Cable support based on environmentally friendly insulating composite material, method for its production and use

Abstract

The application discloses a cable support based on an environment-friendly insulation composite material and a preparation method and application thereof, relates to the technical field of cable support preparation, and the raw material comprises an environment-friendly naphthalene-based polyester, a Naph-PFR flame retardant and other additives; the production process comprises the following steps: 1) calendering molding; 2) mold pressing molding; the environment-friendly naphthalene-based polyester and the Naph-PFR flame retardant are first produced by using environment-friendly materials and recyclable materials, and then are used for the preparation of the cable support, so that a rotatable cable trench support can be obtained. According to the application, the PBN resin is modified by poly-1,4-butanediol adipate, and the Naph-PFR flame retardant of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted with a phosphorus naphthalene heterocycle is synthesized, so that the material is environment-friendly in the production process, has high mechanical strength, excellent insulation and wide-temperature-range fireproof performance, and is especially suitable for existing cable laying operations.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cable support preparation, in particular to an environmentally friendly insulating composite material-based cable support and a preparation method and application thereof. BACKGROUND

[0002] Cables are laid in cable trenches and tunnels, and are generally fixed using supports.

[0003] Glass steel cable supports are composite materials made of synthetic resin as a binder and glass fiber and its products as reinforcing materials, which are called glass fiber reinforced plastics. Because of its high strength, it can be compared with steel, so it is also called glass steel (FRP).

[0004] However, the traditional glass fiber reinforced plastic composite cable trench support uses a large amount of non-degradable adhesive, which will volatilize organic compounds (VOCs) or other toxic substances after production and aging in later use, which is contrary to the current green power grid development concept.

[0005] Therefore, how to generate a cable support that is both economical and environmentally friendly while retaining its flame retardant, insulating, and high mechanical strength is the direction of research for new cable supports. SUMMARY

[0006] The present application relates to the technical field of cable support preparation, in particular to an environmentally friendly insulating composite material-based cable support and a preparation method and application thereof.

[0007] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0008] The present application first proposes an environmentally friendly insulating composite material-based cable support, which comprises the following raw materials:

[0009] 65 parts of environmentally friendly naphthalene-based polyester;

[0010] 18-22 parts of Naph-PFR flame retardant;

[0011] 5-7 parts of alkali-free glass fiber with a length of 6 mm;

[0012] 5-7 parts of basalt fiber;

[0013] 0.8-1.2 parts of silane coupling agent KH-560;

[0014] 0.3-0.5 parts of 2,2'-methylenebis(4-tert-octyl-6-benzotriazole phenol);

[0015] 0.7-1.3 parts of zinc stearate;

[0016] 9-11 parts of nano aluminum hydroxide;

[0017] The aforementioned environmentally friendly naphthyl polyester preparation method comprises the following steps:

[0018] S1, ester exchange reaction

[0019] A reaction kettle with a fractionating column, a nitrogen inlet, temperature and vacuum control is charged with dimethyl 2,6-naphthalene dicarboxylate and 1,4-butanediol;

[0020] After passing N2 at a rate of 0.5 L / min for 15 min, the reaction kettle is heated to 200°C at a rate of 5°C / min;

[0021] After the temperature is stabilized at 200°C±2°C for 1 min, the catalyst solution is injected, and the distilled methanol in the fractionating column is collected;

[0022]

[0023] Zn(II) activates the carbonyl oxygen of dimethyl 2,6-naphthalene dicarboxylate, 1,4-butanediol hydroxyl nucleophilic attack on the ester group, and de-methanol to form a hydroxyl ester monomer.

[0024] S3, polycondensation reaction

[0025] When the volume of collected methanol reaches 40% of the added dimethyl 2,6-naphthalene dicarboxylate, the temperature is increased to 240°C at a rate of 2°C / min, and a stepwise pressure reduction is performed;

[0026] The terminal hydroxyl group of the hydroxyl ester monomer condenses with the terminal ester group, and de-1,4-butanediol forms a polyester chain, and high vacuum (<1 mbar) removes 1,4-butanediol to push the equilibrium to the right.

[0027] Phosphoric acid triethyl ester protonates the catalyst to deactivate it:

[0028]

[0029] After the polycondensation reaction is completed, a naphthyl polyester is obtained;

[0030] S4, modification reaction and post-treatment

[0031] N2 is passed to relieve the vacuum, and polyhexanedioic acid-1,4-butanediol ester with a mass of 5-15% of the mass of the naphthyl polyester is slowly added to the naphthyl polyester, followed by the addition of catalyst tetraisopropyl titanate, and the modification reaction begins:

[0032] Phosphoric acid triethyl ester and active magnesium oxide are added 5 min before the end of the reaction, stirring is stopped, N2 is passed to relieve the vacuum, and a resin melt is obtained;

[0033] The resin melt is quickly poured onto liquid nitrogen-quenched aluminum foil, broken into resin particles, and the resin particles are washed with boiling deionized water for 3 times, and then vacuum dried to obtain the environment-friendly naphthyl polyester.

[0034] The preparation method of the aforementioned Naph-PFR flame retardant comprises the following steps:

[0035] 1) cyclization reaction

[0036] The 2-naphthol toluene solution is stirred at a stirring speed of 300 rpm, cooled to 5℃, and anhydrous ZnCl2 is added; PCl3 is slowly added through a bottom dispersion type dropping head:

[0037] Low temperature (≤20℃) inhibits the hydrolysis of PCl3 and other side reactions such as polysubstitution;

[0038] The temperature is increased to 110℃ to promote ring closure, and the reaction is refluxed for 3h to obtain a mixed solution of chloro-oxaphosphacycle intermediates;

[0039] ZnCl2 activates the phosphorus atom of PCl3 as a Lewis acid, the hydroxyl group of 2-naphthol attacks PCl3, forms a P-O bond through SN2 reaction and releases HCl, and finally closes the ring to generate benzene / naphthene [d] [1,2] oxaphosphacycle, and the reaction occurs:

[0040]

[0041] 2) condensation reaction

[0042] The mixed solution of chloro-oxaphosphacycle intermediates is cooled to 40±5℃ and stirred at 150 rpm, and a 5% mass fraction of Na2CO3 aqueous solution is slowly added;

[0043] After continuing to keep warm and stirring for 30min, stand for 1h, separate the layers, and discard the water layer;

[0044] The organic phase is washed with deionized water for 3 times, the water phase pH is 6-7, and the organic phase is dehydrated by molecular sieve to make the water content ≤200ppm, to obtain the chloro-oxaphosphacycle intermediate;

[0045] 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and antioxidant BHT are added to the chloro-oxaphosphacycle intermediate, vacuum is opened to-0.09MPa, the temperature is increased to 150℃, and after 6h of reaction, gradient cooling is carried out;

[0046] After 2h of crystal growth at 15℃, centrifugal separation is carried out at 3000rpm for 15min to obtain a crystalline filter cake;

[0047] 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide P-H bond nucleophilic substitution (SN2) to chloro, forming P-C bond bonded naphthalene-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, while BHT (antioxidant) inhibits the oxidation side reaction, the reaction equation is:

[0048]

[0049] The crystalline filter cake is rinsed with 10℃ toluene twice, and after the rinsing is completed, it is dried at 60℃ under -0.095MPa vacuum for 12h to obtain a white powder, which is the Naph-PFR flame retardant.

[0050] Toluene is recovered and reused after rectification by a rectification column; the salt-containing wastewater (Na2CO3 / NaCl) after the flame retardant is separated is evaporated and crystallized by MVR to recover inorganic salts.

[0051] Preferably, in S1, the molar ratio of dimethyl 2,6-naphthalene dicarboxylate to 1,4-butanediol is 1:2.2, and 80% of the total volume of 1,4-butanediol is directly put into the reaction kettle, and the remaining 20% of 1,4-butanediol is used to dissolve Zn(CH3COO)2·2H2O to obtain a catalyst solution.

[0052] The molar ratio of Zn(CH3COO)2·2H2O to dimethyl 2,6-naphthalene dicarboxylate is 1:2500.

[0053] The deionized water used for boiling and washing is collected, and after enrichment, Zn 2+ is recovered and reused.

[0054] The resin melt is rapidly cooled, which will cause the catalyst Zn 2+ to precipitate, and after boiling and washing with deionized water, Zn 2+ can be collected.

[0055] Preferably, in S2, the program of stepwise pressure reduction is set as:

[0056] Vacuum to 100mbar, pressure holding for 30min;

[0057] Vacuum to 10mbar, pressure holding for 30min;

[0058] Vacuum to <1mbar, holding for 60-90min.

[0059] Preferably, in S3, the mass of poly-1,4-butanediol adipate is 5-15% of the mass of naphthyl polyester; the mass of titanium isotride is 0.3-0.6% of the total mass of the material in the reaction kettle at this time;

[0060] The conditions and procedures of the modification reaction are set as follows:

[0061] Stirring is started at a stirring speed of 500 rpm, and the temperature is raised to 240℃ at a temperature raising rate of 5℃ / min;

[0062] The reaction is carried out at 240℃ under N2 protection for 1h, and vacuum is gradually drawn:

[0063] First, vacuum is drawn to -0.05MPa and maintained for 30min;

[0064] Then, vacuum is drawn to -0.095MPa, and the reaction is carried out for 1.5-2h;

[0065] The mass ratio of tetraisopropyl titanate, triethyl phosphate and active magnesium oxide is 3:5:5.

[0066] Preferably, in the 1), the mass of 2-naphthol in the 2-naphthol toluene solution accounts for 30% of the total solution mass.

[0067] The addition of PCl3 needs to be carried out in stages, and the specific settings are as follows:

[0068] When the added PCl3 accounts for 0-30% of the total PCl3 volume, the addition temperature is ≤10℃;

[0069] When the added PCl3 accounts for 30-70% of the total PCl3 volume, the addition temperature is ≤15℃;

[0070] When the added PCl3 accounts for 70-100% of the total PCl3 volume, the addition temperature is ≤20℃.

[0071] Preferably, in the preparation method of the Naph-PFR flame retardant, the mass ratio of 2-naphthol, anhydrous ZnCl2, PCl3, Na2CO3 aqueous solution, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, BHT is: 140-150: 0.75: 66-72: 65: 105-111: 0.5.

[0072] Preferably, in the 2), the gradient cooling is specifically set as follows:

[0073] The temperature is lowered to 100℃ at a temperature lowering rate of 1℃ / min;

[0074] The temperature is lowered to 60℃ at a temperature lowering rate of 0.4℃ / min;

[0075] The temperature is lowered to 15℃ at a temperature lowering rate of 0.3℃ / min.

[0076] The application also proposes a preparation method of a cable support based on an environmentally friendly insulating composite material, comprising the following steps:

[0077] ① Calendering

[0078] Put the environment-friendly naphthyl polyester, Naph-PFR flame retardant, 2, 2'-methylene bis (4-tert-octyl-6-benzotriazole phenol), zinc stearate, nano aluminum hydroxide, silane coupling agent KH-560 into the high-speed mixer, and the parameter setting is 80 DEG C, 500 rpm, 15 min;

[0079] Mix the materials, extrude into the same direction double screw impregnator, and set the temperature of 1 zone, 2 zone, 3 zone, 4 zone and die head to 240 DEG C, 260 DEG C, 275 DEG C, 270 DEG C, 265 DEG C respectively; the alkali-free glass fiber is added from the side feeding port;

[0080] Through the three-roll calender with a roller temperature of 110 DEG C, 2-5 mm sheets are made, and the bracket preform is obtained by cutting the blank into a projection area of 120% of the mold;

[0081] ② Molding

[0082] After electrostatic spraying with a 2% mass fraction water-based silicone aqueous solution into the mold, dry the film at 150 DEG C;

[0083] Use an infrared heating plate of 130 DEG C to soften the bracket preform for 90 s; the alkali-free glass fiber is vertically oriented and cross-laid on the bracket preform, and is evenly laid into 3 or more layers;

[0084] The preheated bracket preform is placed into the mold by the mechanical hand, and the molding machine is started, and the program is set as follows:

[0085] The closing speed before contacting the bracket preform is 8 mm / s;

[0086] The closing speed after contacting the bracket preform is 1 mm / s;

[0087] Segmented pressure:

[0088] Stage ① 10 MPa: 30 s;

[0089] Stage ② 25 MPa: pressure maintaining;

[0090] The mold is heated to 185 DEG C at a heating rate of 5 DEG C / min, and the holding time is 2.8 min per mm of the thickness of the product;

[0091] The ejector rod speed is set to push, and the travel is completed within 0.3 s, and the glass steel bracket is pushed out; the glass steel bracket is immediately clamped into the aluminum alloy correction frame, the cooling rate is set to 2 DEG C / min, and the cooling is cooled to room temperature, and the cable bracket based on the environment-friendly insulation composite material is obtained.

[0092] The application of the cable bracket obtained by the preparation method is also proposed, which can be made into a rotatable cable trench bracket composed of a base, a bracket column, a rotatable mechanism and a cable trench bracket;

[0093] In use, the base is fixed at the bottom of the cable well by bolts, and the matched cable trench support is installed on the column support.

[0094] The application is prepared by a molding process, and the molding temperature is as high as 185 DEG C, during which VOCs are inevitably generated and the carbon footprint is increased; however, in terms of the carbon emission factor of typical high polymer composite production, the carbon footprint of the carbon emission of the material production is about 6.5 kgCO2e / kg, and the carbon footprint of the processing process is about 2.2 CO2e / kg;

[0095] The carbon footprint of the life cycle stage of a traditional composite cable support (3 kg) from resource exploitation to product delivery to product scrapping is about 45 kgCO2e, and the application uses a recyclable Zn ion catalyst to replace a heavy metal catalyst containing tin / antimony, so that heavy metal pollution and energy consumption can be reduced; the solvent toluene is recovered by rectification, and the salt-containing wastewater is recovered by MVR evaporation crystallization, so that there is almost no pollution in the raw material acquisition stage; the main carbon source is in the operation of high-energy-consumption equipment such as high-temperature processing, calendering machine and mixing machine, and the carbon footprint index of the whole life cycle stage of the product is reduced by 40%-50% in the comprehensive product life cycle.

[0096] In addition, the three types of solvent residues (toluene), small molecule additives (1,4-butanediol, polyhexanedioic acid-1,4-butanediol ester) and thermal decomposition products of flame retardants are the main sources of VOCs of the application, and the application makes contributions to reducing VOCs through process control, such as flame retardant dehydration, polyester washing and drying, so that the VOCs release amount is reduced to 82 μg / m 3 .

[0097] Compared with the prior art, the application has the following beneficial effects:

[0098] The application adopts a full-component halogen-free design, in terms of the flame-retardant system, a self-developed Naph-PFR (naphthyl phosphorus heterocyclic flame retardant) is used to replace a bromine-containing flame retardant (such as decabromodiphenyl ether), so as to avoid the generation of dioxin and other toxic substances during incineration; in terms of the catalytic system, Zn (CH3COO)2 is used as a recyclable catalyst in the synthesis process, to replace a heavy metal catalyst containing tin / antimony, so as to avoid heavy metal wastewater pollution; the toluene solvent used is also recycled after rectification by a rectification tower and is used for flame retardant synthesis, the single-batch loss rate is low, the salt-containing wastewater (Na2CO3 / NaCl) after the separation of the flame retardant is evaporated and crystallized by MVR, to recover inorganic salts; and the application is an environmentally friendly insulating composite material.

[0099] The application uses 2,6-naphthalene dimethyl acid dimethyl ester to endow the molecular chain with rigidity, improve the size stability and thermal stability of the support, on the basis, through polybutylene adipate-1,4 chain extension toughening, further improve the mechanical properties of the support, replace 2,6-naphthalene dimethyl acid dimethyl ester and 1,4-butanediol with relatively cheap polybutylene adipate-1,4, also reduce the economic burden of producing the application;

[0100] The flame retardant takes 2-naphthol as a skeleton, the naphthalene ring promotes the formation of a dense carbon layer at high temperature, and the aromatic ring structure enhances the graphitization degree of the carbon layer through pi-pi stacking. At the same time, the grafting of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide carries out two-phase flame retardant synergy, that is, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide generates PO· free radicals by decomposition, quenches the combustion chain reaction, and forms a gas-phase flame retardant; the phosphorus heterocycle pyrolysis generates phosphate, catalyzes the dehydration of the polymer into carbon, and forms a condensed-phase flame retardant.

[0101] The Naph-PFR flame retardant and the naphthyl polyester take 2-naphthol as a common skeleton, the naphthalene ring in the flame retardant forms pi-pi stacking with the polyester main chain, significantly improves the interfacial compatibility, and achieves molecular-level coupling.

[0102] It also uses alkali-free glass fiber and basalt fiber as reinforcing materials, so that the application is economic and environmentally friendly, and the strength reaches the engineering application standard.

[0103] The carbon footprint of a traditional composite cable support (3kg) from resource exploitation to product delivery to product scrapping is about 45kgCO2e, while the application uses recyclable Zn ion catalyst to replace heavy metal catalysts containing tin / antimony (reducing heavy metal pollution and energy consumption), the solvent toluene is recovered by distillation, the salt-containing wastewater is recovered by MVR evaporation crystallization, and there is almost no pollution in the raw material acquisition stage; the main carbon source is in the operation of high-energy-consuming equipment such as high-temperature processing, calendering machine and mixer, and the carbon footprint index of the product in the whole life cycle is reduced by 40%-50%.

[0104] The application reduces volatile organic compounds and contributes to reducing VOCs through process control, such as flame retardant dehydration, polyester washing and drying, etc., so that the VOCs emission is reduced to 82μg / m 3 .

[0105] In summary, the application successfully develops an environmentally friendly, insulating, flame-retardant and mechanically excellent cable support of an environmentally friendly insulating composite material. BRIEF DESCRIPTION OF DRAWINGS

[0106] Figure 1 The application produces a rotatable cable trench support.

[0107] In the figure: 1, base, 2, support column, 3, rotatable mechanism, 4, cable trench support. DETAILED DESCRIPTION

[0108] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments.

[0109] The purity of each drug used in the experiment and its manufacturer are shown in Table 1:

[0110] Table 1. Raw drug information

[0111] Example 1:

[0112] The cable support based on the environmentally friendly insulating composite material, and the preparation method and application thereof, include the following steps:

[0113] The preparation method of Naph-PFR flame retardant includes the following steps:

[0114] 1) Cyclization reaction

[0115] Dissolve 2-naphthol in toluene at 80℃ to prepare a 2-naphthol toluene solution with a mass fraction of 30%; stir at a stirring speed of 300 rpm, and cool to 5℃ at a cooling rate of 10℃ / min, then add anhydrous ZnCl2 with a mass ratio of 200:1 to 2-naphthol;

[0116] Slowly add PCl3 through the bottom dispersion drop head:

[0117] When adding 0-30% of PCl3, the addition temperature is ≤10℃;

[0118] When adding 30-70% of PCl3, the addition temperature is ≤15℃;

[0119] When adding 70-100% of PCl3, the addition temperature is ≤20℃;

[0120] Increase the temperature to 110℃ at a heating rate of 1℃ / min, and reflux for 3h to obtain a mixed solution of chloro-oxaphosphorin intermediates;

[0121] 2) Condensation reaction

[0122] Cool the mixed solution of chloro-oxaphosphorin intermediates to 40±5℃, stir at 150 rpm, and slowly add a 5% Na2CO3 aqueous solution; add for 30min;

[0123] After continuing to keep warm and stirring for 30min, stand for 1h to separate the layers, and discard the water layer;

[0124] The organic phase is washed with deionized water for 3 times, the pH of the water phase is 6-7, the organic phase is dehydrated by molecular sieve to make the water content of the organic phase ≤200ppm, to obtain the chloro-oxaphosphorine intermediate;

[0125] The chloro-oxaphosphorine intermediate is added with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and BHT, and the vacuum is opened to-0.09MPa; the temperature is raised to 150℃ at a temperature raising rate of 2℃ / min, and after 6h of reaction, gradient cooling is performed;

[0126] The gradient cooling is specifically set as:

[0127] The temperature is lowered to 100℃ at a temperature lowering rate of 1℃ / min;

[0128] The temperature is lowered to 60℃ at a temperature lowering rate of 0.4℃ / min;

[0129] The temperature is lowered to 15℃ at a temperature lowering rate of 0.3℃ / min;

[0130] After 2h of crystal growth at 15℃, the crystallization filter cake is separated by centrifugation at 3000rpm for 15min;

[0131] The crystallization filter cake is washed twice with 10℃ toluene, and the amount of toluene is 20L / batch, and the wet product is obtained after the washing is completed;

[0132] The wet product is transferred into a vacuum drying machine at 60℃ and-0.095MPa, and dried for 12h to obtain a white powder, which is the Naph-PFR flame retardant.

[0133] The mass ratio of 2-naphthol, anhydrous ZnCl2, PCl3, Na2CO3 aqueous solution, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and BHT is 145:0.75:69:108:0.5.

[0134] The used toluene is recovered and reused after being rectified by a rectification column.

[0135] The preparation method of the environment-friendly naphthyl polyester comprises the following steps:

[0136] S1, raw material preparation

[0137] 2,6-naphthalene dicarboxylic acid dimethyl ester and 1,4-butanediol are put into a reaction kettle with a fractionating column, a nitrogen inlet, temperature and vacuum control, wherein the molar ratio of 2,6-naphthalene dicarboxylic acid dimethyl ester to 1,4-butanediol is 1:2.2, and the amount of 1,4-butanediol put in this time is 80% of the total mass of 1,4-butanediol;

[0138] The remaining 20% of 1,4-butanediol was used to dissolve Zn(CH3COO)2·2H2O to obtain a catalyst solution, wherein the concentration of Zn(CH3COO)2·2H2O was 4×10 -4 mol / mol dimethyl 2,6-naphthalene dicarboxylate;

[0139] S2, ester exchange reaction

[0140] After 15 min of N2purging at a rate of 0.5 L / min, the temperature was raised to 200℃ at a rate of 5℃ / min;

[0141] After the temperature was stabilized at 200℃±2℃ for 1 min, the catalyst solution was injected, and the distilled methanol in the fractionating column was collected;

[0142] S3, polycondensation reaction

[0143] When the volume of the collected methanol reached 40% of the added dimethyl 2,6-naphthalene dicarboxylate, the temperature was raised to 240℃ at a rate of 2℃ / min;

[0144] Stepwise pressure reduction:

[0145] Vacuum was drawn to 100 mbar, and the pressure was maintained for 30 min;

[0146] Vacuum was drawn to 10 mbar, and the pressure was maintained for 30 min;

[0147] Vacuum was drawn to <1 mbar, and the pressure was maintained for 60-90 min;

[0148] After the polycondensation reaction was completed, a naphthyl polyester was obtained;

[0149] S4, modification reaction and post-treatment

[0150] N2was purged to release the vacuum, and polyhexanedioate-1,4-butanediol ester with a mass of 10% of the naphthyl polyester was slowly added to the naphthyl polyester, followed by the addition of a catalyst titanium isopropyl titanate with a mass of 0.3% of the total material; stirring was started at a stirring speed of 500 rpm, and the temperature was raised to 240℃ at a rate of 5℃ / min;

[0151] The reaction was carried out at 240℃ under N2protection for 1 h, and vacuum was gradually drawn:

[0152] First, vacuum was drawn to -0.05 MPa and maintained for 30 min;

[0153] Then, vacuum was drawn to -0.095 MPa, and the reaction was carried out for 1.5-2 h;

[0154] Five minutes before the end of the reaction, add 0.5% of the total mass of materials in the reactor at that time, along with an equal mass of active magnesium oxide. Stop stirring, purge with N2 to release the vacuum, and obtain the resin melt.

[0155] The resin melt was quickly poured onto aluminum foil quenched by liquid nitrogen and broken into resin particles. The resin particles were washed three times with boiling deionized water and then vacuum dried at 80°C for 24 hours to obtain environmentally friendly naphthyl polyester.

[0156] The method for preparing cable supports based on environmentally friendly insulating composite materials includes the following steps:

[0157] ① Calendering

[0158] 65 kg of environmentally friendly naphthyl polyester, 20 kg of Naph-PFR flame retardant, 0.5 kg of 2,2'-methylenebis(4-tert-octyl-6-benzotriazole phenol), 1.3 kg of zinc stearate, 11 kg of nano aluminum hydroxide, and 0.8 kg of silane coupling agent KH-560 were put into a high-speed mixer with the parameters set to 80℃, 500 rpm, and 15 min.

[0159] Mix the materials thoroughly and extrude them into a twin-screw impregnation machine with co-rotating twin screws. Set the temperatures of zones 1, 2, 3, 4 and the die head to 240℃, 260℃, 275℃, 270℃ and 265℃ respectively. Add alkali-free glass fiber from the side feed port.

[0160] The 2-5mm sheet is produced by a three-roll calender with a roll temperature of 110℃, and then cut into blanks with a die projection area of ​​120% to obtain the bracket preform.

[0161] ② Compression molding

[0162] A 2% (w / w) water-based silicone aqueous solution was electrostatically sprayed into the mold and then dried at 150°C to form a film.

[0163] The prefabricated support structure was softened for 90 seconds using an infrared heating plate at 130℃; 5 kg of alkali-free glass fiber and 5 kg of basalt fiber were vertically oriented and cross-laid on the prefabricated support structure, evenly distributed in 5 layers.

[0164] The robotic arm places the preheated bracket preform into the mold, and starts the compression molding machine. The program is set as follows:

[0165] The closing speed before contacting the prefabricated support component is 8 mm / s;

[0166] The closing speed after contacting the prefabricated support component is 1 mm / s;

[0167] Segmented pressurization:

[0168] Stage ① 10MPa: 30s;

[0169] Stage ② 25 MPa: pressure maintaining;

[0170] The mold is heated to 185 DEG C at a heating rate of 5 DEG C / min, and the holding time is 2.8 min per mm of the thickness of the product;

[0171] The ejection rod is set to push at a speed, and the travel is completed within 0.3 s, and the glass steel support is pushed out; the glass steel support is immediately clamped into the aluminum alloy correction frame, the cooling rate is set to 2 DEG C / min, and the cable support based on the environment-friendly insulating composite material is obtained after cooling to room temperature.

[0172] The obtained cable support based on the environment-friendly insulating composite material can be made into a rotatable cable trench support composed of 1, a base, 2, a support column, 3, a rotatable mechanism, and 4, a cable trench support.

[0173] Different from example 1, examples 2-3 are designed and completed according to different formulations:

[0174] Example 2:

[0175] The preparation method and implementation method of the Naph-PFR flame retardant and the environment-friendly naphthyl polyester are the same as those in example 1; but 65 kg of the environment-friendly naphthyl polyester, 20 kg of the Naph-PFR flame retardant, 0.4 kg of 2,2'-methylene bis (4-tert-octyl-6-benzotriazole phenol), 1 kg of zinc stearate, 10 kg of nano aluminum hydroxide, 1 kg of silane coupling agent KH-560, 6 kg of alkali-free glass fiber, and 6 kg of basalt fiber are used.

[0176] Example 3:

[0177] The preparation method and implementation method of the Naph-PFR flame retardant and the environment-friendly naphthyl polyester are the same as those in example 1; but 65 kg of the environment-friendly naphthyl polyester, 20 kg of the Naph-PFR flame retardant, 0.4 kg of 2,2'-methylene bis (4-tert-octyl-6-benzotriazole phenol), 1 kg of zinc stearate, 10 kg of nano aluminum hydroxide, 1 kg of silane coupling agent KH-560, 6 kg of alkali-free glass fiber, and 6 kg of basalt fiber are used.

[0178] The product obtained by the application has an appearance as shown in Figure 1 and is also designed accordingly:

[0179] Example 4: the same as the formulation and experimental method of example 2, but the mass of poly-1,4-butylene adipate is 5% of the mass of the naphthyl polyester;

[0180] Example 5: the same as the formulation and experimental method of example 2, but the mass of poly-1,4-butylene adipate is 15% of the mass of the naphthyl polyester;

[0181] Example 6: Same formulation and experimental procedure as Example 2, but mass ratio of 2-naphthol, PCl3, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 140:69:108;

[0182] Example 7: Same formulation and experimental procedure as Example 2, but mass ratio of 2-naphthol, PCl3, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 150:69:108;

[0183] Example 8: Same formulation and experimental procedure as Example 2, but mass ratio of 2-naphthol, PCl3, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 145:66:108;

[0184] Example 9: Same formulation and experimental procedure as Example 2, but mass ratio of 2-naphthol, PCl3, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 145:72:108;

[0185] Example 10: Same formulation and experimental procedure as Example 2, but mass ratio of 2-naphthol, PCl3, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 145:72:105;

[0186] Example 11: Same formulation and experimental procedure as Example 2, but mass ratio of 2-naphthol, PCl3, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 145:72:111;

[0187] Comparative Example 1: Same formulation and experimental procedure as Example 2, but insufficient poly(l,4-butanediol adipate) diol is added;

[0188] Comparative Example 2: Same formulation and experimental procedure as Example 2, but excess poly(l,4-butanediol adipate) diol is added;

[0189] Comparative Example 3: Same formulation and experimental procedure as Example 2, but insufficient 2-naphthol is added;

[0190] Comparative Example 4: Same formulation and experimental procedure as Example 2, but excess 2-naphthol is added;

[0191] Comparative Example 5: Same formulation and experimental procedure as Example 2, but insufficient PCl3 is added;

[0192] Comparative Example 6: Same formulation and experimental procedure as Example 2, but excess PCl3 is added;

[0193] Comparative Example 7: Same as Example 2 in formulation and experimental method, but with insufficient 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;

[0194] Comparative Example 8: Same as Example 2 in formulation and experimental method, but with excessive 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;

[0195] The specific formulations are shown in Tables 2 and 3:

[0196] Table 2. Formulation of cable support based on environmentally friendly insulating composite material (1)

[0197]

[0198] Table 3. Formulation of cable support based on environmentally friendly insulating composite material (2)

[0199] According to the mechanical properties and heat resistance, insulation of the product obtained by the present application are tested according to "JB / T10216-2013 Cable Bridge for Electric Control Power Distribution"; the carbon footprint is estimated by combining the carbon emission factor of typical high polymer composite material, taking 3 kg as the standard; the VOCs release data of cable support under the condition of 23℃ / 50%RH for 28 days is tested according to ISO 16000-9 standard, and the corresponding results are as follows:

[0200] The performance test data of each item is summarized in Table 4:

[0201] Table 4. Performance test data of each item of cable support

[0202]

[0203] Through data analysis, it can be known that:

[0204] Polybutylene adipate-1,4-butylene glycol as a toughening modifier, by improving the flexibility of polyester segment to improve the toughness of the material, the amount needs to be accurately controlled; if 10 kg in Comparative Example 1 is too small, it will cause the material to be too brittle due to high crystallinity, and the impact strength will drop sharply; if 100 kg in Comparative Example 2 is too much, although it can further improve the impact toughness, it will significantly weaken the rigidity and reduce the bending strength.

[0205] 2-Naphthol, as the flame retardant backbone, is the core structural unit for constructing Naph-PFR flame retardants, directly affecting the char formation efficiency and flame retardant performance of the material. For example, insufficient dosage (80 kg in Comparative Example 3) results in the absence of crucial flame-retardant segments, leading to complete combustion failure of the material; excessive dosage (200 kg in Comparative Example 4) causes over-crosslinking, making the material brittle, and the flame retardant rating can only be maintained at a lower V-2 level. The safe and effective dosage range is 140-150 kg, ensuring UL94 V-0 flame retardancy without significantly degrading mechanical properties.

[0206] PCl3 is the ring-closing agent in flame retardants. Its core function is to form a crucial phosphorus heterocyclic structure with 2-naphthol, which is essential for flame retardant efficiency. Insufficient dosage (30 kg in Comparative Example 5) will lead to incomplete ring-closing reaction and a severe decrease in flame retardant performance; excessive dosage (100 kg in Comparative Example 6) will significantly damage the material's insulation due to increased byproducts. Therefore, it is crucial to strictly control its dosage within a reasonable range to balance flame retardant efficiency and insulation performance.

[0207] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is a flame retardant synergist, primarily exerting its flame-retardant effect in the gas phase and effectively inhibiting combustion dripping. If the dosage of 50 kg in Comparative Example 7 is too low, insufficient char residue and dripping will result in a flame retardant rating of only V-2; if the dosage of 200 kg in Comparative Example 8 is too high, it will impair the thermal stability of the material, and the flame retardant rating will also drop to V-1.

[0208] Reinforcing fibers can significantly improve the flexural strength of materials and suppress deformation under load. The amount of fiber used is significantly positively correlated with mechanical properties: within the range of 10-14 kg, every 1 kg increase in fiber content increases the flexural strength by approximately 11 MPa, while simultaneously reducing deformation. Too low a content results in insufficient load-bearing capacity.

[0209] In summary, the cable support of the present invention is not as mechanically advanced as metal supports, but its overall performance surpasses that of resin supports in accordance with national standards. It is environmentally friendly, insulating, flame-retardant, and has excellent mechanical properties, which can meet the needs of cable well operations and is an ideal choice for the next generation of cable supports.

[0210] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. Cable support based on environmentally friendly insulating composite material, characterized in that, The raw materials include the following weight parts: 65 parts of environmentally friendly naphthyl polyester; 20 parts of Naph-PFR flame retardant; 5-7 parts of alkali-free glass fiber with a length of 6 mm; 5-7 parts of basalt fiber; 0.8-1.2 parts of silane coupling agent KH-560; 0.3-0.5 parts of 2,2'-methylene bis (4-tert-octyl-6-benzotriazole phenol); 0.7-1.3 parts of zinc stearate; 9-11 parts of nano aluminum hydroxide; The preparation process of the environmentally friendly naphthyl polyester includes the following steps: S1, ester exchange reaction A reaction kettle with a fractionating column, a nitrogen inlet, temperature and vacuum control is used to put dimethyl 2,6-naphthalene dicarboxylate and 1,4-butanediol into the kettle; N2 is introduced into the reaction kettle, and the temperature is raised to 200℃; After the temperature is stabilized at 200℃±2℃, the catalyst solution is injected, and the distilled methanol in the fractionating column is collected; S2, polycondensation reaction When the volume of the collected methanol reaches 40% of the volume of dimethyl 2,6-naphthalene dicarboxylate added to the reaction kettle, the temperature is raised to 240℃, and stepwise pressure reduction is performed; after the completion of the polycondensation reaction, a milky white viscous liquid, i.e. naphthyl polyester, is obtained; S3, modification reaction and post-treatment N2 is introduced to relieve the vacuum, and 5-15% of the mass of the naphthyl polyester is slowly added to the naphthyl polyester as polybutylene adipate-1,4-butanediol ester, followed by the addition of catalyst tetraisopropyl titanate to start the modification reaction; After 4h of reaction, triethyl phosphate and active magnesium oxide are added, and stirring is stopped to obtain a resin melt; The resin melt is quickly poured into a quenched mold, broken into resin particles, and washed with boiling deionized water, and then vacuum dried to obtain the environmentally friendly naphthyl polyester; The preparation process of the Naph-PFR flame retardant includes the following steps: 1) cyclization reaction Stir the 2-naphthol toluene solution, cool to 5℃, and add anhydrous ZnCl2; slowly add PCl3: Raise the temperature to 110℃, and reflux to obtain a mixture of chloro-oxaphosphaphane intermediates; 2) condensation reaction Cool the mixture of chloro-oxaphosphaphane intermediates to 40±5℃, stir, and slowly add Na2CO3 aqueous solution; Keep stirring and standing, separate the layers, discard the water layer; Wash the organic phase with deionized water, and adjust the water phase pH to 6-7; dehydrate the organic phase with molecular sieves to make the water content ≤200ppm to obtain chloro-oxaphosphaphane intermediates; Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and antioxidant BHT to the chloro-oxaphosphaphane intermediates, start vacuum, and raise the temperature to 150℃; after 6h of reaction, perform gradient cooling; After low-temperature crystal growth, centrifugal separation is performed to obtain a crystalline filter cake; The crystalline filter cake is washed with cold toluene, vacuum dried after the washing is completed, and a white powder, i.e. Naph-PFR flame retardant, is obtained; In the Naph-PFR flame retardant, the mass ratio of 2-naphthol, anhydrous ZnCl2, PCl3, Na2CO3 aqueous solution, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and BHT is: 140-150:0.75:66-72:65:105-111:0.

5.

2. The environmentally friendly insulation composite based cable support of claim 1, wherein, In the S1, the molar ratio of dimethyl 2,6-naphthalene dicarboxylate to 1,4-butanediol is 1:2.2, 80% of the total volume of 1,4-butanediol is directly put into the reaction kettle, and the remaining 20% of 1,4-butanediol is used to dissolve Zn(CH3COO)2·2H2O to obtain a catalyst solution; The molar ratio of Zn(CH3COO)2·2H2O to dimethyl 2,6-naphthalene dicarboxylate is 1:2500.

3. The environmentally friendly insulation composite based cable support of claim 1, wherein, In the S2, the step-down program is set as: Vacuum to 100 mbar, pressure maintaining for 30 min; Vacuum to 10 mbar, pressure maintaining for 30 min; Vacuum to <1 mbar, maintaining for 60-90 min.

4. The environmentally friendly insulation composite based cable support of claim 1, wherein, In the S3, the mass of titanium isopropyl titanate is 0.3-0.6% of the total material mass in the reaction kettle at this time; The conditions and program of the modification reaction are set as: Start stirring at a stirring speed of 500 rpm, and heat to 240℃ at a heating rate of 5℃ / min; React for 1 h under the protection of N2 at 240℃, and gradually vacuumize: Firstly, vacuumize to -0.05 MPa, and maintain for 30 min; Then, vacuumize to -0.095 MPa, and react for 1.5-2 h; The mass ratio of titanium isopropyl titanate, triethyl phosphate and active magnesium oxide is 3:5:

5.

5. The environmentally friendly insulation composite based cable support of claim 1, wherein, In the 1), the mass of 2-naphthol in the 2-naphthol toluene solution accounts for 30% of the total solution mass; The addition of PCl3 needs to be added in stages, and the specific settings are as follows: The addition temperature is ≤10℃ when adding 0-30% of PCl3; The addition temperature is ≤15℃ when adding 30-70% of PCl3; The addition temperature is ≤20℃ when adding 70-100% of PCl3.

6. The environmentally friendly insulation composite-based cable support of claim 1, wherein, In the 2), the gradient cooling is specifically set as: Cool to 100℃ at a cooling rate of 1℃ / min; Cool to 60℃ at a cooling rate of 0.4℃ / min; Cool to 15℃ at a cooling rate of 0.3℃ / min.

7. A process for the production of an environmentally friendly insulation composite based cable support according to any of claims 1 to 6, characterized in that Comprise the following steps: ① Calendering molding Put the environment-friendly naphthalene-based polyester, Naph-PFR flame retardant, 2,2'-methylene bis(4-tert-octyl-6-benzotriazole phenol), zinc stearate, nano aluminum hydroxide, and silane coupling agent KH-560 into a high-speed mixer; Mix the materials, and extrude into a double-screw impregnator. The alkali-free glass fiber is added from the side feeding port; Pass through a three-roll calendering machine to make 2-5 mm sheets, and cut into a blank that is more than 120% of the projected area of the mold to obtain a bracket preform; ② Molding Use a water-based silicone aqueous solution to electrostatically spray into the mold, and then dry to form a film; Use an infrared heating plate to soften the bracket preform; Vertically orient the basalt fibers, and cross-pile them on the bracket preform to divide and lay them into 3 or more layers; Put the preheated bracket preform into the mold by a mechanical hand, start the molding machine to press and heat, and the heat preservation time is 2.8 min per mm of the thickness of the product; Push out the glass steel bracket by the ejector rod, immediately clamp it into a correction frame, and cool to room temperature to obtain a cable bracket based on an environment-friendly insulating composite material.

8. Use of a cable support produced by the method according to claim 7, characterized in that Make a rotatable cable trench bracket composed of a base, a bracket stand column, a rotatable mechanism, and a cable trench bracket; In use, the base is fixed to the bottom of the cable well by bolts, and the matched cable trench support is installed on the column support.

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