agent, fluorinated silicone and water is strictly controlled to be (10-15): (1-3): (5-8): (20-40): (60-80), the obtained environmentally friendly water supply and drainage wire not only has good flame retardancy, but also has improved high temperature water resistance to a certain extent.

[0056] 2. When the present invention adopts a specific cashew nut shell oil polyester diol and a specific bio-based polyether-polytrimethylene ether glycol, the flexibility, insulation and high temperature water resistance of the environmentally friendly water supply and drainage wire can be further improved through synergistic effect. It is unexpectedly found that the acid and alkali resistance of the environmentally friendly water supply and drainage wire is significantly improved.

[0057] 3. In the present invention, only when specific cashew nut shell liquid Mannich polyol, specific castor oil polyol and specific cashew nut shell liquid polyether diol are used as bio-based polyols, the prepared thermoplastic polyurethane used to prepare the flame-retardant insulating extruded layer has excellent high temperature water resistance and acid and alkali resistance.

[0058] 4. The present invention introduces chitosan oligosaccharide and sodium alginate into the side chains of thermoplastic polyurethane. When the obtained thermoplastic polyurethane is used in the insulating extrusion layer, it not only improves the high temperature water resistance of the environmentally friendly water supply and drainage wires, but also significantly improves the resistance to various organic solvents. When the biomass material includes chitosan oligosaccharide and sodium alginate; the mass ratio of the two is (10-20): (5-8), the effect is best.

[0059] 5. The present invention first coats the core wire with a flame-retardant insulating foam layer, and then coats the flame-retardant insulating extruded layer on the outside of the flame-retardant insulating foam layer, which can avoid separation of the flame-retardant insulating extruded layer and the core wire. At the same time, it is unexpectedly found that the insulation and flexibility of the environmentally friendly water supply and drainage wires are also improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 This is a schematic structural diagram of an environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to Example 1 of the present invention;

[0061] In the figure: 1. core wire; 2. flame retardant insulating foam layer; 3. flame retardant insulating extruded layer; 4. conductor. DETAILED DESCRIPTION

[0062] In order to better explain the present invention, the technical scheme in the embodiments of the present invention will be clearly and completely described below in conjunction with the examples in the embodiments of the present invention. The embodiments described are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other implementation methods obtained by those skilled in the art without making creative work are within the scope of protection of the present invention. The experimental methods in the following embodiments, unless otherwise specified, are conventional methods, and the materials, reagents, etc. used in the following embodiments, unless otherwise specified, can be obtained from commercial channels.

[0063] Example 1

[0064] like Figure 1As shown, the environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating comprises: a core wire 1; a flame retardant insulation foam layer 2 coated on the outside of the core wire; and a flame retardant insulation extrusion layer 3 coated on the flame retardant insulation foam layer;

[0065] The raw materials of the flame retardant insulating foam layer 2 include: cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, composite flame retardant foaming agent and catalyst A; the mass ratio of cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, composite flame retardant foaming agent and catalyst A is 35:65:45:85:0.7;

[0066] The raw materials of the flame retardant insulating extruded layer 3 include, by mass, 70 parts of thermoplastic polyurethane, 40 parts of composite flame retardant foaming agent, and 1.5 parts of antioxidant;

[0067] The preparation method of the composite flame retardant foaming agent comprises the following steps:

[0068] S1, dispersing ammonium polyphosphate and boron nitride in ethanol, adding a silane coupling agent and stirring to react, washing and drying after the reaction is completed to obtain a mixture;

[0069] S2, after the mixture and water are evenly mixed, fluorinated silicone is added, and the mixture is stirred at a speed of 13000 r / min to obtain a composite flame retardant foaming agent;

[0070] The mass ratio of the ammonium polyphosphate, boron nitride, silane coupling agent, fluorinated siloxane and water is 12:2:6:30:70.

[0071] The silane coupling agent is γ-glycidyl ether propyl triethoxy silane (CAS: 2602-34-8).

[0072] The fluorinated siloxane is a mixture of heptadecafluorodecyltriethoxysilane (CAS: 101947-16-4) and tridecafluorooctyltrimethoxysilane (CAS: 85857-16-5), and the mass ratio of the two is 1:1.

[0073] The cashew nut shell oil polyester diol has a hydroxyl value of 98 mgKOH / g and a viscosity of 2650 cps / 25° C. It is purchased from Cardolite, model number: NX-9203.

[0074] The bio-based polyether polyol is a bio-based polyether-polytrimethylene ether glycol, and the molecular weight of the bio-based polyether-polytrimethylene ether glycol is 1000±100 g / mol, and the hydroxyl value is 113.3±11.3 mgKOH / g.

[0075] The catalyst A is triethylenediamine (CAS: 280-57-9).

[0076] The added amount of the ethanol is 30 times the total mass of ammonium polyphosphate (CAS: 14728-39-3) and boron nitride (CAS: 10043-11-5).

[0077] The stirring speed of the stirring reaction in S1 is 400 r / min, the temperature of the stirring reaction is 25° C., and the reaction time is 25 min.

[0078] The stirring time in S2 is 5 min.

[0079] The preparation method of the thermoplastic polyurethane comprises the following steps:

[0080] (1) Mix the bio-based polyol and diisocyanate B, raise the temperature to 70°C, add catalyst B, and react for 2 hours to obtain prepolymer A;

[0081] (2) Dissolve the biomass material in dimethyl sulfoxide, add diisocyanate C and mix, heat to 60°C, add catalyst C, and react for 1 hour to obtain prepolymer B;

[0082] (3) Prepolymer A and prepolymer B are mixed, trimethylolpropane is added and mixed, the temperature is raised to 70°C, and the reaction is carried out for 2 hours to obtain thermoplastic polyurethane.

[0083] The mass ratio of the bio-based polyol, diisocyanate B and catalyst B is 50:35:0.05.

[0084] The ratio of the biomass material, dimethyl sulfoxide (CAS: 67-68-5), diisocyanate C and catalyst C is 12 g: 120 mL: 8 g: 0.005 g.

[0085] The mass ratio of the prepolymer A, the prepolymer B and trimethylolpropane (CAS: 77-99-6) is 3:2:0.2.

[0086] The bio-based polyol includes cashew nut shell oil Mannich polyol, castor oil polyol and cashew nut shell oil polyether diol; the mass ratio of the three is 1:3:2.

[0087] The cashew nut shell oil Mannich polyol has a functionality of 3, a hydroxyl value of 245 mgKOH / g, and a viscosity of 5500 cps / 25° C. It was purchased from Cardolite, model number: NX-9104.

[0088] The castor oil polyol has a functionality of 2, a hydroxyl value of 265 mgKOH / g, and a viscosity of 370 cps / 25° C. It was purchased from Guangzhou Haoyi New Materials Technology Co., Ltd., model: POLYCIN® D-265.

[0089] The cashew nut shell liquid polyether diol has a hydroxyl value of 55 mgKOH / g and a viscosity of 450 cps / 25° C. and is purchased from Cardolite, model number: NX-9212.

[0090] The diisocyanate A is an aliphatic diisocyanate.

[0091] The diisocyanate B and diisocyanate C are both mixtures of aromatic diisocyanate and aliphatic diisocyanate; the mass ratio of the aromatic diisocyanate to the aliphatic diisocyanate is 3:2.

[0092] The aliphatic diisocyanate is isophorone diisocyanate (CAS: 4098-71-9).

[0093] The aromatic diisocyanate is p-phenyl diisocyanate (CAS: 104-49-4).

[0094] The catalyst B and the catalyst C are both dibutyltin dilaurate (CAS: 77-58-7).

[0095] The biomass material includes chitosan oligosaccharide and sodium alginate; the mass ratio of the two is 18:6.

[0096] The antioxidant is antioxidant 1010 (CAS: 6683-19-8).

[0097] The core wire 1 is formed by 6 conductors 4 twisted together in the same direction.

[0098] The conductor 4 is a copper conductor.

[0099] The thickness of the flame retardant insulating foam layer 2 is 0.4 mm.

[0100] The thickness of the flame retardant insulating extruded layer 3 is 0.8 mm.

[0101] The preparation method of environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating comprises the following steps:

[0102] Step 1, mixing cashew nut shell oil polyester diol, bio-based polyether polyol, composite flame retardant foaming agent and catalyst uniformly to obtain component A; placing the core wire in diisocyanate A to obtain component B; adding component A to component B for foaming to obtain a flame retardant insulating foam layer 2 coated on the outside of the core wire;

[0103] Step 2: Mix thermoplastic polyurethane, composite flame retardant foaming agent, lubricant and antioxidant, and extrude them on the outside of the flame retardant insulation foaming layer (flame retardant insulation extrusion layer 3) to obtain an environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating.

[0104] Example 2

[0105] The difference from Example 1 is that the mass ratio of the cashew nut shell liquid polyester diol, the bio-based polyether polyol, the diisocyanate A, the composite flame retardant foaming agent and the catalyst A is 20:80:50:90:1; the rest are the same.

[0106] Example 3

[0107] The difference from Example 1 is that the material of the flame retardant insulating extruded layer includes, by mass, 80 parts of thermoplastic polyurethane, 50 parts of composite flame retardant foaming agent, and 2 parts of antioxidant; the rest are the same.

[0108] Comparative Example 1

[0109] The difference from Example 1 is that the material of the flame retardant insulating foam layer includes: cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, flame retardant, water and catalyst A; the mass ratio of cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, flame retardant, water and catalyst A is 35:65:45:28:57:0.7, the flame retardant includes ammonium polyphosphate and boron nitride, the mass ratio of the two is 12:2, and the rest are the same.

[0110] The preparation method of the environmentally friendly water supply and drainage wire is different from that of Example 1 in that, in step 1, cashew nut shell oil polyester diol, bio-based polyether polyol, flame retardant, water and catalyst are mixed evenly to obtain component A; the core wire is placed in diisocyanate A to obtain component B; component A is added to component B for foaming to obtain a flame retardant insulating foam layer coated on the outside of the core wire; and the rest are the same.

[0111] Comparative Example 2

[0112] The difference from Example 1 is that the mass ratio of the ammonium polyphosphate, boron nitride, silane coupling agent, fluorinated siloxane and water is 20:1:10:50:80, and the rest are the same.

[0113] Comparative Example 3

[0114] The difference from Example 1 is that the cashew nut shell liquid polyester diol has a hydroxyl value of 70 mgKOH / g and a viscosity of 1300 cps / 25° C. It is purchased from Cardolite, model: NX-9201LP, and the rest is the same.

[0115] Comparative Example 4

[0116] The difference from Example 1 is that the bio-based polyether-polytrimethylene ether glycol is replaced by cashew nut shell liquid polyether glycol purchased from Cardolite, model: NX-9212, and the rest are the same.

[0117] Comparative Example 5

[0118] The difference from Example 1 is that the cashew nut shell liquid Mannich polyol is replaced by cashew nut shell liquid polyol purchased from Cardolite, model: NX-5285, and the rest are the same.

[0119] Comparative Example 6

[0120] The difference from Example 1 is that the functionality of the castor oil polyol is 4, the hydroxyl value is 280 mgKOH / g, the viscosity is 1259 cps / 25°C, and it is purchased from Guangzhou Haoyi New Materials Technology Co., Ltd., model: POLYCIN® M-280, and the rest are the same.

[0121] Comparative Example 7

[0122] The difference from Example 1 is that the cashew nut shell liquid polyether diol is replaced by bio-based polytrimethylene ether glycol, purchased from Guangzhou Haoyi New Materials Technology Co., Ltd., model: PO3G H500, and the rest are the same.

[0123] Comparative Example 8

[0124] The difference from Example 1 is that the biomass material is chitosan oligosaccharide, and the rest is the same.

[0125] Comparative Example 9

[0126] The difference from Example 1 is that sodium alginate is replaced by cellulose, and the rest is the same.

[0127] Comparative Example 10

[0128] The difference from Example 1 is that the flame retardant insulating extruded layer is directly extruded onto the core wire, and the rest is the same.

[0129] Test Example: The environmentally friendly water supply and drainage wires obtained in Examples 1-3 and Comparative Examples 1-10 were tested as follows:

[0130] 1. Insulation: Tested in accordance with GB / T 3048.5-2007, the results are shown in Table 1;

[0131] 2. High temperature water resistance: Place the environmental protection water supply and drainage wire in 80℃ water for 1 month and then take it out to measure its insulation resistivity. If the volume resistivity is ≥1×10^ 11 Ω·cm -1 It is marked as qualified, otherwise it is unqualified. The results are shown in Table 1;

[0132] 3. Acid and alkali resistance: Soak the environmentally friendly water supply and drainage wires in 98% sulfuric acid and 30% sodium hydroxide for 1 month and then take them out. Measure the weight change of the environmentally friendly water supply and drainage wires before and after soaking, and calculate the weight loss rate = (weight before soaking - weight after soaking) / weight before soaking × 100%. The results are shown in Table 1.

[0133] 4. Flexibility: According to the flexibility measurement and evaluation method disclosed in publication number CN103189933B, the environmental protection water supply and drainage wire is flexed and extended in the flexion and extension test, and the number of flexion and extension cycles before fracture occurs is measured. The case where the number of flexion and extension cycles is 1,000 cycles is recorded as qualified, and the case where it is less than 1,000 is recorded as unqualified. The results are shown in Table 1;

[0134] 5. Flame retardancy: According to the vertical flame retardancy test VW-1 specified in UL1581, if all three tests are qualified, it is qualified, otherwise it is unqualified. The results are shown in Table 1;

[0135] 6. Organic solvent resistance: At 50°C, place the environmentally friendly water supply and drainage wires in phenol, xylene, chloroform, cyclohexane, and dichloromethane respectively, immerse them for 5 hours, then take them out and observe whether there are cracks on the surface of the environmentally friendly drainage wires. If there are no cracks, it is qualified, otherwise it is unqualified. The results are shown in Table 2.

[0136] Table 1 Test results of insulation, high temperature water resistance, acid and alkali resistance, flexibility and flame retardancy of environmentally friendly water supply and drainage wires of Examples 1-3 and Comparative Examples 1-10

[0137]

[0138] It can be seen from Table 1 that the environmentally friendly water supply and drainage wires of Examples 1-3 have good insulation performance, high temperature water resistance, acid and alkali resistance, and flexibility;

[0139] In Comparative Example 1, since the composite flame retardant foaming agent was not prepared, the flame retardant and water were directly used for foaming, and the high temperature resistance and flame retardancy of the obtained environmentally friendly water supply and drainage wire were unqualified, and the acid and alkali resistance was affected;

[0140] Comparative Example 2: Due to the change in the mass ratio of ammonium polyphosphate, boron nitride, silane coupling agent, fluorinated siloxane and water in the preparation process of the composite flame retardant foaming agent, the flame retardancy of the obtained environmentally friendly water supply and drainage wire was unqualified, and the acid and alkali resistance was affected;

[0141] Comparative Example 3 Due to the replacement of the cashew nut shell oil polyester diol model, the environmentally friendly water supply and drainage wire obtained has unqualified high temperature resistance, unqualified flexibility, and poor acid and alkali resistance;

[0142] In Comparative Example 4, due to the replacement of the type of bio-based polyether polyol, the obtained environmentally friendly water supply and drainage wire has unqualified high temperature resistance, unqualified flexibility, and poor acid and alkali resistance;

[0143] In Comparative Example 5, since the cashew nut shell liquid Mannich polyol is replaced by cashew nut shell liquid polyol, in Comparative Example 6, since the functionality of castor oil polyol is 4, the hydroxyl value is 280 mgKOH / g, and the viscosity is 1259 cps / 25°C, and in Comparative Example 7, since the cashew nut shell liquid polyether diol is replaced by bio-based polytrimethylene ether diol, that is, in Comparative Examples 5-7, since the raw materials for preparing thermoplastic polyurethane are changed, the high temperature resistance of the obtained environmentally friendly water supply and drainage wires is unqualified, and the acid and alkali resistance is poor; the flexibility of Comparative Examples 5 and 6 is unqualified;

[0144] In Comparative Example 8, since the biomass material is chitosan oligosaccharide, and in Comparative Example 9, since sodium alginate is replaced by cellulose, that is, Comparative Examples 8-9 change the composition of biomass materials, the environmentally friendly water supply and drainage wires obtained have unqualified high temperature resistance and poor acid and alkali resistance;

[0145] Since Comparative Example 10 only has a flame-retardant insulating extruded layer, the obtained environmentally friendly water supply and drainage wire is unqualified in terms of high temperature resistance, flexibility and flame retardancy, and its insulation and acid and alkali resistance are particularly poor.

[0146] Table 2 Solvent resistance test results of environmentally friendly water supply and drainage wires of Examples 1-3 and Comparative Examples 1-10

[0147]

[0148] It can be seen from Table 2 that:

[0149] In Comparative Example 1, since no composite flame retardant foaming agent was prepared, the flame retardant and water were directly used for foaming, and in Comparative Example 2, since the mass ratio of ammonium polyphosphate, boron nitride, silane coupling agent, fluorinated siloxane and water in the preparation process of the composite flame retardant foaming agent was changed, the environmentally friendly water supply and drainage wires obtained in Comparative Example 1 and Comparative Example 2 were not resistant to dichloromethane;

[0150] Comparative Example 3: Due to the replacement of the cashew nut shell oil polyester diol model, the environmentally friendly water supply and drainage wire obtained is not resistant to xylene;

[0151] In Comparative Example 4, due to the replacement of the type of bio-based polyether polyol, the obtained environmentally friendly water supply and drainage wire is not resistant to xylene and phenol;

[0152] Comparative Example 5 Since cashew nut shell oil Mannich polyol is replaced with cashew nut shell oil polyol, the obtained environmentally friendly water supply and drainage wire is not resistant to cyclohexane and dichloromethane;

[0153] Comparative Example 6 Since the functionality of castor oil polyol is 4, the hydroxyl value is 280 mgKOH / g, and the viscosity is 1259 cps / 25°C, the obtained environmentally friendly water supply and drainage wire is only resistant to chloroform;

[0154] In Comparative Example 7, since cashew nut shell liquid polyether diol is replaced with bio-based polytrimethylene ether glycol, the obtained environmentally friendly water supply and drainage wire is only resistant to xylenol and chloroform;

[0155] In Comparative Example 8, since the biomass material is chitosan oligosaccharide, and in Comparative Example 9, since sodium alginate is replaced by cellulose, that is, due to the change in the composition of the biomass material, the obtained environmentally friendly water supply and drainage wire is only resistant to dichloromethane;

[0156] Since Comparative Example 10 only has a flame-retardant insulating extrusion layer, the obtained environmentally friendly water supply and drainage wire is not resistant to phenol and xylene.

[0157] The above description is only a specific embodiment of the present invention, and does not limit the patent scope of the present invention. Any equivalent transformation made by the present invention, or directly or indirectly applied in other related technical fields, is also included in the patent protection scope of the present invention.

Claims

1. Environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating, characterized in that: include: Core wire; A flame retardant insulating foam layer wrapped around the core wire; and a flame retardant insulating extruded layer coated on the outside of the flame retardant insulating foam layer; The raw materials of the flame retardant insulating foam layer include: cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, composite flame retardant foaming agent and catalyst A; the mass ratio of cashew nut shell oil polyester diol, bio-based polyether polyol, diisocyanate A, composite flame retardant foaming agent and catalyst A is (20-40): (60-80): (40-50): (70-90): (0.5-1); The raw materials of the flame retardant insulation extrusion layer include, by weight: 60-80 parts of thermoplastic polyurethane, 30-50 parts of composite flame retardant foaming agent, and 1-2 parts of antioxidant; The preparation method of the composite flame retardant foaming agent comprises the following steps: Dispersing ammonium polyphosphate and boron nitride in ethanol, adding a silane coupling agent, stirring and reacting, washing and drying after the reaction is completed to obtain a mixture; The mixture is mixed evenly with water, and then fluorinated silicone is added, and stirred to obtain a composite flame retardant foaming agent; The mass ratio of the ammonium polyphosphate, boron nitride, silane coupling agent, fluorinated siloxane and water is (10-15): (1-3): (5-8): (20-40): (60-80); The catalyst A is selected from at least one of triethylenediamine and tetramethylethylenediamine; The diisocyanate A is an aliphatic diisocyanate.

2. The environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to claim 1 is characterized in that: The cashew nut shell oil polyester diol has a hydroxyl value of 80-100 mgKOH / g and a viscosity of 2500-2800 cps / 25°C.

3. The environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to claim 1 is characterized in that: The bio-based polyether polyol is a bio-based polyether-polytrimethylene ether glycol, and the molecular weight of the bio-based polyether-polytrimethylene ether glycol is 900-1100 g / mol and the hydroxyl value is 102-124.6 mgKOH / g.

4. The environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to claim 1 is characterized in that: The preparation method of the thermoplastic polyurethane comprises the following steps: Mix the bio-based polyol and diisocyanate B, raise the temperature to 60-80°C, add catalyst B, and react for 0.5-2h to obtain prepolymer A; Dissolve the biomass material in dimethyl sulfoxide, add diisocyanate C and mix, heat to 60-80°C, add catalyst C, react for 0.5-2h to obtain prepolymer B; Prepolymer A and prepolymer B are mixed, trimethylolpropane is added and mixed, the temperature is raised to 60-80°C, and the reaction is carried out for 0.5-2h to obtain thermoplastic polyurethane; The diisocyanate B and diisocyanate C are both a mixture of an aromatic diisocyanate and an aliphatic diisocyanate; the mass ratio of the aromatic diisocyanate to the aliphatic diisocyanate is (3-4):(1-2); The catalyst B and the catalyst C are both selected from at least one of dibutyltin dilaurate and stannous octoate.

5. The environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to claim 4 is characterized in that: The mass ratio of the bio-based polyol, diisocyanate B and catalyst B is (40-60): (20-40): (0.02-0.08).

6. The environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to claim 4 is characterized in that: The ratio of the biomass material, dimethyl sulfoxide, diisocyanate C and catalyst C is (5-15) g: (50-150) mL: (5-10) g: (0.001-0.01) g.

7. The environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to claim 4 is characterized in that: The mass ratio of the prepolymer A, prepolymer B and trimethylolpropane is (2-4): (1-3): (0.1-0.3).

8. The environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to claim 4 is characterized in that: The bio-based polyol includes cashew nut shell oil Mannich polyol, castor oil polyol and cashew nut shell oil polyether diol; the mass ratio of the three is 1: (3-5): (1-3).

9. The environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to claim 4, characterized in that: The biomass material includes chitosan oligosaccharide and sodium alginate; the mass ratio of the two is (10-20): (5-8).

10. The method for preparing the environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation coating according to any one of claims 1 to 9, characterized in that: The following steps are involved: The cashew nut shell oil polyester diol, the bio-based polyether polyol, the composite flame retardant foaming agent and the catalyst A are uniformly mixed to obtain component A; the core wire is placed in the diisocyanate A to obtain component B; the component A is added to the component B for foaming to obtain a flame retardant insulating foaming layer coated on the outside of the core wire; Thermoplastic polyurethane, composite flame retardant foaming agent, lubricant and antioxidant are mixed and extruded on the outside of the flame retardant insulation foam layer to obtain an environmentally friendly water supply and drainage wire based on polyurethane modified flame retardant insulation sheathing.

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